WO2011020603A1 - Elément de sécurité à changement de couleur - Google Patents

Elément de sécurité à changement de couleur Download PDF

Info

Publication number
WO2011020603A1
WO2011020603A1 PCT/EP2010/005069 EP2010005069W WO2011020603A1 WO 2011020603 A1 WO2011020603 A1 WO 2011020603A1 EP 2010005069 W EP2010005069 W EP 2010005069W WO 2011020603 A1 WO2011020603 A1 WO 2011020603A1
Authority
WO
WIPO (PCT)
Prior art keywords
radiation
colorant
luminescence
color
excitation
Prior art date
Application number
PCT/EP2010/005069
Other languages
German (de)
English (en)
Inventor
Edward Springmann
Original Assignee
Bundesdruckerei 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 filed Critical Bundesdruckerei Gmbh
Priority to CN201080036208.9A priority Critical patent/CN102549106B/zh
Priority to EP10748052A priority patent/EP2467444A1/fr
Publication of WO2011020603A1 publication Critical patent/WO2011020603A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/56—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing sulfur
    • C09K11/562—Chalcogenides
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/50—Sympathetic, colour changing or similar inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/22—Luminous paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/62—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing gallium, indium or thallium
    • C09K11/621—Chalcogenides
    • C09K11/623—Chalcogenides with zinc or cadmium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
    • C09K11/881—Chalcogenides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/89—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing mercury
    • C09K11/892—Chalcogenides
    • 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

Definitions

  • the invention relates to a color which comprises at least one colorant which emits a luminescence radiation upon irradiation with electromagnetic excitation radiation.
  • the invention further relates to security elements and value and / or
  • Security elements used. Security elements are structural units or
  • Components of a security document which are intended to at least complicate or completely prevent a verification of a genuineness of the security document and / or a forgery, falsification, and / or imitation.
  • Each security element thus has at least one security feature which can not be generated by simple photographic duplication.
  • security elements in the prior art watermarks, holograms, security prints, i. Printing produced by special printing methods and / or printing compositions, etc. known.
  • Value and / or security documents are documents that are at least one
  • Security feature or include a security element.
  • each value and / or security document itself is also a security element.
  • Value and / or security documents include i.a. Passports, visas, driving licenses, ID cards, motor vehicle tickets, documents of value such as banknotes, shares, credit cards, tickets, vouchers, lottery tickets, etc., but also labels or the like.
  • Colorant is according to DIN 55943 the collective name for all coloring substances.
  • Colorants are subdivided on the one hand into organic and inorganic, on the other hand in pigments and dyes. Colorants have absorption and / or emission properties in the ultraviolet, visible and / or infrared spectral range of the light and thus lead to the color impression of the colorant.
  • Paints are preparations containing at least one colorant.
  • inks usually comply with other ingredients,
  • binders in particular binders, solvents, functional materials, additives and / or auxiliaries.
  • colors are applied to a substrate by means of printing processes.
  • Conventional printing methods include high-, flat-, gravure-, through- and digital printing, in particular offset in the embodiments wet and dry offset, flexographic printing, gravure gravure printing,
  • Intaglio printing screen printing, inkjet printing, laser printing and thermal transfer printing.
  • Some security elements include colorants that exhibit photoluminescence. In the case of photoluminescence, the luminescence radiation is emitted as a result of light excitation (photoexcitation) with electromagnetic radiation.
  • Safety elements exhibit an emission of fluorescence radiation, in particular in the visible wavelength range, upon excitation with electromagnetic radiation, for example irradiation with UV light. These are not an aid to verify a source of radiation that generates the appropriate excitation radiation.
  • Such security features are referred to as level 2 features.
  • Security features, new security documents, new colors, which are suitable for use in security documents and security elements, and / or to provide methods for the production of security elements and / or value and / or security documents, the photoluminescence and hereby a reliable verifying feature For example, show an optical effect, as well as novel methods for verification of security elements and / or value and / or security documents to create.
  • the invention is therefore based on the object, a color, a security element, a value and / or security document and a method for producing a
  • the invention is based on the observation that some colorants show a time-dependent fluorescence behavior during the continuous photoexcitation.
  • Observation is used to create a novel color, a novel security element, a novel value and / or security document, a process for its production and a novel verification process.
  • Proposed is inter alia a color comprising at least one colorant, which under irradiation with electromagnetic excitation radiation a
  • Luminescence radiation in particular a fluorescence radiation in the visible
  • the colorant emits initially under the irradiation a luminescence radiation whose intensity decreases or nearly disappears during continuous irradiation with the excitation radiation within a first time interval
  • the colorant is such that after a regeneration period in which the colorant is not irradiated with the excitation radiation, the effect described under a) can be observed again. It is important that the colorant is or is chosen so that the colorant is in a state after the regeneration period in which it can be stimulated to luminescence again. This means that no chemical
  • Conversion of the colorant takes place in the form of a fundamental destruction of the colorant.
  • the decrease in intensity is detectable and / or perceptible in a simple and reliable manner both for a human observer and for a machine verification device which detects the luminescence radiation.
  • a color according to the invention thus has a colorant which emits a luminescence radiation upon irradiation with electromagnetic excitation radiation, wherein the colorant initially emits a luminescence radiation under the irradiation, the intensity of which decreases or nearly disappears during continuous irradiation with the excitation radiation within a first time interval, and so obtain is that after a regeneration period in which the colorant is not irradiated with the excitation radiation, the luminescence can be observed again.
  • a security element and a value and / or security document can be produced by inserting and / or applying the corresponding color with the described properties into or onto a substrate of the security element becomes. It is understood that the introduction must be such that, on the one hand, photoexcitation of the colorant in the finished security element or security and / or security document and also leakage of the emitted luminescence radiation out of the security element or security and / or security document are possible got to.
  • Security elements or the proposed color, when used in a value and / or security document or security element, is the simple verification with existing UV lamps to stimulate the luminescence and the unaltered visual inspection, as already performed, for example, at cash registers.
  • An imitation counterfeit which is produced with commercially available colorants according to the prior art, does not have the temporal behavior of the luminescence according to the invention and can thus be recognized as counterfeiting even in the case of a simple and rapid check by untrained personnel.
  • Luminescence radiation of the at least one colorant is different, so that in a color addition of the luminescence with the further luminescence radiation in a human observer, a color impression is caused, which differs from the
  • Color impressions which are caused solely by the luminescence radiation and / or solely by the further luminescence radiation differs.
  • the second colorant any colorant exhibiting photoluminescence can be used.
  • a second colorant is thus present in addition to the first colorant.
  • the second colorant preferably does not exhibit the effect according to the invention, so that the luminescence of the second colorant can be regarded as constant over the period of observation.
  • the second colorant has a color impression different from the first colorant.
  • the first colorant is green and the second colorant is red.
  • a mixed shade of red and green would first be observed which, depending on the mixing ratio, produces a possibly yellow color impression.
  • the color impression changes to red. This is also true After the decay of the first luminescence still luminescence to observe, so that the verification is simplified.
  • a colorant is used as the second colorant, which itself does not decrease the intensity of the luminescence radiation with continued irradiation with
  • Rare earth-doped pigments and passivated semiconductor materials so-called core-shell materials, eg CdTe / ZnS, carbon nanotubes, and stable organic dyes ; in particular condensed aromatic dyes used.
  • the security element initially emits luminescence radiation of two different wavelengths. Due to the color addition, the combination of these luminescent radiation causes a color impression of a mixed color. If the intensity of the luminescence radiation of the one colorant decreases or even almost completely disappears, the intensity ratio of the two luminescence radiation changes in favor of the further luminescence radiation of the further colorant. The color impression produced thus approaches or assumes the color impression which is caused by the further luminescence radiation of the further colorant.
  • the emission spectra of the colorants are different.
  • Colorant significantly different colors of the luminescent radiation, for example, red and green.
  • the colorant comprises a semiconductor having a bandgap of 0.2 to 5 eV.
  • a semiconductor has an occupied valence band (VB) and an unoccupied conduction band (CB).
  • VB occupied valence band
  • CB unoccupied conduction band
  • the absorption of electromagnetic radiation can raise an electron from the VB to the CB.
  • the VB creates a so-called hole.
  • the electron and hole quickly relax in the way that the electron occupies the lowest energetic state in the CB and the hole occupies the highest energetic state in the VB.
  • spontaneous (or stimulated) emission the electron can emit a photon into the VB
  • the electron which is located in the CB after excitation can be transferred to an energetically slightly lower antibonding orbital of a ⁇ -system or an energetically lower CB of another semiconductor become.
  • an electron may also be released, for example, from an on-surface sulfur atom, present as an oxide in the -2 oxidation state, to the VB with oxidation of the sulfur.
  • the expert can set the energetic position of the further level and the spatial distance targeted.
  • an aromatic system can be selectively adjusted by targeted variation of the ligands on the aromatic system.
  • the spatial distance can be adjusted specifically.
  • the colorant comprises a
  • a multi-level electronic system having a plurality of electronic levels, the plurality of electronic levels including at least one stimulated level excitable with the excitation radiation, a radiation output level, and a radiation end level, the luminance radiation being radiantly transposed from the one
  • a de-excitation of the stimulated by the excitation radiation colorant via a first decay channel (Abregungskanal), which extends over the radiation output level and the Radiantendabide under transmission of the luminescence radiation, and at least one competing second decay channel, wherein an average
  • Decay channel transit time of the first decay channel is less than the first time interval and another average decay channel transit time of the at least one second decay channel is greater than the first time interval and shorter than the regeneration period.
  • a second decay channel which leads directly to a ground state, is not necessary.
  • the second channel may also be characterized by a level to which the system transitions from an excited state and from which emission of luminescent radiation is not possible. However, the system can return from this level to the excited state. From the excited state, the system can return to the ground state by emitting luminescent radiation.
  • the colorant comprises a pigment comprising the radiation output level and the radiation end level, wherein the pigment is coupled with an external structure to an electronic system, the second decay channel comprising a so-called external level, in the presence of which upon excitation generated charge carriers can be localized on the external structure.
  • the colorant is first excited from a ground state in the excited state.
  • a charge carrier a hole or an electron
  • this charge carrier can each be assigned to a level of the electronic system.
  • Carrier also a state to be defined, the one associated with the corresponding level.
  • the average time required for depletion via the first decay channel is referred to herein as channel transit time.
  • the levels that the excited carrier undergoes in the first decay channel during depletion can all be localized to the color pigment.
  • the at least one longer lived level of the second decay channel may be associated with a change of the charge carrier to an external structure which forms an electronic system with the pigment. This longer lived level is preferably energetically close to a level of the first decay channel. If necessary, it is slightly lower in energy terms than that
  • Decay channels prefer the first decay channel. Due to the fact that during the irradiation with the excitation radiation, a plurality of excitation relaxation cycles, which take place over the first decay channel, it happens again and again that also a degeneration runs over the second decay channel.
  • the pigment does not return to the ground state "on the fly", that is, on a statistical average in the decay channel transit time of the first decay channel, and thus can not initially participate in the luminescent radiation generation, since the colorant comprises a plurality of similar color pigments, the luminescence decreases not abruptly, but steadily decreasing continuously the number of pigments, with which the decay runs over the second decay channel, which for example covers the above-mentioned level, from which no radiant disintegration is possible, increases steadily the number of at
  • Decay channels so that the ground state is finally reached. This takes place on a statistical average after the further channel transit time of the further decay channel.
  • the time intervals are adapted to the respective application.
  • Regeneration period is usually one or more orders of magnitude longer than the first time interval.
  • the colorant is selected.
  • the colorant is preferably a direct semiconductor, in particular an Il / Vl semiconductor, eg CdS or HgTe, or an Ill / V semiconductor, eg InAs or GaP.
  • the pigments can also be present in a size in which the size-quantization effect can be used to set the electronic structure and therefore also the wavelength of the emitted luminescence radiation in a targeted manner.
  • Organic pigments can also be used.
  • a shell, ligands or a matrix are suitable in which the pigment is embedded.
  • the lifetime of the longer-lived level located in the further decay channel can be influenced and / or adjusted via the choice of the constituents of the shell, of the ligand (s) and / or of a matrix material.
  • the external structure may consist of an organic ligand shell.
  • ligands on surfaces of Il / Vl and III / V semiconductors are thiols, amines, phosphines, carboxylates.
  • the ligands may have further functional groups, in particular to provide levels into which charge carriers can be incorporated.
  • the functional groups may be aromatics,
  • the ligands are preferably selected such that the lowest unoccupied molecular orbital (LUMO) is just below the valence band (VB) of the core material or the highest occupied molecular orbital (HOMO) just above the conduction band (CB).
  • LUMO lowest unoccupied molecular orbital
  • VB valence band
  • HOMO highest occupied molecular orbital
  • the external structure may further consist of an inorganic shell.
  • the material of the shell has electronic states so that a charge carrier, electron or hole, can be accommodated.
  • a luminescent CdSe core may be surrounded by a ZnS cladding, the ZnS having an n-type doping, for example, due to sulfur vacancies or incorporation of Br ' (ionic radius 196 pm) instead of S 2' (ionic radius 195 pm). This allows holes to be transferred from the "pigment core" to the shell of the pigment. In CdSe-Kem remains an electron.
  • Between the core and the shell may be another layer, in particular to achieve an adaptation of the crystal lattice. Typical examples are CdSe / CdS / ZnS structures, whereby the transition from CdS to ZnS can be gradual.
  • an electron-hole pair is generated in CdSe. This can recombine under the emission of luminescent radiation.
  • a charge carrier may be delivered to the shell of organic ligands or inorganic material. If a further electron-hole pair is generated in the CdSe core by renewed excitation, this recombines very quickly due to the additional free charge carrier, so that no luminescence can be observed.
  • the external structure preferably adapted to the pigment, is or is selected such that the regeneration period is at least an order of magnitude longer than the first time interval. In a verification, the decay of the fluorescence is first observable. Immediately thereafter, however, the effect is observable that no fluorescence occurs.
  • a security element with a first colorant which initially emits a luminescence radiation under the irradiation whose intensity decreases or almost disappears during continuous irradiation with the excitation radiation within a first time interval, and
  • b) is such that after a regeneration period, in which the colorant is not irradiated with the excitation radiation, the effect described under a) can be observed again, for example, can be used for banknotes that are to be used multiple times.
  • the security feature the decrease in the intensity of the observed luminescence or, when used in combination with another, a time-stable luminescence colorants, a color change is observed.
  • the banknote is genuine and will be accepted as a form of payment if the effect is observed.
  • the color described here in production or in a method for producing a security element and / or in such a way that the at least one color applied to a substrate of a security document, in particular imprinted.
  • the substrates used are plastic films as well as paper or pulp-based layers, which are often stacked together to form the security document.
  • the individual substrate layers may be assembled into a document body in the form of a card in a high pressure, high temperature lamination process.
  • the imprint it is possible to encode information, for example in the form of alphanumeric characters, a one- or two-dimensional line or dot code, and so on.
  • the substrate which is for example a foil made of a thermoplastic plastic or polycarbonate, is integrated as an inner layer in the security document, preferably in the context of a lamination process.
  • Security document this is irradiated with excitation radiation.
  • a resulting luminescence radiation is detected and, in at least one wavelength range, the intensity of the luminescence radiation is detected in a time-resolved manner during the continuous irradiation.
  • the security element or the security and / or security document is verified as genuine if the intensity of the luminescence radiation in the one
  • Wavelength range decreases with continuous irradiation with the Anreungsstrahlijn ⁇ within a first time interval or almost disappears.
  • the irradiation of the security element or the security and / or security document is interrupted for a regeneration period and then an irradiation of the security element or of the security and / or security document with the excitation radiation is performed again and the intensity of the luminescence radiation is again detected time-resolved in the at least one wavelength range and the security element or the value and / or
  • At least one wavelength range is detected by evaluating a color impression of the total luminescence radiation in the visible wavelength range and verifying security element or value and / or security document as genuine, if the color impression is of a mixed color impression within a first time interval when radiation with the excitation radiation persists.
  • Color addition of the luminescence radiation of a first colorant and a second Colorant results, changes in a color impression that is wholly or almost entirely determined by the luminescence of the second colorant.
  • Fig. 2 is a schematic representation of the occurring during the excitation and de-excitation
  • Fig. 3 is a schematic representation of a multi-level electronic system for
  • Fig. 5 is a schematic representation of a direct semiconductor system for
  • FIG. 1 schematically shows two graphs 1, 2 which, as abscissa 3, comprise the same time scale.
  • Excitation radiation which is preferably UV light and has an excitation wavelength ⁇ Anr egu ⁇ g removed. 6 along the ordinate of the lower graph 2 is a luminescence intensity 7 an observable or observed luminescence of a colorant of a security element having a luminescence wavelength ⁇ s is Lumine z e nz i ablated.
  • the excitation is set.
  • Regeneration period within which there is no irradiation of the colorant with the excitation radiation (for example, UV radiation), is at a renewed excitation between the times t s and t 10 again to observe a luminescence whose
  • Fig. 2 is schematically illustrated by four graphs 11, 12, 13, 14, which
  • Intensities and color impressions are perceptible to a security element in which, in combination with the at least one colorant, a behavior as described above with reference to FIG. 1, at least one further colorant is used, which during the excitation a constant luminescence intensity 16 (FIG. neglecting
  • Graphs 11 and 12 show sections of graphs 1 and 2.
  • the luminescence intensity 16 of the at least one further colorant is plotted along the ordinate 15. During the excitation with the excitation radiation, the luminescence intensity 16 of the at least one further colorant is constant.
  • Applied security element which is spanned with the luminescence radiation of the at least one colorant with the wavelength ⁇ Lum ⁇ ne s z en z i and the luminescence ⁇ lambda nz2.
  • the value zero is assigned no color impression.
  • Excitation duration decreases the luminescence intensity of the at least one colorant 5 absolutely and above all in relation to the luminescence intensity 16 of the at least one further colorant.
  • the color impression changes towards the color impression 2, which is caused by the luminescence radiation of the at least one further colorant.
  • the maximum luminescence intensity 7 at time t 2 is significantly greater than the luminescence intensity 16 at time t 2 .
  • the perception of the Luminescent light of the first colorant to be significantly stronger than the perception of the second luminescent light. This is the case, for example, when the first colorant has a green luminescence and the second colorant has a red luminescence. For green light, the human eye is relatively sensitive. At the time t 2 , the green light dominates the perception even at comparable intensity. Due to the falling intensity of the green luminescence radiation, the perception shifts to red at time t 3 .
  • the first green phosphor may be CdSe and the second may be a europium doped material
  • Fig. 3 is a schematic illustration of a multilevel electronic system of a colorant of a colorant for illustrating the observable effect.
  • electromagnetic excitation radiation hv excitation in an excited level 23 instead. From this excited level 23 is a non-radiative transition 24 in a
  • the luminescence is 28 hv lum i n ez z with the
  • Decay channel throughput time This is orders of magnitude shorter than the first time interval AT 1 , which is described in connection with FIGS. 1 and 2.
  • the further decay channel or channel (the terms are regarded as synonyms) additionally comprises a longer-lived level 36. Its lifetime is longer than the first time interval .DELTA.T1 according to FIGS. 1 and 2. Thus, if a degeneration takes place via the second decay channel, this decreases corresponding color particles of the colorant no longer participate in the excitation-de-excitation cycle within the first time interval AT 1 . Only after the regeneration period, the color particle is again almost 100%
  • a further decay channel transit time of the further decay channel is shorter by a factor of 3 than the regeneration period, because then the intensity at time t 8 to about 95% of the intensity at time X 2
  • the longer-lived level 36 is energetically almost degenerate to the radiation output level 25.
  • other energy schemes are also possible.
  • the further decay channel which is not absolutely necessary, likewise runs over the radiating transition 26, in this case virtually no luminescence is observed, since the excitation occurs statistically on a very large time scale.
  • Fig. 4 is a schematic representation for illustrating the occurring
  • a pigment 41 of the at least one colorant is coupled to an external structure 42, which is exemplified here as a shell, so that a multi-level electronic system is formed, as illustrated, for example, in FIG.
  • Luminescence radiation hv Lum i neszenz a "destruction" of the electron-hole pair and the de-excitation to the ground level. As indicated above points 43, this process can be repeated as long as the stimulus persists.
  • the de-excitation does not occur immediately via the radiant transition. Rather, for example, the hole h + migrates here to the external structure 42. The system is now in the longer-lived level. Only after a period of time which is longer than the first time period does the de-excitation take place into the basic level, for example also via the radiating transition, after the hole h + has again "migrated" onto the pigment 41.
  • Fig. 5 is a schematic representation of a direct semiconductor system of a
  • Color particle of a colorant for the purpose of illustrating the observable effect.
  • Excitation radiation hv Anreun g 53 in a conduction band (CB) 51 instead. From the excited state of the electron, relaxation takes place rapidly and without radiation to the lowest energy level of the CB 51. Relaxation 58 of the hole also takes place at the highest level of VB 50. From this state, electron and hole can recombine in a bright transition 57 of luminescence hv luminescence 54.
  • level 52 This level, for example, belongs to a ligand molecule located on the semiconductor surface. This level 52 is energetically just below the CB 51. If an electron is excited in the CB 51, then there is in addition to the radiating transition 57 the possibility that the electron passes through a non-radiative transition 59 in the level 52.
  • the color particle leaves a hole as a single charge carrier. Generated by absorption of additional electromagnetic excitation radiation hv Anre g g 53 un another electron-hole pair, as occurs nonradiative recombination. The color particle is no longer capable of emitting luminescence hv luminescence 54. By a non-radiative transition 60, the electron can get back into the CB 51.
  • transition 59 can take place. Since the transition 60 is energetically less favorable, the transition 60 is slower, so that most of the color particles have an occupied level 52, the luminescence of the colorant is extinguished. If there is no longer any suggestion, transition 59 can no longer take place. All charge carriers, which pass through the junction 60 into the CB 51, can via the radiant junction 57
  • the described colorants are preferably incorporated in one color for processing. This is then used for the production of security elements, value and / or security documents or even of substrates or materials which are used for the production of security elements or security and / or security documents, for example for the production of substrate layer films, the mentioned

Abstract

L'invention concerne un élément de sécurité et un agent de coloration, comprenant au moins une matière colorante qui émet, par irradiation par un rayonnement d'excitation électromagnétique, un rayonnement luminescent, a) l'agent de coloration émettant tout d'abord, par irradiation, un rayonnement luminescent, dont l'intensité décroît, par irradiation persistante par le rayonnement d'excitation, dans un premier intervalle de temps, ou disparaît presque complètement, et b) l'agent de coloration étant composé de telle façon qu'après un court espace de temps de régénération, au cours duquel l'agent de coloration n'est pas irradié par le rayonnemement d'excitation, l'effet décrit sous a) est de nouveau observé. L'invention concerne en outre des documents de valeur et/ou de sécurité qui comprennent un tel élément de sécurité ou un tel agent de coloration.
PCT/EP2010/005069 2009-08-21 2010-08-18 Elément de sécurité à changement de couleur WO2011020603A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201080036208.9A CN102549106B (zh) 2009-08-21 2010-08-18 带颜色转变的安全单元
EP10748052A EP2467444A1 (fr) 2009-08-21 2010-08-18 Elément de sécurité à changement de couleur

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102009038356A DE102009038356A1 (de) 2009-08-21 2009-08-21 Sicherheitselement mit Farbumschlag
DE102009038356.5 2009-08-21

Publications (1)

Publication Number Publication Date
WO2011020603A1 true WO2011020603A1 (fr) 2011-02-24

Family

ID=42751790

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2010/005069 WO2011020603A1 (fr) 2009-08-21 2010-08-18 Elément de sécurité à changement de couleur

Country Status (4)

Country Link
EP (1) EP2467444A1 (fr)
CN (1) CN102549106B (fr)
DE (1) DE102009038356A1 (fr)
WO (1) WO2011020603A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE202014102264U1 (de) 2014-05-14 2014-06-06 Bkp Berolina Polyester Gmbh & Co. Kg Schlauchliner mit einem visuellen Aushärtungsindikator
DE102014209074B3 (de) * 2014-05-14 2015-07-02 Bkp Berolina Polyester Gmbh & Co. Kg Schlauchliner mit einem visuellen Aushärtungsindikator
WO2015086713A3 (fr) * 2013-12-10 2015-08-06 Bundesdruckerei Gmbh Élément de sécurité à effet dépendant d'un champ et excitable par uv
CN105150715A (zh) * 2015-08-19 2015-12-16 中钞油墨有限公司 动态防伪元件及其制备方法和应用
US11282321B2 (en) 2017-09-21 2022-03-22 Giesecke+Devrient Currency Technology Gmbh Optical storage phosphor, method for checking an authenticity feature, device for carrying out a method, authenticity feature and value document

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011108180B4 (de) 2011-07-20 2014-12-24 Sensor Instruments Entwicklungs- Und Vertriebs Gmbh Verfahren und Vorrichtung zum Identifizieren eines photolumineszierenden Materials
DE102016007066A1 (de) 2016-06-08 2017-12-14 Giesecke+Devrient Currency Technology Gmbh Verfahren zur Absicherung von Wertdokumenten mit gedächtnisbehaftetem Merkmalssystem
DE102017103780A1 (de) 2017-02-23 2018-08-23 Tailorlux Gmbh Verfahren zur Identifizierung eines Materials bzw. Materialgemisches
DE102019122010A1 (de) * 2019-08-15 2021-02-18 Polysecure Gmbh Gegenstand, der Fluoreszenz-Markerpartikel umfasst, und Verfahren zur Identifizierung desselben

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6602671B1 (en) 1998-09-18 2003-08-05 Massachusetts Institute Of Technology Semiconductor nanocrystals for inventory control
WO2004089640A2 (fr) 2003-04-04 2004-10-21 Angstrom Technologies, Inc. Procedes et compositions d'encre pour images de securite a impression invisible pourvues de multiples caracteristiques d'authentification
WO2004114204A1 (fr) 2003-06-24 2004-12-29 National Research Counsil Of Canada Codage spectral par nanocristaux semi-conducteurs fluorescents pour identification de documents et applications de securite
EP1793330A2 (fr) 2005-11-30 2007-06-06 Pitney Bowes, Inc. Marquages multispectrals combinés pour documents
EP2025525A1 (fr) 2007-08-13 2009-02-18 Xerox Corporation Matériau de marquage luminescent à base de points quantiques

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6602671B1 (en) 1998-09-18 2003-08-05 Massachusetts Institute Of Technology Semiconductor nanocrystals for inventory control
WO2004089640A2 (fr) 2003-04-04 2004-10-21 Angstrom Technologies, Inc. Procedes et compositions d'encre pour images de securite a impression invisible pourvues de multiples caracteristiques d'authentification
WO2004114204A1 (fr) 2003-06-24 2004-12-29 National Research Counsil Of Canada Codage spectral par nanocristaux semi-conducteurs fluorescents pour identification de documents et applications de securite
EP1793330A2 (fr) 2005-11-30 2007-06-06 Pitney Bowes, Inc. Marquages multispectrals combinés pour documents
EP2025525A1 (fr) 2007-08-13 2009-02-18 Xerox Corporation Matériau de marquage luminescent à base de points quantiques

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015086713A3 (fr) * 2013-12-10 2015-08-06 Bundesdruckerei Gmbh Élément de sécurité à effet dépendant d'un champ et excitable par uv
DE202014102264U1 (de) 2014-05-14 2014-06-06 Bkp Berolina Polyester Gmbh & Co. Kg Schlauchliner mit einem visuellen Aushärtungsindikator
DE102014209074B3 (de) * 2014-05-14 2015-07-02 Bkp Berolina Polyester Gmbh & Co. Kg Schlauchliner mit einem visuellen Aushärtungsindikator
WO2015172903A1 (fr) 2014-05-14 2015-11-19 Bkp Berolina Polyester Gmbh & Co. Kg Gaine de réfection pour conduite, pourvue d'un indicateur visuel de durcissement
CN105150715A (zh) * 2015-08-19 2015-12-16 中钞油墨有限公司 动态防伪元件及其制备方法和应用
US11282321B2 (en) 2017-09-21 2022-03-22 Giesecke+Devrient Currency Technology Gmbh Optical storage phosphor, method for checking an authenticity feature, device for carrying out a method, authenticity feature and value document

Also Published As

Publication number Publication date
EP2467444A1 (fr) 2012-06-27
DE102009038356A1 (de) 2011-03-24
CN102549106B (zh) 2015-04-22
CN102549106A (zh) 2012-07-04

Similar Documents

Publication Publication Date Title
EP2467444A1 (fr) Elément de sécurité à changement de couleur
EP0980763B1 (fr) Document de securité avec des colorants optiquement excitables pour validation
DE19907697A1 (de) Wertdokument
EP1436774A1 (fr) Document de valeur et marquage de securite au moyen d'une substance de marquage
DE102008050768B3 (de) Sicherheitsmerkmal auf Basis Lumineszenz emittierender Stoffe, Wert- und Sicherheitsdokument mit einem solchen Sicherheitsmerkmal, ein Verfahren sowie eine Vorrichtung zur Verifikation eines solchen Sicherheitsmerkmals
EP3409500B1 (fr) Dispositif, objet pourvu de caractéristique de sécurité et procédé de fabrication d'un dispositif pour une caractéristique de sécurité
AT502868B1 (de) Sicherheitselement
EP1200272B1 (fr) Document de valeur
EP1673739A2 (fr) Document de valeur
EP2651654B1 (fr) Élément de sécurité activable
EP3332982A1 (fr) Élément de sécurité pourvu de marques luminescentes
WO2022218920A1 (fr) Procédé de marquage et d'identification univoques de produits
WO2009040126A1 (fr) Document de sécurité à caractéristique de validité, son procédé de production et dispositif de contrôle
DE10326645A1 (de) Wertdokument mit einem Sicherheitselement und Verfahren zur Herstellung des Wertdokuments
WO2005035270A2 (fr) Document de valeur
EP3079921B1 (fr) Élément de sécurité à effet dépendant d'un champ et excitable par uv, procédé de vérification d'un élément de sécurité et composition couleur structural
DE102022000101A1 (de) Optisch variables Sicherheitselement
EP4251431A1 (fr) Procédé permettant de marquer des produits ayant une caractéristique de sécurité optique avec une dimension temporelle
DE102022125865A1 (de) Foliensicherheitselement mit Selektionsschicht, Herstellungsverfahren, Prüfverfahren und Datenträger mit Foliensicherheitselement
DE102019127948A1 (de) Verfahren zur Identitätsüberprüfung eines Erzeugnisses und ein Erzeugnis mit einem Prüfabschnitt
DE10116315A1 (de) Farbcodierung zur Kennzeichnung von Gegentänden

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201080036208.9

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10748052

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2010748052

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE