Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
• • 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
  • B42D25/382—Special inks absorbing or reflecting infrared light
• • 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
  • B42D25/387—Special inks absorbing or reflecting ultraviolet light
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/08—Metals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/40—Glass
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/205—Compounds containing groups, e.g. carbamates
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09D133/08—Homopolymers or copolymers of acrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/61—Additives non-macromolecular inorganic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/61—Additives non-macromolecular inorganic
  • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/66—Additives characterised by particle size
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/08—Metals
  • C08K2003/0806—Silver
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/08—Metals
  • C08K2003/085—Copper
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/08—Metals
  • C08K2003/0893—Zinc
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K9/00—Use of pretreated ingredients
  • C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers

Definitions

• the present invention relates to the field of security documents and more particularly banknotes.
• varnish formulation making it possible to confer, in addition to the basic property of reinforcing the resistance to soiling, resistance to microscopic soiling and more particularly protection against bacteria, microscopic fungi, in particular yeasts, and viruses. .
• the banknote is one of the most widely traded information documents in the world.
• excessive soiling hinders the visibility of the banknote authentication signs, forcing central banks to withdraw banknotes from circulation and reissue cleaner banknotes.
• One of the solutions envisaged for reducing the frequency of renewal consists in applying to the surface of the printed ticket, once most of the printing steps have been completed, a generally overprinting varnish which makes it possible to give the ticket increased resistance to soiling.
• this solution is insufficient to effectively combat microscopic soiling and provide protection against microbes.
• banknotes in circulation because of their handling and exchanges from hand to hand, are carriers of sometimes pathogenic microbes and in particular bacteria, microscopic fungi, in particular yeasts and viruses.
• the presence of mold can degrade cellulosic substrates.
• the curing of the applied varnish generally requires a UV crosslinking process which requires irradiation of the coated substrate under high intensity UV.
• the anti-microbial active ingredients used must not be degraded during this stage of the varnishing printing process. They should not be photosensitive.
• the distribution of the anti-microbial active agents used within the varnish film must be very homogeneous, sufficiently so that the surface interface of the varnished printed substrate, that is to say the outer surface layer of the document has the same sufficient biocidal activity.
• the present invention is specifically aimed at providing a new varnish, in particular for overprinting, satisfying all of these requirements.
• the present invention is principally aimed at a protective varnish hardened by sand by radiation, in particular UV, comprising at least one compound which can be set by cationic or radical route and at least one metal chosen from silver, copper, zinc and theirs. mixtures characterized in that said metal is in the state of zero oxidation state and in a supported particulate form.
• a varnish according to the invention further contains at least one fungicide.
• the invention therefore relates very particularly to a protective varnish curable by radiation, in particular UV, comprising:
• fungicide comprising at least iodopropynyl butylcarbamate, IPBC, and - at least one metal chosen from silver, copper, zinc and their mixtures, characterized in that said metal is in the state of zero oxidation state and in a supported particulate form.
• the varnish has a biocidal activity and in particular at least bactericidal or bacteriostatic, preferably at least bactericidal. More generally, the varnish has a bactericidal, bacteriostatic and / or virucidal activity, preferably bactericidal and virucidal.
• the metal in the state of zero oxidation state is supported by a particulate inorganic material and preferably a particulate phosphate glass.
• the metal comprises at least silver.
• the inventors have found that the supported zero degree metals according to the invention do not interfere with the UV irradiation process required to cure the varnish.
• a varnish incorporating these materials still has the expected or even improved durability properties, including anti-fouling property, and can remain transparent.
• the combination of IPBC with this metal in the state of zero oxidation and in a supported particulate form advantageously improves the antimicrobial properties of a varnish.
• the invention also relates to an object coated on all or part of one of its external faces with a deposit of hardened varnish formed from a curable varnish according to the invention.
• Said object is in particular intended to be touched or handled. It is for example a handle, a button, a touch screen, a packaging, an information medium in particular a document or a security element and preferably a Bank note.
• Said object is for example made of a material chosen from among a sheet of glass, paper, cardboard, plastic, textile, an optical structure in particular made up of a layer or a combination of layers of functional resins.
• the invention relates in particular to a security element or document, for example made of paper or plastic, coated on all or part of one of its external faces with a deposit of hardened varnish formed from a varnish. curable according to the invention.
• the invention preferably relates to a security document coated on all or part of one of its external faces with a deposit of hardened varnish formed from a curable varnish according to the invention.
• the security document is surface treated, on at least one of its faces, with a hardened varnish film formed from said curable varnish according to the invention.
• this document incorporates one or more security elements and is advantageously a bank note.
• the invention also relates to a method of manufacturing such an object comprising at least the steps of
• the invention relates more particularly to a method of manufacturing such a security document comprising at least the steps of
• the contacting of the surface to be treated of said object, in particular security document, with the varnish in accordance with the invention can be carried out by a printing process, in particular flexographic, gravure, or screen printing, by spraying, by application to the brush or brush or by any other coating process.
• the invention relates to the use of a varnish in accordance with the invention for producing a protective coating or a protective layer on a security document and preferably a bank note. It further relates to the use of a varnish in accordance with the invention to improve the resistance to soiling of a security document and preferably a bank note.
• varnish according to the invention to impart antimicrobial properties to a security document and preferably a banknote.
• a zero oxidation metal is a metal whose atoms are in a nonionic form.
• the expressions "zero metal”, “metal” and “zero oxidation metal” will be used to denote this state of unoxidized metal.
• this metal is chosen from silver, zinc, copper and their mixtures.
• the zero metal comprises at least silver and in particular consists of silver.
• the expression "in a supported particulate form” means that the metal is supported by a particulate inorganic material. More particularly, the metal is immobilized on the surface and where appropriate in the depth of this material. This material may in particular consist of a matrix in which the zero metal is dispersed.
• the inorganic material loaded with zero metal can be chosen from zeolites and glasses, in particular phosphated.
• the material is a glass and more particularly a phosphate glass.
• Phosphated glass advantageously has high stability during a UV crosslinking process.
• the particle size of the material loaded or even doped with zero metal is thus preferably less than 10 ⁇ m and preferably less than 5 ⁇ m.
• the size of the particles can in particular be measured by SEM imaging or by DLS (dynamic light scattering).
• the particle size can more particularly be defined by the diameter D98, that is to say the diameter such that 98% of the particles by weight have a size smaller than said diameter.
• the charge rate of the zero degree metal material ranges from 0.5% to 3%, especially 1.0% to 2.5%, by weight based on its total loaded weight.
• the varnish may also contain other mineral particles, the function of which may be in particular to adjust the level of gloss of the finished varnish film, in particular silica particles. This is particularly relevant in the context of overprint varnishes.
• a cured varnish containing zero metal charged particles according to the invention and IPBC exhibits the expected bactericidal and virucidal properties.
• the varnish contains silver metal supported on a particulate material of glass and preferably of phosphated glass.
• the metal silver is in the form of silver particles in a matrix of phosphated glass.
• This matrix has the advantage of being permeable to Ag + silver ions and therefore of allowing the passage / mobility of Ag + silver ions.
• Ag-i- ions which possess the bactericidal activity are generated by bringing silver of zero oxidation degree, dispersed in the varnish, into contact with ambient humidity or during contamination, for example by droplets including sputum.
• a material of this type is marketed in particular under the name Ultrafresh CA16 from the company Thomson Research Associates Inc.
• protection varnish denotes a varnish useful for providing resistance to soiling advantageously combined with antimicrobial protection to a security document on the surface of which it is applied.
• antimicrobial qualifies a biocidal activity in particular bactericidal, fungicidal, in particular yeasticidal, virucidal and / or algicidal, that is to say which kills the microorganism in question, but also a bacteriostatic activity and / or fungistatic, that is to say which inhibits the growth of bacteria and microscopic fungi.
• radiation curable varnish covers, within the meaning of the invention, varnishes which solidify under Infra Red / Hot Air and UV drying.
• the varnish considered according to the invention comprises one or more curable compounds.
• a curable compound is a compound capable of polymerizing, crosslinking or polycondensing, where appropriate, with other compounds, in response to a stimuli in this case infrared heating or UV irradiation and if necessary in the presence of an additional compound called initiator, and thus irreversibly form a solid film under ambient conditions (room temperature, daylight irradiation, etc.).
• it is a varnish which can be hardened by UV-visible radiation. In other words, it solidifies under UV drying.
• acrylic varnishes for example, acrylic varnishes, varnishes comprising an epoxy base, or varnishes comprising an acrylate base are particularly suitable. It is preferably a varnish comprising an acrylate base.
• It may in particular be a varnish based on monomers from the polyalkylacrylate family, a varnish based on an unsaturated acrylic resin or else a varnish based on monomers from the cycloaliphatic epoxy family.
• This latter family polymerizes to give a polyepoxide matrix by virtue of initiators, in particular photo-initiators, such as onium salts activated under ultraviolet light.
• a photoinitiator with free radicals such as for example an onium salt in particular in the image of the cations and anions of sulfonium where appropriate substituted.
• the varnish can further comprise a free radical photoinitiator.
• the curable varnish according to the invention is thus preferably the precursor of a cured varnish of polyepoxide or polyacrylate type, and more preferably of polyepoxide type.
• a cured varnish of polyepoxide or polyacrylate type and more preferably of polyepoxide type.
• these varnishes mention may be made, for example, of the polyepoxide varnish sold under the name “Sicpaprotect” (reference 889368 for paper substrates or 889354 for polymer substrates) from Sicpa, and the polyacrylate varnishes sold under the name “Wessco Protector. 36.389.19 ”by Schmidt Rhyner.
• the varnish according to the invention is a cationic varnish.
• the varnish according to the invention is an overprint varnish which is particularly useful for security documents.
• the varnishes according to the invention are advantageously fluid to easily form films by application to the surfaces to be treated.
• a varnish according to the invention can be deposited on the surface of a support by any suitable method and for example by flexographic printing, gravure or screen printing methods or even blade coating methods. air, curtain sleeping or roll sleeping.
• the viscosity of the varnish according to the invention can be adjusted via the nature and / or amount of the solvent medium in which the curable compound (s) is or are formulated.
• viscosity of between 30 mPa.s and 40 Pa.s, in particular between 50 mPa.s and 20 Pa.s, measured at ambient temperature and pressure.
• the viscosities of the compositions can be measured by conventional methods.
• the varnish in hardened form can be completely transparent. This pseudo invisibility of the applied varnish is, for obvious reasons, particularly interesting.
• the varnishes according to the invention prove to be particularly advantageous for constituting overprinting varnishes for an information medium such as tickets. They do not obstruct the visibility of the security elements integrated in these notes.
• a varnish according to the invention can comprise from 0.001% to 0.2% by weight, preferably from 0.003% to 0.015%, and more preferably less than 0.01%, or even less than 0.008% of metal of oxidation degree equal to zero with respect to its total weight.
• the varnish according to the invention contains at least iodopropynyl butylcarbamate,
• IPBC IP-based polystyrene-maleic anhydride copolymer
• Troy Chemical Company marketed by the company Troy Chemical Company under the name Fungitrol C450.
• a varnish in accordance with the invention may comprise from 0.1% to 5.0%, preferably from 1% to 4%, and more preferably from 1.5% to 3.5%, by weight of IPBC in relation to its total weight.
• the metal in the state of zero oxidation state and the IPBC are used in a metal / IPBC weight ratio varying from 0.0007 to 0.01, preferably from 0.0008 to 0.007, preferably from 0.001 to 0.005, and more preferably from 0.0015 to 0.004, or even from 0.0017 to 0.0034.
• the varnish can advantageously include ancillary anti-microbial agents, provided that they are compatible with a formulation in a non-aqueous medium and with irradiation, in particular UV.
• a varnish according to the invention further contains at least one fungicide distinct from IPBC.
• the composition according to the invention contains at least one fungistatic and / or fungicidal agent chosen from compounds based on isothiazoline or isothiazolone derivatives, on zinc zeolite and on triclosan.
• the varnish according to the invention contains as fungistatic and / or fungicidal agent at least one compound chosen from p - ((diiodomethyl) sulfonyl) toluol and methyl-1H-benzimidazol-2-ylcarbamate.
• a varnish in accordance with the invention may comprise from 0.1% to 2.0%, preferably from 0.5% to 1.5%, by weight of fungicide (s) relative to its total weight.
• a varnish in accordance with the invention can comprise from 0.1% to 5.0%, preferably from 1% to 4%, and more preferably from 1.5% to 3.5%, by weight of fungicide ( s) in relation to its total weight.
• the varnish according to the invention is very particularly suitable for forming a protective and in particular anti-microbial coating on the surface of security documents intended to be handled relatively frequently.
• a “security document intended to be handled relatively frequently” is a medium handled at least twice manually by the same individual or at least two distinct individuals.
• a manual manipulation can consist of at least one contact, for example a grasp, by at least part of a hand.
• the security documents considered according to the invention are also intended for use in an ambient atmosphere and not for use in a liquid medium.
• the security document intended to be handled relatively frequently in accordance with the invention may in particular be based on papermaking fibers known to those skilled in the art, for example cellulosic fibers (in particular cotton fibers) and / or organic fibers.
• natural fibers other than cellulosic and / or synthetic fibers for example such as polyester or polyamide fibers, and / or optionally mineral fibers, for example such as glass fibers.
• the security document is based on materials, in particular cellulose fibers, and in particular paper.
• the security document is based on natural organic fibers other than cellulosic.
• the security document is based on plastic materials, and in particular synthetic fibers or a plastic sheet.
• the security document can also be a plastic film, and in particular a bi-stretched film based on polyethylene or polypropylene. It may be, for example, a saturated polyester such as poly (ethylene terephthalate). It can also be a polycarbonate or polyvinyl chloride (PVC) film.
• a plastic film and in particular a bi-stretched film based on polyethylene or polypropylene. It may be, for example, a saturated polyester such as poly (ethylene terephthalate). It can also be a polycarbonate or polyvinyl chloride (PVC) film.
• PVC polyvinyl chloride
• the security document can also be multilayer, in particular laminated or laminated.
• the security document according to the invention incorporates at least one security element allowing the authentication of said sheet.
• said security element is chosen from visual devices, in particular optically variable devices, called OVDs, holograms, lenticular devices, elements with an interference effect, in particular iridescent elements, liquid crystals, pigments with an interference effect. magnetically orientable and multilayer interference structures.
• optically variable devices may be present on security threads embedded in the document or on tapes or patches affixed or printed on the document.
• Another visual security feature is the watermarks made during a banknote manufacturing process.
• said security element can be chosen from so-called luminescent elements, revealable under UV or IR, these luminescent elements being able to be in the form of particles, fibrettes, planchettes, security thread of bands or patches affixed or printed on the security document.
• said security element can be chosen from automatically detectable elements, in particular optically or magnetically, these detectable elements commonly called markers or taggants being integrated into the fibrous substrate or into visual or luminescent security elements.
• a security document according to the invention can also include a radio frequency identification device, called RFID, also providing an identification and traceability function to the security sheet.
• RFID radio frequency identification device
• the security document in accordance with the invention can thus be a passport, a bank note, an identity card, a driving license, an access card, a loyalty card, a photocopy card, a debit card. canteen, a playing card, a collectible card, a means of payment, in particular a payment card.
• the security document considered according to the invention is a security sheet, in particular a printed sheet, which incorporates at least one security element allowing the authentication of the sheet and preferably is a bank note.
• the security document in accordance with the invention is coated on all or part of one of its faces with a deposit of hardened varnish formed from a curable varnish according to the invention.
• the security document may comprise from 0.25 ppm to 3.1 ppm of metal derived from the zero oxidation metal present in the varnish relative to its total weight. It can also include 100 ppm to 1200 ppm of IPBC based on its total weight.
• the security document in accordance with the invention is surface treated, on at least one of its faces, with a hardened varnish film formed from a curable varnish according to the invention.
• the security document face is brought into contact with a curable varnish according to the invention under conditions effective to form a deposit and preferably in the form of a film, of curable varnish and the deposit thus formed is exposed. to radiation to harden said varnish.
• Bringing the varnish into contact with the surface to be treated of the document means that the varnish is deposited on at least part of the surface of the document to be treated.
• the formation of this varnish deposit is carried out under usual conditions.
• the printing processes in particular flexographic, gravure, or screen printing, by spraying, by application with a brush or brush or by any other coating process.
• the varnish is hardened by drying the curable varnish.
• This drying can be carried out by exposure to infrared irradiation or by UV using a suitable lamp.
• the deposit can be formed by applying approximately 0.5 to 5 g / m 2 , in particular 1.5 to 2.5 g / m 2 , or even approximately 1.5 to 2 g / m 2 of curable varnish. .
• the varnish film advantageously makes it possible to give the corresponding security document antibacterial, antifungal and antiviral properties without modifying the appearance of the varnish film or its durability reinforcing properties.
• the antimicrobial activities can in particular be evaluated by the tests of the antifungal, anti-yeast, antibacterial and antiviral properties detailed in the chapter below entitled materials and methods.
• a banknote coated with a hardened varnish derived from a curable varnish according to the invention has an increased resistance to soiling compared to that of an untreated banknote.
• a varnish according to the invention makes it possible to improve the barrier properties, particularly the resistance to soiling of a security document, in particular a bank note, that is to say that this use can in particular prevent or reduce the formation and / or the deposit of dirt.
• Varnishing operations These are carried out recto / verso (R ° / V °) with a 1-group flexographic machine with an in-line UV drying unit, on a 1-sided calendered vellum paper (100% cotton) (i.e. ie provided with a dry stamp without ink produced with the intaglio printing process).
• a 1-group flexographic machine with an in-line UV drying unit
• a 1-sided calendered vellum paper (100% cotton) i.e. ie provided with a dry stamp without ink produced with the intaglio printing process.
• an Anilox value 6 cm 3 / m 2 and a flexographic plate with a solid color are used.
• Anilox corresponds to the surface volume of ink or varnish that the flexographic printing cylinder called "Anilox cylinder" is able to transfer to the flexographic printing plate.
• Influenza A H1N1 ATCC VR1469
• Coronavirus HcoV-229 E Other viral strains can be used, in particular Influenza A H1N1 (ATCC VR1469) or Coronavirus HcoV-229 E.
• Fritsch the resistance to soiling was tested according to the so-called "dry soiling" test (Fritsch test). This is a vibrating device ("Analyette 3 Pro" from the company Fritsch) where small glass balls are spread and encrusted on a paper test tube, a messy composition based on sand, peat, activated carbon, flour. , and glycerin mono-oleate (fatty substance present in sebum). Fe test lasts 15 minutes. The luminance of an initially determined area, in particular without printing, is measured several times before and after exposure to the messy composition. The difference obtained or AF *, makes it possible to characterize the grip of the dirt on the banknote: the lower it is, the better the resistance to dry dirt.
• Test kit The test kit produced according to TAPPI T559 CM-12 standard is used to assess the oil resistance of the sample.
• F gloss is measured at an angle of 60 ° according to ISO 2813.
• a cationic UV varnish composition (viscosity of approximately 60s DIN 4) is prepared from 99.7% of a reference cationic UV varnish (hereinafter “varnish VI”) sold under the reference 889 368 by the company Sicpa and 0.3% Ultrafresh CA16 from Thomson Research Associates Inc.
• varnish VI a reference cationic UV varnish sold under the reference 889 368 by the company Sicpa and 0.3% Ultrafresh CA16 from Thomson Research Associates Inc.
• the varnish VI (100%).
• the two varnishes are applied with an Anilox of 6 cm 3 / m 2 .
• the coatings formed are tested for their resistance to water, dirt and oil according to the protocols described in the Materials and methods chapter.
• Ultrafresh CA16 is prepared according to the protocol detailed below:
• composition according to Example 2 Application of the composition according to Example 2 and characterization of the biocidal properties, and of the barrier properties including the resistance to soiling of the varnish formed.
• the varnishes considered (varnish according to the invention of Example 2 and TEMOIN varnish without Fugitrol or Ultrafresh) are applied with an Anilox of 6 cm 3 / m 2 on the same substrate as Example 1.
• Tables 2 and 3 give an account of the antifungal properties tested according to the protocols detailed in the Materials and methods chapter. Four measurements are carried out on each side of the samples (front and back), ie 8 measurements per sample.
• the substrate with varnish according to the invention exhibits marked bactericidal activity. Indeed, the unvarnished substrate exhibits no or weak protection and the TEMOIN varnished substrate exhibits moderate bacteriostatic protection. The treatment therefore makes it possible to confer effective antibacterial protection.
• Table 5 below gives an account of the barrier properties including the resistance to soiling of the varnish according to the invention compared to the TEMOIN varnish.
• the color changes compared to a ticket with varnish V 1 are very small with the varnish according to the invention and not significant in view of the standard deviations.
• the treatment therefore also has the advantage of not impacting the colors.
• Example 4 Preparation of a composition in accordance with the invention
• Ultrafresh CA 16 is prepared according to the protocol detailed in example 2 with in this case 20 g of Fungitrol C450 incorporated in 977 g of varnish V 1.
• Example 5 Application of the composition according to Example 4 and characterization of the biocidal properties, and barriers including the resistance to soiling of the varnish formed.
• varnishes considered (varnish F1 according to the invention of Example 4 and TEMOIN varnish) are applied with an anilox of 6 cm 3 / m 2 on the same substrate as in Example 1.
• Tables 8 and 9 give an account of the antifungal properties tested as in Example 3 according to the protocols detailed in the Materials and Methods chapter.
• the TEMOIN varnish does not provide antifungal protection, unlike the varnish according to the invention. It can be observed that increasing the amount of IPBC increases the size of the zone of inhibition.
• the varnish according to the invention confers a yeasticidal property on the sample with 100% mortality after 24 hours.
• the substrate with varnish according to the invention exhibits marked bactericidal activity.
• the treatment therefore makes it possible to confer effective antibacterial protection.
• Table 12 below gives an account of the antiviral properties of the varnish according to the invention and of the CONTROL varnish compared to an unvarnished sample indicated as a reference in the table.
• the percentage reduction between T0 and T5h corresponds to the percentage reduction in viral load after 5 hours of contact time.
• the line “antiviral activity vs. reference ” corresponds to the reduction in viral load between T0 and T5h of the sample considered compared to the reference expressed in log.
• the varnish according to the invention has an activity which can be considered as virucidal with a reduction percentage almost equal to 100%.
• the gain compared to the TEMOIN varnish is significant with a reduction of the viral load 220 times greater.
• Table 13 below gives an account of the barrier properties including resistance to soiling and of the varnish according to the invention compared to the TEMOIN varnish.
• the antiviral activity is tested according to the protocol detailed in the Materials and methods chapter and reported in Table 14. The results of the F1 varnish, detailed in Example 5, are also included for comparison.
• the information carrier is also a paper substrate for banknotes based on cotton fibers, related to the paper substrate used for the previous examples.
• the varnishes considered are applied with an Anilox of 7 cm 3 / m 2 on this substrate according to the varnishing protocol detailed in the Materials and methods chapter.
• the antiviral activity is then tested according to the protocol detailed in the Materials and methods chapter.
• Example 8 Application of the composition according to Example 4 on a plastic support and characterization of the biocidal properties of the varnish formed
• a varnish Fl ′ is prepared like the varnish Fl described in Example 4, according to the protocol described in Example 2, the varnish VI being replaced by a varnish sold under the reference 889354 by the company Sicpa (hereinafter "varnish VU"). The contents are expressed as a percentage by mass in the varnish.
• the information medium is a plastic substrate for “Guardian” banknotes marketed by the company CCL Secure.
• the antiviral activities indicated in Table 16 below are characterized using the antiviral control according to the ISO 21702: 2019 standard (measurement of the antiviral activity on plastic surfaces and other non-porous surfaces). [Table 16]
• the antiviral protection of the varnish F1 is verified on a plastic substrate.

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