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WO2019115636A2 - Procédé de fabrication d'une substance de marqueur de sécurité ainsi que procédés d'authentification et d'identification d'un objet et système d'identification - Google Patents

Procédé de fabrication d'une substance de marqueur de sécurité ainsi que procédés d'authentification et d'identification d'un objet et système d'identification Download PDF

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Publication number
WO2019115636A2
WO2019115636A2 PCT/EP2018/084608 EP2018084608W WO2019115636A2 WO 2019115636 A2 WO2019115636 A2 WO 2019115636A2 EP 2018084608 W EP2018084608 W EP 2018084608W WO 2019115636 A2 WO2019115636 A2 WO 2019115636A2
Authority
WO
WIPO (PCT)
Prior art keywords
substance
luminescent
security
luminescent substance
security marker
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.)
Ceased
Application number
PCT/EP2018/084608
Other languages
German (de)
English (en)
Other versions
WO2019115636A3 (fr
Inventor
Kristin Unthan
Andreas Grosse
Dirk Mollenhauer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Km Innopat GmbH
Original Assignee
Km Innopat 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 Km Innopat GmbH filed Critical Km Innopat GmbH
Priority to EP18825607.7A priority Critical patent/EP3723997A2/fr
Publication of WO2019115636A2 publication Critical patent/WO2019115636A2/fr
Publication of WO2019115636A3 publication Critical patent/WO2019115636A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • B42D25/30—Identification or security features, e.g. for preventing forgery
    • B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
    • B42D25/378—Special inks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/30—Identification or security features, e.g. for preventing forgery
    • B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
    • B42D25/378—Special inks
    • B42D25/387—Special inks absorbing or reflecting ultraviolet light
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/40—Manufacture
    • B42D25/405—Marking
    • B42D25/41—Marking using electromagnetic radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/40—Manufacture
    • B42D25/405—Marking
    • B42D25/415—Marking using chemicals
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6408—Fluorescence; Phosphorescence with measurement of decay time, time resolved fluorescence
    • G—PHYSICS
    • G06—COMPUTING OR CALCULATING; COUNTING
    • G06K—GRAPHICAL DATA READING; PRESENTATION OF DATA; RECORD CARRIERS; HANDLING RECORD CARRIERS
    • G06K19/00—Record carriers for use with machines and with at least a part designed to carry digital markings
    • G06K19/06—Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the kind of the digital marking, e.g. shape, nature, code
    • G06K19/06009—Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the kind of the digital marking, e.g. shape, nature, code with optically detectable marking
    • G06K19/06046—Constructional details
    • G06K19/0614—Constructional details the marking being selective to wavelength, e.g. color barcode or barcodes only visible under UV or IR
    • G—PHYSICS
    • G06—COMPUTING OR CALCULATING; COUNTING
    • G06K—GRAPHICAL DATA READING; PRESENTATION OF DATA; RECORD CARRIERS; HANDLING RECORD CARRIERS
    • G06K19/00—Record carriers for use with machines and with at least a part designed to carry digital markings
    • G06K19/06—Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the kind of the digital marking, e.g. shape, nature, code
    • G06K19/08—Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the kind of the digital marking, e.g. shape, nature, code using markings of different kinds or more than one marking of the same kind in the same record carrier, e.g. one marking being sensed by optical and the other by magnetic means
    • G06K19/10—Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the kind of the digital marking, e.g. shape, nature, code using markings of different kinds or more than one marking of the same kind in the same record carrier, e.g. one marking being sensed by optical and the other by magnetic means at least one kind of marking being used for authentication, e.g. of credit or identity cards
    • G06K19/14—Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the kind of the digital marking, e.g. shape, nature, code using markings of different kinds or more than one marking of the same kind in the same record carrier, e.g. one marking being sensed by optical and the other by magnetic means at least one kind of marking being used for authentication, e.g. of credit or identity cards the marking being sensed by radiation
    • G—PHYSICS
    • G07—CHECKING-DEVICES
    • G07D—HANDLING OF COINS OR VALUABLE PAPERS, e.g. TESTING, SORTING BY DENOMINATIONS, COUNTING, DISPENSING, CHANGING OR DEPOSITING
    • G07D7/00—Testing specially adapted to determine the identity or genuineness of valuable papers or for segregating those which are unacceptable, e.g. banknotes that are alien to a currency
    • G07D7/06—Testing specially adapted to determine the identity or genuineness of valuable papers or for segregating those which are unacceptable, e.g. banknotes that are alien to a currency using wave or particle radiation
    • G07D7/12—Visible light, infrared or ultraviolet radiation
    • G07D7/1205—Testing spectral properties
    • G—PHYSICS
    • G07—CHECKING-DEVICES
    • G07D—HANDLING OF COINS OR VALUABLE PAPERS, e.g. TESTING, SORTING BY DENOMINATIONS, COUNTING, DISPENSING, CHANGING OR DEPOSITING
    • G07D7/00—Testing specially adapted to determine the identity or genuineness of valuable papers or for segregating those which are unacceptable, e.g. banknotes that are alien to a currency
    • G07D7/20—Testing patterns thereon
    • G07D7/202—Testing patterns thereon using pattern matching
    • G07D7/205—Matching spectral properties

Definitions

  • the invention relates to a method for producing a security marker fabric and to a corresponding security marker fabric and to an object having a marker with such a security marker fabric. Furthermore, the invention relates to methods for authenticating and authenticating an object and to an authentication system for authenticating an object.
  • an examination of the authenticity of an object is then irradiated with at least a part of the object in or on which the security marker should be located, with an excitation signal, usually with light in the UV range or in the visible range, and then that of the luminescent substance generated response signal detected and analyzed.
  • Another feature that can be used for verification is the cooldown of the luminescence emission.
  • a pulse-shaped excitation signal is output and then checked, after which time the response signal has decayed by a certain value.
  • a precise spectral measurement makes it possible to identify a luminescent substance precisely. If a security marker substance is used which contains a plurality of luminescent substances, then the detected spectrum can be unfolded and the individual constituents can thus be determined. For most luminescent substances, the cooldowns from the literature are then known. Thus, the counterfeit security of the security feature is not improved by additional measurement of the persistence time.
  • the production of the phosphors should be done so as to later material types
  • plastics in a recycling process it is clear that the phosphors must be reproducibly produced even in large quantities. Accordingly, for example, a change in the size and / or shape of the phosphor is carried out by grinding and subsequent sieving of the millbase in fractions of different particle size, to which then a particular decay constant can be assigned.
  • these decay constants must be highly precise and reproducible in the long term. Accordingly, there is also the danger here that counterfeiters reproduce such a marker as soon as they know the procedure for the production of the phosphor.
  • This object is achieved by a method for producing a security marker according to claim 1, a security marker according to claim 7, an object according to claim 8, by methods for authentication and authentication of an object according to claims 9 and 10, in particular by a method for determining a temporal response behavior of luminescent materials, as well as by an authentication system according to claim 16.
  • At least one luminescent substance preferably the afterglow function of this luminescent substance, is specifically or deliberately individually irreproducibly modified.
  • a luminescent substance may be any luminescent substance or luminescent substance, or else a combination (mixture) of luminescent phosphors, which may be both a fluorescent substance and a phosphorescent substance.
  • this may be a light conversion substance or light conversion luminescent substance which is irradiated with the light of a specific frequency range and emits a light in another frequency range.
  • afterglow function (or “life distribution”) is the To understand temporal Abkling , ie the relative signal strength of the response signal of the luminescent substance or thethanerstoffs with the luminescent substance as a function of time from the turn-off time of an excitation signal with which the luminescent substance or safety marker substance was excited.
  • the persistence function may also depend on the excitation wavelength and / or the wavelength emitted (as used, for example, in time-resolved emission spectroscopy - TRES).
  • a corresponding security marker substance comprises at least one such individually irreproducibly modified luminescent substance (also referred to below as “individualized luminescent substance”). Preferably, this has an individually irreproducibly modified persistence function.
  • the security marker substance can consist only of this individualized luminescent substance or of a mixture of such individualized luminescent substances. However, as will be explained later, it can also be introduced into a carrier, for example a paste or liquid, which can then optionally be further processed.
  • a carrier for example a paste or liquid
  • An object according to the invention for example an arbitrary component, a spare part, a medicament or a document such as money, check cards or access cards etc., is provided with a marking with a corresponding security marker material.
  • the security marker substance may be a security marker coating material, such as a lacquer, a colorant or the like, which can then be applied to the product completely or in sections, for example in a security print, on and / or in the object. or introduced. Likewise, it can be printed on a security label or the like, which is then connected to the product so that it can not be removed without destroying it.
  • a security marker substance or luminescent substance directly into the building material for the object, for example into a plastic for producing the object in an injection molding process, by extrusion or in an additive manufacturing process, etc.
  • Label liquids with the help of individualized luminescent substances by introducing them into the liquid. It is also possible to use several markings with different security marker materials on one object in order to further increase security.
  • a marking is arranged on and / or in the object which comprises a security marker material according to the invention.
  • a marking can be given by the security marker substance itself, which is introduced, for example, in the material of which the object or a part of the object consists.
  • the security marker substance can also be connected to the object in any other way. For example, a marking by a full-surface or partial coating of the object, for example by painting, done with such a security marker fabric.
  • a security marker material may also be printed on the object or other visible markings, such as, for example, the brand, a type designation, etc., which are then additionally used as a security marker for an authentication.
  • a security marker substance arranged on or in the object is irradiated with an excitation signal, for example a pulse, and the irreproducibly individualized luminescent substance is thus excited and a response signal generated thereby or the impulse response is detected and analyzed.
  • an excitation signal for example a pulse
  • an authentication system for authentification of an object based on a security marker substance arranged on and / or in the object, which has an individualized luminescent substance or a mixture of such luminescent substances as described above, has at least the following components:
  • An excitation signal transmitting device for example in the form of a radiation source, preferably light source (preferably an LED, an OLED, a semiconductor laser, in particular a laser diode, or the like) with a suitable drive unit for irradiating theracemarkerstoffs (including irradiation of only a portion ofracemarkerstoffs to understand) with an excitation signal.
  • a radiation source preferably light source (preferably an LED, an OLED, a semiconductor laser, in particular a laser diode, or the like) with a suitable drive unit for irradiating theexcellentmarkerstoffs (including irradiation of only a portion ofprofilemarkerstoffs to understand) with an excitation signal.
  • a response signal receiving device for detecting a response signal may be, for example, one or more radiation detectors, preferably one or more photodiodes, phototransistors or photodetectors with associated readout electronics.
  • An analysis device for analyzing the response signal in order then to determine whether the luminescence generated by means of the excitation signal in the security marker substance shows the appropriate characteristics.
  • this authentication system should be easy to handle in many applications, for example for checking bills in banks or shops or at an entry control of a security area or during a product delivery, it is preferable to use the excitation signal transmitting device and the response signal receiving device.
  • TIR total internal reflection
  • the scanner unit for example integrated in the TIR lens, has a suitable shielding means, such as a partition wall, a dichroic beam splitter or the like, to shield the photodetector from the direct signal from the LED.
  • a suitable shielding means such as a partition wall, a dichroic beam splitter or the like, to shield the photodetector from the direct signal from the LED.
  • the drive unit, the read-out electronics and also the analysis device could likewise be integrated into such a scanner unit. For this purpose, an embodiment will be given later.
  • Such an authentication system or such a scanner unit can preferably also be designed as a portable device.
  • the analysis device can also be completely or partially realized in the form of software.
  • a largely software-based implementation has the advantage that existing analysis devices can be modified in a simple manner by a software update, if the analysis methods are changed to further increase the security.
  • particularly advantageous refinements and developments of the invention emerge from the dependent claims and the following description, wherein the independent claims of a claim category can also be developed analogously to the dependent claims and exemplary embodiments or descriptive parts of another claim category, and In particular, individual features of different exemplary embodiments or variants can also be combined to form new exemplary embodiments or variants.
  • the afterglow function of the luminescent substance is preferably intentionally or intentionally modified individually irreproducibly.
  • This modification is preferably carried out in such a way that an individualized luminescent substance or safety marker substance does not differ spectrally from its unmodified starting material, ie the luminescent substance or safety marker material prior to the modification.
  • an individualized luminescent substance or safety marker substance does not differ spectrally from its unmodified starting material, ie the luminescent substance or safety marker material prior to the modification.
  • potential counterfeiters can not already see the modification on the basis of the spectrum and can thus draw conclusions about the modification.
  • This procedure makes it possible to use the afterglow function of a security marker substance not redundantly in addition to the spectral parameters or other parameters as a security feature.
  • a number of other activator atoms which function in appropriate host lattices as a phosphor ion are also known.
  • the most Commonly used LED phosphor is the Cer 3+ doped yttrium aluminum garnet (YAG: Ce).
  • YAG Cer 3+ doped yttrium aluminum garnet
  • the short afterglow time of about 65 ns represents a particular metrological difficulty for the use of cerium-activated garnet phosphors.
  • Preferred activator ions are: europium, terbium, manganese, manganese, praseodymium, cerium, samarium, dysbrosium, thulium.
  • activator ions used include: europium 2+, europium 3+, terbium 3+, manganese 2+, manganese 4+, praseodymium 3+, cerium 3+, samarium 3+, dysbrosium 3+, thulium 3+.
  • sensitizer activator phosphors exist in which an ion serves to absorb incident excitation radiation (the sensitizer), which transfers its excitation energy to the light-emitting ion (the activator), which then is responsible for the radiant energy output of the system is.
  • luminescent substances are used from the group:
  • Garnet phosphors such as Y 3 AL 5 0i 2 : Ce 3+ ,
  • phosphors containing europium most preferably EU 2+ phosphors, such as phosphors of the group:
  • phosphors are borates such as in particular:
  • RE B0 3 EU 3+
  • RE B0 3 Tb 3+ .
  • the luminescent substance may preferably be aware of a degradation, ie. H. damage.
  • Targeted damage reduces the quantum efficiency, ie the ratio of the number of emitted and absorbed photons.
  • quantum efficiency ie the ratio of the number of emitted and absorbed photons.
  • the relationship between quantum efficiency and associated transition rates is known in the literature (see, for example, Birks, J.B.: Fluorescence Quantum Yield Measurements, Journal of Research vol 80A, National Bureau of Standards, 1976).
  • t is the time since the excitation signal was switched off and P is the (luminescence) decay time (which could also be referred to as "luminescence lifetime").
  • P is the (luminescence) decay time (which could also be referred to as "luminescence lifetime").
  • This type of decay behavior is based on the assumption of an ensemble of identical and non-interacting centers, similar to radioactive decay. In crystallographically perfect materials, that is to say in an infinitely extended crystal without defects, in which each activator ion is isolated and unaffected by neighboring activator ions (ie with very low doping amount) is in an identical crystal environment, this assumption is fulfilled to a good approximation.
  • ⁇ is referred to as "stretching exponent".
  • the value of ß can be understood as "width" of the decay duration distribution, ie how far the individual decay duration contributions deviate from the average decay time.
  • An exact mathematical assignment of the extension exponent to the form of the decay distribution is the subject of current research, for example in the field of theoretical solid-state physics.
  • the extension exponent ß provides only a single further characteristic for the description of a decay behavior and is therefore limited in its informative value, as no detailed elucidation about the form of the distribution of the decay times is possible.
  • a preferred description of the temporal decay behavior is provided by the so-called "lifetime distribution analysis”. In this case, the decay behavior is displayed by specifying a large number of the cooldowns involved with their respective relative contributions.
  • the decay time of a single activator ion is given by where k
  • the afterglow function of the luminescent substance is individually irreproducibly modified, then this modified afterglow function is generally no longer meaningfully describable by an indication of a simple decay constant-unlike, for example, the aforementioned WO 2017/085294 A1 ,
  • a targeted degradation of the luminescent substance can take place in different ways, in particular by mechanical, chemical, photochemical, electromagnetic, thermal or other physical loading or a combination thereof.
  • a degradation preferably takes place by introducing energy into the luminescent substance, more preferably according to one or more of the following methods:
  • radiation energy particularly preferably electromagnetic radiation energy, very particularly preferably UV radiation
  • chemical energy such as hydrolysis (endothermic "dissolution in water"), oxidation by boiling in boric acid (endothermic), washing in acids or, depending on the material system, alkalis, oxidation by diffusion of oxygen (thermal treatment in 02 -containing atmosphere), reduction by diffusion of hydrogen (thermal aftertreatment in an H2-containing atmosphere, "forming gas”), H2-outdiffusion by thermal aftertreatment in vacuum, vapor-phase equilibration by diffusion of foreign atoms (for example lithium, calcium, iron, Boron, phosphorus (the element)) from the gas phase, etc.
  • a combination of said methods can be used.
  • a thermal treatment with a suitable temperature / time combination under different gas atmospheres leads to virtually all luminescent substances to a degradation and thus to a modification of the afterglow function.
  • Such annealing is preferably carried out for at least 12 minutes, more preferably for at least 15 minutes, more preferably for at least 20 minutes, and most preferably for at least 30 minutes.
  • the introduction of mechanical energy into the luminescent particles also leads to the formation of dislocations and crystal defects in the host lattice of the phosphors.
  • an irreproducible broadening of a particle size distribution of the luminescent substance can also be carried out for individually irreproducible modification.
  • Both the introduction of mechanical energy and the broadening of a particle size distribution can be achieved by grinding the luminescence Substance, unless subsequently again a classification of particles according to their particle sizes, for example by a sieving process, takes place.
  • the luminescent leads to the introduction of defects in the crystal environment of the activator ion. Since the luminescence properties of the typical activator ions depend strongly on their crystal field environment, even small changes show in part significant changes, both in the temporal and the spectral behavior of the luminescent substance.
  • Lattice defects lead to spatial displacements of the lattice atoms and thus to a change in the distances to the activator ion.
  • the altered crystal field can now enable energy to be transported to places in the grid that were locked to energy before it was damaged.
  • a defect resulting from mechanical action for example an offset or a defect, can also absorb excitation energy and then radiate it as a phonon, ie as a lattice vibration and thus as waste heat, without radiation.
  • ground unsubstituted luminescent substance or a mixture of such substances may accordingly be used as security marker material.
  • the milled luminescent substance intentionally remains unshifted and it is thus deliberately exploited that the particle size distribution of the luminescent substance was changed, ie broadened, by grinding in an unforeseeable manner, since particles with very different sizes are present after milling.
  • mechanical energy can also be introduced into the luminescent substance particles by ultrasound processors.
  • water vapor under high pressure for example of at least 0.2 MPa and more preferably below 1 MPa
  • elevated temperature for example at least 125 ° C and more preferably less than 200 ° C
  • strongly hydrolyzing acts.
  • silicate phosphors react sensitively to this form of degradation.
  • combined exposure at elevated temperature, for example, even above 200 ° C, and intense blue or ultraviolet light irradiation (eg, with a power density greater than 10 W / cm 2 ) under a suitable atmosphere would occur in almost all phosphors lead to a significant degradation.
  • different degradation methods or combinations of degradation methods are preferably used for different luminescent substances.
  • silicate phosphors are sensitive to hydrolysis, so that a hydrothermal aging process is particularly suitable here.
  • garnet phosphors such as Y 3 AL 5 O 12 : Ce 3+
  • Y 3 AL 5 O 12 : Ce 3+ are very stable and can only be changed by extreme loads, for example in an excessive grinding process.
  • Nitridic and oxy-nitridic phosphors show, depending on the composition, clear photochemical reactions. Therefore, such luminescent substances are modified in their use according to the invention in a security marker, preferably by photochemical aging.
  • nitride phosphors are well degraded at temperatures above 350 ° C and under intense irradiation with short wavelength light.
  • a security marker substance it is particularly preferable to mix a plurality of individually irreproducibly modified luminescent substances. This increases the security even further.
  • a suitable "aging reactor” together with source phosphors to the companies which must ensure the authentication of objects.
  • the company concerned can thus individually modify its own luminescent material. This means that the company itself is the manufacturer of the security feature and is the only one who has knowledge of the process parameters, which further enhances security.
  • fi (t), f 2 (t), f 3 (t), ... are the afterglow and decay distributions of the individualized luminescent substances ai, a 2 , a 3 ... are weighting factors which determine the ratio in which the luminescent substances were mixed. That is, the response of the different individualized luminescent substances is superimposed additively and thus forms a sum of different decay time distributions.
  • Such individualized luminescent substances or mixtures of individualized luminescent substances can preferably be introduced into a carrier for producing the safety marker substance.
  • a carrier may be a base paste, a varnish, a paint, etc.
  • such a carrier is composed of a suspension of binders, fillers, resins and / or acrylates and other additives.
  • the carrier can for example be based on both a solvent-based and a water-containing suspension.
  • Such base pastes or lacquers with the individualized luminescent substances or mixtures of luminescent substances incorporated therein can then be marketed, for example, directly as security marker pastes or security marker lacquers, in particular in the form of printing lacquers, and the companies wishing to protect their products , they can then continue mixing on their own to create their own individual security marker that only they own. This means that it is also possible to mix carriers with different individualized luminescent substances and / or with different mixtures of individualized luminescent substances.
  • additives may also be added to it, for example fluorescence quenchers.
  • fluorescence quenchers In the field of organic phosphors (for example rhodamine, coumarin, fluorescine) certain molecules can act as quenchers (quenchers) through energy transfer processes. Molecules such as CCI 4 (carbon tetra-chloride), or DNP (di-nitro-phenol) quench the fluorescence emission of some organic phosphors already measurable in ppm concentrations.
  • quenchers such as CCI 4 (carbon tetra-chloride), or DNP (di-nitro-phenol) quench the fluorescence emission of some organic phosphors already measurable in ppm concentrations.
  • CCI 4 carbon tetra-chloride
  • DNP di-nitro-phenol
  • dyes, pigments or nanoparticles are used, which are subsequently inactivated in combination with the carrier and thus allow compatibility only to certain carriers. Ie. It is possible to adjust the combinability with certain carriers, for example pastes or paints, by way of such an additive. This can further increase security within the supply chain.
  • a luminescent substance can also be provided with an additive in the form of a catalyst which particularly facilitates degradation of the phosphor.
  • a catalyst which particularly facilitates degradation of the phosphor.
  • these may be soaps or acids.
  • At least one wetting aid can be added to the luminescent substances before and / or during degradation.
  • Preferred wetting aids may be, for example, surfactants. Whether and which wetting aids, in which quantities are used, may depend in particular on the particular degradation process and the selected luminescent substances.
  • silicate-based luminescent substances show a certain hydrolysis and acid sensitivity. It is therefore advantageous in the case of harmful treatment to ensure that the particles are adequately wetted.
  • surfactants z. B. in conjunction with corresponding acids as grinding aids.
  • mechanical alloying may occur during high-energy milling. Emerging small "particle debris" recombine under the influence of mechanical energy to larger particles. Prevention of this process may be advantageous here for modifying the luminescent substances. If the particles are ground in a solution of polysiloxanes, these molecular chains are deposited on the surface of the particle debris produced by the grinding immediately after their formation. This surface coating hinders the particles from approaching each other and thus reduces mechanical reagglomeration. Another possible advantage is the often associated with such a coating hydrophobing of the particles.
  • the powder material treated in this way has a strongly modified flow behavior and can be better dispersed in water-free media, for example paints.
  • At least one value preferably several sample values of a value range (i.e. , H. a section) of an afterglow function of the individualized luminescent substance or luminescent substance mixture of the security marker substance.
  • the entire afterglow function can also be measured. From the sequence of samples thus measured, several parameters of afterglow functions can also be determined, for example with the aid of a parameter estimation method.
  • a "recognition" (or “security marker information”) of the individualized security marker substance can be determined based on this value or value range or the entire afterglow function.
  • Such an identifier can then be compared with an identifier obtained from an authorized, authenticated entity to confirm the authenticity of the entity.
  • Such an identifier may be, for example, a hash value or the like.
  • a spectral value preferably a plurality of samples of a value range of a spectral persistence function of the individualized luminescent substance or luminescent substance mixture of the security marker substance. Under such a spectral Nachleuchtfunktion is a temporal change in the spectrum to understand, especially in a luminescent mixture.
  • the authentication system should be able to measure spectrally resolved, i. H.
  • the response signal receiving device and the readout electronics as well as the analysis device must be designed accordingly.
  • a plurality of response signal receiving units can be combined to form a response signal receiving device, which detect the light in different spectral regions in each case.
  • a plurality of photodiodes which operate in different spectral ranges and / or are provided with different optical filters.
  • It is also possible to measure temporally sequentially different spectral components by using a monochromator and / or adjustable filters or an optical spectrometer or otherwise modifying the spectral reception range of the response signal receiving device.
  • the amplitude ratios of the spectral luminous intensities or also the amplitude ratios of the individual luminescent substances contained in the luminescent substance mixture and their temporal change can then be determined. These too Information can then for example be included in an identifier of the individualized security marker substance and thus used to authenticate the object.
  • the security marker substance is excited to luminescence as mentioned and illuminated with an appropriate wavelength and then values or samples of the afterglow function are measured at defined times after an excitation, that is to say from the point of time when no longer being excited. which can be done with the help of the response signal receiving device.
  • this value may simply be the intensity of the response signal or, at a spectral resolution, the intensity as a function of the frequency.
  • the determination or measurement of the afterglow function of the security marker substance preferably takes place with a resolution of nanoseconds to seconds.
  • the lingering times of conventional luminescent substances without these having been modified according to the invention are between 50 ns and a few minutes.
  • the decay times could possibly also continue to decrease significantly, which is why it is necessary to measure correspondingly fast in order to determine the afterglow function.
  • the demands on the dynamic range of the response signal receiving device are correspondingly high.
  • the authentication system ie the excitation signal transmitting device and / or the response signal receiving device, preferably comprises a fast microcontroller and a fast analog / digital converter, eg. As a flash ADC or a cascade converter, for sampling and digitizing the analog measurement signals (the response signal) and also for triggering the excitation signal source (eg., An LED). If one or more LEDs or one or more laser diodes are actually used for the emission of the excitation signal, then the excitation signal transmitting device can preferably have a drive circuit for fast generation of an excitation signal, in which the LED or laser diode is biased with a bias voltage during its blocking, which is just below the diffusion and forward voltage of the LED or laser diode.
  • a fast microcontroller eg. As a flash ADC or a cascade converter, for sampling and digitizing the analog measurement signals (the response signal) and also for triggering the excitation signal source (eg., An LED).
  • the excitation signal transmitting device can preferably have a drive circuit
  • the space charge zone is reduced and, when the LED or laser diode is switched on, the room temperature is avoided. zone must be completely degraded.
  • the switching on and off of the LED or the laser diode can be considerably accelerated and thus particularly fast signal sequences or individual pulses within the excitation signal can be generated, such as the PRBS pulse sequences explained in detail later.
  • the security marker substance is excited several times at a time interval, and then a measurement takes place at different time intervals, in each case after the last excitation, in order to scan the afterglow function in a plurality of excitation periods and to record the sampled values.
  • a measurement takes place at different time intervals, in each case after the last excitation, in order to scan the afterglow function in a plurality of excitation periods and to record the sampled values.
  • periodic sequential sampling can be performed with a periodic optical excitation, the response signal in successive periods of the excitation signal is detected gradually, more time for the analog / digital conversion and the subsequent processing steps are provided.
  • suggestions of the security marker substance take place over a longer time window, for example over a multiple, e.g. three to five times the "longest lived" parts in the total persistence function g (t), d. H. the energy of the stimulus is distributed over a longer time window.
  • the luminescent substance or the luminescent substance mixture is regarded as a transmission system which transmits the excitation signal into the response signal, it can be deduced analogously to the Shannon information theory valid in communication technology that by extending the measurement time and maximizing the size Bandwidth of the test signal, d. H.
  • the excitation signal a large time-bandwidth product of the excitation signal is achieved and an improved accuracy and thus a higher reproducible resolution and noise immunity is achieved by the information redundancy gained thereby, in particular an improvement of the signal / interference power. ratio.
  • the bandwidth of the excitation signal is preferably changed by using a pulsed excitation signal with pulses of different length and / or distances from one another, ie the interval time durations and the frequency spectrum of the excitation signals are changed. This is not to be confused with the excitation frequency of the radiation or the light spectrum used in the excitation signal.
  • the evaluation algorithm used for such a "broadband" measurement method is then preferably a correlation analysis.
  • the theory for a correlation analysis is z. Eg in Isermann, Rolf: Identification of dynamic systems: Volume I: frequency response measurement, Fourier analysis, correlation analysis, introduction to parameter estimation; Springer Berlin Heidelberg, 1992. Although linear systems are assumed, according to the invention this method is also used in the present nonlinear system.
  • the cross-correlation function cp xy (t) from the input signal x (t) and output signal y (t) of a transfer element is equal to the convolution product of the pulse response g (t) of the transmission system and the autocorrelation function cp xx (t) of the input signal:
  • the determination of the impulse response g (t) identifies all system properties.
  • the luminescent substance or the luminescent substance mixture is considered as "transfer element" in this sense, and the excitation signal x (t) is regarded as the input signal and the response signal y (t) as the output signal of the "transfer element".
  • the afterglow function g (t) sought is equal to the impulse response which results from the portions of the response signal y (t) correlated with the excitation signal x (t). It is preferably calculated as if it were a linear, time-invariant system. However, it is assumed that the excitation signal is not so strong that the luminescent substance or the luminescent substance mixture saturates, which can be avoided without further ado. In this case, it can therefore also be assumed with sufficient accuracy that, according to equation (6), the cross-correlation function cp xy (t) can be calculated from the excitation signal x (t).
  • the response signal y (t) is equal to the convolution product of the impulse response of the "transmission element", namely the searched afterglow function g (t), and the autocorrelation function f cc (t) of the excitation signal x (t).
  • the current of the exciting LED or laser diode or a signal representing the current for example a digital control signal for the current, as an input signal and the photocurrent of suitable photodetectors or a signal, which the measured illuminance and above also represents the photocurrent can be used as an output signal to calculate the afterglow function g (t) with the equation (6).
  • the photocurrent is converted via a current / voltage converter in the output voltage, which is then used in digitized form as an output signal.
  • Such a determination of the afterglow function by means of a cross-correlation of the excitation signal and a response signal measured during the excitation or a cross-correlation-like function is basically also applicable if no individualized luminescent substance according to the invention is used, and is therefore also inventive in its own right.
  • this method is particularly suitable for measuring the afterglow functions of individualized luminescent substances or luminescent substance mixtures or corresponding security marker substances according to the invention, since such substances generally have an individually modified after-luminescent function which should be identified as precisely as possible.
  • an analog noise signal (the roughness refers to the temporal amplitude distribution of the radiation pulses of the excitation signal) may also be used as the excitation signal, but such analog noise signals are associated with a relatively high generation and processing effort.
  • PRBS pseudo random bitstream
  • a method according to the invention for determining a temporal response behavior, in particular a life-time distribution function, of luminescent materials based on a digital pseudorandom sequence-like excitation can be advantageously and advantageously used in many areas, independently of a security marking or security application.
  • pseudo-random signals are digital pseudo-random signals of maximum length (maximum length pseudo random bit streams). So far, such signals from telecommunications for code division, band spreading and encryption are known. Explanations on this can be found, for example, in DE 36 42 771 or in Baier, P.W., Pandit, M .: Spread Spectrum Communication Systems; Advances in Electronics and Electron Physics 53, Academic Press, New York, 1980, pp. 209-267. Such PRBS signals have similar characteristics to analog noise signals. In particular, their frequency spectrum is extremely broad. Its autocorrelation function is a recurrent Dirakimpuls according to the periodicity. Such digital pseudo noise signals are determined in the true sense and can be generated, for example, via suitably fed back shift registers. When measuring the impulse response via digital pseudo-random signals, the energy required for measuring is also distributed over a large time interval as desired, instead of a short-time, high-energy excitation pulse.
  • an excitation LED or other suitable radiation source is acted on or driven by a PRBS-shaped current, ie a current which has pulses in accordance with a PRBS signal.
  • the desired impulse response or persistence function g (t) can be calculated without great computational effort and thus particularly fast.
  • the PRBS-shaped excitation signal has a substantially constant power density spectrum. Its Fourier transform is the diraciform autocorrelation function cp 0 .
  • the autocorrelation function cp xx (t) of a PRBS-shaped current, in this case of the excitation signal x (t) can therefore be considered a priori to be the value of the Dirak pulse cp 0 .
  • equation (6) for this case simplifies as follows:
  • the cross and autocorrelation functions are also periodic.
  • the cross-correlation function can then be calculated by integrating a period:
  • the typical physical model for describing the temporal behavior of the luminescence intensity of a phosphor is, as mentioned, an exponential decay. Two measurements at different times allow a complete characterization. However, as explained above, the combination of several different security markers inevitably produces a non-mono-exponential decay dynamic.
  • the complete safety information is not contained in a single afterglow function or decay time, but in the complete overall afterglow function or the overall stored afterglow functions or even in the decay duration spectrum or a spectral overall afterglow function. On the one hand, this results in the particularly preferred possibilities for increasing the security level, both via the number of afterglow functions or the duration of the decay, as well as via their respective intensity components.
  • the methods can therefore lead to a particularly accurate and secure object authentication, preferably using methods of estimation theory via parameter estimation an identifier of the individualizedbiemarkerstoffs from the individual Nachleuchtfunktion or total Nachleuchtfunktion is determined to verify the security marker material.
  • the safety marker substance is preferably classified on the basis of the measured characteristics, for example on the basis of the measured afterglow function.
  • the measured samples of the output signal can be used directly at defined times of the decay function.
  • parameters of the total persistence duration function g (t) can be determined from the measured sampled values of the output signal, for example by a parameter estimation method. B. by applying curves. The samples and / or parameters can be sorted into defined (tolerance) boxes in order to classify the security marker.
  • such an identifier ie. H. the security marker information
  • the digitalized security marker material digitally signed.
  • the characteristic of the security marker can be measured first. Metrologically, this can be done in the same way as described above for the authentication. representation from the identifier can be determined, which then preferably digitally signed, that is cryptographically secured in a digital signature.
  • asymmetrical methods are suitable for this, whereby the information is preferably encrypted with a private secret key and decrypted with a public key.
  • a possibly compromised private key can then be exchanged relatively easily and, accordingly, a new public key can be made available to the persons who are subsequently to perform an authentication of the object with the aid of the security marker substance.
  • the authenticity is guaranteed. Is error correction procedures ensured that the same characteristic is always determined for a single security marker sample, for example by categorizing or sorting or classifying the measured values in "boxes" (as mentioned above), or when This can be unambiguously classified unambiguously in another way, it can be mapped irreversibly with a collision-free one-way function (for example, a hash value, such as a SHA-3 value).
  • a collision-free one-way function for example, a hash value, such as a SHA-3 value.
  • the life information is not stored and transmitted directly, but rather a digital signature calculated therefrom, which does not allow any conclusions to be drawn about the received parameters. The calculation of this signature requires the knowledge of a secret private key, which is made available only to an authenticated customer on a second channel.
  • a marking arranged on and / or in the object may also comprise a security code, for example an opto-electronically readable security code, such as a barcode, in particular a 2D code, for example a QR code.
  • a security code for example an opto-electronically readable security code, such as a barcode, in particular a 2D code, for example a QR code.
  • Authentication or identity information can in turn be accommodated in this, but in particular the identifier of the security marker substance can also be coded therein, for example the digitally signed identifier.
  • a security code created with a security marker fabric, for example, printed.
  • the encrypted information can be read out with a measuring device and both can be compared with one another.
  • a measuring device can also be a combined measuring device with which the measurement of the characteristics of the security marker substance can be carried out simultaneously or successively and the (coded) identifier can be read.
  • a high level of security can also be achieved by matching the test data on a server, for example if the characteristics of the afterglow function or the values measured for the persistence function, preferably encrypted and digitally signed, are transmitted to a server who then performs the further analysis to determine if it is a wrong or a true object.
  • a partial analysis could take place on site, z. B. that first an identifier, if necessary, by performing a classification, determined and transmitted in unmodified form or after coding for further testing to the server.
  • a comparison value for the identifier in particular also in coded, for example, digitally signed form, can also be transmitted to an authentication system on site or at its analysis device.
  • Different variants are possible here, in particular also combinations of the different methods. For secure data transmission, known data transmission methods for security-critical information can be used.
  • the authentication system can be integrated into a device for the entry of goods and / or into a merchandise management system in order to check the authenticity of incoming goods with the methods according to the invention.
  • FIG. 1 shows a simplified flow chart of a possible sequence of an exemplary embodiment of the method according to the invention for generating a security marker substance
  • FIG. 2 shows a representation of the afterglow functions of two batches of a luminescent substance, which were each exposed to a degradation process with the same parameters, and for comparison the afterglow function of the unchanged, original luminescent substance, FIG.
  • FIG. 3 shows a simplified flowchart for generating a security marker substance by mixing security marker substances according to the invention
  • FIG. 4 shows a representation of a first overall afterglow function of a luminescent substance mixture and of the afterglow functions of the individual luminescent substances
  • FIG. 5 shows a representation of a second overall afterglow function of a luminescent substance mixture and of the afterglow functions of the individual luminescent substances
  • FIG. 6 shows a representation of a third overall afterglow function of a luminescent substance mixture and of the afterglow functions of the individual luminescent substances
  • FIG. 7 is a schematic sectional view of an exemplary embodiment of an object having a marking with a security marker material according to the invention.
  • FIG. 8 shows a plan view of the object with the marking according to FIG. 7,
  • FIG. 9 a schematic representation of an embodiment of an authentication system according to the invention.
  • FIG. 10 shows a simplified circuit diagram for an exemplary embodiment of a preferred excitation signal transmitting device
  • FIG. 11 shows an instance network for an exemplary embodiment of an authentication with an authentication system according to FIG. 9, FIG.
  • FIG. 12 shows a schematic representation of a further exemplary embodiment of an authentication system according to the invention, Figures 13 to 16 afterglow functions of two batches of the same luminescent each after a degradation by introducing thermal energy.
  • FIG. 1 schematically shows how two luminescent substances Li, L 2 are each subjected to a targeted artificial aging, wherein these aging processes A 1 , A 2 are represented here by two process blocks.
  • This aging can be carried out by means of the methods already described above, for example by mechanical, chemical, photochemical, electromagnetic, thermal or other physical loads or combinations thereof, wherein the method is preferably selected such that it is suitable for the selected luminescent substance Li, L 2 is particularly well suited.
  • the individualization of a luminescent substance by a targeted degradation reference may be made to FIG.
  • two afterglow functions f a (t), f b (t) are shown in comparison with the afterglow function f e (t) of the unchanged, original luminescent substance, which originate from two different batches of the same original luminescent substance, each with the same Conditions or parameters was artificially aged.
  • the luminescent substance is an orthosilicate conversion luminescent substance.
  • the degradation was carried out by grinding for several hours under room temperature and normal ambient pressure in an acidic environment (pH 3) with the addition of a small amount of a wetting aid, here surfactant.
  • the after-light functions f a (t), f b (t), f e (t) were measured from the individualized luminescent substances thus obtained by the method described above, with light having a wavelength of 404 nm being used as the excitation signal.
  • the relative intensity or light intensity I is plotted against the initial value l 0 over the time t in ns in each case.
  • the after-glow functions f a (t) and f b (t) are measurably different, although they are the same luminescent starting material and the same aging process was used under the same conditions.
  • the cooldowns were increased (at first sight unexpectedly, but as explained above) to the afterglow function f e (t) of the unchanged, original luminescent substance.
  • the luminescent substance was thereby irreproducible, ie not plannable or specifically reproducible, modified and provided with a unique characteristic (comparable to a fingerprint).
  • the security marker substance S, Si, S 2 , S 3 can be, for example, a security marker coating material, such as a paint or a lacquer, which is applied to an object for authentication or with which a security code is applied to the object or an object as unsolvable as possible or not destructively releasable - linked label is printed.
  • the security marker material can also be a material which is used to produce the object itself or at least parts of it, for example a plastic material from which the object is then pressed or produced in some other way. Ultimately, this depends on the choice of the carrier T.
  • an identifier of the security marker substance S is then determined, if appropriate after a suitable classification, for example a hash value HW.
  • this can then z. B. encrypted by means of a private key PS and thus a digital signature DS are generated which contains the identifier of the security marker substance S and from which can be decrypted with knowledge of the associated public key again the identifier HW.
  • This form of digital signature ensures that the characteristic value actually comes from an authorized person, namely from the manufacturer of the security marker substance or the person who by means of the security marker substance legally authenticates the authenticity of the object.
  • the digital signature DS can then be suitably left to all the places that later have to perform an authentication of the object.
  • FIG. 4 shows a total afterglow function g (t) is shown, which is composed of the indi- vidual Nachleuchtfunktionen fi (t), f 2 (t), f 3 (t), f 4 (t), f 5 (t) of a total of five different individualized individual luminescent substances.
  • the exact form of this total afterglow function g (t) also depends on the mixing ratios of the individual individualized luminescent substances. In the example in FIG. 4, all five luminescent substances have the same proportion. For this purpose, reference is again made to FIGS. 5 and 6. In FIG.
  • a first luminescent substance with the afterglow function fi (t) is mixed with a second individualized luminescent substance with its own afterglow function f 2 (t) in equal proportions, thereby obtaining a total afterglow function g (t).
  • the first individualized luminescent substance with the afterglow function fi (t) was mixed in equal proportions with a third individualized luminescent substance with an afterglow function f 3 (t), whereby a different total Afterglow function g (t), which, as a comparison of FIGS. 5 and 6 shows, clearly differs from the total afterglow function g (t) of FIG. 5, although both fall exponentially.
  • the relative intensity or illuminance I with respect to the initial intensity (I 0 ) over the time t is given in relation to a normalization factor t 0 in order to achieve a normalization to the value 1.
  • t 0 is the measuring time of the overall function.
  • FIGS. 13 to 16 show measurement results from an experiment in which an individual irreproducible modification of the afterglow function of the luminescent substance was carried out by artificial aging or degradation solely by introducing thermal energy, in this case specifically by tempering in a muffle furnace, and the afterglow functions such as were measured above.
  • orthosilicates f530 as luminescent material were divided into two equal batches (identical amounts) and both batches were run in similar timings parallel in time, in the same muffle furnace, at 700 ° C for 10, 20, 30 and 40 minutes respectively annealed. Ie. both batches of the same luminescent substance went through the same experimental procedure.
  • FIGS. 13 to 16 each show the afterglow function NC1 (time decay curve) of the charge 1 in comparison to the afterglow function NC2 of the charge 2.
  • the afterglow function in the figures is shown in each case by the relative intensity or illumination intensity I with respect to the initial intensity (l 0 ) over time t (here in ns).
  • the afterglow function NC0 for the still untreated luminescent substance is shown at the top.
  • the afterglow functions NC1, NC2 of the two batches are shown after annealing at 700 ° C over a period of 10 minutes.
  • FIG. 14 shows the afterglow functions NC1, NC2 of the two batches after annealing over a period of 20 minutes, FIG. 15 after annealing over a period of 30 minutes and FIG. 16 finally after annealing over a period of 40 minutes.
  • the multi-exponential decrease in the afterglow function of batch 1 decreases less and less until the 30-minute tempering period than that of batch 2 and, surprisingly, this effect has reversed when measured over 40 minutes.
  • the figures clearly show that the modification of the afterglow function of the luminescent substance is actually individually irreproducible within the meaning of the invention.
  • the characteristic value HW shown schematically in FIG. 1 or the digital signature DS generated therefrom can be referenced, for example, in a marking M to the item to be authenticated Object O are printed.
  • the security marker substance S is preferably used.
  • FIGS. 7 and 8 show a greatly enlarged section through such an object O in the region of the marking M
  • FIG. 8 shows a plan view of this object O with the marking M.
  • the object can be for example a pass.
  • the mark M may be, for example, any security code SC, such as - as shown in Figure 8 - a bar code, a QR code or the like.
  • the marking M was printed, as mentioned, with the security marker substance S, which comprises, for example, the carrier T and an individualized luminescent substance contained therein or a mixture of such individualized luminescent substances Ll-i, Ll 2 consists.
  • the authentication of this mark M can then be done by means of an authentication system 20, as z. B. is shown in Figure 9.
  • the authentication system 20 is represented as a transportable security scanner unit 20 which is easy to handle for the person who is to check the authenticity of the object.
  • This is a preferred exemplary embodiment which works with a maximum length pseudo random bit stream as an excitation signal and a cross correlation analysis of the response signal generated in order to obtain the persistence function, as described above.
  • other methods can also be used in which the individualized security marker substance S in the marker M is excited and the response signal generated thereby is measured and evaluated.
  • the authentication system 20 has an excitation signal transmitting device 30, which-in simplified terms-essentially comprises an LED 3 (possibly also a group of LEDs) which is controlled via a voltage / current converter 2, which in turn is controlled by a PRBS generator 1.
  • the output of an excitation signal can be triggered by means of a user interface 14, for example a push button, a touch button or the like.
  • FIG. 10 shows a preferred exemplary embodiment for the construction of an excitation signal transmission device 30, which is suitable for a particularly fast generation of the pseudo-complausible digital light signals.
  • a bias voltage source 33 was built into the power stage for generating the excitation light signal by means of the light emitting diode 3, which prevents the space charge zone of the LED 3 must be completely degraded when through the PRBS pulse generator 1 via the transistor 32 (which here as a switch for the LED 3 acts) is turned off.
  • the positive bias voltage through the bias source 33 is so large that the LED 3 is already biased to just below its breakdown voltage with open switch or locked transistor 32, but no current flows from the current source.
  • the current source consists of the voltage source given by the operating voltage BS and the series resistor 31.
  • G denotes the ground potential or ground.
  • the bias source 33 can be realized, for example, by a small amplifier or a tens diode to achieve the desired voltage drop.
  • a protection diode 34 (the diode 34 may alternatively be replaced by a suitably sized resistor) is inserted in front of the bias source 33 and the light emitting diode 3, which prevents the short circuiting of the bias source 33 when the transistor 32 is conductive.
  • the transistor 32 is here controlled by the pulse generator 1 (PRBS generator) by means of a typical emitter circuit. Via the resistor 39, the base current is generated, and the capacitor 38 connected in parallel provides for an acceleration of the circuit, as well as the three diodes 35, 36, 37 within the circuit arrangement.
  • PRBS generator pulse generator
  • the generated PRBS-shaped excitation signal which is emitted by the light-emitting diode 3, then passes to the mark M (see FIG. 9) and is converted there by the individualized luminescent substance LI into the response signal, which is detected by at least one photodetector 4 (FIG. a photodiode 4) of a response signal receiving device 40 is detected here.
  • the light-emitting diode or laser diode 3 or the light-emitting diodes and the photodetector 4 or the photodetectors, as shown in FIG. 9, are preferably equipped with a common optical system which appropriately directs or reflects the light signals.
  • TIR Total Internal Reflection
  • the light of the response signal is coupled back into the TIR lens 16 via this intensity / reflection means 19 of the TIR lens 16 and then reaches the photodiodes 4.
  • a suitable shading device 17 for example a kind of partition or the like, and / or via an excitation filter upstream of the photodiode 4, for example notch or edge filters, the light emitting diode 3 is so separated from the photodiode 4, that this is not illuminated directly.
  • the shading device 17 could also be embodied, for example, as a kind of partition or the like.
  • the photodiode can be provided with an excitation, notch or edge filter.
  • the coupling of the light-emitting diodes 3 and the photodetector 4 with the TIR lens 16 takes place, for example, by means of a suitable immersion fluid 18, which has approximately the same refractive index as the TIR lens 16, which can be made of plastic, for example.
  • the TIR lens 16 is here preferably constructed like a dome or a semi-cylinder.
  • an optical system of suitable reflectors, for. B. a concave mirror, and / or lenses, in particular front lenses on the E i n t ri tts- / Au s t ri ttsf I e c h e of a concave mirror, are constructed.
  • the signal measured by the photodetector 4 is fed to a signal converter 5, which forwards the analog detector output signal to an analog / digital converter 6, preferably with an upstream sample / hold element, which at the output carries the digital signals of an evaluation unit 11 passes.
  • a suitable code reading device 50 for example in the form of a conventional laser scanner or a camera with a corresponding evaluation device, may also be provided in this authentication system 20 or the security scanner unit 20, as shown schematically here. to read a barcode, QR code or other security code SC.
  • FIG. 9 shows this code reading device 50 next to the TIR lens, ie the user who wishes to check a code can first read the security code SC of the marking M with this code reading device 50 and then, as shown in FIG. Verify the authenticity of the security code SC by means of the security marker substance S in the ink of the security code SC.
  • a code reading device 50 directly, for example into the optical system, which is used by the excitation signal transmitting device and the response signal receiving device.
  • the code reader 50 may also be coupled to the TIR lens 16 at any suitable location.
  • a PRBS voltage Up RB s (t) is generated, which is then supplied to the voltage / current converter 2 to generate a PRBS current IpRBs (t) for the LED 3 to create.
  • This process has already been explained with reference to FIG. 10 to a specific preferred stress build-up.
  • the LED 3 then emits a spectral PRBS excitation signal x (t).
  • An irradiated security marker substance S then outputs a light response signal y (t) with a certain afterglow function g (t) due to the individualized luminescent substances contained therein, which is to be precisely determined in the context of the further method.
  • This response signal y (t) is detected by the photodetector 4, which correspondingly generates a photocurrent I P (t) which is supplied to a current-voltage converter 5 in order to convert the signal into a voltage U P (t).
  • the voltage signal U P (t) is then fed to a fast analog / digital converter 6 (which has, for example, a cascade circuit), which outputs a digitized voltage signal U K (t) at its output and transmits it to a correlator 7.
  • a fast analog / digital converter 6 which has, for example, a cascade circuit
  • This correlator 7 is also the PRBS voltage signal U P R B s (t) also supplied in digitized form, ie the correlator 7 are in digitized form before two signals, which represent the excitation signal x (t) and the response signal y (t) ,
  • the calculations can be performed to determine the afterglow function g (t) according to equations (7) and (8). Unless, as mentioned above, one spectral measurement is carried out, it is accordingly possible to determine in each case such afterglow function for different frequency ranges, which overall result in a spectral afterglow function g s (t).
  • the correlator 7 can be, for example, part of the evaluation electronics 11, which can then contain further components in order to further evaluate the measured afterglow function g (t) (or gs (t)).
  • g (t) or gs (t)
  • a simple overall afterglow function g (t) is assumed.
  • this afterglow function g (t) can then possibly be classified in a suitable manner and an identifier HW can be determined, for example in the form of a hash value HW.
  • This hash value HW can then be compared in a comparator 9 with a desired hash value HW 'in order to verify the authenticity of the mark M and to output an authentication signal AS, for example on a display device 15 of the authentication system 20 (see FIG.
  • the certification result can be transferred via an interface 13 to other locations, for example a merchandise management system.
  • Such an interface 13 may be a wired or wireless interface.
  • ECDSA Elliptic Curve Digital Signature Algorithm
  • This digital signature DS can be contained, for example, in the security code SC, which was previously read by the code reader 50 of the security scanner unit 20.
  • the digital signature DS it would also be possible for the digital signature DS to be permanently stored in a memory 12 or to be received via an interface, for example the interface 13, from an external location and then stored in the memory 12, for example for further use.
  • the public key OS can also be received via such an interface 13 and stored in the memory 12.
  • FIG. 12 shows a further exemplary embodiment for a simple hardware-technical realization of an authentication system 20 'for the application of the method according to the invention.
  • the excitation of the mark M on the object O takes place here again by emitting an x (t) PRBS excitation signal through one or more (UV) LEDs 3 of the excitation signal transmitting device 30 ', which in turn via a constant current source 2' with a digital pseudo-random signal is applied.
  • a PRBS generator which is implemented here in a simple manner (for example in the form of software) on a microcontroller 21.
  • the response signal or luminescence signal y (t) is detected by a response signal receiving device 40 'which has a photodiode 4' operating as a base sensor (to which a bias voltage U v of, for example, 2.4 V is applied) whose photocurrent is above one Measuring amplifier 22 is converted into a voltage, which in turn is digitized via an analog / digital converter 6. Its supply voltages + U b and -U b , eg ⁇ 6 V, are applied to the measuring amplifier.)
  • the calculation of the cross-correlation function and thus of the impulse response takes place here in an evaluation electronics 11 ', which in turn can be implemented (for example as software) in the microcontroller 21. Also, the analog / digital converter 6 may be integrated on the input side into the microcontroller 21.
  • the measuring amplifier 22 thus forms a type of analog signal converter 5 'together with a resistor R which is connected in parallel in the usual way. To further increase the interference suppression and accuracy, this resistor R can be replaced by a capacitor. The integrating measurement realized in this way suppresses high-frequency interference. The integration can be numerically calculated back in the calculation in the microcontroller 21.
  • a plurality of photodiodes with different optical filters arranged in front of them can be used, and thus decay functions at different wavelengths can be measured.
  • the system can each with use of different LEDs or laser diodes with different wavelengths are excited.
  • a combination with the methods described in the cited DE 10 2004 016 249 A1 is also possible, for example by mixing the luminescent substances described there with the security marker substances of the invention described here or the like.
  • the density of the modified conversion phosphors may also be measured and quantified. If a base material or a basic substance is mixed with the conversion phosphors, at later times or processing steps, in addition to authentication, a blend or dilution may be determined from the measured intensity loss. This can be used advantageously for the detection of manipulations of basic materials.
  • Application examples are the blending of cotton by cellulose or the dilution of cosmetics.
  • biocompatible conversion phosphors or their incorporation into a biocompatible matrix can also detect dilution of pharmaceutical products, such as anticancer drugs, with saline solutions.
  • pharmaceutical products such as anticancer drugs
  • indefinite article "on” or “one” does not exclude that the characteristics in question may also be present multiple times.
  • unit does not exclude that it consists of several interacting sub-components, which may also be spatially distributed if necessary.

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Abstract

L'invention concerne un procédé de fabrication d'une substance de marqueur de sécurité (S, S1, S2, S3), au moins une substance luminescente (L1, L2), de préférence une fonction de rémanence (f1(t), f2(t), f3(t), f4(t), f5(t), g(t)) de la substance luminescente (L1, L2) étant modifiée individuellement de manière non reproductible. En outre, l'invention concerne un marqueur de sécurité (S, S1, S2, S3) comprenant au moins une telle substance luminescente (LI1, LI2) modifiée individuellement ainsi qu'un objet (O) doté d'un marquage (M) avec une telle substance de marqueur de sécurité (S, S1, S2, S3). En outre, l'invention concerne des procédés d'authentification et d'identification d'un objet (O) et un système d'identification (20) permettant d'identifier un objet (O).
PCT/EP2018/084608 2017-12-14 2018-12-12 Procédé de fabrication d'une substance de marqueur de sécurité ainsi que procédés d'authentification et d'identification d'un objet et système d'identification Ceased WO2019115636A2 (fr)

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DE102017130027.9A DE102017130027A1 (de) 2017-12-14 2017-12-14 Verfahren zum Herstellen eines Sicherheitsmarkerstoffs sowie Verfahren zur Authentifizierung und zur Authentifikation eines Objekts und Authentifikationssystem
DE102017130027.9 2017-12-14

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DE102020104115A1 (de) * 2020-02-17 2021-08-19 Bundesdruckerei Gmbh Verfahren zum Überprüfen eines smartphone-verifizierbaren Sicherheitsmerkmals, Smartphone-verifizierbares Sicherheitsmerkmal und Wert- oder Sicherheitsdokument
DE102020120669B4 (de) 2020-08-05 2022-10-06 Leibniz-Institut für Oberflächenmodifizierung e.V. Authentifizierungsmarker zur Authentifizierung eines Gegenstandes, Verfahren zur Herstellung eines Authentifizierungsmarkers, mit einem Authentifizierungsmarker markierter Gegenstand und Verfahren zur Prüfung eines mit einem Authentifizierungsmarker markierten Gegenstands
WO2023017347A1 (fr) 2021-08-12 2023-02-16 Leuchtstoffwerk Breitungen Gmbh Procédé de détermination de l'authenticité d'un objet

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