WO2010006583A2 - Procédé de fabrication d'un produit de sécurité et/ou de valeur comprenant des régions présentant une émission de luminescence différente - Google Patents

Procédé de fabrication d'un produit de sécurité et/ou de valeur comprenant des régions présentant une émission de luminescence différente Download PDF

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Publication number
WO2010006583A2
WO2010006583A2 PCT/DE2009/000916 DE2009000916W WO2010006583A2 WO 2010006583 A2 WO2010006583 A2 WO 2010006583A2 DE 2009000916 W DE2009000916 W DE 2009000916W WO 2010006583 A2 WO2010006583 A2 WO 2010006583A2
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WO
WIPO (PCT)
Prior art keywords
security
string
pigments
marking layer
pattern
Prior art date
Application number
PCT/DE2009/000916
Other languages
German (de)
English (en)
Other versions
WO2010006583A3 (fr
Inventor
Oliver Muth
Manfred Paeschke
Burkhard Krietsch
Matthias Kuntz
Andreas Walter
Original Assignee
Bundesdruckerei Gmbh
Merck Patent Gmbh
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 Bundesdruckerei Gmbh, Merck Patent Gmbh filed Critical Bundesdruckerei Gmbh
Priority to EP20090775927 priority Critical patent/EP2296912B1/fr
Publication of WO2010006583A2 publication Critical patent/WO2010006583A2/fr
Publication of WO2010006583A3 publication Critical patent/WO2010006583A3/fr

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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
    • B42D25/20—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof characterised by a particular use or purpose
    • B42D25/29—Securities; Bank notes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/30—Identification or security features, e.g. for preventing forgery
    • B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
    • B42D25/378—Special inks
    • B42D25/387—Special inks absorbing or reflecting ultraviolet light

Definitions

  • the invention relates to a method for producing a security and / or value product, in particular a security and / or value document, comprising the following method steps: a substrate is coated with a marking layer containing a luminescent substance, becomes a pattern formed by the luminescence emission of the luminescent substance a string is formed, and the string is readably applied to the security and / or value product as an identifier string and / or readably integrated therein.
  • the invention further relates to a security and / or value product which can be produced by means of such a method and to a method for verifying such a security and / or value product.
  • a method for the production of security marks is known.
  • a pattern of particles for example metal particles, is formed, which are randomly distributed in the marking layer.
  • a random pattern which is unique with very high statistical probability for the security and / or value product concerned, ie different security and / or value products differ by the respective random patterns.
  • the random pattern of a security and / or value product is recorded in a spatially resolved and intensity-resolved manner, a characteristic string is generated from the recording and the string is affixed to the security and / or value product as an identification string.
  • an intensity threshold in the determination of the character string in the course of production, an intensity threshold must also be defined in the simplest case, which differs from “dark” in the context of the pattern "bright". This requires a corresponding calibration of devices with which a recording of the Random pattern for verification purposes.
  • the intensities may be changed by surface contamination, abrasion, etc. in the course of use of the security and / or value product, for example, in durable security and / or value products, such as
  • Electroluminescent substance is an electrically conductive
  • Electroluminescent substance and high luminescence emission can be achieved at moderate excitation conditions.
  • the invention is based on the technical problem of specifying a security and / or value product with a luminescence pattern as well as a correlated identity string attached to it, for example, on the security and / or value product, which is easier to produce and reliable in the verification "false-negative”. Avoids results.
  • the invention teaches a method for producing a security and / or value product, in particular a security and / or value document, comprising the following method steps: a) a substrate is provided with a marking layer containing a preferably particulate luminescent substance and optionally b) optionally an excitation of the luminescent substance, so that the luminescent substance has a detectable luminescence emission, c) a plurality of subregions of the marking layer, a defined and for the
  • step c) the pattern generated in step c) is assigned a character string in a preferably one-to-one manner
  • e ) in the Step d) associated string is applied to the security and / or value product readable as an identifier string and / or legibly integrated therein and / or stored in a database system (centralized or decentralized).
  • the invention is based on the recognition that defined and predetermined patterns can be generated by targeted modification of the luminescence in partial regions of the marking layer, as a result of which
  • security and / or value product includes in particular security and / or value documents.
  • Security and / or value documents are, for example: identity cards, passports, ID cards,
  • Access cards visas, tax stamps, tickets, Driving licenses, motor vehicle papers, banknotes, checks, postage stamps, credit cards, any chip cards and adhesive labels (eg for product protection).
  • Products which do not fall under the concept of security and / or value document are labels, consignment notes, inspection certificates, vouchers as well as all everyday products which can be forged and which can be unambiguously identified as originals by the application of the security feature according to the invention.
  • a substrate is a flat support structure based on synthetic and / or natural organic polymers.
  • a substrate may consist of one layer or of a stacked composite of several layers. Basically, all materials, as usual in the technology of security and / or value products, can be used. Only, for example, are suitable materials for a substrate or for various layers of a substrate called: paper materials, printing layers,
  • PC Polycarbonate
  • PET general polyester
  • plastics such as polycarbonates or polyphthalphthalates. In the case of layers of plastics, these may be formed as films.
  • a cover layer preferably of a transparent plastic, can be applied to the marking layer. It is also possible to apply several different transparent cover layers.
  • the marking layer can be applied over the entire surface of the substrate, or only on a partial surface of the substrate. In the latter case, a cover layer which may have been set up needs to be transparent only above the partial surface of the substrate carrying the marking layer, but may nevertheless also cover the entire surface of the substrate and also be transparent over its entire surface.
  • the application of the marking layer can take place in all customary ways. These include printing techniques. Suitable printing methods in principle are all printing processes known and customary in the production of security and / or value products, such as offset printing, letterpress printing, offset coating, flexographic printing, screen printing, thermal sublimation printing, gravure printing, in particular gravure gravure printing and intaglio printing, the so-called overprint varnish process , as well as all non-contact printing processes. Preferably, however, the marking layer is applied by screen printing. But also, for example, doctoring, brushing, stamping, casting, painting, dipping, flow method, roll or screen application method or application by air brush can be used.
  • Prefabricated (polymer) film or solid layer is attached to the substrate, for example by means of gluing or lamination.
  • the manner of applying the marking layer is completely irrelevant to the invention and the above variants are only intended as a few of many possible examples.
  • the change in the partial areas of the marking layer applied in step b) is imperceptible to the human eye when illuminated with visible light and in daylight intensity, but can only be ascertained with the aid of technical aids such as magnifying glass, detectors, etc. ,
  • Intensity of the luminescence from a reference sub-area of the sub-area by at least 5%, better at least 10%, preferably at least 20%, based on the intensity of the luminescence from a comparison sub-area, which is outside the subregions.
  • a weakening of the luminescence emission means - under constant excitation conditions - a decrease in the intensity of the luminescence from a reference partial area of the partial area by at least 5%, more preferably at least 10%, preferably at least 20%, based on the intensity of the luminescence from a comparison partial area which is outside the partial areas lies.
  • a pattern denotes a defined distribution of partial areas within the marker layer and in Directions parallel to a major surface of the marking layer.
  • the marking layer need not be formed as a single layer, but may in turn be formed of marking sub-layers which are connected to one another in a stacked manner, wherein other (transparent) layers can also be interposed between marking sub-layers.
  • the pattern can not only by a lateral distribution (in directions parallel to a major surface of the marking layer) of the sub-areas (as in a
  • Single layer but also be formed over a vertical distribution (orthogonal to the main surface). In general, however, only the lateral distribution will be determined, but with an additional vertical distribution but also taking into account the vertical distribution by spatially resolved measurement of the luminescence with a different from the surface normal and predetermined angle of incidence takes place.
  • the sections typically have one
  • the areal extent may basically be provided in any desired form, but typically a circular shape, rectangular shape, square shape or a shape of a regular polygon will be provided.
  • a pattern and a string are uniquely assigned to each other when exactly one pattern of a
  • String is assigned and vice versa.
  • each pattern is assigned exactly one string, then more than one pattern may be associated with a string.
  • the assignment can basically be done in any way. It is preferred if the character sequence is calculated from the pattern by means of a predetermined algorithm. Then, an inherent verification is possible without external database, since then only the predetermined algorithm must be applied to the measured pattern in the course of verification, in which case a direct comparison of the thus determined string with the read identifier string is possible.
  • a suitable algorithm may be the calculation of a hash value from the pattern, including its coordinates with respect to at least one reference point of the security and / or value product (viewed in projection orthogonal to a major surface of the marker layer).
  • the assignment is unique, so that even with hash functions, depending on the complexity, so-called collisions can be tolerated to some extent. Because in the verification yes the pattern is read, determined by means of the predetermined hash function, the string and compared with the identity string. It does not matter that in the event of a collision, another security and / or value may exist with a different pattern, which results in the same string when the hash function is used (collision). Conveniently, however, the target amount of the hash function is chosen so large that at most few collisions are to be expected.
  • the Target amount of hash function for example, at least 10 4 , better at least 10 5 , preferably at least 10 6 , different elements, such as alphanumeric characters, be large.
  • suitable hash algorithms reference is additionally made to the specialist literature on this subject.
  • the application or integration of the identification string on or into the security and / or value product can be carried out by means of all techniques customary for the personalization of a security and / or value product. This includes labeling, for example by laser, printing, for example inkjet printing, u.v.m. Since the pattern is predetermined and defined for each security and / or value product, the correlated character string is also predetermined and defined for each security and / or value product.
  • the identity string is then arranged below the marking layer, within the marking layer, or above the marking layer.
  • An identification string is readable if it is readable by the human eye and / or with technical aids.
  • An identifier string may be formed, for example, as an alphanumeric string, for example as a serial number. But it is also possible that the identifier string is encoded, for example as a barcode or the like.
  • Suitable luminescent substances are all commercially available luminescence-indicating substances. These include fluorescent (life of the excited state usually less than 10 "6 or 10 " 9 s) or phosphorescent (lifetime of the excited state usually greater than IGT 6 s) substances, photoluminophores, electroluminophores, cathodoluminophores, chemoluminophores, bioluminophores, thermoluminophores, anti-Stokes Luminants, triboluminophores and sonoluminophores.
  • Luminophores can be based on inorganic systems such as Y 2 Ü 2 S: Eu or ZnSrCu, but also on organic systems such as fluorescein.
  • Electroluminophores are particulate materials which are inorganic compounds of Groups II and VI of the Periodic Table, for example ZnS or CdS doped or activated with metals such as Cu, Mn or Ag.
  • particulate luminescent substances based on predominantly Mn, Sr or rare earth activated silicates, aluminates, phosphates, tungstates, germanates, borates, etc., in particular substances based on Zr ⁇ SiO 4 IMn or particulate organic polymers or mixtures of the aforementioned compounds are used. Additional reference is made to the reference S. Shionoya et al., Phosphor Handbook, especially Chapter 9, Electroluminescent materials, CRC Press, 1999.
  • Electroluminescent substances emit visible radiation after excitation in an alternating electric field.
  • a luminescent substance emits visible radiation after excitation in an alternating electric field.
  • Electroluminescence shows, the emission of visible light is preferably alone or predominantly by the excitation in an alternating electric field and possibly to a lesser extent by excitation by irradiation with light of the ultraviolet or infrared spectral range.
  • the excitation of the photoluminescence it is preferred for the excitation of the photoluminescence to take place by means of UV radiation, electrical alternating fields not being required.
  • the particles of the luminescent substance are preferably in the form of microencapsulated compounds or sheath / core particles, wherein the core through the
  • Luminescent substance is formed.
  • Suitable materials for the shell are both organic polymers and various metal oxides in question.
  • the essential function of the jacket is to protect the core from environmental influences, resistance and durability
  • Emissivity of the core can be detrimental.
  • the aging resistance can be increased by means of the jacket.
  • a filter function can be exercised, both with respect to incident radiation and emitted radiation.
  • an electroluminescent Kerns of the mantle function as a UV filter, which reliably prevents luminescence under UV irradiation.
  • the marking layer may also contain a plurality of different luminescent substances. It is then expedient for the different luminescent substances to be excited differently (for example UV / electric alternating fields) and / or for different emission wavelengths.
  • the particle size of particulate luminescent substances may be selected according to the technology used to prepare the marking layer. For example, in the case of printing techniques, the particle size will typically be in the range of 0.2 to 50 microns, especially 2 to 30 microns. In flexographic printing even particle sizes up to 200 ⁇ m can still be applied. However, for techniques such as brushing, the particle size can be up to 100 ⁇ m and more, up to 500 ⁇ m.
  • the marking layer may additionally contain a pigment containing an electrically conductive material or a mixture of various such pigments.
  • Electrically conductive pigments contain or consist of at least one electrically conductive layer.
  • the electrically conductive layer may, for example, comprise or consist of one or more metal oxides which have been rendered conductive by means of doping, for example tin oxide, zinc oxide, indium oxide and / or titanium oxide. For doping Ga, Al, In, Th, Ge, Sn, P, Ar, Sb, Se, Te, W and / or F come into question.
  • a carrier layer for example based on titanium dioxide, synthetic or natural mica, other layered silicates, glass, silicon dioxide, and / or Al 2 O 3 , and then carry the electrically conductive layer, preferably being enveloped by this layer .
  • other layers may also be present, for example containing metal oxides, metal oxide hydrates, metal suboxides, metal fluorides, metal nitrides, metal oxynitrides or mixtures of such substances.
  • the carrier layer and / or other layers, if provided, and / or the electrically conductive layer are optically transparent or im Substantially transparent, ie they transmit at least 10%, preferably at least 70% of the incident light.
  • the transparent or semitransparent layers can be colorless or colored.
  • the color properties of the electrically conductive pigments can also be modified by the additional layers, in particular if they are located below the conductive layer or between the carrier layer layer and the conductive layer.
  • the application of other layers on the electrically conductive layer can adapt the conductivity of the electrically conductive layer in accordance with specifications.
  • the electrically conductive pigment is preferably a mica coated with at least one electrically conductive metal oxide layer, in particular antimony-doped tin oxide.
  • one or more metal oxide layers for example a titanium oxide layer, may be provided on or below the electrically conductive layer.
  • the diameter of an electrically conductive pigment is preferably in the range of 0.1 ⁇ m to 500 ⁇ m, preferably 2 ⁇ m to 100 ⁇ m, particularly preferably 5 ⁇ m to 70 ⁇ m. A narrow particle size distribution is preferred.
  • platelet-shaped electrically conductive pigments are used.
  • the aspect ratio (diameter / thickness) of platelet-shaped conductive pigments is typically at least 2: 1, in particular at least 10: 1, more preferably at least 100: 1.
  • Particularly transparent with high conductivity are electrically conductive platelet-shaped pigments whose number-weighted mean grain area F50 (grain area: size of a main area) is at least 150 ⁇ m 2 , in particular at least 200 ⁇ m 2 .
  • the number-weighted proportion of pigments having a grain area of preferably less than 80 ⁇ m 2 is not more than 33%, in particular less than 25%, based on the total amount of electrically conductive pigment. Even better is a proportion with a particle size less than 40 ⁇ m 2 of not more than 15%, in particular not more than 10%. This reduction of fines reduces light scattering and thus haze of the marking layer.
  • Suitable electrically conductive pigments are commercially available, for example, from Merck KGaA.
  • the marking layer additionally comprises an organic or inorganic (absorption) color pigment and / or an effect pigment or a mixture of various such pigments.
  • This may be, for example, at least one platelet-shaped effect pigment and / or an organic or inorganic color pigment.
  • Platelet-shaped effect pigments are platelet-shaped pearlescent pigments, predominantly transparent or semitransparent interference pigments and metallic effect pigments. Also liquid crystal pigments, so-called LCPs (Liquid Crystal Pigments), or structured polymer platelets, so-called holographic pigments, are included. These platelet-shaped pigments are composed of one or more layers of possibly different materials.
  • Pearlescent pigments consist of transparent platelets with a high refractive index and show a characteristic pearlescence when oriented parallel through multiple reflection. Such pearlescent pigments, which additionally show interference colors, are referred to as interference pigments.
  • platelet-shaped effect pigments preferably interference pigments or metallic effect pigments are used which on an inorganic platelet-shaped support at least one coating of a metal, metal oxide, metal oxide or have mixtures thereof, a metal mixed oxide, metal suboxide, metal oxynitride, metal fluoride, BiOCl or a polymer.
  • the metallic effect pigments preferably have at least one metal layer.
  • the inorganic platelet-shaped support preferably consists of natural or synthetic mica, kaolin or other sheet silicates, of glass, SiO 2 , TiO 2 , Al 2 O 3 , Fe 2 O 3 , polymer platelets, graphite platelets or metal flakes, such as aluminum, titanium, Bronze, silver, copper, gold, steel or various metal alloys. Preference is given to supports of mica, glass, graphite, SiO 2 , TiC> 2 and Al 2 O 3 or mixtures thereof.
  • the size of these carriers is not critical per se. As a rule, they have a thickness of between 0.01 and 5 ⁇ m, in particular between 0.05 and 4.5 ⁇ m.
  • the extension in the length or width is usually between 1 and 250 ⁇ m, preferably between 2 and 200 ⁇ m and in particular between 2 and 100 ⁇ m. They usually have an aspect ratio (ratio of the average diameter to the average particle thickness) of 2: 1 to 25000: 1, and in particular from 3: 1 to 2000: 1.
  • Coatings of metals are preferably made of aluminum, titanium, chromium, nickel, silver, zinc, molybdenum, tantalum, tungsten, palladium, copper, gold, platinum or alloys containing them.
  • the metal fluoride used is preferably MgF 2 .
  • multilayer effect pigments are particularly preferably used. These have on a platelet-shaped, preferably non-metallic carrier several layers, which preferably consist of the aforementioned materials and different refractive indices in such a way that in each case at least two layers of different refractive index are alternately on the carrier, wherein the refractive indices in the individual layers differ by at least 0.1 and preferably by at least 0.3.
  • the layers located on the carrier can be both almost transparent and colorless as well as transparent and colored or semitransparent.
  • LCPs which consist of crosslinked, oriented, cholesteric liquid crystals, or else also known as holographic pigments structured polymer platelets can be used as platelet-shaped effect pigments.
  • the platelet-shaped effect pigments described above may be present individually or in admixture in the security element according to the present invention.
  • the platelet-shaped effect pigments used according to the invention are preferably transparent or semitransparent.
  • semitransparent pigments transmit at least 10%, transparent pigments, however, at least 70% of the incident visible light.
  • Such platelet-shaped effect pigments are preferably used, since their transparency in a security and / or valuable product contributes to a large variety of possible background or background colors and at the same time does not impair the intensity of the light emission produced by electroluminescence.
  • a flake-form effect pigment is used which leaves a different visually perceptible color and / or brightness impression at different illumination and / or viewing angles.
  • this property is called a color flop.
  • pigments which have a color flop produce non-duplicable color and gloss impressions in the security and / or value products produced therewith, which are readily perceptible to the naked eye without any aids.
  • Such pigments are also referred to as optically variable.
  • the optically variable platelet-shaped effect pigments have, for example, three optically clearly distinguishable discrete colors under at least two different illumination or viewing angles at least two and at most four, but preferably under two different illumination or viewing angles two or three different illumination or viewing angles.
  • optically variable platelet-shaped effect pigments can also be used which, when tilted over different illumination and / or viewing angles, produce a color gradient, i. many different shades, such as the typical pearlescence, have. Even such diffuse color changes are easily detectable by the human eye.
  • the platelet-shaped effect pigments used according to the invention are present in an oriented form in the marking layer or the security and / or desired product, i. they are aligned almost parallel to the surfaces of the security product provided with the security element.
  • alignment is already effected essentially by means of the customary methods used for applying the security element, for example customary printing methods.
  • platelet-like effect pigments for example, the commercially available interference pigments, which are available, for example, under the names Iriodin®, Colorstream®, Xirallic® or Securalic® from Merck KGaA, Mearlin® from Mearl, metallic effect pigments from Eckhard and goniochromatic (optically variable ) Effect pigments like For example, Variochrom® from BASF, Chromafflair® from Flex Products Inc., Helicone® from Wacker or holographic pigments from Spectratec and other similar commercially available pigments are used. This list, however, is to be considered as illustrative and not exhaustive.
  • inorganic color pigments are all common transparent and opaque white, colored and black pigments, such as Powell Blau,
  • Benzimidazoles copper phthalocyanine, azo pigments, perinones, anthanthrones, other phthalocyanines, anthraquinones, indigo, thioindigo and their derivatives, or carmine red are mentioned.
  • titanium dioxide and zinc oxide are given by way of example only.
  • the particle size of the inorganic and organic color pigments is not critical, but must be adapted to the requirements of the application of the security element on or in a security product, for example with a printing process to be adjusted. The same applies analogously, as noted for the luminescent substance and / or the electrically conductive pigments.
  • the luminescent substance may form a random pattern in the marking layer.
  • the security and / or value product provided with the marking layer can be subjected to a recording of the random pattern, in which case a hash value is again calculated, for example, from the random pattern and second identifier string, for example, as part of a serial number, is applied to the security and / or value product or integrated therein, according to the identifier string described above.
  • An (additional) verification can then be done by detecting the random pattern, calculating the identifier string (with the same algorithm as in the above calculation of the second identifier string) and comparing it with the second identifier string attached to or in the security and / or value product.
  • the modulation of the luminescence emission in the subregions of step c) can be made possible, for example, by the marking layer additionally having a laser-sensitive pigment. Then, by irradiation by means of laser light of a given dose rate, either an increase in the permittivity of components of the marking layer in the immediate vicinity
  • the subregions consequently form a pattern which is particularly bright in an alternating electric field, while in the second case, on the other hand, a negative pattern is formed, as it were, by the comparatively dark subregions.
  • the former can be achieved with comparatively low dose rates of the laser, the latter with comparatively high dose rates.
  • the dose rate suitable for a marking layer with a specific composition for one of the two cases can be determined in each case by means of simple experiments or test series, for example, the marking layer is irradiated to different predetermined locations with different dose rates associated with the sites and then the gain and / or reduction the electroluminescence is recorded quantitatively. When observing the desired quantitative change, the dose rate associated with the site is the appropriate one. It is also possible to reduce the photoluminescence of corresponding luminescent substances by, for example, pyrolysis.
  • the presence of a laser-sensitive pigment is not absolutely necessary.
  • a laser pattern similar to the above can be generated.
  • a local melting in the marking layer and thus in the immediate vicinity of the luminescent substance is generated.
  • This alters the spatial distribution of the electrically conductive material-containing pigment as compared to the unfused environment within the marking layer.
  • This results in a change in the field displacement and, in the case of an electroluminophor, consequently a local change in the luminescence upon excitation with electric fields.
  • an amplification or attenuation of the electroluminescence in the areas irradiated by the laser can thereby be achieved.
  • the electrically conductive material-containing pigment itself is a laser-sensitive Pigment.
  • the local irradiation by laser then alters both the dielectric properties of the environment of the luminescent substance and the electrical properties of the electrically conductive material itself, again with the consequence of the modulation
  • laser-sensitive pigments all known in the technological field of safety and / or value products pigments can be used. They may be formed, for example, from organic polymers which have a high absorption of the laser radiation, for example PET, ABS, polystyrene, PPO, polyphenylene sulfide,
  • the particle size is typically in the range from 01 to 100 ⁇ m, in particular 0.1 to 50 ⁇ m, preferably 1 to 20 ⁇ m.
  • the polymer particles may further contain light-sensitive fillers or pigments, for example in an amount of from 0.1 to 90% by weight, based on the laser-sensitive pigment. These may also be electrically conductive pigments and / or effect pigments and / or dyes, as described above.
  • basic Cu (II) hydroxide phosphate used. Specifically, a product of the heating of blue Cu (II) orthophosphate (Cu 3 (PO 4 ) 2 * 3H 2 O) to 100 to 200 0 C is formed and a molecular formula Cu 3 (PO 4 ) 2 * Cu (OH) 2 has. Further suitable copper phosphates are: Cu 3 (PO 4 ) 2 * 3Cu (OH) 2 ,
  • Suitable laser radiation has a wavelength in the range 150 nm to 10,600 nra, in particular 150 nm to 1100 nm.
  • C0 2 lasers (10600 nm), Nd: YAG lasers (1064 nm and 532 nm, respectively), and pulsed UV lasers (excimer lasers) can be used, for example.
  • the energy density is generally in the range of 0.3 mJ / cm 2 to 50 J / cm 2 , in particular in the range 0.3 mJ / cm 2 to 10 J / cm 2 .
  • Marking layer as explained above, for example, by applying a preparation with the pigments discussed above, for example by way of printing on the substrate.
  • the above-mentioned pigments, substances and particles are in the
  • the concentration of the luminescent substance in the preparation is 0.01 to 20 wt .-%, preferably 1 to 10 based on the preparation.
  • the electrically conductive pigment is generally present in a concentration of from 0.0 to 20% by weight, in particular from 0.01 to about 20% by weight, preferably from 1 to 10% by weight, based on the preparation, in this before.
  • Color pigments are to contain these in the preparation in a concentration of 0.01 to 40 wt .-%, preferably 2 to 20 wt .-%, based on the preparation.
  • these are contained in the preparation in a concentration of 0.01 to 20 wt .-%, preferably 0.1 to 10 wt .-%, based on the preparation .
  • the pigments and particles mentioned can be added to the preparation individually or in a mixture. This can be done in the form of powdered pigments and particles. However, the abovementioned pigments and particles are preferably introduced into the preparation individually or in a mixture of at least two different types of flowable pigment preparations or dry preparations.
  • a pigment preparation or a dry preparation can be prepared from a mixture of a particulate substance having electroluminescent properties and a transparent electrically conductive pigment, optionally still one or more effect and / or color pigments and optionally the laser-sensitive pigment are added.
  • Flowable pigment preparations are understood in particular to be pastes or pastes which, in addition to the pigments mentioned, may also contain binders, solvents and optionally one or more additives.
  • the dry preparations mentioned generally contain the same additives, but with a largely reduced solvent content.
  • dry preparations are also regarded as preparations which contain 0 to 8% by weight, preferably 2 to 8% by weight and in particular 3 to 6% by weight of water and / or a solvent or solvent mixture. These dry preparations are preferably as pearlets,
  • Such flowable pigment preparations and dry preparations facilitate the transport, storage and uniform introduction of the pigments into the printing ink, prevent segregation of pigments and other constituents and promote good redispersing behavior of the printing inks.
  • the preparation contains one or more suitable binders, typically in an amount of 5 to 70 wt .-%, and optionally other additives such as solvents, for example in an amount of 5 to 70 wt .-%, and additives such as adhesion promoters , Dispersing aids, drying accelerators, photoinitiators and the like, which are common in such formulations, in an amount of typically 0.1 to 20 wt .-%.
  • the above proportions by weight always add up to 100 wt .-%.
  • the relevant components are then present in quantities which are calculated from the deduction of the proportion of the solvents from the preparation. It is understood that these binders and additives are adapted to the printing process to be used and that the composition has an adequate viscosity.
  • the marking layer can also be prefabricated.
  • Suitable layered materials include papers of various types or polymeric materials, but may also be textile materials, etc.
  • the marking layer When the marking layer is based on a polymeric layer, it has two surfaces lying essentially parallel to one another and contains the various pigments described above in the variants and options described.
  • the concentrations of the various substances and, if appropriate, adjusted pigments are basically in ranges as described above for the preparation, only based on the weight of the marking layer.
  • the substances and pigments used are introduced into the polymeric matrix preferably in the form of masterbatches. These contain, in addition to the pigment constituents and substances, suitable amounts of binders, solvents and, if appropriate, further customary auxiliaries and additives. In this case, all thermoplastics which are opposite to the luminescent substance as well as polymers can be used as polymers If necessary, additional inert pigments and substances show an inert behavior.
  • the polymers should not be electrically conductive or enhance the electrical conductivity of the polymeric layer.
  • the marking layer in the case of electroluminescent substances, it is particularly expedient if the marking layer as such is not continuously electrically conductive, although it contains electrically conductive pigments, since otherwise short circuits may occur.
  • the marking layer is transparent. Therefore, transparent polymers are preferably used. This applies, for example, to polystyrene, polyvinyl chloride, polycarbonate and their mixed and graft polymers, polyvinylidene chloride and fluoride, polyamides, polyolefins, polyacrylic and vinyl esters, thermoplastic polyurethanes, cellulose esters and the like. They could be used singly or in suitable mixtures.
  • the marking layer may additionally contain customary auxiliaries and additives such as fillers, UV stabilizers, inhibitors, flame retardants, lubricants, plasticizers, solvents, dispersants and additional dyes or organic and / or inorganic color pigments.
  • the marking layer is preferably produced by various suitable methods such as film casting, spin coating, extrusion process, calendering or compression molding, but in particular by extrusion processes or by a blown film process.
  • the various starting materials are mixed together and processed in suitable, generally known systems to polymer layers in the form of films of different thickness or thin plates.
  • platelet-shaped pigments effect pigments and possibly also the electrically conductive pigments
  • effect pigments and possibly also the electrically conductive pigments are aligned on the surfaces of the tools and are therefore oriented in the resulting polymeric layers substantially parallel to the surfaces of the polymeric layer. Stretching and pulling operations during film blowing or as subordinate steps to extruding further reinforce this orientation of the pigments. During the subsequent cooling, this orientation is fixed. A segregation or settling behavior of the pigment mixture used can not be determined in the finished marking layers. Care should be taken, however, that no excessive shearing forces act on the pigment components to prevent their destruction.
  • the luminescent substance and optionally furnished pigments can also be introduced into paper raw materials or textile raw materials to form the marking layer.
  • a marking layer is produced by adding, in addition to the constituents mentioned, all base materials and auxiliaries which are customary in particular in papermaking. Changes in the usual procedure do not result from the luminescent substance and, if appropriate, pigments. Rather, their concentration is chosen so that all current methods, such as papermaking, can be applied. These are known in the art and therefore need not be closer be explained. However, as already described above, care should be taken to ensure that the pigments are not damaged or destroyed in the production process of the papers and textiles, and that in the resulting paper or textile no continuous electrical
  • Paper-based substrates are all common types of papers, but especially security papers with basis weights up to. 200 g / m 2 , preferably those of cotton fibers and / or textile materials, can be used.
  • the invention further relates to a security and / or valuable product, in particular security and / or value document, obtainable by a method according to the invention.
  • the substrate may be formed by the security and / or value product itself.
  • the marking layer is arranged on a flat substrate, which then in turn attached to the security and / or value product, for example glued etc., or integrated therein, for example, laminated, etc., is.
  • the substrate may consist of a layer or else be multilayered.
  • the invention also relates to a method for verifying a security and / or value product, in particular a security product according to the invention and / or value product, wherein the security and / or value product is exposed to the luminescence stimulating conditions, with a spatially resolved and intensity-resolved recording of the Safety and / or value product Lumineszenzstrahlung emitted, wherein the pattern is determined by identifying the subregions with increased or decreased luminescence emission, wherein from the pattern, the associated string is determined, with an identifier string is read from the security and / or value product and / or from a database, wherein the string is compared with the string of identities, the security and / or value product being deemed to be false if the string and string are not matched, and true if the string and string match.
  • a spatially resolved and intensity-resolved recording can be obtained, for example, by means of a camera which simultaneously or scans a two-dimensional image. Only as a suitable camera be a camera with a two-dimensional CCD chip and a CCD chip upstream optics called.
  • the recording is generated either at exactly predetermined positioning of the security and / or value product relative to the camera and excitation of the luminescence, or the pattern contains a for all security and / or value products same and equal positioned reference pattern, based on which a coordinate definition of the recorded Subareas can be done. Then an alignment is not required.
  • the reference pattern may have been generated in accordance with the subregions, whereby the recording then inherently contains the reference pattern and an evaluation of the pattern is readily possible in terms of data technology.
  • the invention will be explained in more detail by way of embodiments that merely represent embodiments. Show it:
  • Figure 1 Top view of a marking layer before modulation of the luminescence emission under luminescence excitation
  • Figure 2 Top view of a marking layer after modulation of the luminescence emission below
  • a preparation is prepared with the following components: 5-70% by weight of resin / binder system, 5-70% by weight of solvent, 0-15% by weight, in particular 0.1-15% by weight of catalysts / Initiators, 0-20 wt .-%, in particular 0.1-20 wt .-% additives, 0.1 to 20 wt .-% luminescent substance or a mixture of different luminescent substances, for example a mixture of one or more Elektroluminophor and one or a plurality of photoluminophores, wherein the ratio of electroluminophore to photoluminophore can be between 0.1: 99.9 and 99.9: 0.1, in particular between 20:80 and 80:20, 0-25 wt .-%, in particular 5-25 %
  • effect pigment in particular interference pigment, or a mixture of different effect pigments, and also from 0.1 to 10% by weight of laser-sensitive pigment or a mixture various such pigments, wherein the sum of all components always gives 100
  • the resin / binder system for example, reactive monomers, oligomers, prepolymers, such as mono-, di-, and / or trifunctional acrylates are suitable.
  • Commercially available systems include, for example, the Laromer® series (BASF), SR-9003 or SR-415 (Sartomer), melamine impregnating resins, such as the Kauramin® or Kaurit® series (BASF), for example -752, -753, -786 or -787, or polymer dispersions, such as the Kauro-pal® series (BASF), for example -937 or 938.
  • varnishes based on nitrocellulose or linseed oil can be used.
  • Suitable solvents are all solvents customary in organic chemistry with the proviso that pigments used thereof are not dissolved or dissolved. These include alcohols such as methanol, ethanol or isopropanol, ketones such as acetone or 2-Bunanon, esters such as ethyl acetate, halogenated solvents such as dichloromethane, and / or aromatics such as toluene or xylene.
  • the essential solvent is water, and in small amounts, typically below 20 wt .-%, usually less than 10 wt .-%, based on the solvent, and organic solvents may be present.
  • catalysts / initiators conventional photoinitiators, such as Irgacure® 2020, Irgacure® 819 or Darocure® 1173 (all Ciba) can be used.
  • photoinitiators such as Irgacure® 2020, Irgacure® 819 or Darocure® 1173 (all Ciba) can be used.
  • Kauramin® or Kauramit® resins are the for example, the hardener 527 or 529 (BASF) suitable.
  • Free-radical formers such as, for example, azo-isobutyronitrile, can also be used.
  • Suitable additives are adjuvants, such as
  • Antifoaming agents for example Byk-020 or -052 from Byk
  • surfactants for example Baysilone from Bayer or Byk-306 or 310 from Byk
  • preservatives for example Borchers Sl from Borchers
  • suitable additives Ullmann's chemical encyclopedia, Wiley Verlag, electronic edition 2007, keyword “Paint Additives” or www.borchers.de referenced.
  • Suitable electroluminophores are described, for example, in the reference S. Shionoya et al., Phosphor Handbook, Chapter 9, Electroluminescent Materials, CRC Press, 1999.
  • Suitable photoluminophores are described for example in the reference Ullmann's chemical encyclopedia, Wiley Verlag, electronic edition 2007, keyword "Luminescent Materials”.
  • the luminescent substance generally has a coarse-grained structure, for example a d90 value (diameter range, which comprises 90% by weight of the particles, remainder typically a fine fraction of 5-50 ⁇ m.)
  • the size distribution is very narrow, in particular practically monomodal.
  • Useful interference pigments include, for example, the aforementioned products of various companies.
  • Useful laser-sensitive pigments are described, for example, in the document EP 0 991 523 B1.
  • a marking layer is obtained which exhibits a luminescence according to FIG. 1 upon excitation with alternating electric fields.
  • the luminescent points are considerably more numerous and randomly distributed than the simplified representation, and thus result in a random pattern.
  • the diameter of a drawn point should stand for the intensity of electroluminescence.
  • a further random pattern obtainable under UV excitation which results from the excitation of the photoluminophore.
  • FIGS. 1 and 2 show a greatly enlarged section of the marking layer, in which the intensity of the luminescence emission varies with the size of the points shown. In this case, large dots in FIG. 2 mean a high luminescence intensity, and small dots correspondingly low luminescence intensities.
  • a laser sweeps according to a predetermined path the shown and through the predetermined path of the laser beam
  • predetermined subregions where in the subregions a local pyrolysis by the strong absorption of the laser radiation in the laser-sensitive pigment and its immediate environment (diameter up to 10 microns to the center of a laser-sensitive
  • Pigments takes place.
  • the permittivity in the immediate vicinity of a laser-sensitive pigment is reduced, with the result that an electroluminophore in this environment can no longer be excited to luminescence with the alternating electric field of the same frequency and intensity as in Example 1.
  • the partial regions show a reduced electroluminescence compared with the other regions, as shown diagrammatically in FIG. 2 by the smaller points.
  • the pyrolysis is due to the control of the laser, as described locally limited, so that the pyrolyzed areas are practically imperceptible in normal daylight and with the human eye without technical aids.
  • step 3 Since in step 3 the path of the laser is predetermined via the marking layer, the position and orientation of the subregions are also predetermined and known.
  • a hash value can then be calculated from the orientation and position of the subregions by means of a usual hash algorithm as the identity string.
  • This hash value is made in the form of a string as part of a marking layer and thus assigned to the security and / or value product serial number.
  • the identification sequence or serial number can then be written into the marking layer in the same process step as the generation of the partial regions by means of laser marking.
  • the subregions or locally highly resolved form the subregions of the marking layer a hidden and inherent to the serial number or the identifier string redundant individual security feature, which is extremely difficult to replicate.
  • the replica would also, if at all possible, require the individual replication of each individual security and / or value product or its marking layer, which would represent an extreme technological effort from the point of view of afterimages.
  • Example 4 Verification of a Security and / or
  • Example 3 The security and / or desired product or its marking layer obtained in Example 3 is exposed to an alternating electric field whose frequency and intensity correspond approximately to the conditions of Examples 1 or 2. At the same time, by means of a two-dimensionally resolving CCD camera, the pattern formed from the subregions of FIG. 2 as well as the serial number or the
  • Identity string read out From the pattern, a hash value is calculated with the algorithm of Example 3 and compared with the read-out identity string. If they match, the security and / or value product is verified, and if not matched, it is most likely a forgery.

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  • Business, Economics & Management (AREA)
  • Accounting & Taxation (AREA)
  • Finance (AREA)
  • Credit Cards Or The Like (AREA)
  • Printing Methods (AREA)

Abstract

L'invention concerne un procédé de fabrication d'un produit de sécurité et/ou de valeur, en particulier d'un document de sécurité et/ou de valeur, ce procédé comprenant les étapes suivantes : a) un substrat est recouvert d'une couche de marquage contenant une substance luminescente; b) une pluralité de régions de la couche de marquage est modifiée, de manière à former un motif défini individuel pour le produit de sécurité et/ou de valeur, de telle sorte que l'émission de luminescence de la substance luminescente soit amplifiée ou réduite dans lesdites régions; c) une chaîne de caractères est associée au motif créé à l'étape b), de préférence de manière biunivoque; d) la chaîne de caractères associée lors de l'étape c) est appliquée de manière lisible sur le produit de sécurité et/ou de valeur et/ou intégrée de manière lisible dans celui-ci comme chaîne de caractères d'identification. L'invention concerne en outre un produit de sécurité et/ou de valeur pouvant être obtenu par ce procédé, ainsi qu'un procédé de vérification d'un tel produit de sécurité et/ou de valeur.
PCT/DE2009/000916 2008-07-16 2009-06-26 Procédé de fabrication d'un produit de sécurité et/ou de valeur comprenant des régions présentant une émission de luminescence différente WO2010006583A2 (fr)

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WO2021013759A1 (fr) * 2019-07-19 2021-01-28 Bundesdruckerei Gmbh Procédé pour évaluer des matériaux luminescents anti-stokes non résistants volatils sur des documents de valeur
US11886947B2 (en) 2020-12-22 2024-01-30 Leuchtstoffwerk Breitungen Gmbh Method for uniquely marking objects

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CN103201118B (zh) 2010-11-08 2015-01-07 尤尼卡技术股份有限公司 用于借助uv激光在着色的衬底上生成彩色图像的方法和装置以及由此制成的产品
DE102012201016A1 (de) 2012-01-24 2013-07-25 Bundesdruckerei Gmbh Dokumentbasierter Schlüssel
DE102012219905A1 (de) 2012-10-31 2014-04-30 Bundesdruckerei Gmbh Verfahren und Vorrichtung zur Prüfung eines Sicherheitselements
DE102013007811A1 (de) 2013-05-07 2014-11-13 Giesecke & Devrient Gmbh Verfahren zur Markierung eines Merkmalstoffes, Sicherheitsmerkmal, Wertdokument und Verfahren zur Prüfung desselben
DE102016215002A1 (de) * 2016-08-11 2018-03-01 Bundesdruckerei Gmbh Verfahren und Vorrichtung zur Identifikation zumindest eines Sicherheitselementsmindestens eines Sicherheitsmerkmals eines Sicherheitserzeugnisses
WO2018162938A1 (fr) 2017-03-10 2018-09-13 Fraunhofer-Gesellschaft Zur Forderung Der Angewandten Forschung E.V. Procédés et système de marquage et de détection d'une unité physique résistante aux clones
DE102018115146A1 (de) * 2018-06-24 2019-12-24 Industry365 Ug (Haftungsbeschränkt) Verfahren zur Herstellung für das menschliche Auge nicht sichtbarer und nicht kopierbarer Sicherheitselemente in einer Abbildung sowie Verfahren zum Authentizitätsnachweis von Produkten auf Basis des Abgleichs von ungleichen Informationen sowie gedruckte Abbildung

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US11886947B2 (en) 2020-12-22 2024-01-30 Leuchtstoffwerk Breitungen Gmbh Method for uniquely marking objects

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