WO2023213976A1 - Wallpaper having biocidal properties - Google Patents
Wallpaper having biocidal properties Download PDFInfo
- Publication number
- WO2023213976A1 WO2023213976A1 PCT/EP2023/061865 EP2023061865W WO2023213976A1 WO 2023213976 A1 WO2023213976 A1 WO 2023213976A1 EP 2023061865 W EP2023061865 W EP 2023061865W WO 2023213976 A1 WO2023213976 A1 WO 2023213976A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- dry weight
- wallpaper
- deposit
- polymeric
- styrene
- Prior art date
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- 230000003115 biocidal effect Effects 0.000 title claims abstract description 54
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- 229960004670 didecyldimethylammonium chloride Drugs 0.000 claims description 22
- RUPBZQFQVRMKDG-UHFFFAOYSA-M Didecyldimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC RUPBZQFQVRMKDG-UHFFFAOYSA-M 0.000 claims description 21
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/02—Amines; Quaternary ammonium compounds
- A01N33/12—Quaternary ammonium compounds
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
- E04F13/00—Coverings or linings, e.g. for walls or ceilings
- E04F13/002—Coverings or linings, e.g. for walls or ceilings made of webs, e.g. of fabrics, or wallpaper, used as coverings or linings
Definitions
- the present invention aims to provide a wallpaper having biocidal properties, as well as a process for manufacturing such wallpaper.
- Wallpapers are classically used for interior decoration, in particular to constitute wall coverings dedicated to providing a visual decorative effect.
- CN 106 088 495, CN 106 079 763 and CN 106 079 785 offer wallpapers comprising an anti-mold and antibacterial layer using in particular zeolite loaded with silver and didecyl dimethyl ammonium chloride. More precisely, these are wallpapers whose anti-mold and antibacterial properties require the superposition on 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 target wallpaper with antiviral properties.
- the object of the present invention is precisely to propose a wallpaper that performs well in terms of biocidal properties, in particular antiviral properties, and also has the advantage of being developed according to an easy implementation protocol. In particular, it does not require tedious and expensive technical development of the wallpaper manufacturing process itself.
- the present invention also aims to provide wallpaper with antimicrobial properties, in particular antiviral properties, suitable for interior decoration.
- the present invention aims primarily at a wallpaper with biocidal properties of which all or part of the external face 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, acrylates, methacrylates, aliphatic or aromatic, 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.
- the present invention aims at a wallpaper with biocidal properties of which all or part of the external face 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, acrylates, methacrylates, aliphatic or aromatic, styrene and mixtures thereof, and also containing from 0.05% to 6% by dry weight of at least one salt of non-polymeric quaternary ammonium relative to the total dry weight of said deposit, and said deposit comprising at least one polyamine-amide-epichlorohydrin (PAAE) resin.
- PAAE polyamine-amide-epichlorohydrin
- this deposit is in the form of a layer or even a film and as such forms a coating in particular as detailed below.
- wallpaper with biocidal properties also comprises a woven or non-woven fibrous support on the surface of one of the faces of which the binding agent deposit is present.
- these wallpapers are effective in terms of antimicrobial activity, in particular antibacterial and antiviral.
- the presence of the deposit does not negatively impact the decorative properties of the wallpaper.
- the present invention relates to a process for manufacturing a wallpaper with biocidal properties, in particular as described above, comprising at least the steps consisting of: a) having a wallpaper, the case optionally treated on the surface of 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:
- DD AC didecyl dimethyl ammonium chloride
- 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,
- PAAE polyamine-amide-epichlorohydrin
- the present invention relates to the use of a composition, in particular as described above, comprising:
- DD AC didecyl dimethyl ammonium chloride
- 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,
- PAAE polyamide-poly amine-epichlorohydrin resin
- the composition used in the process and the 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 wallpaper using various techniques. printing.
- the composition is applied to the wallpaper by rotogravure or flexographic.
- the term antimicrobial describes a biocidal activity, in particular bactericidal, fungicidal, yeasticidal, virucidal and/or algaecidal, that is to say which kills the microorganism considered but also a bacteriostatic and/or fungistatic activity c that is to say which inhibits the growth of bacteria and microscopic fungi.
- 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 growth and /or reduce the density of microorganisms such as viruses, fungi, bacteria, algae and/or yeasts, etc.
- coating we mean a film-type deposit located at the surface of a support, or if necessary in the superficial part of the thickness of the treated support. The support thus treated has, thanks to this deposit, surface biocidal properties.
- an agent is said to be a binding agent 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 its durability. It is conventionally used in the composition of varnishes, inks, lacquers and paints.
- polymeric binder agent may be a single polymeric binder compound or a mixture of two or more polymeric binder compounds.
- dry weight also known as “weight of active material” designates without contrary indication the mass content of said compound, without any volatile solvents in which it is formulated, for example water.
- the term wallpaper means 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.
- the wallpaper with biocidal properties, object of the invention has the specificity of possessing at least on its external face dedicated to providing a visual decorative effect, a deposit of at least one binding agent polymer containing at least one non-polymeric quaternary ammonium salt with biocidal effect.
- This decorative effect may be of a color nature and/or include decorative patterns in relief.
- the side of the wallpaper opposite this side with a decorative effect is for its part dedicated to being applied to the surface of a substrate that is generally wall-mounted but can of course be of any other nature.
- both sides of the wallpaper may include a deposit with a biocidal effect.
- 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, acrylates, methacrylates, aliphatic or aromatic, styrene and their mixtures.
- 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.
- 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, 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.
- 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, or even at least 99% by weight, or even 100% by weight of acrylic and methacrylic acid monomers, acrylates,
- the polymeric binding agent is in particular devoid of monomeric units other than acrylic, methacrylic, acrylate, methacrylate and styrene monomeric units.
- the polymeric binding agent may comprise, or even consist of, one or more polymer(s) chosen from acrylic homo-polymers and co-polymers, acrylate homo-polymers and co-polymers, homo-polymers and co-polymers.
- methacrylics, methacrylate homopolymers and co-polymers, styrene homo-polymers and co-polymers, and their mixtures in particular being chosen from polyacrylics, poly acrylates, polymethacrylics, polymethacrylates, polystyrenes, styrene copolymers - acrylics, styrene-methacrylic copolymers, styrene-acrylate copolymers, styrene-methacrylate copolymers and their mixtures.
- the polymeric binding agent comprises, or even consists of, at least one styrene-acrylic and/or styrene-acrylate copolymer.
- NeoCryl XK-30 DSM an emulsion of acrylic copolymers marketed in solution at 41-43% by dry weight under the name NeoCryl XK-30 DSM by the company Coating Resins B.V,
- the average molecular mass of the polymeric binding agent by weight (Mw) is advantageously greater than 80 g/mol and preferably greater than 86 g/mol.
- the deposit is advantageously formed at a rate of 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 said polymeric binding agent relative to the total dry weight of said deposit.
- the deposit is devoid of annexed polymeric binding agent(s).
- the deposit is devoid of polymeric binding agent(s) distinct from those obtained by polymerization of at least one monomer chosen from acrylic and methacrylic acids, acrylates, methacrylates, styrene and mixtures thereof.
- 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.
- the polymeric binder component contains at least one non-polymeric quaternary ammonium salt.
- These quaternary ammonium salts generally comprise at least one quaternary ammonium cation with an appropriate anion.
- the cation is more particularly of the following formula:
- Ri, R2, R3 and R4 possibly being of various nature.
- Ri, R2, R3 and R4 can be chosen, independently of each other, from alkyl, aryl, alkylaryl, arylalkyl, cycloalkyl, aromatic or non-aromatic heterocyclic, or alkenyl groups, said groups being able to be substituted or not, linear or branched, and optionally interrupted by one or more heteroatoms, for example, by one or more oxygen atoms, or by one or more phosphinate groups.
- two or more of the groups Ri, R2, R3 and R4 can form together, with the nitrogen atom which supports them, a substituted or unsubstituted heterocyclic ring.
- the groups Ri, R2, R3 and R4 are alkyl groups, preferably linear, in particular C to C20.
- the groups Ri, R2, R3 and R4 together comprise at least four carbon atoms.
- the total number of carbon atoms of the groups Ri, R2, R3 and R4 can be at least 10.
- at least one of the groups Ri, R2, R3 and R4, in particular two of the Ri, R2, R3 and R4 comprise from 6 to 20 carbon atoms, in particular from 8 to 18 carbon atoms.
- the anion of the quaternary ammonium salt may in particular be chosen from halide anions, for example chloride, fluoride, bromide or iodide and sulphonate anions.
- the anion of the quaternary ammonium salt may be a chloride.
- non-polymeric quaternary ammonium salts may more particularly be of the following formula
- the quaternary ammonium salt used as an anti-microbial agent according to the invention can be of formula (CH3) n (A) m N + X', in which n is 2 and m is 2 and A, identical or different, are as defined above for Ri, R2, R3 and R4.
- A identical or different, in particular identical, can represent linear alkyl groups in C ⁇ to C20, in particular in Cs to Cis, in particular in Cs to C12.
- DDAC didecyl dimethyl ammonium chloride
- dioctyl dimethyl ammonium chloride dioctyl decyl dimethyl ammonium chloride.
- the non-polymeric quaternary ammonium salt is non-silicone and preferably is at least didecyl dimethyl ammonium chloride (DDAC).
- DDAC didecyl dimethyl ammonium chloride
- 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 salt(s). ) of non-polymeric quaternary ammonium(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 (DD AC), relative to the total dry weight of binding agent.
- DD AC didecyl dimethyl ammonium chloride
- 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 salts of non-polymeric quaternary ammonium, 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 chloride dimethyl ammonium (DD AC), relative to the total dry weight of the deposit.
- DD AC didecyl chloride dimethyl ammonium
- the deposit comprises at least 0.05 to 6% by dry weight of didecyl dimethyl ammonium chloride (DD AC) relative to the total dry weight of the deposit and from 94 to 99.95% by weight. dry, preferably from 94.5 to 99.5% by dry weight of polymeric binding agent comprising, or even consisting of, one or more polymer(s) chosen from polyacrylics, poly acrylates, 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.
- DD AC didecyl dimethyl ammonium chloride
- the deposit can of course include other compounds conventionally considered for surface coatings, in particular with regard to the biocidal activity sought according to the invention.
- the deposit may include one or more biocidal agents, in particular bacteriostatic, bactericidal, fungistatic, fungicidal, yeasticidal, algicidal, virucidal, distinct from a non-polymeric quaternary ammonium salt, called ancillary biocidal agents.
- biocidal agents in particular bacteriostatic, bactericidal, fungistatic, fungicidal, yeasticidal, algicidal, virucidal, distinct from a non-polymeric quaternary ammonium salt, called ancillary biocidal agents.
- these agents can also be selected for their safety for humans under the conditions of implementation according to the invention.
- 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.
- the deposit contains at least one bacteriostatic and/or bactericidal agent chosen from compounds based on chitosan or derived from chitin, zinc zeolite, silver ions, silver in supported particulate form and triclosan and their mixtures.
- the deposit contains at least one fungistatic and/or fungicidal agent chosen from compounds based on isothiazoline or derivatives of isothiazolone, chitosan or derivatives of chitin, zinc zeolite, silver ions, silver in supported particulate form and triclosan.
- the deposit also contains at least one fungistatic and/or fungicidal agent based on p-[(Diiodomethyl)sulfonyl]toluol.
- the deposit also contains at least one fungistatic and/or fungicidal agent based on methyl-1H-benzimidazol-2-ylcarbamate.
- the deposit also contains at least 3-iodo-2-propynylbutyl carbamate (IPBC).
- IPBC 3-iodo-2-propynylbutyl carbamate
- the deposit also contains at least one virucide in particular of natural origin.
- the term “virucidal” designates any compound having the capacity to kill or inhibit viruses.
- the virucide according to the present invention is more particularly dedicated to killing and/or inhibiting a pathogenic virus against mammals and more particularly against humans.
- Such viruses may be naked viruses or enveloped viruses.
- virucide of natural origin we mean any virucide that pre-exists in nature or can be synthesized from natural compounds existing in nature.
- 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 environment containing them, or by synthesis from natural compounds.
- virucides we can in particular cite monolaurin which can be obtained by synthesis from glycerol and lauric acid.
- the term monolaurin is intended to designate both naturally pre-existing monolaurin and that obtained by synthesis from glycerol and lauric acid.
- the virucide of natural origin can be chosen in particular from monolaurin, lactoferrin and essential oils exhibiting antiviral activity, such as for example laurel essential oil.
- the ancillary biocide is at least monolaurin.
- the deposit may comprise from 0.05 to 10% by dry weight, for example from 0.2 to 6% by dry weight, of annexed biocidal agent(s), in particular virucidal agent(s). (s) of natural origin, relative to the total dry weight of the deposit.
- the deposit further comprises at least one filler, in particular mineral.
- 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.
- This filler can be chosen from mineral fillers in particular silica, in particular colloidal, 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 among organic fillers, in particular plastic fillers or pigments.
- the deposit comprises at least silica.
- the deposit can 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 dry weight. total deposit.
- the deposit further comprises at least one polyamine-amide-epichlorohydrin (PAAE) resin.
- PAAE polyamine-amide-epichlorohydrin
- Such a component is particularly advantageous for giving the coating increased surface qualities and in particular improving its resistance to wet abrasion.
- the deposit can 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.
- 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.
- the deposit is a single-layer coating.
- the deposit is in particular in the form of a single layer, notably homogeneous, of which the different components 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 mix.
- the deposit consists of from 0.05 to 6% by dry weight of didecyl dimethyl ammonium chloride (DD AC) relative to the total dry weight of the deposit, from 94 to 99.95% in dry weight, preferably from 94.5 to 99.5% by dry weight of polymeric binding agent comprising, or even consisting of, one or more polymer(s) chosen from polyacrylics, poly acrylates, 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 said deposit,
- DD AC didecyl dimethyl ammonium chloride
- PAAE polyamine-amide-epichlorohydrin
- the deposit may consist of 0.05 to 6% by dry weight of didecyl dimethyl ammonium chloride (DD AC) relative to the total dry weight of the deposit, from 94 to 99.95% by dry weight, preferably from 94.5 to 99.5% by dry weight of polymeric binding agent comprising, or even consisting of, one or more polymer(s) chosen from polyacrylics, poly acrylates, 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 said deposit,
- DD AC didecyl dimethyl ammonium chloride
- wallpaper with biocidal properties generally includes a fibrous support.
- the deposition of binding agent of wallpaper with biocidal properties is on the external surface and preferably in contact with a woven or non-woven fibrous support.
- the fibrous support may comprise natural, artificial and/or synthetic fibers, in particular chosen from cellulose, polyester, cotton fibers, and mixtures thereof.
- the fibrous support may be of the paper type, in particular based on cellulose fibers.
- the fibrous support can also be a non-woven fibrous support in the form of an assembly of compressed fibers, in particular based on a mixture of cellulose and polyester fibers.
- the fibrous support can also comprise on the surface of its decorative effect side a polymeric layer, in particular waterproof.
- the deposit of binding agent required according to the invention is then placed on the surface, in particular in contact, of this polymeric layer generally formed of at least one vinyl polymer, in particular of polyvinyl chloride.
- wallpaper with biocidal properties can be formed from vinyl coated wallpaper.
- wallpaper with biocidal properties has a weight ranging from 80 to 200 g/m 2 .
- a wallpaper with biocidal properties according to the invention advantageously possesses the expected biocidal properties, in particular bactericidal and antiviral.
- Wallpaper with biocidal properties is particularly dedicated to killing and/or inhibiting a pathogenic virus against mammals and more particularly humans.
- viruses may be naked viruses or enveloped viruses.
- retroviruses As a representative of the viruses pathogenic for humans capable of being considered according to the invention, mention may more particularly be made of retroviruses, cytomegaloviruses, rotaviruses, paramyxoviruses, polioviruses, hantaviruses, coxsackie viruses, encephalomyocarditis, picomaviruses including rhinoviruses, DNA or RNA viruses in particular flaviviridae, the AIDS virus, influenza viruses and in particular H INI, coronaviruses and in particular coronaviruses with human infection Hcov-229E, Hcov-0C43, SARS-COV-2, smallpox virus, yellow fever virus, hepatitis C virus, Ebola viruses, herpes viruses, Epstein-Barr virus, the varicella-zoster virus, the rubella virus, or even the simian virus 40 or SV40.
- retroviruses cytomegaloviruses, rotaviruse
- biocidal quaternary ammonium salt(s) in a deposit of polymeric binding agent, does not alter the manifestation additional properties of the coating, such as for example the shine or its durability on the support, and in particular the absence of detachment following exposure to dry or wet friction.
- the present invention also relates to a process for manufacturing wallpaper with biocidal properties, in particular as described above, comprising at least the steps consisting of: a) having a wallpaper, where appropriate treated on the surface of 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:
- DD AC didecyl dimethyl ammonium chloride
- 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,
- PAAE polyamine-amide-epichlorohydrin
- a coating is formed on all or part of the external face dedicated to providing the desired visual decorative effect.
- the composition used according to the invention comprises at least one non-polymeric quaternary ammonium salt, in particular as described above.
- 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 minus one non-polymeric quaternary ammonium salt, in particular didecyl dimethyl ammonium chloride, relative to the total dry weight of the composition.
- 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, acrylates, methacrylates, aliphatic or aromatic, styrene and their mixtures.
- the polymeric binding agent considered in the composition is of polymeric nature and used in the form of a dispersion, solution or emulsion, in particular an aqueous one, preferably an aqueous dispersion or emulsion.
- 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.
- 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, relative to the dry weight of the composition.
- the composition comprises from 0.1% to 10% by dry weight of at least one non-polymeric quaternary ammonium salt, in particular of 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 of 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.
- 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 above.
- 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.
- 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 agent annex biocide relative to the total dry weight of the composition.
- 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.
- the composition used in the process according to the invention is fluid. It can 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.
- the viscosities of the compositions according to the invention can be measured by conventional methods.
- a Brookfield viscometer with axis no. 2 at 100 revolutions per minute (ISO 2555) is preferred as measuring equipment, ensuring that the torque measured by the device or less than 0.5 mN.m. If the torque is greater than this value, it is necessary to choose an axis of higher degree.
- 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 to treat the surface of wallpaper. with said composition.
- the wallpaper to be treated in step a) is devoid of biocidal properties.
- the method according to the invention comprises a preliminary step of manufacturing the wallpaper to be treated.
- steps b) and/or c) can be carried out directly following the manufacture of the wallpaper to be treated.
- the contacting in step b) can be carried out by spraying, by size press surfacing, by coating, by printing, by immersion in a bath.
- it is produced by inkjet printing, rotogravure, flexographic, pencil coating, padding, digital printing or flexographic overprinting, preferably by rotogravure, flexographic, screen printing, pencil coating or flexographic overprinting and more preferably by rotogravure or flexographic.
- - inkjet can advantageously have a viscosity between 5 and 30 mPa.s,
- - in rotogravure can advantageously have a viscosity of between 10 and 150 mPa.s,
- - in flexographic can advantageously have a viscosity of 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
- the - in size-press surfacing can advantageously have a viscosity of between 20 and 100 mPa.s.
- the composition has a viscosity of between 10 and 50 mPa.s and the contacting is carried out by rotogravure or the composition has a viscosity of between 10 and 500 mPa.s and the contacting is carried out by flexographic or by flexographic overprinting.
- 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 the where appropriate by diluting the composition in particular with water.
- Drying can be carried out at a temperature ranging from 30 to 250°C.
- the coating thus produced turns out to have very satisfactory durability and excellent qualities. In addition, it presents efficient biocidal activity.
- 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 process according to the invention.
- composition described above lends itself, in view of its specificities, advantageously to use as a varnish, ink, lacquer or paint.
- DD AC Didecyl dimethyl ammonium chloride
- 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 a biocidal composition according to the invention
- composition is prepared from an aqueous medium into which the commercial form of the polymeric binding agent considered is introduced. After obtaining a homogeneous mixture, the DD AC is then added. The preparation is carried out at Rayneri.
- Example 2 Preparation and characterization of the anti-microbial performances of a wallpaper conforming to the invention, formed from the composition of Example 1
- the support considered is a 160 g/m 2 wallpaper (two papers laminated, 70 and 90 g/m 2 respectively).
- the composition is applied by the rotogravure process with an average deposition rate of 1 to 8 g/m 2 by dry weight. More precisely, the deposition rate is 3 g/m 2 .
- Table 2 reports the measured anti-microbial performances.
Abstract
The invention relates to wallpaper having biocidal properties, all or part of the outer face of which is intended to provide a decorative visual effect, comprising a deposit of at least one polymeric binder, said binder being obtained by polymerisation of at least one monomer chosen from aliphatic or aromatic methacrylates, acrylates, methacrylic acids, acrylic acids, styrene and mixtures thereof, and further containing from 0.05% to 6% by dry weight of at least one non-polymeric quaternary ammonium salt based on the total dry weight of said deposit, and said deposit comprising at least one polyaminoamide-epichlorohydrin (PAE) resin.
Description
Description Description
Titre : Papier-peint à propriétés biocides Title: Wallpaper with biocidal properties
Domaine technique Technical area
La présente invention vise à proposer un papier-peint possédant des propriétés biocides, ainsi qu’un procédé de fabrication d’un tel papier-peint. The present invention aims to provide a wallpaper having biocidal properties, as well as a process for manufacturing such wallpaper.
Technique antérieure Prior art
Les papier-peints sont classiquement utilisés pour la décoration intérieure, en particulier pour constituer des revêtements muraux dédiés à procurer un effet décoratif visuel. Wallpapers are classically used for interior decoration, in particular to constitute wall coverings dedicated to providing a visual decorative effect.
Or, les espaces intérieurs peuvent être propices à la contamination par un ou plusieurs microorganismes pathogènes, et donc à leur propagation, ce qui peut être générateur de maladies épidémiques et pandémiques. A ce titre, il a déjà été envisagé de mettre à profit les revêtements muraux à des fins de décontamination au sein d’habitacles. However, indoor spaces can be conducive to contamination by one or more pathogenic microorganisms, and therefore to their spread, which can generate epidemic and pandemic diseases. As such, it has already been considered to use wall coverings for decontamination purposes within passenger compartments.
Par exemple, CN 106 088 495, CN 106 079 763 et CN 106 079 785 proposent des papiers- peints comprenant une couche anti-moisissure et antibactérienne mettant en œuvre notamment de la zéolithe chargée en argent et du chlorure de didécyl diméthyl ammonium. Plus précisément, il s’agit de papier-peints dont les propriétés anti-moisissure et antibactérienne nécessitent la superposition au niveau du papier peint à traiter, de plusieurs couches de compositions distinctes, dont certaines sont anti-moisissures et/ou antibactériennes. Pour des raisons évidentes, la fabrication de tels papiers-peints est complexe. Enfin, ces documents ne visent pas des papier-peints aux propriétés antivirales.For example, CN 106 088 495, CN 106 079 763 and CN 106 079 785 offer wallpapers comprising an anti-mold and antibacterial layer using in particular zeolite loaded with silver and didecyl dimethyl ammonium chloride. More precisely, these are wallpapers whose anti-mold and antibacterial properties require the superposition on 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 target wallpaper with antiviral properties.
La présente invention a précisément pour objet de proposer un papier-peint performant en termes de propriétés biocides, notamment antivirales, et ayant également pour avantage d’être élaboré selon un protocole aisé de mise en œuvre. En particulier, il ne nécessite pas d’aménagement technique fastidieux et dispendieux du procédé de fabrication du papier peint proprement dit. The object of the present invention is precisely to propose a wallpaper that performs well in terms of biocidal properties, in particular antiviral properties, and also has the advantage of being developed according to an easy implementation protocol. In particular, it does not require tedious and expensive technical development of the wallpaper manufacturing process itself.
La présente invention vise également à proposer un papier-peint doté de propriétés antimicrobiennes, en particulier antivirales, adapté à la décoration intérieure. The present invention also aims to provide wallpaper with antimicrobial properties, in particular antiviral properties, suitable for interior decoration.
Elle vise également un procédé simplifié pour le traitement de surface biocide d’un papier- peint.
Résumé de l’invention It also aims at a simplified process for the biocidal surface treatment of wallpaper. Summary of the invention
Ainsi, la présente invention vise à titre principal, un papier-peint à propriétés biocides dont tout ou partie de la face externe dédiée à procurer un effet décoratif visuel, comporte un dépôt d’au moins un agent liant polymérique, ledit agent liant étant obtenu par polymérisation d’au moins un monomère choisi parmi les acides acryliques et méthacryliques, les acrylates, méthacrylates, aliphatiques ou aromatiques, styrène et leurs mélanges, et contenant en outre de 0,05 % à 6 % en poids sec d’au moins un sel d’ammonium quaternaire non polymérique par rapport au poids sec total dudit dépôt. Thus, the present invention aims primarily at a wallpaper with biocidal properties of which all or part of the external face 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, acrylates, methacrylates, aliphatic or aromatic, 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.
Plus particulièrement, la présente invention vise un papier-peint à propriétés biocides dont tout ou partie de la face externe dédiée à procurer un effet décoratif visuel, comporte un dépôt d’au moins un agent liant polymérique, ledit agent liant étant obtenu par polymérisation d’au moins un monomère choisi parmi les acides acryliques et méthacryliques, les acrylates, méthacrylates, aliphatiques ou aromatiques, styrène et leurs mélanges, et contenant en outre de 0,05 % à 6 % en poids sec d’au moins un sel d’ammonium quaternaire non polymérique par rapport au poids sec total dudit dépôt, et ledit dépôt comprenant au moins une résine polyamine-amide-épichlorydrine (PAAE). More particularly, the present invention aims at a wallpaper with biocidal properties of which all or part of the external face 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, acrylates, methacrylates, aliphatic or aromatic, styrene and mixtures thereof, and also containing from 0.05% to 6% by dry weight of at least one salt of non-polymeric quaternary ammonium relative to the total dry weight of said deposit, and said deposit comprising at least one polyamine-amide-epichlorohydrin (PAAE) resin.
Selon une variante particulière, ce dépôt se présente sous la forme d’une couche ou encore d’un film et à ce titre forme un revêtement notamment tel que détaillé ci- après. 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.
Comme détaillé ci-après, le papier-peint à propriétés biocides comprend également un support fibreux tissé ou intissé à la surface de l’une des faces duquel est présent le dépôt d’agent liant. As detailed below, wallpaper with biocidal properties also comprises a woven or non-woven fibrous support on the surface of one of the faces of which the binding agent deposit is present.
Comme il ressort des exemples, les inventeurs ont montré que ces papier-peints sont performants en termes d’activité antimicrobienne, en particulier antibactérienne et antivirale. De plus, la présence du dépôt n’impacte pas négativement les propriétés décoratives du papier-peint. As can be seen 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.
Selon un autre de ses aspects, la présente invention vise un procédé de fabrication d’un papier-peint à propriétés biocides, notamment tel que décrit précédemment, comprenant au moins les étapes consistant à : a) disposer d’un papier peint, le cas échéant traité en surface d’au moins une de ses faces avec au moins un polymère vinylique, b) mettre en contact au moins tout ou partie de la face dudit papier-peint dédiée à procurer
un effet décoratif visuel avec une composition, ladite composition comprenant : According to another of its aspects, the present invention relates to a process for manufacturing a wallpaper with biocidal properties, in particular as described above, comprising at least the steps consisting of: a) having a wallpaper, the case optionally treated on the surface of 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:
- au moins un sel d’ammonium quaternaire non polymérique, notamment du chlorure de didécyl diméthyl ammonium (DD AC), - at least one non-polymeric quaternary ammonium salt, in particular didecyl dimethyl ammonium chloride (DD AC),
- au moins un agent liant polymérique obtenu par polymérisation d’au moins un monomère choisi parmi les acides acryliques et méthacryliques, les acrylates, méthacrylates, aliphatiques ou aromatiques, styrène et leurs mélanges, - 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,
- optionnellement au moins une charge, en particulier minérale, notamment de la silice, et- optionally at least one filler, in particular mineral, in particular silica, and
- optionnellement au moins un agent biocide distinct d’un sel d’ammonium quaternaire non polymérique, et - optionally at least one biocidal agent distinct from a non-polymeric quaternary ammonium salt, and
- optionnellement au moins une résine polyamine-amide-épichlorydrine (PAAE) pour former un dépôt à propriétés biocides c) sécher ledit dépôt et d) optionnellement, gaufrer à chaud ou à froid ledit papier peint, de préférence après séchage dudit dépôt. - optionally at least one polyamine-amide-epichlorohydrin (PAAE) resin to form a deposit with biocidal properties c) dry said deposit and d) optionally, hot or cold emboss said wallpaper, preferably after drying of said deposit.
Selon encore un autre de ses aspects, la présente invention a pour objet l’utilisation d’une composition, en particulier telle que décrite précédemment, comprenant : According to yet another of its aspects, the present invention relates to the use of a composition, in particular as described above, comprising:
- au moins un sel d’ammonium quaternaire non polymérique, notamment du chlorure de didécyl diméthyl ammonium (DD AC), - at least one non-polymeric quaternary ammonium salt, in particular didecyl dimethyl ammonium chloride (DD AC),
- au moins un agent liant polymérique obtenu par polymérisation d’au moins un monomère choisi parmi les acides acryliques et méthacryliques, acrylates, méthacrylates, aliphatiques ou aromatiques, styrène et leurs mélanges, - 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,
- optionnellement au moins une charge, en particulier minérale, notamment de la silice, et- optionally at least one filler, in particular mineral, in particular silica, and
- optionnellement au moins un agent biocide distinct d’un sel d’ammonium quaternaire non polymérique, et - optionally at least one biocidal agent distinct from a non-polymeric quaternary ammonium salt, and
- optionnellement au moins une résine polyamide-poly amine-épichlorhydrine, (PAAE), pour conférer des propriétés biocides, notamment antivirales, à un papier-peint. - optionally at least one polyamide-poly amine-epichlorohydrin resin (PAAE), to confer biocidal properties, in particular antiviral properties, to a wallpaper.
En particulier, la composition mise en œuvre dans le procédé et l’utilisation selon l’invention possède une viscosité allant de 5 mPa.s à 10 Pa.s, en particulier de 10 mPa.s à 5 Pa.s, et plus particulièrement de 10 à 500 mPa.s à une température allant de 20 à 25°C et à pression atmosphérique. Elle peut ainsi être appliquée sur le papier-peint par diverses techniques
d’impression. Avantageusement, la composition est appliquée sur le papier-peint par héliogravure ou flexographic. In particular, the composition used in the process and the 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 wallpaper using various techniques. printing. Advantageously, the composition is applied to the wallpaper by rotogravure or flexographic.
Au sens de l’invention, le terme antimicrobien qualifie une activité biocide en particulier bactéricide, fongicide, levuricide, virucide et/ou algicide, c’est-à-dire qui tue le microorganisme considéré mais également une activité bactériostatique et/ou fongistatique c’est-à-dire qui inhibe la croissance des bactéries, et champignons microscopiques. For the purposes of the invention, the term antimicrobial describes a biocidal activity, in particular bactericidal, fungicidal, yeasticidal, virucidal and/or algaecidal, that is to say which kills the microorganism considered but also a bacteriostatic and/or fungistatic activity c that is to say which inhibits the growth of bacteria and microscopic fungi.
Au sens de l’invention, les termes « composé ou agent biocide » ou « biocide », équivalents aux termes « composé ou agent antimicrobien », désignent, d’une manière générale, tout composé efficace pour réguler et/ou inhiber la croissance et/ou réduire la densité de microorganismes tels que des virus, champignons, bactéries, algues et/ou levures, etc Comme déjà précisé ci-dessus, au sens de l’invention par « revêtement », on entend un dépôt de type film localisé à la surface d’un support, voire le cas échéant dans la partie superficielle de l’épaisseur du support traité. Le support ainsi traité possède grâce à ce dépôt des propriétés biocides surfaciques. 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 growth and /or reduce the density of microorganisms such as viruses, fungi, bacteria, algae and/or yeasts, etc. As already specified above, in the sense of the invention by “coating”, we mean a film-type deposit located at the surface of a support, or if necessary in the superficial part of the thickness of the treated support. The support thus treated has, thanks to this deposit, surface biocidal properties.
Au sens de l’invention, un agent est dit liant au regard de son aptitude à contribuer, après séchage et/ou réticulation de la composition appliquée en surface d’un support, à la formation d’un dépôt solide, voire d’un revêtement, de dureté suffisante pour assurer à ce dernier une pérennité. Il entre conventionnellement dans la composition des vernis, des encres, des laques et des peintures. For the purposes of the invention, an agent is said to be a binding agent 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 its durability. It is conventionally used in the composition of varnishes, inks, lacquers and paints.
Dans la présente description, le terme agent liant polymérique peut être un unique composé liant polymérique ou un mélange de deux ou plus de composés liants polymériques. In the present description, the term polymeric binder agent may be a single polymeric binder compound or a mixture of two or more polymeric binder compounds.
Au sens de l’invention, « poids sec », dit encore « poids en matière active », désigne sans indication contraire la teneur massique dudit composé, sans les éventuels solvants volatils dans lesquels il est formulé, par exemple l’eau. For the purposes of the invention, "dry weight", also known as "weight of active material", designates without contrary indication the mass content of said compound, without any volatile solvents in which it is formulated, for example water.
Description détaillée
detailed description
Au sens de l’invention, on entend désigner sous le terme papier-peint, un papier-peint déjà adhéré en tant que revêtement en surface d’un substrat tel qu’un mur par exemple, ou un papier non adhéré par exemple simplement conditionné à l’état d’un rouleau ou se présentant sous la forme de feuilles d’échantillon.
Comme précisé ci-dessus, le papier-peint à propriétés biocides, objet de l’invention, a pour spécificité de posséder au moins au niveau de sa face externe dédiée à procurer un effet décoratif visuel, un dépôt d’au moins un agent liant polymérique contenant au moins un sel d’ammonium quaternaire non polymérique à effet biocide. For the purposes of the invention, the term wallpaper means 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. As specified above, the wallpaper with biocidal properties, object of the invention, has the specificity of possessing at least on its external face dedicated to providing a visual decorative effect, a deposit of at least one binding agent polymer containing at least one non-polymeric quaternary ammonium salt with biocidal effect.
Cet effet décoratif peut être de nature coloriel et/ou comprendre des motifs décoratifs en relief. This decorative effect may be of a color nature and/or include decorative patterns in relief.
La face du papier-peint opposée à cette face à effet décoratif est pour sa part dédiée à être appliquée en surface d’un substrat généralement mural mais pouvant être bien sûr de toute autre nature. The side of the wallpaper opposite this side with a decorative effect is for its part dedicated to being applied to the surface of a substrate that is generally wall-mounted but can of course be of any other nature.
Selon une variante particulière, les deux faces du papier-peint peuvent comporter un dépôt à effet biocide. According to a particular variant, both sides of the wallpaper may include a deposit with a biocidal effect.
Agent liant polymérique Polymeric binding agent
Comme précisé ci-dessus, un agent liant selon l’invention est de nature polymérique. L’agent liant polymérique est obtenu par polymérisation d’au moins un monomère choisi parmi les acides acryliques et méthacryliques, les acrylates, méthacrylates, aliphatiques ou aromatiques, styrène et leurs mélanges. 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, acrylates, methacrylates, aliphatic or aromatic, styrene and their mixtures.
En particulier, l’agent liant polymérique est obtenu par polymérisation d’au moins 50 % en poids, plus particulièrement au moins 80 % en poids, notamment au moins 95 % en poids, voire au moins 99 % en poids, voire encore 100 % en poids, d’un monomère choisi parmi les acides acryliques et méthacryliques, les acrylates, méthacrylates, styrène et leurs mélanges, par rapport au poids total des monomères. 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.
De préférence, l’agent liant polymérique est un copolymère obtenu par polymérisation d’au moins un monomère choisi parmi les acides acryliques et méthacryliques, les acrylates, les méthacrylates et leurs mélange avec au moins un monomère styrène, le copolymère étant en particulier obtenu par polymérisation d’au moins 50 % en poids, plus particulièrement au moins 80 % en poids, notamment au moins 95 % en poids, voire au moins 99 % en poids, voire encore 100 % en poids de monomères acides acryliques et méthacryliques, acrylates, méthacrylates et/ou styrène par rapport au poids total des monomères. 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, 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.
L’agent liant polymérique est en particulier dénué d’unités monomériques différentes des unités monomériques acrylique, méthacryliques, acrylates, méthacrylates et styrènes.
L’agent liant polymérique peut comprendre, voire consister en, un ou plusieurs polymère(s) choisi(s) parmi les homo-polymères et co-polymères acryliques, les homo-polymères et copolymères acrylates, les homo-polymères et co-polymères méthacryliques, les homo- polymères et co-polymères méthacrylates, les homo-polymères et co-polymères de styrène, et leurs mélanges, notamment être choisis parmi les polyacryliques, les poly acrylates, les polyméthacryliques, les polyméthacrylates, les polystyrènes, les copolymères styrène- acryliques, les copolymères styrène-méthacryliques, les copolymères styrène-acrylates, les copolymères styrène-méthacrylates et leurs mélanges. The polymeric binding agent is in particular devoid of monomeric units other than acrylic, methacrylic, acrylate, methacrylate and styrene monomeric units. The polymeric binding agent may comprise, or even consist of, one or more polymer(s) chosen from acrylic homo-polymers and co-polymers, acrylate homo-polymers and co-polymers, homo-polymers and co-polymers. methacrylics, methacrylate homopolymers and co-polymers, styrene homo-polymers and co-polymers, and their mixtures, in particular being chosen from polyacrylics, poly acrylates, polymethacrylics, polymethacrylates, polystyrenes, styrene copolymers - acrylics, styrene-methacrylic copolymers, styrene-acrylate copolymers, styrene-methacrylate copolymers and their mixtures.
En particulier, l’agent liant polymérique comprend, voire consiste en, au moins un copolymère styrène- acrylique et/ou styrène- acrylate. In particular, the polymeric binding agent comprises, or even consists of, at least one styrene-acrylic and/or styrene-acrylate copolymer.
A titre illustratif d’agents liants polymériques commerciaux convenant à l’invention, on peut notamment citer : As an illustration of commercial polymeric binding agents suitable for the invention, the following may be cited in particular:
- une émulsion de copolymères acryliques commercialisée en solution à 41-43 % en poids sec sous la dénomination NeoCryl XK-30 DSM par la société Coating Resins B.V,- an emulsion of acrylic copolymers marketed in solution at 41-43% by dry weight under the name NeoCryl XK-30 DSM by the company Coating Resins B.V,
- une émulsion acrylique commercialisée en solution à 42-44 % en poids sec sous la dénomination Ottopol K12T par la société Gellner Industrial, - an acrylic emulsion marketed in solution at 42-44% by dry weight under the name Ottopol K12T by the company Gellner Industrial,
- une émulsion acrylique commercialisée en solution à 48 % en poids sec sous la dénomination Texicryl 13-400 par la société Scott Bader SAS, - an acrylic emulsion marketed in solution at 48% by dry weight under the name Texicryl 13-400 by the company Scott Bader SAS,
- une émulsion acrylique commercialisée en solution à 50,8 % en poids sec sous la dénomination Texicryl 9107 par la société Scott Bader, et - an acrylic emulsion marketed in solution at 50.8% by dry weight under the name Texicryl 9107 by the company Scott Bader, and
- une solution styrène- acrylate commercialisée en solution à 36.6 % en poids sec. - a styrene-acrylate solution marketed as a 36.6% solution by dry weight.
La masse moléculaire moyenne de l’agent liant polymérique en poids (Mw) est avantageusement supérieure à 80 g/mol et de préférence supérieure à 86 g/mol. The average molecular mass of the polymeric binding agent by weight (Mw) is advantageously greater than 80 g/mol and preferably greater than 86 g/mol.
Le dépôt est avantageusement formé à raison de 94 % à 99,95 % en poids sec, de préférence de 95 à 99,5 % en poids sec, et plus préférentiellement de 95 à 99 % en poids sec dudit agent liant polymérique par rapport au poids total sec dudit dépôt. The deposit is advantageously formed at a rate of 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 said polymeric binding agent relative to the total dry weight of said deposit.
En particulier, le dépôt est dénué d’agent(s) liant(s) polymérique(s) annexe(s). En d’autres termes, le dépôt est dénué d’agent(s) liant(s) polymérique(s) distinct(s) de ceux obtenus par
polymérisation d’au moins un monomère choisi parmi les acides acryliques et méthacryliques, les acrylates, méthacrylates, styrène et leurs mélanges. In particular, the deposit is devoid of annexed polymeric binding agent(s). In other words, the deposit is devoid of polymeric binding agent(s) distinct from those obtained by polymerization of at least one monomer chosen from acrylic and methacrylic acids, acrylates, methacrylates, styrene and mixtures thereof.
Composé biocide à base d’ammonium quaternaire Biocidal compound based on quaternary ammonium
Des sels d’ammonium quaternaire sont connus comme étant des agents antimicrobiens et/ou microbicides, et plus particulièrement comme agents bactériostatiques (ou antibactériens) et/ou bactéricides et/ou fongistatiques (ou antifongiques) et/ou fongicides. 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.
Comme précisé ci-dessus le composant agent liant polymérique contient au moins un sel d’ammonium quaternaire non polymérique. As specified above, the polymeric binder component contains at least one non-polymeric quaternary ammonium salt.
Ces sels d’ammonium quaternaire comprennent d’une manière générale au moins un cation ammonium quaternaire avec un anion approprié. These quaternary ammonium salts generally comprise at least one quaternary ammonium cation with an appropriate anion.
Le cation est plus particulièrement de formule suivante : The cation is more particularly of the following formula:
[Chem 1]
avec Ri, R2, R3 et R4 pouvant être de nature diverse. Par exemple, Ri, R2, R3 et R4 peuvent être choisis, indépendamment les uns des autres, parmi des groupes alkyle, aryle, alkylaryle, arylalkyle, cycloalkyle, hétérocyclique aromatique ou non aromatique, ou alcényle, lesdits groupes pouvant être substitués ou non, linéaires ou ramifiés, et éventuellement interrompu par un ou plusieurs hétéroatomes, par exemple, par un ou plusieurs atomes d’oxygène, ou par un ou plusieurs groupements phosphinates. [Chem 1] with Ri, R2, R3 and R4 possibly being of various nature. For example, Ri, R2, R3 and R4 can be chosen, independently of each other, from alkyl, aryl, alkylaryl, arylalkyl, cycloalkyl, aromatic or non-aromatic heterocyclic, or alkenyl groups, said groups being able to be 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.
Alternativement, deux ou plus des groupes Ri, R2, R3 et R4 peuvent former ensemble, avec l’atome d’azote qui les supporte, un cycle hétérocyclique substitué ou non substitué. Alternatively, two or more of the groups Ri, R2, R3 and R4 can form together, with the nitrogen atom which supports them, a substituted or unsubstituted heterocyclic ring.
Selon un mode de réalisation particulier, les groupes Ri, R2, R3 et R4 sont des groupes alkyles, de préférence linéaires, en particulier en Ci à C20. According to a particular embodiment, the groups Ri, R2, R3 and R4 are alkyl groups, preferably linear, in particular C to C20.
Les groupes Ri, R2, R3 et R4 comprennent ensemble au moins quatre atomes de carbone. En particulier, le nombre total d’atomes de carbone des groupes Ri, R2, R3 et R4 peut être d’au moins 10. De préférence, au moins l’un des groupes Ri, R2, R3 et R4, en particulier deux des
Ri, R2, R3 et R4, comprennent de 6 à 20 atomes de carbones, en particulier de 8 à 18 atomes de carbone. The groups Ri, R2, R3 and R4 together comprise at least four carbon atoms. In particular, the total number of carbon atoms of the groups Ri, R2, R3 and R4 can be at least 10. Preferably, at least one of the groups Ri, R2, R3 and R4, in particular two of the Ri, R2, R3 and R4 comprise from 6 to 20 carbon atoms, in particular from 8 to 18 carbon atoms.
L’ anion du sel d’ammonium quaternaire peut être notamment choisi parmi des anions d’halogénure, par exemple chlorure, fluorure, bromure ou iodure et des anions sulfonates. De préférence, l’anion du sel d’ammonium quaternaire peut être un chlorure. The anion of the quaternary ammonium salt may in particular be chosen from halide anions, for example chloride, fluoride, bromide or iodide and sulphonate anions. Preferably, the anion of the quaternary ammonium salt may be a chloride.
Les sels d’ammonium quaternaire non polymériques peuvent être plus particulièrement de formule suivante The non-polymeric quaternary ammonium salts may more particularly be of the following formula
[Chem 2] [Chem 2]
(CH3)n(A)mN+X-, dans laquelle A est tel que défini précédemment pour Ri, R2, R3 et R4; X" est un anion tel que défini précédemment, n est un entier compris entre 1 et 3, de préférence 2 ou 3 ; m est un entier compris entre 1 et 3, de préférence 1 ou 2, sous réserve que la somme n+m vaut 4. Lorsque m vaut 2 ou 3, les groupes A peuvent être identiques ou différents, en particulier identiques. (CH 3 ) n (A) m N + X-, in which A is as defined above for Ri, R2, R3 and R4; " is 4. When m is 2 or 3, the groups A can be identical or different, in particular identical.
De préférence, le sel d’ammonium quaternaire mis en œuvre comme agent anti-microbien selon l’invention peut être de formule (CH3)n(A)mN+X', dans laquelle n vaut 2 et m vaut 2 et A, identiques ou différents, sont tels que définis ci-dessus pour Ri, R2, R3 et R4. Preferably, the quaternary ammonium salt used as an anti-microbial agent according to the invention can be of formula (CH3) n (A) m N + X', in which n is 2 and m is 2 and A, identical or different, are as defined above for Ri, R2, R3 and R4.
En particulier, A, identiques ou différents, en particulier identiques, peuvent représenter des groupes alkyles linéaires en CÔ à C20, en particulier en Cs à Cis, notamment en Cs à C12.In particular, A, identical or different, in particular identical, can represent linear alkyl groups in CÔ to C20, in particular in Cs to Cis, in particular in Cs to C12.
A titre d’exemples, on peut citer le chlorure de didécyl diméthyl ammonium (DDAC), le chlorure de dioctyl diméthyl ammonium, le chlorure d’ octyl décyl diméthyl ammonium. As examples, we can cite didecyl dimethyl ammonium chloride (DDAC), dioctyl dimethyl ammonium chloride, octyl decyl dimethyl ammonium chloride.
Selon un mode de réalisation particulier, le sel d’ammonium quaternaire non polymérique est non siliconé et de préférence est au moins du chlorure de didécyl diméthyl ammonium (DDAC). According to a particular embodiment, the non-polymeric quaternary ammonium salt is non-silicone and preferably is at least didecyl dimethyl ammonium chloride (DDAC).
En particulier, l’agent liant polymérique contient de 0,05 à 6 % en poids sec, de préférence de 0,5 à 5,5 % en poids sec, et plus préférentiellement de 1 à 5 % en poids sec de sel(s) d’ammonium quaternaire non polymérique(s), et plus particulièrement contient de 0,05 à 6 % en poids sec, de préférence de 0,5 à 5,5 % en poids sec, et plus préférentiellement de 1 à
5 % en poids sec de chlorure de didécyl diméthyl ammonium (DD AC), par rapport au poids sec total d’agent liant. 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 salt(s). ) of non-polymeric quaternary ammonium(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 (DD AC), relative to the total dry weight of binding agent.
En particulier, l’agent liant polymérique contient de 0,05 à 6 % en poids sec, de préférence de 0,5 à 5,5 % en poids sec, et plus préférentiellement de 1 à 5 % en poids sec de sels d’ammonium quaternaire non polymériques, et plus particulièrement contient de 0,05 à 6 % en poids sec, de préférence de 0,5 à 5,5 % en poids sec, et plus préférentiellement de 1 à 5 % en poids sec de chlorure de didécyl diméthyl ammonium (DD AC), par rapport au poids sec total du dépôt. 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 salts of non-polymeric quaternary ammonium, 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 chloride dimethyl ammonium (DD AC), relative to the total dry weight of the deposit.
Selon un mode de réalisation particulier, le dépôt comprend au moins de 0,05 à 6 % en poids sec de chlorure de didécyl diméthyl ammonium (DD AC) par rapport au poids sec total du dépôt et de 94 à 99,95 % en poids sec, de préférence de 94,5 à 99,5 % en poids sec d’agent liant polymérique comprenant, voire consistant en, un ou plusieurs polymère(s) choisi(s) parmi les polyacryliques, les poly acrylates, les polyméthacryliques, les polyméthacrylates, les polystyrènes, les copolymères styrène-acryliques, les copolymères styrène-acrylates, les copolymères styrène-méthacryliques, les copolymères styrène-méthacrylates et leurs mélanges par rapport au poids sec total du dépôt. According to a particular embodiment, the deposit comprises at least 0.05 to 6% by dry weight of didecyl dimethyl ammonium chloride (DD AC) relative to the total dry weight of the deposit and from 94 to 99.95% by weight. dry, preferably from 94.5 to 99.5% by dry weight of polymeric binding agent comprising, or even consisting of, one or more polymer(s) chosen from polyacrylics, poly acrylates, 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.
Outre les composés essentiels, le dépôt peut bien entendu comprendre d’autres composés classiquement considérés pour les revêtements de surface, notamment au regard de l’activité biocide recherchée selon l’invention. In addition to the essential compounds, the deposit can of course include other compounds conventionally considered for surface coatings, in particular with regard to the biocidal activity sought according to the invention.
Ainsi, le dépôt peut comprendre un ou plusieurs agents biocides, notamment bactériostatiques, bactéricides, fongistatiques, fongicides, levuricides, algicides, virucides, distincts d’un sel d’ammonium quaternaire non polymérique, dits agents biocides annexes. Bien entendu, ces agents peuvent par ailleurs être sélectionnés pour leur innocuité pour l’homme dans les conditions de mise en œuvre selon l’invention. Thus, the deposit may include one or more biocidal agents, in particular bacteriostatic, bactericidal, fungistatic, fungicidal, yeasticidal, algicidal, virucidal, distinct from a non-polymeric quaternary ammonium salt, called ancillary biocidal agents. Of course, these agents can also be selected for their safety for humans under the conditions of implementation according to the invention.
Ce ou ces agents biocides annexes peuvent notamment être choisi(s) parmi le p- [(Diiodométhyl) sulfonyl] toluol, le carbamate de 3-iodo-2-propynylbutyle, le méthyl-lH- benzimidazol-2-ylcarbamate, la monolaurine, les composés à base d’isothiazoline ou dérivés d’isothiazolone, de chitosan ou dérivés de chitine, de zéolithe de zinc, d’ions d’argent,
notamment le chlorure d’argent, d’argent sous forme particulaire supportée, de triclosan, de sel d’ammonium quaternaire polymérique et leurs mélanges. 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.
Selon une variante, le dépôt contient au moins un agent bactériostatique et/ou bactéricide choisi parmi les composés à base de chitosan ou dérivés de la chitine, de zéolithe de zinc, d’ions argent, d’argent sous forme particulaire supportée et de triclosan et leurs mélanges.According to a variant, the deposit contains at least one bacteriostatic and/or bactericidal agent chosen from compounds based on chitosan or derived from chitin, zinc zeolite, silver ions, silver in supported particulate form and triclosan and their mixtures.
Selon une variante, le dépôt contient au moins un agent fongistatique et/ou fongicide choisi parmi les composés à base d’isothiazoline ou dérivés d’isothiazolone, de chitosan ou dérivés de chitine, de zéolithe de zinc, d’ions d’argent, d’argent sous forme particulaire supportée et de triclosan. According to a variant, the deposit contains at least one fungistatic and/or fungicidal agent chosen from compounds based on isothiazoline or derivatives of isothiazolone, chitosan or derivatives of chitin, zinc zeolite, silver ions, silver in supported particulate form and triclosan.
Selon une variante, le dépôt contient en outre au moins un agent fongistatique et/ou fongicide à base de p-[(Diiodométhyl)sulfonyl]toluol. According to a variant, the deposit also contains at least one fungistatic and/or fungicidal agent based on p-[(Diiodomethyl)sulfonyl]toluol.
Selon une variante, le dépôt contient en outre au moins un agent fongistatique et/ou fongicide à base de méthyl-lH-benzimidazol-2-ylcarbamate. According to a variant, the deposit also contains at least one fungistatic and/or fungicidal agent based on methyl-1H-benzimidazol-2-ylcarbamate.
Selon une variante préférée, le dépôt contient en outre au moins du carbamate de 3-iodo-2- propynylbutyle (IPBC). According to a preferred variant, the deposit also contains at least 3-iodo-2-propynylbutyl carbamate (IPBC).
Selon une autre variante, le dépôt contient en outre au moins un virucide en particulier d’origine naturelle. According to another variant, the deposit also contains at least one virucide in particular of natural origin.
Au sens de la présente invention, le terme « virucide » désigne tout composé possédant la capacité de tuer ou d’inhiber les virus. For the purposes of the present invention, the term “virucidal” designates any compound having the capacity to kill or inhibit viruses.
Le virucide selon la présente invention est plus particulièrement dédié à tuer et/ou à inhiber un virus pathogène à l’égard des mammifères et plus particulièrement de F Homme. The virucide according to the present invention is more particularly dedicated to killing and/or inhibiting a pathogenic virus against mammals and more particularly against humans.
De tels virus peuvent être des virus nus ou des virus enveloppés. Such viruses may be naked viruses or enveloped viruses.
Par « virucide d’origine naturelle », on entend désigner tout virucide préexistant dans la nature ou pouvant être synthétisé à partir de composés naturels existant dans la nature.By “virucide of natural origin”, we mean any virucide that pre-exists in nature or can be synthesized from natural compounds existing in nature.
Les virucides d’origine naturelle utilisables dans le cadre de la présente invention peuvent ainsi être obtenus soit par extraction et purification à partir d’un milieu naturel les contenant, soit par synthèse à partir de composés naturels. 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 environment containing them, or by synthesis from natural compounds.
A titre d’exemple de tels virucides, on peut notamment citer la monolaurine qui peut être obtenue par synthèse à partir de glycérol et d’acide laurique. As an example of such virucides, we can in particular cite monolaurin which can be obtained by synthesis from glycerol and lauric acid.
Au sens de l’invention, le terme monolaurine entend désigner à la fois la monolaurine préexistant naturellement et celle obtenue par synthèse à partir de glycérol et d’acide laurique.
Selon un mode de réalisation, le virucide d’origine naturelle peut être notamment choisi parmi la monolaurine, la lactoferrine et les huiles essentielles présentant une activité antivirale, comme par exemple l’huile essentielle de laurier. 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. According to one embodiment, the virucide of natural origin can be chosen in particular from monolaurin, lactoferrin and essential oils exhibiting antiviral activity, such as for example laurel essential oil.
Dans un mode de réalisation préféré, le biocide annexe est au moins la monolaurine. In a preferred embodiment, the ancillary biocide is at least monolaurin.
A titre illustratif, le dépôt peut comprendre de 0,05 à 10 % en poids sec, par exemple de 0,2 à 6 % en poids sec, d’agent(s) biocide(s) annnexe(s), notamment de virucide(s) d’origine naturelle, par rapport au poids sec total du dépôt. As an illustration, the deposit may comprise from 0.05 to 10% by dry weight, for example from 0.2 to 6% by dry weight, of annexed biocidal agent(s), in particular virucidal agent(s). (s) of natural origin, relative to the total dry weight of the deposit.
Selon un autre mode de réalisation particulier, le dépôt comprend en outre au moins une charge, en particulier minérale. According to another particular embodiment, the deposit further comprises at least one filler, in particular mineral.
Un tel composant est notamment avantageux pour conférer au revêtement des qualités de surface accrues et notamment améliorer son coefficient de friction ou modifier sa brillance. Cette charge peut être choisie parmi les charges minérales notamment la silice, notamment colloïdale, les silicates de sodium, les aluminosilicates de sodium, les carbonates de calcium naturels ou précipités, le talc, le kaolin naturel ou calciné, l’hydrate d’alumine, le dioxyde de titane, les silicates d’aluminium, le sulfate de baryum, et leurs mélanges, et parmi les charges organiques, notamment des charges ou pigments plastiques. De préférence, le dépôt comprend au moins de la silice. 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. This filler can be chosen from mineral fillers in particular silica, in particular colloidal, 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 among organic fillers, in particular plastic fillers or pigments. Preferably, the deposit comprises at least silica.
Le dépôt peut ainsi comprendre de 0,01 % à 20 % en poids sec, de préférence de 0,1 % à 10 % en poids sec de charge(s), en particulier minérale, notamment de la silice, par rapport au poids sec total du dépôt. The deposit can 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 dry weight. total deposit.
Selon un autre mode de réalisation particulier, le dépôt comprend en outre au moins une résine polyamine-amide-épichlorydrine (PAAE). According to another particular embodiment, the deposit further comprises at least one polyamine-amide-epichlorohydrin (PAAE) resin.
Un tel composant est notamment avantageux pour conférer au revêtement des qualités de surface accrues et notamment améliorer sa résistance à l’abrasion humide. Such a component is particularly advantageous for giving the coating increased surface qualities and in particular improving its resistance to wet abrasion.
Le dépôt peut ainsi comprendre de 0,01 % à 10 % en poids sec, de préférence de 0,05 % à 5 % en poids sec de PAAE, par rapport au poids sec total du dépôt. The deposit can 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.
De préférence, l’agent liant polymérique et le ou les sel(s) d’ammonium quaternaire non polymérique(s) sont présents dans ledit dépôt, notamment sous la forme d’un revêtement, sous la forme d’un mélange intime. En particulier, le dépôt est un revêtement monocouche. Le dépôt est en particulier sous la forme d’une unique couche, notamment homogène, dont
les différents composants tels que l’agent liant polymérique, le ou les sel(s) d’ammonium quaternaire non polymérique(s), et le cas échéant une ou des charges et/ou un ou des agents biocides annexes sont sous la forme d’un mélange intime. 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, notably homogeneous, of which the different components 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 mix.
Ainsi, selon un mode de réalisation particulier, le dépôt consiste en de 0,05 à 6 % en poids sec de chlorure de didécyl diméthyl ammonium (DD AC) par rapport au poids sec total du dépôt, de 94 à 99,95 % en poids sec, de préférence de 94,5 à 99,5 % en poids sec d’agent liant polymérique comprenant, voire consistant en, un ou plusieurs polymère(s) choisi(s) parmi les polyacryliques, les poly acrylates, les polyméthacryliques, les polyméthacrylates, les polystyrènes, les copolymères styrène-acryliques, les copolymères styrène-acrylates, les copolymères styrène-méthacryliques, les copolymères styrène-méthacrylates et leurs mélanges par rapport au poids sec total dudit dépôt, Thus, according to a particular embodiment, the deposit consists of from 0.05 to 6% by dry weight of didecyl dimethyl ammonium chloride (DD AC) relative to the total dry weight of the deposit, from 94 to 99.95% in dry weight, preferably from 94.5 to 99.5% by dry weight of polymeric binding agent comprising, or even consisting of, one or more polymer(s) chosen from polyacrylics, poly acrylates, 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 said deposit,
- optionnellement au moins une charge, en particulier minérale, notamment de la silice, et- optionally at least one filler, in particular mineral, in particular silica, and
- optionnellement au moins un agent biocide distinct d’un sel d’ammonium quaternaire non polymérique, et - optionally at least one biocidal agent distinct from a non-polymeric quaternary ammonium salt, and
- optionnellement au moins une résine polyamine-amide-épichlorydrine (PAAE). - optionally at least one polyamine-amide-epichlorohydrin (PAAE) resin.
Plus particulièrement, le dépôt peut consister en de 0,05 à 6 % en poids sec de chlorure de didécyl diméthyl ammonium (DD AC) par rapport au poids sec total du dépôt, de 94 à 99,95 % en poids sec, de préférence de 94,5 à 99,5 % en poids sec d’agent liant polymérique comprenant, voire consistant en, un ou plusieurs polymère(s) choisi(s) parmi les polyacryliques, les poly acrylates, les polyméthacryliques, les polyméthacrylates, les polystyrènes, les copolymères styrène-acryliques, les copolymères styrène-acrylates, les copolymères styrène-méthacryliques, les copolymères styrène-méthacrylates et leurs mélanges par rapport au poids sec total dudit dépôt, More particularly, the deposit may consist of 0.05 to 6% by dry weight of didecyl dimethyl ammonium chloride (DD AC) relative to the total dry weight of the deposit, from 94 to 99.95% by dry weight, preferably from 94.5 to 99.5% by dry weight of polymeric binding agent comprising, or even consisting of, one or more polymer(s) chosen from polyacrylics, poly acrylates, 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 said deposit,
- optionnellement au moins une charge, en particulier minérale, notamment de la silice, et- optionally at least one filler, in particular mineral, in particular silica, and
- optionnellement au moins un agent biocide distinct d’un sel d’ammonium quaternaire non polymérique, et - optionally at least one biocidal agent distinct from a non-polymeric quaternary ammonium salt, and
- au moins une résine polyamine-amide-épichlorydrine (PAAE).
Comme précisé ci-dessus, le papier-peint à propriétés biocides comprend généralement un support fibreux. - at least one polyamine-amide-epichlorohydrin (PAAE) resin. As specified above, wallpaper with biocidal properties generally includes a fibrous support.
En particulier, le dépôt d’agent liant du papier-peint à propriétés biocides est en surface externe et de préférence au contact d’un support fibreux tissé ou intissé. In particular, the deposition of binding agent of wallpaper with biocidal properties is on the external surface and preferably in contact with a woven or non-woven fibrous support.
Le support fibreux peut comprendre des fibres naturelles, artificielles et/ou synthétiques, notamment choisies parmi les fibres de cellulose, de polyester, de coton, et leurs mélanges. En particulier, le support fibreux peut être de type papier, notamment à base de fibres de cellulose. Le support fibreux peut aussi être un support fibreux intissé sous la forme d’un assemblage de fibres compressées, notamment à base d’un mélange de fibres de cellulose et de polyester. The fibrous support may comprise natural, artificial and/or synthetic fibers, in particular chosen from cellulose, polyester, cotton fibers, and mixtures thereof. In particular, the fibrous support may be of the paper type, in particular based on cellulose fibers. The fibrous support can also be a non-woven fibrous support in the form of an assembly of compressed fibers, in particular based on a mixture of cellulose and polyester fibers.
Le support fibreux peut également comprendre en surface de sa face à effet décoratif une couche polymérique, notamment imperméable. Le dépôt d’agent liant requis selon l’invention, est alors disposé en surface, en particulier au contact, de cette couche polymérique formée généralement d’au moins un polymère vinylique, en particulier de polychlorure de vinyle. En particulier, le papier-peint à propriétés biocides peut être formé à partir d’un papier-peint couché vinyl. The fibrous support can also comprise on the surface of its decorative effect side a polymeric layer, in particular waterproof. The deposit of binding agent required according to the invention is then placed on the surface, in particular in contact, of this polymeric layer generally formed of at least one vinyl polymer, in particular of polyvinyl chloride. In particular, wallpaper with biocidal properties can be formed from vinyl coated wallpaper.
En particulier, le papier-peint à propriétés biocides possède un grammage allant de 80 à 200 g/m2. In particular, wallpaper with biocidal properties has a weight ranging from 80 to 200 g/m 2 .
Comme il ressort des exemples ci-après, un papier-peint à propriétés biocides selon l’invention possède avantageusement, les propriétés biocides attendues, en particulier bactéricides et antivirales. As emerges from the examples below, a wallpaper with biocidal properties according to the invention advantageously possesses the expected biocidal properties, in particular bactericidal and antiviral.
Après un temps de contact de 24 heures avec les souches E.coli et S.aureus selon la norme ISO 20743, une activité antibactérienne bonne à excellente est mesurée, avec des activités de 100 % et 99,26 % de réduction du titre bactérien. After a contact time of 24 hours with the E.coli and S.aureus strains according to the ISO 20743 standard, good to excellent antibacterial activity is measured, with activities of 100% and 99.26% reduction in the bacterial titer.
Après un temps de contact de 5 heures avec les souches Coronavirus à infection humaine HcoV-229E et HcoV-OC43 selon la norme ISO 21702:2019 ou ASTME 1093, une activité antivirale bonne à excellente est mesurée, selon les critères de la norme ISO 18184:2019-06 annexe 5 et tout particulièrement une activité antivirale très forte contre les virus de la famille des virus enveloppés avec des activités supérieures à 1,3 log de réduction du titre viral.After a contact time of 5 hours with the human-infected Coronavirus strains HcoV-229E and HcoV-OC43 according to standard ISO 21702:2019 or ASTME 1093, good to excellent antiviral activity is measured, according to the criteria of standard ISO 18184. :2019-06 annex 5 and particularly very strong antiviral activity against viruses of the enveloped virus family with activities greater than 1.3 log reduction in viral titer.
Le papier-peint à propriétés biocides est particulièrement dédié à tuer et/ou à inhiber un virus pathogène à l’égard des mammifères et plus particulièrement de l’Homme.
De tels virus peuvent être des virus nus ou des virus enveloppés. Wallpaper with biocidal properties is particularly dedicated to killing and/or inhibiting a pathogenic virus against mammals and more particularly humans. Such viruses may be naked viruses or enveloped viruses.
A titre représentatif des virus pathogènes pour l’homme susceptibles d’être considérés selon l’invention, on peut plus particulièrement citer les rétrovirus, les cytomégalovirus, les rotavirus, les paramyxovirus, les poliovirus, les hantavirus, les virus coxsackie, le virus de l'encéphalomyocardite, les picomavirus dont les rhinovirus, les virus à ADN ou à ARN notamment les flaviviridae, le virus du SIDA, les virus de la grippe et notamment le H INI, les coronavirus et notamment les coronavirus à infection humaine Hcov-229E, Hcov-0C43, SARS-COV-2, le virus de la variole, le virus de la fièvre jaune, le virus de l’hépatite C, les virus Ebola, les virus de l’herpès, le virus d’Epstein-Barr, le virus varicelle-zona, le virus de la rubéole, ou encore le virus simien 40 ou SV40. As a representative of the viruses pathogenic for humans capable of being considered according to the invention, mention may more particularly be made of retroviruses, cytomegaloviruses, rotaviruses, paramyxoviruses, polioviruses, hantaviruses, coxsackie viruses, encephalomyocarditis, picomaviruses including rhinoviruses, DNA or RNA viruses in particular flaviviridae, the AIDS virus, influenza viruses and in particular H INI, coronaviruses and in particular coronaviruses with human infection Hcov-229E, Hcov-0C43, SARS-COV-2, smallpox virus, yellow fever virus, hepatitis C virus, Ebola viruses, herpes viruses, Epstein-Barr virus, the varicella-zoster virus, the rubella virus, or even the simian virus 40 or SV40.
En outre et contre toute attente, la présence d’une quantité efficace en termes d’efficacité antimicrobienne, de sel(s) d’ammonium quaternaire biocide(s), dans un dépôt d’agent liant polymérique, n’altère pas la manifestation de propriétés annexes du revêtement, comme par exemple la brillance ou sa pérennité sur le support, et notamment l’absence de décollement suite à une exposition de frottement sec ou humide. In addition and against all expectations, the presence of an effective quantity in terms of antimicrobial effectiveness, of biocidal quaternary ammonium salt(s), in a deposit of polymeric binding agent, does not alter the manifestation additional properties of the coating, such as for example the shine or its durability on the support, and in particular the absence of detachment following exposure to dry or wet friction.
Procédé de préparation du papier peint selon l’invention Process for preparing wallpaper according to the invention
La présente invention vise également un procédé de fabrication d’un papier-peint à propriétés biocides, notamment tel que décrit précédemment, comprenant au moins les étapes consistant à : a) disposer d’un papier peint, le cas échéant traité en surface d’au moins une de ses faces avec au moins un polymère vinylique, b) mettre en contact au moins tout ou partie de la face dudit papier-peint dédiée à procurer un effet décoratif visuel avec une composition, ladite composition comprenant : The present invention also relates to a process for manufacturing wallpaper with biocidal properties, in particular as described above, comprising at least the steps consisting of: a) having a wallpaper, where appropriate treated on the surface of 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:
- au moins un sel d’ammonium quaternaire non polymérique, notamment du chlorure de didécyl diméthyl ammonium (DD AC), - at least one non-polymeric quaternary ammonium salt, in particular didecyl dimethyl ammonium chloride (DD AC),
- au moins un agent liant polymérique obtenu par polymérisation d’au moins un monomère choisi parmi les acides acryliques et méthacryliques, les acrylates, méthacrylates, aliphatiques ou aromatiques, styrène et leurs mélanges, - 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,
- optionnellement au moins une charge, en particulier minérale, notamment de la silice, et- optionally at least one filler, in particular mineral, in particular silica, and
- optionnellement au moins un agent biocide distinct d’un sel d’ammonium quaternaire non
polymérique, et - optionally at least one biocidal agent distinct from a non-quaternary ammonium salt polymeric, and
- optionnellement au moins une résine polyamine-amide-épichlorydrine (PAAE) pour former un dépôt à propriétés biocides c) sécher ledit dépôt et d) optionnellement, gaufrer à chaud ou à froid ledit papier peint, de préférence après séchage dudit dépôt. - optionally at least one polyamine-amide-epichlorohydrin (PAAE) resin to form a deposit with biocidal properties c) dry said deposit and d) optionally, hot or cold emboss said wallpaper, preferably after drying of said deposit.
En particulier, à l’issu du séchage, un revêtement est formé sur tout ou partie de la face externe dédiée à procurer l’effet décoratif visuel recherché. In particular, following drying, a coating is formed on all or part of the external face dedicated to providing the desired visual decorative effect.
La composition mise en œuvre selon l’invention comprend au moins un sel d’ammonium quaternaire non polymérique, notamment tel que décrit précédemment. En particulier, la composition comprend de 0,05 % à 6 % en poids sec, de préférence de 0,5 % à 5,5 % en poids sec, et plus préférentiellement de 1 % à 5 % en poids sec, d’au moins un sel d’ammonium quaternaire non polymérique, notamment de chlorure de didécyl diméthyl ammonium, par rapport au poids sec total de la composition. 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 minus one non-polymeric quaternary ammonium salt, in particular didecyl dimethyl ammonium chloride, relative to the total dry weight of the composition.
Elle comprend également au moins un agent liant polymérique, notamment tel que décrit précédemment, obtenu par polymérisation d’au moins un monomère choisi parmi les acides acryliques et méthacryliques, les acrylates, méthacrylates, aliphatiques ou aromatiques, styrène et leurs mélanges. 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, acrylates, methacrylates, aliphatic or aromatic, styrene and their mixtures.
De préférence, l’agent liant polymérique considéré dans la composition est de nature polymérique et mis en œuvre sous une forme de dispersion, de solution ou d’émulsion, notamment aqueuse, de préférence d’une dispersion ou émulsion aqueuse. Preferably, the polymeric binding agent considered in the composition is of polymeric nature and used in the form of a dispersion, solution or emulsion, in particular an aqueous one, preferably an aqueous dispersion or emulsion.
Comme il ressort de ce qui précède, cette composition peut comprendre de 94 % à 99,95 % en poids sec, de préférence de 95 % à 99,5 % en poids sec, et plus préférentiellement de 95 % à 99 % en poids sec, d’agent liant polymérique obtenu par polymérisation d’au moins un monomère choisi parmi les acides acryliques et méthacryliques, les acrylates, méthacrylates, aliphatiques ou aromatiques, styrène et leurs mélanges, par rapport au poids sec de la composition.
En particulier, la composition comprend de 0,1 % à 10 % en poids sec d’au moins un sel d’ammonium quaternaire non polymérique, notamment de chlorure de didécyl diméthyl ammonium, et de 90 à 99,9 % en poids sec d’agent(s) liant(s) polymérique(s) par rapport au poids total de la composition, de préférence de 0,5 % à 5 % en poids sec d’au moins un sel d’ammonium quaternaire non polymérique, notamment de chlorure de didécyl diméthyl ammonium, et de 95 à 99,5 % en poids sec de liant(s) polymérique(s) par rapport au poids sec total de la composition. As can be seen 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, acrylates, methacrylates, aliphatic or aromatic, styrene and their mixtures, relative to the dry weight of the composition. In particular, the composition comprises from 0.1% to 10% by dry weight of at least one non-polymeric quaternary ammonium salt, in particular of 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 of 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.
La composition comprend optionnellement au moins une charge et/ou au moins un agent biocide distinct d’un sel d’ammonium quaternaire non polymérique, notamment tels que décrits précédemment. 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 above.
En particulier, la composition comprend de 0,01 % à 20 % en poids sec, de préférence de 0,1 % à 10 % en poids sec, et plus préférentiellement de 0,5 % à 8 % en poids sec, de charge, en particulier minérale, notamment de silice, par rapport au poids sec total de la composition.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.
En particulier, la composition comprend de 0,05 % à 10 % en poids sec, de préférence de 0,2 % à 6 % en poids sec, et plus préférentiellement de 0,2 % à 5 % en poids sec, d’agent biocide annexe par rapport au poids sec total de la composition. 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 agent annex biocide relative to the total dry weight of the composition.
En particulier, la composition comprend de 0,01 % à 10 % en poids sec, de préférence de 0,05 % à 5 % en poids sec, et plus préférentiellement de 0,1 % à 2 % en poids sec, de résine PAAE par rapport au poids sec total de la composition. 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.
La composition mise en œuvre dans le procédé selon l’invention est fluide. Elle peut posséder une viscosité allant de 5 mPa.s à 10 Pa.s, en particulier de 10 mPa.s à 5 Pa.s, et plus particulièrement de 10 à 500 mPa.s, à une température variant de 20 à 25°C et à pression atmosphérique. The composition used in the process according to the invention is fluid. It can 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.
Les viscosités des compositions selon l’invention peuvent être mesurées par des méthodes conventionnelles. La sélection de la méthode de mesure de même que l’appareillage de mesure adéquats notamment au regard de l’échelle de viscosité de la composition considérée relève clairement des compétences de l’homme de l’art. The viscosities of the compositions according to the invention can be measured by conventional methods. The selection of the measurement method as well as the appropriate measuring equipment, particularly with regard to the viscosity scale of the composition considered, clearly falls within the skills of those skilled in the art.
Par exemple, pour une composition possédant une viscosité manifestement inférieure à 2 Pa.s, il est privilégié comme appareillage de mesure un viscosimètre Brookfield avec l’axe n°2 à 100 tours par minute (ISO 2555) en veillant à ce que le couple mesuré par l’appareil
soit inférieur à 0,5 mN.m. Si le couple est supérieur à cette valeur, il est nécessaire de choisir un axe de degré supérieur. For example, for a composition having a viscosity clearly less than 2 Pa.s, a Brookfield viscometer with axis no. 2 at 100 revolutions per minute (ISO 2555) is preferred as measuring equipment, ensuring that the torque measured by the device or less than 0.5 mN.m. If the torque is greater than this value, it is necessary to choose an axis of higher degree.
Cette viscosité peut être ajustée au regard de la fonction particulière attachée à la composition à savoir constituer par exemple un vernis, une encre, une laque ou une peinture, mais également au mode d’application considéré pour traiter la surface d’un papier-peint avec ladite composition. 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 to treat the surface of wallpaper. with said composition.
En particulier, le papier-peint à traiter en étape a) est dénué de propriétés biocides. In particular, the wallpaper to be treated in step a) is devoid of biocidal properties.
En particulier, le procédé selon l’invention comprend une étape préalable de fabrication du papier-peint à traiter. Par exemple, les étapes b) et/ou c) peuvent être réalisées directement à l’issu de la fabrication du papier-peint à traiter. In particular, the method according to the invention comprises a preliminary step of manufacturing the wallpaper to be treated. For example, steps b) and/or c) can be carried out directly following the manufacture of the wallpaper to be treated.
La mise en contact en étape b) peut être réalisée par pulvérisation, par surfaçage size press, par enduction, par impression, par immersion dans un bain. En particulier, elle est réalisée par impression jet d’encre, héliogravure, flexographic, couchage au crayon, foulardage, impression digitale ou surimpression flexographique, de préférence par héliogravure, par flexographic, par sérigraphie, par couchage au crayon ou par surimpression flexographique et plus préférentiellement par héliogravure ou flexographic. 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 produced by inkjet printing, rotogravure, flexographic, pencil coating, padding, digital printing or flexographic overprinting, preferably by rotogravure, flexographic, screen printing, pencil coating or flexographic overprinting and more preferably by rotogravure or flexographic.
Ainsi, à température et pression ambiante, la composition utilisée : Thus, at ambient temperature and pressure, the composition used:
- en jet d’encre peut avantageusement présenter une viscosité entre 5 et 30 mPa.s, - inkjet can advantageously have a viscosity between 5 and 30 mPa.s,
- en héliogravure peut avantageusement présenter une viscosité comprise entre 10 et 150 mPa.s, - in rotogravure can advantageously have a viscosity of between 10 and 150 mPa.s,
- en flexographic peut avantageusement présenter une viscosité comprise entre 10 et 500 mPa.s, - in flexographic can advantageously have a viscosity of between 10 and 500 mPa.s,
- en surimpression flexographique peut avantageusement présenter une viscosité comprise entre 10 et 500 mPa.s, - in flexographic overprinting can advantageously have a viscosity of between 10 and 500 mPa.s,
- en couchage par lame d’air peut avantageusement présenter une viscosité comprise entre 50 et 200 mPa.s, - in air-blade coating can advantageously have a viscosity of between 50 and 200 mPa.s,
- en couchage rideau peut avantageusement présenter une viscosité comprise entre 5 et 500 mPa.s, et/ou - in curtain coating can advantageously have a viscosity of between 5 and 500 mPa.s, and/or
- en surfaçage size -press peut avantageusement présenter une viscosité comprise entre 20 et 100 mPa.s.
De préférence, la composition possède une viscosité comprise entre 10 et 50 mPa.s et la mise en contact est réalisée par héliogravure ou la composition possède une viscosité comprise entre 10 et 500 mPa.s et la mise en contact est réalisée par flexographic ou par surimpression flexographique. - in size-press surfacing can advantageously have a viscosity of between 20 and 100 mPa.s. Preferably, the composition has a viscosity of between 10 and 50 mPa.s and the contacting is carried out by rotogravure or the composition has a viscosity of between 10 and 500 mPa.s and the contacting is carried out by flexographic or by flexographic overprinting.
La viscosité de la composition fluide selon l’invention est notamment ajustable à travers le choix de la ou les nature(s) et la ou les quantité(s) en agent(s) liant polymérique(s) requis selon l’invention voire le cas échéant par dilution de la composition notamment avec de l’eau. 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 the where appropriate by diluting the composition in particular with water.
Le séchage peut être réalisé à une température allant de 30 à 250°C. Drying can be carried out at a temperature ranging from 30 to 250°C.
Le revêtement ainsi réalisé s’avère manifester une pérennité très satisfaisante et d’excellentes qualités. De plus, il présente une activité biocide performante. The coating thus produced turns out to have very satisfactory durability and excellent qualities. In addition, it presents efficient biocidal activity.
La présente invention vise également l’utilisation d’une composition telle que décrite précédemment pour conférer des propriétés biocides, notamment antivirales, à un papier- peint, notamment à un papier-peint tel que le papier-peint à traiter en étape a) du procédé selon l’invention. 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 process according to the invention.
La composition décrite précédemment se prête, au regard de ses spécificités, avantageusement à une utilisation à titre de vernis, encre, laque ou peinture. The composition described above lends itself, in view of its specificities, advantageously to use as a varnish, ink, lacquer or paint.
Les exemples figurant ci-après sont présentés à titre illustratif et non limitatif de modes de réalisation de l’invention. The examples appearing below are presented by way of illustration and not limitation of embodiments of the invention.
EXEMPLES EXAMPLES
Matériels et méthodes Materials and methods
Les matières premières suivantes ont été utilisées : The following raw materials were used:
- Chlorure de didécyl diméthyl ammonium (DD AC) commercialisé en solution à 80 % en poids MA (matière active) de DD AC, par l’une des sociétés THOR, STEPAN EUROPE et LONZA - Didecyl dimethyl ammonium chloride (DD AC) marketed in solution at 80% by weight MA (active ingredient) of DD AC, by one of the companies THOR, STEPAN EUROPE and LONZA
- Un copolymère styrène-acrylate commercialisé en solution à 36,6 % en poids MA - A styrene-acrylate copolymer marketed in solution at 36.6% by weight MA
- Une résine PAAE commercialisée en solution à 14,8 % en poids MA sous la dénomination FennoStrenght® XO par la Société Kemira.
Dans les exemples qui suivent et sauf indication contraire, les % en poids sont exprimés en % en poids des produits commerciaux sources en composés selon l’invention. - A PAAE resin marketed in solution at 14.8% by weight MA under the name FennoStrength® XO by the Kemira Company. In the examples which follow and unless otherwise indicated, the % by weight are expressed as % by weight of the commercial products sources of compounds according to the invention.
1. Test des propriétés antibactériennes 1. Testing for antibacterial properties
Elles sont caractérisées à l’aide du contrôle antibactérien par méthode de transfert selon la norme ISO 20743 réalisé avec les souches E.coli et S.aureus et un temps de contact de 24 heures. They are characterized using antibacterial control by transfer method according to the ISO 20743 standard carried out with the E.coli and S.aureus strains and a contact time of 24 hours.
2. Test des propriétés antivirales 2. Testing for antiviral properties
Tous les tests réalisés avec la souche Coronavirus HcoV-229E sont réalisés selon la norme ISO 21702:2019 adaptée avec un temps de contact de 5h. 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.
Tous les tests réalisés avec la souche Coronavirus OC43 (ATCC VR-1558) sont réalisés selon la norme ASTM E1053 adaptée avec un temps de contact de 5h. All tests carried out 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.
Les résultats, exprimés en log, correspondent à la réduction de la charge virale pour les temps de contact considérés par rapport à une référence dépourvue de traitement antimicrobien. The results, expressed in log, correspond to the reduction in viral load for the contact times considered compared to a reference without antimicrobial treatment.
Exemple 1 : Préparation d’une composition biocide selon l’invention Example 1: Preparation of a biocidal composition according to the invention
La composition est préparée à partir d’un milieu aqueux dans lequel est introduit la forme commerciale de l’agent liant polymérique considéré. Après obtention d’un mélange homogène, le DD AC est ensuite ajouté. La préparation est réalisée au Rayneri. The composition is prepared from an aqueous medium into which the commercial form of the polymeric binding agent considered is introduced. After obtaining a homogeneous mixture, the DD AC is then added. The preparation is carried out at Rayneri.
Les proportions mises en œuvre sont indiquées en tableau 1. The proportions implemented are indicated in table 1.
[Tableau 1]
[Table 1]
Exemple 2 : Préparation et caractérisation des performances anti-microbiennes d’un papier-peint conforme à l’invention, formé à partir de la composition de l’exemple 1 Le support considéré est un papier-peint 160 g/m2 (deux papiers contrecollés, respectivement de 70 et 90 g/m2). La composition est appliquée par procédé d’héliogravure avec un taux de dépose moyen de 1 à 8 g/m2 en poids sec. Plus précisément, le taux de dépose est de 3 g/m2. Example 2: Preparation and characterization of the anti-microbial performances of a wallpaper conforming to the invention, formed from the composition of Example 1 The support considered is a 160 g/m 2 wallpaper (two papers laminated, 70 and 90 g/m 2 respectively). The composition is applied by the rotogravure process with an average deposition rate of 1 to 8 g/m 2 by dry weight. More precisely, the deposition rate is 3 g/m 2 .
Le tableau 2 rend compte des performances anti-microbiennes mesurées. Table 2 reports the measured anti-microbial performances.
[Tableau 2]
[Table 2]
Claims
1. Papier-peint à propriétés biocides dont tout ou partie de la face externe dédiée à procurer un effet décoratif visuel, comporte un dépôt d’au moins un agent liant polymérique, ledit agent liant étant obtenu par polymérisation d’au moins un monomère choisi parmi les acides acryliques et méthacryliques, les acrylates, méthacrylates, aliphatiques ou aromatiques, styrène et leurs mélanges, et contenant en outre de 0,05 % à 6 % en poids sec d’au moins un sel d’ammonium quaternaire non polymérique par rapport au poids sec total dudit dépôt, et ledit dépôt comprenant au moins une résine polyamine-amide- épichlorydrine (PAAE). 1. Wallpaper with biocidal properties, all or part of the external face 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 chosen monomer among acrylic and methacrylic acids, acrylates, methacrylates, aliphatic or aromatic, 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 to the total dry weight of said deposit, and said deposit comprising at least one polyamine-amide-epichlorohydrin (PAAE) resin.
2. Papier-peint à propriétés biocides selon la revendication 1, dont ledit sel d’ammonium quaternaire non polymérique est au moins du chlorure de didécyl diméthyl ammonium (DD AC). 2. Wallpaper with biocidal properties according to claim 1, of which said non-polymeric quaternary ammonium salt is at least didecyl dimethyl ammonium chloride (DD AC).
3. Papier-peint à propriétés biocides selon la revendication 1 ou 2, ledit agent liant contenant de 0,05 à 6 % en poids sec et de préférence de 0,5 à 5,5 % en poids sec, de sel(s) d’ammonium quaternaire non polymérique(s), notamment de chlorure de didécyl diméthyl ammonium (DD AC), par rapport au poids sec total d’agent liant. 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 salt(s). non-polymeric quaternary ammonium(s), in particular didecyl dimethyl ammonium chloride (DD AC), relative to the total dry weight of binding agent.
4. Papier-peint à propriétés biocides selon l’une quelconque des revendications précédentes, ledit agent liant polymérique étant un copolymère obtenu par polymérisation d’au moins un monomère choisi parmi les acides acryliques et méthacryliques, les acrylates, les méthacrylates et leur mélange avec au moins un monomère styrène. 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. Papier-peint à propriétés biocides selon l’une quelconque des revendications précédentes, ledit agent liant polymérique comprenant, voire consistant en, un ou plusieurs polymère(s) choisi(s) parmi les homo-polymères et co-polymères acryliques, les homo-polymères et co-polymères acrylates, les homo-polymères et co-polymères méthacryliques, les homo-polymères et co-polymères méthacrylates, les homo-polymères et co-polymères de styrène, et leurs mélanges, notamment parmi les polyacryliques, les poly acrylates, les polyméthacryliques, les polyméthacrylates, les polystyrènes, les copolymères styrène-acryliques, les copolymères styrène-méthacryliques, les copolymères styrène-acrylates, les copolymères styrène-méthacrylates et leurs mélanges, et plus
particulièrement comprend, voire consiste en, au moins un copolymère styrène-acrylique et/ou styrène- acrylate . 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 homo-polymers and co-polymers, acrylate homo-polymers and co-polymers, methacrylic homo-polymers and co-polymers, methacrylate homo-polymers and co-polymers, styrene homo-polymers and co-polymers, and their mixtures, in particular among polyacrylics, poly acrylates, 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. Papier-peint à propriétés biocides selon l’une quelconque des revendications précédentes, ledit dépôt étant formé à raison de 94 à 99,95 % en poids sec, de préférence de 95 à 99,5 % en poids sec, et plus préférentiellement de 95 à 99 % en poids sec, dudit agent liant polymérique par rapport au poids sec total dudit dépôt. 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 from 95 to 99% by dry weight, of said polymeric binding agent relative to the total dry weight of said deposit.
7. Papier-peint à propriétés biocides selon l’une quelconque des revendications précédentes, ledit dépôt comprenant en outre un ou plusieurs agent(s) biocide(s) distinct(s) d’un sel d’ammonium quaternaire non polymérique, de préférence choisi(s) parmi le p-[(Diiodométhyl) sulfonyl] toluol, le carbamate de 3-iodo-2- propynylbutyle, le méthyl-lH-benzimidazol-2-ylcarbamate, la monolaurine, les composés à base d’isothiazoline ou dérivés d’isothiazolone, de chitosan ou dérivés de chitine, de zéolithe de zinc, d’ions d’argent, notamment le chlorure d’argent, d’argent sous forme particulaire supportée, de triclosan, de sel d’ammonium quaternaire polymérique et leurs mélanges, et plus préférentiellement comprenant en outre au moins du carbamate de 3-iodo-2- propynylbutyle (IPBC). 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, isothiazoline-based compounds or derivatives isothiazolone, chitosan or chitin derivatives, zinc zeolite, silver ions, in particular silver chloride, silver in supported particulate form, triclosan, polymeric quaternary ammonium salt and their mixtures, and more preferably further comprising at least 3-iodo-2-propynylbutyl carbamate (IPBC).
8. Papier-peint à propriétés biocides selon l’une quelconque des revendications précédentes, ledit dépôt comprenant en outre au moins une charge, en particulier minérale, notamment de la silice. 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. Papier-peint à propriétés biocides selon l’une quelconque des revendications précédentes, ledit dépôt comprenant de 0,01 % à 10 % en poids sec, de préférence de 0,05 % à 5 % en poids sec de PAAE, par rapport au poids sec total du dépôt. 9. Wallpaper with biocidal properties according to any one of the preceding claims, said deposit comprising from 0.01% to 10% by dry weight, preferably from 0.05% to 5% by dry weight of PAAE, relative to to the total dry weight of the deposit.
10. Papier-peint à propriétés biocides selon l’une quelconque des revendications précédentes, ledit dépôt étant un revêtement monocouche. 10. Wallpaper with biocidal properties according to any one of the preceding claims, said deposit being a single-layer coating.
11. Papier-peint à propriétés biocides selon l’une quelconque des revendications précédentes, dont le dépôt d’agent liant est en surface externe et de préférence au contact d’un support fibreux tissé ou intis sé. 11. Wallpaper with biocidal properties according to any one of the preceding claims, in which the deposit of binding agent is on the external surface and preferably in contact with a woven or non-woven fibrous support.
12. Papier-peint à propriétés biocides selon l’une quelconque des revendications précédentes, comportant un support fibreux, notamment tissé ou intissé, comprenant en surface de sa face à effet décoratif une couche polymérique, ledit dépôt d’agent liant étant en particulier disposé en surface, notamment au contact, de ladite couche
polymérique formée d’au moins un polymère vinylique, de préférence de polychlorure de vinyle. 12. 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 placed on the surface, in particular in contact, of said layer polymer formed from at least one vinyl polymer, preferably polyvinyl chloride.
13. Papier-peint à propriétés biocides selon l’une quelconque des revendications précédentes, possédant un grammage allant de 80 à 200 g/m2. 13. Wallpaper with biocidal properties according to any one of the preceding claims, having a weight ranging from 80 to 200 g/m 2 .
14. Procédé de fabrication d’un papier-peint à propriétés biocides, notamment tel que défini selon l’une quelconque des revendications précédentes, comprenant au moins les étapes consistant à : a) disposer d’un papier peint, le cas échéant traité en surface d’au moins une de ses faces avec au moins un polymère vinylique, b) mettre en contact au moins tout ou partie de la face dudit papier-peint dédiée à procurer un effet décoratif visuel avec une composition, ladite composition comprenant : 14. Process for manufacturing wallpaper with biocidal properties, in particular as defined according to any one of the preceding claims, comprising at least the steps consisting of: a) having wallpaper, where appropriate treated in surface of 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:
- au moins un sel d’ammonium quaternaire non polymérique, notamment du chlorure de didécyl diméthyl ammonium (DD AC), - at least one non-polymeric quaternary ammonium salt, in particular didecyl dimethyl ammonium chloride (DD AC),
- au moins un agent liant polymérique obtenu par polymérisation d’au moins un monomère choisi parmi les acides acryliques et méthacryliques, les acrylates, méthacrylates, aliphatiques ou aromatiques, styrène et leurs mélanges, - 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,
- au moins une résine PAAE, - at least one PAAE resin,
- optionnellement au moins une charge, en particulier minérale, notamment de la silice, et- optionally at least one filler, in particular mineral, in particular silica, and
- optionnellement au moins un agent biocide distinct d’un sel d’ammonium quaternaire non polymérique, pour former un dépôt à propriétés biocides et c) sécher ledit dépôt d) optionnellement gaufrer à chaud ou à froid ledit papier-peint à propriétés biocides, de préférence après séchage dudit dépôt. - optionally at least one biocidal agent distinct from a non-polymeric quaternary ammonium salt, to form a deposit with biocidal properties and c) dry said deposit d) optionally hot or cold emboss said wallpaper with biocidal properties, preferably after drying of said deposit.
15. Procédé selon la revendication précédente, la mise en contact en étape b) étant réalisée par impression jet d’encre, héliogravure, flexographic, couchage au crayon, foulardage, impression digitale ou surimpression flexographique, de préférence par héliogravure ou flexographic. 15. Method according to the preceding claim, the contacting in step b) being carried out by inkjet printing, rotogravure, flexographic, pencil coating, padding, digital printing or flexographic overprinting, preferably by rotogravure or flexographic.
16. Procédé selon la revendication 14 ou 15, dans lequel ledit agent liant polymérique est mis en œuvre sous la forme d’une dispersion ou émulsion aqueuse. 16. Method according to claim 14 or 15, in which said polymeric binding agent is used in the form of an aqueous dispersion or emulsion.
17. Procédé selon l’une quelconque des revendications 14 à 16, ladite composition possédant une viscosité allant de 5 mPa.s à 10 Pa.s, en particulier de 10 mPa.s
à 5 Pa.s, et plus particulièrement de 10 à 500 mPa.s à une température allant de 20 à 25°C et à pression atmosphérique. 17. Method according to any one of claims 14 to 16, said composition having a viscosity ranging from 5 mPa.s to 10 Pa.s, in particular 10 mPa.s at 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.
18. Procédé selon l’une quelconque des revendications 14 à 17, ladite composition comprenant de 0,01 % à 10 % en poids sec, de préférence de 0,05 % à 5 % en poids sec, et plus préférentiellement de 0, 1 % à 2 % en poids sec, de résine PAAE par rapport au poids sec total de la composition. 18. Method according to any one of claims 14 to 17, said composition comprising 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.
19. Procédé selon l’une quelconque des revendications 14 à 18, ladite composition se présentant sous la forme d’un vernis, d’une encre, d’une laque ou d’une peinture. 19. Method according to any one of claims 14 to 18, said composition being in the form of a varnish, an ink, a lacquer or a paint.
20. Procédé selon l’une quelconque des revendications 14 à 19, la composition comprenant de 0,05 % à 6 % en poids sec d’au moins un sel d’ammonium quaternaire non polymérique, notamment de chlorure de didécyl diméthyl ammonium, et de 94 à 99,95 % en poids sec d’agent(s) liant(s) polymérique(s) par rapport au poids sec total de la composition, de préférence de 0,5 % à 5,5 % en poids sec d’au moins un sel d’ammonium quaternaire non polymérique, notamment de chlorure de didécyl diméthyl ammonium, et de 95 à 99,5 % en poids sec d’agent(s) liant(s) polymérique(s) par rapport au poids sec total de la composition. 20. Method according to any one of claims 14 to 19, the composition comprising from 0.05% to 6% by dry weight of at least one non-polymeric quaternary ammonium salt, in particular of didecyl dimethyl ammonium chloride, and from 94 to 99.95% by dry weight of polymeric binder(s) relative to the total dry weight of the composition, preferably from 0.5% to 5.5% by dry weight d 'at least one non-polymeric quaternary ammonium salt, in particular didecyl dimethyl ammonium chloride, and 95 to 99.5% by dry weight of polymeric binder(s) relative to the dry weight total composition.
21. Utilisation d’une composition, en particulier telle que décrite dans l’une quelconque des revendications 16 à 20, comprenant : 21. Use of a composition, in particular as described in any one of claims 16 to 20, comprising:
- au moins un sel d’ammonium quaternaire non polymérique, notamment du chlorure de didécyl diméthyl ammonium (DD AC), - at least one non-polymeric quaternary ammonium salt, in particular didecyl dimethyl ammonium chloride (DD AC),
- au moins un agent liant polymérique obtenu par polymérisation d’au moins un monomère choisi parmi les acides acryliques et méthacryliques, les acrylates, méthacrylates, aliphatiques ou aromatiques, styrène et leurs mélanges, - 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,
- au moins une résine PAAE - at least one PAAE resin
- optionnellement au moins une charge, en particulier minérale, notamment de la silice, et- optionally at least one filler, in particular mineral, in particular silica, and
- optionnellement au moins un agent biocide distinct d’un sel d’ammonium quaternaire non polymérique, pour conférer des propriétés biocides, notamment antivirales, à un papier-peint.
- optionally at least one biocidal agent distinct from a non-polymeric quaternary ammonium salt, to confer biocidal properties, in particular antiviral properties, to a wallpaper.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FRFR2204311 | 2022-05-06 | ||
| FR2204311A FR3135271A1 (en) | 2022-05-06 | 2022-05-06 | Wallpaper with biocidal properties |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2023213976A1 true WO2023213976A1 (en) | 2023-11-09 |
Family
ID=83280207
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2023/061865 WO2023213976A1 (en) | 2022-05-06 | 2023-05-04 | Wallpaper having biocidal properties |
Country Status (2)
| Country | Link |
|---|---|
| FR (2) | FR3135271A1 (en) |
| WO (1) | WO2023213976A1 (en) |
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| FR3099768B1 (en) | 2019-08-06 | 2021-08-06 | Oberthur Fiduciaire Sas | Security paper |
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- 2022-05-06 FR FR2204311A patent/FR3135271A1/en active Pending
- 2022-12-15 FR FR2213465A patent/FR3135272A1/en active Pending
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2023
- 2023-05-04 WO PCT/EP2023/061865 patent/WO2023213976A1/en unknown
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Also Published As
| Publication number | Publication date |
|---|---|
| FR3135272A1 (en) | 2023-11-10 |
| FR3135271A1 (en) | 2023-11-10 |
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