Wallpaper with biocidal properties

Abstract

Wallpaper with biocidal properties The invention relates to a wallpaper with biocidal properties, all or part of the outer face of which, dedicated to providing a visual decorative effect, comprises a deposit of at least one polymeric binding agent, said binding agent being obtained by polymerization of at least one monomer chosen from acrylic and methacrylic acids, aliphatic or aromatic acrylates, methacrylates, styrene and mixtures thereof, and further containing from 0.05% to 6% by dry weight of at least one non-polymeric quaternary ammonium salt relative to the total dry weight of said deposit. Figure for abstract: None

Description

Title of the invention: Wallpaper with biocidal properties Technical field

[0001] The present invention aims to provide a wallpaper having biocidal properties, as well as a method for manufacturing such a wallpaper. Prior art

[0002] Wallpapers are classically used for interior decoration, in particular to constitute wall coverings dedicated to providing a visual decorative effect.

[0003] However, interior spaces can be conducive to contamination by one or more pathogenic microorganisms, and therefore to their propagation, which can generate epidemic and pandemic diseases. In this respect, it has already been considered to use wall coverings for decontamination purposes within passenger compartments.

[0004] For example, CN 106 088 495, CN 106 079 763 and CN 106 079 785 propose wallpapers comprising an anti-mold and antibacterial layer using in particular silver-loaded zeolite and didecyl dimethyl ammonium chloride. More specifically, these are wallpapers whose anti-mold and antibacterial properties require the superposition, at the level of the wallpaper to be treated, of several layers of distinct compositions, some of which are anti-mold and / or antibacterial. For obvious reasons, the manufacture of such wallpapers is complex. Finally, these documents do not relate to wallpapers with antiviral properties.

[0005] The present invention has the specific aim of proposing a wallpaper which is effective in terms of biocidal properties, in particular antiviral properties, and which also has the advantage of being produced according to an easy-to-use protocol. In particular, it does not require any tedious and expensive technical adjustments to the wallpaper manufacturing process itself.

[0006] The present invention also aims to provide a wallpaper with antimicrobial properties, in particular antiviral properties, suitable for interior decoration.

[0007] It also aims at a simplified process for the biocidal surface treatment of wallpaper. Summary of the invention

[0008] Thus, the present invention primarily aims at a wallpaper with biocidal properties, all or part of the external face of which is dedicated to providing a visual decorative effect, comprises a deposit of at least one polymeric binding agent, said binding agent being obtained by polymerization of at least one monomer chosen from acrylic and methacrylic acids, aliphatic or aromatic acrylates, methacrylates, styrene and their mixtures, and further containing from 0.05% to 6% by dry weight of at least one non-polymeric quaternary ammonium salt relative to the total dry weight of said deposit.

[0009] According to a particular variant, this deposit is in the form of a layer or even a film and as such forms a coating in particular as detailed below.

[0010] As detailed below, the wallpaper with biocidal properties also comprises a woven or non-woven fibrous support on the surface of one of the faces of which the deposit of binding agent is present.

[0011] As is evident from the examples, the inventors have shown that these wallpapers are effective in terms of antimicrobial activity, in particular antibacterial and antiviral. In addition, the presence of the deposit does not negatively impact the decorative properties of the wallpaper.

[0012] According to another of its aspects, the present invention relates to a method for manufacturing a wallpaper with biocidal properties, in particular as described above, comprising at least the steps consisting of: (a) have wallpaper, where appropriate treated on the surface of at least one of its sides with at least one vinyl polymer, b) bringing into contact at least all or part of the face of said wallpaper dedicated to providing a visual decorative effect with a composition, said composition comprising: - at least one non-polymeric quaternary ammonium salt, in particular didecyl dimethyl ammonium chloride (DDAC), - at least one polymeric binding agent obtained by polymerization of at least one monomer chosen from acrylic and methacrylic acids, aliphatic or aromatic acrylates, methacrylates, styrene and their mixtures, - optionally at least one filler, in particular mineral, in particular silica, and - optionally at least one biocidal agent distinct from a non-polymeric quaternary ammonium salt, and - optionally at least one polyamine-amide-epichlorohydrin (PAAE) resin to form a deposit with biocidal properties c) drying said deposit and d) optionally, hot or cold emboss said wallpaper, preferably after drying said deposit.

[0013] According to yet another of its aspects, the present invention relates to the use of a composition, in particular as described above, comprising: - at least one non-polymeric quaternary ammonium salt, in particular didecyl dimethyl ammonium chloride (DDAC), - at least one polymeric binding agent obtained by polymerization of at least one monomer chosen from acrylic and methacrylic acids, acrylates, methacrylates, aliphatic or aromatic, styrene and their mixtures, - optionally at least one filler, in particular mineral, in particular silica, and - optionally at least one biocidal agent distinct from a non-polymeric quaternary ammonium salt, and - optionally at least one polyamide-polyamine-epichlorohydrin resin (PAAE), to confer biocidal properties, particularly antiviral, to wallpaper.

[0014] In particular, the composition used in the method and use according to the invention has a viscosity ranging from 5 mPa.s to 10 Pa.s, in particular from 10 mPa.s to 5 Pa.s, and more particularly from 10 to 500 mPa.s at a temperature ranging from 20 to 25°C and at atmospheric pressure. It can thus be applied to the wallpaper by various printing techniques. Advantageously, the composition is applied to the wallpaper by gravure printing or flexography.

[0015] For the purposes of the invention, the term antimicrobial qualifies a biocidal activity, in particular bactericidal, fungicidal, yeasticidal, virucidal and / or algicidal, that is to say which kills the microorganism in question, but also a bacteriostatic and / or fungistatic activity, that is to say which inhibits the growth of bacteria and microscopic fungi.

[0016] For the purposes of the invention, the terms “biocidal compound or agent” or “biocide”, equivalent to the terms “antimicrobial compound or agent”, designate, in general, any compound effective for regulating and / or inhibiting the growth and / or reducing the density of microorganisms such as viruses, fungi, bacteria, algae and / or yeasts, etc.

[0017] As already specified above, within the meaning of the invention, by "coating" is meant a film-type deposit located on the surface of a support, or even where appropriate in the superficial part of the thickness of the treated support. The support thus treated has, thanks to this deposit, surface biocidal properties.

[0018] For the purposes of the invention, an agent is said to be a binder with regard to its ability to contribute, after drying and / or crosslinking of the composition applied to the surface of a support, to the formation of a solid deposit, or even a coating, of sufficient hardness to ensure the latter's durability. It is conventionally included in the composition of varnishes, inks, lacquers and paints.

[0019] In the present description, the term polymeric binding agent may be a single polymeric binder compound or a mixture of two or more polymeric binder compounds.

[0020] For the purposes of the invention, “dry weight”, also known as “weight of active material”, designates, unless otherwise indicated, the mass content of said compound, without any volatile solvents in which it is formulated, for example water. Detailed description Wallpaper

[0021] For the purposes of the invention, the term wallpaper is intended to denote a wallpaper already adhered as a surface covering of a substrate such as a wall for example, or an unadhered paper for example simply packaged in the form of a roll or in the form of sample sheets.

[0022] As specified above, the wallpaper with biocidal properties, object of the invention, has the specificity of having at least at the level of its external face dedicated to providing a visual decorative effect, a deposit of at least one polymeric binding agent containing at least one non-polymeric quaternary ammonium salt with a biocidal effect.

[0023] This decorative effect may be of a colorful nature and / or include decorative patterns in relief.

[0024] The face of the wallpaper opposite this decorative effect face is for its part intended to be applied to the surface of a substrate, generally a wall substrate, but which can of course be of any other nature.

[0025] According to a particular variant, both sides of the wallpaper may include a deposit with a biocidal effect. Polymeric binding agent

[0026] As specified above, a binding agent according to the invention is of polymeric nature. The polymeric binding agent is obtained by polymerization of at least one monomer chosen from acrylic and methacrylic acids, aliphatic or aromatic acrylates, methacrylates, styrene and their mixtures.

[0027] In particular, the polymeric binding agent is obtained by polymerization of at least 50% by weight, more particularly at least 80% by weight, in particular at least 95% by weight, or even at least 99% by weight, or even 100% by weight, of a monomer chosen from acrylic and methacrylic acids, acrylates, methacrylates, styrene and their mixtures, relative to the total weight of the monomers.

[0028] Preferably, the polymeric binding agent is a copolymer obtained by polymerization of at least one monomer chosen from acrylic and methacrylic acids, acrylates, methacrylates and their mixture with at least one styrene monomer, the copolymer being in particular obtained by polymerization of at least 50% by weight, more particularly at least 80% by weight, in particular at least 95% by weight weight, or even at least 99% by weight, or even 100% by weight of acrylic and methacrylic acid monomers, acrylates, methacrylates and / or styrene relative to the total weight of the monomers.

[0029] The polymeric binding agent is in particular free of monomeric units other than acrylic, methacrylic, acrylate, methacrylate and styrene monomeric units.

[0030] The polymeric binding agent may comprise, or even consist of, one or more polymer(s) chosen from acrylic homopolymers and copolymers, acrylate homopolymers and copolymers, methacrylic homopolymers and copolymers, methacrylate homopolymers and copolymers, styrene homopolymers and copolymers, and mixtures thereof, in particular being chosen from polyacrylics, polyacrylates, polymethacrylics, polymethacrylates, polystyrenes, styrene-acrylic copolymers, styrene-methacrylic copolymers, styrene-acrylate copolymers, styrene-methacrylate copolymers and mixtures thereof.

[0031] In particular, the polymeric binding agent comprises, or even consists of, at least one styrene-acrylic and / or styrene-acrylate copolymer.

[0032] By way of illustration of commercial polymeric binding agents suitable for the invention, mention may in particular be made of:

[0033] - an emulsion of acrylic copolymers marketed in solution at 41-43% in dry weight under the name NeoCryl XK-30 DSM by the company Coating Resins BV,

[0034] - an acrylic emulsion marketed in solution at 42-44% by dry weight under the name Ottopol K12T by the company Gellner Industrial,

[0035] - an acrylic emulsion marketed in solution at 48% by dry weight under the name nomination Texicryl 13-400 by the company Scott Bader SAS,

[0036] - an acrylic emulsion marketed in solution at 50.8% by dry weight under the name Texicryl 9107 by the Scott Bader company, and

[0037] - a styrene-acrylate solution marketed in solution at 36.6% by dry weight.

[0038] The weight average molecular weight of the polymeric binding agent (Mw) is advantageously greater than 80 g / mol and preferably greater than 86 g / mol.

[0039] The deposit is advantageously formed at a rate of 94% to 99.95% by dry weight, preferably 95 to 99.5% by dry weight, and more preferably 95 to 99% by dry weight of said polymeric binding agent relative to the total dry weight of said deposit.

[0040] In particular, the deposit is free of any additional polymeric binding agent(s). In other words, the deposit is free of any polymeric binding agent(s) other than those obtained by polymerization of at least one monomer chosen from acrylic and methacrylic acids, acrylates, methacrylates, styrene and their mixtures. Quaternary ammonium biocidal compound

[0041] Quaternary ammonium salts are known as antimicrobial and / or microbicidal agents, and more particularly as bacteriostatic (or antibacterial) and / or bactericidal and / or fungistatic (or antifungal) and / or fungicidal agents.

[0042] As specified above, the polymeric binding agent component contains at least one non-polymeric quaternary ammonium salt.

[0043] These quaternary ammonium salts generally comprise at least one quaternary ammonium cation with a suitable anion.

[0044] The cation is more particularly of the following formula:

[0045] [Chem.l]

[0046] with RH R2, R3 and R4 possibly being of diverse nature. For example, RH R2, R3 and R4 may be chosen, independently of one another, from alkyl, aryl, alkylaryl, arylalkyl, cycloalkyl, aromatic or non-aromatic heterocyclic, 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.

[0047] Alternatively, two or more of the RH groups R2, R3 and Ri may together form, with the nitrogen atom which supports them, a substituted or unsubstituted heterocyclic ring.

[0048] According to a particular embodiment, the RH groups R2, R3 and R4 are alkyl groups, preferably linear, in particular C1 to C20.

[0049] The groups Rb R2, R3 and R4 together comprise at least four carbon atoms. In particular, the total number of carbon atoms of the groups Rb R2, R3 and R4 may be at least 10. Preferably, at least one of the groups Rb R2, R3 and R4, in particular two of the groups Rb R2, R3 and R4, comprise from 6 to 20 carbon atoms, in particular from 8 to 18 carbon atoms.

[0050] The anion of the quaternary ammonium salt may in particular be chosen from halide anions, for example chloride, fluoride, bromide or iodide and sulfonate anions. Preferably, the anion of the quaternary ammonium salt may be a chloride.

[0051] The non-polymeric quaternary ammonium salts may more particularly be of the following formula

[0052] [Chem.2] (CH3)n(A)mN+X-,

[0053] in which A is as defined above for Rb R2, R3 and R4; X is an anion as defined above, n is an integer between 1 and 3, preferably 2 or 3; m is an integer between 1 and 3, preferably 1 or 2, provided that the sum n+m is 4. When m is 2 or 3, the A groups may be the same or different, in particular identical.

[0054] Preferably, the quaternary ammonium salt used as an antimicrobial agent according to the invention may be of formula (CH3)n(A)mN+X, in which n is 2 and m is 2 and A, identical or different, are as defined above for RB R2, R3 and R4.

[0055] In particular, A, identical or different, in particular identical, may represent linear alkyl groups from C6 to C20, in particular from C8 to C18, in particular from C8 to C12.

[0056] Examples that may be mentioned include didecyl dimethyl ammonium chloride (DDAC), dioctyl dimethyl ammonium chloride, octyl decyl dimethyl ammonium chloride.

[0057] According to a particular embodiment, the non-polymeric quaternary ammonium salt is non-silicone and preferably is at least didecyl dimethyl ammonium chloride (DDAC).

[0058] In particular, the polymeric binding agent contains from 0.05 to 6% by dry weight, preferably from 0.5 to 5.5% by dry weight, and more preferably from 1 to 5% by dry weight of non-polymeric quaternary ammonium salt(s), and more particularly contains from 0.05 to 6% by dry weight, preferably from 0.5 to 5.5% by dry weight, and more preferably from 1 to 5% by dry weight of didecyl dimethyl ammonium chloride (DDAC), relative to the total dry weight of binding agent.

[0059] In particular, the polymeric binding agent contains from 0.05 to 6% by dry weight, preferably from 0.5 to 5.5% by dry weight, and more preferably from 1 to 5% by dry weight of non-polymeric quaternary ammonium salts, and more particularly contains from 0.05 to 6% by dry weight, preferably from 0.5 to 5.5% by dry weight, and more preferably from 1 to 5% by dry weight of didecyl dimethyl ammonium chloride (DDAC), relative to the total dry weight of the deposit.

[0060] According to a particular embodiment, the deposit comprises at least

[0061] - from 0.05 to 6% by dry weight of didecyl dimethyl ammonium chloride (DDAC) per relative to the total dry weight of the deposit and

[0062] - from 94 to 99.95% by dry weight, preferably from 94.5 to 99.5% by dry weight of agent polymeric binder comprising, or even consisting of, one or more polymer(s) chosen from polyacrylics, polyacrylates, polymethacrylics, polymethacrylates, polystyrenes, styrene-acrylic copolymers, styrene-acrylate copolymers, styrene-methacrylic copolymers, styrene-methacrylate copolymers and their mixtures relative to the total dry weight of the deposit.

[0063] In addition to the essential compounds, the deposit can of course comprise other compounds conventionally considered for surface coatings, in particular with regard to the biocidal activity sought according to the invention.

[0064] Thus, the deposit may comprise one or more biocidal agents, in particular bacteriostatic, bactericidal, fungistatic, fungicidal, yeasticidal, algicidal, virucidal, distinct from a non-polymeric quaternary ammonium salt, called additional biocidal agents.

[0065] Of course, these agents can also be selected for their safety for humans under the conditions of implementation according to the invention.

[0066] This or these additional biocidal agents may in particular be chosen from p-[(Diiodomethyl)sulfonyl]toluol, 3-iodo-2-propynylbutyl carbamate, methyl-1H-benzimidazol-2-ylcarbamate, monolaurin, compounds based on isothiazoline or isothiazolone derivatives, chitosan or chitin derivatives, zinc zeolite, silver ions, in particular silver chloride, silver in supported particulate form, triclosan, polymeric quaternary ammonium salt and mixtures thereof.

[0067] According to one variant, the deposit contains at least one bacteriostatic and / or bactericidal agent chosen from compounds based on chitosan or chitin derivatives, zinc zeolite, silver ions, silver in supported particulate form and triclosan and mixtures thereof.

[0068] According to one variant, the deposit contains at least one fungistatic and / or fungicidal agent chosen from compounds based on isothiazoline or isothiazolone derivatives, chitosan or chitin derivatives, zinc zeolite, silver ions, silver in supported particulate form and triclosan.

[0069] According to one variant, the deposit further contains at least one fungistatic and / or fungicidal agent based on p-[(Diiodomethyl)sulfonyl]toluol.

[0070] According to one variant, the deposit further contains at least one fungistatic and / or fungicidal agent based on methyl-1H-benzimidazol-2-ylcarbamate.

[0071] According to a preferred variant, the deposit further contains at least 3-iodo-2-propynylbutyl carbamate (IPBC).

[0072] According to another variant, the deposit further contains at least one virucide, in particular of natural origin.

[0073] For the purposes of the present invention, the term “virucide” designates any compound having the capacity to kill or inhibit viruses.

[0074] The virucide according to the present invention is more particularly dedicated to killing and / or inhibiting a virus pathogenic to mammals and more particularly to humans.

[0075] Such viruses may be naked viruses or enveloped viruses.

[0076] By “virucide of natural origin” is meant any virucide pre-existing in nature or capable of being synthesized from natural compounds existing in nature.

[0077] The virucides of natural origin which 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.

[0078] As an example of such virucides, mention may in particular be made of monolaurin which can be obtained by synthesis from glycerol and lauric acid.

[0079] For the purposes of the invention, the term monolaurin is intended to designate both naturally pre-existing monolaurin and that obtained by synthesis from glycerol and lauric acid.

[0080] According to one embodiment, the virucide of natural origin may in particular be chosen from monolaurin, lactoferrin and essential oils exhibiting antiviral activity, such as for example bay essential oil.

[0081] In a preferred embodiment, the ancillary biocide is at least monolaurin.

[0082] For illustration purposes, the deposit may comprise from 0.05 to 10% by dry weight, for example from 0.2 to 6% by dry weight of additional biocidal agent(s), in particular virucide(s) of natural origin, relative to the total dry weight of the deposit.

[0083] According to another particular embodiment, the deposit further comprises at least one filler, in particular mineral.

[0084] Such a component is particularly advantageous for giving the coating increased surface qualities and in particular improving its coefficient of friction or modifying its shine.

[0085] This filler may be chosen from mineral fillers, in particular silica, in particular colloidal silica, sodium silicates, sodium aluminosilicates, natural or precipitated calcium carbonates, talc, natural or calcined kaolin, alumina hydrate, titanium dioxide, aluminum silicates, barium sulfate, and mixtures thereof, and from organic fillers, in particular plastic fillers or pigments. Preferably, the deposit comprises at least silica.

[0086] The deposit may thus comprise from 0.01% to 20% by dry weight, preferably from 0.1% to 10% by dry weight of filler(s), in particular mineral, in particular silica, relative to the total dry weight of the deposit.

[0087] According to another particular embodiment, the deposit further comprises at least one polyamine-amide-epichlorohydrin (PAAE) resin.

[0088] Such a component is particularly advantageous for giving the coating increased surface qualities and in particular improving its resistance to wet abrasion.

[0089] The deposit may thus comprise from 0.01% to 10% by dry weight, preferably from 0.05% to 5% by dry weight of PAAE, relative to the total dry weight of the deposit.

[0090] Preferably, the polymeric binding agent and the non-polymeric quaternary ammonium salt(s) are present in said deposit, in particular in the form of a coating, in the form of an intimate mixture. In particular, the deposit is a single-layer coating. The deposit is in particular in the form of a single layer, in particular homogeneous, the various components of which such as the polymeric binding agent, the non-polymeric quaternary ammonium salt(s), and where appropriate one or more fillers and / or one or more additional biocidal agents are in the form of an intimate mixture.

[0091] Thus, according to a particular embodiment, the deposit consists of

[0092] - from 0.05 to 6% by dry weight of didecyl dimethyl ammonium chloride (DDAC) per relative to the total dry weight of the deposit,

[0093] - from 94 to 99.95% by dry weight, preferably from 94.5 to 99.5% by dry weight of agent polymeric binder comprising, or even consisting of, one or more polymer(s) chosen from polyacrylics, polyacrylates, polymethacrylics, polymethacrylates, polystyrenes, styrene-acrylic copolymers, styrene-acrylate copolymers, styrene-methacrylic copolymers, styrene-methacrylate copolymers and mixtures thereof relative to the total dry weight of said deposit, - optionally at least one filler, in particular mineral, in particular silica, and - optionally at least one biocidal agent distinct from a non-polymeric quaternary ammonium salt, and

[0094] - optionally at least one polyamine-amide-epichlorohydrin (PAAE) resin.

[0095] As specified above, wallpaper with biocidal properties generally comprises a fibrous support.

[0096] In particular, the deposit of binding agent of the wallpaper with biocidal properties is on the external surface and preferably in contact with a woven or non-woven fibrous support.

[0097] The fibrous support may comprise natural, artificial and / or synthetic fibers, notably chosen from cellulose, polyester, cotton fibers, and their mixtures.

[0098] In particular, the fibrous support may be of the paper type, in particular based on cellulose fibers. The fibrous support may also be a non-woven fibrous support in the form of an assembly of compressed fibers, in particular based on a mixture of fibers of cellulose and polyester.

[0099] The fibrous support may also comprise on the surface of its decorative effect face a polymeric layer, in particular a waterproof one. The deposit of binding agent required according to the invention is then placed on the surface, in particular in contact, with this polymeric layer generally formed from at least one vinyl polymer, in particular polyvinyl chloride. In particular, the wallpaper with biocidal properties may be formed from a vinyl-coated wallpaper.

[0100] In particular, the wallpaper with biocidal properties has a weight ranging from 80 to 200 g / m2.

[0101] As is apparent from the examples below, a wallpaper with biocidal properties according to the invention advantageously has the expected biocidal properties, in particular bactericidal and antiviral.

[0102] After a contact time of 24 hours with E.coli and S.aureus strains according to ISO 20743, good to excellent antibacterial activity is measured, with activities of 100% and 99.26% reduction in bacterial titer.

[0103] After a contact time of 5 hours with the human-infected Coronavirus strains HcoV-229E and HcoV-OC43 according to ISO 21702:2019 or ASTME 1093, good to excellent antiviral activity is measured, according to the criteria of ISO 18184:2019-06 annex 5 and in particular very strong antiviral activity against viruses of the enveloped virus family with activities greater than 1.3 log reduction in viral titer.

[0104] The wallpaper with biocidal properties is particularly dedicated to killing and / or inhibiting a virus pathogenic to mammals and more particularly to humans.

[0105] Such viruses may be naked viruses or enveloped viruses.

[0106] As a representative of the viruses pathogenic to humans that may be considered according to the invention, we can more particularly cite retroviruses, cytomegaloviruses, rotaviruses, paramyxoviruses, polioviruses, hantaviruses, coxsackieviruses, the encephalomyocarditis virus, picornaviruses including rhinoviruses, DNA or RNA viruses in particular flaviviridae, the AIDS virus, influenza viruses and in particular H1N1, coronaviruses and in particular human-infecting coronaviruses Hcov-229E, Hcov-0C43, SARS-COV-2, the smallpox virus, the yellow fever virus, the hepatitis C virus, the Ebola viruses, the herpes viruses, the Epstein-Barr virus, the varicella-zoster virus, the rubella virus, or even the simian virus 40 or SV40.

[0107] Furthermore and against all expectations, the presence of an effective quantity in terms of antimicrobial efficacy, of biocidal quaternary ammonium salt(s), in a deposit of polymeric binding agent, does not alter the manifestation of additional properties of the coating, such as for example the shine or its durability on the support, and including the absence of detachment following exposure to dry or wet friction.

[0108] Process for preparing wallpaper according to the invention

[0109] The present invention also relates to a method for manufacturing a wallpaper with biocidal properties, in particular as described previously, comprising at least the steps consisting of: (a) have wallpaper, where appropriate treated on the surface of at least one of its sides with at least one vinyl polymer, b) bringing into contact at least all or part of the face of said wallpaper dedicated to providing a visual decorative effect with a composition, said composition comprising: - at least one non-polymeric quaternary ammonium salt, in particular didecyl dimethyl ammonium chloride (DDAC), - at least one polymeric binding agent obtained by polymerization of at least one monomer chosen from acrylic and methacrylic acids, aliphatic or aromatic acrylates, methacrylates, styrene and their mixtures, - optionally at least one filler, in particular mineral, in particular silica, and - optionally at least one biocidal agent distinct from a non-polymeric quaternary ammonium salt, and - optionally at least one polyamine-amide-epichlorohydrin (PAAE) resin to form a deposit with biocidal properties c) drying said deposit and d) optionally, hot or cold emboss said wallpaper, preferably after drying said deposit.

[0110] In particular, after drying, a coating is formed on all or part of the external face dedicated to providing the desired visual decorative effect.

[0111] The composition used according to the invention comprises at least one non-polymeric quaternary ammonium salt, in particular as described above. In particular, the composition comprises from 0.05% to 6% by dry weight, preferably from 0.5% to 5.5% by dry weight, and more preferably from 1% to 5% by dry weight, of at least one non-polymeric quaternary ammonium salt, in particular didecyl dimethyl ammonium chloride, relative to the total dry weight of the composition.

[0112] It also comprises at least one polymeric binding agent, in particular as described above, obtained by polymerization of at least one monomer chosen from acrylic and methacrylic acids, aliphatic or aromatic acrylates, methacrylates, styrene and their mixtures.

[0113] Preferably, the polymeric binding agent considered in the composition is of a nature polymeric and implemented in the form of a dispersion, solution or emulsion, in particular aqueous, preferably an aqueous dispersion or emulsion.

[0114] As is apparent from the above, this composition may comprise from 94% to 99.95% by dry weight, preferably from 95% to 99.5% by dry weight, and more preferably from 95% to 99% by dry weight, of polymeric binding agent obtained by polymerization of at least one monomer chosen from acrylic and methacrylic acids, aliphatic or aromatic acrylates, methacrylates, styrene and their mixtures, relative to the dry weight of the composition.

[0115] In particular, the composition comprises from 0.1% to 10% by dry weight of at least one non-polymeric quaternary ammonium salt, in particular didecyl dimethyl ammonium chloride, and from 90 to 99.9% by dry weight of polymeric binding agent(s) relative to the total weight of the composition, preferably from 0.5% to 5% by dry weight of at least one non-polymeric quaternary ammonium salt, in particular didecyl dimethyl ammonium chloride, and from 95 to 99.5% by dry weight of polymeric binder(s) relative to the total dry weight of the composition.

[0116] The composition optionally comprises at least one filler and / or at least one biocidal agent distinct from a non-polymeric quaternary ammonium salt, in particular as described previously.

[0117] In particular, the composition comprises from 0.01% to 20% by dry weight, preferably from 0.1% to 10% by dry weight, and more preferably from 0.5% to 8% by dry weight, of filler, in particular mineral, in particular silica, relative to the total dry weight of the composition.

[0118] In particular, the composition comprises from 0.05% to 10% by dry weight, preferably from 0.2% to 6% by dry weight, and more preferably from 0.2% to 5% by dry weight, of additional biocidal agent relative to the total dry weight of the composition.

[0119] In particular, the composition comprises from 0.01% to 10% by dry weight, preferably from 0.05% to 5% by dry weight, and more preferably from 0.1% to 2% by dry weight, of PAAE resin relative to the total dry weight of the composition.

[0120] The composition used in the process according to the invention is fluid. It may have a viscosity ranging from 5 mPa.s to 10 Pa.s, in particular from 10 mPa.s to 5 Pa.s, and more particularly from 10 to 500 mPa.s, at a temperature varying from 20 to 25°C and at atmospheric pressure.

[0121] The viscosities of the compositions according to the invention can be measured by conventional methods. The selection of the measuring method as well as the appropriate measuring equipment, particularly with regard to the viscosity scale of the composition in question, clearly falls within the skills of a person skilled in the art.

[0122] For example, for a composition having a viscosity clearly less than 2 Pa.s, a Brookfield viscometer is preferred as measuring equipment. with axis No. 2 at 100 revolutions per minute (ISO 2555) ensuring that the torque measured by the device is less than 0.5 mN.m. If the torque is greater than this value, it is necessary to choose an axis of a higher degree.

[0123] This viscosity can be adjusted with regard to the particular function attached to the composition, namely constituting for example a varnish, an ink, a lacquer or a paint, but also to the method of application considered for treating the surface of a wallpaper with said composition.

[0124] In particular, the wallpaper to be treated in step a) is devoid of biocidal properties.

[0125] In particular, the method according to the invention comprises a prior step of fa manufacturing of the wallpaper to be treated. For example, steps b) and / or c) can be carried out directly after manufacturing the wallpaper to be treated.

[0126] The contacting in step b) can be carried out by spraying, by size press surfacing, by coating, by printing, by immersion in a bath. In particular, it is carried out by inkjet printing, gravure printing, flexography, pencil coating, padding, digital printing or flexographic overprinting, preferably by gravure printing, by flexography, by screen printing, by pencil coating or by flexographic overprinting and more preferably by gravure printing or flexography.

[0127] Thus, at room temperature and pressure, the composition used: - in inkjet can advantageously have a viscosity between 5 and 30 mPa.s, - in gravure printing can advantageously have a viscosity of between 10 and 150 mPa.s, - in flexography can advantageously have a viscosity between 10 and 500 mPa.s, - in flexographic overprinting can advantageously have a viscosity of between 10 and 500 mPa.s, - in air blade coating can advantageously have a viscosity of between 50 and 200 mPa.s, - in curtain coating can advantageously have a viscosity of between 5 and 500 mPa.s, and / or - in size-press surfacing can advantageously have a viscosity between 20 and 100 mPa.s.

[0128] Preferably, the composition has a viscosity of between 10 and 50 mPa.s and the contacting is carried out by gravure printing or the composition has a viscosity of between 10 and 500 mPa.s and the contacting is carried out by flexography or by flexographic overprinting.

[0129] The viscosity of the fluid composition according to the invention is in particular adjustable through the choice of the nature(s) and the quantity(s) of polymeric binding agent(s) required according to the invention or even, where appropriate, by dilution of the com- position especially with water.

[0130] Drying can be carried out at a temperature ranging from 30 to 250°C.

[0131] The coating thus produced proves to have very satisfactory durability and excellent qualities. In addition, it has high-performance biocidal activity.

[0132] The present invention also relates to the use of a composition as described above to confer biocidal properties, in particular antiviral properties, to a wallpaper, in particular to a wallpaper such as the wallpaper to be treated in step a) of the method according to the invention.

[0133] The composition described above lends itself, in view of its specificities, advantageously to use as varnish, ink, lacquer or paint.

[0134] The examples appearing below are presented for illustrative and non-limiting purposes of embodiments of the invention. EXAMPLES Materials and methods

[0135] The following raw materials were used:

[0136] - Didecyl dimethyl ammonium chloride (DDAC) marketed as a 50% solution % or 80% by weight MA (active ingredient) of DD AC, by one of the companies THOR, STEPAN EUROPE and LONZA

[0137] - An acrylic copolymer marketed in solution at 41-43% by dry weight under the NeoCryl XK-30 DSM designation by Coating Resins BV

[0138] - An acrylic emulsion marketed in solution at 48% by weight MA under the name Texicryl 13-400 by the company Scott Bader SAS.

[0139] - A styrene-acrylate copolymer marketed in solution at 36.6% by weight MA

[0140] - A PAAE resin marketed in solution at 14.8% by weight MA under the denomination FennoStrenght® XO mination by Kemira Company.

[0141] In the examples which follow and unless otherwise indicated, the % by weight are expressed as % by weight of the commercial products which are sources of compounds according to the invention.

[0142] 1. Test of antibacterial properties

[0143] They are characterized using antibacterial control by transfer method according to ISO 20743 standard carried out with E.coli and S.aureus strains and a contact time of 24 hours.

[0144] 2. Test of antiviral properties

[0145] All tests carried out with the Coronavirus HcoV-229E strain are carried out according to the ISO 21702:2019 standard adapted with a contact time of 5 hours.

[0146] All tests performed with the Coronavirus OC43 strain (ATCC VR-1558) are carried out according to the ASTM E1053 standard adapted with a contact time of 5 hours.

[0147] The results, expressed in log, correspond to the reduction in viral load for the contact times considered compared to a reference without antimicrobial treatment. Example 1: Preparation of biocidal compositions

[0148] The compositions are prepared from an aqueous medium into which the commercial form of the polymeric binding agent in question is introduced. After obtaining a homogeneous mixture, the DD AC is then added. The preparations are carried out using a Rayneri.

[0149] The proportions used are indicated in table 1.

[0150] [Tables 1] Composition 1 (% by weight) 2 (% by weight) Texicryl 13-400 acrylic emulsion 97 Styrene-acrylate solution at 36.6% by weight of MA 97.8 PAAE resin at 14.8% by weight of MA 0.2 Commercial DDAC solution at 80% by weight of MA 0.7 Commercial DDAC solution at 50% by weight of MA Water Qsp 100 Qsp100 Viscosity (mPa.s) H8 120

[0151] Example 2: Preparation and characterization of the antimicrobial performances of wallpapers conforming and not conforming to the invention, formed from the compositions of Example 1

[0152] Composition 1: The support considered is a 400g / m2 paper substrate.

[0153] The composition is applied by bar coating with an average deposition rate of 3 to 8 g / m2 dry weight. More specifically, the deposition rate is 3.5 g / m2 for composition 1.

[0154] Composition 2: The support considered is a 160 g / m2 wallpaper (two laminated papers, respectively 70 and 90 g / m2). The composition is applied by rotogravure process with an average deposition rate of 1 to 8 g / m2 in dry weight. More precisely, the deposition rate is 3 g / m2 for composition 2.

[0155] Table 2 reports the measured antimicrobial performances.

[0156] [Tables2] Antimicrobial performance Composition 1 Composition 2 Average deposit in g / nr dry of coating 3 Antibacterial ISO 20743 E. coli 100 Antibacterial ISO 20743 S. auretis 99.26 Antiviral AS TME 1053 corona virus OC43 33 1.4

Claims

Claims

1. Wallpaper with biocidal properties, all or part of the external face of which is dedicated to providing a visual decorative effect, comprises a deposit of at least one polymeric binding agent, said binding agent being obtained by polymerization of at least one monomer chosen from acrylic and methacrylic acids, aliphatic or aromatic acrylates, methacrylates, styrene and their mixtures, and further containing from 0.05% to 6% by dry weight of at least one non-polymeric quaternary ammonium salt relative to the total dry weight of said deposit, and said deposit comprising at least one polyamine-amide-epichlorohydrin (PAAE) resin.

2. A biocidal wallpaper according to claim 1, wherein said non-polymeric quaternary ammonium salt is at least didecyl dimethyl ammonium chloride (DDAC).

3. Wallpaper with biocidal properties according to claim 1 or 2, said binding agent containing from 0.05 to 6% by dry weight and preferably from 0.5 to 5.5% by dry weight, of non-polymeric quaternary ammonium salt(s), in particular didecyl dimethyl ammonium chloride (DDAC), relative to the total dry weight of binding agent.

4. Wallpaper with biocidal properties according to any one of the preceding claims, said polymeric binding agent being a copolymer obtained by polymerization of at least one monomer chosen from acrylic and methacrylic acids, acrylates, methacrylates and their mixture with at least one styrene monomer.

5. Wallpaper with biocidal properties according to any one of the preceding claims, said polymeric binding agent comprising, or even consisting of, one or more polymer(s) chosen from acrylic homopolymers and copolymers, acrylate homopolymers and copolymers, methacrylic homopolymers and copolymers, methacrylate homopolymers and copolymers, styrene homopolymers and copolymers, and mixtures thereof, in particular from polyacrylics, polyacrylates, polymethacrylics, polymethacrylates, polystyrenes, styrene-acrylic copolymers, styrene-methacrylic copolymers, styrene-acrylate copolymers, styrene-methacrylate copolymers and mixtures thereof, and more particularly comprises, or even consists of, at least one styrene-acrylic and / or styrene-acrylate copolymer.

6. Wallpaper with biocidal properties according to any one of the preceding claims, said deposit being formed at a rate of 94 to 99.95% by dry weight, preferably 95 to 99.5% by dry weight, and more preferably 95 to 99% by dry weight, of said polymeric binding agent relative to the total dry weight of said deposit.

7. Wallpaper with biocidal properties according to any one of the preceding claims, said deposit further comprising one or more biocidal agent(s) distinct from a non-polymeric quaternary ammonium salt, preferably chosen from p-[(Diiodomethyl)sulfonyl]toluol, 3-iodo-2-propynylbutyl carbamate, methyl-1H-benzimidazol-2-ylcarbamate, monolaurin, compounds based on isothiazoline or isothiazolone derivatives, chitosan or chitin derivatives, zinc zeolite, silver ions, in particular silver chloride, silver in supported particulate form, triclosan, polymeric quaternary ammonium salt and mixtures thereof, and more preferably further comprising at least 3-iodo-2-propynylbutyl carbamate (IPBC).

8. Wallpaper with biocidal properties according to any one of the preceding claims, said deposit further comprising at least one filler, in particular mineral, in particular silica.

9. Wallpaper with biocidal properties according to any one of the preceding claims, said deposit being a single-layer coating.

10. Wallpaper with biocidal properties according to any one of the preceding claims, the deposit of binding agent is on the external surface and preferably in contact with a woven or non-woven fibrous support.

11. Wallpaper with biocidal properties according to any one of the preceding claims, comprising a fibrous support, in particular woven or non-woven, comprising on the surface of its decorative effect face a polymeric layer, said deposit of binding agent being in particular arranged on the surface, in particular in contact, of said polymeric layer formed of at least one vinyl polymer, preferably polyvinyl chloride.

12. Wallpaper with biocidal properties according to any one of the preceding claims, having a grammage ranging from 80 to 200 g / m2.

13. Method for manufacturing a wallpaper with biocidal properties, in particular as defined according to any one of the preceding claims, comprising at least the steps of: a) providing a wallpaper, where appropriate surface-treated with at least one of its faces with at least one vinyl polymer, b) bringing into contact at least all or part of the face of said wallpaper dedicated to providing a visual decorative effect with a composition, said composition comprising: - at least one non-polymeric quaternary ammonium salt, in particular didecyl dimethyl ammonium chloride (DDAC), - at least one polymeric binding agent obtained by polymerization of at least one monomer chosen from acrylic and methacrylic acids, acrylates, methacrylates, aliphatic or aromatic, styrene and mixtures thereof, - optionally at least one filler, in particular mineral, in particular silica, and - at least one PAAE resin, and - optionally at least one biocidal agent other than a non-polymeric quaternary ammonium salt, to form a deposit with biocidal properties and c) drying said deposit d) optionally hot or cold embossing said wallpaper with biocidal properties, preferably after drying said deposit.

14. Method according to the preceding claim, the contacting in step b) being carried out by inkjet printing, gravure printing, flexography, pencil coating, padding, digital printing or flexographic overprinting, preferably by gravure printing or flexography.

15. A method according to claim 13 or 14, wherein said polymeric binding agent is implemented in the form of an aqueous dispersion or emulsion.

16. A method according to any one of claims 13 to 15, said composition having a viscosity ranging from 5 mPa.s to 10 Pa.s, in particular from 10 mPa.s to 5 Pa.s, and more particularly from 10 to 500 mPa.s at a temperature ranging from 20 to 25°C and at atmospheric pressure.

17. A method according to any one of claims 13 to 16, said composition being in the form of a varnish, an ink, a lacquer or a paint.

18. A method according to any one of claims 13 to 17, the composition comprising from 0.05% to 6% by dry weight of at least one non-polymeric quaternary ammonium salt, in particular didecyl dimethyl ammonium chloride, and from 94 to 99.95% by dry weight of polymeric binding agent(s) relative to the total dry weight of the composition, preferably from 0.5% to 5.5% by dry weight of at least one non-polymeric quaternary ammonium salt, in particular didecyl dimethyl ammonium chloride, and from 95 to 99.5% by dry weight of polymeric binding agent(s) relative to the total dry weight of the composition.

19. Use of a composition, in particular as described in any one of claims 15 to 18, comprising: - at least one non-polymeric quaternary ammonium salt, in particular didecyl dimethyl ammonium chloride (DDAC), - at least one polymeric binding agent obtained by polymerization of at least one monomer chosen from acrylic and methacrylic acids, aliphatic or aromatic acrylates, methacrylates, styrene and their mixtures, - optionally at least one filler, in particular mineral, in particular silica, and - optionally at least one biocidal agent distinct from a non-polymeric quaternary ammonium salt, and - at least one PAAE resin to confer biocidal properties, particularly antiviral, to wallpaper.