Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
  • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
  • D06N3/18—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
  • A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
  • A01N59/16—Heavy metals; Compounds thereof
• • 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
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
  • D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
  • D06M15/256—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing fluorine
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
  • D06M23/10—Processes in which the treating agent is dissolved or dispersed in organic solvents; Processes for the recovery of organic solvents thereof
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
  • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
  • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
  • D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
  • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
  • D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06N3/047—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds with fluoropolymers
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
  • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
  • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
  • D06N3/128—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with silicon polymers
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
  • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
  • D06N3/18—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials
  • D06N3/183—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials the layers are one next to the other
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
  • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
  • D06N3/18—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials
  • D06N3/186—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials one of the layers is on one surface of the fibrous web and the other layer is on the other surface of the fibrous web
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
  • D06N2201/00—Chemical constitution of the fibres, threads or yarns
  • D06N2201/02—Synthetic macromolecular fibres
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
  • D06N2203/00—Macromolecular materials of the coating layers
  • D06N2203/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06N2203/044—Fluoropolymers
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
  • D06N2203/00—Macromolecular materials of the coating layers
  • D06N2203/06—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06N2203/066—Silicon polymers
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
  • D06N2205/00—Condition, form or state of the materials
  • D06N2205/10—Particulate form, e.g. powder, granule
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
  • D06N2209/00—Properties of the materials
  • D06N2209/16—Properties of the materials having other properties
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
  • D06N2209/00—Properties of the materials
  • D06N2209/16—Properties of the materials having other properties
  • D06N2209/1671—Resistance to bacteria, mildew, mould, fungi
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
  • D06N2211/00—Specially adapted uses
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
  • D06N2211/00—Specially adapted uses
  • D06N2211/12—Decorative or sun protection articles
  • D06N2211/14—Furniture, upholstery

Definitions

• Composite membrane comprising a fluoropolymer or silicone surface layer comprising silver, its manufacturing process and its use as a virucide
• the invention relates to the field of composite membranes, more specifically fabrics impregnated or coated with non-stick hydrophobic polymers with low surface energy, typically used as furniture coverings, for example seat coverings, protective tarpaulins or elements of modular structures
• the invention relates more particularly to a novel composite membrane structure which has both an antiviral action, a good 'cleanability' by the solvents and antiseptics commonly used, typically isopropanol, a good abrasion resistance, a good aptitude. to be assembled either by adding filler strips or by a standard welding process, and good fire resistance. It can be used in the medical environment or for health reasons.
• silver for example in the form of particles of nanometric size (or nanoparticles)
• silver nanoparticles are used in dressings where they have been coated by impregnation, or are dispersed in polymers molded into blocks constituting all or part of medical devices which are for example catheters or orthopedic implants, any particularly to limit the formation of pathogenic biofilm (as described for example in US 9625065).
• textiles such as surgical drapes, masks or surgical drapes can also contain silver nanoparticles, deposited by impregnation and present at the heart of the material.
• these textile articles are not waterproof or easily assembled, for example by welding.
• Silver is therefore commonly used for its bactericidal properties. However, it was very recently observed that silver also has antiviral properties (Thesis n ° 120,
• bacteria and viruses are different entities, whether by size (viruses have on average a size about a thousand times smaller than that of bacteria which have a size of about 1 mhi), by structure (the virus is considered a biological entity and the bacterium is a living organism), or through genetic material (bacteria are prokaryotes with DNA and RNA; viruses have only one of these acids) .
• US 2016/184874 describes a fabric covered with a polymer layer, the use of this fabric, as well as a process for its manufacture.
• the polymer can be a fluoropolymer or a polysiloxane (paragraph [0027]).
• the polymer layer contains silver nanoparticles.
• the process for preparing this fabric includes a step of applying the polymer to the fabric (paragraph [0037]), for example by lamination or impregnation (paragraph [0039]).
• the antimicrobial effect of this fabric is attributed to silver nanoparticles, the size of which is preferably less than 100 nm (paragraphs [0042] to [0044]).
• the thickness of the polymer layer is 100 to 500 ⁇ m, preferably 150 to 450 mhi, even more preferably 200 to 400 mhi (paragraph [0036)), which is high.
• the invention therefore consists in providing a composite membrane having an antiviral action, as well as a method of manufacturing such a membrane.
• the invention relates to a composite membrane comprising at least one fabric, said membrane comprising a surface polymer layer, said surface polymer layer comprising silver and at least one polymer chosen from fluoropolymers and silicones, and said membrane being such that the silver (4; 40) is in the form of silver supported by a mineral matrix in powder form, the particle size of the matrix being and strictly greater than 0.1 mhi and strictly less than 20 pm.
• the polymer of the surface polymer layer consists of a fluoropolymer or a silicone.
• the membrane may further comprise at least one intermediate polymer layer, for example a layer of polyurethane or a layer of polyvinyl chloride (PVC) or a layer of silicone or a layer of fluoropolymer, the surface polymer layer. being present at least in part on the intermediate polymeric layer furthest from the fabric, which preferably comprises the same polymer as the polymeric surface layer.
• the surface polymer layer is therefore the layer of the composite membrane in contact with the outside, furthest from the fabric.
• One or more intermediate polymer layers can be deposited on each side of the membrane without one side necessarily being coated with the same number of intermediate polymer layers and the same nature and thickness of layer (s) as the other corresponding side.
• the mass content of silver in the polymer layer is in the range 0.00001 to 10%, preferably 0.0005 to 5%, even more preferably 0.001 to 3% (by weight%).
• silver is actively antiviral in its smallest more or less associated elemental size, that this associated elemental form occurs in the form of very small colloidal-like particles called nanoparticles (in which case the medium dispersion of silver is water), or else dissolved in an aqueous medium, or inserted into mineral matrices with a particle size of the order of micrometers (which makes it possible to handle it in powder form, which can be used in solvents).
• the silver thus introduced into a surface polymer layer confers antiviral activity on the composite membrane, while maintaining its usual properties, that is to say resistance to cleaning by most of the antiseptics used in the sanitary fields.
• composite membrane thus has an advantageous lifetime.
• Another of the advantages of the invention is that the composite membrane can be easily assembled with another membrane, generally composite, either by filler strip or by welding, typically by heat-sealing, without losing the antiviral properties. This allows modular assembly of the composite membranes according to the invention according to the needs of the end user, which is particularly valuable.
• the main methods of assembling composite membranes are welds such as hot air assemblies, high frequency assemblies, thermal assemblies and ultrasonic assemblies; and assemblies by filler band. All these assembly methods can be carried out on the composite membrane of the invention without the latter losing its antiviral action.
• the composite membrane according to the invention makes it possible to deactivate the viruses in the environments used or inhabited by humans, by an antiviral function, that is to say which destroys the viruses by surface contact, in the absence of any human cleaning intervention, in just a few minutes of contact.
• the fabric is chosen from wovens, nonwovens, grids, knits, and mixtures thereof, preferably from wovens and nonwovens.
• the fabric is made of a textile material and comprises threads or fibers based on a material chosen from the group formed by glass, polyesters including aromatic polyesters (such as for example the commercial product Vectran ® from the company Kuraray), polyamides including aromatic polyamides (such as for example the commercial product Kevlar ® from the company Dupont), polyacrylates, viscoses, nylons, cottons, polyvinyl acetates , polyvinyl alcohols and their mixtures.
• the fabric is a polyester woven or nonwoven, typically a high tenacity polyester.
• the surface polymer layer has been deposited by impregnation, typically by padding.
• the composite membrane does not include an intermediate polymer layer, although the presence of at least one intermediate polymer layer is not excluded according to the invention.
• the surface polymer layer then has an average thickness in the range of 5 to 100 ⁇ m, preferably 5 to 80 ⁇ m, even more preferably 5 to 50 ⁇ m.
• the surface polymer layer has been deposited by coating, typically by deposition by doctor blade on a cylinder (“roll coat” or other) or by varnishing. In this case, it is preferred that the composite membrane comprises at least one intermediate polymeric layer.
• the surface polymer layer then has an average thickness of in the range of 0.5 to 20 mhi, preferably from 1 to 12 ⁇ m, even more preferably from 2 to 10 mhi.
• the average thickness is between 4 and 8mhi.
• the thickness can vary from one point to another of the surface polymer layer, typically by + or - 3 mhi.
• the polymeric intermediate layer can also contain at least one additive such as a pigment, for example a nickel titanate, or else a titanium dioxide; at least one flame retardant filler such as antimony trioxide, alumina trihydrate, zinc borate or calcium carbonate; a fungicide and / or any other additive known to those skilled in the art.
• a pigment for example a nickel titanate, or else a titanium dioxide
• at least one flame retardant filler such as antimony trioxide, alumina trihydrate, zinc borate or calcium carbonate
• fungicide and / or any other additive known to those skilled in the art can also contain at least one additive such as a pigment, for example a nickel titanate, or else a titanium dioxide; at least one flame retardant filler such as antimony trioxide, alumina trihydrate, zinc borate or calcium carbonate; a fungicide and / or any other additive known to those skilled in the art.
• the silver is supported by a mineral matrix which is in the form of a powder dispersed or not in a liquid medium.
• Silver which has the antiviral function is present in the mineral (or inorganic) matrix.
• the matrix is in the form of a powder comprising an atomic lattice in which silver atoms are inserted.
• the silver is gathered in the matrix, preferably in the form of particles of silver.
• the matrix acts as a reservoir for the silver that will be available on the surface of the composite membrane to destroy viruses.
• Silver can also be on the surface of the grains of the mineral matrix.
• the matrix must have a particle size compatible with the thickness of the surface polymer layer, that is to say generally a particle size strictly less than 20 mhi, preferably strictly less than 5 mhi. In all cases, this size is generally greater than or equal to 0.1 ⁇ m.
• the particle size of the matrix is most often in the range of 0.1 to 20 ⁇ m, preferably 0.1 to 5 ⁇ m.
• size is meant according to the invention the largest dimension of the particle.
• the d98 of the particles of the matrix containing silver is less than 18 ⁇ m, preferably less than 10 ⁇ m, and the d50 of the matrix containing silver is less than or equal to 6 ⁇ m. , preferably less than or equal to 3 ⁇ m.
• d98 is meant the maximum size made by 98% of the particles (by number).
• d50 is meant the maximum size made by 50% of the particles (by number).
• the silver content in the matrix is generally between 0.01 and 10%, preferably between 0.1 and 5%, more preferably between 1 and 3%, in% by weight relative to the matrix.
• the mass content of silver in the surface polymer layer is in the range from 0.01 to 5%, preferably from 0.05 to 3%, even more preferably from 0.05 to 2%, in% by weight. This content is expressed relative to the element silver and is calculated after the polymer layer has dried.
• the polymer is generally chosen from the group formed by silicones and fluoropolymers. They are low surface energy polymers and therefore hydrophobic.
• the polymeric surfaces of the silicone or fluorinated type are easily cleanable due to a low surface tension. They also exhibit low safety and reactivity with the skin (ISO 10993-5 non-cytotoxic and 10993-10 non-irritable).
• silicones and fluorinated polymers of PVDF type are advantageously biocompatible and easily cleanable because they are resistant to disinfectants including isopropanol which is widely used for example in hydroalcoholic gels.
• the composite membranes according to the invention find multiple applications in the medical world because they also have the antiviral function
• the silicone is preferably a polysiloxane.
• the silicone is chosen from the group comprising polydimethylsiloxanes, poldiyphenylsiloxanes, oligosiloxanes, polyaminosiloxanes, polyvinylsiolxanes and their copolymers.
• copolymer is meant according to the invention a polymer resulting from the copolymerization of at least two types of chemically different monomer.
• homopolymer is meant according to the invention a polymer resulting from the polymerization of a single type of monomer.
• (co) polymer is meant according to the invention polymer or copolymer.
• Silicone polymers usable in the solvent phase are known in the trade, such as the product Elastosil ® RD 6620 F further comprising a crosslinker and a catalyst, Wacker.
• the fluoropolymer is generally polyvinylidene fluoride (or PVDF), or a polymer based on tetrafluoroethylene, hexafluoropropylene, and vinylidene fluoride, also called THV, PTFE, fluorinated ethylene propylene (FEP), perfluoroalkoxy (PF A ) and in general, many fluoropolymers, as well as fluorinated acrylics and methacrylics, taken alone or as a mixture.
• the fluoropolymer is PVDF.
• the surface polymer layer can also comprise at least one additive chosen from UV stabilizers, matting agents, thermal stabilizers, flame retardant compounds and pigments.
• the UV stabilizer is preferably present when the composite membrane is to be used outdoors.
• the UV stabilizer is preferably selected from benzotriazoles, triazines and, even more preferably selected from triazines, for example the commercial product Tinuvin ® 400 (hydroxytriazine) from BASF.
• the mattifying agent is generally organic or inorganic, preferably chosen from polymeric additives of polymethyl urea type or inorganic additives of fumed silica type. It usually makes it possible to provide the surface polymer layer with the desired finish appearance (gloss, satin, mat, etc.),
• the flame retardant compound is generally selected from the group consisting of aluminum trihydrate, magnesium hydroxide, silicas, zeolites, antimony trioxide (Sb203), calcium carbonate (CaCO3) as well as inorganic pigments. .
• the surface polymer layer can be transparent or colored, typically by adding at least one pigment to the polymer composition.
• the pigment is for example chosen from the group formed by titanium dioxide (white), carbon black, phthalocyanine, or mixtures thereof.
• the surface polymer layer does not comprise a sulfur compound. This advantageously makes it possible to preserve the antiviral property of the membrane, linked to the silver particles present in the surface polymer layer.
• step (c) depositing on at least one side optionally coated from step (a) with a layer of the polymer composition from step (b), to a given thickness;
• the solvent is generally chosen from solvents capable of dissolving the polymer, depending on the nature of the polymer.
• the solvent is chosen from the group formed by water, ketones such as methyl ethyl ketone (or MEK), acetone, diethyl ketone, methyl isobutyl ketone, diisobutyl ketone, gamma butyrolactone or cyclohexanone; alcohols (non-cyclic) such as ethyl alcohol, isopropyl alcohol, N-propyl alcohol, benzyl alcohol or furfuril alcohol; cyclic alcohols such as cyclohexanol; acetates such as ethyl acetate or butyl acetate; ketone alcohols such as diacetone alcohol (DAA); cyclic ethers such as tetrahydrofuran (THF), propylene glycol monoethyl ether acetate, methoxypropyl acetate; aromatic solvent
• the solvent is an aqueous medium. This is referred to as an aqueous route.
• aqueous medium a liquid phase generally comprising several chemical species, of which water is the majority constituent and dissolved chemical species which are in the minority.
• the solvent is chosen from the group formed by ketones such as methyl ethyl ketone (or MEK), acetone, diethyl ketone, methyl isobutyl ketone, diisobutyl ketone, gamma butyrolactone or cyclohexanone; alcohols (non-cyclic) such as ethyl alcohol, isopropyl alcohol, N-propyl alcohol, benzyl alcohol or furfuril alcohol; cyclic alcohols such as cyclohexanol; acetates such as ethyl acetate or butyl acetate; ketone alcohols such as diacetone alcohol (DAA); cyclic ethers such as tetrahydrofuran (THF), propylene glycol monoethyl ether acetate, methoxypropyl acetate; aromatic solvents such as toluene or xylene; hydrocarbon solvents such as heptane
• ketones such as
• step (c) is carried out by impregnation, the average thickness of the layer polymer being in the range of 5 to 100 ⁇ m, preferably 5 to 80 ⁇ m, even more preferably 5 to 50 ⁇ m.
• the impregnation uses aqueous and solvent-based polymer compositions substantially similar to those described below for the coating.
• the technique of padding is very widespread. It generally consists in passing the surface of the fabric or of the coated fabric, preferably of the fabric, in a bath containing the fluid impregnating polymer composition, then expressing the excess fluid absorbed by applying a pressure between two squeezing rollers, or wringers, and finally to pass through a drying oven.
• a polymer composition comprising an organic solvent (or diluent)
• it is desirable to then remove the solvent for example to subject this article membrane to a heat treatment to remove the solvent.
• solvent generally in gaseous form.
• step (c) is carried out by coating.
• the average thickness of the polymer layer being in the range of 0.5 to 20 ⁇ m, preferably 1 to 12 ⁇ m, even more preferably 2 to 10 ⁇ m.
• the silver in a first case is present in the form of silver particles supported by a mineral matrix and optionally added to other elements such as liposome vesicles for the viroblock product NPJ03 from the company HeiQ .
• a silicone dispersion can be the commercial products TCS 7110 A ® and TCS7110 B ® from the company Elkem, often used as a mixture with one another.
• An aqueous dispersion of PVDF, typically mixed with an acrylic polymer which may contain different ratios of acrylic, can be for example the products of trade Kynar Aquatec ® FMA-12 (50 PVDF -50 acrylic ratio) or Kynar Aquatec ® CRX (70 PVDF -30 acrylic ratio) from ARKEMA
• the polymer composition of step (b) can be a commercial product to which is added, generally by mixing, the matrix. It is also possible to manufacture it as is known to the person skilled in the art, typically by mixing the constituents of the polymer composition. When it comprises, as explained above, an additive, this additive has also been mixed within the polymer composition as is known to the person skilled in the art.
• the method of the invention makes it possible to apply to a coated membrane at least one deposit of a few micrometers of varnish film in which silver particles supported by a matrix in powder form have been dispersed, and to do so. adhere, while retaining the properties of said membrane.
• the invention advantageously makes it possible to have made it possible to produce a very thin and very resistant layer of varnish, as will be demonstrated in the examples.
• the varnish film according to the invention adheres to the coated membrane and is resistant to abrasion, water, dirt, and a large number of detergents, the most widely used of which is isopropanol, alone or mixed.
• the polymer composition according to the invention can be formulated to have a particular desired appearance (mattness, gloss, etc.) or a particular resistance (such as UV resistance when using the membrane according to invention outdoors), as explained above.
• the invention relates to the use of a membrane according to the invention or manufactured according to the process according to the invention, as a virucide, generally in the field of technical textiles.
• Figure 1 is a schematic sectional view of a first embodiment of the membrane of the invention.
• Figure 2 is an enlargement of Figure 1.
• Figure 3 is a schematic sectional view of a second embodiment of the membrane of the invention.
• Figure 4 is an enlargement of Figure 3.
• Figure 5 is a photograph taken by transmission electron microscopy (or TEM) of powder particles of an embodiment according to the invention. It shows the micrometric dimension of such particles.
• the composite membrane 1 of Figure 1 comprises a core or textile reinforcement 2 consisting of a weaving of high tenacity polyester threads, formed of warp threads 22 intersecting with weft threads 21 and 23.
• 'woven core 2 has been coated on both sides with two layers of polymer such as silicone 41 and 42 respectively on each side, layer 42 being enlarged in Figure 2.
• Layer 42 comprises a matrix in powder form 4 comprising silver particles, said powder being dispersed within layer 42.
• the composite membrane 10 of FIG. 3 comprising the same core or textile reinforcement 2.
• the woven core 2 was then on its two faces of two successive layers of polymer such as silicone respectively 34 then 36 on one face and 33 then 35 on the other side.
• two layers 44 and 43 respectively have been deposited on each coated face, layer 43 being enlarged in FIG. 4.
• Layer 43 comprises a matrix in the form of powder 40 comprising silver particles, said powder. being dispersed within layer 43.
• the varnish produced by simple mixing, had the following composition (in parts by weight):
• Silver product Viroblock ® NPJ03 from the company HEIQ: 20 (such that the average size of the agglomerates (titanium dioxide - silver chloride) of reaction mass is approximately 1.56 ⁇ 71 ⁇ m)
• the varnish produced by simple mixing, comprised an aqueous dispersion of a PVDF-acrylic copolymer of the trade name Kynar Aquatec ® FMA 12 from the company ARKEMA and the silver produced Viroblock ® NPJ03 from the company HEIQ in the following proportions (parts in weight) :
• the varnish included a solvent-based silicone varnish, Elastosil ® RD 6620 F, from Wacker, formulated with the crosslinking and catalyst compounds recommended by the manufacturer; to which was added 3% of BCA 21-41.
• Test demonstrating the weldability and making of the composite membranes according to the invention Tests were carried out on a high-frequency bench and / or industrial heating press, to verify that the resistance of the polymers on the fabric was sufficient.
• the silicone composite membranes were assembled using an EVC (hot vulcanizable elastomer) type conveyor belt.
• the PVDF composite membranes were assembled either hot (hot press) or by high frequency depending on the grade. After this assembly by high frequency or thermal, with or without supply band, the force necessary to open the weld according to the protocol described in standard EN 15619 Annex C.
• the value found had to be equal to or greater than the value 20N over a width of 5 cm to ensure sufficient strength of the assemblies and tightness.
• Virological analyzes are carried out by determining the infectious titers on MRC5 cells (ATCC CCL-171) in limiting dilution. Cytopathogenic effects (CPE) readings are taken after 6 days of incubation at 37 ° and 5% C02.
• CPE Cytopathogenic effects
• the test was performed against a reference coated membrane, that is, a membrane containing no silver.
• the human coronavirus HCoV-229E which is part of the enveloped alpha coronas virus family, was used in the test.
• the contact time between the membrane (comparative or according to the invention) and the solution containing the virus is 60 min. Two environmental conditions were tested:
• the solution comprising the virus was deposited in an amount of 50 to 100 ⁇ L and the amount of virus deposited was 105 TCID50 (for Infectious Dose in Tissue Culture 50%: titre required to cause infection in 50% of the inoculated cell cultures) .
• the results were, for each composite membrane according to the invention, a reduction of more than 90% of the viral load at 60 min of contact, whether for the virus. alone or for the virus with mucus and saliva.
• the sample was placed so that it was completely submerged in isopropanol.
• the composite membranes according to the invention have made it possible to obtain results qualifying the cleaning as "good", whether for betadine or for eosine
• the composite membranes according to the invention have resistance to cleaning with isopropanol, as well as an antiviral action, while while retaining the desired properties of the corresponding comparative composite membranes.

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• 2020
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