EP4340610A1 - Composition antivirale pour le traitement de surface d'un article - Google Patents

Composition antivirale pour le traitement de surface d'un article

Info

Publication number
EP4340610A1
EP4340610A1 EP22728625.9A EP22728625A EP4340610A1 EP 4340610 A1 EP4340610 A1 EP 4340610A1 EP 22728625 A EP22728625 A EP 22728625A EP 4340610 A1 EP4340610 A1 EP 4340610A1
Authority
EP
European Patent Office
Prior art keywords
composition
silver
dry weight
article
quaternary ammonium
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.)
Pending
Application number
EP22728625.9A
Other languages
German (de)
English (en)
French (fr)
Inventor
Henri Rosset
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.)
Oberthur Fiduciaire SAS
Original Assignee
Oberthur Fiduciaire SAS
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 Oberthur Fiduciaire SAS filed Critical Oberthur Fiduciaire SAS
Publication of EP4340610A1 publication Critical patent/EP4340610A1/fr
Pending legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
    • 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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A01N25/10—Macromolecular compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02—Amines; Quaternary ammonium compounds
    • A01N33/12—Quaternary ammonium compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/028—Polyamidoamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/028—Polyamidoamines
    • C08G73/0286—Preparatory process from polyamidoamines and epihalohydrins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/028—Polyamidoamines
    • C08G73/0293—Quaternisation of polyamidoamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/02—Polyamines
    • 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
    • C09D129/00—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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/36—Biocidal agents, e.g. fungicidal, bactericidal, insecticidal agents

Definitions

  • the invention relates to a composition for treating the surface of an article, in particular a substrate, in particular a sheet, capable of providing it with antiviral properties.
  • Said article is in particular intended to be touched or handled relatively frequently. It is used in particular for the manufacture of an information medium intended to be handled relatively frequently.
  • the invention aims in particular to propose a substrate, for example a fibrous substrate intended for the manufacture of banknotes, endowed on the surface with improved antiviral properties.
  • the means of payment such as a banknote, a check or a meal ticket, an identity document, such as a identification, visa, passport or driver's license, lottery ticket, transport ticket, tax sticker or stamp, playing card, packaging, book, magazine, etc.
  • the users of these objects may be carriers of pathogenic microorganisms, in particular viruses, liable to generate more or less serious epidemic and pandemic diseases and, in fact, be liable to contaminate any medium in contact with them.
  • this support is intended to be subsequently handled by one or more other users, it in turn becomes an important vehicle for the dissemination of microorganisms, with regard to other people.
  • the banknote As a currency of exchange during commercial transactions, the banknote is one of the most manipulated information carriers in the world and therefore represents a potential vector for the transmission of diseases.
  • Application WO 2012/063176 also describes fluid compositions capable of forming a coating exhibiting antiviral activity, based on virucides of natural origin, such as monolaurin.
  • viruses without envelope or "naked” which consist of a genome, DNA or RNA and a capsid of viral proteins
  • enveloped viruses which have in addition to an envelope consisting of a double lipid layer in which viral proteins are integrated.
  • the family of coronaviruses (Coronaviridae), including the coronavirus SARS-CoV-2, responsible for coronavirus disease 2019 (COVID-19), belongs to this second category of virus.
  • the present invention aims precisely to meet this need.
  • the present invention thus proposes a new composition for the surface treatment of an article, in particular of a substrate, exhibiting particularly advantageous antiviral properties.
  • the invention relates, according to a first of its aspects, to an antiviral composition for the surface treatment of an article, in particular capable of forming a coating on the surface of an article, comprising:
  • PAAE resin at least one polyamide-polyamine-epichlorohydrin resin, called PAAE resin
  • biocidal agents including at least one silver-based compound, in particular a silver salt such as silver chloride (AgCl) and/or a quaternary ammonium-based compound, in particular a salt quaternary ammonium, polymeric or not, in particular didecyl dimethyl ammonium chloride (DDAC).
  • silver salt such as silver chloride (AgCl)
  • DDAC didecyl dimethyl ammonium chloride
  • Said antiviral composition according to the invention more particularly further comprises at least one binding agent, in particular as defined in the following text.
  • a composition according to the invention also comprises at least 3-iodo-2-propynylbutyl carbamate (denoted IPBC) and/or diiodomethyl-p-tolyl sulfone (denoted DIMTS).
  • IPBC 3-iodo-2-propynylbutyl carbamate
  • DIMTS diiodomethyl-p-tolyl sulfone
  • composition according to the invention preferably implements a combination of biocidal agents comprising:
  • At least one silver-based compound in particular a silver salt such as silver chloride (AgCl) and/or a quaternary ammonium-based compound, in particular a quaternary ammonium salt, in particular not polymeric, such as DDAC; and . at least 3-iodo-2-propynylbutyl carbamate (denoted IPBC) and/or diiodomethyl-p-tolyl sulfone (denoted DIMTS).
  • a silver salt such as silver chloride (AgCl)
  • a quaternary ammonium-based compound in particular a quaternary ammonium salt, in particular not polymeric, such as DDAC
  • at least 3-iodo-2-propynylbutyl carbamate denotedoted IPBC
  • DIMTS diiodomethyl-p-tolyl sulfone
  • composition according to the invention comprising at least one PAAE resin and one or more biocidal agents as indicated above, is referred to as the “antiviral treatment composition according to the invention” or more simply “composition according to the invention”.
  • surface treatment is meant the fact of applying a composition to the surface of an article, so that the treated surface has the desired antiviral properties.
  • the surface treatment of an article according to the invention leads to the formation of a localized coating on the surface of said article and/or in the superficial part of the thickness of the article.
  • a surface treatment process according to the invention leads to the formation of a coating located at least at the outer surface of the article, in particular of the substrate, treated according to the invention.
  • the surface treatment according to the invention can lead to the formation of a localized coating totally on the surface of the article, in other words without penetration of the composition into the thickness of the article.
  • Polyamide-polyamine-epichlorohydrin resins known by the abbreviation "PAAE” are cationic resins which are resistant to the wet state, commonly implemented in the mass for the manufacture of paper substrates, in order to improve their resistance to wet state. These resins are then introduced “en masse”, in other words into the fibrous suspension during the production of the paper support.
  • PAAE resins in a formulation intended for the surface treatment of an article, in particular of a substrate, for example for the treatment of a fibrous substrate by surfacing, in combination with one or more biocidal agents, in order to improve the antiviral activity of the coating formed.
  • the presence of the PAAE resin makes it possible to stimulate/reinforce the antiviral activity exhibited by the surface treatment composition comprising at least one compound based on silver and/or based on quaternary ammonium.
  • antiviral or “virucidal” is meant the ability of a compound, composition or coating to inhibit the growth of viruses or to kill viruses.
  • the antiviral composition or coating according to the present invention is more particularly dedicated to inhibiting and/or killing pathogenic viruses with regard to mammals and more particularly to humans.
  • a PAAE resin according to the invention together with one or more biocides as considered according to the invention, preferably a combination of biocides as described above, advantageously allows access to a coating having good antiviral performance, both against naked viruses and enveloped viruses.
  • the antiviral activity of a substrate treated according to the invention can be evaluated according to standard methods, as described in the examples which follow, for example vis-à-vis bacteriophage MS2, virus representative of naked viruses, according to standard ISO18184 :2019-06 and against the human coronavirus Hcov-OC43, an enveloped virus representative of the family of coronaviruses to which SARS-COV2 belongs, according to the ASTME 1053 standard.
  • the invention thus relates, according to another of its aspects, to the use of at least one PAAE resin as an additive for improving the antiviral properties of a composition intended for the surface treatment of an article, in particular of a substrate, in particular a fibrous substrate, comprising one or more biocides including at least one silver-based compound, in particular a silver salt and/or at least one quaternary ammonium-based compound, in particular a quaternary ammonium salt, such as DD AC.
  • an antiviral treatment composition or a coating formed according to the invention combines at least one PAAE resin, at least one silver-based compound, in particular a silver salt such as silver chloride and preferably at least IPBC and/or DIMTS.
  • an antiviral treatment composition or a coating formed according to the invention combines at least one PAAE resin, at least one quaternary ammonium-based compound, in particular a quaternary ammonium salt, such as DDAC and preferably at least IPBC and/or DIMTS.
  • compositions according to the invention can be intended for the surface treatment of various articles, in particular of substrates, in particular in sheet form, and more particularly intended to be handled frequently by a large number of people, and therefore capable of carrying pathogenic microorganisms, in particular viral ones.
  • substrates in particular in sheet form
  • pathogenic microorganisms in particular viral ones.
  • sheet substrates for packaging or for the production of information carriers.
  • they can be intended for the surface treatment of a substrate, in particular of a sheet, intended for the manufacture of an information carrier, in particular of a fibrous substrate intended for the manufacture of a document secured.
  • security documents can be cited banknotes, manipulated at least hundreds of times during their lifetime.
  • the present invention also describes a process for treating the surface of an article, in particular a substrate, intended to provide it with antiviral properties, comprising the application to the surface of said article of a composition or several compositions, comprising at at least one PAAE resin and one or more biocides including at least one silver-based compound, in particular a silver salt and/or at least one quaternary ammonium-based compound, in particular a quaternary ammonium salt, such as DDAC.
  • a composition or several compositions comprising at at least one PAAE resin and one or more biocides including at least one silver-based compound, in particular a silver salt and/or at least one quaternary ammonium-based compound, in particular a quaternary ammonium salt, such as DDAC.
  • It relates more particularly to a process for treating the surface of an article, in particular a substrate, intended to provide it with antiviral properties, comprising: the application to the surface of said article of a composition or several compositions, comprising at least one PAAE resin and one or more biocides including at least one silver-based compound, in particular a silver salt and/or at least one quaternary ammonium-based compound, in particular an ammonium salt quaternary, such as DDAC; and the formation of a coating present at least on the surface of said treated article, comprising at least said PAAE resin and said biocidal agent or agents.
  • the surface treatment method according to the invention may comprise the application to the surface of said article of a single antiviral treatment composition according to the invention, as defined previously, combining at least said PAAE resin and said biocide(s) mentioned above.
  • the invention also relates to the use of a composition according to the invention, comprising at least one PAAE resin and one or more biocides including at least one silver-based compound, in particular a silver salt and/or at at least one quaternary ammonium compound, in particular a quaternary ammonium salt, such as DDAC, to impart antiviral properties to all or part of the surface of an article, in particular to all or part of the surface of at least one of the faces of a substrate.
  • the surface treatment method according to the invention may comprise the successive application of at least two distinct compositions comprising, taken in combination, at least said PAAE resin and the said biocide(s) mentioned above, a step drying that can optionally be implemented between two application steps.
  • the said composition(s) for the surface treatment of the substrate can more particularly be applied by spraying, sizing, impregnation, printing, overprinting on an at least partially printed surface, surfacing, coating or depositing on the surface to be treated.
  • the invention also relates to a method for forming an antiviral coating on all or part of the surface of at least one of the faces of an article, in particular of a substrate, said method comprising the application on the surface said article of a composition or several compositions, comprising at least one PAAE resin and one or more biocides including at least one silver-based compound, in particular a silver salt and/or at least one silver-based compound quaternary ammonium, in particular a quaternary ammonium salt, such as DD AC.
  • the invention relates to an article surface-treated by a process according to the invention, as defined above, said article being in particular a substrate, in particular in sheet form.
  • the invention relates more specifically to a substrate, in particular a sheet, in particular intended for the manufacture of an information carrier, in particular of a fibrous substrate intended for the manufacture of a secure document, such as a banknote, provided on at least part of one of its faces, with a coating such as obtained from an antiviral treatment composition according to the invention, incorporating at least one PAAE resin and one or several biocides including at least one silver-based compound, in particular a silver salt, and/or at least one quaternary ammonium-based compound, in particular a quaternary ammonium salt, such as DD AC.
  • a process for manufacturing a substrate as defined above comprising at least one step of forming, over all or part of the surface of at least one of the faces of said substrate, a coating incorporating at least said PAAE resin and the said biocide(s) considered according to the invention, including at least one silver-based compound, in particular a silver salt, and/or at least one quaternary ammonium-based compound, in particular a quaternary ammonium salt, such as DDAC.
  • composition(s) implemented for the surface treatment according to the invention can comprise one or more additional compounds, in particular with regard to their mode of application and their destination.
  • composition preferably comprises an aqueous surfacing agent preferably incorporating glycerol.
  • the antiviral treatment compositions according to the invention can be, for example, compositions, in particular aqueous, of varnish, in particular of overprint varnish, of ink or of lacquer.
  • a composition according to the invention may contain, in addition to said PAAE resin and said biocide or biocides, in particular said aforementioned combination of biocidal agents, at least one of the components conventionally considered in this type of coating formulations, for example at least one agent binder, as described in the following text.
  • the invention combines, in order to access particularly advantageous antiviral properties, at least one PAAE resin with one or more biocidal agents, including at least one silver-based compound, in particular a silver salt and/ or a quaternary ammonium compound, in particular DD AC.
  • a composition according to the invention may comprise one or more polyamide-polyamine-epichlorohydrin resins, denoted PAAE resins.
  • PAAE resin denotes a single PAAE resin or a mixture of at least two PAAE resins.
  • polyamide-polyamine-epichlorohydrin resins also called “polyamide amine epichlorohydrin”
  • polyamide amine epichlorohydrin are usually used in papermaking, by being introduced into the mass of the cellulosic fibrous substrate, in order to give the paper material a resistance in the wet state. .
  • the PAAE resin implemented according to the invention may in particular be a polymer of adipic acid, diethylenetriamine and epichlorohydrin.
  • the PAAE resin can be prepared by synthetic routes known to those skilled in the art, by implementing a first step of condensation between adipic acid and diethylenetriamine, followed by the reaction of the polyamide polyamine resin thus formed with the epichlorohydrin to form said PAAE resin.
  • PAAE resins are also commercially available.
  • the PAAE resin has a low chloride content.
  • Such resins with a low chloride content are particularly advantageous in the field of banknotes, in order to limit the risks of corrosion of security elements, in particular magnetic elements, for example security threads, which are sometimes sensitive to corrosion.
  • An antiviral treatment composition according to the invention may in particular comprise from 0.015 to 0.6% by dry weight, in particular from 0.075 to 0.45% by dry weight and more particularly from 0.075 to 0.3% by dry weight of resin (s) PAAE, relative to the total weight of said composition.
  • dry weight also called “weight of active material” is meant the mass content of said compound, without any volatile solvents in which it is formulated, for example water.
  • the amount of PAAE resin(s) in a surface treatment composition according to the invention is preferably between 0.24 and 8.82% by dry weight, in particular between 1.2 and 6.66% by dry weight and more particularly from 1.2 to 4.6% relative to the total dry weight of the composition.
  • the total dry weight of the composition means the sum of the masses of the compounds used in the formulation of said composition, excluding volatile solvents, in particular the water. These volatile solvents are eliminated during the formation of the coating according to the invention, after drying of the composition applied to the surface of the article.
  • the content of a given compound expressed as a percentage by dry weight relative to the total dry weight of the composition according to the invention, thus corresponds to the mass percentage by dry weight of said compound relative to the dry weight of the coating formed from said composition.
  • an antiviral treatment composition comprises, as biocidal agent(s), at least one silver-based compound, in particular a silver salt and/or at least a compound based on quaternary ammonium, in particular a quaternary ammonium salt, for example didecyl dimethyl ammonium chloride (DDAC).
  • biocidal agent(s) at least one silver-based compound, in particular a silver salt and/or at least a compound based on quaternary ammonium, in particular a quaternary ammonium salt, for example didecyl dimethyl ammonium chloride (DDAC).
  • DDAC didecyl dimethyl ammonium chloride
  • biocidal agent or “biocide”, equivalent to the terms “anti-microbial agent”, designate, in general, any agent effective in regulating and/or inhibiting the growth and/or reduce the density of microorganisms such as viruses, fungi, bacteria, yeasts, etc.
  • biocidal agent or the combination of biocidal agents as considered according to the invention advantageously exhibits an antimicrobial effect against viruses, in other words an antiviral or virucidal activity, in particular both vis-à-vis naked viruses and enveloped viruses.
  • Silver compounds in particular silver salts, and quaternary ammonium compounds, in particular quaternary ammonium salts, are known as antimicrobial agents and/or microbicides, in particular as bacteriostatic agents (or antibacterials) and/or bactericides.
  • Silver-based compounds having antimicrobial properties are known to those skilled in the art.
  • silver salts in particular chosen from silver nitrate, chloride or thiosulphate.
  • the silver salt used as antimicrobial agent according to the invention is silver chloride. It may also be silver in a supported particulate form. The silver (zero degree of oxidation) is more particularly supported by a particulate inorganic material, for example chosen from zeolites and glasses, in particular phosphated.
  • the particle size of the material loaded or further doped with silver is 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 less than said diameter.
  • the loading rate of the zero degree silver material varies in particular from 0.5% to 3%, in particular from 1.0% to 2.5%, by weight relative to its total loaded weight.
  • the silver implemented as an antimicrobial agent according to the invention is silver supported by a particulate material made of glass and preferably of phosphated glass. More specifically, the silver metal is in the form of silver particles in a phosphate glass matrix. This matrix has the advantage of being permeable to silver Ag + ions and therefore of allowing passage/mobility of silver Ag + ions. These Ag + ions which have bactericidal activity are generated by bringing silver of zero oxidation state, dispersed in the surface treatment composition, into contact with ambient humidity or during contamination, for example by droplets in particular of sputum.
  • a material of this type is sold in particular under the name Ultrafresh CA 16 by the company Thomson Research Associates Inc.
  • Quaternary ammonium compounds in particular quaternary ammonium salts, are also known as antimicrobial and/or microbicidal agents, and more particularly as bacteriostatic (or antibacterial) and/or bactericidal and/or fungistatic (or antifungal) agents ) and/or fungicides.
  • Quaternary ammonium salts generally include at least one quaternary ammonium cation with an appropriate anion.
  • the cation is more particularly of the following structure:
  • Ri, R 2 , R 3 and R 4 being able to be of various nature.
  • Ri, R 2 , R 3 and R 4 can be chosen, independently of each other, from alkyl, aryl, alkylaryl, arylalkyl, cycloalkyl, heterocyclic aromatic or non-aromatic, or alkenyl groups, said groups possibly being substituted or not, linear or branched, and optionally interrupted by one or more heteroatoms, for example, by one or more oxygen atoms, or by one or more phosphinate groups.
  • two or more of the groups Ri, R 2 , R 3 and R 4 can together form, with the nitrogen atom which supports them, a substituted or unsubstituted heterocyclic ring.
  • the groups Ri, R 2 , R 3 and R 4 are alkyl groups, preferably linear, in particular C 1 to C 20 .
  • the Ri, R 2 , R 3 and R 4 groups together comprise at least four carbon atoms.
  • the total number of carbon atoms of the groups Ri, R 2 , R 3 and R 4 can be at least 10.
  • at least one of the groups Ri, R 2 , R 3 and R 4 , in particular two of Ri, R 2 , R 3 and R 4 comprise from 6 to 20 carbon atoms, in particular from 8 to 18 carbon atoms.
  • the anion of the quaternary ammonium salt may in particular be chosen from halide anions, for example chloride, fluoride, bromide or iodide, and sulphonate anions.
  • the anion of the quaternary ammonium salt can be a chloride.
  • non-polymeric quaternary ammonium salts may more particularly have the following formula:
  • the quaternary ammonium salt used as an antimicrobial agent according to the invention can be of formula ( ⁇ 3 ⁇ 4) h (A) pi N + C , in which n is 2 and m is 2 and A, identical or different, are as defined above for Ri, R 2 , R 3 and R 4 .
  • A which are identical or different, in particular identical, can represent linear C 8 to C 20 , in particular C s to C 12 , in particular C s to C 12 , linear alkyl groups.
  • an antiviral treatment composition according to the invention uses at least didecyl dimethyl ammonium chloride (DDAC).
  • the quaternary ammonium-based compound can also be a polymeric quaternary ammonium salt, that is to say a compound whose chemical formula includes a repetition of “quaternary ammonium” units.
  • Such a so-called polymeric quaternary ammonium salt can be derived from at least one compound of formula (I) of which at least one of Ri, R 2 , R 3 and R 4 carries a polymerizable function, in particular d a function containing ethylenic unsaturation(s) and more particularly chosen from (meth)acrylate and allylic functions.
  • the compound based on quaternary ammonium can be obtained by polymerization of at least one quaternary ammonium salt of formula (I) above, in which two of Ri, R 2 , R 3 and R 4 are groups carriers of an allylic function, in particular are allylic groups; the others preferably being alkyl groups, in particular C1 to C6, in particular C1 to C 4 , in particular methyl groups.
  • the compound based on quaternary ammonium is a polymer of diallyldialkylammonium chloride.
  • it may be the polymer of diallyldimethylammonium chloride, denoted polyDADMAC.
  • PolyDADMAC can be synthesized by radical polymerization of DADMAC in the presence of a peroxide as a catalyst; or else be commercially available.
  • a composition according to the invention may comprise at least one biocidal agent chosen from silver salts, in particular silver chloride, silver in a form supported particle, in particular supported by a particulate inorganic material, for example glass and preferably phosphate glass; quaternary ammonium salts, polymeric or non-polymeric, in particular chosen from didecyl dimethyl ammonium chloride (DD AC) and diallyldialkylammonium chloride polymers, for example diallyldimethylammonium chloride polymer (polyDADMAC), and mixtures thereof.
  • DD AC didecyl dimethyl ammonium chloride
  • polyDADMAC diallyldialkylammonium chloride polymers
  • An antiviral treatment composition according to the invention preferably comprises the said biocidal compound(s) based on silver, in particular of the silver salt(s) type, and/or the said compound(s) ) biocide(s) based on quaternary ammonium, in particular of the quaternary ammonium salt(s) type, in an amount of 0.004 to 1% by dry weight, in particular from 0.004 to 0.75% by dry weight, by relative to the total weight of the treatment composition.
  • the said biocidal compound(s) based on silver are present in a proportion of 0.004 to 0.04% by dry weight, in particular from 0.004 to 0.02% by dry weight , relative to the total weight of the treatment composition.
  • the said biocidal compound(s) based on quaternary ammonium, in particular as defined previously, for example DD AC are present in a proportion of 0.05 to 1% by dry weight, in particular of 0.25 to 0.75% by dry weight, relative to the total weight of the treatment composition.
  • the said biocidal compound(s) based on silver ions, in particular of the silver salt type, and/or the said biocidal compound(s) based on quaternary ammonium, in particular as defined above, preferably represent 0.07 to 18% by dry weight, in particular from 0.07 to 14% by dry weight, relative to the total dry weight of the antiviral composition.
  • the said biocidal compound(s) based on silver are present in a proportion of 0.07 to 0.7% by dry weight, in particular of 0.07 to 0.35 % by dry weight, relative to the total dry weight of the antiviral composition.
  • a composition according to the invention comprises a combination of biocides comprising:
  • IPBC 3-iodo-2-propynylbutyl carbamate
  • DIMTS diiodomethyl-p-tolyl sulfone
  • IPBC and DIMTS are more particularly known as fungistatic and/or fungicidal agents.
  • an antiviral treatment composition according to the invention preferably combines:
  • bacteriostatic and/or bactericidal agent chosen from silver-based compounds, in particular silver salts such as silver chloride, quaternary ammonium-based compounds, in particular salts of polymeric or non-polymeric quaternary ammonium compounds, such as DDAC or polyDADMAC, and mixtures thereof;
  • IPBC 3-iodo-2-propynylbutyl carbamate
  • DIMTS diiodomethyl-p-tolyl sulfone
  • 3-iodo-2-propynylbutyl carbamate also called “iodopropynyl butylcarbamate” and noted “IPBC”
  • diiodomethyl-p-tolyl sulfone also called “p-[(diiodomethyl)sulphonyl] toluene” and noted “DIMTS”
  • fungistatic and/or fungicidal agents and algistatic and/or algicidal agents. They generally come in the form of an aqueous dispersion.
  • biocidal agents are commercially available.
  • An antiviral treatment composition according to the invention preferably comprises T IPBC and/or DIMTS in an amount of 0.1 to 0.6% by dry weight, in particular from 0.2 to 0.6% by dry weight, per relative to the total composition weight.
  • an antiviral treatment composition according to the invention comprises at least one silver-based compound, in particular a silver salt, in particular silver chloride and at least IPBC.
  • a composition according to the invention comprises at least one compound based on quaternary ammonium, in particular a quaternary ammonium salt, in particular DDAC and at least IPBC.
  • a composition according to the invention comprises at least one silver salt, in particular silver chloride, and at least DIMTS.
  • a composition according to the invention comprises at least one compound based on quaternary ammonium, in particular a quaternary ammonium salt, in particular DDAC, and at least DIMTS.
  • composition according to the invention may comprise one or more additional biocides, other than the specific compounds mentioned above.
  • biocidal compounds may be of various natures provided that they do not impact the effect of the combination according to the invention of said PAAE resin with said silver-based and/or ammonium-based compound(s). aforesaid quaternary, if necessary combined with IPBC and/or DIMTS.
  • biocides can be chosen from bacteriostatic, bactericidal, fungistatic, yeasticidal, fungicidal and/or virucidal agents.
  • They may be, for example, compounds based on isothiazoline or derivatives of isothiazolone, compounds based on chitosan or derivatives of chitin, zinc zeolite, triclosan and mixtures thereof.
  • composition according to the invention may in particular comprise one or more additional virucides, for example of natural origin.
  • coronaviruses for example SARS-COV2, HcoV-OC43 or HcoV-229E
  • retroviruses for example SARS-COV2, HcoV-OC43 or HcoV-229E
  • cytomegaloviruses for example SARS-COV2, HcoV-OC43 or HcoV-229E
  • paramyxoviruses for example SARS-COV2, HcoV-OC43 or HcoV-229E
  • paramyxoviruses for example SARS-COV2, HcoV-OC43 or HcoV-229E
  • polioviruses for example SARS-COV2, HcoV-OC43 or HcoV-229E
  • retroviruses for example SARS-COV2, HcoV-OC43 or HcoV-229E
  • retroviruses for example SARS-COV2, HcoV-OC43 or HcoV-229E
  • cytomegaloviruses for example SARS-COV2, HcoV-OC43 or H
  • virucide of natural origin we mean any virucide that pre-exists in nature or that can be synthesized from natural compounds that exist in nature.
  • the virucides of natural origin that can be used in the context of the present invention can thus be obtained either by extraction and purification from a natural medium containing them, or by synthesis from natural compounds.
  • virucides By way of example of such virucides, mention may in particular be made of monolaurin which can be obtained by synthesis from glycerol and lauric acid.
  • monolaurin is intended to designate both monolaurin that preexists naturally and that obtained by synthesis from glycerol and lauric acid.
  • the virucide of natural origin can be chosen in particular from monolaurin, lactoferrin and essential oils exhibiting antiviral activity, such as for example laurel essential oil.
  • an antiviral treatment composition according to the invention does not comprise any biocidal agent other than the said compound(s) based on silver ions and/or based on quaternary ammonium, where appropriate. combined with IPBC or DIMTS as previously described.
  • the potentiating effect of the antiviral activity obtained due to the addition of said PAAE resin, makes it possible to envisage the implementation of a total quantity of biocidal agents, in particular virucidal agents, reduced.
  • an antiviral treatment composition according to the invention comprises a total content by dry weight of biocidal agents, in particular as considered according to the invention, less than or equal to 1%, in particular between 0, 1 and 0.7% by weight, relative to the total weight of said composition.
  • said biocidal agent(s) as considered according to the invention in particular said silver and/or quaternary ammonium salt(s), optionally combined with IPBC and/or DIMTS, preferably represent from 1.5 to 15% by dry weight, in particular from 1.5 to 10% by dry weight, relative to the total dry weight of said composition.
  • a surface treatment composition according to the invention may comprise at least:
  • bacteriostatic and/or bactericidal agents chosen from silver-based compounds, in particular salts of silver such as silver chloride, compounds based on quaternary ammonium, in particular polymeric or non-polymeric quaternary ammonium salts such as DD AC and polyDADMAC; and mixtures thereof;
  • fungistatic agents and/or fungicides chosen from 3-iodo-2 carbamate - propynylbutyl (IPBC), diiodomethyl-p-tolyl sulfone (DIMTS) and mixtures thereof, the contents being expressed relative to the total dry weight of said composition.
  • IPBC 3-iodo-2 carbamate - propynylbutyl
  • DIMTS diiodomethyl-p-tolyl sulfone
  • an antiviral treatment composition according to the invention is adjusted with regard to the application for which it is intended, for example as varnish, in particular overprint varnish, ink, lacquer, etc. and the mode of application considered for treating the surface of the substrate with said composition, as detailed in the following text.
  • a composition according to the invention is preferably a fluid composition, in particular having a viscosity, measured at 60° C., of between 30 mPa.s and 40 Pa.s, in particular between 50 mPa.s and 25 Pa.s.
  • the viscosity of a composition can be measured by conventional methods.
  • a Brookfield viscometer with axis No. 2 at 100 revolutions per minute (ISO 2555) is preferred as measuring equipment.
  • This viscosity can be adjusted with regard to the destination of the composition and its mode of application.
  • the viscosity of the treatment composition according to the invention can in particular be adjusted via the nature and/or quantity of the solvent medium associated with the compounds required according to the invention, or even via the addition and adjustment of the quantity of binder ( s) if present at the level of a composition according to the invention.
  • An antiviral treatment composition according to the invention may comprise an aqueous or organic solvent medium.
  • the solvent medium is chosen in particular with regard to the type of composition targeted.
  • the solvent medium can be monophasic or biphasic.
  • a solvent medium according to the invention may be in the form of an oil-in-water or water-in-oil emulsion.
  • composition according to the invention may comprise, as solvent medium, water, an organic solvent, an oil or a mixture thereof.
  • a composition according to the invention is an aqueous composition, the solvent medium preferably being formed of water.
  • it may comprise said PAAE resin and said biocidal agent or agents considered according to the invention in water.
  • An antiviral treatment composition according to the invention may also comprise one or more additional components, in particular chosen from the compounds conventionally used in the type of composition considered, provided that their presence does not affect the antiviral properties conferred by the combination of said PAAE resin and said biocidal agent(s) according to the invention.
  • a composition according to the invention comprises at least one binder, in particular a polymer binder.
  • a composition according to the invention also comprises at least one pigment.
  • Binding agents are in particular compounds conventionally used in compositions intended for the treatment of paper, varnish and/or ink. Their function is generally to ensure the dispersion of the particles such as the pigments if present within the composition and to contribute, after drying and/or crosslinking of the composition applied to the surface of a support, to the formation of a film of sufficient hardness to ensure its durability.
  • the binding agents can be chosen in particular from resins, waxes, gums and mixtures thereof.
  • the resins can be chosen in particular from cycloaliphatic, acrylic, vinyl, ketone, polyester, polyurethane and aldehyde epoxy resins.
  • waxes that can be used according to the invention, mention may be made of:
  • - mineral waxes for example paraffin, petroleum jelly, lignite or microcrystalline waxes or ozokerites
  • waxes including polyolefin waxes, in particular polyethylene waxes, and waxes obtained by Fisher-Tropsch synthesis,
  • silicone waxes in particular linear substituted polysiloxanes; mention may be made, for example, of polyether silicone waxes, alkyl or alkoxy-dimethicones having from 16 to 45 carbon atoms, alkyl methicones such as the C30-C45 alkyl methicone sold under the trade name "AMS C 30" by
  • waxes suitable for the invention mention may in particular be made of hydrocarbon waxes such as beeswax, lanolin wax, and China insect waxes; rice bran wax, carnauba wax, candelilla wax, ouricury wax, esparto wax, berry wax, shellac wax, japan wax and sumac wax; montan wax, orange and lemon waxes, microcrystalline waxes, paraffins and ozokerite; polyethylene waxes, waxes obtained by the Fisher-Tropsch synthesis and waxy copolymers as well as their esters.
  • hydrocarbon waxes such as beeswax, lanolin wax, and China insect waxes
  • montan wax orange and lemon waxes, microcrystalline waxes, paraffins and ozokerite
  • the gums can be chosen, for example, from gum arabic, gum tragacanth, cassia gum, gutter gum, shellac gum, sandarac gum, mastic gum or gum resin.
  • a composition according to the invention in particular an aqueous composition according to the invention, comprises at least one binder, in particular hydrophilic, in particular a polymer binder, and more particularly a binder chosen from polyalcohols, of preferably polyvinyl alcohols (PVA).
  • PVA polyvinyl alcohols
  • An antiviral treatment composition according to the invention preferably comprises from 1 to 40% by dry weight, in particular from 2 to 20% by dry weight, of one or more binders, in particular of PVA type, relative to the total weight of composition.
  • the said binder(s), in particular of the PVA type are present in a mass proportion by dry weight of between 30 and 90% by dry weight, in particular between 50 and 80% by dry weight, relative to the total dry weight. of said composition.
  • a composition according to the invention may also comprise at least one humectant. This is in particular the case for a composition intended to be applied by surface surfacing of a substrate.
  • a humectant is a compound capable of providing a moisturizing or hygroscopic effect.
  • humectants can be very particularly considered, in the context of the present invention, compounds of the polyol type, such as, for example, glycerin, also called glycerol, propylene glycol, polyethylene glycol, butylene glycol, glyceryl triacetate, or even sorbitol.
  • the humectant considered is chosen from the following compounds: pidolic acid (PCA) and its derivatives (arginine PCA, copper PCA, ethylhexyl PCA, lauryl PCA, magnesium PCA, sodium PCA, zinc PCA, etc.
  • the humectant is chosen from polyols and more particularly glycerol.
  • An antiviral treatment composition according to the invention may preferably comprise from 0.5 to 4% by dry weight, for example from 1 to 3% by dry weight, of humectant(s), and in particular of glycerol , relative to its total weight.
  • an antiviral treatment composition according to the invention may comprise, in a solvent medium, in particular in an aqueous solvent medium:
  • biocides including at least one silver-based compound, in particular a silver salt and/or a quaternary ammonium-based compound, in particular a quaternary ammonium salt, as described previously, in particular at least silver chloride and/or DD AC, and preferably at least one fungistatic and/or fungicidal agent chosen from 3-iodo-2-propynylbutyl carbamate (IPBC), diiodomethyl-p -tolyl sulfone (DIMTS) and mixtures thereof;
  • IPBC 3-iodo-2-propynylbutyl carbamate
  • DIMS diiodomethyl-p -tolyl sulfone
  • At least one binder in particular a polyvinyl alcohol (PVA);
  • PVA polyvinyl alcohol
  • At least one additive in particular at least one humectant such as glycerol.
  • a surface treatment composition according to the invention comprises:
  • fungistatic and/or fungicidal agent chosen from IPBC and/or DIMTS;
  • the antiviral treatment composition is an aqueous composition, in particular an aqueous surfacing composition. It preferably comprises at least one humectant, in particular glycerol.
  • an antiviral composition according to the invention is intended for the surface treatment of an article.
  • the articles or objects considered according to the invention are in particular objects or articles capable of carrying viruses, and therefore articles intended to be touched or handled relatively frequently.
  • an article intended to be handled relatively frequently is an article 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 the hand.
  • substrates in particular intended for the manufacture of an information medium, for example banknotes or cards such as smart cards, or intended for packaging; plastic objects such as, for example, computer keyboards and mice, touch screens, keyboards, screens and telephone handsets, children's toys, care, medical or health instructions, fingernails, music, work clothes, tools, upholstery, handles, knobs, packaging.
  • plastic objects such as, for example, computer keyboards and mice, touch screens, keyboards, screens and telephone handsets, children's toys, care, medical or health instructions, fingernails, music, work clothes, tools, upholstery, handles, knobs, packaging.
  • Said object is for example made of a material chosen from among glass, paper, cardboard, plastic, a textile, etc.
  • the invention relates to the surface treatment of a substrate, in particular in the form of a sheet.
  • the substrate treated according to the invention can be of varied nature.
  • the substrate under consideration according to the invention may in particular be a porous substrate, in particular fibrous, and more particularly a paper based on fibers known to those skilled in the art, for example cellulosic fibers (in particular cotton fibers) and/ or natural organic fibers other than cellulose and/or synthetic fibers, for example polyester or polyamide fibers, and/or optionally mineral fibers, for example glass fibers.
  • cellulosic fibers in particular cotton fibers
  • natural organic fibers other than cellulose and/or synthetic fibers
  • polyester or polyamide fibers for example polyester or polyamide fibers
  • optionally mineral fibers for example glass fibers.
  • the substrate in particular of the paper type, has a weight of between 10 g/m 2 and 300 g/m 2 , more particularly between 50 g/m 2 and 150 g/m 2 , or even between 65 g/m 2 and 150 g/m 2 .
  • the grammage can be measured by conventional methods, for example according to ISO 536:2019.
  • the substrate considered according to the invention in particular in the form of a sheet, is based on cellulosic fibers.
  • the substrate considered according to the invention in particular in the form of a sheet, is based on natural organic fibers other than cellulosic.
  • the substrate considered according to the invention in particular in the form of a sheet, is based on plastic materials, and in particular synthetic fibers.
  • the substrate may be a plastic film, and in particular a bi-stretched film based on polyethylene like the Polyart® material marketed by the company Arjobex. It is more particularly a sheet comprising a coextruded support, made from at least one polymer material, comprising for example a core layer and at least one skin layer, the core layer comprising voids.
  • the synthetic substrate can also be made of BOPP (bi-oriented polypropylene), in particular a film based on BOPP, in particular for banknotes. Such films are, for example, marketed under the names Guardian by the company CCL Secure and Safeguard by the company De La Rue.
  • the substrate can also be a multilayer substrate, in particular laminated or laminated. Said multilayer substrate comprises in particular at least one layer based on cellulosic or plastic materials as described previously.
  • the synthetic substrate may in particular be a paper-plastic multilayer hybrid substrate, for example paper-plastic-paper or plastic-paper-plastic, such as the substrates for security documents marketed under the names EverFit by the Banque de France, Hybrid by the Fouisenthal Company, Durasafe by the Fandqart Company.
  • the substrate considered according to the invention is based on mineral fibers.
  • the substrate under consideration according to the invention may be intended in particular for the preparation of an information medium, in particular an information medium intended to be handled relatively frequently.
  • Fe information medium considered according to the invention can be a passport, an identity card, a driver's license, an access card, a loyalty card, a photocopy card, a canteen card, a credit card. game, a collectible card, a means of payment, in particular a payment card, a banknote, a purchase voucher or a receipt, a ticket for access to cultural or sporting events, a certificate of authenticity, or even a packaging, a book, a geographical map, a label, an envelope or a magazine.
  • the present invention finds particular application in the field of secure documents, in particular banknotes.
  • the substrate considered according to the invention can thus be a substrate for a secure document, in particular a substrate, in particular in sheet form, intended for the manufacture of banknotes.
  • the invention thus relates to an information medium, in particular a security document, in particular a banknote, comprising a substrate treated according to the invention.
  • the substrate for the secure document may comprise a watermark, as well as any other usual security elements, of first, second or third level.
  • security elements some are detectable by eye, in daylight or in artificial light, without the use of a particular device.
  • additional security elements include, for example, colored fibers or planks, threads printed or metallized totally or partially. These security elements are said to be first level.
  • security elements can only be detected using a relatively simple device, such as an ultraviolet (UV) or infrared (IR) emitting lamp.
  • UV ultraviolet
  • IR infrared
  • These security elements include, for example, fibers, boards, bands, threads or particles. These security elements may or may not be visible to the naked eye, being for example luminescent under the illumination of a Wood lamp emitting at a wavelength of 365 nm. These security elements are said to be of second level.
  • Other types of security elements require a more sophisticated device for their detection. These security elements are for example capable of generating a specific signal when they are subjected, simultaneously or not, to one or more external excitation sources. The automatic detection of the signal makes it possible to authenticate, if necessary, the document.
  • These security elements comprise, for example, tracers in the form of active materials, particles or fibers, capable of generating a specific signal when these tracers are subjected to optronic, electrical, magnetic or electromagnetic excitation. These security elements are said to be third level.
  • the security element(s) present within the secure document according to the invention may have first, second or third level security characteristics.
  • the method according to the invention is a surface treatment method.
  • it is intended to form a coating (film or layer) comprising the compounds required according to the invention, located on the surface of said article and/or in the superficial part of the thickness of the article.
  • the surface treatment method according to the invention may thus comprise the penetration of said composition(s) implemented into the superficial part of the thickness of the substrate.
  • the composition or said compositions for the surface treatment according to the invention penetrate(s) the substrate over less than 15% of its thickness, in particular over less than 10% of its thickness.
  • the surface treatment method according to the invention therefore differs from so-called "mass” treatments, which aim to incorporate one or more compounds at the level of the mass of the substrate, most often at the time of its design, for example in the fibrous suspension during the development of the paper support.
  • the surface treatment process according to the invention leads to a coating present at least on the surface of said treated article, preferably only on the surface of said article (without penetration).
  • the method according to the invention does not include steps for forming one or more layers superimposed on the antiviral coating formed according to the invention comprising at least said PAAE resin and said biocidal agent or agents.
  • the article treated according to the invention has at least one of its faces, said surface coating; in other words, said antiviral coating forms at least part of the external surface of the article treated according to the invention.
  • the surface treatment process according to the invention proceeds more particularly by applying, to the surface to be treated of said article, a composition or several compositions, the said composition(s) comprising at least the said PAAE resin and at least the said agent(s). biocides as considered according to the invention, followed by a drying step.
  • the coating formed according to the invention can be obtained via the application of an antiviral treatment composition according to the invention as described previously, in particular of a single antiviral treatment composition according to the invention, or, alternatively, by the successive application of at least two distinct compositions.
  • the antiviral treatment method according to the invention comprises the application of an antiviral treatment composition according to the invention, as defined previously, comprising at least said PAAE resin and at least the said biocides including at least one compound based on silver and/or based on quaternary ammonium, for example silver chloride and/or DDAC, followed by a drying step.
  • an antiviral treatment composition according to the invention comprising at least said PAAE resin and at least the said biocides including at least one compound based on silver and/or based on quaternary ammonium, for example silver chloride and/or DDAC, followed by a drying step.
  • the antiviral treatment method according to the invention comprises the successive application of at least two distinct compositions, said compositions comprising, taken in combination, at least said PAAE resin and at least said biocide(s) as considered according to the invention, a drying step possibly being implemented between two application steps, followed by a drying step.
  • each of the compositions can have the characteristics as indicated previously for a composition according to the invention, in particular in terms of nature of the solvent medium and of additional compounds possibly present.
  • compositions are adjusted to allow the formation of a coating, as obtained from a single antiviral treatment composition according to the invention, said coating incorporating all of the compounds required according to the invention to lead to the manifestation of the desired effect in terms of potentiation of the antiviral activity by said PAAE resin.
  • Said composition(s) can be applied to the surface of said article, in particular of said substrate, by spraying, sizing, impregnation, printing, for example by offset printing, by gravure printing, by flexography; overprinting on an at least partially printed surface, for example by flexographic overprinting; surfacing, coating or depositing on the surface to be treated.
  • composition(s) for the surface treatment according to the invention is adjusted with regard to the nature of the article whose surface is to be treated.
  • said composition or compositions in particular for application to the surface of a substrate, in particular fibrous, are applied by surfacing, sizing or coating.
  • the treatment can be localized on a part of the surface of the article, or be carried out on the entire surface of the article.
  • the treatment can be localized on a part of at least one of the faces of the substrate and, in general, more particularly on the face intended to be touched or handled.
  • a drying step is implemented after application of said composition(s) to the surface of the article, this drying step being intended in particular to remove the solvent(s) present in said composition(s).
  • the antiviral treatment composition according to the invention may for example constitute a composition, in particular aqueous, of varnish, in particular of overprint varnish, of ink, of lacquer or of paint.
  • the said binder(s) present in the composition may be, for example, a varnish or a cellulose, polyurethane or acrylic ink.
  • the treatment is carried out on the two opposite faces of the substrate, in particular of the sheet substrate.
  • the process for surface treatment of a substrate according to the invention can comprise the deposition on at least one faces, in particular on the two opposite faces of said substrate, preferably by surfacing, sizing or coating, of an antiviral treatment composition according to the invention, preferably of an aqueous composition as described previously.
  • the deposition can for example be carried out using a size press.
  • the fibrous substrate may have undergone a prior treatment, in particular an impregnation, a surfacing, a sizing or a coating, in particular a coating, before the application of the composition according to the invention.
  • the surface treatment process may comprise the successive deposits, preferably by surfacing, sizing or coating, of two compositions, one comprising at least said biocidal agent or said combination of biocidal agents as considered according to the invention, and the other comprising at least said PAAE resin, a drying step possibly being implemented between two deposition steps.
  • the deposits can for example be made using a size press.
  • Example Example 1 is a diagrammatic representation of the invention.
  • All the substrates are prepared from a sheet of paper that can be used as paper to make a banknote.
  • the sheet of paper is formed on a so-called round-shaped paper machine with a fabric comprising a pattern allowing a watermark to be made, as follows:
  • window thread in English terminology
  • the sheet is dried at around 100°C.
  • the substrates thus prepared are treated successively, in a size press, with formulations 1 and 2 as indicated in the following table 1.
  • the formulations are prepared by mixing the various compounds in water. The contents are indicated by weight of active ingredient or “dry weight” relative to the total weight of each of the formulations.
  • the antiviral activity of all the treated substrates is evaluated as follows.
  • the test for antiviral activity against bacteriophage MS2, a bacteria virus of the naked virus family, is based on the ISO18184:2019-06 standard.
  • these supports are placed in the presence of particular bacteria which have the property of being hosts of the MS2 phages: the measurement of the number of lysis plaques or plaques viral (or PFU for “Plate-forming unit”) after culture then makes it possible to trace the quantity of MS 2 phages sought.
  • an antiphagic activity deduce an antiphagic activity (denoted A), defined as follows:
  • A log (Ci s)-log (Eis) with Cis the average number of viral plaques (PFU) obtained over 3 trials, on an untreated control sample (Polyethersulfone (PES) inactive); and Eis the average number of viral plaques (PFU) obtained over 3 tests, after 18 hours of contact with each of the supports treated according to Example 1.
  • the test for antiviral activity against the human coronavirus Hcov-OC43 an enveloped virus representative of the family of coronaviruses of which SARS-COV2 is a member, is based on the ASTM E1053 standard.
  • the human coronavirus virus Hcov-OC43 was propagated and counted using the Most Probable Number (MPN) method, using the cell line (ATCC CCL-244) of a human ileocaecal colorectal adenocarcinoma HCT-8 as host. Cells were grown in cell culture flasks in 6-well plates.
  • the virus was counted in infectious units according to the assay methodology described in Standard Method 9510 (APHA, 2012 equivalent to EPA/600/R-95/178 and EPA/600/4/84/013 updated). up to date).
  • dMEM medium Dulbecco's Modified Eagle's medium
  • FBS fetal calf serum medium
  • the cells were regularly monitored under the microscope for signs of degeneration. Cells showing signs of infectivity in the flasks (cytopathic effects, CPE) were counted as positive (+) and those without CPE as negative (-). The most probable number of infectious virus in a sample is then calculated using the MPNCALC software (version 0.0.0.23).
  • the frozen viral stock (typically 1.10 8 ui/ml) was thawed rapidly in a water bath at 35°C.
  • the virus suspension contained 2% FBS and was used within 15 minutes of thawing.
  • the virus suspension was enumerated by carrying out tenth-fold serial dilutions in PB S, then was inoculated onto HCT8 cells as described above.
  • the evaluation test was adapted from the ASTM E1053 protocol (“Standard Practice to Assess Virucidal Activity of Chemicals Intended for Disinfection of Inanimate, Nonporous Environmental Surfaces”).
  • the papers to be tested were cut into square sections of 25 mm side. Three sections of each of the treated papers to be tested and two sections of a reference paper (inactive cotton paper) were placed in sterile Petri dishes 100 mm in diameter. 100 ml of the viral suspension was applied evenly to the surface of each of the sections of paper to be evaluated; the inoculum was at least 5 mm away from the edges of the sample. The inoculum was allowed to dry for one hour and the petri dishes were covered and incubated for an additional 4 hours at 20-22°C in a biological safety cabinet (total contact time was 5 hours). Then, each of the samples (3 treated paper sections and 2 control sections) were transferred to a 50 ml conical bottom centrifuge tube (Corning, USA) containing 10 ml of sterile D/E neutralizing culture broth.
  • the collected samples were placed on an orbital shaker and shaken at low speed for 15 minutes. Then, tenth dilutions of the suspensions were made in PBS. The number of viable (infectious) virus units in samples is determined using the Most Probable Number (MPN) method described previously.
  • MPN Most Probable Number
  • Antiviral activity is defined as follows:
  • test of antiviral activity on bacteriophage MS2 demonstrate the effect of the presence of PAAE resin on the potentiation of antiviral activity.
  • the paper treated according to the invention II shows a significantly improved antiviral activity on bacteriophage MS2, compared to non-compliant CCI paper whose surfacing treatment does not include the implementation of a PAAE resin.

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EP22728625.9A 2021-05-17 2022-05-13 Composition antivirale pour le traitement de surface d'un article Pending EP4340610A1 (fr)

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