EP2730425B1 - Imagerie en couleur de précurseurs de documents de sécurité - Google Patents

Imagerie en couleur de précurseurs de documents de sécurité Download PDF

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Publication number
EP2730425B1
EP2730425B1 EP12192155.5A EP12192155A EP2730425B1 EP 2730425 B1 EP2730425 B1 EP 2730425B1 EP 12192155 A EP12192155 A EP 12192155A EP 2730425 B1 EP2730425 B1 EP 2730425B1
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EP
European Patent Office
Prior art keywords
colour
laser
security document
color
laser markable
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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EP12192155.5A
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German (de)
English (en)
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EP2730425A1 (fr
Inventor
Bart Waumans
Paul Callant
Bart Aerts
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.)
Agfa Gevaert NV
Agfa Gevaert AG
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Agfa Gevaert NV
Agfa Gevaert AG
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Application filed by Agfa Gevaert NV, Agfa Gevaert AG filed Critical Agfa Gevaert NV
Priority to EP12192155.5A priority Critical patent/EP2730425B1/fr
Priority to PCT/EP2013/073014 priority patent/WO2014072275A1/fr
Priority to US14/441,603 priority patent/US10245866B2/en
Priority to CN201380059110.9A priority patent/CN104768767B/zh
Publication of EP2730425A1 publication Critical patent/EP2730425A1/fr
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Publication of EP2730425B1 publication Critical patent/EP2730425B1/fr
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    • 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
    • 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
    • B41M3/008—Sequential or multiple printing, e.g. on previously printed background; Mirror printing; Recto-verso printing; using a combination of different printing techniques; Printing of patterns visible in reflection and by transparency; by superposing printed artifacts
    • 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
    • B41M5/34—Multicolour thermography
    • 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
    • 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
    • B41M5/34—Multicolour thermography
    • B41M5/345—Multicolour thermography by thermal transfer of dyes or pigments
    • 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
    • B41M5/382—Contact thermal transfer or sublimation processes
    • B41M5/38207—Contact thermal transfer or sublimation processes characterised by aspects not provided for in groups B41M5/385 - B41M5/395

Definitions

  • This invention relates to colour imaging of security document precursors with the aim of producing security documents that are difficult to falsify.
  • Articles are laser marked in order to ensure product safety and authenticity.
  • packaging material of pharmaceuticals is laser marked to enable a consumer to verify the genuineness of a product.
  • Laser marked security cards are widely used for various applications such as identification purposes (ID cards) and financial transfers (credit cards).
  • ID cards identification purposes
  • financial transfers credit cards
  • Such cards typically consist of a laminated structure consisting of various papers or plastic laminates and layers wherein some of them may carry alphanumeric data and a picture of the card holder. So called 'smart cards' can also store digital information by including an electronic chip in the card body.
  • laser marking Two techniques frequently used for preparing security documents are laser marking and laser engraving.
  • laser engraving is often incorrectly used for laser marking.
  • a colour change is observed by local heating of material in the bulk of the article, while in laser engraving material is removed by ablation.
  • laser marking employed in the manufacture of security documents consists solely of a "black” laser marking method via the carbonization of a polymer, usually-polycarbonate as disclosed in e.g. EP 2181858 A (AGFA) .
  • AGFA EP 2181858 A
  • US 4720449 discloses a thermal imaging method for producing colour images on a support carrying at least one layer of a colourless compound, such as di- or triarylmethane, by conversion of electromagnetic radiation into heat.
  • the laser beams may have different wavelengths in a range above 700nm with at least about 60 nm apart so that each imaging layer having a different infrared absorber may be exposed separately to convert a colourless triarylmethane compound into a coloured form.
  • WO 2009/106036 A discloses a method for producing a security and value document containing a polymer laminate formed from a basic polymer laminate and a polymer coating.
  • the polymer coating has a printable substrate layer that can absorb a diffusible ink printed by thermosublimation or inkjet printing.
  • the polymer laminate can be laser marked through pyrolysis (carbonization).
  • EP 537484 discloses a similar method for producing a colour picture is congruently superimposed on a gray-tone picture formed by a laser.
  • EP 2181851 A discloses that a dye image in a dye diffusion transfer image receptor layer comprising a polymeric mordant could be laser engraved, while no laser engraving appeared to be possible with dye images obtained with other imaging techniques such as thermal dye sublimation and inkjet.
  • EP 2332738 A discloses the laser perforation of a security document precursor with two or more holes near a perimeter edge surface of the precursor, wherein at least one of the holes is filled with a coloured material by e.g. inkjet ink printing, so that the coloured material is visible from a direction perpendicular on the perimeter edge surface.
  • US 2009201321 A discloses a system integrating a digital press with an ink jet device to form a security document including a xerographic portion and an invisible inkjet ink portion, in order to produce documents in a continuous inline process.
  • the present invention provides a method of producing a security document including the steps as defined in claim 1.
  • the present invention provides a method wherein two colour imaging techniques are used to compose a single colour image.
  • the use of different imaging techniques require that the images of both imaging techniques are positioned carefully in register to each other. Misalignment of the images composing the colour image is immediately visible upon inspection.
  • Another advantage is that by using different imaging techniques that colours which are difficult to reproduce by one imaging technique can be reproduced by the second imaging technique.
  • spot colours like Coca ColaTM red or IBMTM blue can be easily reproduced by UV curable inkjet printing in the second part of the colour image, while this may be a challenge in reproducing them by colour laser marking.
  • polymeric support and "foil”, as used herein, mean a self-supporting polymer-based sheet, which may be associated with one or more adhesion layers e.g. subbing layers. Supports and foils are usually manufactured through extrusion.
  • layer is considered not to be self-supporting and is manufactured by coating it on a (polymeric) support or foil.
  • leuco dye refers to compounds which can change from essentially colourless to coloured when heated.
  • PET is an abbreviation for polyethylene terephthalate.
  • PETG is an abbreviation for polyethylene terephthalate glycol, the glycol indicating glycol modifiers which are incorporated to minimize brittleness and premature aging that occur if unmodified amorphous polyethylene terephthalate (APET) would be used in the production of cards.
  • APET amorphous polyethylene terephthalate
  • PET-C is an abbreviation for crystalline PET, i.e. a biaxially stretched polyethylene terephthalate. Such a polyethylene terephthalate support has excellent properties of dimensional stability.
  • security feature corresponds with the normal definition as adhered to in the "Glossary of Security Documents - Security features and other related technical terms” as published by the Consilium of the Council of the European Union on September 12, 2012 (Version: v. 09916-08.R.2.C.1.en) on its website: http://www.consilium.europa.eu/prado/EN/glossaryPopup.html.
  • alkyl means all variants possible for each number of carbon atoms in the alkyl group i.e. methyl, ethyl, for three carbon atoms: n-propyl and isopropyl; for four carbon atoms: n-butyl, 1-isobutyl, 2-isobutyl and tertiary-butyl; for five carbon atoms: n-pentyl, 1,1-dimethyl-propyl, 2,2-dimethylpropyl and 2-methyl-butyl, etc.
  • a substituted or unsubstituted alkyl group is preferably a C 1 to C 6 -alkyl group.
  • a substituted or unsubstituted alkenyl group is preferably a C 2 to C 6 -alkenyl group.
  • a substituted or unsubstituted alkynyl group is preferably a C 2 to C 6 -alkynyl group.
  • a substituted or unsubstituted aralkyl group is preferably phenyl group or naphthyl group including one, two, three or more C 1 to C 6 -alkyl groups.
  • a substituted or unsubstituted alkaryl group is preferably a C 1 to C 6 -alkyl group including an aryl group, preferably a phenyl group or naphthyl group.
  • a substituted or unsubstituted aryl group is preferably a substituted or unsubstituted phenyl group or naphthyl group.
  • a cyclic group includes at least one ring structure and may be a monocyclic- or polycyclic group, meaning one or more rings fused together.
  • a heterocyclic group is a cyclic group that has atoms of at least two different elements as members of its ring(s).
  • the counterparts of heterocyclic groups are homocyclic groups, the ring structures of which are made of carbon only.
  • a substituted or unsubstituted heterocyclic group is preferably a five- or six-membered ring substituted by one, two, three or four heteroatoms, preferably selected from oxygen atoms, nitrogen atoms, sulphur atoms, selenium atoms or combinations thereof.
  • An alicyclic group is a non-aromatic homocyclic group wherein the ring atoms consist of carbon atoms.
  • heteroaryl group means a monocyclic- or polycyclic aromatic ring comprising carbon atoms and one or more heteroatoms in the ring structure, preferably, 1 to 4 heteroatoms, independently selected from nitrogen, oxygen, selenium and sulphur.
  • heteroaryl groups include, but are not limited to, pyridinyl, pyridazinyl, pyrimidyl, pyrazyl, triazinyl, pyrrolyl, pyrazolyl, imidazolyl, (1,2,3,)- and (1,2,4)-triazolyl, pyrazinyl, pyrimidinyl, tetrazolyl, furyl, thienyl, isoxazolyl, thiazolyl, isoxazolyl, and oxazolyl.
  • a heteroaryl group can be unsubstituted or substituted with one, two or more suitable substituents.
  • a heteroaryl group is a monocyclic ring, wherein the ring comprises 1 to 5 carbon atoms and 1 to 4 heteroatoms.
  • substituted in e.g. substituted alkyl group means that the alkyl group may be substituted by other atoms than the atoms normally present in such a group, i.e. carbon and hydrogen.
  • a substituted alkyl group may include a halogen atom or a thiol group.
  • An unsubstituted alkyl group contains only carbon and hydrogen atoms.
  • a substituted alkyl group, a substituted alkenyl group, a substituted alkynyl group, a substituted aralkyl group, a substituted alkaryl group, a substituted aryl, a substituted heteroaryl and a substituted heterocyclic group are preferably substituted by one or more substituents selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, 1-isobutyl, 2-isobutyl and tertiary-butyl, ester, amide, ether, thioether, ketone, aldehyde, sulfoxide, sulfone, sulfonate ester, sulphonamide, -Cl, -Br, -I, -OH, -SH, -CN and -NO 2 .
  • the present invention provides a method of producing a security document including the steps as defined in claim 1.
  • the second part of the colour image includes one or more chromatic colours.
  • Achromatic colours are white, black and grey, i.e. having no particular hue.
  • the first part of the colour image is made by colour laser marking two colour laser markable layers producing different colours, more preferably one colour laser markable layer producing a cyan or blue colour and the other colour laser markable layer producing a magenta or red colour, while the second part of the colour image is made by a second imaging technique providing the complementary colour yellow or green, more preferably yellow.
  • the integration of the three colours e.g. cyan, magenta and yellow, provides a full colour image of chromatic colours.
  • the one or more chromatic colours in the second part of the colour image may include a spot colour.
  • a spot colour is a custom colour, e.g. Coca ColaTM red or IBMTM blue, which may be very difficult to match using the colour laser marking imaging technique.
  • spot colours can be applied much more easily by using specific colour dyes or pigments by e.g. inkjet printing or thermosublimation printing.
  • the imaging technique used for producing the second part of the colour image is an imaging technique different from laser marking.
  • Using a laser for the second part of the colour image makes falsification much easier, since the alignment of the first and second parts of the colour image requires only a minor adaptation of laser optics.
  • the exact alignment of the first and second parts of the colour image becomes much more difficult.
  • a forger only has one opportunity to falsify a security document, thus by limiting the number of trials for aligning the first and second parts of the colour image the security of a security document is enhanced.
  • the second imaging technique is a technique allowing variable data to be applied.
  • a preferred second imaging technique allowing variable data printing is inkjet printing, more preferably UV curable inkjet printing. UV curable inkjet printing does not require the presence of a specific ink-absorbing layer on the polymeric overlay contrary to aqueous or solvent inkjet printing.
  • Other preferred second imaging techniques include xerography and particularly thermosublimation printing.
  • the ZebraTM P310i is a reliable security card printer for applying single side thermosublimation or thermotransfer prints in monochrome or four colors.
  • the security document precursors includes preferably one or two colour laser markable layers on a transparent polymeric support, more preferably on the same transparent polymeric support wherein one colour laser markable layer is present on one side of the transparent polymeric support and the other colour laser markable layer is present on the opposite side.
  • the two colour laser markable layers wherein the colour laser markable layer closest to the core support includes an infrared dye IR-1 with a maximum absorption in the infrared region at the wavelength ⁇ max (IR-1), while the other colour laser markable layer includes an infrared dye IR-2 with a maximum absorption in the infrared region at the wavelength ⁇ max (IR-2)
  • ⁇ max (IR) is the wavelength of the absorption maximum in the infrared spectrum from 700 to 1500 nm.
  • the ⁇ max (IR-1) and ⁇ max (IR-2) are preferably measured by absorption spectroscopy on a coated layer, since the value of ⁇ max may differ somewhat, although usually no more than 10 nm, on the type of solvent used in an infrared dye solution.
  • the condition is fulfilled that of 800 nm ⁇ ⁇ max (IR-2) ⁇ 1000 nm, preferably 830 nm ⁇ ⁇ max (IR-2) ⁇ 980 nm, more preferably 850 nm ⁇ ⁇ max (IR-2) ⁇ 960 nm and most preferably 900 nm ⁇ ⁇ max (IR-2) ⁇ 940 nm.
  • the infrared dye IR-1 has an absorption maximum in the infrared region ⁇ max (IR-1) ⁇ 1000 nm, more preferably ⁇ max (IR-1) ⁇ 1020 nm and most preferably ⁇ max (IR-1) ⁇ 1040 nm.
  • a security document is obtained after colour laser marking and imaging a security document precursor with the second imaging technique.
  • the security document is preferably selected from the group consisting of a passport, a personal identification card and a product identification document.
  • the security document has a format as specified by ISO 7810.
  • ISO 7810 specifies three formats for identification documents: ID-1 with the dimensions 85.60 mm x 53.98 mm, and a thickness of 0.76 mm as specified in ISO 7813, as used for bank cards, credit cards, driving licences and smart cards; ID-2 with the dimensions 105 mm x 74 mm, as used in German identity cards, with typically a thickness of 0.76 mm; and ID-3 with the dimensions 125 mm x 88 mm, as used for passports and visa's.
  • the security cards include one or more contactless integrated circuits then a larger thickness is tolerated, e.g. 3 mm according to ISO 14443-1.
  • the color laser marked article is a security document including electronic circuitry, more preferably the electronic circuitry includes a RFID chip with an antenna and/or a contact chip. Inclusion of electronic circuitry makes forgery more difficult.
  • the security document precursor may include three or more color laser markable layers for increasing the color gamut.
  • two color laser markable layers each include a different leuco dye for forming a color having an absorption maximum ⁇ max (VIS-1) and ⁇ max (VIS-2) in the visible spectrum of 400 nm to 700 nm.
  • a) and b) are fulfilled: a) 500 nm ⁇ ⁇ max (VIS-1) ⁇ 600 nm and b) 600 nm ⁇ ⁇ max (VIS-2) ⁇ 700 nm.
  • the security document precursor is also capable of producing a black color.
  • the black color is produced by using the infrared laser, preferably the infrared laser used for the color laser markable layer capable of forming a cyan or blue color image on laser marking, in different laser operation modes as disclosed by WO 2012/076493 (AGFA) .
  • AGFA WO 2012/076493
  • the advantage of using the infrared laser of the color laser markable layer forming a cyan or blue color image is that a neutral black color is formed which is more appealing than a brownish black color which would be formed on using the infrared laser for the color laser markable layer capable of forming e.g. a yellow or a magenta color image on laser marking.
  • the security document precursor includes a laser markable polymeric support or a laser markable layer for generating a black color as disclosed by EP 2463109 A (AGFA) also capable of producing different shades of black.
  • the laser markable polymeric support for generating a black color may be an additional foil or laminate, but is preferably the (opaque) core support or a transparent polymeric support of the color laser markable layer.
  • the security document precursor is preferably to a large degree symmetrical or more preferably completely symmetrical.
  • Completely symmetrical means that the same type and number of layers and foils are present on both sides of the core support.
  • the advantage thereof is that curl of the security document precursor is minimized.
  • An asymmetrical security document precursor often exhibits curl and usually requires a thermal relaxation in order to obtain e.g. a flat asymmetrical ID card.
  • the security document precursor includes one or more biaxially stretched polyester films, more preferably the outermost films or polymeric overlays of the security document precursor are biaxially stretched polyester films.
  • biaxially stretched polyester preferably biaxially stretched polyethylene terephthalate overlays
  • the one or more colour laser markable layers for producing the first part of the colour image by colour laser marking are adequately protected against falsification due to being located between two biaxially stretched polyester films.
  • the color laser markable layers preferably contain an infrared dye for the conversion of electromagnetic radiation into heat when the color laser markable layer is exposed by the infrared laser.
  • a color laser markable layer includes a leuco dye and preferably at least an infrared dye, and a polymeric binder. Color is produced in the color laser markable layer by a chemical reaction converting the substantially colorless leuco dye into a dye, wherein the chemical reaction is triggered by local heating with an infrared laser having an emission wavelength matching the absorption maximum of the infrared dye. Preferably, a laser emission wavelength is selected within a range of ⁇ 30 nm of the absorption maximum in the infrared region ⁇ max (IR) of the infrared dye.
  • the infrared dye not only delivers the heat for the color forming action, but also has the advantage that there is no or minimal absorption in the visible spectrum and thus there is no or minimal interference with the color formed by the laser markable layer. This makes a pure white background possible, which is often desired in a security document.
  • the color laser markable layers can be coated onto a support by any conventional coating technique, such as dip coating, knife coating, extrusion coating, spin coating, slide hopper coating and curtain coating.
  • the laser markable layer is coated with a slide hopper coater or a curtain coater, more preferably coated onto a transparent polymeric support including a subbing layer.
  • the dry thickness of the color laser markable layer is preferably between 4 and 40 g/m 2 , more preferably between 5 and 25 g/m 2 , and most preferably between 6 and 15 g/m 2 .
  • the color laser markable layers include different infrared dyes and color forming compounds.
  • the infrared dyes differ in wavelength of maximum absorption ⁇ max so that they can be addressed by different infrared lasers with corresponding emission wavelengths causing color formation only in the color laser markable layer of the addressed infrared dye.
  • the color laser marked article preferably contains two color laser markable layers having different infrared dyes and different leuco dyes on the same side of a core support for producing a multi-colored article.
  • the different infrared dyes have an absorption maximum in the infrared region which differs preferably by at least 60 nm, more preferably at least 80 nm and most preferably at least 100 nm.
  • infrared dyes include, but are not limited to, polymethyl indoliums, metal complex IR dyes, indocyanine green, polymethine dyes, croconium dyes, cyanine dyes, merocyanine dyes, squarylium dyes, chalcogenopyryloarylidene dyes, metal thiolate complex dyes, bis(chalcogenopyrylo)polymethine dyes, oxyindolizine dyes, bis(aminoaryl)polymethine dyes, indolizine dyes, pyrylium dyes, quinoid dyes, quinone dyes, phthalocyanine dyes, naphthalocyanine dyes, azo dyes, (metalized) azomethine dyes and combinations thereof.
  • the infrared dye is preferably present in the color laser markable layer in an amount of 0.01 to 1.0 g/m 2 , more preferably in an amount of 0.02 to 0.5 g/m 2 and most preferably in an amount of 0.05 to 0.2 g/m 2 .
  • An amount of less than 0.01 g/m 2 requires a too high laser power and an amount of more than 0.5 g/m 2 may result in background discoloration.
  • the infrared dye for the colour laser markable closest to the core support is selected from the group consisting of quinoline dyes, indolenine dyes, especially a benzo[cd]indoline dye.
  • Such infrared dyes preferably absorb above 1000 nm.
  • a particular preferred infrared dye is 5-[2,5-bis[2-[1-(1-methylbutyl)benz[cd]indol-2(1H)-ylidene]ethylidene]cyclopentylidene]-1-butyl-3-(2-methoxy-1-methylethyl)- 2,4,6(1H,3H,5H)-pyrimidinetrione (CASRN 223717-84-8), which has an absorption maximum ⁇ max of 1052 nm making it very suitable for a Nd-YAG laser having an emission wavelength of 1064 nm.
  • the infrared dye for the outermost colour laser markable layer is selected from the group consisting of quinoline dyes, indolenine dyes, especially benzo[e]indolenine dyes, and benzo[f]indolenine dyes.
  • Such infrared dyes preferably absorb below 1000 nm.
  • the color laser markable layer includes a polymeric binder.
  • a polymeric binder There is no real limitation on the type of polymeric binder for so far it allows color formation.
  • the laser markable layer preferably includes a polymeric binder comprising vinyl acetate and at least 85 wt% of vinyl chloride based on the total weight of the binder.
  • a polymeric binder comprising vinyl acetate and at least 85 wt% of vinyl chloride based on the total weight of the binder.
  • Particularly preferred polymeric binders are disclosed in EP 2463110 A (AGFA).
  • the polymeric binder in the laser markable layer is preferably a copolymer including at least 85 wt% of a vinyl chloride and 1 wt% to 15 wt% of vinyl acetate, more preferably a copolymer including at least 90 wt% of a vinyl chloride and 1 wt% to 10 wt% of vinyl acetate with all wt% based on the total weight of the binder.
  • the polymeric binder includes at least 4 wt% of vinyl acetate based on the total weight of the binder.
  • the advantage of having at least 4 wt% of vinyl acetate in the polymeric binder is that the solubility of the polymeric binder is drastically improved in preferred coating solvents, such as methyl ethyl ketone.
  • the polymeric binder consists of vinyl chloride and vinyl acetate.
  • the polymeric binder is preferably selected from polycarbonate (PC), polybutylene terephthalate (PBT), polyvinyl chloride (PVC), polystyrene (PS) and copolymers thereof, such as e.g. aromatic polyester-carbonate, styrene acrylonitrile and acrylonitrile butadiene styrene (ABS).
  • PC polycarbonate
  • PBT polybutylene terephthalate
  • PVC polyvinyl chloride
  • PS polystyrene
  • ABS acrylonitrile butadiene styrene
  • the polymeric binder is preferably present in the color laser markable layer in an amount of 3 to 30 g/m 2 , more preferably in an amount of 5 to 20 g/m 2 .
  • a leuco dye is a compound which changes from essentially colorless to colored when heated, e.g. by laser marking.
  • a number of classes of leuco dyes are preferred for the laser markable layer of the present invention, for example: azines such as oxazines, diazines and thiazines; triarylmethanes such as fluoresceins, rhodamines and rhodols; ketazines; barbituric acid leuco dyes and thiobarbituric acid leuco dyes.
  • the leuco dye is preferably present in the color laser markable layer in an amount of 0.5 to 5.0 g/m 2 , more preferably in an amount of 1.0 to 3.0 g/m 2 .
  • reaction mechanisms and leuco dyes are suitable to form a colored dye.
  • the reaction mechanism can be represented by: Leuco dye-FG ⁇ Dye wherein FG represents a fragmenting group.
  • a preferred leuco dye (CASRN104434-37-9) is shown in EP 174054 A (POLAROID) which discloses a thermal imaging method for forming color images by the irreversible unimolecular fragmentation of one or more thermally unstable carbamate moieties of an organic compound to give a visually discernible color shift from colorless to colored.
  • the fragmentation of a leuco dye may be a two-step reaction mechanism represented by: Leuco-dye-FG ⁇ [Leuco-dye] ⁇ Colored Dye wherein FG represents a fragmenting group.
  • the fragmentation of a leuco dye may be catalyzed or amplified by acids and acid generating agents.
  • the leuco dyes G-(1) to G-(17) disclosed by US 6100009 (FUJI) are catalyzed or amplified by polymeric acid generating agents based on A-(1) to A-(52), which are also suitable as acid generating agents in the present invention.
  • the reaction mechanism can be represented by: Leuco-dye + H-donor-FG ⁇ Leuco-dye + H-donor ⁇ Colored Dye wherein FG represents a fragmenting group.
  • a preferred H-donor-FG compound includes an ester group as part of its chemical structure (the rest of the compound is represented by the group T) which by laser heating forms a carboxylic acid group:
  • a more preferred H-donor-precursor includes a carbonate group, e.g. a tBOC group, as part of its chemical structure (the rest of the compound is represented by the group T) which by laser heating forms a phenol group: Preferred carbonate groups are given on page 8 of EP 605149 A (JUJO PAPER).
  • the H-donor-FG compound contains 2 carbonate groups.
  • H-donor-FG compound The most preferred H-donor-FG compound is: HDP.
  • the synthesis of compound HDP (CASRN 129104-70-7) is given on page 31 of EP 605149 A (JUJO PAPER) for the compound (19).
  • the fragmentation of the H-donor-FG compound above also leads to the formation of a compound having a melting temperature lower than room temperature (20°C).
  • the formation of such a compound can be used as an additional security feature.
  • the compound having a melting temperature lower than room temperature may disturb a second laser marking (falsification of a security document) by the formation of visible blisters.
  • the reaction mechanism can be represented by: Leuco-dye + H-donor-RG ⁇ Leuco-dye + H-donor ⁇ Colored Dye wherein RG represents a rearranging group.
  • a preferred H-donor-RG compound is capable of forming a compound having an allyl substituted phenol group as part of its chemical structure (the rest of the compound is represented by the group T) by laser heating:
  • Preferred H-donor-RG compounds include 4,4'-diallyloxy diphenylsulfone whereof the synthesis is disclosed by EP 1452334 A (RICOH).
  • the color formation according to the mechanisms 2 and 3 above are two-component reactions involving a leuco dye and a hydrogen donor-precursor, i.e. a 'H-donor-FG compound' or 'H-donor-RG compound', while the first reaction mechanism is an one-component reaction.
  • the advantage of using a two-component reaction for the color formation is that the stability, especially the shelf-life stability, can be enhanced.
  • the probability of undesired color formation due to environment heating is decreased by going from a single step reaction to a two step reaction involving the formation of the H-donor followed by a reaction of the formed H-donor with the leuco dye.
  • the preferred color formation mechanism is the protonation of a leuco dye after fragmentation of the H-donor since it includes both advantages of the blister formation security feature and the enhanced shelf-life stability.
  • a combination is used of 4,4'-Bis(tert-butoxycarbonyloxy)diphenylsulfone (CASRN 129104-70-7) as the H-donor-FG compound with the leuco dye crystal violet lactone (CASRN 1552-42-7) for producing a blue color.
  • the cyan color forming compound has a structure according to Formula CCFC:
  • the magenta color forming compound has a structure according to Formula MCFC: wherein R, R', R" are independently selected from the group consisting of hydrogen, a linear alkyl group, a branched alkyl group, an aryl and aralkyl group; or R' and R" are linked to form a heterocyclic ring.
  • the magenta color forming compound has a structure according to Formula MCFC, the R, R', R" may independently represent a linear alkyl group, a branched alkyl group, an aryl or an aralkyl group substituted by at least one functional group containing an oxygen atom, a sulphur atom or a nitrogen atom.
  • magenta color forming compounds include the compounds M-1 to M-6 of Table 1.
  • magenta color forming compound has a structure according to Formula MCFC2:
  • the red color forming compound has a structure according to Formula RCFC:
  • the yellow color forming compound has a structure according to Formula YCFC: wherein R, R' are independently selected from a group consisting of a linear alkyl group, a branched alkyl group, an aryl and aralkyl group.
  • the yellow color forming compound has a structure according to Formula YCFC, wherein R and R' independently represent a linear alkyl group, a branched alkyl group, an aryl or an aralkyl group substituted by at least one functional group containing an oxygen atom, a sulphur atom or a nitrogen atom.
  • a particularly preferred yellow color forming compound is the compound according to Formula YCFC wherein both R and R' are methyl.
  • the leuco dye is preferably present in the laser markable layer in an amount of 0.01 to 2.0 g/m 2 , more preferably in an amount of 0.1 to 1.0 g/m 2 .
  • the fragmentation of a leuco dye in a color laser markable layer according to the present invention may be catalyzed or amplified by acids and acid generating agents.
  • Suitable thermal acid generating agents may be the polymeric acid generating agents based on the ethylenically unsaturated polymerizable compounds A-(1) to A-(52) disclosed by US 6100009 (FUJI).
  • Suitable non-polymeric acid generating agents are, for example, the compounds E-(1) to E-(90) disclosed by US 6100009 (FUJI) lacking the ethylenically unsaturated polymerizable group.
  • the thermal acid generating agent is preferably present in the amount of 1 to 20 wt%, more preferably 5 to 15 wt% based on the total dry weight of the laser markable layer.
  • the color laser markable layer preferably the outermost color laser markable layer may include at least one stabilizer, preferably a UV stabilizer.
  • Suitable commercially available stabilizers include 6-O-paimitoyl-L-ascorbic acid (CASRN137-66-6) from BASF; TOCOBLENDTM L70 IP (CASRN1406-66-2) from VITABLEND NEDERLAND BV; gallic acid ethyl ester (CASRN831-61-8) from ACROS; 3,6-dithia-1,8-octanediol (CASRN5244-34-8) from ALDRICH; IrganoxTM 1035 (CASRN41484-35-9) from CIBA; ADK STAB PEP36 (CASRN80693-00-1) from PALMAROLE; calcium stearate; TinuvinTM 292 (CASRN 41556-26-7), TinuvinTM 400 (CASRN 192662-79-6), TinuvinTM P (CASRN2440-22-4), TinuvinTM 1130 (CASRN 104810-48-2) and TinuvinTM 123 (CASRN 122586-52-1) from BASF; Irg
  • Particularly preferred stabilizers include a phenol stabilizer sterically hindered by a ring containing three nitrogen atoms represented by Formula (Stabi-I): or Formula (Stabi-II): wherein R1 to R7 is each independently selected from the group consisting of hydrogen, an alkyl group containing 1 to 12 carbon atoms and an alkoxy group containing 1 to 12 carbon atoms; R8 represents hydrogen or a halogen atom; R9 and R10 is each independently selected from the group consisting of hydrogen, an alkyl group containing 1 to 6 carbon atoms and an aryl group containing 1 to 12 carbon atoms; and R11 to R14 is each independently selected from the group consisting of an alkyl group containing 1 to 6 carbon atoms.
  • R1 to R7 is each independently selected from the group consisting of hydrogen, an alkyl group containing 1 to 8 carbon atoms, more preferably an alkyl group containing 1 to 6 carbon atoms, and an alkoxy group containing 1 to 8 carbon atoms, more preferably an alkoxy group containing 1 to 6 carbon atoms.
  • R9 and R10 is each independently selected from the group consisting of hydrogen, an alkyl group containing 1 to 8 carbon atoms, more preferably an alkyl group containing 1 to 6 carbon atoms, and an aryl group containing 1 to 12 carbon atoms, more preferably an alkyl group containing 1 to 10 carbon atoms.
  • R5 and R6 both represent hydrogen.
  • R11 to R14 all represent methyl and preferably R9 and/or R10 represent methyl or phenyl.
  • R8 represents a chlorine atom.
  • R9 and/or R10 represent a phenyl substituted by an alkyl group or a napthyl group.
  • the color laser markable laminate includes a phenol stabilizer sterically hindered by a ring containing three nitrogen atoms and is selected from the group consisting of IS-1 to IS-4 shown here below.
  • the stabilizer is preferably present in a colour laser markable layer, but may also be present in another layer, for example, an outer layer.
  • An outer layer is a layer more distant from the (opaque) core support than the laser markable layers on the same side of the opaque core support.
  • one or more organic solvents may be used.
  • the use of an organic solvent facilitates the dissolution of the polymeric binder and specific ingredients such as the infrared dye.
  • a preferred organic solvent is methylethylketone (MEK) because it combines a high solubilizing power for a wide range of ingredients and it provides, on coating the color laser markable layer, a good compromise between the fast drying of the layer and the danger of fire or explosion thereby allowing high coating speeds.
  • MEK methylethylketone
  • the color laser markable layers are coated on a transparent polymeric support. If a polymeric foil, e.g. the polymeric overlay, is located between the color laser markable layer and the infrared laser for laser marking it, then the polymeric foil is transparent for the light of the infrared lasers in at least that area used for laser marking.
  • the polymeric foils used a support or overlay are also transparent for visual light so that the color formed in the color laser markable layers can be well observed.
  • the polymeric support for a laser markable layer is preferably a transparent (bi)axially stretched polymeric support, more preferably a transparent (bi)axially stretched polyester support, and most preferably a transparent (bi)axially stretched polyethylene terephthalate support.
  • the transparent polymeric overlay is preferably selected from the group consisting of an axially stretched polyethylene terephthalate support, a biaxially stretched polyethylene terephthalate support, an axially stretched polyethylene naphthalate support and a biaxially stretched polyethylene naphthalate support.
  • both the transparent polymeric support for the colour laser markable layers and the outermost polymeric foil are a biaxially stretched polyethylene terephthalate support.
  • the color laser markable layer may be coated directly on the polymeric support or on a subbing layer provided on the polymeric support for improving adhesion of the laser markable layer, thereby making falsification through delamination more difficult.
  • Suitable polymeric supports and overlays include cellulose acetate propionate or cellulose acetate butyrate, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyamides, polycarbonates, polyimides, polyolefins, polyvinylchlorides, polyvinylacetals, polyethers and polysulphonamides.
  • the transparent polymeric overlay(s) is a biaxially stretched polyethylene terephthalate foil (PET-C foil) which is very durable and resistant to mechanical influences (flexion, torsion, scratches), chemical substances, moisture and temperature ranges.
  • PET-C foil polyethylene terephthalate foil
  • This is especially useful for security documents such as identification cards and credit cards for which the average daily usage has augmented substantially from less than 1 time per week to 4 times per day.
  • the card body has to withstand not only this increased usage, but also the associated storage conditions. Cards are no longer safely tucked away in cabinets at home or seldom-opened wallets, but are now loosely put away in pockets, purses, sport bags etc. - ready for immediate use.
  • PVC polyvinylchloride
  • PC polycarbonate
  • the transparent polymeric support and overlays are preferably a single component extrudate, but may also be co-extrudate.
  • Polyester supports and especially polyethylene terephthalate supports are preferred because of their excellent properties of dimensional stability.
  • a subbing layer is preferably employed to improve the bonding of layers, foils and/or laminates to the support.
  • PET-C foils and supports are well-known to a person skilled in the art of preparing suitable supports for silver halide photographic films.
  • GB 811066 ICI
  • ICI teaches a process to produce biaxially oriented polyethylene terephthalate foils and supports.
  • the polyethylene terephthalate is preferably biaxially stretched with a stretching factor of at least 2.0, more preferably at least 3.0 and most preferably a stretching factor of about 3.5.
  • the temperature used during stretching is preferably about 160°C.
  • the core support may be a transparent or translucent support, but is preferably an opaque core support, more preferably having a white or a pastel color, most preferably a white color, for allowing easily readable information and viewable color images.
  • an opaque white core support is also that a color image is more appealing since colors usually are more vibrant with a white background.
  • Preferred opaque white core supports include resin coated paper supports, such as polyethylene coated paper and polypropylene coated paper, and synthetic paper supports such as SynapsTM synthetic paper of Agfa-Gevaert NV.
  • useful high-quality polymeric supports for the present invention include opaque white polyesters and extrusion blends of polyethylene terephthalate and polypropylene. Also TeslinTM may be used as support.
  • a white opacifying layer can be coated onto a transparent polymeric support, such as those disclosed above.
  • the opacifying layer preferably contains a white pigment with a refractive index greater than 1.60, preferably greater than 2.00, and most preferably greater than 2.60.
  • the white pigments may be employed singly or in combination. Suitable white pigments include C.I. Pigment White 1, 3, 4, 5, 6, 7, 10, 11, 12, 14, 17, 18, 19, 21, 24, 25, 27, 28 and 32.
  • Preferably titanium dioxide is used as pigment with a refractive index greater than 1.60. Titanium oxide occurs in the crystalline forms of anatase type, rutile type and brookite type. In the present invention the rutile type is preferred because it has a very high refractive index, exhibiting a high covering power.
  • the transparent polymeric supports , (opaque) core supports and polymeric overlays may be provided with one or more subbing layers. This has the advantage that the adhesion between a layer and the support is improved.
  • subbing layers for this purpose are well known in the photographic art and include, for example, polymers of vinylidene chloride such as vinylidene chloride/acrylonitrile/acrylic acid terpolymers or vinylidene chloride/methyl acrylate/itaconic acid terpolymers.
  • subbing layers are well-known in the art of manufacturing polyester supports for silver halide photographic films.
  • preparation of such subbing layers is disclosed in US 3649336 (AGFA), GB 1441591 (AGFA) and EP 2374602 A (AGFA).
  • Suitable vinylidene chloride copolymers include: the copolymer of vinylidene chloride, N-tert.-butylacrylamide, n-butyl acrylate, and N-vinyl pyrrolidone (e.g.70:23:3:4), the copolymer of vinylidene chloride, N-tert.-butylacrylamide, n-butyl acrylate, and itaconic acid (e.g. 70:21:5:2), the copolymer of vinylidene chloride, N-tert.-butylacrylamide, and itaconic acid (e.g.
  • the subbing layer has a dry thickness of no more than 2 ⁇ m or preferably no more than 200 mg/m 2 .
  • the security document precursor may include additional layers and/or foils.
  • Such an additional layer can, for example, be an adhesive layer, a layer including UV stabilizers for protecting color images against bleaching or a layer containing an infrared antihalation dye for improving the sharpness of a colour laser marked image.
  • An adhesive foil may be interlaminated in order to make falsification by delamination more difficult.
  • an adhesive layer may be applied as a layer on top of e.g. a color laser markable layer.
  • the use of an adhesive foil instead of an adhesive layer has the advantage is that an adhesive foil does not extract some of the more soluble ingredients in the laser markable layer like an adhesive layer can do upon coating and drying. Variation in the concentration of the soluble ingredients leads to inconsistencies in the color production during laser marking.
  • Suitable adhesive foils include pressure-sensitive and thermo-sensitive adhesive foils.
  • a range of so-called hot melt foils are well-known to one skilled in the art of security films and security documents.
  • a preferred hot melt foil in the present invention is a polyurethane foil.
  • Suitable commercially available hot melt foils include PlatilonTM ID5051, a 35 ⁇ m polyurethane foil available from Epurex.
  • Other suitable hot melt foils are ScapaTM Thermofoil G160 and G161.
  • PETG Another preferred adhesive foil is PETG. Contrary to biaxially oriented polyethylene terephthalate, a non-oriented PETG foil softens rapidly near the glass transition temperature and can thus also be used for adhesive purposes.
  • the adhesive foil is made of a non-chlorinated polymer.
  • Adhesive foils based on a chlorinated polymer may cause background discoloration.
  • Preferred adhesive foils include polyester, polyester urethane, polyether urethane or polyolefin hot melt foils.
  • the adhesive is applied as an adhesive layer on a color laser markable layer or on polymeric support, this may be performed by methods such as solvent coating, casting, or hot melt extrusion.
  • thermo adhesive compositions are disclosed in WO 2009/063058 (AGFA).
  • Preferred thermo adhesive layers are based on a hydroxyl-functional, partially-hydrolyzed vinyl chloride/vinyl acetate resin such as, for example, available under the trade name of UCAR(TM) VAGD Solution vinyl resin from Dow Chemical Company.
  • the adhesive foil preferably has a thickness smaller than 65 ⁇ m, more preferably smaller than 50 ⁇ m and most preferably smaller than 40 ⁇ m.
  • the security document may include one or more additional security features to increase the difficulty for falsifying the document.
  • One solution consists in superimposing lines or guilloches on an identification picture such as a photograph.
  • Other solutions consist in adding security elements such as information printed with ink that reacts to ultraviolet radiation, micro-letters concealed in an image or text etc.
  • Suitable other security features such as anti-copy patterns; guilloches; line patterns; endless text; miniprint; microprint; nanoprint; rainbow coloring; barcodes including 2D-barcodes; colored fibres; fluorescent fibres and planchettes; fluorescent pigments including fluorescent hi-lites; OVD (Optically Variable Device) and DOVID (Diffractive Optically Variable Image Device) such as holograms, 2D and 3D holograms, holograms with kinematic effects like KinegramsTM; overprint; relief embossing; perforations; metallic pigments; magnetic material; metameric colors; microchips such as RFID chips; images made with OVI (Optically Variable Ink) such as iridescent and photochromic ink; images made with thermochromic ink; phosphorescent pigments and dyes; watermarks including single tone, duotone and multitone watermarks; ghost images and security threads.
  • OVI Optically Variable Ink
  • the present invention further provides an apparatus for producing a security document including a first device and a second device as defined in claim 12.
  • the first device for producing a first part of a colour image by colour laser marking preferably includes two infrared lasers, one infrared laser having an emission wavelength between 1000 nm and 1200 nm and the other infrared laser having an emission wavelength between 800 nm and 1000 nm.
  • the second device for producing a second part of the colour image is a thermosublimation printer.
  • the second device for producing a second part of the colour image is an inkjet printer, more preferably a UV curable inkjet printer.
  • the first and second devices are integrated into the apparatus for producing a security document in such a manner that the first and second parts of a colour image produced by the devices are accurately aligned.
  • the aligning of the first and second devices along the transport belongs to the normal technical skills of a person skilled in the art of constructing imaging apparatuses, and can even be accomplished by trial and error methods without calculations by the skilled person.
  • the first and second devices are integrated in such a manner that a security document is first colour laser marked by the first device before being imaged by the second device.
  • the advantage is that possible absorption in the infrared region of colour produced by the second device cannot interfere with the infrared absorption by the colour laser markable layers.
  • CCE is Bayhydrol H 2558, a anionic polyester urethane (37.3%) from BAYER. Resorcinol from Sumitomo Chemicals. Par is a dimethyltrimethylolamine formaldehyde resin from Cytec industries. PAR-sol is a 40wt% aqueous solution of Par. PEA is TospearlTM 120 from Momentive Performance materials. PEA-sol is a 10wt% (50/50) aqueous/ethanol dispersion of PEA. DowfaxTM 2A1 from Pilot Chemicals C is a Alkyldiphenyloxide disulfonate (4.5%wt%). DOW-sol is a 2.5wt% solution of DowfaxTM 2A1 in isopropanol. SurfynolTM 420 from Air Products is a non ionic surfactant. Surfynsol is a 2.5wt% solution of SurfynolTM 420 in isopropanol.
  • MEK is an abbreviation used for methylethylketone.
  • SolvinTM 557RB is a vinylchloride-vinylacetate copolymer with 11 % vinyl acetate, provided by SOLVAY.
  • SolvinSol is a 12.5 wt% solution of SolvinTM 557RB in MEK.
  • HDP is the hydrogen donor-precursor CASRN 129104-70-7 prepared according to the synthesis given on page 31 of EP 605149 A (JUJO PAPER) for the compound (19).
  • BLD is crystal violet lactone (CASRN 1552-42-7) available from YAMADA CHEMICAL CO.
  • MLD is a bisindolylphthalide leuco dye (CASRN50292-95-0) available as PergascriptTM Red I6B from BASF.
  • IR-2sol is a 0.15 wt% solution in MEK of the infrared dye CASRN 223717-84-8 having an absorption maximum at 1052 nm and was prepared in the same manner as disclosed by paragraphs [0150] to [0159] of EP 2463109 A (AGFA).
  • IR-3 was synthesized as follows via the intermediates IR-INT1 and IR-INT2:
  • intermediate INT-7 was performed as follows. 10 mol of dimethylformamide and 3 mol phosphoryl chloride were heated up to 65°C. Then 1 mol of cyclopentanon was dropped to this mixture. After one hour of stirring at 60°C, the reaction mixture was poured into 2 I water containing 7 mol sodium acetate. INT-7 was filtered and dried. The yield was 60%.
  • the synthesis of the intermediate INT-B was performed as follows. 1 mol of 1,1,2-trimethyl-1H-benzo[e]indole (CASRN41532-84-7) and 2 mol of n-butyl bromide were stirred in 0.5 I sulfolane for four hours at 100°C.
  • INT-B was filtered, washed with ethyl acetate and dried. The yield was 61%.
  • INT-7 4.75 g; 30 mmol
  • INT-B 20.8 g; 60 mmol
  • ethanol 100 mL
  • triethylamine 12.1 g; 120 mmol
  • acetic acid anhydride 12.2 g; 120 mmol
  • the reaction mixture was cooled to 20 °C and isopropanol (100 mL) was added.
  • the precipitated IR-absorber was isolated by filtration, washed with EtOAc (20 mL) and dried in vacuo. Yield (crude) of IR-INT1 was 16 g (73%).
  • the absorption maximum of IR-INT1 measured in methanol was 844 nm.
  • IR-INT1 16 g; 22 mmol
  • acetonitrile 200 mL
  • potassium nonafluorobutanesulfonate CASRN29420-49-3 from TCI Europe N.V.; 8.1 g; 24 mmol
  • this mixture was heated at 70 °C for 15 minutes.
  • water 100 mL
  • the precipitated IR-absorber was isolated by filtration, washed consecutively with a mixture of acetonitrile / water 2/1 (20 mL), methyl tert. butylether (MTBE) (20 mL) and dried in vacuo.
  • the yield of IR-INT2 was 14 g (67%).
  • the absorption maximum of IR-INT2 measured in methanol was 844 nm.
  • IR-INT2 (1.65 g; 1,73 mmol) in methanol (15 mL) under nitrogen at room temperature is added sodium benzenesulfinate (CASRN873-55-2 from Aldrich; 0.297 g; 1,81 mmol). After stirring for 2 hours the precipitated IR-absorber was isolated by filtration, washed with MTBE (5 mL) and dried in vacuo. The yield of IR-3 was 1.2 g (65%). The absorption maximum measured in methanol was 910 nm. The absorption maximum of IR-3 measured in CH 2 Cl 2 including 6.5 x 10 -6 wt% of methanesulfonic acid was 923 nm.
  • IR-3sol is a 0.15 wt% solution in MEK of the infrared dye IR-3.
  • CORE is a 500 ⁇ m opaque PETG core available as PET-G 500 type 9311 from WOLFEN.
  • the optical density was measured in reflection using a spectrodensitometer Type Macbeth TR924 using a visual filter.
  • This example illustrates the production of a security document in accordance with the invention.
  • the security document is produced in two steps by first colour laser marking a security document precursor and then in a second step applying a complementary colour on the polymeric overlay by thermosublimation.
  • a coating composition SUB-1 was prepared by mixing the components according to Table 2 using a dissolver. Table 2 wt% of components SUB-1 deionized water 76.66 CCE 18.45 Resorcinol 0.98 PAR-sol 0.57 PEA-sol 0.68 DOW-sol 1.33 Surfynsol 1.33
  • a 1100 ⁇ m thick polyethylene terephthalate sheet was first longitudinally stretched and then coated on both sides with the coating composition SUB-1 to a wet thickness of 10 ⁇ m. After drying, the longitudinally stretched and coated polyethylene terephthalate sheet was transversally stretched to produce a double side subbed 63 ⁇ m thick sheet PET1, which was transparent and glossy.
  • the coating compositions BCOL1 and MCOL1 were prepared in the same way by mixing the components according to Table 3 using a dissolver.
  • Table 3 wt% of components BCOL1 MCOL1 MEK 16.87 0.07 SolvinSol 60.00 53.65 IR-2sol 20.00 --- IR-3sol --- 40.70 HDP 1.63 2.13 BLD 1.50 --- MLD --- 3.45
  • the coating composition BCOL1 was coated with an Elcometer Bird Film Applicator (from ELCOMETER INSTRUMENTS) on one side of the PET-C support PET1 at a coating thickness of 100 ⁇ m and subsequently dried for 2 minutes at 20°C on the film applicator and for a further 15 minutes in an oven at 75°C.
  • an Elcometer Bird Film Applicator from ELCOMETER INSTRUMENTS
  • the coating composition MCOL1 was coated with an Elcometer Bird Film Applicator (from ELCOMETER INSTRUMENTS) on the opposite side of the PET-C support PET1 coated with BCOL1 at a coating thickness of 100 ⁇ m and subsequently dried for 2 minutes at 20°C on the film applicator and for a further 15 minutes in an oven at 75°C to deliver the colour laser markable security laminate IL1.
  • an Elcometer Bird Film Applicator from ELCOMETER INSTRUMENTS
  • An assembly was made of, in order, a white opaque core support CORE, the colour laser markable security laminate IL1 and a polymeric overlay PET1, wherein the side coated with BCOL1of the colour laser markable security laminate IL1 faces the white opaque core support CORE.
  • the security document precursor SDP-1 was then first colour laser marked with a cyan and magenta part of a colour image by two infrared lasers of different emission wavelength , and then a yellow part of the colour image was printed in register with the cyan and magenta part of the colour image using thermosublimation printer.
  • a first optically pumped semiconductor laser emitting at 920 nm (Genesis MX 920-4000 MTM from COHERENT) was used for producing a magenta coloured wedge of ten 1 cm x 1 cm square boxes of increasing optical density up to a maximum optical density of 1.29 in the colour laser markable layer coated from MCOL1.
  • the laser was used at a power level of 4.9 W, a dither of 0.025, a scan speed of 100 mm/s and at a pulse repetition rate of 1.2 kHz.
  • a second optically pumped semiconductor laser emitting at 1064 nm (Genesis MX 1064-10000 MTM from COHERENT) was used for producing a blue coloured wedge of ten 1cm x 1cm square boxes of increasing optical density up to a maximum optical density of 1.15 in the colour laser markable layer coated from BCOL1.
  • the laser was used at a power level of 5.5, a dither of 0.025, a scan speed of 100 mm/s and at a pulse repetition rate of 1.2 kHz.

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Claims (15)

  1. Procédé pour la production d'un document de sécurité, comprenant les étapes consistant à :
    a) produire une première partie d'une image couleur par marquage au laser couleur d'un précurseur de document de sécurité en utilisant des colorants leuco, et
    b) produire une deuxième partie de l'image couleur en utilisant une deuxième technique d'imagerie qui est différente du marquage au laser et qui n'utilise pas de laser,
    caractérisé en ce que les première et deuxième parties de l'image couleur sont positionnées en registre l'une par rapport à l'autre.
  2. Procédé selon la revendication 1, caractérisé en ce que la deuxième partie de l'image couleur comprend une ou plusieurs couleurs chromatiques.
  3. Procédé selon la revendication 2, caractérisé en ce que lesdites une ou plusieurs couleurs chromatiques comprennent une couleur d'accompagnement.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que la deuxième technique d'imagerie est l'impression par thermosublimation.
  5. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que la deuxième technique d'imagerie est l'impression à jet d'encre.
  6. Procédé selon la revendication 5, caractérisé en ce que l'impression à jet d'encre est l'impression à jet d'encre utilisant des encres pour impression à jet d'encre durcissable par rayonnement ultraviolet.
  7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que la première partie de l'image couleur est formée par deux couches marquables au laser couleur.
  8. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que le précurseur de document de sécurité comprend un ou plusieurs films de polyester biaxialement étirés.
  9. Procédé selon la revendication 8, caractérisé en ce que les films extérieurs du précurseur de document de sécurité sont des films de polyester biaxialement étirés.
  10. Procédé selon la revendication 8 ou 9, caractérisé en ce qu'au moins une desdites une ou plusieurs couches marquables au laser couleur utilisées pour produire la première partie de l'image couleur par marquage au laser couleur est située entre deux films de polyester biaxialement étirés.
  11. Procédé selon l'une quelconque des revendications 1 à 10, caractérisé en ce que la deuxième technique d'imagerie produit une couleur jaune.
  12. Appareil pour la production d'un document de sécurité, comprenant un premier dispositif servant à produire une première partie d'une image couleur par marquage au laser couleur d'un précurseur de document de sécurité en utilisant des colorants leuco et un deuxième dispositif servant à produire une deuxième partie de l'image couleur, caractérisé en ce que les première et deuxième parties de l'image couleur sont positionnées en registre l'une par rapport à l'autre et que le deuxième dispositif ne comprend pas de lasers.
  13. L'appareil selon la revendication 12, caractérisé en ce que le deuxième dispositif est une imprimante à thermosublimation.
  14. L'appareil selon la revendication 12, caractérisé en ce que le deuxième dispositif est une imprimante à jet d'encre.
  15. L'appareil selon la revendication 14, caractérisé en ce que l'imprimante à jet d'encre est une imprimante à jet d'encre utilisant des encres pour impression à jet d'encre durcissable par rayonnement ultraviolet.
EP12192155.5A 2012-11-12 2012-11-12 Imagerie en couleur de précurseurs de documents de sécurité Not-in-force EP2730425B1 (fr)

Priority Applications (4)

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EP12192155.5A EP2730425B1 (fr) 2012-11-12 2012-11-12 Imagerie en couleur de précurseurs de documents de sécurité
PCT/EP2013/073014 WO2014072275A1 (fr) 2012-11-12 2013-11-05 Imagerie en couleurs de précurseurs de document de sécurité
US14/441,603 US10245866B2 (en) 2012-11-12 2013-11-05 Colour imaging of security document precursors
CN201380059110.9A CN104768767B (zh) 2012-11-12 2013-11-05 安全文件前体的彩色成像

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CN104768767B (zh) 2017-08-29
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CN104768767A (zh) 2015-07-08

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