Antiviral composition for surface treatment of articles

Abstract

The present invention relates to an antiviral composition for surface treatment of an article, the antiviral composition comprising: At least one polyamide-polyamine-epichlorohydrin resin (known as a PAAE resin), and one or more biocides, wherein the one or more biocides include at least one silver-based compound and / or one quaternary ammonium-based compound; The present invention relates to an antiviral composition comprising the above compound. The present invention also relates to a method for the surface treatment of an article, in particular a substrate, intended to impart antiviral properties, comprising applying one or more compositions comprising at least said PAAE resin and one or more said biocides to the surface of said article, and also to the article surface-treated via said method.

Description

[Technical field]

[0001] The present invention relates to a composition for treating the surface of an article, in particular a substrate, especially a sheet, which is capable of imparting antiviral properties to said article, in particular intended to be touched or handled relatively frequently, and which is used in particular for producing information carriers intended to be handled relatively frequently.

[0002] The invention is particularly aimed at proposing substrates, such as fibrous substrates intended for the production of banknotes, which have improved antiviral surface properties. [Background technology]

[0003] In modern society, there is an ever-increasing number of articles or materials, such as carriers for conveying information, that are intended to be handled daily and frequently by many people.

[0004] Non-limiting examples of these information carriers may include, inter alia, payment instruments such as banknotes, cheques or restaurant tickets, identity documents such as ID cards, visas, passports or driver's licenses, lottery tickets, travel vouchers, tax discs or tax stamps, playing cards, packaging, books, magazines, etc.

[0005] However, users of these objects may be carriers of pathogenic microorganisms, especially viruses, which may cause epidemic and pandemic diseases to various degrees, and thus may contaminate any substrate with which they come into contact, and when this substrate is intended to be continuously handled by one or more other users, it becomes an important means for transmitting microorganisms to other people.

[0006] As a medium of exchange in commerce, paper money is one of the most widely handled carriers of information in the world and is therefore a potential vector for the transmission of disease.

[0007] The addition of bacteriostatic and / or bactericidal agents and fungistatic and / or fungicidal agents to information carriers has already been proposed in WO 03 / 084326.

[0008] Patent application WO 2012 / 063176 also describes fluid compositions based on naturally occurring virucidal agents, such as monolaurin, capable of forming coatings with antiviral activity.

[0009] For obvious reasons, it is an ongoing objective to optimize the antiviral properties offered by surface treatments on these supports, in particular to achieve good antiviral efficacy against a broad range of viruses.

[0010] According to the structure of the virus, two main different types of viruses can be distinguished: viruses lacking an envelope, known as "naked" viruses, which consist of a genome, DNA or RNA, and a capsid of viral proteins; and viruses known as "enveloped" viruses, which additionally have an envelope consisting of a double lipid layer in which the viral proteins are embedded. The Coronaviridae family, which includes, for example, the SARS-CoV-2 coronavirus responsible for the coronavirus disease 2019 (COVID-19), belongs to this second category of viruses. Summary of the Invention [Problem to be solved by the invention]

[0011] Therefore, in order to prevent the risks of contamination associated with the handling of various objects intended to be frequently handled by an unspecified number of people, in particular information carriers such as banknotes, it is desirable to be able to impart good antiviral properties, preferably antiviral activity against a broad spectrum of both naked and enveloped viruses, to the surfaces of these objects.

[0012] The present invention is particularly directed to meeting this need. [Means for solving the problem]

[0013] The present invention therefore proposes novel compositions for the surface treatment of articles, in particular substrates, which have particularly advantageous antiviral properties.

[0014] More particularly, according to a first aspect thereof, the present invention relates to an antiviral composition for the surface treatment of an article, which composition is particularly suitable for forming a coating on the surface of an article, said composition comprising: at least one polyamide-polyamine-epichlorohydrin resin (known as a PAAE resin); and one or more biocides, wherein the one or more biocides comprise at least one compound based on silver, in particular a silver salt, such as silver chloride (AgCl), and / or one compound based on quaternary ammonium, in particular a quaternary ammonium, in particular a quaternary ammonium salt, which may or may not be polymeric, especially didecyldimethylammonium chloride (DDAC).

[0015] The antiviral composition according to the invention more particularly also comprises at least one binding agent, in particular at least one binding agent as defined herein below.

[0016] Preferably, the composition according to the invention also comprises at least 3-iodo-2-propynyl butylcarbamate (denoted as IPBC) and / or diiodomethyl-p-tolylsulfone (denoted as DIMTS).

[0017] Thus, the compositions according to the invention preferably use a combination of biocides comprising: at least one compound based on silver, in particular a silver salt, such as silver chloride (AgCl), and / or one compound based on quaternary ammonium, in particular a quaternary ammonium salt, which is in particular a non-polymeric quaternary ammonium salt, such as DDAC; and At least 3-iodo-2-propynyl butylcarbamate (hereinafter referred to as IPBC) and / or diiodomethyl-p-tolylsulfone (hereinafter referred to as DIMTS). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] Hereinafter, a composition according to the present invention comprising at least one PAAE resin and one or more biocides as described above is referred to as the "antiviral treatment composition according to the present invention" or more simply as the "composition according to the present invention."

[0019] The term "surface treatment" is intended to indicate the application of the composition to the surface of an article such that the treated surface has the desired antiviral properties. In particular, the surface treatment of an article according to the invention results in the formation of a localized coating on the article surface and / or in the superficial part of the thickness of said article.

[0020] Preferably, the surface treatment method according to the invention results in the formation of a coating located at least on the outer surface of the article, particularly the substrate, treated according to the invention. In a particular embodiment, the surface treatment according to the invention may result in the formation of a coating located completely on the surface of the article, in other words without penetration of the composition into the thickness of the article.

[0021] Polyamide-polyamine-epichlorohydrin resins (known by the abbreviation PAAE) are cationic wet-strength resins commonly used in the bulk manufacture of paper substrates to improve their wet strength. These resins are then introduced "in bulk", that is to say in fibrous suspensions, during the manufacture of the paper support.

[0022] To the inventors' knowledge, it has not been proposed to use such PAAE resins in combination with one or more biocides in formulations intended for the surface treatment of articles, especially substrates, for example by surface treatment of fibrous substrates, in order to improve the antiviral activity of the coatings formed.

[0023] Surprisingly, as shown in the examples below, the inventors have found that by adding, according to the invention, a PAAE resin together with one or more biocides as indicated above in an antiviral composition intended for the surface treatment of an article, in other words an antimicrobial coating, the antiviral activity exhibited by the surface thus treated can be significantly increased.

[0024] Thus, the presence of the PAAE resin makes it possible to stimulate / enhance the antiviral activity exhibited by the surface treatment composition comprising at least one silver-based compound and / or one quaternary ammonium-based compound.

[0025] The terms "antiviral" or "virucidal" refer to the ability of a compound, composition, or coating to inhibit the growth of or kill viruses.

[0026] The antiviral coatings or compositions according to the invention are more particularly intended to inhibit and / or kill viruses that are pathogenic to mammals, and more particularly to humans.

[0027] The use of the PAAE resins according to the invention together with one or more of the biocides considered according to the invention, preferably a combination of the biocides mentioned above, can advantageously result in coatings with good antiviral performance against both naked and enveloped viruses.

[0028] The antiviral activity of substrates treated according to the invention can be evaluated, for example, by standard methods described in the examples below against the bacteriophage MS2, i.e. a representative of naked viruses, according to standard ISO 18184:2019-06, and against the human coronavirus Hcov-OC43, i.e. a representative of the enveloped virus of the coronavirus family to which SARS-COV2 belongs, according to standard ASTM E 1053.

[0029] Thus, according to another of its aspects, the present invention relates 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 articles, in particular substrates, in particular fibrous substrates, comprising one or more biocides including at least one compound based on silver, in particular a silver salt and / or at least one compound based on quaternary ammonium, in particular a quaternary ammonium salt, such as DDAC.

[0030] Advantageously, according to certain embodiments, the antiviral treatment composition or coating formed according to the present invention combines at least one PAAE resin with at least one silver-based compound, particularly a silver salt such as silver chloride, and preferably at least IPBC and / or DIMTS.

[0031] According to another particular embodiment, the antiviral treatment composition or coating formed according to the present invention combines at least one PAAE resin with at least one compound based on quaternary ammonium, particularly a quaternary ammonium salt, such as DDAC, and preferably at least IPBC and / or DIMTS.

[0032] As will be explained in detail hereinafter, the compositions according to the invention can be intended for the surface treatment of various articles, especially substrates, in particular sheet substrates, which are more particularly intended to be frequently handled by a large number of people and therefore prone to carrying pathogenic microorganisms, especially viral microorganisms. This concerns in particular sheet substrates for packaging or for producing information carriers.

[0033] In particular, they can be intended for the surface treatment of substrates, in particular sheets, intended for the manufacture of information carriers, in particular fibrous substrates intended for the manufacture of security documents, examples of which may be mentioned banknotes, which are handled at least several hundred times during their period of circulation.

[0034] The present invention also relates to a method for the surface treatment of an article, in particular a substrate, intended to impart antiviral properties, comprising the steps of: The above method describes applying one or more compositions to the surface of the article, wherein the composition comprises at least one PAAE resin and one or more biocides, wherein the one or more biocides comprise at least one silver-based compound, particularly a silver salt, and / or at least one quaternary ammonium-based compound, particularly a quaternary ammonium salt, such as DDAC.

[0035] More particularly, the subject of the present invention is a method for treating the surface of an article, in particular a substrate, to give it antiviral properties, comprising the steps of: The above method comprising: applying one or more compositions to a surface of the article, the compositions comprising at least one PAAE resin and one or more biocides, the one or more biocides comprising at least one silver-based compound, particularly a silver salt, and / or at least one quaternary ammonium-based compound, particularly a quaternary ammonium salt, such as DDAC; and forming a coating present at least on the surface of the treated article comprising at least the PAAE resin and one or more of the biocides.

[0036] As detailed herein below, according to a first embodiment variant, 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 above, combining at least said PAAE resin with one or more biocides as described above.

[0037] The present invention also relates to a method of use of a composition according to the invention for imparting 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 face of a substrate, which composition comprises at least one PAAE resin and one or more biocides, the one or more biocides comprising 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.

[0038] According to another embodiment variant, the surface treatment method according to the invention may comprise successively applying at least two different compositions comprising at least said PAAE resin in combination with one or more biocides as described above, where a drying step is optionally carried out between the two application steps.

[0039] One or more of said compositions for the treatment of a substrate surface may more particularly be applied to the surface to be treated by spraying, sizing, impregnation, printing, overprinting on an at least partially printed surface, surface treatment, coating or deposition.

[0040] The present invention also relates to a method of forming an antiviral coating on all or a portion of the surface of at least one side of an article, particularly a substrate, comprising applying one or more compositions to the surface of the article, the one or more compositions comprising at least one PAAE resin and one or more biocides, wherein the one or more biocides comprise at least one silver-based compound, particularly a silver salt, and / or at least one quaternary ammonium-based compound, particularly a quaternary ammonium salt, such as DDAC.

[0041] According to another of its aspects, the present invention relates to an article, as defined above, which has been surface treated via a process according to the invention, said article being in particular a substrate, in particular in sheet form.

[0042] In particular, the present invention relates more particularly to substrates, in particular sheets, intended for the manufacture of information carriers, in particular fibrous substrates intended for the manufacture of security documents, such as banknotes, provided on at least a portion of one of its faces with a coating such as obtained from an antiviral treatment composition according to the present invention, in which at least one PAAE resin and one or more biocides are incorporated, in which the one or more biocides comprise at least one compound based on silver, in particular a silver salt, and / or at least one compound based on quaternary ammonium, in particular a quaternary ammonium salt, such as DDAC.

[0043] The present invention also relates to a method for producing a substrate as defined above, comprising at least one step of forming, on all or part of the surface of at least one side of said substrate, a coating incorporating at least said PAAE resin and one or more of said biocides considered according to the invention, wherein said coating comprises at least one compound based on silver, in particular a silver salt, and / or at least one compound based on quaternary ammonium, in particular a quaternary ammonium salt, such as DDAC.

[0044] Moreover, as will be described in more detail hereinafter, one or more of the compositions used for the surface treatment according to the invention may comprise one or more additional compounds, particularly with regard to their mode of application and intended purpose.

[0045] For example, in the case of a composition intended for surface treating the surface of a substrate, the composition preferably comprises an aqueous surface treatment agent, preferably an aqueous surface treatment agent incorporating glycerol.

[0046] The antiviral treatment composition according to the invention may for example be a composition of a varnish, especially an overprint varnish, an ink or a lacquer, in particular an aqueous composition.

[0047] The composition according to the invention may comprise, in addition to said PAAE resin and one or more of said biocides, in particular the above-mentioned combinations of several of said biocides, at least one of the ingredients customarily considered in coating formulations of this type, such as at least one binder as described herein below.

[0048] Other characteristics, variants and advantages of the antiviral treatment composition according to the invention, as well as its implementation for the surface treatment of articles, in particular substrates, will be more clearly understood on reading the following description and examples, given as non-limiting illustrations of the invention.

[0049] In the remainder of this specification, the expressions "to," "a range of," and "a change of" are equivalent and are intended to include the limit unless expressly stated otherwise.

[0050] Antiviral Treatment Composition

[0051] As indicated above, in order to achieve particularly advantageous antiviral properties, the present invention combines at least one PAAE resin with one or more biocides, wherein the one or more biocides include at least one silver-based compound, particularly at least one silver-based compound, particularly a silver salt, and / or one quaternary ammonium-based compound, particularly DDAC.

[0052] 1 or more PAAE resin

[0053] The compositions according to the invention may contain one or more polyamide-polyamine-epichlorohydrin resins (known as PAAE resins).

[0054] Hereinafter, unless otherwise specified, the term "PAAE resin" refers to a single PAAE resin or a combination of at least two PAAE resins.

[0055] As indicated above, polyamide-polyamine-epichlorohydrin resins, also known as "polyamidoamine-epichlorohydrin" resins, are commonly used in the paper industry and are incorporated into a large proportion of cellulosic fibrous materials to impart wet strength to the paper material.

[0056] The PAAE resin used according to the invention may in particular be a polymer of adipic acid, diethylenetriamine and epichlorohydrin.

[0057] Thus, a PAAE resin may be obtained from adipic acid, diethylenetriamine (DETA) and epichlorohydrin. The PAAE resin may be prepared via a synthetic route known to those skilled in the art by carrying out a first condensation step between adipic acid and diethylenetriamine, followed by reacting the polyamidepolyamine resin thus formed with epichlorohydrin to form the PAAE resin.

[0058] PAAE resins are also commercially available, for example FennoStrength from the company Kemira. 登録商標 Mention may be made of the resin sold under the trade name XO.

[0059] Preferably, the PAAE resin has a low chloride content. This is especially true for FennoStrength 登録商標 This is the case for the resin sold under the name XO. Resins with such a low chloride content are particularly advantageous in the banknote sector, as they reduce the risk of corrosion of security elements, especially magnetic elements such as security threads, which can be sensitive to corrosion.

[0060] The 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, more in particular from 0.075% to 0.3% by dry weight, of one or more PAAE resins, relative to the total weight of the composition.

[0061] The term "dry weight", also known as "weight of active substance", is intended to indicate the mass content of said compound, without including any volatile solvents with which it is incorporated, such as water.

[0062] The amount of one or more PAAE resins in the surface treatment composition according to the invention is preferably from 0.24% to 8.82% by dry weight, in particular from 1.2% to 6.66% by dry weight, more in particular from 1.2% to 4.6% by dry weight, based on the total dry weight of the composition.

[0063] The total dry weight of the composition means the sum of the masses of the compounds used in the formulation of said composition, excluding the volatile solvents, in particular water, which are removed during the formation of the coating according to the invention, after drying of the composition applied to the surface of the article.

[0064] Thus, the content of a given compound expressed as a dry weight percentage relative to the total dry weight of the composition according to the invention corresponds to the dry weight percentage of said compound relative to the dry weight of the coating formed from said composition.

[0065] Biocides

[0066] As indicated above, the antiviral treatment composition according to the invention comprises, as one or more biocides, 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 didecyldimethylammonium chloride (DDAC).

[0067] For purposes of this invention, the term "biocidal agent" or "biocide" is equivalent to the term "antimicrobial agent" and generally refers to any agent that is effective in controlling and / or inhibiting the growth and / or reducing the density of microorganisms, such as viruses, fungi, bacteria, yeasts, etc.

[0068] The biocide or combination of biocides considered according to the invention advantageously has an antibacterial effect against viruses, in other words antiviral or virucidal activity, and is in particular effective against both naked and enveloped viruses.

[0069] Silver-based compounds, in particular silver salts, and quaternary ammonium-based compounds, in particular quaternary ammonium salts, are known as antibacterial and / or microbiocidal agents, in particular bacteriostatic or (antibacterial) and / or bactericidal agents.

[0070] Silver-based compounds that have antibacterial properties are known to those skilled in the art.

[0071] They may in particular be silver salts, in particular chosen from silver nitrate, silver chloride or thiosulphate. Preferably, the silver salt used as antimicrobial agent according to the invention is silver chloride.

[0072] Alternatively, they may be silver in supported particulate form: silver (oxidation state zero) more particularly supported by a particulate inorganic material, for example selected from zeolites and glasses, especially phosphate glasses.

[0073] The particle size of the silver-loaded or silver-doped material is preferably less than 10 μm, more preferably less than 5 μm. The particle size can in particular be measured by SEM imaging or DLS (dynamic light scattering). The particle size can in particular be defined by the diameter D98, i.e. the diameter below which 98% of the particles by weight are smaller.

[0074] The loaded content of silver in zero oxidation state in the material is in particular in the range of 0.5% to 3% by weight, in particular 1.0% to 2.5% by weight, relative to the total content.

[0075] In particular, the silver used as an antimicrobial agent according to the invention is silver supported on a particulate material made of glass, preferably a phosphate glass. More precisely, the silver metal is in the form of silver particles in a phosphate glass matrix. This matrix is ​​made of Ag + Permeable to silver ions, therefore, Ag + The advantage of this is that it allows the passage / transport of silver ions. These silver ions (Ag +) is produced when zero oxidation state silver dispersed in a surface treatment composition is exposed to ambient humidity or during contamination by droplets, particularly sputum.

[0076] Materials of this type are sold inter alia by Thomson Research Associates Inc. under the name Ultrafresh CA16.

[0077] Quaternary ammonium based compounds, in particular quaternary ammonium salts, are also known as antimicrobial and / or microbicidal agents, more particularly bacteriostatic (or bactericidal) agents and / or bactericidal agents and / or fungistatic (antifungal) agents and / or fungicidal agents.

[0078] They are more particularly polymeric or non-polymeric quaternary ammonium salts.

[0079] Quaternary ammonium salts generally contain at least one quaternary ammonium cation with a suitable anion.

[0080] The cation is more particularly of the following structure: [ka] Here, R 1 , R 2 , R 3 , and R 4 may be of different nature. For example, R 1 , R 2 , R 3 , and R 4may be selected independently from each other from an alkyl group, an aryl group, an alkylaryl group, an arylalkyl group, a cycloalkyl group, an aromatic or non-aromatic heterocyclic group, or an alkenyl group, which groups may be substituted or unsubstituted, linear or branched, and may optionally be interrupted by one or more heteroatoms, such as one or more oxygen atoms or one or more phosphinic acid groups.

[0081] Alternatively, R ≥ 2 1 Group, R 2 Group, R 3 Groups and R 4 The groups, together with the nitrogen atom to which they belong, may form a substituted or unsubstituted heterocyclic ring.

[0082] According to a particular embodiment, R 1 Group, R 2 Group, R 3 Groups and R 4 The group is an alkyl group, preferably a linear alkyl group, in particular a C 1 ~C 20 is an alkyl group.

[0083] R 1 Group, R 2 Group, R 3 Groups and R 4 The groups together contain at least 4 carbon atoms. 1 Group, R 2 Group, R 3 Groups and R 4 The total number of carbon atoms in the group may be at least 10. Preferably, R 1 Group, R 2 Group, R 3 Groups and R 4 At least one of the groups, in particular R 1 Group, R 2 Group, R 3 Groups and R 4 Two of the groups contain from 6 to 20 carbon atoms, in particular from 8 to 18 carbon atoms.

[0084] The anion of the quaternary ammonium salt may in particular be selected from halide anions, such as chloride, fluoride, bromide or iodide, and sulfonate anions. Preferably, the anion of the quaternary ammonium salt may be chloride.

[0085] The non-polymeric quaternary ammonium salt may more particularly have the formula: (CH 3 ) n (A) m N + X - Here, A is R 1 , R 2 , R 3 , and R 4 with the definition proposed above for X - is an anion as defined above; n is an integer from 1 to 3, preferably 2 or 3; m is an integer from 1 to 3, preferably 1 or 2, with the proviso that the sum of n+m is equal to 4. When m is 2 or 3, the A groups may be the same or different, in particular they are identical.

[0086] Preferably, the quaternary ammonium salt used as the antibacterial agent according to the present invention has the following formula: (CH 3 ) n (A) m N + X - where n is 2, m is 2, A may be the same or different, and R 1 , R 2 , R 3 and R 4 is as defined above.

[0087] In particular, A may be the same or different, in particular may be identical, and may be a linear C 6 ~C 20 , especially C 8 ~C 18 , especially C 8 ~C 12 , or an alkyl group thereof.

[0088] As examples there may be mentioned didecyldimethylammonium chloride (DDAC), dioctyldimethylammonium chloride and octyldecyldimethylammonium chloride.

[0089] According to a particular embodiment, the antiviral treatment composition according to the invention uses at least didecyldimethylammonium chloride (DDAC).

[0090] The quaternary ammonium based compounds may also be polymeric quaternary ammonium salts, ie, compounds that contain repeating "quaternary ammonium" units.

[0091] Such "polymeric" quaternary ammonium salts are 1 , R 2 , R 3 , and R 4 At least one of the compounds may be derived from at least one compound of formula (I) having a polymerizable function, in particular a functional group containing one or more ethylenic unsaturations, more particularly a functional group selected from (meth)acrylate functional groups and allyl functional groups.

[0092] In particular, the quaternary ammonium based compound may be obtained by polymerizing at least one of the above-mentioned quaternary ammonium salts of formula (I), in which R 1 , R 2 , R 3 and R 4 Two of the groups are groups having an allyl function, in particular allyl groups, and the others are preferably alkyl groups, in particular C 1 ~C 6 , especially C 1 ~C 4 , in particular a methyl group.

[0093] According to a particular embodiment, the quaternary ammonium based compound is a polymer of diallyldialkylammonium chloride. In particular, it may be a polymer of diallyldimethylammonium chloride, called polyDADMAC.

[0094] PolyDADMAC may be synthesized by radical polymerization of DADMAC in the presence of a peroxide catalyst or it may be commercially available.

[0095] Thus, the compositions according to the invention may comprise at least one biocide selected from silver salts, in particular silver chloride, silver in supported particulate form, in particular silver supported by a particulate inorganic material, such as glass, preferably a phosphate glass; polymeric or non-polymeric quaternary ammonium salts, in particular the above-mentioned quaternary ammonium salts selected from didecyldimethylammonium chloride (DDAC) and polymers of diallyldialkylammonium chloride, such as polymers of diallyldimethylammonium chloride (polyDADMAC), and combinations thereof.

[0096] The antiviral treatment composition according to the invention preferably comprises one or more of said biocidal compounds based on silver, in particular of the silver salt type, and / or one or more biocidal compounds based on quaternary ammonium, in particular of the quaternary ammonium salt type, in an amount of 0.004% to 1% by dry weight, in particular 0.004% to 0.75% by dry weight, relative to the total weight of the treatment composition.

[0097] Preferably, the one or more biocidal compounds based on silver, in particular of the silver salt type, are present in an amount of from 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.

[0098] Preferably, the one or more biocidal compounds based on quaternary ammonium, in particular the one or more biocidal compounds based on quaternary ammonium as defined above, such as DDAC, are present in an amount of from 0.05% to 1% by dry weight, in particular from 0.25% to 0.75% by dry weight, based on the total weight of the treatment composition.

[0099] The one or more biocidal compounds based on silver ions, in particular of the silver salt type, and / or the one or more biocidal compounds based on quaternary ammonium, in particular the quaternary ammonium compounds defined above, preferably represent between 0.07% and 18% by dry weight, in particular between 0.07% and 14% by dry weight, relative to the total dry weight of the antiviral composition.

[0100] Preferably, the one or more biocidal compounds based on silver, in particular of silver salt type, are present in an amount ranging from 0.07% to 0.7% by dry weight, in particular from 0.07% to 0.35% by dry weight, relative to the total dry weight of the antiviral composition.

[0101] Preferably, the biocidal compound based on a quaternary ammonium, in particular a quaternary ammonium as defined above, such as DDAC, is present in an amount between 0.8% and 18% by dry weight, in particular between 4% and 14% by dry weight, relative to the total dry weight of the antiviral composition.

[0102] As indicated above, according to a preferred embodiment, the composition according to the invention comprises: at least one compound based on silver and / or at least one said biocidal compound based on quaternary ammonium, in particular a quaternary ammonium as defined above; and At least 3-iodo-2-propynyl butylcarbamate (IPBC) and / or at least diiodomethyl-p-tolylsulfone (DIMTS) Contains a combination of biocides including:

[0103] IPBC and DIMTS are known in particular as fungistatic and / or fungicidal agents.

[0104] Thus, the antiviral treatment composition according to the present invention preferably comprises: at least one PAAE resin; at least one bacteriostatic and / or bactericidal agent, which may be selected from silver-based compounds, in particular silver salts, such as silver chloride, quaternary ammonium-based compounds, in particular polymeric or non-polymeric quaternary ammonium salts, such as DDAC or polyDADMAC, and combinations thereof; at least one fungistatic and / or fungicidal agent, selected from 3-iodo-2-propynyl butylcarbamate (IPBC), diiodomethyl-p-tolylsulfone (DIMTS), and combinations thereof; Combine with.

[0105] 3-iodo-2-propynyl butylcarbamate, also known as "iodopropynyl butylcarbamate" and referred to as "IPBC", and diiodomethyl-p-tolylsulfone, also known as "p-[(diiodomethyl)sulfonyl]toluene" and referred to as "DIMTS", among others, are commonly known as fungistatic and / or fungicidal agents, as well as algistatic or algicidal agents. They are generally in the form of aqueous dispersions.

[0106] Such biocides are commercially available.

[0107] The antiviral treatment composition according to the present invention preferably contains IPBC and / or DIMTS in a proportion of 0.1% to 0.6% by dry weight, in particular 0.2% to 0.6% by dry weight, relative to the total weight of the composition.

[0108] In particular, the amount of IPBC and / or DIMTS in the composition according to the invention may represent between 1.9% and 10.5% by dry weight, and in particular between 1.9% and 3.77% by dry weight, relative to the total dry weight of the composition.

[0109] According to a particular embodiment, the antiviral treatment composition according to the invention comprises at least one compound based on silver, in particular a silver salt, in particular silver chloride, and at least IPBC.

[0110] According to another particular embodiment, the composition according to the invention comprises at least one compound based on quaternary ammonium, especially a quaternary ammonium salt, in particular DDAC and at least IPBC.

[0111] According to another particular embodiment, the composition according to the invention comprises at least one silver salt, in particular silver chloride, and at least DIMTS.

[0112] According to another particular embodiment, the 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.

[0113] It will be appreciated that compositions according to the present invention may contain one or more additional biocides in addition to the specific compounds mentioned above.

[0114] These biocidal compounds may be of diverse nature, provided that they do not affect the effectiveness of the combination according to the invention of the PAAE resin with one or more compounds based on silver and / or one or more compounds based on quaternary ammonium, optionally in combination with IPBC and / or DIMTS.

[0115] Moreover, it goes without saying that these agents are selected having regard to their harmlessness to humans under the conditions of use according to the invention.

[0116] These additional biocides may be selected from bacteriostatic agents, bactericidal agents, fungistatic agents, yeasticidal agents, fungicidal agents and / or virucidal agents.

[0117] These include, for example, compounds based on isothiazolone or isothiazolone derivatives, compounds based on chitosan or chitin derivatives, zinc zeolites, triclosan, and combinations thereof.

[0118] The compositions according to the invention may in particular contain one or more supplementary virucides, for example one or more supplementary virucides of natural origin.

[0119] Representatives of viruses that are pathogenic for humans and that may be considered according to the invention are, in particular, coronaviruses (e.g. SARS-COV2, HcoV-OC43 or HcoV-229E), retroviruses, cytomegaloviruses, rotaviruses, paramyxoviruses, polioviruses, hantaviruses, coxsackie viruses, encephalomyocarditis virus, picornaviruses, such as the abovementioned picornaviruses, including rhinoviruses, DNA or RNA viruses, in particular flaviviridae, AIDS virus, Ebola virus, influenza viruses, smallpox virus, yellow fever virus, and the like. Mention may be made of the following viruses: hepatitis C virus, herpes viruses, Epstein-Barr virus, varicella-zoster virus, rubella virus, simian virus 40, or SV40.

[0120] The term "naturally occurring virucide" refers to any virucide that already exists in nature or any virucide that can be synthesized from natural compounds that exist in nature.

[0121] Thus, naturally occurring virucidal agents which may be used in the context of the present invention may be obtained by extraction and purification from the natural medium which contains them, or by synthesis from natural compounds.

[0122] As an example of such a virucide, mention may especially be made of monolaurin, which can be obtained by synthesis from glycerol and lauric acid.

[0123] For purposes of the present invention, the term "monolaurin" is intended to denote both naturally occurring monolaurin and monolaurin synthetically obtained from glycerol and lauric acid.

[0124] According to a particular embodiment, the naturally occurring virucidal agent may be chosen, inter alia, from monolaurin, lactoferrin, and essential oils having antiviral activity, such as bay laurel essential oil.

[0125] According to a particular embodiment, the antiviral treatment composition according to the invention does not contain any biocides other than the silver ion based compounds and / or the quaternary ammonium based compounds, optionally in combination with IPBC or DIMTS as described above.

[0126] Advantageously, the enhanced antiviral activity obtained by the addition of the PAAE resin allows for the use of reduced total amounts of biocides, particularly virucides.

[0127] According to a particular embodiment, the antiviral treatment composition according to the invention has a total dry weight content of biocides, in particular of the biocides considered according to the invention, of less than or equal to 1% by weight, in particular between 0.1% and 0.7% by weight, relative to the total weight of said composition.

[0128] In particular, the one or more biocides considered according to the invention, in particular the silver salts and / or quaternary ammonium salts, optionally combined with IPBC and / or DIMTS, preferably represent between 1.5% and 15% by dry weight, in particular between 1.5% and 10% by dry weight, relative to the total dry weight of the composition.

[0129] According to a particular embodiment, the surface treatment composition according to the invention comprises: 0.24% to 8.82% by dry weight, specifically 1.2% to 6.66% by dry weight, more specifically 1.2% to 4.6% by dry weight of one or more PAAE resins; 0.07% to 18% by dry weight, in particular 0.07% to 14% by dry weight, of one or more bacteriostatic and / or bactericidal agents, which are selected from silver-based compounds, in particular silver salts, such as silver chloride, quaternary ammonium-based compounds, in particular polymeric or non-polymeric quaternary ammonium salts, such as DDAC and polyDADMAC; and combinations thereof; 1.9% to 10.5% by dry weight, in particular 1.9% to 3.77% by dry weight, of one or more fungistatic and / or fungicidal agents, selected from 3-iodo-2-propynyl butylcarbamate (IPBC), diiodomethyl-p-tolylsulfone (DIMTS), and combinations thereof. It may include at least Here, the content is expressed relative to the total dry weight of the composition.

[0130] Surface treatment composition formulation

[0131] It will be understood that the formulation of the antiviral treatment composition according to the invention, for example as a varnish, especially an overprint varnish, an ink or a lacquer, is adjusted with respect to the use for which it is intended and with respect to the application mode envisaged for treating a substrate surface with said composition, as detailed herein below.

[0132] The composition according to the invention is preferably a fluid composition, in particular a fluid composition having a viscosity measured at 60° C. of 30 mPa.s to 40 Pa.s, in particular 50 mPa.s to 25 Pa.s.

[0133] The viscosity of the composition may be measured by conventional methods. The selection of an appropriate measurement method and device is clearly within the capabilities of a person skilled in the art, especially with regard to the viscosity scale of the composition under consideration.

[0134] For example, for compositions having a viscosity significantly less than 2 Pa.s, a Brookfield viscometer (ISO 2555) with spindle No. 2 at 100 rpm is the preferred measuring device.

[0135] This viscosity can be adjusted with respect to the purpose of the composition and the form of application.

[0136] The viscosity of the treatment composition according to the invention can in particular be adjusted via the nature and / or amount of the solvent medium associated with the compound required according to the invention, or via the addition and adjustment of the amount of one or more binders, if present in the composition according to the invention.

[0137] Solvent medium

[0138] Antiviral treatment compositions according to the present invention may comprise an aqueous or organic solvent medium, the solvent medium being selected with particular regard to the type of composition intended.

[0139] The solvent medium may be a one-phase medium or a two-phase medium, for example, the solvent medium according to the invention may be in the form of an oil-in-water or water-in-oil emulsion.

[0140] Generally, compositions according to the present invention may comprise, as a solvent medium, water, an organic solvent, an oil, or a combination thereof.

[0141] According to a particular embodiment, the composition according to the invention is an aqueous composition, where the solvent medium is preferably water, in particular it may comprise said PAAE resin considered according to the invention and one or more of said biocides in water.

[0142] Additional Compounds

[0143] The antiviral treatment composition according to the invention may also contain one or more additional components, in particular one or more selected from compounds conventionally used in the type of composition under consideration, provided that their presence does not affect the antiviral properties provided by the combination of said PAAE resin with said one or more biocides according to the invention.

[0144] The nature of said additional compound or compounds is selected with respect to the type of composition under consideration and its mode of application.

[0145] Preferably, the composition according to the invention comprises at least one binder, in particular a polymeric binder.

[0146] According to one particular embodiment, the composition according to the invention also comprises at least one pigment.

[0147] Said binders are in particular compounds customarily used in paper, varnish and / or ink processing compositions, where their function is generally to ensure the dispersion of particles, such as pigments, when present in the composition, and to contribute to the formation of a film of sufficient hardness to ensure the durability of said support, after drying and / or crosslinking of the composition applied to the surface of said support.

[0148] The binder may be selected from resins, waxes, gums, and combinations thereof, among others.

[0149] The resin may be selected from cycloaliphatic epoxy resins, acrylic resins, vinyl resins, ketone resins, polyester resins, polyurethane resins, and aldehyde resins, among others.

[0150] Among the waxes that may be used according to the invention, mention may be made of: vegetable waxes, such as carnauba wax, candelilla wax, ouricury wax, Japanese wax, cocoa butter wax, cork wax, or sugarcane fiber wax; Mineral waxes, such as paraffin wax, petroleum jelly wax, lignite wax, microcrystalline wax or ozokerites; Synthetic waxes, such as polyolefin waxes, especially polyethylene waxes, and waxes obtained by the Fischer-Tropsch synthesis; Silicone waxes, especially substituted linear polysiloxanes; for example, polyether silicone waxes, alkyl or alkoxy dimethicones containing 16 to 45 carbon atoms, such as those sold under the trade name AMS C 30 by Dow Corning. 30 ~C 45 Alkylmethicones may be mentioned, Hydrogenated oils, and / or any combination thereof.

[0151] As examples of waxes suitable for the present invention, mention may be made in particular of hydrocarbon waxes, such as beeswax, lanolin wax, Chinese insect waxes, rice bran wax, carnauba wax, candelilla wax, ouricury wax, esparto grass wax, berry wax, shellac wax, Japan wax and sumac wax; montan wax, orange wax and lemon wax, microcrystalline waxes, paraffin and ozokerite; polyethylene waxes, waxes and wax-like copolymers obtained by the Fischer-Tropsch synthesis, and also esters thereof.

[0152] The gums may be selected, for example, from acacia gums, tragacanth gums, cassia gums, gutte gums, shellac gums, sandarac gums, mastic gums or resin gums.

[0153] According to a particular embodiment, the composition according to the invention, in particular the aqueous composition according to the invention, comprises at least one binder, especially a binder chosen from hydrophilic binders, in particular polymeric binders, more in particular polyhydric alcohols, preferably polyvinyl alcohol (PVA).

[0154] The 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 the PVA type, relative to the total weight of the composition.

[0155] Preferably, the one or more binders, in particular of the PVA type, are present in a mass proportion ranging from 30% to 90% by dry weight, in particular from 50% to 80% by dry weight, relative to the total dry weight of the composition.

[0156] The composition according to the invention may also comprise at least one moisturizing agent, this being especially the case for compositions intended to be applied by surface treatment to the surface of a substrate.

[0157] A humectant is a compound capable of imparting a moisturizing or hygroscopic effect.

[0158] As representatives of these moisturizing agents, in the context of the present invention there may in particular be considered polyol type compounds, such as glycerol, propylene glycol, polyethylene glycol, butylene glycol, glyceryl triacetate or sorbitol.

[0159] According to another embodiment variant, the moisturizing agents considered are chosen from the following compounds: pydoric acid (PCA) and its derivatives (such as arginine PCA, copper PCA, ethylhexyl PCA, lauryl PCA, magnesium PCA, sodium PCA, zinc PCA, etc.), calcium gluconate, fructose, glucose, isomalt, lactose, maltitol, mannitol, polydextrose, sorbitol, sucrose or xylitol, glycyrrhizic acid and its derivatives, histidine, hyaluronic acid and its salts (such as sodium hyaluronate), silk, keratin or soybean hydrolysates, phytanetriol, silk or urea.

[0160] According to a preferred embodiment variant, the humectant is chosen from polyols, and more particularly glycerol.

[0161] The antiviral treatment composition according to the invention may preferably contain from 0.5% to 4% by dry weight, for example from 1% to 3% by dry weight, of a humectant, especially glycerol, relative to the total weight of the composition.

[0162] According to a particular embodiment, the antiviral treatment composition according to the invention is provided in a solvent medium, in particular in an aqueous solvent medium, at least one PAAE resin; one or more biocides, for example at least one silver-based compound, in particular a silver salt and / or one quaternary ammonium-based compound, in particular the quaternary ammonium salts mentioned above, in particular at least silver chloride and / or DDAC, and Preferably, at least one fungistatic and / or fungicidal agent, which are selected from 3-iodo-2-propynyl butylcarbamate (IPBC), diiodomethyl-p-tolylsulfone (DIMTS) and combinations thereof; at least one binder, in particular polyvinyl alcohol (PVA); Optionally, at least one additive, in particular at least one humectant, such as glycerol. Includes.

[0163] Preferably, the surface treatment composition according to the invention comprises: 0.24% to 8.82% by dry weight, particularly 1.2% to 6.66% by dry weight, more preferably 1.2% to 4.6% by dry weight of one or more PAAE resins; 0.07% to 18% by dry weight, in particular 0.07% to 14% by dry weight, of at least one biocide, wherein the at least one biocide is selected from silver-based compounds, in particular silver salts, quaternary ammonium-based compounds, in particular quaternary ammonium salts, and combinations thereof, in particular selected from at least silver chloride and / or DDAC; Optionally, from 1.9% to 10.5% by dry weight, in particular from 1.9% to 3.77% by dry weight, of at least one fungistatic and / or fungicidal agent, wherein they are selected from IPBC and / or DIMTS; 30% to 90% by dry weight, in particular 50% to 80% by dry weight, of one or more binders, in particular PVA type binders Including, Here, the percentages are expressed relative to the total dry weight of the composition.

[0164] According to a particular embodiment, the antiviral treatment composition is an aqueous composition, in particular an aqueous surface treatment composition, which preferably comprises at least one humectant, in particular glycerol.

[0165] Surface Treatment Method

[0166] As indicated above, the antiviral composition according to the present invention is intended for the surface treatment of articles.

[0167] Articles or objects according to the invention are especially those that are susceptible to transmitting viruses and are therefore intended to be touched or handled relatively frequently.

[0168] For purposes of the present invention, an item intended to be handled relatively frequently is an item that is manually handled at least twice by the same individual or at least two different individuals. Manual handling may include at least one contact, e.g., grasping, by at least a part of a hand.

[0169] These may be substrates, especially substrates for producing information carriers, such as banknotes or cards, e.g. smart cards, or substrates for packaging; plastic objects, such as computer keyboards and mice, touch screens, telephone keyboards, screens and handsets, children's toys, medical or health care instructions, nails, musical instruments, work clothes, tools, furniture fabrics, handles, buttons, packaging.

[0170] The object may be made of a material selected from, for example, glass, paper, cardboard, plastic, textile, and the like.

[0171] According to a particular embodiment, the present invention relates to the surface treatment of a substrate, in particular a sheet-like substrate.

[0172] The substrates treated according to the present invention may be of various nature.

[0173] The substrate considered according to the invention may be a porous substrate, in particular a fibrous substrate, more in particular a paper based on fibers known to the person skilled in the art, such as cellulosic fibers (in particular cotton fibers) and / or non-cellulosic natural organic fibers and / or synthetic fibers, such as polyester fibers or polyamide fibers, and / or optionally mineral fibers, such as glass fibers.

[0174] In particular, the substrate, especially the paper type substrate, is preferably 10 g / m 2 ~300g / m 2 , more particularly 50 g / m 2 ~150g / m 2 , or even 65 g / m 2 ~150g / m 2 , which can be measured via conventional methods, for example according to standard ISO 536:2019.

[0175] According to one particular embodiment, the substrate considered according to the invention is based on cellulosic fibers, in particular in the form of a sheet.

[0176] According to another embodiment, the substrates considered according to the invention, in particular those in the form of sheets, are based on natural organic fibres other than cellulosic fibres.

[0177] According to yet another embodiment, the substrate considered according to the invention, in particular in the form of a sheet, is based on a plastic material, in particular synthetic fibers.

[0178] The substrate may be a plastic film, in particular a bi-oriented polyethylene-based film, such as Polyart® sold by the company Arjobex. 登録商標 More particularly, it may be a sheet comprising a coextruded support made of at least one polymeric material, for example comprising a core layer and at least one skin layer, where the core layer comprises voids.

[0179] The synthetic substrate may also be BOPP (bi-oriented polypropylene), in particular a BOPP-based film, especially a BOPP-based film for banknotes, such as those sold, for example, under the name Guardian by CCL Secure and under the name Safeguard by De La Rue.

[0180] The substrate may also be a multi-layer substrate, in particular a laminated or laminated multi-layer substrate, which in particular comprises at least one layer based on a cellulose material or a plastic material, as described above.

[0181] The synthetic substrate may in particular be a multilayer paper-plastic hybrid substrate, such as a paper-plastic-paper or plastic-paper-plastic hybrid substrate, such as the substrates for security documents sold under the name EverFit by the Banque de France, under the name Hybrid by the company Louisenthal and under the name Durasafe by the company Landqart.

[0182] According to yet another particular embodiment, the substrate considered according to the invention is based on mineral fibres.

[0183] As indicated above, the substrates considered according to the invention may in particular be those intended for the preparation of information carriers, in particular information carriers intended to be frequently handled by relative stations.

[0184] Information carriers considered according to the invention may be a passport, an identity card, a driver's license, an access card, a loyalty card, a photocopy card, a canteen card, a playing card, a collector's card, a payment instrument, in particular a payment card, a banknote, a voucher or a receipt, an entrance ticket for a cultural or sporting event, a certificate of authenticity, or a package, a book, a geographical map, a label, an envelope or a magazine.

[0185] The invention is particularly applicable in the field of security documents, especially banknotes.

[0186] Substrates considered according to the invention may therefore be substrates for security documents, in particular substrates intended for the production of banknotes, especially sheet-like substrates.

[0187] The present invention therefore relates to an information carrier, for example an information carrier as described above, in particular a security document, in particular a banknote, comprising a substrate treated according to the invention.

[0188] Substrates for security documents may include watermarks as well as other conventional first, second or third level security elements.

[0189] Some security elements can be visually detected in daylight or artificial light without the use of any special equipment. These additional security elements include, for example, colored fibers or planchettes, or fully or partially printed or metallized wires. These are referred to as first level security elements.

[0190] Other types of security elements can only be detected using relatively simple equipment, such as ultraviolet (UV) or infrared (IR) emitting lamps. These security elements include, for example, fibers, planchettes, strips, threads, particles. These security elements may be visible or invisible to the naked eye, for example emitting light under the illumination of a Wood lamp emitting light at a wavelength of 365 nm. These security elements are referred to as second level elements.

[0191] Other types of security elements require more sophisticated equipment for their detection. For example, these security elements can generate a specific signal when subjected to one or more external excitation sources simultaneously or under other conditions. By automatically detecting said signal, the document can be authenticated if necessary. These security elements include, for example, tracers in the form of active substances, particles or fibers, which can generate a specific signal when subjected to photoelectronic, electrical, magnetic or electromagnetic excitation. These security elements are referred to as third level elements.

[0192] One or more security elements present in a security document according to the present invention may have first level, second level or third level security functionality.

[0193] As indicated above, the method according to the invention is a surface treatment method, in other words 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 within the superficial part of the thickness of said article.

[0194] Thus, the surface treatment method according to the invention may comprise the penetration of the one or more compositions used into the surface part of the thickness of the substrate. Preferably, the one or more compositions for surface treatment according to the invention penetrate into the substrate to less than 15%, in particular to less than 10%, of its thickness.

[0195] The surface treatment method according to the present invention is consequently distinguished from "bulk" treatments, which are directed to the incorporation of one or more compounds into the bulk of the substrate, usually at the manufacturing stage, e.g. in a fibrous suspension during the manufacture of a paper support.

[0196] Preferably, the surface treatment method according to the invention results in a coating that is at least present (without penetrating) on ​​the surface of said treated article, preferably only on the surface of said article.

[0197] In particular, the method according to the present invention does not include any step for forming one or more layers superimposed on the antiviral coating formed according to the present invention, comprising at least said PAAE resin and one or more said biocides.

[0198] Thus, an article treated according to the invention has said surface coating on at least one of its faces, in other words said antiviral coating forms at least a part of the outer surface of an article treated according to the invention.

[0199] The surface treatment method according to the invention proceeds more particularly by applying to the surface to be treated of said article one or more compositions, said one or more compositions comprising at least said PAAE resin and at least one or more of said biocides considered according to the invention, followed by a drying step.

[0200] The coating formed according to the present invention can be obtained through the application of an antiviral treatment composition according to the present invention as described above, in particular a single antiviral treatment composition according to the present invention, or alternatively by the sequential application of at least two different compositions.

[0201] Thus, according to one particular embodiment, the antiviral treatment method according to the invention comprises applying an antiviral treatment composition according to the invention, as defined above, comprising at least said PAAE resin and at least one or more said biocides, wherein said biocides comprise at least one silver-based compound and / or a quaternary ammonium-based compound, such as silver chloride and / or DDAC, followed by a drying step.

[0202] In another particular embodiment, the antiviral treatment step according to the invention comprises the successive application of at least two different compositions, said compositions comprising, in combination, at least said PAAE resin considered according to the invention and at least one or more of said biocides, a drying step may optionally be performed between the two application steps, followed by a drying step.

[0203] When at least two different compositions are used for the antiviral treatment according to the invention, each of said compositions may have the characteristics as indicated above for the composition according to the invention, in particular in terms of the nature of the solvent medium and any additional compounds present.

[0204] The conditions under which the composition is used are adjusted to allow the formation of a coating as obtained from a single antiviral treatment composition according to the invention, wherein said coating incorporates all the compounds required according to the invention to lead to the manifestation of the desired effect in terms of enhancing the antiviral activity of the PAAE resin.

[0205] One or more of the compositions may be applied to the surface of the article, in particular the surface of the substrate, by spraying, sizing, impregnation, printing (e.g. offset printing, gravure printing, flexographic printing), overprinting an at least partially printed surface (e.g. flexographic overprinting), surface treatment, coating or deposition onto the surface to be treated.

[0206] It is understood that the mode of application of one or more of said compositions for surface treatment according to the invention is adjusted with respect to the nature of the article whose surface is to be treated.

[0207] Preferably, one or more of the compositions are applied by surface treatment, sizing or coating, especially for application to the surface of a substrate, especially a fibrous substrate.

[0208] Any equipment that allows such a treatment to be carried out may be used to apply the composition, for example impregnators, size presses, air knife coaters, doctor blade coaters, curtain coaters, gravure coaters (rotogravure), screen printers, flexographic printers.

[0209] The treatment may be applied locally to a portion of the surface of the article or to the entire surface of the article. In the case of the treatment of substrates, particularly sheets, the treatment may be applied locally to a portion of at least one side of the substrate, generally, and more particularly, to the surface intended to be touched or handled.

[0210] Generally, a drying step is carried out after application of said composition(s) to the surface of the article, said drying step being intended in particular to remove said solvent(s) present in said composition(s).

[0211] The antiviral treatment composition according to the invention may for example constitute a varnish, especially an overprint varnish, an ink, a lacquer or a paint composition, especially an aqueous composition.

[0212] Depending inter alia on the nature of the binder or binders present in the composition, it may be, for example, a cellulose, polyurethane or acrylic varnish or ink.

[0213] Preferably, when treating the surface of a substrate, in particular when treating the surface of a substrate as described above, the treatment is carried out on two opposite faces of the substrate, in particular a sheet substrate.

[0214] According to a particular embodiment, a method for the surface treatment of a substrate according to the invention, in particular a fibrous substrate, for example a substrate in the form of a sheet of paper, may comprise the deposition, preferably by surface treatment, sizing or coating, of an antiviral treatment composition according to the invention, preferably an aqueous composition as described above, on at least one face, in particular both opposing faces, of said substrate.

[0215] The stack can be produced, for example, using a sizing press.

[0216] The fibrous base material may have undergone a previous treatment, especially an impregnation, a surface treatment, a sizing or a spreading, especially a coating, before the application of the composition according to the invention.

[0217] According to an embodiment variant, the surface treatment method may comprise the successive deposition, preferably by surface treatment, sizing or coating, of two compositions, one of which comprises at least said biocide or said combination of biocides considered according to the invention and the other of which comprises at least said PAAE resin, a drying step optionally being carried out between the two deposition steps.

[0218] The stack can be produced, for example, using a sizing press.

[0219] The examples given below are presented as non-limiting illustrations of the present invention.

[0220] Working Example

[0221] Example 1

[0222] Preparation of treated paper

[0223] All substrates are prepared from sheets of paper suitable as paper for making banknotes.

[0224] The sheet of paper is formed on a "round" paper machine equipped with wires containing a pattern that allows the watermark to be applied as follows: The cotton fibre pulp is suspended in water and refined in a Shoepper-Riegler at 60°C. A wet strength agent of poly(amido-amine-epichlorohydrin) resin is added at about 2.5% by dry weight of the cotton fibers. Iridescent planchettes are also introduced into this suspension; A window thread is introduced using known techniques such that the window thread appears in a window on the surface of the paper as the sheet is formed; and The sheet is dried at about 100°C.

[0225] The substrate thus prepared is treated in a sizing press sequentially with Formulation 1 and Formulation 2 as shown in Table 1 below.

[0226] The formulations are prepared by mixing the various compounds in water. The contents are given as the weight of active substance relative to the total weight of each of the formulations or as "dry weight".

[0227] They are applied successively to both sides of a paper substrate using a sizing press and subsequently dried at 105° C. for 10 minutes.

[0228] [Table 1]

[0229] *For PVA, the first two digits indicate the viscosity at 4% and the last two digits indicate the degree of hydrolysis (%). (1) Viscosity was measured using a Brookfield viscometer at spindle number 2, 100 rpm (ISO 2555).

[0230] Example 2

[0231] Assessment of antiviral activity

[0232] The antiviral activity of all treated substrates was evaluated as follows.

[0233] Antiviral activity against bacteriophage MS2

[0234] The test for antiviral activity against bacteriophage MS2, i.e. a bacterial virus of the Naked Virus family, is based on standard ISO18184:2019-06.

[0235] The principle is as follows: MS2 phages are deposited on the support to be tested, then the number of active MS2 phages is assessed a first time at t=0, immediately after contacting the phages with the support to be tested, and then a second time 18 hours after contacting.

[0236] To assess the number of active MS2 phages on the supports to be tested at a given time, these supports are placed in the presence of specific bacteria that have the property of being hosts to the MS2 phages. After incubation, measuring the number of lysis zones or virus plates (or PFUs of "plaque-forming units") allows the desired amount of MS2 phages to be determined.

[0237] Therefore, an anti-phage activity (denoted as A) can be deduced, which is defined as follows: A=log(C 18 )-log(E 18 ) Here, C 18 is the average number of viral plaques (PFU) obtained in triplicate tests on an untreated control sample (inert polyethersulfone (PES)); and E 18 is the average number of viral plaques (PFU) obtained in triplicates after 18 hours of contact with each of the substrates treated according to Example 1.

[0238] The antiviral activity results obtained for each of the carriers treated according to Example 1 are summarized in Table 2 below.

[0239] Antiviral activity against human coronavirus Hcov-OC43

[0240] The test for antiviral activity against the human coronavirus Hcov-OC43, an enveloped virus representative of the coronavirus family to which SARS-COV2 belongs, is based on the ASTM E 1053 standard.

[0241] Cell culture infectivity assay

[0242] Human coronavirus Hcov-OC43 was propagated in the human ileocaecal colorectal adenocarcinoma cell line HCT-8 (ATCC CCL-244) and counted using the Most Probable Number (MPN) method. Cells were cultured in cell culture flasks in 6-well plates.

[0243] For enumeration, viruses were counted as infectious units according to the assay method described in standard method 9510 (APHA, 2012, equivalent to EPA / 600 / R-95 / 178 and EPA / 600 / 4 / 84 / 013 updates).

[0244] Briefly, an aliquot of virus-containing sample was inoculated onto a freshly prepared monolayer of HCT8 cells (approximately 90% confluent). The cells were then incubated in dMEM (Dulbecco's modified Eagle's medium); 2% fetal calf serum (FBS, Mediatech, USA) at 35°C and 5% CO. 2 The flasks were cultured at 4°C for 10-14 days. The cells were periodically observed under a microscope for signs of degeneration. Cells in the flasks showing signs of infectivity (cytopathic effects, CPE) were counted as positive (+) and cells without CPE as negative (-). The most probable number of infectious viruses in the samples was then calculated using MPNCALC software (version 0.0.0.23).

[0245] For experiments, frozen virus stocks (typically 1 × 10 8 Virus suspensions (IU / ml) were rapidly thawed in a water bath at 35°C. The virus suspensions contained 2% FBS and were used within 15 min after thawing. Virus suspensions were counted by 10-fold serial dilution in PBS and then inoculated onto HCT8 cells as described above.

[0246] Evaluation of treated paper samples

[0247] The evaluation test was adapted from ASTM protocol E 1053 (Standard Practice to Assess Virucidal Activity of Chemicals Intended for Disinfection of Inanimate, Nonporous Environmental Surfaces).

[0248] Specifically, the test strips were cut into 25 mm squares. Three pieces of each treated test strip and two pieces of reference strip (inert cotton paper) were placed in a sterile 100 mm diameter petri dish. 100 ml of virus suspension was evenly applied to the surface of each test strip to be evaluated. The inoculum was applied at least 5 mm away from the edge of the sample. The inoculum was allowed to dry for 1 hour, and the petri dish was then covered and incubated at 20-22°C for an additional 4 hours in a biological safety chamber (total contact time was 5 hours). Next, each of the samples (three treated strips and two control strips) was transferred to a 50 ml conical bottom centrifuge tube (Corning, USA) containing 10 ml of sterile D / E neutralizing broth.

[0249] The collected samples were placed on an orbital shaker and shaken at low speed for 15 min. Subsequently, 10-fold dilutions of the suspension were made in PBS. The number of viable (infectious) viral units in the samples was determined using the most probable number (MPN) method as previously described.

[0250] Antiviral activity is defined as follows: A = log(MPN 対照 )-log(MPN 処理された) Here, MPN is the number of sheets per 1000, compared to the control paper (MPN 対照 ) and treated test strips (MPN 処理された) is the average value of the Most Probable Number of Viral Infectious Units of the evaluated samples determined by the method described above after a contact time of 5 hours.

[0251] The results are shown in Table 2 below:

[0252] [Table 2]

[0253] The antiviral activity of the combination of Iocide AgCl and IPBC appears to be too strong to make it possible to distinguish between the results obtained with papers treated according to inventions I1 and I2 and those obtained with the non-compliant paper CC1. Thus, 100% killing of the Hcov-OC43 coronavirus was obtained after 5 hours of contact.

[0254] Antiviral activity tests against bacteriophage MS2 show the effect of the presence of PAAE resin on enhancing antiviral activity. Thus, the paper treated according to the invention I1 shows significantly improved antiviral activity against bacteriophage MS2 compared to non-compliant paper CC1, whose surface treatment does not include the use of PAAE resin.

[0255] This antiviral effect is further enhanced by using higher PAAE resin content (I2 treated paper).

[0256] When tested against coronaviruses SARS-COV2 and HCoV-229E according to the standard ISO 21702:2019 protocol, I1 paper showed antiviral activity of 1.6 log and 2.5 log, respectively.

Claims

1. 1. An antiviral composition suitable for forming a coating on a surface of an article, comprising: At least one polyamide-polyamine-epichlorohydrin resin (known as a PAAE resin), and one or more biocides, wherein the one or more biocides include at least one silver-based compound and / or one quaternary ammonium-based compound; The antiviral composition comprising:

2. 10. The composition of claim 1, wherein the PAAE resin is formed from adipic acid, diethylenetriamine and epichlorohydrin.

3. The composition of claim 1 , wherein the one or more PAAE resins represent from 0.24% to 8.82% by dry weight, based on the total dry weight of the composition.

4. 10. The composition of claim 1 comprising at least one biocide selected from silver salts, silver in supported particulate form, polymeric or non-polymeric quaternary ammonium salts, and combinations thereof.

5. 2. The composition according to claim 1, wherein the one or more compounds based on silver and / or the one or more compounds based on quaternary ammonium represent from 0.07% to 18% by dry weight relative to the total dry weight of the composition.

6. 2. The composition of claim 1, wherein the composition comprises at least 3-iodo-2-propynyl butylcarbamate (IPBC) and / or diiodomethyl-p-tolylsulfone (DIMTS).

7. 2. The composition of claim 1 comprising at least one silver-based compound and at least IPBC.

8. The composition of claim 1 , wherein the composition comprises at least one binder.

9. The composition of claim 1 , wherein the composition comprises at least one of an aqueous or organic solvent medium.

10. The composition of claim 1 , wherein the composition comprises at least one moisturizing agent.

11. 1. A method for the surface treatment of an article intended to impart antiviral properties, comprising the steps of: applying one or more compositions to the surface of the article, wherein the compositions comprise: At least one polyamide-polyamine-epichlorohydrin resin (known as a PAAE resin), and one or more biocides, wherein the one or more biocides include at least one silver-based compound and / or one quaternary ammonium-based compound; and forming a coating present at least on a surface of said treated article comprising at least said PAAE resin and one or more of said biocides. The method comprising:

12. The method of claim 11 , wherein the composition or at least one of the compositions also comprises at least one binder.

13. 12. The method of claim 11, comprising applying a single antiviral composition according to any one of claims 1 to 10 to the surface of the article.

14. 12. The method of claim 11, comprising the steps of sequentially applying at least two different compositions comprising at least said PAAE resin in combination with one or more of said biocides, wherein a drying step is optionally performed between two application steps.

15. 12. The method of claim 11 , wherein the one or more compositions are applied onto the surface to be treated by spraying, sizing, impregnation, printing, overprinting on an at least partially printed surface, surface treatment, coating or deposition.

16. An article that has been surface treated via the method of claim 11.

17. 17. Article according to claim 16, wherein said article is a substrate intended for the manufacture of an information carrier.

18. 20. An information carrier comprising a substrate according to claim 17.

19. 1. Use of at least one polyamide-polyamine-epichlorohydrin resin as an additive to improve the antiviral properties of a composition intended for the surface treatment of an article, the composition comprising one or more biocides, the biocides comprising at least one compound based on silver and / or at least one compound based on quaternary ammonium.