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
  • D06N3/04—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
  • D06N3/06—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 polyvinylchloride or its copolymerisation products
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
  • B29D99/00—Subject matter not provided for in other groups of this subclass
  • B29D99/005—Producing membranes
• • 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
  • D06M15/248—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing chlorine
• • 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
  • D06M23/08—Processes in which the treating agent is applied in powder or granular form
• • 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
  • D06N3/18—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
  • D06N2203/00—Macromolecular materials of the coating layers
  • D06N2203/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06N2203/045—Vinyl (co)polymers
  • D06N2203/048—Polyvinylchloride (co)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
  • D06N2205/02—Dispersion
  • D06N2205/023—Emulsion, aqueous dispersion, latex
• • 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
  • D06N2205/103—Nanoparticles
• • 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
  • D06N2211/12—Decorative or sun protection articles
  • D06N2211/14—Furniture, upholstery

Definitions

• the invention relates to the field of coated membranes, more specifically coated fabrics typically used as protective tarpaulins.
• the invention relates more particularly to a novel membrane structure which has both good abrasion resistance, good ability to be assembled by a standard welding process, good fire resistance and antiviral action.
• a membrane can also be cleaned with commonly used antiseptics. It can be used in the medical environment or for health reasons.
• PVC polyvinyl chloride
• PVC-coated textiles have the advantage of being able to be easily assembled by heat-welding, to allow a production adapted to the shape to be produced while preserving the waterproofing of the membrane.
• 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.
• textiles such as surgical drapes, masks or surgical drapes can also contain nanoparticles of silver, coated by impregnation and present at the heart of the material.
• these textile articles are not waterproof or heat-sealable. In these various applications, the silver is used essentially by impregnation or extrusion.
• Silver is also known for applications outside of the medical field.
• silver nanoparticles make it possible to fight against the bacteria that cause bad odors and also to prevent fungal infections. In this case, they are integrated by extrusion during spinning or during the finishing of the textile by impregnation.
• silver nanoparticles release Ag + ions during the washing cycle, which allows better disinfection of the laundry.
• 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 in size (viruses have on average a size about a thousand times smaller than that of bacteria which have a minimum size of about 1 pm), for structure (the virus is considered a biological entity and the bacterium is a living organism), or by the genetic material (bacteria are prokaryotes with DNA and RNA; viruses have only one of these acids).
• Patent application CN 108894005 describes an antibacterial artificial leather based on polyvinyl chloride (PVC) made of a base fabric which may be a fabric, with an intermediate layer bonded to the fabric layer by an adhesive layer, a surface PVC layer and an environmental protection layer.
• the environmental protection layer acts as a varnish and comprises water-based polyurethane and an antibacterial agent comprising an organic antibacterial component composed of nanometric particles which is preferably nano chitosan and an inorganic antibacterial component composed of particles. nanometric.
• the inorganic antibacterial component can be nanosilver, nanodinc, nanopper, or nanotitanium or their oxides.
• the environmental protection layer is made from an aqueous, non-solvent medium.
• the antibacterial agent necessarily includes an organic component and an inorganic component, otherwise the effect will not can be obtained (as demonstrated in Comparative Examples 2 and 3).
• the invention therefore consists in providing a coated membrane having antiviral action, as well as a method of manufacturing such a membrane.
• the invention relates to a coated and varnished membrane, said membrane comprising at least one fabric comprising at least one side coated with at least one layer of polyvinyl chloride, and at least one film of varnish on said coated side. of the membrane, said varnish film comprising a polymeric binder and silver in the form of a silver element of size less than 250 nm, said membrane being such that the varnish film has an average thickness within the range of 0 , 5 to 20 ⁇ m and such that the mass content of silver in the varnish film is in the range 0.00001 to 3%.
• the coated side of the fabric can be coated with at least one layer of polymer, for example a layer of polyurethane or a layer of PVC, then the layer of polyvinyl chloride.
• the polyvinyl chloride layer is therefore an outer layer (that is to say the furthest from the fabric) on which the varnish film rests, itself in contact with the outside (relative to the fabric).
• One or more layers of polymer (s) can be deposited on each face of the membrane without one face necessarily being coated with the same number of layers and the same nature and thickness of layer (s) as the other corresponding face.
• silver element of size less than 250 nm is meant according to the invention a silver atom (elementary), or else a silver nanoparticle of size less than 250 nm, preferably in the range of 1. at 250 nm. The particle size is thus generally qualified as nanometric.
• size is meant according to the invention the largest dimension of the particle. Obviously, a silver atom meets the criterion of size less than 250 nm.
• the silver nanoparticles are less than 150 nm in size, preferably in the range of 1 to 150 nm. Even more preferably, the silver nanoparticles have a size of less than 100 nm, preferably in the range of 1 to 100 nm.
• the silver is in the form of silver atoms (originating from silver ions dissolved in the varnish before depositing the varnish film), or else particles of nanometric size which can reach 250 nm of silver. (from silver nanoparticles dispersed in the varnish before depositing the varnish film).
• This small size advantageously allows maximum efficiency of the antiviral function given the very large surface availability it induces and the nanometric size of viruses.
• the mass content of silver in the varnish film is preferably in the range of 0.0005 to 2%, even more preferably from 0.001 to 1%. This content is expressed relative to the element silver and calculated after the film has dried.
• the membrane according to the invention is most often in a strip of suitable length, typically 50 m, and a width (or width) of up to 5 m.
• this membrane is easily rollable or foldable, and transportable, which favors possible handling and logistics operations.
• the silver particles present in the varnish confer antiviral activity on the coated and varnished membrane, while maintaining its usual properties, that is to say resistance to cleaning by most of the antiseptics used in the fields. sanitary and / or medical, as well as abrasion resistance.
• Such a membrane thus has an advantageous lifetime.
• Another of the advantages of the invention is that the coated and varnished membrane can be easily welded, typically by heat-welding, to another membrane, generally coated and varnished, without losing its antiviral action. This allows modular assembly of the membranes according to the invention according to the needs of the end user, which is particularly appreciable.
• the membrane according to the invention makes it possible to limit or even stop the proliferation of viruses in the environments used or inhabited by humans, by an antiviral action, that is to say which kills the viruses by surface contact, in the absence of any human cleaning intervention, in just a few minutes of contact.
• fabric is meant according to the invention a textile material.
• the fabric constitutes the core or frame of the coated and varnished membrane.
• 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, 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 mixtures thereof.
• polyesters including aromatic polyesters such as, for example, commercial product Vectran ® from the company Kuraray
• polyamides including aromatic polyamides such as for example the commercial product Kevlar ® from the company Dupont
• polyacrylates such as for example the commercial product Kevlar ® from the company Dupont
• the fabric is a polyester woven or nonwoven, typically high tenacity polyester.
• the polyvinyl chloride layer comprises polyvinyl chloride, at least one plasticizer and at least one heat stabilizer.
• the plasticizer is generally present in an amount in the range of 30 to 100 parts by weight based on 100 parts by weight of PVC.
• the heat stabilizer is generally present in an amount in the range of 0.5 to 10 parts by weight based on 100 parts by weight of PVC.
• the polyvinyl chloride layer is generally deposited on the fabric or on the fabric previously coated with at least one layer of polymer such as a layer of polyurethane or PVC, by a coating step by means of a coating. paste which is coated the membrane, in a manner known to those skilled in the art.
• the PVC resin in powder form obtained from polymerization in emulsion or micro-suspension of vinyl chloride monomer
• plastisol a liquid plasticizer
• the PVC 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 membrane does not contain any other antibacterial compound than silver (which can play this role in addition to its antiviral action). It is even more particularly preferred that the membrane does not contain any compound. organic antibacterial. It is particularly impossible for the membrane to contain chitosan in any form whatsoever.
• the plasticizer is chosen in the usual way for the person skilled in the art, depending on the applications and the properties required for the membrane. It is generally of the ester type, typically chosen from phthalates, phosphates and adipates. For example, if cold resistance is required, an adipate type plasticizer such as dicotyl adipate (DOA) is generally used.
• DOA dicotyl adipate
• plasticizers such as diisononyl phthalate (DINP), available for example from the companies BASF and Exxon, but also diisodecyl phthalate (DIDP), dioctyl terephthalate (DOTP), di (2-propylheptyl) phthalate (DPHP), 1,2-cyclohexane dicarboxylic acid (DINCH), 2-ethylhexyl diphenyl phosphate (Santicizer ® 141 from the company Valtris), tris (2-ethylhexyl) trimellitate (TOTM) or a bio-based plasticizer such as Polysorb ® ID37 from Roquette.
• DINP diisononyl phthalate
• DIDP diisodecyl phthalate
• DDPHP di (2-propylheptyl) phthalate
• DINCH 1,2-cyclohexane dicarboxylic acid
• Santicizer ® 141 from the company Val
• the thermal stabilizer which is added to the plastisol, is a metal salt such as a barium and zinc salt, or a calcium and zinc salt, or a tin-based compound.
• the heat stabilizer can also be an organic compound. It makes it possible to gel the plastisol at a temperature typically between 140 and 200 ° C without degradation of the PVC.
• a standard plastisol formula that can be used according to the invention can be, in parts by weight, as follows:
• the varnish film has an average thickness preferably in the range of 1 to 12 ⁇ m, even more preferably 2 to 10 ⁇ m.
• the thickness is between 4 and 8 ⁇ m.
• the appearance of the outer surface of the film follows the appearance of the PVC layer before the film was deposited and is therefore not completely smooth.
• the thickness can vary from point to point of the film by + or - 3 ⁇ m.
• the film of varnish is transparent.
• the polymeric binder is chosen from the group formed by polyester polyurethanes, polyether polyurethanes, polycarbonate polyurethanes, silicone modified polyurethanes, acrylics, acrylates, acrylate copolymers, acrylic copolymers, acrylic styrenes. , ethylene vinyl acetates, and mixtures thereof.
• Polyurethanes constitute a class of polymers whose composition and structure can be very variable, thanks to the reagents used to synthesize them. They are obtained by the polyaddition reaction of polyols and polyisocyanates. The molar mass of the final polymer will depend on the stoichiometric conditions of the OH (alcohol) and NCO (isocyanate) functions and on the progress of the reaction.
• the synthesis is carried out by incorporating an emulsifier, most often internal (integrated into the polymer chain), very often of a hydrophilic nature in order to make stabilization of the polymer in water possible.
• Three hydrophilic groups are mainly used:
• Anionic groups (ionized carboxylic or sulfonic group)
• Cationic groups protonated tertiary amine
• the synthesis is done by adding at least one emulsifier.
• the synthesis is carried out by adding segments of water-soluble polymers.
• the varnish film can be transparent or colored, typically by adding at least one pigment to the varnish.
• the pigment is for example chosen from the group formed by titanium dioxide (white), carbon black, phthalocyanine, and mixtures thereof. Particularly preferably, the pigment does not include a sulfur atom.
• the invention relates to a method of manufacturing a membrane according to the invention, comprising the following steps:
• step (c) depositing on the coated side from step (a) a film of the varnish from step (b), to a thickness in the range of 0.5 to 20 ⁇ m;
• step (d) drying the varnish film from step (c), resulting in the obtaining of the coated and varnished membrane.
• the method comprises an additional step, subsequent to step (d), of calendering the coated and varnished membrane obtained in step (d).
• the term "varnish” means a liquid, colored or not, which has the ability to form a film, after application to a substrate and drying.
• the polymeric binder which comprises at least one organic synthetic compound, is one of the essential components of the varnish.
• aqueous medium is meant according to the invention a liquid phase generally comprising several chemical species, of which water is the majority constituent and chemical species dissolved or in suspension which are in the minority.
• the method of the invention makes it possible to apply to a coated membrane at least one deposit of a few micrometers of varnish in which the silver has been dispersed or dissolved, to make it adhere, while retaining the properties of said membrane. , especially its weldability.
• weldability is the ability of the coated and varnished membrane to be welded.
• the main methods of welding PVC coated membranes are hot air assemblies, high frequency assemblies, thermal assemblies and ultrasonic assemblies.
• the varnish film according to the invention does not form a barrier to the fusion of the two PVC layers of two different membranes and does not hinder their interpenetration.
• the varnish according to the invention adheres to the coated membrane and is resistant to abrasion, water, dirt, and certain detergents. If necessary, the varnish according to the invention can be formulated to have a particular desired appearance (mattness, shine, etc.) or a particular resistance (such as UV resistance when the membrane according to the invention is used. outdoors), as explained below.
• the desired finish appearance can be provided by the addition of an organic or inorganic matting agent, preferably chosen from polymethyl urea or inorganic polymeric additives of fumed silica type.
• a particular resistance such as, for example, resistance to water and to UV, may be provided by combining a binder of polyurethane type, preferably of polycarbonate type, in combination with anti UV additives, preferably of HALS type (for " Hindered Amine Light Stabiizer ”, for amine-based stabilizer, such as the commercial products Tinuvin ® NOR from the company BASF).
• the varnish may contain an additive making it possible to achieve the required abrasion resistance, of polymeric or inorganic type, preferably of polysiloxane type.
• the silver is generally provided in the context of the invention by the aqueous medium (solution or dispersion) which is generally of two kinds.
• the particle size of less than 250 nm according to the invention is maximum in order to ensure the stability of its particles in solubilization or in dispersion in water.
• the silver is present in the varnish in the form of a dispersion of colloidal silver of particles of nanometric size less than 250 nm, preferably less than 150 nm and even more preferably less than 100 nm in size.
• the size is preferably greater than 1nm. This size makes it possible to ensure optimum stability of the dispersions.
• there are several processes for producing such dispersions described for example in the thesis of R.
• the level of silver in the dispersion is generally in the range of 10 ppm to 10,000 ppm, preferably 10 to 5000 ppm, more preferably 10 to 4000 ppm.
• the company Cerion also markets silver dispersions of particles of nanometric sizes (less than 10 nm).
• the polymeric binder has the same polarity as that of the aqueous medium containing the silver.
• the binder is cationic if the silver particles are made by the commercial product Viroblock ® NPJ03 of HeiQ society. It may then be the RU-13 537 ®, which is a cationic polyether polyurethane of the Stahl, or the RU-68002 ®, which is a cationic polyurethane polyester of Stahl, or the ROLFLEX ® Cl society Lamberti, which is a cationic polyurethane polycarbonate from the company Lamberti.
• the silver is present in the varnish in the form of Ag + ion dissolved in the varnish, preferably in the form of complexes solvated in water, even more preferably in the form of soluble complexes in the varnish.
• water generally chosen from the group formed by silver nitrates AgNCh, silver chlorides AgCl and mixtures thereof.
• commercial products comprising these complexes are generally coupled to organic binders such as acrylate polymers. This makes it possible to use these products in direct textile impregnation without any other formulation as well as, advantageously, to stabilize the silver ions in the aqueous medium.
• the company Sanitized markets the product Sanitized ® Tl 115, which is a dispersion of silver nitrate at less than 0.5% by weight in the presence of an anionic acrylate binder at a pH in the range of 9.5. to 11.5.
• Zschimmer et Schwarz markets the product Lefasol ® MTV13002-1, which is an aqueous dispersion based on silver chloride and an anionic acrylate polymer binder.
• the varnish generally also comprises at least one additive such as:
• an adhesion promoter e.g., a silane with epoxy function as Deolink ® TE 100 which is 3- (2,3-epoxypropoxy) propyl] - triethoxysilane of DOG society;
• a spreading agent for example a polysiloxane such as TEGO GLIDE ® 482 which is a dimethylpolysiloxane of the company Evonik Tego ® Coatosil or 77 which is a trisiloxane of Momentive;
• a polysiloxane such as TEGO GLIDE ® 482 which is a dimethylpolysiloxane of the company Evonik Tego ® Coatosil or 77 which is a trisiloxane of Momentive
• an anti-foaming agent for example a polysiloxane as Byk ® 1724 BYK company or Byk ® 022 is a polysiloxane BYK company; and
• a slip agent such as (a) a polyethylene wax emulsion such as Joncryl ® Wax 35 from BASF or TEGO GLIDE 440 ®, which is a siloxane polyether copolymer and the Evonik Tego.
• a polyethylene wax emulsion such as Joncryl ® Wax 35 from BASF or TEGO GLIDE 440 ®, which is a siloxane polyether copolymer and the Evonik Tego.
• the varnish further comprises an adhesion promoter, a spreading agent, an anti-foam agent and a slip agent.
• the varnish according to the invention advantageously has a homogeneous and smooth surface.
• the surface should not be sticky.
• the varnish can also comprise at least one additional additive chosen from UV stabilizers, thermal stabilizers and pigments.
• 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.
• FIG. 2 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.
• FIG. 4 Figure 4 is an enlargement of Figure 3.
• the coated and varnished membrane 1 of Figure 1 comprising a core or textile reinforcement 2 consisting of a weaving of high tenacity polyethylene threads, formed of warp threads 22 intersecting with weft threads 21 and 23.
• the woven core 2 has been coated on both sides with a layer of PVC respectively 31 and 32.
• two varnish films 41 and 42 respectively have been deposited on each coated side, the film 42 being enlarged in FIG. 2.
• the film 42 comprises silver 4, dispersed within the film 42.
• the coated and varnished membrane 10 of FIG. 3 comprising the same core or textile reinforcement 2.
• the woven core 2 has been coated on both sides with two successive layers of PVC respectively 34 then 36 on one side and 33 then 35 on one side. 'other face.
• two varnish films 44 and 43 respectively have been deposited on each coated face, the film 43 being enlarged in FIG. 4.
• the film 43 comprises silver 40 of nanometric size, dispersed within the film. 43.
• the money used was a colloidal dispersion, commercial product Viroblock ® NPJ03 of HeiQ society.
• the varnish was manufactured 48 hours before its use, its storage having been carried out at a temperature above 5 ° C.
• the varnish had the following composition (in parts by weight)
• Adhesion promoter 1; Deolink ® TE 100 which is a 3- (2,3-Epoxypropoxy) propyl] - triethoxysilane from the company DOG
• TEGO GLIDE ® 482 which is a dimethylpolysiloxane from the company TEGO Evonik
• the thickness of the varnish when dried was about 5-7 ⁇ m. It was checked by optical measurement on a microtomic section of the membrane slice.
• Virological analyzes are carried out by determining the infectious titers on MRC5 cells (ATCC CCL-171) in limiting dilution. Cytopathogenic effects (PCE) readings are taken after 6 days of incubation at 37 ° and 5% CO2.
• 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 10 5 TCID50 (for 50% Tissue Culture Infectious Dose: titer required to cause infection in 50% of the inoculated cell cultures. ).
• the results were, for the membrane coated and varnished according to the invention, a reduction in the viral load of 99.9% at 60 min of contact, whether for the virus alone or for the virus with mucus and saliva.
• Tests were carried out on an industrial high frequency bench, to verify that the varnish film did not form a barrier to the fusion of two PVC layers and did not interfere with their interpenetration during the welding of two membranes according to the invention. with each other. After this assembly by high frequency, 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 announced in the technical sheet of the product which is 9daN over a width of 5 cm.
• the measured values were 11 daN / 5 cm for the membrane coated and varnished according to the invention, against 10 daN / 5 cm for the comparative membrane, which therefore validated the test for the two membranes.
• the membrane according to the invention made it possible to obtain results qualifying the cleaning as good, whether for betadine or for eosin.
• the membrane coated and varnished according to the invention has an antiviral action, while retaining the desired properties of adhesion of the varnish, weldability and resistance to cleaning.

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• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
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• Chemical Kinetics & Catalysis (AREA)
• Inorganic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Biochemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Microbiology (AREA)
• Mechanical Engineering (AREA)
• Laminated Bodies (AREA)
• Separation Using Semi-Permeable Membranes (AREA)

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• 2020
  • 2020-04-24 FR FR2004133A patent/FR3109591B1/fr active Active
• 2021
  • 2021-04-23 WO PCT/FR2021/050715 patent/WO2021214422A1/fr unknown
  • 2021-04-23 US US17/920,563 patent/US20230151539A1/en active Pending
  • 2021-04-23 EP EP21731229.7A patent/EP4139517A1/de active Pending
  • 2021-04-23 CN CN202180030704.1A patent/CN115443357A/zh active Pending

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