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WO2009077536A2 - Procédé de préparation de documents de sécurité inviolables et document de sécurité inviolable - Google Patents

Procédé de préparation de documents de sécurité inviolables et document de sécurité inviolable Download PDF

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Publication number
WO2009077536A2
WO2009077536A2 PCT/EP2008/067649 EP2008067649W WO2009077536A2 WO 2009077536 A2 WO2009077536 A2 WO 2009077536A2 EP 2008067649 W EP2008067649 W EP 2008067649W WO 2009077536 A2 WO2009077536 A2 WO 2009077536A2
Authority
WO
WIPO (PCT)
Prior art keywords
crosslinkable composition
abhesive
copolymers
meth
vinyl ester
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.)
Ceased
Application number
PCT/EP2008/067649
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English (en)
Other versions
WO2009077536A3 (fr
Inventor
Eddie Daems
Julien Gillot
Luc Leenders
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
Original Assignee
Agfa Gevaert NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Agfa Gevaert NV filed Critical Agfa Gevaert NV
Publication of WO2009077536A2 publication Critical patent/WO2009077536A2/fr
Publication of WO2009077536A3 publication Critical patent/WO2009077536A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/30—Identification or security features, e.g. for preventing forgery
    • B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
    • B42D25/378—Special inks
    • 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
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0011—Pre-treatment or treatment during printing of the recording material, e.g. heating, irradiating
    • 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
    • B41M5/0029—Formation of a transparent pattern using a liquid marking fluid
    • 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
    • B42D25/21—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof characterised by a particular use or purpose for multiple purposes
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/30—Identification or security features, e.g. for preventing forgery
    • B42D25/309—Photographs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/30—Identification or security features, e.g. for preventing forgery
    • B42D25/328—Diffraction gratings; Holograms
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B41M7/0081—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using electromagnetic radiation or waves, e.g. ultraviolet radiation, electron beams
    • B42D2033/32—
    • 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
    • B42D25/40—Manufacture
    • B42D25/45—Associating two or more layers

Definitions

  • the invention relates to a method for preparing security documents secured against alteration and tempering.
  • Value documents according to the present invention are bank notes, cheque forms, shares, certificates, postage stamps, air tickets, labels for product protection, identity documents, passports and the like.
  • Bank notes are normally manufactured from so-called security papers consisting of cotton fibers and have special security features, such as a security thread at least partly incorporated into the paper, and a watermark.
  • the period of circulation of a bank note depends on how much it is stressed. Certain denominations are preferably used in financial transactions and thus have a shorter period of circulation due to the greater wear and tear due to environmental influences.
  • the main cause for a restricted period of circulation of bank notes is seen to be early soiling. Since bank note paper is very porous, it has a large surface area or high surface roughness. Even if the resulting projections and cavities are in orders of magnitude which cannot be resolved by the human eye, they offer ideal conditions for dirt deposits in comparison with a smooth surface.
  • WO 98/15418 discloses a security document, such as a banknote, comprising a single flexible sheet formed from a substrate bearing indicia, said sheet having a first portion of transparent plastics material, and a security device provided at a second position of the sheet spaced laterally from the transparent first portion, wherein the transparent first portion includes self-verification means to verify or inspect the security device when the sheet is bent, folded or twisted to bring the first and second portions into register with one another.
  • the usual and time-tested security elements such as portrait watermark and windowed security thread must be forgone, as well as the special properties such as sound and feel of bank note paper.
  • WO 96/28610 discloses a method for producing security paper which includes a security feature, which method comprises forming paper in a wet state, which paper incorporates one or more security features, applying to the paper a sizing agent, thereafter applying to one or both sides of the sized paper a coating comprising an unpigmented polyurethane which may optionally comprise a functional additive provided that the presence of the functional additive does not increase the opacity of the paper by more than 1%, thereafter drying the paper, said coating composition being such as to provide a film, when cast on a glass surface, having a Konig hardness of from 15 to 130 seconds, and also passing the water resistance test as defined by the following steps: a) the total formulation to be used in the coating is cast on a glass plate so as to produce a film with a dry weight of 80g/m 2 ; b) the film is initially dried at 23 0 C.
  • the film is weighed before being wetted and tested for tensile strength, Young's Modulus and is visually checked for any change in its transparency; d) a sample of the film is boiled in water containing 10g/L Na 2 CO 3 for 30 mins; e) the film is then rinsed in cold water and the steps b) to c) are then repeated; wherein when the film is dried and re-weighed the film meets the following criteria: i) the wet tensile strength and Young's Modulus of the boiled film is not less than 90% of the initial film wet tensile strength and Young's Modulus; ii) the film shows no perceptible loss of transparency, and iii) the dried weight of the film is not less than 98% of the original weight.
  • Multilayer substrates comprising a film core coated on both sides with paper plies have also been proposed.
  • the strength of this laminate is increased in comparison with a pure paper substrate, but the soiling problem with the exterior paper layers is not solved. So as not to excessively increase the total thickness of such bank notes, the paper plies must moreover be designed very thin, so that the usual security features such as security thread or watermark can no longer be optimally incorporated.
  • US 2007/0017647Al discloses a security paper for producing value documents, exemplified by bank notes, passports or identification documents, comprising a flat substrate provided at least partly with a dirt-repellent protective layer for extending the life time and fitness for circulation, wherein the protective layer comprises at least two lacquer layers, a first lower one of said lacquer layers being formed by a physically drying lacquer layer applied to the substrate which makes contact with the substrate therebelow and closes its pores, and a second upper one of said lacquer layers protecting the substrate from physical and chemical influences.
  • the first lower lacquer layer is preferably elastic, is preferably formed by a water-based dispersion lacquer layer, preferably comprises a polyurethane, and is preferably based on a water-based dispersion of aliphatic polyester polyurethanes or styrene-acrylic polyurethanes .
  • a water-based dispersion lacquer layer preferably comprises a polyurethane, and is preferably based on a water-based dispersion of aliphatic polyester polyurethanes or styrene-acrylic polyurethanes .
  • physically drying lacquer not defined in US 2007/0017647A1 to mean a lacquer drying or hardening to form a tight film at room temperature or on slight heating by evaporation of solvent or suspension medium, the degree of polymerization and/or molar mass of the binders remaining unchanged during this process e.g. coalescence of binder particles.
  • Identification cards and documents such as driving licenses, national or government identification cards, bank cards, credit cards, controlled access cards and smart cards, carry certain items of information which relate to the identity of the bearer. Examples of such information or variable data include name, address, date of birth, signature and photo of the bearer.
  • the ID cards or documents may in addition carry invariant data, i.e., data common to a large number of cards, for example the name of an employer, the name of the issuing authority and the name of a country.
  • a typical national passport is personalized by ink-jet-printing a citizen' s biographical and biometric information onto the data page of a blank passport consisting of a back and front cover and pages of security paper with security printing.
  • the ink-jet-ink is partly absorbed in the security paper and any attempt to remove the ink will also destroy the surface of the page.
  • the information can be overwritten.
  • a transparent (possibly optically variable) foil is laminated on top of the data page as a whole or locally over the top of the image of the citizen. The thinness of the foli and its binding to the biographical data makes forgery/alteration difficult. However, under certain circumstances the laminate foil can be integrally removed making it possible to alter the biographic data.
  • aqueous primer compositions comprising at least one polymer selected from the group consisting of vinyl ester homopolymers, vinyl ester copolymers, hydrolyzed vinyl ester homopolymers and hydrolyzed vinyl ester copolymers to a paper-based security document drying to a transparent layer prior to the application of a protective crosslinkable liquid composition to the paper-based security document crosslinking to a glossy transparent layer is able to delay strike-through of the protective crosslinkable liquid composition sufficiently long to enable a crosslinkable composition to be applied and crosslinked without significant penetration into the security paper and moreover that the resulting protective layers are solvent-resistant i.e. survived the crosscut adhesion test after 24 hours immersion in acetone.
  • the primer and crosslinkable compositions are totally transparent and the gloss of the image being protected is substantially unchanged or increased by the coating, although deeper in colour, as would be expected with a transparent coating. No significant dulling or matting of the image is observed with the primer composition of the present invention.
  • a process for preparing a tamperproof security document comprising in order the steps of a) providing a security document comprising security paper having at least one image on at least one outermost surface of the security paper; b) applying by printing, coating or other application process an aqueous primer composition on at least one of the outermost surfaces of the security paper over the at least one image thereby forming a primer coating on at least the at least one image; c) drying said primer coating; d) optionally curing said primer composition; e) applying by printing, coating or other application process a crosslinkable composition over said primer coating; and f) curing said printed or coated crosslinkable composition, wherein said primer composition comprises at least one polymer selected from the group consisting of vinyl ester homopolymers, vinyl ester copolymers, hydrolyzed vinyl ester homopolymers and hydrolyzed vinyl ester copolymers.
  • a process for preparing a tamperproof security document comprising in order the steps of a) applying by printing, coating or other application process an aqueous primer composition on at least one of the outermost surfaces of a security paper to provide a primer print or primer layer; b) drying said primer print or primer layer; c) optionally curing said primer print or primer layer; d) providing at least one image over said dried and optionally cured primer print or primer layer; e) applying by printing, coating or other application process a crosslinkable composition over the at least one image; and f) curing said printed or coated crosslinkable composition, wherein said primer composition comprises at least one polymer selected from the group consisting of vinyl ester homopolymers, vinyl ester copolymers, hydrolyzed vinyl ester homopolymers and hydrolyzed vinyl ester copolymers.
  • a print comprising a security paper carrying a printed image on at least one side thereof, wherein said at least one printed image is provided with a primer composition comprising at least one polymer selected from the group consisting of one polymer selected from the group consisting of vinyl ester homopolymers, vinyl ester copolymers, hydrolyzed vinyl ester homopolymers and hydrolyzed vinyl ester copolymers.
  • a primer composition comprising at least one polymer selected from the group consisting of vinyl ester homopolymers, vinyl ester copolymers, hydrolyzed vinyl ester homopolymers and hydrolyzed vinyl ester copolymers for preventing the penetration of crosslinkable composition into security papers.
  • adhered agent means a substance that prevents adhesion of a material, either to itself or to other materials.
  • printing means application by a conventional impact or non-impact printing process including but not restricted to ink-jet printing, intaglio printing, screen printing, flexographic printing, offset printing, stamp printing, gravure printing and xerographic printing.
  • security document means bank notes, cheque forms, shares, certificates, postage stamps, air tickets, labels for product protection, identity documents, passports and the like.
  • identity document means a document bearing identifying data about the product or the individual whose name appears thereon.
  • ID documents include credit cards, bank cards, phone cards, passports, driving licences, network access cards, employee badges, debit cards, security cards, visas, immigration documentation, national ID cards, citizenship cards, social security cards, security badges, certificates, identification cards or documents, voter registration cards, police ID cards, border crossing cards, legal instruments, security clearance badges and cards, gun permits, gift certificates or cards, membership cards and badges.
  • security paper as used m disclosing the present invention, means a paper used in a security document.
  • image means any way of representing information, such as pictures, logos, photographs, barcodes and text.
  • the image may also comprise some form of a "security pattern", such as small dots, thin lines, holograms, microprint and Moire inducing patterns which may be produced using fluorescent inks, phosphorescent inks, pearlescent inks or other optically variable inks, such as metameric inks.
  • ink means a liquid which can be printed using conventional printing techniques and is not confined to liquids containing at least one colorant .
  • vinyl-monomer means a substance comprising a single vinyl group capable of chain polymerization.
  • polyvmyl-monomer as used m disclosing the present invention, means a substance comprising a more than one vinyl group capable of chain polymerization e.g. a divinyl-monomer with two vinyl groups, a trivinyl-monomer with three vinyl groups, a tetravmyl-monomer with four vinyl groups.
  • substantially non-printable abhesive surface means a surface which does not lend itself to efficient deposition of an ink by a conventional printing technique and/or to deposits of ink with substantially no adhesion to the abhesive surface.
  • substantially non-lammatable abhesive surface means a surface which does not lend itself to efficient lamination and/or to laminates with substantially no adhesion to the abhesive surface.
  • porous pigment means a pigment with detectable pores detectable using techniques such as porosimetry i.e. contains pores m an open (unfilled) state. These pores can be micropores defined by IUPAC as pores sizes ⁇ 2 nm, mesopores defined by IUPAC as pore sizes of 2 to 50 nm or macropores defined by IUPAC as pore sizes greater than 50 nm. Porous pigments often have very high specific surface areas (BET) e.g. 100 to greater than 1500 m 2 /g associated with particle sizes greater than 1 ⁇ m and have measurable pore volumes e.g. 1.2mL/g for SYLOIDTM W300. Examples of porous pigments are silica gels such as SIPERNATTM 570, SIPERNATTM 700 and SIPERNATTM 220 from Degussa and SYLOIDTM W300 from W. R. Grace.
  • BET specific surface areas
  • a “layer or foil exclusive of porous pigment”, as used in disclosing the present invention, means a layer or foil which does not contain porous pigment particles i.e. porous particles containing pores m an open (unfilled) state and does not include a layer or foil containing porous pigment, whose pores have been filled e.g. with a curable liquid.
  • the term "UV” as used m disclosing the present invention is an abbreviation for ultraviolet radiation.
  • electromagnetic radiation means electromagnetic radiation m the wavelength range of 100 to 400 nm.
  • actinic radiation as used m disclosing the present invention means electromagnetic radiation capable of initiating photochemical reactions.
  • thermal initiator as used in disclosing the present invention means an initiator which generates initiating species upon exposure to heat.
  • the term "functional group” as used m disclosing the present invention means an atom or group of atoms, acting as a unit, that has replaced a hydrogen atom m a hydrocarbon molecule and whose presence imparts characteristic properties to this molecule.
  • the term "polyfunctional” means more than one functional group.
  • dispersion means an intimate mixture of at least two substances, one of which, called the dispersed solid phase or colloid, is uniformly distributed in a finely divided state through the second substance, called the dispersion medium.
  • wt% is used m disclosing the present invention as an abbreviation for % by weight.
  • substituted means that one or more of the carbon atoms and/or that a hydrogen atom of one or more of carbon atoms m an aliphatic group, an aromatic group or an alicyclic hydrocarbon group, are replaced by an oxygen atom, a nitrogen atom, a halogen atom, a silicon atom, a sulphur atom, a phosphorous atom, selenium atom or a tellurium atom.
  • substituents include hydroxyl groups, ether groups, carboxylic acid groups, ester groups, amide groups and amine groups.
  • aspects of the present invention have been realized by a process for preparing a tamperproof security document comprising in order the steps of a) providing a security document comprising security paper having at least one image on at least one outermost surface of the security paper; b) applying by printing, coating or other application process an aqueous primer composition on at least one of the outermost surfaces of the security paper over the at least one image thereby forming a primer coating on at least the at least one image; c) drying said primer coating; d) optionally curing said primer composition; e) applying by printing, coating or other application process a crosslinkable composition over said primer coating; and f) curing said printed or coated crosslinkable composition, wherein said primer composition comprises at least Aspects of the present invention have also been realized by a process for preparing a tamperproof security document comprising in order the steps of a) applying by printing, coating or other application process an aqueous primer composition on at least one of the outermost surfaces of a security paper to provide a primer print
  • the process comprises the further steps of g) applying by printing, coating or other application process an abhesive crosslinkable composition over the cured crosslinkable composition; and h) curing the abhesive crosslinkable composition, which is preferably applied by a printing process and particularly preferably by an ink-jet printing process.
  • the crosslinkable composition is printed or coated according to a second image, thereby increasing the problems for the potential forger.
  • the second image may comprise some form of a "security pattern", such as small dots, thin lines, holograms, microprint and Moire inducing patterns which may be produced using fluorescent inks, phosphorescent inks, pearlescent inks or other optically variable inks, such as metameric inks.
  • the crosslinkable composition is printed or coated according to a second image and an abhesive crosslinkable composition is printed or coated on the second image according to a third image, thereby increasing the problems for the potential forger still further.
  • the crosslinkable composition can be a dispersion or a solution with the dispersion medium or solvent being aqueous or non-aqueous and if non-aqueous it can be inert or react in the crosslinking process. If inert the dispersion medium or solvent will usually be evaporated.
  • the image on at least one side of the security paper is applied by ink-jet printing.
  • the primer composition is printed using ink- jet printing.
  • the primer composition is applied pattern- wise.
  • the crosslinkable composition is printed using ink-jet printing.
  • the crosslinkable composition is applied pattern-wise .
  • the crosslinkable composition is cured by UV- radiation.
  • the crosslinkable composition is an abhesive crosslmkable composition, which is printed using ink-jet printing .
  • the crosslmkable composition is an abhesive crosslmkable composition, which is cured by UV-radiation.
  • the process comprises the further steps of g) applying by printing, coating or other application process an abhesive crosslmkable composition over the cured crosslmkable composition; and h) UV-curmg the printed or coated abhesive crosslmkable composition.
  • At least one of the primer compositions and the crosslmkable composition is printed using mk-jet printing or if an abrasive crosslmkable composition is also applied at least one of the primer compositions, the crosslmkable composition and the abrasive crosslmkable composition is printed using mk-]et printing.
  • the compositions have to have a viscosity of less than 15 mPas at the jetting temperature.
  • the image or parts of the image can be provided by any suitable imaging method or combination of imaging methods.
  • Invariant data may be applied by any impact printing technique, such as offset printing, flexographic printing, gravure, screen-printing, mk-jet printing and xerographic printing.
  • any impact printing technique such as offset printing, flexographic printing, gravure, screen-printing, mk-jet printing and xerographic printing.
  • mk-jet printing is the preferred choice since additional security features can be included in the mk-jet inks.
  • the security paper used m different types of security document varies with document type. They are generally based on non-wood fibres such as abaca, cotton, flax, hemp or sisal, although synthetic paper is used for some identity documents, student cards and labels. Compositions used include:
  • Security paper is generally rag paper, always wood-free, watermarked and chemically impregnated. It is very reactive and strong. Security papers carry identification marks which help to prevent counterfeiting e.g. dyes and watermarks. Security paper is also specially treated to prevent erasure, alteration or duplication of any writing or printing on its surface.
  • JETGUARDTM is used for the pages of passports, visas and identity cards .
  • the primer composition used m the process, according to the present invention comprises at least one polymer selected from the group consisting of vinyl ester homopolymers, vinyl ester copolymers, hydrolyzed vinyl ester homopolymers and hydrolyzed vinyl ester copolymers.
  • Suitable vinyl esters include vinyl acetate and vinyl versatic acid esters (or vinyl versatates) .
  • Versatic acids are highly branched C9 - C ⁇ aliphatic carboxylic esters (Rompps Chemie- Lexikon, 7 e edition, p. 3803) .
  • Commercially available vinyl versatates wich are particularly suited are following compounds:
  • R3 is CH3 ; Rl and R2 taken together are C7H25 ;
  • - VeoVa 10 (trade mark of Shell Chemicals Co.) : tert-decanoic acid, ethenyl ester ; other names: tert-decanoic acid, vinyl ester ; versatic 10 acid, ethenyl ester ; CAS No. 26544-09-2 ; in formula (I) R3 is CH3 ; Rl and R2 taken together are CgH]_7 ;
  • VoVa 11 (trade mark of Shell Chemicals Co.) : tert-undecanoic acid, ethenyl ester ; CAS No. 163633-66-7 ; in formula (I) R3 is CH3 ; Rl and R2 taken together are CgH ⁇ ;
  • Craynor 152 can be prepared as shown in the scheme below:
  • the primer composition is exclusive of a polyurethane .
  • the primer composition is exclusive of an aliphatic polyester polyurethane or a styrene-acrylic polyurethane.
  • PVAc poly (vinyl acetate)
  • Suitable hydrolyzed vinyl ester homopolymers and vinyl ester copolymers include:
  • PVAc poly (vinyl acetate) # contains silanol groups ** tert-decanoic acid, ethenyl ester
  • MOWIOL and POVAL are registered trade marks belonging to Kuraray
  • the primer composition further comprises a surfactant, which may be nonionic or ionic.
  • the crosslmkable composition further comprises a surfactant, which may be nonionic or ionic.
  • Suitable nonionic surfactants include:
  • Surfactant no. 01 ZONYL® FSN, a 40% by weight solution of F (CF 2 CF 2 ) i_
  • Surfactant no. 03 ZONYL® FS300, a 40% by weight aqueous solution of a fluorinated surfactant, from DuPont;
  • Surfactant no. 04 ZONYL® FSO, a 50% by weight solution of F(CF 2 CF 2 ) 1
  • Surfactant no. 06 TEGOGLIDE® 410, a polysiloxane-polymer copolymer surfactant, from Goldschmidt;
  • Surfactant no. 07 TEGOWET®, a polysiloxane-polyester copolymer surfactant, from Goldschmidt;
  • Surfactant no. 08 FLUORAD® FC431: CF 3 (CF 2 ) 7 SO 2 (C 2 H 5 )N-CH 2 CO-(OCH 2 CH 2 ) n OH from 3M;
  • Surfactant no. 09 FLUORAD® FC126, a mixture of the ammonium salts of perfluorocarboxylic acids, from 3M;
  • Surfactant no. 10 Polyoxyethylene-10-lauryl ether
  • a particularly preferred non-ionic surfactant is ZONYL® FSO 100.
  • Suitable anionic surfactants include:
  • Surfactant no. 11 ZONYL® 7950, a fluorinated surfactant, from DuPont ;
  • Surfactant no. 12 ZONYL® FSA, 25% by weight solution of
  • Surfactant no. 13 ZONYL® FSE, a 14% by weight solution of
  • Surfactant no. 14 ZONYL® FSJ, a 40% by weight solution of a blend of
  • Surfactant no. 15 ZONYL® FSP, a 35% by weight solution of
  • Surfactant no. 17 ZONYL® TBS: a 33% by weight solution of F (CF 2 CF 2 ) 3
  • Surfactant no. 18 Ammonium salt of perfluoro-octanoic acid
  • the primer composition further comprises an ionic fluorosurfactant .
  • the ionic fluorinated surfactant comprises a perfluo ⁇ nated group, with a CF 3 (CF 2 J n - group wherein n is at least 3 being preferred and a CF 3 (CF 2 J n - group wherein n is at least 5 being particularly preferred.
  • the ionic fluorinated surfactant is an anionic, a cationic or amphoteric fluorinated surfactant.
  • the ionic fluorinated surfactant is an anionic fluorosurfactant, with anionic fluorosurfactants with sulphonate, sulphate, phosphate or carboxylate groups being preferred.
  • Suitable anionic fluorinated surfactants include:
  • Suitable cationic fluorinated surfactants are:
  • Suitable amphoteric fluorinated surfactants are:
  • the crosslinkable composition comprises at least one initiator, at least one vinyl-monomer and at least one polyvmyl-monomer .
  • the crosslinkable composition further comprises at least one organic solvent.
  • the at least one polyvinyl monomer is a divinyl monomer.
  • the at least one vinyl-monomer is an acrylate or methacrylate .
  • the at least one polyvinyl- monomer is a poly-acrylate monomer or a poly-methacrylate monomer.
  • the crosslinkable composition comprises a combination of monomers, oligomers and/or prepolymers.
  • the monomers, oligomers and/or prepolymers may possess different degrees of functionality, and a mixture including combinations of mono-, di-, tri- and higher functionality monomers, oligomers and/or prepolymers may be used.
  • the curable compound (s) used in the curable liquid for the method for preparing a tamperproof ID document according to the present invention can be any monomer and/or oligomer found in Polymer Handbook, Vol. 1 & 2, 4th edition. Edited by J. BRANDRUP, et al. Wiley-Interscience, 1999.
  • Suitable examples of monomers include: acrylic acid, meth- acrylic acid, maleic acid (or their salts) , maleic anhydride; alkyl- (meth) acrylates (linear, branched and cycloalkyl) such as methyl- (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate and 2-ethylhexyl (meth) acrylate; aryl(meth)- acrylates such as benzyl (meth) acrylate and phenyl (meth) -acrylate; hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) -acrylate and hydroxypropyl (meth) acrylate; (meth) acrylates with other types of functionalities (e.g.
  • oxirane amino, polyethylene oxide, phosphate- substituted) such as glycidyl (meth) acrylate, dimethylaminoethyl- (meth) acrylate, methoxypolyethyleneglycol (meth) acrylate and tri- propyleneglycol (meth) acrylate phosphate; allyl derivatives such as allyl glycidyl ether; styrenics such as styrene, 4-methyl-styrene, 4-hydroxystyrene, and 4-acetoxystyrene; (meth) acrylonitrile; (meth)- acrylamides (including N-mono and N, N-disubstituted) such as N-benzyl (meth) acrylamide; maleimides such as N-phenyl maleimide, N-benzyl maleimide and N-ethyl maleimide; vinyl derivatives such as vinylcaprolactam, vinylpyrrolidone,
  • Preferred monomers and oligomers are selected from 1,6-hexane- diol acrylate, alkoxylated aliphatic diacrylates, alkoxylated hexanediol diacrylate, alkoxylated neopentyl glycol diacrylate, di- ethylene glycol diacrylate, dipropyleneglycol diacrylate, ethoxy- lated(l ⁇ ) bisphenol A diacrylate, neopentyl glycol diacrylate, tri- ethylene glycol diacrylate, tripropylene glycol diacrylate, 2(2- ethoxyethoxy) ethyl acrylate, isobornyl methacrylate, isobornyl acrylate, isodecyl acrylate, lauryl acrylate, tetrahydrofurfuryl acrylate, tridecyl acrylate, tridecyl methacrylate, ditrimethylol- propane tetraacrylate, dipenta
  • Suitable vinyl-monomers include:
  • Suitable polyvinyl-monomers include:
  • UV-photoinitiators for the crosslinkable composition comprises at least one UV- imtiator .
  • the crosslinkable composition comprises at least one UV-mitiator selected from the group consisting of: benzoin, benzoin ethers, benzil, benzil ketal derivatives, ⁇ - dialkoxyacetophenones, ⁇ -hydroxy-alkyl-phenones, ⁇ -amino-alkyl- phenones, acyl-phosphme oxides, benzophenone, benzophenone derivatives, xanthones, amines, benzanthrone (BZA), thioxanthone derivatives, thioxanthone, thiotitanoces amines and Michler' s Ketone derivatives 4 , 4' -bis (diethylammo) benzophenone
  • UV-photomitiators suitable for use in the primer, crosslinkable and abhesive crosslinkable compositions of the present invention have to be compatible with a water-containing hydrophilic environment and to have a UV-light absorption compatible with the UV-light source used.
  • UV-photomitiators suitable for use m the compositions of the present invention preferably do not evaporate, sublime, decompose or substantially lose their activity in other ways upon subjection to a short drying/heating step e.g. upon heating for 3 minutes at 130 0 C.
  • the at least one UV- photoinitiator used m at least one of the primer composition, the crosslinkable composition and the abhesive crosslinkable composition has a half-life of greater than 3 minutes when heated to 130°C.
  • Suitable UV-photomitiators include both low molecular weight compounds and oligomers, such as the ESACURE® range of photoinitiators produced by Lamberti Spa. Furthermore, suitable UV- photoinitiators also include cationic and free radical UV- photoimtiators .
  • UV-photomitiators suitable for use in the compositions of the present invention include:
  • the dispersion medium or solvent in crosslmkable composition may comprise monomers and/or oligomers and/or water and/or organic solvents, such as alcohols, fluorinated solvents and dipolar aprotic solvents.
  • the curable liquids preferably do not comprise an evaporable component, but, sometimes, it can be advantageous to incorporate an extremely small amount of an organic solvent in such inks to improve adhesion to the surface of the ink-receiver after UV curing.
  • the added solvent can be any amount in the range that does not cause problems of solvent resistance and VOC, and preferably 0.1-5.0 wt%, and particularly preferably 0.1-3.0 wt%, each based on the total weight of the curable liquid.
  • Suitable organic solvents include alcohol, aromatic hydrocarbons, ketones, esters, aliphatic hydrocarbons, higher fatty acids, carbitols, cellosolves, higher fatty acid esters.
  • Suitable alcohols include, methanol, ethanol, propanol and 1-butanol, 1- pentanol, 2-butanol, t-butanol.
  • Suitable aromatic hydrocarbons include toluene, and xylene.
  • Suitable ketones include methyl ethyl ketone, methyl isobutyl ketone, 2, 4-pentanedione and hexafluoroacetone .
  • glycol, glycolethers, N-methylpyrrolidone, N, N-dimethylacetamid, N, N-dimethylformamid may be used.
  • At least one of the primer composition, the crosslinkable composition and, if applicable, the abhesive crosslinkable composition further comprises at least one luminescent entity e.g. a bead, fibre, particle or dye comprises at least one fluorescent compound or at least one phosphorescent compound to introduce additional security features.
  • Luminescent beads and fibres are usually too large to be jettable.
  • UV-fluorescent and phosphorescent compounds include TinopalTM grades such as TinopalTM SFD, UvitexTM grades such as UvitexTM NFW and UVITEXTM OB from CIBA-GEIGY SPECIALTY CHEMICALS; LUMILUXTM luminescent pigments from HONEYWELL; KEYFLUORTM dyes and pigments from KEYSTONE; LeukophorTM grades from CLARIANT; BlancophorTM grades such as BlancophorTM REU and BlancophorTM BSU from BAYER; and fluorescent dyes from SYNTHEGEN.
  • TinopalTM grades such as TinopalTM SFD, UvitexTM grades such as UvitexTM NFW and UVITEXTM OB from CIBA-GEIGY SPECIALTY CHEMICALS; LUMILUXTM luminescent pigments from HONEYWELL; KEYFLUORTM dyes and pigments from KEYSTONE; LeukophorTM grades from CLARIANT; BlancophorTM grades such
  • At least one of the primer composition, the crosslinkable composition and, if applicable, the abhesive crosslmkable composition further comprises at least one fluorescent compound in a concentration of 0.1 to 20 wt% based on the total weight of the composition applicable, with 1 to 10 wt% being preferred.
  • the crosslmkable composition further comprises at least one biocide.
  • Suitable biocides for the curable liquid used m the method for preparing a tamperproof ID document according to the present invention include sodium dehydroacetate, 2-phenoxyethanol, sodium benzoate, sodium pyridmethion-1-oxide, ethyl p-hydroxybenzoate and 1, 2-benzisothiazolin-3-one and salts thereof.
  • a preferred biocide for the curable liquid is ProxelTM GXL available from ZENECA COLOURS.
  • a biocide is preferably added in an amount of 0.001 to 3 wt.%, more preferably 0.01 to 1.00 wt . %, each based on the curable liquid.
  • the crosslmkable composition is abhesive or the crosslmkable composition is printed or coated with an abhesive crosslmkable composition, wherein the abhesive crosslmkable composition further comprises at least one initiator, at least one vinyl-monomer, at least one polyvmyl-monomer and at least one abherent agent.
  • Suitable abhesive crosslmkable compositions include "SCOTCHGARD®” Phototool Protector from 3M, which is a solvent-free, low-viscosity solution with the following composition:
  • 3- (t ⁇ methoxysilyl) propyl glycidyl ether is the polyme ⁇ zable abherent agent.
  • This solution is ink-jettable, has a viscosity at 25°C of 11.4 mPa.s and a surface tension of 23.6 mN/m.
  • the abherent agent used in the abhesive crosslinkable composition used in the process, according to the present invention causes the outermost layer to have a difficult-to-wet surface.
  • This surface preferably has a surface energy of less than 28 mJ/m 2 .
  • the abherent agent must be present in the cured outermost layer produced with the abhesive crosslinkable composition in a polymeric form otherwise it can be easily removed by wiping and using a strong organic solvent such as toluene or a chlorinated solvent. Low molecular weight fluorosurfactants are not suitable abherent agents in the present invention.
  • a single abherent agent or a mixture of abherent agents may be used as long as the abhesive properties of the outermost layer are obtained.
  • the abherent agent may be present in the abhesive crosslinkable composition as a polymerizable compound or as a polymeric abherent agent or a combination of both.
  • the abherent agent is a silicone-modified or a fluorinated polymerizable compound.
  • the abherent agent is preferably exclusive of epoxysilanes modified with oxyalkylene ether groups.
  • the crosslinkable composition is abhesive or the crosslinkable composition is printed or coated with an abhesive crosslinkable composition, wherein the abhesive crosslinkable composition further comprises at least one abherent agent selected from the group consisting of fluorinated (meth) acrylates and fluorinated ethylenes.
  • the crosslinkable composition is abhesive or the crosslinkable composition is printed or coated with an abhesive crosslinkable composition, wherein the abhesive crosslinkable composition further comprises at least one polymeric abherent agent selected from the group consisting of a polytetrafluoroethylene, copolymers of fluorinated ethylene, polymers of fluorinated (meth) acrylates, copolymers of fluorinated (meth) acrylates, perfluoro (alkyl vinyl ether) s and polyvinylidene fluoride .
  • the abhesive crosslinkable composition further comprises at least one polymeric abherent agent selected from the group consisting of a polytetrafluoroethylene, copolymers of fluorinated ethylene, polymers of fluorinated (meth) acrylates, copolymers of fluorinated (meth) acrylates, perfluoro (alkyl vinyl ether) s and polyvinylidene fluoride .
  • the crosslinkable composition is abhesive or the crosslinkable composition is printed or coated with an abhesive crosslinkable composition
  • the abhesive crosslinkable composition further comprises at least one polymeric abherent agent selected from the group consisting of polymers of fluorinated (meth) acrylates and copolymers of fluorinated (meth) acrylates, wherein the fluorinated (meth) acrylate is selected from the group consisting of 2, 2 , 2-trifluoroethyl- ⁇ -fluoroacrylate (TFEFA), 2,2,2-trifluoroethyl-methacrylate (TFEMA), 2,2,3,3- tetrafluoropropyl- ⁇ -fluoroacrylate (TFPFA) , 2,2, 3, 3-tetrafluoro- propyl-methacrylate (TFPMA), 2, 2 , 3, 3, 3-pentafluoropropyl- ⁇ - fluor
  • TFEFA 2-trifluoroethyl- ⁇ -fluoro
  • the crosslinkable composition is abhesive or the crosslinkable composition is printed or coated with an abhesive crosslinkable composition
  • the abhesive crosslinkable composition further comprises an abherent agent selected from the group consisting of silicone-modified (meth) acrylates and epoxy- functional silane compounds, the epoxy-functional silane compound being preferably selected from the group consisting of ⁇ -glycidoxy- propyl trimethoxysilane, ⁇ -glycidoxypropyl triethoxysilane, ⁇ - glycidoxyethyl trimethoxysilane, ⁇ - (3, 4-epoxy-cyclohexyl) propyl trimethoxysilane and ⁇ - ( 3, 4-epoxycyclohexyl) ethyl trimethoxysilane.
  • the crosslinkable composition is abhesive or the crosslinkable composition is printed or coated with an abhesive crosslinkable composition
  • the abhesive crosslinkable composition further comprises a polymeric abherent agent selected from the group consisting of polymers of dimethylsiloxane acrylate, copolymers of dimethylsiloxane acrylate, dimethyl siloxane modified polyethers, polymers of silicone-modified (meth) acrylates, copolymers of silicone-modified (meth) acrylates, dimethyl siloxane modified polyesters, silicone glycol copolymers, polymers of epoxy- functional silane compounds and copolymers of epoxy-functional silane compounds, the epoxy-functional silane compound being selected from the group consisting of ⁇ -glycidoxy-propyl trimethoxysilane, ⁇ -glycidoxypropyl triethoxysilane, ⁇ -glycidoxyethyl
  • Abherent agents suitable as polymerizable compound constitute preferably from 20 to 99.6%, more preferably 24 to 90%, and most preferably 30 to 80% by weight of the total composition of the abhesive crosslinkable composition.
  • Abherent agents suitable as a polymerizable compound include silicone-modified (meth) acrylates, fluorinated (meth) acrylates, fluorinated ethylenes and epoxy-functional silane compounds.
  • Preferred silicone-modified acrylates include EbecrylTM 350 (silicon diacrylate) and EbecrylTM 1360 (silicon hexaacrylate) from UCB, Belgium; ActilaneTM 800 (silicon acrylate) from AKZO-NOBEL NV; and CN990TM (siliconized urethane acrylate oligomer) from SARTOMER.
  • suitable epoxy-silanes include ⁇ -glycidoxypropyl trimethoxysilane, ⁇ -glycidoxypropyl triethoxysilane, ⁇ - glycidoxyethyl trimethoxysilane, (- (3, 4-epoxycyclohexyl ) propyl trimethoxysilane, ⁇ - (3, 4-epoxycyclohexyl ) ethyl trimethoxysilane, and the like.
  • the most preferred epoxy-silane compound is ⁇ -glycidoxypropyl trimethoxysilane.
  • suitable epoxy-silanes include (metha) acryl- oxyalkylalkoxysilanes such as (- (meth) acryloxypropyltrimethoxy- silane, (- (meth) acryloxypropyltriethoxysilane and (- (meth) acryloxy- propyl-triisopropoxysilane; (meth) acryloxyalkylalkoxyalkyl si lanes such as (- (meth) acryloxypropylmethyldimethoxysilane and (-(meth)- acryl-oxypropylmethyldiethoxysilane; vinyltrimethoxysilane, vinyltri-ethoxysilane, vinyltriisopropoxysilane, aryltriethoxy- silane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane and vinyltris (2-methoxyethoxy) silane .
  • metalha acryl- oxyalkylalkoxysilanes such as (-
  • the abherent agent present in the cured layer produced with the abhesive crosslinkable composition may be selected from the group consisting of polymers of dimethylsiloxane; copolymers of dimethylsiloxane; dimethyl siloxane-modified polyethers; dimethyl siloxane modified polyesters; silicone glycol copolymers; polymers of fluorinated ethylene such as polytetra-fluoroethylene, polyvinylfluoride and polyvinylidene fluoride (PVDF); copolymers of fluorinated ethylene such as a fluorinated ethylene/propylene copolymers and ethylene/tetrafluoroethylene copolymers; polymers of fluorinated (meth) acrylates; copolymers of fluorinated (meth) acrylates; and perfluoro (alkyl vinyl ether) s.
  • PVDF polyvinylidene fluoride
  • At least one of the crosslinkable composition and if applicable the abhesive crosslinkable composition is cured by exposure to actinic radiation, by thermal curing and/or by electron beam curing.
  • a preferred means of radiation curing is ultraviolet radiation.
  • the curing is performed by an overall exposure to actinic radiation, by overall thermal curing and/or by overall electron beam curing.
  • the curing means may be arranged in combination with the print head of the ink-jet printer, travelling therewith so that the curable liquid is exposed to curing radiation very shortly after being jetted.
  • a static fixed radiation source may be employed, e.g. a source of curing UV radiation, connected to the radiation source by means of flexible radiation conductive means such as a fibre optic bundle or an internally reflective flexible tube .
  • the actinic radiation may be supplied from a fixed source to the radiation head by an arrangement of mirrors including a mirror upon the radiation head.
  • the source of radiation arranged not to move with the print head may also be an elongated radiation source extending transversely across the ink-receiver surface to be cured and adjacent the transverse path of the print head so that the subsequent rows of images formed by the print head are passed, stepwise or continually, beneath that radiation source.
  • Any ultraviolet light source may be employed as a radiation source, such as, a high or low pressure mercury lamp, a cold cathode tube, a black light, an ultraviolet LED, an ultraviolet laser, and a flash light, if part of the emitted light can be absorbed by the photo-initiator or photo-initiator system.
  • the preferred source is one exhibiting a relatively long wavelength UV-contribution having a dominant wavelength of 300-400 nm.
  • a UV-A light source is preferred due to the reduced light scattering therewith resulting in more efficient interior curing.
  • UV radiation is generally classed as UV-A, UV-B, and UV-C as follows :
  • UV-A 400 nm to 320 nm
  • UV-B 320 nm to 290 nm
  • UV-C 290 nm to 100 nm.
  • At least one of the printed or coated primer composition, crosslinkable composition and, if applicable, abhesive crosslinkable composition is cured consecutively or simultaneously using two light sources of different wavelengths or illuminance.
  • the first UV source can be selected to be rich in UV-C, in particular in the range of 260 nm-200 nm.
  • the second UV source can then be rich in UV-A, e.g. a gallium-doped lamp, or a different lamp high in both UV-A and UV-B.
  • the use of two UV sources has been found to be advantageous e.g. a fast curing speed.
  • the ink-jet printer often includes one or more oxygen depletion units.
  • the oxygen depletion units place a blanket of nitrogen or other relatively inert gas (e.g. CO 2 ), with adjustable position and adjustable inert gas concentration, in order to reduce the oxygen concentration in the curing environment. Residual oxygen levels are usually maintained as low as 200 ppm, but are generally in the range of 200 ppm to 1200 ppm.
  • Thermal curing can be performed image-wise by use of a thermal head, a heat stylus, hot stamping, a laser beam, etc. If a laser beam is used, then preferably an infrared laser is used in combination with an infrared absorbing substance in the curable liquid .
  • At least one of the primer composition, the crosslinkable composition and if applicable the abhesive crosslinkable composition is printed by a conventional printing process including but not restricted to ink-jet printing, intaglio printing, screen printing, flexographic printing, offset printing, stamp printing and gravure printing.
  • ink- jet printing the curable liquid is jetted by one or more printing heads ejecting small droplets of liquid in a controlled manner through nozzles onto an ink-receiver surface, which is moving relative to the printing head(s) .
  • a preferred printing head for the ink-jet printing system according to the present invention is a piezoelectric head.
  • Piezoelectric ink-jet printing is based on the movement of a piezoelectric ceramic transducer when a voltage is applied thereto.
  • the application of a voltage changes the shape of the piezoelectric ceramic transducer in the printing head creating a void, which is then filled with ink.
  • the ceramic expands to its original shape, ejecting a drop of ink from the print head.
  • the method for preparing a tamperproof ID document according to the present invention is not restricted to piezoelectric ink-jet printing.
  • Other ink-jet printing heads can be used and include various types, such as a continuous type and thermal, electrostatic and acoustic drop on demand type.
  • the liquid must be ejected readily from the printing heads, which puts a number of constraints on the physical properties of the ink, e.g. a low viscosity at the jetting temperature, which may vary from 25°C to HO 0 C, a surface energy such that the printing head nozzle can form the necessary small droplets, a homogenous liquid capable of rapid conversion to a dry printed area.
  • a low viscosity at the jetting temperature which may vary from 25°C to HO 0 C
  • a surface energy such that the printing head nozzle can form the necessary small droplets
  • a homogenous liquid capable of rapid conversion to a dry printed area.
  • the viscosity of the curable liquid used in the ink-jet printing method according to the present invention is preferably lower than 30 mPa.s, more preferably lower than 15 mPa.s, and most preferably between 2 and 10 mPas at a shear rate of 100 s "1 and a jetting temperature between 10 and 55°C.
  • the ink-jet printing head normally scans back and forth in a transversal direction across the moving ink-receiver surface. Often the ink-jet print head does not print on the way back. Bidirectional printing is preferred for obtaining a high areal throughput. Particularly preferred, is printing in a "single pass printing process", which can be performed by using page wide ink-jet printing heads or multiple staggered ink-jet printing heads which cover the entire width of the ink-receiver surface. In a single pass printing process the ink-jet printing heads usually remain stationary and the ink-receiver surface is transported under the ink-jet printing heads.
  • a print comprising a security paper carrying a printed image on at least one side thereof, wherein said at least one printed image is provided with a primer composition comprising at least one polymer selected from the group consisting of one polymer selected from the group consisting of vinyl ester homopolymers, vinyl ester copolymers, hydrolyzed vinyl ester homopolymers and hydrolyzed vinyl ester copolymers .
  • the primer composition is provided with a coating of a crosslinkable composition.
  • the crosslinkable composition is cured.
  • the crosslinkable composition is abhesive.
  • the primer composition is provided with a coating of a crosslinkable composition, which is itself provided with an abhesive crosslinkable composition.
  • the primer composition is provided with a coating of a crosslinkable composition, which is itself provided with a cured abhesive crosslinkable composition.
  • the primer composition is provided with a coating of an abhesive crosslinkable composition or is provided with a coating of a crosslinkable composition, which is itself provided with an abhesive crosslinkable composition, wherein the abhesive crosslinkable composition further comprises at least one abherent agent selected from the group consisting of fluorinated (meth) acrylates and fluorinated ethylenes.
  • the primer composition is provided with a coating of an abhesive crosslinkable composition or is provided with a coating of a crosslinkable composition, which is itself provided with an abhesive crosslinkable composition, wherein the abhesive crosslinkable composition further comprises at least one polymeric abherent agent selected from the group consisting of a polytetra- fluoro-ethylene, copolymers of fluorinated ethylene, polymers of fluorinated (meth) acrylates, copolymers of fluorinated (meth)- acrylates, perfluoro (alkyl vinyl ether) s and polyvinylidene fluoride, the fluorinated (meth) acrylate being preferably selected from the group consisting of 2, 2 , 2-trifluoroethyl- ⁇ -fluoroacrylate (TFEFA), 2,2,2-trifluoroethyl-methacrylate (TFEMA), 2,2,3,3- tetrafluoride, a polytetra- fluoro-ethylene
  • the primer composition is provided with a coating of an abhesive crosslinkable composition or is provided with a coating of a crosslinkable composition, which is itself provided with an abhesive crosslinkable composition, wherein the abhesive crosslinkable composition further comprises an abherent agent selected from the group consisting of silicone-modified (meth) acrylates and epoxy-functional silane compounds, the epoxy- functional silane compound being preferably selected from the group consisting of ⁇ -glycidoxypropyl trimethoxysilane, ⁇ -glycidoxypropyl triethoxysilane, ⁇ -glycidoxyethyl trimethoxysilane, ⁇ - (3, 4-epoxy- cyclohexyl) propyl trimethoxysilane and ⁇ - (3, 4-epoxycyclohexyl) ethyl trimethoxysilane .
  • an abherent agent selected from the group consisting of silicone-modified (meth) acrylates and epoxy-functional si
  • the primer composition is provided with a coating of an abhesive crosslinkable composition or is provided with a coating of a crosslinkable composition, which is itself provided with an abhesive crosslinkable composition, wherein the abhesive crosslinkable composition further comprises a polymeric abherent agent selected from the group consisting of polymers of dimethyl- siloxane acrylate, copolymers of dimethylsiloxane acrylate, dimethyl siloxane modified polyethers, polymers of silicone-modified (meth) acrylates, copolymers of silicone-modified (meth) acrylates, dimethyl siloxane modified polyesters, silicone glycol copolymers, polymers of epoxy-functional silane compounds and copolymers of epoxy-functional silane compounds, the epoxy-functional silane compound being preferably selected from the group consisting of ⁇ - glycidoxypropyl trimethoxysilane, ⁇ -glycidoxypropyl trieth
  • the primer composition is provided with a coating of a crosslinkable composition, which further comprises at least one luminescent entity.
  • the primer composition is provided with a coating of an abhesive crosslinkable composition or is provided with a coating of a crosslinkable composition, which is itself provided with an abhesive crosslinkable composition, wherein the abhesive crosslinkable composition further comprises at least one luminescent entity.
  • the security documents with improved tamper-proofing realized with the process, according to the present invention can be used for a wide variety of security applications including, but not limited to, bank notes, cheque forms, shares, certificates, postage stamps, air tickets, labels for product protection and identity documents .
  • PCC 01 (jettable with a Xaar UPH ink-jet printing head) :
  • Solvent resistance was evaluated by immersing the coated security paper m acetone for 24 hours at room temperature and then evaluating the adhesion as described above. The test result was evaluated as:
  • the primer composition coating was then overcoated with a doctor blade with the abhesive crosslmkable composition "SCOTCHGARD®" or PCC 1 to the liquid thickness given m Table 1 and then immediately UV-cured m a DRSE-120 conveyor from Fusion UV Systems Ltd with a VPS/1600 UV lamp (speed 20 m/mm, 50% UV power setting giving over a width of 20 cm and a length m the transport direction of 0.8 cm: a UV-A intensity of 4.310 W/cm 2 , a UVB intensity of 1.071 W/cm 2 and a UVC intensity of 0.120 W/cm 2 ) .
  • the UV-curmg process was completed m less than 1 second. Table 1 :
  • polyvinyl esters such as poly (vinyl acetate) and vinyl ester copolymers such as copolymers of ethylene
  • vinyl acetate and vinyl versatate provide primer layers, which prevent penetration of a crosslmkable composition such as "SCOTCHGARD®" .
  • Primer compositions with aqueous dispersion of vinyl esters provide for penetration prevention at lower polyvinyl ester concentrations .
  • the resulting coating configuration exhibits excellent adhesion and solvent resistance on security paper. Addition of the ionic fluorosurfactant AFS35 to the primer composition either brought about no improvement or in the case of Polymer nr . 04 reduced the solvent resistance observed.
  • DRSE-120 conveyor from Fusion UV Systems Ltd with a VPS/1600 UV lamp (speed 20 m/min, 50% UV power setting giving over a width of 20 cm and a length m the transport direction of 0.8 cm: a UV-A intensity of 4.310 W/cm 2 , a UVB intensity of 1.071 W/cm 2 and a UVC intensity of 0.120 W/cm 2 ) .
  • the UV-cu ⁇ ng process was completed in less than 1 second.
  • PVAc poly (vinyl acetate)
  • PVAc poly (vinyl acetate)

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Abstract

L'invention porte sur un procédé de préparation d'un document de sécurité inviolable et consistant, dans l'ordre, à : a) obtenir un document de sécurité présentant au moins une image sur au moins une surface située le plus à l'extérieur du papier de sécurité; b) à appliquer, par impression, couchage ou tout autre procédé d'application, une composition de primaire aqueuse sur au moins une des surfaces le plus à l'extérieur du papier de sécurité et sur la ou les images, afin de former une couche de primaire sur au moins la ou les images; c) à faire sécher ladite couche de primaire; d) éventuellement, à faire durcir ladite composition de primaire; e) à appliquer, par impression, couchage ou tout autre procédé d'application, une composition réticulable sur ladite couche de primaire; et f) à faire durcir ladite composition réticulable déposée par impression ou par couchage; ladite composition de primaire contenant au moins un polymère sélectionné dans le groupe constitué par les homopolymères des esters vinyliques, les copolymères des esters vinyliques, les homopolymères des esters vinyliques hydrolysés et les copolymères des esters vinyliques hydrolysés; et un imprimé incluant un papier de sécurité portant, sur une de ses faces au moins, une image imprimée, la ou les images imprimées étant pourvues d'une composition de primaire contenant au moins un polymère sélectionné dans le groupe constitué par les homopolymères des esters vinyliques, les copolymères des esters vinyliques, les homopolymères des esters vinyliques hydrolysés et les copolymères des esters vinyliques hydrolysés.
PCT/EP2008/067649 2007-12-19 2008-12-16 Procédé de préparation de documents de sécurité inviolables et document de sécurité inviolable Ceased WO2009077536A2 (fr)

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Cited By (5)

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Publication number Priority date Publication date Assignee Title
FR2979358A1 (fr) * 2011-08-31 2013-03-01 Arjowiggins Security Support d'information destine a l'impression sur presses a toner liquide.
FR2980491A1 (fr) * 2011-09-27 2013-03-29 Oberthur Technologies Procede de traitement de surface d'un document de securite
WO2014036740A1 (fr) * 2012-09-10 2014-03-13 Celanese Emulsions Gmbh Liants d'éthylène d'acétate de vinyle fonctionnalisés pour revêtements de papier et de carton
US9358576B2 (en) 2010-11-05 2016-06-07 International Paper Company Packaging material having moisture barrier and methods for preparing same
US9365980B2 (en) 2010-11-05 2016-06-14 International Paper Company Packaging material having moisture barrier and methods for preparing same

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE186345T1 (de) * 1995-03-13 1999-11-15 Rue De Int Ltd Sicherheitspapier
DE19510974A1 (de) * 1995-03-24 1996-09-26 Drescher Geschaeftsdrucke Einlagiges Papiererzeugnis
US7022385B1 (en) * 2001-10-04 2006-04-04 Nucoat, Inc. Laminated imaged recording media
DE10327083A1 (de) * 2003-02-11 2004-08-19 Giesecke & Devrient Gmbh Sicherheitspapier und Verfahren zur Herstellung desselben
GB2419110A (en) * 2004-10-14 2006-04-19 Nicholas John Murray An authentication article encapsulated in a curable coating on a substrate
EP1940981A1 (fr) * 2005-10-21 2008-07-09 Agfa-Gevaert N.V. Procede de preparation de documents d'identification inviolables
WO2007045580A1 (fr) * 2005-10-21 2007-04-26 Agfa Graphics Nv Kit de liquides durcissables et procedes d'impression a jet d'encre

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9358576B2 (en) 2010-11-05 2016-06-07 International Paper Company Packaging material having moisture barrier and methods for preparing same
US9365980B2 (en) 2010-11-05 2016-06-14 International Paper Company Packaging material having moisture barrier and methods for preparing same
FR2979358A1 (fr) * 2011-08-31 2013-03-01 Arjowiggins Security Support d'information destine a l'impression sur presses a toner liquide.
WO2013030784A1 (fr) * 2011-08-31 2013-03-07 Arjowiggins Security Support d'information destine a l'impression sur presses a toner liquide
FR2980491A1 (fr) * 2011-09-27 2013-03-29 Oberthur Technologies Procede de traitement de surface d'un document de securite
WO2013045496A1 (fr) * 2011-09-27 2013-04-04 Oberthur Fiduciaire Sas Procede de traitement de surface d'un billet de banque
CN103998685A (zh) * 2011-09-27 2014-08-20 欧贝特信托公司 用于处理钞票的表面的方法
AU2012314478B2 (en) * 2011-09-27 2016-11-03 Oberthur Fiduciaire Sas Method for treating the surface of a banknote
RU2611503C2 (ru) * 2011-09-27 2017-02-27 Обертур Фидюсьер Сас Способ поверхностной обработки банкноты
WO2014036740A1 (fr) * 2012-09-10 2014-03-13 Celanese Emulsions Gmbh Liants d'éthylène d'acétate de vinyle fonctionnalisés pour revêtements de papier et de carton

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