EP1284322A1 - Composition de marquage de sécurité - Google Patents

Composition de marquage de sécurité Download PDF

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Publication number
EP1284322A1
EP1284322A1 EP02291986A EP02291986A EP1284322A1 EP 1284322 A1 EP1284322 A1 EP 1284322A1 EP 02291986 A EP02291986 A EP 02291986A EP 02291986 A EP02291986 A EP 02291986A EP 1284322 A1 EP1284322 A1 EP 1284322A1
Authority
EP
European Patent Office
Prior art keywords
luminescence
components
doped
conversion
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP02291986A
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German (de)
English (en)
Other versions
EP1284322B1 (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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Filing date
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 composition of safety marking with light cascade.
  • the security marking compositions comprising photoluminescent elements have been used since many years to minimize the risk of reproduction by fraudsters of legal documents or economic documents, especially banknotes.
  • a security marking composition comprising a organic matrix in which are incorporated at least a fluorescent component and at least one phosphorescent component forming between them a luminous cascade, that is, one of the components has a range of lengths of excitation waves that corresponds at least partially with the luminescence wavelength range of the other component.
  • a security marking composition presents the advantage of realizing a true encoding of the light, the fraudster being unable to when submitting the document containing the composition to a determined 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 compared to previous compositions.
  • composition of security marking comprising an organic matrix in which at least two components are incorporated photoluminescents forming a luminous cascade, one at less components having a luminescence according to a upward conversion.
  • Luminescence according to a conversion ascending (anti-Stokes effect or "Up-Conversion"), a luminescence in a range of lower wavelengths at the excitation wavelength of the component concerned, as opposed to luminescence according to a downward conversion (Stokes effect) for which the luminescence is produced in a range of lengths waves greater than the excitation wavelength as is usually the case for most components photoluminescents, in particular the components described in EP 265 323. It is thus multiplied the number of combinations made by the cascade and therefore increases the difficulty of determining the components entering the composition.
  • the composition further comprises a luminous cascade of which the components all have a luminescence according to a conversion down.
  • At least one of the components has luminescence according to upward and downward conversions.
  • the security marking composition according to the invention comprises an organic matrix formed by example by a binder of acrylic resin, and a mixture photoluminescence representing about 20% by weight of the composition, the photoluminescent mixture comprising a part of zinc sulphide doped with silver, a part of sulphide of zinc doped with copper, a part of calcium sulphide doped with europium and samarium, and a part of vanadate of yttrium doped with neodymium.
  • zinc sulphide doped with silver is a fluorescent component, that is, its luminescence ceases immediately after the cessation of the excitation, and has luminescence in a downward conversion, that is to say, it is excited by radiation in a range of wavelengths from around 200 nm at about 370 nm, and then emits a luminescence in a first range of wavelengths between about 400 nm and 500 nm.
  • Yttrium vanadate is also a fluorescent component. He is excited by a radiation in a range of wavelengths ranging from about 250 nm to about 370 nm, and then emit luminescence in a range of wavelengths included between about 800 nm and 900 nm.
  • Zinc sulphide doped with silver forms with calcium sulphide doped with europium and at the samarium, a first luminous cascade in which calcium sulphide emits luminescence according to a downward conversion by an excitation in a range of wavelengths between approximately 450 nm and 580 nm and emission in a range of lengths between about 600 nm and 700 nm, and the Yttrium vanadate forms with calcium sulphide a second luminous cascade in which the sulfide 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 between 600 nm and 700 nm.
  • Copper-doped zinc sulphide is a component phosphorescent, that is, whose luminescent emission continues beyond the cessation of excitement, and emits luminescence according to a downconversion, the excitation being caused by radiation at a wavelength of the order of 370 nm and the emission luminescent being produced mainly for a length wave of the order of 500 nm.
  • Zinc sulphide doped copper thus also forms a luminous cascade with calcium sulphide doped with europium and samarium but the two components of this luminous cascade then have a luminescence in a downward conversion.
  • the composition according to the invention has a pink color when set under ultraviolet radiation it has a color white and when kept in the dark after cessation of ultraviolet radiation it presents a pale green color.
  • the invention can be realized with a single luminous cascade of which one of the components has a luminescence according to a conversion descendant and the other a luminescence according to a upstream conversion, for example using only Yttrium vanadate, which has a luminescence according to a descending conversion and calcium sulphide which is then excited only in its upward conversion.
  • a cascade with a first excited component in the ultraviolet and emitting in the infrared (the yttrium vanadate), and a second component excited in 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 depending on the dopant used.
  • rare earth oxysulfides which have a luminescence according to a downward or upward conversion depending on the dopant used.
  • Europium doped yttrium oxysulfide can be used which has a luminescence according to a rising conversion.
  • composition includes both fluorescent and phosphorescent components, this can also be done with components exclusively fluorescent, for example a composition not containing copper-doped zinc sulfide.
  • calcium sulphide can also be 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)
  • Dental Preparations (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

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.

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 connaít 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
FR0110806A FR2828698B1 (fr) 2001-08-14 2001-08-14 Composition de marquage de securite a cascade lumineuse
FR0110806 2001-08-14

Publications (2)

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

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

Country Status (11)

Country Link
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)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006099642A1 (fr) * 2005-03-21 2006-09-28 Oesterreichische Banknoten- Und Sicherheitsdruck Gmbh Element de securite
EP1760134A1 (fr) * 2005-08-30 2007-03-07 Viktor Ivanovich Petrik Compositions anti-Stokes avec fluorescence blanche et procédés d'identification et de protection de timbres fiscaux, billets de banque, titres, documents et produits

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102010028818A1 (de) 2010-05-10 2011-11-10 Swiss Authentication Research And Development Ag Kombination von Lumineszenzstoffen
EP3342601B1 (fr) 2017-01-02 2019-03-27 Polska Wytwornia Papierow Wartosciowych S.A. Document de sécurité

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0265323A1 (fr) * 1986-10-10 1988-04-27 Banque De France Objet fiduciaire de sécurité permettant une authentification visuelle ou optique
US4897300A (en) * 1987-08-19 1990-01-30 Gao Gesellschaft Fuer Automation Und Organisation Mbh Security paper

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE461359B (sv) * 1987-06-30 1990-02-05 Global Security Ab Saett och anordning foer osynlig maerkning av sedlar eller vaerdehandlingar
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, 41542 Dormagen Dispensierelement zur Überprüfung von Banknoten

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0265323A1 (fr) * 1986-10-10 1988-04-27 Banque De France Objet fiduciaire de sécurité permettant une authentification visuelle ou optique
US4897300A (en) * 1987-08-19 1990-01-30 Gao Gesellschaft Fuer Automation Und Organisation Mbh Security paper

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006099642A1 (fr) * 2005-03-21 2006-09-28 Oesterreichische Banknoten- Und Sicherheitsdruck Gmbh Element de securite
US7656511B2 (en) 2005-03-21 2010-02-02 Oesterreichische Banknoten-Und Sicherheitsdruck Gmbh Security element
AU2006227581B2 (en) * 2005-03-21 2011-07-07 Oesterreichische Banknoten- Und Sicherheitsdruck Gmbh Security element
EP1760134A1 (fr) * 2005-08-30 2007-03-07 Viktor Ivanovich Petrik Compositions anti-Stokes avec fluorescence blanche et procédés d'identification et de protection de timbres fiscaux, billets de banque, titres, documents et produits

Also Published As

Publication number Publication date
DE60210378D1 (de) 2006-05-18
MD2403C2 (ro) 2004-09-30
FR2828698B1 (fr) 2003-11-21
ES2257519T3 (es) 2006-08-01
MA25711A1 (fr) 2003-04-01
MD2403B1 (en) 2004-03-31
DE60210378T2 (de) 2006-10-19
OA12478A (fr) 2006-05-24
ATE322576T1 (de) 2006-04-15
FR2828698A1 (fr) 2003-02-21
EP1284322B1 (fr) 2006-04-05
TNSN02074A1 (fr) 2004-03-05
PT1284322E (pt) 2006-05-31
DK1284322T3 (da) 2006-05-29

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