EP2244884B1 - Dokument mit sichtbarem und variablem sicherheitszeichen - Google Patents
Dokument mit sichtbarem und variablem sicherheitszeichen Download PDFInfo
- Publication number
- EP2244884B1 EP2244884B1 EP09719819.6A EP09719819A EP2244884B1 EP 2244884 B1 EP2244884 B1 EP 2244884B1 EP 09719819 A EP09719819 A EP 09719819A EP 2244884 B1 EP2244884 B1 EP 2244884B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- substance
- following formula
- fact
- different
- groups
- 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.)
- Not-in-force
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Classifications
-
- 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
- B41M3/142—Security printing using chemical colour-formers or chemical reactions, e.g. leuco-dye/acid, photochromes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
- B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
- B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
- B42D25/20—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof characterised by a particular use or purpose
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
- B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
- B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
- B42D25/20—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof characterised by a particular use or purpose
- B42D25/29—Securities; Bank notes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44F—SPECIAL DESIGNS OR PICTURES
- B44F1/00—Designs or pictures characterised by special or unusual light effects
- B44F1/08—Designs or pictures characterised by special or unusual light effects characterised by colour effects
- B44F1/10—Changing, amusing, or secret pictures
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/28—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using thermochromic compounds or layers containing liquid crystals, microcapsules, bleachable dyes or heat- decomposable compounds, e.g. gas- liberating
- B41M5/286—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using thermochromic compounds or layers containing liquid crystals, microcapsules, bleachable dyes or heat- decomposable compounds, e.g. gas- liberating using compounds undergoing unimolecular fragmentation to obtain colour shift, e.g. bleachable dyes
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- B42D2035/24—
Definitions
- the present invention relates to a document, in particular fiduciary, which has on the surface at least one security sign with variable visual perception.
- security sign means a mark of whatever form (text, numbers, drawings, grid lines, etc.) that has or has no meaning, and the nature and / or manner of which affixing to the document was made to make the reproduction of the document particularly complex, if not impossible.
- variable visual perception is meant that this security sign is perceived by the observer, according to the conditions implemented for this observation, at least in two different ways.
- an optical variable ink (Optical Variable Ink) meets this qualification because, depending on the viewing angle, at least two different color perceptions are possible.
- fiducial printing inks designed to obtain safe visual effects are mixtures of substances that are difficult to obtain and / or whose formulation is complex.
- the document US Patent 20050127336 proposes to check security documents such as banknotes with changing color marks including photothermochromes.
- Article Tetrahedron Vol. 49 (1993), No. 37, pp. 8267-8310 refers to organic materials for reversible storage of optical data.
- Article Tetrahedron Vol. 61 (2005), pp. 3719-3723 relates to the phenomenon of selective photocommutation of a dyad with diarylethene and spiropyran units.
- the main purpose of the present invention is to further improve the security of documents, in particular fiduciary documents, which have on the surface at least one security sign with variable visual perception.
- Another aim is to propose a document whose authenticity and, conversely, falsification, is easily controllable by means of simple, inexpensive and widespread devices.
- the invention relates to a document, in particular a fiduciary document, which comprises on the surface a security mark with variable visual perception, characterized in that said mark consists of a material which includes a part possessing properties photochromes and another part having photothermochromic properties.
- the security level of the document is raised compared to a document incorporating only a photochromic material.
- the material contains a first photochromic substance and a second photothermochromic substance.
- the sign of the document according to the invention is applied to the latter by any suitable known printing method.
- the active substance (s) will be incorporated in a printable vehicle such as an ink, a colorless varnish, for example used in flexographic printing.
- the surface layer has a substance density assayed such that the visual effect perceived by the observer results from the combination of the visual effect of each layer.
- the upper layer is not sufficiently thick and / or dense to mask the substance of the lower layer.
- the two active substances are initially colorless and are able to change color in the same wavelength range ( ⁇ 1 ⁇ 50 nm).
- the active substance belonging to the class of photothermochromes can return colorless to room temperature in a relatively short time (for example of the order of 10 minutes).
- the other active substance, belonging to the photochromic class becomes colorless only by irradiation at a known wavelength ⁇ 2 , generally much greater than ⁇ 1 .
- Color means a color itself, but also a shade. Thus, if the colors C P and C T are respectively blue and red, the color perceived under ⁇ 1 will be purple. However, it can be envisaged that the colors of C P and C T are vermilion red and dark red, the perceived color being dark red. However, when the photothermochrome substance becomes colorless again, the perceived color will be vermilion red.
- the goal is to raise the security level of a color transition from a simple photochromic, which is binary in nature, to a ternary or even higher level where the return to the initial state passes through an intermediate color shade perfectly distinguishable from the initial state and the final state.
- the stimulus that makes it possible to obtain this intermediate color is of a different nature (thermal energy supply) from that which makes it possible to obtain the final shade (irradiation under UV) as well as that which allows the return to the initial state (irradiation at a monochromatic wavelength in the visible spectrum).
- the speed of obtaining the intermediate color depends on the amount of thermal energy brought and the locking on this intermediate color can only be unlocked under irradiation at a specific monochromatic wavelength in the visible spectrum (this also works with sunlight).
- the photochromic substance belongs to the family of diarylethenes and corresponds to formula (Ia) below.
- R 1 and R 2 which may be identical or different, represent, independently of one another, an alkyl radical which may or may not be substituted by heteroatomic groups.
- the X and Y groups which may be identical or different, represent, independently of one another, heteroatoms or methylenes which may or may not be substituted by aromatic rings or heteroatoms.
- the group Z represents a heteroatom or a methylene group optionally substituted by electron donor or acceptor groups.
- This family of compounds is known to change color under the action of a specific wavelength ⁇ 1, lying between 200 and 400 nm, following the transformation illustrated below:
- the reverse reaction is known to be able to be carried out by irradiation at a wavelength ⁇ 2 generally greater than 500 nm.
- the photochromic family of diarylethenes corresponds to formula (II).
- the group R is a hydrogen or a halogen
- R 1 and R 2 which are identical or different, represent, independently of one another, an alkyl radical which may or may not be substituted by heteroatomic groups
- R 3 and R 4 which are identical or different, represent independently of each other donor groups or acceptors of electrons.
- X and Y are methylenic groups or heteroatoms.
- the photochromic of the family of diarylethenes corresponds to formula (IIIa).
- This compound is known to change color according to the transformation below.
- the photochromic substance preferentially belongs to the fulgid family and corresponds to the generic formula (IVa).
- R 1 , R 3 and R 4 which may be identical or different, represent, independently of each other, alkyl, cycloalkyl, aromatic or heteroaromatic rings, which may or may not be substituted by heteroatomic groups.
- the Ar group is an aromatic ring.
- This family of compounds is known to change color under the action of a specific wavelength ⁇ 1 , between 200 and 400 nm, according to the transformation below.
- the reverse reaction is known to be able to be performed by irradiation at a wavelength ⁇ 2 generally greater than 500 nm.
- the photochromic family of fulgids corresponds to formula (V). in which R 1 . R 3 , R 4 , R 5 and R 6 , which may be identical or different, represent, independently of each other, alkyl, cycloalkyl, aromatic or heteroaromatic rings, which may or may not be substituted by heteroatomic groups.
- the photochromic of the fulgid family corresponds to the formula (VIa).
- This compound is known to change color according to the transformation below.
- the photothermochromic substance advantageously belongs to the family of spiropyrans and corresponds to the following formula (VIIa).
- R 1 , R 2 which may be identical or different, represent, independently of one another, donor or acceptor groups electron.
- the groups R 3 , R 4 and R 5 which may be identical or different, represent, independently of each other, alkyl or cycloalkyl radicals, which may or may not be substituted by heteroatomic groups.
- the groups X, Y and Z which may be identical or different, represent, independently of one another, a heteroatom or a methylene group which may or may not be substituted by alkyl or cycloalkyl radicals.
- This family of compounds is known to change color under the action of a specific wavelength ⁇ 1 , between 200 and 400 nm, according to the following transformation.
- the reverse reaction is known to be able to be carried out thermally in a range of temperature varying around the ambient temperature in relatively short time. It is accelerated by a supply of thermal energy.
- the photothermochrome of the family of spiropyrans can meet the following formula (VII).
- R 1 , R 2 which may be identical or different, represent, independently of one another, electron donor or acceptor groups.
- the photothermochrome of the family of spiropyrans will have the following formula (IXa).
- This compound is known to change color according to the following transformation.
- the photothermochromic substance preferably belongs to the family of stilbenes and corresponds to the following formula (Xa).
- R 1 , R 2 , R 3 , R 4 , R 5 and R 6 which may be identical or different, represent, independently of one another, alkyl, cycloalkyl, aromatic or heteroaromatic rings, substituted or unsubstituted by heteroatomic groups.
- the group X represents a nitrogen atom or a carbon.
- This family of compounds is known to change color under the action of a specific wavelength ⁇ 1 , between 200 and 400 nm, depending on the transformation.
- the reverse reaction is known to be able to be carried out thermally in a range of temperature varying around the ambient temperature in relatively short time. It is accelerated by a supply of thermal energy.
- n an integer from 1 to 20.
- the photochromic and thermophotochromic substances in the case where they are separated, but also in the case where fragments exhibiting these properties are on the same molecule, will for example be advantageously incorporated in an ink, a varnish, printable on a natural support (paper ) or synthetic (polymers) by all existing printing techniques and especially those commonly used in the field of fiduciary printing (offset, intaglio, screen printing, flexography, typography ).
- the formulation containing said substances may also form a layer in an assembly constituting a heat transfer film and be deposited by the same technique.
- a flexographic varnish doped at 1% by weight with the substances mentioned here will be used to print the mark or the desired sign.
- a 365 nm UV lamp irradiates the printed sign, which changes color in a few seconds. Then, either waiting for a natural relaxation of the thermophotochrome or by accelerating the latter by a supply of thermal energy (for example with a device such as a hair dryer), the element changes color and stabilizes on its intermediate color stable. Finally irradiation under a small single-spectral lamp centered for example on 588 nm allows the return to the initial state colorless.
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- Business, Economics & Management (AREA)
- Accounting & Taxation (AREA)
- Finance (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Glass Compositions (AREA)
Claims (17)
- Dokument, insbesondere Wertdokument, das an der Oberfläche ein Sicherheitszeichen mit variabler visueller Wahrnehmbarkeit umfasst, dadurch gekennzeichnet, dass das Zeichen aus einem Material, das einen Anteil, welcher photochrome Eigenschaften aufweist, und einem anderen Anteil, welcher photothermochrome Eigenschaften aufweist, umfasst, gebildet wird.
- Dokument nach Anspruch 1, dadurch gekennzeichnet, dass das Material eine erste photochrome Substanz sowie auch eine zweite photothermochrome Substanz enthält.
- Dokument nach Anspruch 2, dadurch gekennzeichnet, dass die erste und die zweite Substanz innerhalb des Materials vermischt sind.
- Dokument nach Anspruch 2, dadurch gekennzeichnet, dass die erste und die zweite Substanz getrennte und innerhalb des Materials übereinander liegende Schichten bilden.
- Dokument nach einem der Ansprüche 2 bis 4, dadurch gekennzeichnet, dass die erste und die zweite Substanz die folgenden Eigenschaften aufweisen:• sie sind in einem Ausgangszustand bei Tageslicht farblos oder gefärbt;• sie nehmen jeweils eine unterschiedliche Farbe an, wenn sie einem Licht einer Wellenlänge λ1 ausgesetzt werden derart, dass die wahrgenommene Farbe dann die Kombination der unterschiedlichen Farben ist, wobei diese Farben ihrerseits von jenen des Ausgangszustands verschieden sind;• die zweite Substanz kehrt in ihren Ausgangszustand zurück, wenn sie einer Wärmebehandlung unterzogen wird,• die erste Substanz kehrt in ihren Ausgangszustand zurück, wenn sie einem Licht einer Wellenlänge λ2 ausgesetzt wird, wobei λ2 von λ1 verschieden ist.
- Dokument nach einem der Ansprüche 2 bis 5, dadurch gekennzeichnet, dass die erste Substanz in dem farblosen Ausgangszustand der folgenden Formel (Ia):- R1 und R2, die gleich oder verschieden sind, unabhängig voneinander für einen durch Heteroatom-Gruppen substituierten oder nicht substituierten Alkylrest stehen;- die Gruppen X und Y, die gleich oder verschieden sind, unabhängig voneinander für Heteroatome oder Methylengruppen, die durch Alkylreste, Cycloalkylreste, aromatische Zyklen oder Heteroatome substituiert sind oder nicht, stehen;- die Gruppe Z für ein Heteroatom oder eine Methylengruppe, die durch Elektronendonor- oder -akzeptorgruppen substituiert ist oder nicht, steht.
- Dokument nach Anspruch 6, dadurch gekennzeichnet, dass die erste Substanz im farblosen Ausgangszustand der folgenden Formel (II) entspricht:- die Gruppe R ein Wasserstoff oder ein Halogen ist;- R1 und R2, die gleich oder verschieden sind, unabhängig voneinander für einen durch Heteroatom-Gruppen substituierten oder nicht substituierten Alkylrest stehen;- R3 und R4, die gleich oder verschieden sind, unabhängig voneinander für Elektronendonor- oder -akzeptorgruppen stehen;- X und Y Heteroatome oder Methylengruppen, die durch Alkylreste, Cycloalkylreste, aromatische Zyklen oder Heteroatome substituiert sind oder nicht, sind.
- Dokument nach einem der Ansprüche 2 bis 5, dadurch gekennzeichnet, dass die erste Substanz im farblosen Ausgangszustand der folgenden Formel (IVa):
- Dokument nach Anspruch 9, dadurch gekennzeichnet, dass die erste Substanz im farblosen Ausgangszustand der folgenden Formel (V) entspricht:
- Dokument nach einem der Ansprüche 2 bis 11, dadurch gekennzeichnet, dass die zweite Substanz im farblosen Ausgangszustand der folgenden Formel (VIIa):- R1 und R2, die gleich oder verschieden sind, unabhängig voneinander für Elektronendonor- oder -akzeptorgruppen stehen;- die Gruppen R3, R4 und R5, die gleich oder verschieden sind, unabhängig voneinander für Alkylreste, Cycloalkylreste, die durch Heteroatom-Gruppen substituiert sind oder nicht, stehen;- die Gruppen X, Y und Z, die gleich oder verschieden sind, unabhängig voneinander für ein Heteroatom oder eine Methylengruppe, die durch Alkylreste, Cycloalkylreste substituiert ist oder nicht, stehen.
- Dokument nach Anspruch 12, dadurch gekennzeichnet, dass die zweite Substanz im farblosen Ausgangszustand der folgenden Formel (VIII) entspricht:- R1 und R2, die gleich oder verschieden sind, unabhängig voneinander für Elektronendonor- oder -akzeptorgruppen stehen;- die Gruppen R3, R4, R5, R6 und R7, die gleich oder verschieden sind, unabhängig voneinander für Alkylreste, Cycloalkylreste, die durch Heteroatom-Gruppen substituiert sind oder nicht, stehen.
- Dokument nach Anspruch 1, dadurch gekennzeichnet, dass das Material eine einzige Substanz enthält, die zugleich photochrome wie auch photothermochrome Eigenschaften aufweist.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL09719819T PL2244884T3 (pl) | 2008-02-25 | 2009-02-25 | Dokument zawierający znak zabezpieczający o zmiennej percepcji wizualnej |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0801008A FR2927840B1 (fr) | 2008-02-25 | 2008-02-25 | "document comportant une marque de securite a perception visuelle variable" |
PCT/FR2009/000203 WO2009112723A2 (fr) | 2008-02-25 | 2009-02-25 | Document comportant une marque de securite a perception visuelle variable |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2244884A2 EP2244884A2 (de) | 2010-11-03 |
EP2244884B1 true EP2244884B1 (de) | 2014-10-01 |
Family
ID=39811712
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP09719819.6A Not-in-force EP2244884B1 (de) | 2008-02-25 | 2009-02-25 | Dokument mit sichtbarem und variablem sicherheitszeichen |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP2244884B1 (de) |
FR (1) | FR2927840B1 (de) |
PL (1) | PL2244884T3 (de) |
WO (1) | WO2009112723A2 (de) |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB8828091D0 (en) * | 1988-12-01 | 1989-01-05 | Traqson Ltd | Security marking |
US5289547A (en) * | 1991-12-06 | 1994-02-22 | Ppg Industries, Inc. | Authenticating method |
US6881915B2 (en) * | 2001-01-31 | 2005-04-19 | Spectra Systems Corporation | Contrast enhancing marking system for application of unobtrusive identification and other markings |
US7094368B2 (en) * | 2003-12-10 | 2006-08-22 | Transitions Optical, Inc. | Pyrano-quinolines, pyrano-quinolinones, combinations thereof, photochromic compositions and articles |
-
2008
- 2008-02-25 FR FR0801008A patent/FR2927840B1/fr not_active Expired - Fee Related
-
2009
- 2009-02-25 PL PL09719819T patent/PL2244884T3/pl unknown
- 2009-02-25 EP EP09719819.6A patent/EP2244884B1/de not_active Not-in-force
- 2009-02-25 WO PCT/FR2009/000203 patent/WO2009112723A2/fr active Application Filing
Also Published As
Publication number | Publication date |
---|---|
FR2927840B1 (fr) | 2016-01-22 |
PL2244884T3 (pl) | 2015-03-31 |
FR2927840A1 (fr) | 2009-08-28 |
WO2009112723A3 (fr) | 2009-10-29 |
WO2009112723A2 (fr) | 2009-09-17 |
EP2244884A2 (de) | 2010-11-03 |
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