EP1284322B1 - Composition de marquage de sécurité - Google Patents

Composition de marquage de sécurité Download PDF

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Publication number
EP1284322B1
EP1284322B1 EP02291986A EP02291986A EP1284322B1 EP 1284322 B1 EP1284322 B1 EP 1284322B1 EP 02291986 A EP02291986 A EP 02291986A EP 02291986 A EP02291986 A EP 02291986A EP 1284322 B1 EP1284322 B1 EP 1284322B1
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EP
European Patent Office
Prior art keywords
conversion
luminescence
components
composition
doped
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.)
Expired - Lifetime
Application number
EP02291986A
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German (de)
English (en)
Other versions
EP1284322A1 (fr
Inventor
Maurice Perron
Thierry Dumery
Jean-Michel Grimal
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.)
Banque de France
Original Assignee
Banque de France
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Publication date
Application filed by Banque de France filed Critical Banque de France
Publication of EP1284322A1 publication Critical patent/EP1284322A1/fr
Application granted granted Critical
Publication of EP1284322B1 publication Critical patent/EP1284322B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/40—Agents facilitating proof of genuineness or preventing fraudulent alteration, e.g. for security paper
    • D21H21/44—Latent security elements, i.e. detectable or becoming apparent only by use of special verification or tampering devices or methods
    • D21H21/48—Elements suited for physical verification, e.g. by irradiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
    • B41M3/14—Security printing
    • B41M3/144—Security printing using fluorescent, luminescent or iridescent effects

Definitions

  • the present invention relates to a light cascade security marking composition.
  • Safety marking compositions comprising photoluminescent elements have been used for many years to minimize the risk of fraudulent reproduction of legal documents or economic documents, in particular banknotes.
  • document EP-A-265 323 discloses a security marking composition
  • a security marking composition comprising an organic matrix in which at least one fluorescent component and at least one phosphorescent component forming a luminous cascade are incorporated therein, that is, that is, one of the components has a range of excitation wavelengths that at least partially matches the luminescence wavelength range of the other component.
  • Such a composition has the advantage of realizing a true encoding of the light, the fraudster being unable, when submitting the document bearing the composition to radiation of a specific wavelength, to establish a direct relationship between the observed final luminescence and the wavelength of the initial radiation.
  • the composition described in this document therefore has a significant advantage over prior compositions.
  • a security marking composition comprising an organic matrix in which are incorporated at least two photoluminescent components forming a luminous cascade, one of which less of the components having a luminescence according to a rising conversion.
  • luminescence according to a rising conversion is meant a luminescence in a wavelength range below the excitation wavelength of the component concerned, as opposed to a luminescence in a downward conversion (Stokes effect) for which luminescence is produced in a wavelength range greater than the excitation wavelength as is generally the case for most photoluminescent components, in particular the components described in EP 265 323. This multiplies the number of combinations made by the cascade and thus increases the difficulty of determining the components used in the composition.
  • the composition further comprises a light cascade whose components all have a luminescence according to a downward conversion.
  • a light cascade whose components all have a luminescence according to a downward conversion.
  • At least one of the components has a luminescence according to upward and downward conversions.
  • the security marking composition according to the invention comprises an organic matrix formed for example by an acrylic resin binder, and a photoluminescent mixture representing approximately 20% by weight of the composition, the photoluminescent mixture. consisting of one part of silver-doped zinc sulphide, one part of copper-doped zinc sulphide, one part of calcium sulphide doped with europium and samarium, and one part of vanadate of yttrium doped with neodymium.
  • the silver-doped zinc sulfide is a fluorescent component, i.e., its luminescence ceases immediately upon cessation of excitation, and has luminescence in a downward conversion. That is, it is excited by radiation in a wavelength range of about 200 nm to about 370 nm, and then emits luminescence in a first wavelength range of about 400 nm. nm and 500 nm.
  • Yttrium vanadate is also a fluorescent component. It is excited by radiation in a wavelength range of about 250 nm to about 370 nm, and then emits luminescence in a wavelength range of about 800 nm to 900 nm.
  • Silver doped zinc sulphide forms with europium and samarium doped calcium sulphide a first light cascade in which calcium sulphide emits luminescence in a downward conversion by excitation in a range of lengths. between about 450 nm and 580 nm and an emission in a wavelength range between about 600 nm and 700 nm, and yttrium vanadate forms with calcium sulphide a second light cascade in which the sulphide of calcium emits luminescence according to a rising conversion by excitation in the wavelength range covering the luminescence range of yttrium vanadate (800 to 900 nm), and a luminescent emission in the range of wavelengths included between 600 nm and 700 nm.
  • Copper-doped zinc sulfide is a phosphorescent component, i.e., whose luminescent emission continues beyond the cessation of excitation, and emits luminescence in a downward conversion, the excitation being caused by radiation at a wavelength of the order of 370 nm and the luminescent emission being produced mainly for a wavelength of the order of 500 nm.
  • Copper-doped zinc sulphide thus also forms a luminous cascade with calcium sulphide doped with europium and samarium but the two components of this light cascade then have luminescence according to a downward conversion.
  • the composition according to the invention has a pink color, when it is put under ultraviolet radiation it has a white color and when it is kept in the dark after cessation of ultraviolet radiation it has a color pale green.
  • the calcium sulphide doped with europium and samarium has a luminescence both in a downward conversion and in a upward conversion
  • the invention can be realized with a single light cascade of which one of the components has a down-conversion luminescence and the other one up-conversion luminescence, for example using only yttrium vanadate, which has a down-conversion luminescence and calcium sulphide which does not is then excited only in his upward conversion.
  • a cascade is thus produced with a first component excited in the ultraviolet and emitting in the infrared (yttrium vanadate), and a second component excited in the infrared and emitting in the visible range (sulphide calcium).
  • composition according to the invention may also be carried out with rare earth oxysulfides which have a luminescence according to a downward or upward conversion as a function of the dopant used.
  • rare earth oxysulfides which have a luminescence according to a downward or upward conversion as a function of the dopant used.
  • europium doped yttrium oxysulfide can be used which has a luminescence according to a rising conversion.
  • composition comprises both fluorescent and phosphorescent components
  • this can also be achieved with exclusively fluorescent components, for example a composition not containing copper-doped zinc sulfide.
  • calcium sulphide can also be doped exclusively with europium or samarium.

Landscapes

  • Luminescent Compositions (AREA)
  • Paints Or Removers (AREA)
  • Illuminated Signs And Luminous Advertising (AREA)
  • Road Signs Or Road Markings (AREA)
  • Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Dental Preparations (AREA)

Description

  • La présente invention concerne une composition de marquage de sécurité à cascade lumineuse.
  • Les compositions de marquage de sécurité comportant des éléments photoluminescents sont utilisées depuis de nombreuses années pour minimiser le risque de reproduction par des fraudeurs de documents juridiques ou de documents économiques, en particulier les billets de banque.
  • A ce propos, on connaît du document EP-A-265 323 une composition de marquage de sécurité comportant une matrice organique dans laquelle sont incorporés au moins un composant fluorescent et au moins un composant phosphorescent formant entre eux une cascade lumineuse, c'est-à-dire que l'un des composants a une gamme de longueurs d'ondes d'excitation qui correspond au moins partiellement avec la gamme de longueurs d'ondes de luminescence de l'autre composant. Une telle composition présente l'avantage de réaliser un véritable encodage de la lumière, le fraudeur se trouvant dans l'impossibilité, lorsqu'il soumet le document portant la composition à un rayonnement de longueur d'onde déterminée, d'établir une relation directe entre la luminescence finale observée et la longueur d'onde du rayonnement initial. La composition décrite dans ce document présente donc un avantage sensible par rapport aux compositions antérieures.
  • Toutefois, la lutte contre la reproduction frauduleuse de documents est une course perpétuelle entre la recherche par les producteurs de documents d'une sécurité plus grande contre la contrefaçon et la recherche par les fraudeurs de contourner les mesures de sécurité.
  • Selon l'invention, on propose une composition de marquage de sécurité comportant une matrice organique dans laquelle sont incorporés aux moins deux composants photoluminescents formant une cascade lumineuse, l'un au moins des composants ayant une luminescence selon une conversion remontante.
  • On entend par luminescence selon une conversion remontante (effet anti-Stokes ou "Up-Conversion"), une luminescence dans une gamme de longueurs d'ondes inférieures à la longueur d'onde d'excitation du composant concerné, par opposition à une luminescence selon une conversion descendante (effet Stokes) pour laquelle la luminescence est produite dans une gamme de longueurs d'ondes supérieures à la longueur d'onde d'excitation comme c'est généralement le cas pour la plupart des composants photoluminescents, en particulier les composants décrits dans le document EP 265 323. On multiplie ainsi le nombre de combinaisons réalisées par la cascade et on augmente donc la difficulté de détermination des composants entrant dans la composition.
  • Selon une version avantageuse de l'invention, la composition comporte en outre une cascade lumineuse dont les composants ont tous une luminescence selon une conversion descendante. Ainsi, on augmente encore la complexité des réactions de la composition et par voie de conséquence la difficulté d'analyser celle-ci.
  • Selon encore un aspect avantageux de l'invention, au moins l'un des composants a une luminescence selon des conversions remontante et descendante.
  • Selon un exemple de réalisation particulier non limitatif, la composition de marquage de sécurité selon l'invention comporte une matrice organique formée par exemple par un liant de résine acrylique, et un mélange photoluminescent représentant environ 20 % en poids de la composition, le mélange photoluminescent comportant une part de sulfure de zinc dopé à l'argent, une part de sulfure de zinc dopé au cuivre, une part de sulfure de calcium dopé à l'europium et au samarium, et une part de vanadate d'yttrium dopé au neodyme.
  • Dans ce mélange, le sulfure de zinc dopé à l'argent est un composant fluorescent, c'est-à-dire que sa luminescence cesse immédiatement après l'arrêt de l'excitation, et a une luminescence selon une conversion descendante, c'est-à-dire qu'il est excité par un rayonnement dans une gamme de longueurs d'ondes allant d'environ 200 nm à environ 370 nm, et émet alors une luminescence dans une première gamme de longueurs d'ondes comprise entre environ 400 nm et 500 nm. Le vanadate d'yttrium est aussi un composant fluorescent. Il est excité par un rayonnement dans une gamme de longueurs d'ondes allant d'environ 250 nm à environ 370 nm, et émet alors une luminescence dans une gamme de longueurs d'ondes comprise entre environ 800 nm et 900 nm. Le sulfure de zinc dopé à l'argent forme avec le sulfure de calcium dopé à l'europium et au samarium, une première cascade lumineuse dans laquelle le sulfure de calcium émet une luminescence selon une conversion descendante par une excitation dans une gamme de longueurs d'ondes comprise entre environ 450 nm et 580 nm et une émission dans une gamme de longueurs d'ondes comprise entre environ 600 nm et 700 nm, et le vanadate d'yttrium forme avec le sulfure de calcium une seconde cascade lumineuse dans laquelle le sulfure de calcium émet une luminescence selon une conversion remontante par une excitation dans la gamme de longueurs d'ondes recouvrant la gamme de luminescence du vanadate d'yttrium (800 à 900 nm), et une émission luminescente dans la gamme de longueurs d'ondes comprises entre 600 nm et 700 nm.
  • Le sulfure de zinc dopé au cuivre est un composant phosphorescent, c'est-à-dire dont l'émission luminescente se poursuit au-delà de la cessation de l'excitation, et émet une luminescence selon une conversion descendante, l'excitation étant provoquée par un rayonnement à une longueur d'onde de l'ordre de 370 nm et l'émission luminescente étant produite principalement pour une longueur d'onde de l'ordre de 500 nm. Le sulfure de zinc dopé au cuivre forme donc également une cascade lumineuse avec le sulfure de calcium dopé à l'europium et au samarium mais les deux composants de cette cascade lumineuse ont alors une luminescence selon une conversion descendante.
  • A la lumière de jour, la composition selon l'invention présente une couleur rose, lorsqu'elle est mise sous un rayonnement ultraviolet elle présente une couleur blanche et lorsqu'elle est maintenue dans l'obscurité après cessation du rayonnement ultraviolet elle présente une couleur vert pâle.
  • Bien entendu, l'invention n'est pas limitée à l'exemple de composition décrit et on peut y apporter des modifications sans sortir du cadre de l'invention tel que défini par les revendications.
  • En particulier, bien que dans l'exemple décrit le sulfure de calcium dopé à l'europium et au samarium ait une luminescence à la fois selon une conversion descendante et selon une conversion remontante, l'invention peut être réalisée avec une seule cascade lumineuse dont l'un des composants a une luminescence selon une conversion descendante et l'autre une luminescence selon une conversion remontante, par exemple en utilisant uniquement du vanadate d'yttrium, qui a une luminescence selon une conversion descendante et du sulfure de calcium qui n'est alors excité que dans sa conversion remontante. On réalise ainsi une cascade avec un premier composant excité dans l'ultraviolet et émettant dans l'infrarouge (le vanadate d'yttrium), et un second composant excité dans l'infrarouge et émettant dans le domaine visible (le sulfure de calcium).
  • La composition selon l'invention peut également être réalisée avec des oxysulfures de terre rare qui ont une luminescence selon une conversion descendante ou remontante en fonction du dopant utilisé. A titre d'exemple on peut utiliser de l'oxysulfure d'yttrium dopé à l'europium qui a une luminescence selon une conversion remontante.
  • Bien que la composition décrite comporte à la fois des composants fluorescents et phosphorescents, celle-ci peut également être réalisée avec des composants exclusivement fluorescents, par exemple une composition ne contenant pas de sulfure de zinc dopé au cuivre. En outre, on notera que le sulfure de calcium peut également être dopé exclusivement à l'europium ou au samarium.

Claims (6)

  1. Composition de marquage de sécurité comportant une matrice organique dans laquelle sont incorporés aux moins deux composants photoluminescents formant une cascade lumineuse, caractérisée en ce qu'au moins l'un des composants a une luminescence selon une conversion remontante.
  2. Composition selon la revendication 1, caractérisée en ce que la cascade lumineuse comporte un premier composant excité dans l'ultraviolet et émettant dans l'infrarouge, et un second composant excité dans l'infrarouge et émettant dans le visible.
  3. Composition selon la revendication 1, caractérisée en ce qu'elle comporte en outre une cascade lumineuse dont les composants ont tous une luminescence selon une conversion descendante.
  4. Composition selon la revendication 3, caractérisée en ce qu'au moins l'un des composant a une luminescence selon des conversions remontante et descendante.
  5. Composition selon la revendication 4, caractérisée en ce qu'elle comporte du sulfure de zinc dopé à l'argent mélangé à du sulfure de calcium dopé à l'europium et au samarium, ou un mélange de ces dopants, et du vanadate d'yttrium dopé au néodyme.
  6. Composition selon la revendication 5, caractérisée en ce qu'elle comporte en outre du sulfure de zinc dopé au cuivre.
EP02291986A 2001-08-14 2002-08-07 Composition de marquage de sécurité Expired - Lifetime EP1284322B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0110806 2001-08-14
FR0110806A FR2828698B1 (fr) 2001-08-14 2001-08-14 Composition de marquage de securite a cascade lumineuse

Publications (2)

Publication Number Publication Date
EP1284322A1 EP1284322A1 (fr) 2003-02-19
EP1284322B1 true EP1284322B1 (fr) 2006-04-05

Family

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EP02291986A Expired - Lifetime EP1284322B1 (fr) 2001-08-14 2002-08-07 Composition de marquage de sécurité

Country Status (11)

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EP (1) EP1284322B1 (fr)
AT (1) ATE322576T1 (fr)
DE (1) DE60210378T2 (fr)
DK (1) DK1284322T3 (fr)
ES (1) ES2257519T3 (fr)
FR (1) FR2828698B1 (fr)
MA (1) MA25711A1 (fr)
MD (1) MD2403C2 (fr)
OA (1) OA12478A (fr)
PT (1) PT1284322E (fr)
TN (1) TNSN02074A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT502868B1 (de) * 2005-03-21 2008-06-15 Oebs Gmbh Sicherheitselement
US20070044679A1 (en) * 2005-08-30 2007-03-01 Petrik Viktor I White-fluorescent anti-stokes compositions and methods
DE102010028818A1 (de) 2010-05-10 2011-11-10 Swiss Authentication Research And Development Ag Kombination von Lumineszenzstoffen
PT3342601T (pt) 2017-01-02 2019-06-11 Polska Wytwornia Papierow Wartosciowych S A Um documento de segurança

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2605123B1 (fr) * 1986-10-10 1989-07-07 Bric Objet fiduciaire ou de securite permettant une authentification visuelle ou optique
SE461359B (sv) * 1987-06-30 1990-02-05 Global Security Ab Saett och anordning foer osynlig maerkning av sedlar eller vaerdehandlingar
ATE77427T1 (de) * 1987-08-19 1992-07-15 Gao Ges Automation Org Sicherheitspapier.
DE3915638B4 (de) * 1989-05-12 2006-06-08 Giesecke & Devrient Gmbh Sicherheitsdokument mit darin eingebettetem Sicherheitselement mit visuell und maschinell prüfbaren Kennzeichen und Sicherheitselement für ein Sicherheitsdokument
DE4114732A1 (de) * 1991-05-06 1992-11-12 Helmut Dr Bayer Sicherheitskennzeichnung fuer papiere und andere materialien mit ebenen oberflaechen
US5639126A (en) * 1995-06-06 1997-06-17 Crane & Co., Inc. Machine readable and visually verifiable security threads and security papers employing same
DE19735293C2 (de) * 1997-08-14 2003-06-12 Bundesdruckerei Gmbh Wert- und Sicherheitserzeugnis mit Lumineszenzelement
RU2150749C1 (ru) * 1999-02-09 2000-06-10 Петрик Виктор Иванович Средство защиты от подделки ценных бумаг и документов (варианты)
FR2813134B1 (fr) * 2000-08-21 2004-01-16 Banque De France Procede d'authentification de documents sensibles
DE10056462A1 (de) * 2000-11-14 2002-05-23 Giesecke & Devrient Gmbh Fluoreszenzstoff und Verfahren zu dessen Herstellung
DE20116951U1 (de) * 2001-10-09 2001-12-13 Khulusi Gelan Dispensierelement zur Überprüfung von Banknoten

Also Published As

Publication number Publication date
TNSN02074A1 (fr) 2004-03-05
DE60210378T2 (de) 2006-10-19
FR2828698B1 (fr) 2003-11-21
OA12478A (fr) 2006-05-24
ES2257519T3 (es) 2006-08-01
DE60210378D1 (de) 2006-05-18
FR2828698A1 (fr) 2003-02-21
ATE322576T1 (de) 2006-04-15
MA25711A1 (fr) 2003-04-01
DK1284322T3 (da) 2006-05-29
PT1284322E (pt) 2006-05-31
EP1284322A1 (fr) 2003-02-19
MD2403B1 (en) 2004-03-31
MD2403C2 (ro) 2004-09-30

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