WO2022180133A1 - Method for sanitizing or sterilizing the surface of an article having a fluoropolymer coating - Google Patents

Method for sanitizing or sterilizing the surface of an article having a fluoropolymer coating Download PDF

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Publication number
WO2022180133A1
WO2022180133A1 PCT/EP2022/054583 EP2022054583W WO2022180133A1 WO 2022180133 A1 WO2022180133 A1 WO 2022180133A1 EP 2022054583 W EP2022054583 W EP 2022054583W WO 2022180133 A1 WO2022180133 A1 WO 2022180133A1
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Prior art keywords
composition
polymer
article
solvent
group
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PCT/EP2022/054583
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French (fr)
Inventor
Mattia Bassi
Fiorenza D'aprile
Valeriy KAPELYUSHKO
Elena GRIGNANI
Laura ZARATIN
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Solvay Specialty Polymers Italy S.P.A.
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Publication of WO2022180133A1 publication Critical patent/WO2022180133A1/en

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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
    • C09D127/00—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 a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/08—Materials for coatings
    • A61L29/085—Macromolecular materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/08—Materials for coatings
    • A61L31/10—Macromolecular materials
    • 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
    • C09D127/00—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 a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09D127/16—Homopolymers or copolymers of vinylidene fluoride
    • 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
    • C09D127/00—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 a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09D127/18—Homopolymers or copolymers of tetrafluoroethene
    • 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
    • C09D129/00—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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
    • 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
    • C09D137/00—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 a heterocyclic ring containing oxygen; Coating compositions based on derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2202/00—Aspects relating to methods or apparatus for disinfecting or sterilising materials or objects
    • A61L2202/20—Targets to be treated
    • A61L2202/24—Medical instruments, e.g. endoscopes, catheters, sharps
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/60—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
    • A61L2300/606—Coatings

Definitions

  • the present invention relates to protective coatings for medical devices, equipment and PPE that are resistant to sanification and sterilization technologies, imparting durability and promoting safe use and re-use of the same.
  • Sterilization and sanitization are techniques used to, respectively, eliminate or reduce the microorganisms that are in or on a material. During sterilization process all microorganisms, harmful or not, are killed. During sanitization the number of microorganic pathogens is reduced to a level where they can’t be harmful.
  • Sterilization is mostly used in health care centers on medical instruments, such as surgical tools. Such tools have to be sterilized since they are used on different patients. Thus, sterilization prevents the transfer of diseases, bacteria, or viruses from one patient to another.
  • Sanitization is mainly intended as cleaning and disinfection in non healthcare settings for surface and textile in indoor environments in the context of environmental contamination and pathogens persistence on different surfaces.
  • Ozone A more efficient, safer, and less expensive sterilization agent is ozone (O3).
  • Ozone can easily be generated from oxygen, especially hospital grade oxygen.
  • Ozone gas generators may also be used in sanitization processes in healthcare and non-healthcare indoor environments, as described for example in JP2004130006A.
  • UV light ultraviolet light
  • EP 1973578 relates to methods for producing sanitary health care environments, such as the operating room or other ambulatory treatment facilities, by utilizing ultraviolet irradiation and ozone to destroy viruses, bacteria, and fungus.
  • materials coated with polymers can be sensitive to sterilization procedures, which may damage the coating by causing it to delaminate from the surface of the device or equipment, or may alter the chemical properties of materials in the coating.
  • these type of polymer coatings are affected by one or more cycles of sanitization technologies, which may cause significant polymer chain scission and a substantial reduction in molecular weight, with a consequent substantial change in polymer properties, negatively affecting the medical device or equipment after sanitizing.
  • the Applicant faced the problem of providing a polymer suitable for coating the surfaces of an article such as medical device, equipment or PPE, said polymer being such to provide a durable protective coating towards dry/low-temperature sanitization methods of medical devices to promote safe reuse.
  • the present invention relates to a method for sanitizing or sterilizing the surface of an article contaminated with pathogens selected from viruses, bacteria, and fungus, said article having a polymer coating, the method comprising the following steps: a) providing an article having at least one surface onto which a polymer coating is to be applied; b) providing a polymer coating composition [composition (C)] for application onto the article; and c) applying the composition (C) obtained in step b) onto the at least one surface of the article provided in step a) to obtain a coated article; then d) exposing the coated article to sanitisation or sterilisation means, wherein the polymer coating composition (C) comprises: i) at least one fluoropolymer [polymer (F)] selected from the group consisting of:
  • - polymers (F-1) comprising recurring units derived from: • perfluorodioxoles of formula (I): wherein Ri , R2, R3 and R4, equal to or different from each other, are independently selected from the group consisting of -F, a C1-C6 fluoroalkyl group, optionally comprising one or more oxygen atoms;
  • TFE tetrafluoroethylene
  • HFP hexafluoropropylene
  • VF1 vinyl fluoride
  • VF3 trifluoroethylene
  • CTFE chlorotrifluoroethylene
  • TFE tetrafluoroethylene
  • HFP hexafluoropropylene
  • the present invention provides for sanitized or sterilized coated articles obtainable by the above method.
  • parentheses “(%)” before and after symbols or numbers identifying formulae or parts of formulae has the mere purpose of better distinguishing that symbol or number with respect to the rest of the text; thus, said parentheses could also be omitted.
  • weight percent indicates the content of a specific component in a mixture, calculated as the ratio between the weight of the component and the total weight of the mixture.
  • weight percent (wt %) indicates the ratio between the weight of the recurring units of such monomer over the total weight of the polymer/copolymer.
  • TSC total solid content
  • weight percent (wt %) indicates the ratio between the weight of all non-volatile ingredients in the liquid.
  • the term “article contaminated with pathogens” indicates any object having at least a surface that can be suitably coated by a polymer coating composition (C) that needs to be sterilized due to the presence, at least onto the external surface, of pathogens such as viruses, bacteria, and fungus.
  • An article may include, for example, without limitation, medical devices, equipment or PPEs.
  • the articles can be formed by a variety of elements and having at least different types of basic materials, such as plastics, metals, glasses, ceramic, textiles, etc.
  • the polymer coating composition (C) can be used on a variety of surfaces.
  • a “medical device” is to be intended in a broad sense as including any instrument, apparatus, machine, appliance, implant, or other similar or related article, including any component or part, which is intended for use in the cure, mitigation, treatment, or prevention of disease, of a human or animal.
  • plastic materials for medical devices are polymers such as polyurethanes and their copolymers, or block polyetheramides or other polymeric materials including polyvinyl chloride, polyamide, silicone, block copolymers styrene-ethylene / butylene-styrene (SEBS), block copolymers of styrene isoprene-styrene (SIS), copolymers in Block of styrene-ethylene / propylene-styrene (SEPS), ethylene-vinyl acetate copolymers (EVA), polyethylene (PE), metallocene catalyzed polyethylene, and copolymers of ethylene and propylene or mixtures thereof.
  • polymers such as polyurethanes and their copolymers, or block polyetheramides or other polymeric materials including polyvinyl chloride, polyamide, silicone, block copolymers styrene-ethylene / butylene-styrene (SEBS), block copo
  • equipment is to be intended as any patient- care equipment (such as respirators, diagnostic equipment, shunts, body scopes, wheel chairs, beds, etc.), or surgical and diagnostic equipment.
  • PPE personal protective equipment
  • a “textile” is any woven or non-woven fabric or article, or garment including, but not limited to, all types found in the consumer and industrial markets including, but not limited to, those made of cotton, poly cotton blends, wool, aramids, polyurethanes, olefins, polyactids, nylons, silk, hemp, rayon, flax, jute, acrylics, polyesters, those made from many other synthetic or natural fibers and mixtures thereof.
  • the polymer coating composition (C) can be used to effectively reduce the microorganisms population of health care surfaces and equipment.
  • Health care surface refers to a surface of an instrument, a device, a cart, a cage, furniture, a structure, a building, or the like that is employed as part of a health care activity.
  • Health care surfaces are found in hospital, surgical, infirmity, birthing, mortuary, and clinical diagnosis rooms. These surfaces can be those typified as “hard surfaces” (such as walls, floors, bed-pans, etc.), or textiles (such as surgical garments, draperies, bed linens, bandages, etc.).
  • a polymer coating composition (C) comprising: i) at least one fluoropolymer [polymer (F)j selected from the group consisting of:
  • - polymers (F-1) comprising recurring units derived from: • perfluorodioxoles of formula (I): wherein Ri , R 2 , R 3 and R 4 , equal to or different from each other, are independently selected from the group consisting of -F, a C 1 -C 6 fluoroalkyl group, optionally comprising one or more oxygen atoms;
  • TFE tetrafluoroethylene
  • HFP hexafluoropropylene
  • VF1 vinyl fluoride
  • VF3 trifluoroethylene
  • CTFE chlorotrifluoroethylene
  • TFE tetrafluoroethylene
  • HFP hexafluoropropylene
  • fluorinated monomer By the expression “at least one fluorinated monomer, it is hereby intended to denote a polymer comprising recurring units derived from one or more than one fluorinated monomers.
  • fluorinated monomers In the rest of the text, the expression “ fluorinated monomers” is understood, for the purposes of the present invention, both in the plural and the singular, that is to say that it denote both one or more than one fluorinated monomers as defined above.
  • per in the expression “perfluorodioxoles” and in the term “ perfluoroolefin” means that the monomer can be fully or partially fluorinated.
  • the polymers (F-1) more preferably comprise recurring units derived from at least one perfluorodioxole of formula (I): wherein Ri , F3 ⁇ 4, F3 ⁇ 4 and R 4 , equal to or different from each other, are independently selected from the group consisting of -F, a C 1 -C 3 perfluoroalkyl group, e.g. -CF 3 , -C 2 F 5 , -C 3 F 7 , and a C 1 -C 3 perfluoroalkoxy group optionally comprising one oxygen atom, e.g.
  • TFE tetrafluoroethylene
  • perfluorodioxoles class having structure (I) preferably used in the present invention are mentioned in EP 633256; still more preferably 2,2,4- trifluoro-5-trifluoromethoxy-1,3-dioxole (TTD) is used.
  • TTD 2,2,4- trifluoro-5-trifluoromethoxy-1,3-dioxole
  • TFE tetrafluoroethylene
  • Non-limitative examples of suitable polymers (F-1) include, notably, those commercially available under the trademark name HYFLON® AD from Solvay Specialty Polymers Italy S.p.A. and TEFLON® AF from E. I. Du Pont de Nemours and Co.
  • the polymers (F-2) preferably comprise recurring units derived from vinylidene fluoride (VDF) and recurring units derived from at least one C3- Ce perfluoroolefins, such as hexafluoropropene (HFP).
  • VDF vinylidene fluoride
  • HFP hexafluoropropene
  • suitable polymers (F-2) include, notably, those commercially available under the trademark name Solef®from Solvay Specialty Polymers Italy S.p.A..
  • the polymer (F) is typically manufactured by suspension or emulsion polymerization processes.
  • Polymer (F) can either be semi-crystalline or amorphous.
  • semi-crystalline is intended to denote a polymer (F) which possesses a detectable melting point. It is generally understood that a semi-crystalline polymer (F) possesses a heat of fusion determined according to ASTM D 3418 of advantageously at least 0.4 J/g, preferably of at least 0.5 J/g, more preferably of at least 1 J/g.
  • amorphous is hereby intended to denote a polymer (F) having a heat of fusion of less than 5 J/g, preferably of less than 3 J/g, more preferably of less than 2 J/g as measured by Differential Scanning Calorimetry (DSC) at a heating rate of 10°C/min according to ASTM D- 3418-08.
  • DSC Differential Scanning Calorimetry
  • the amount of one or more comonomers in polymers (F-1) and (F-2) is to be such to bring either to semi-crystalline or to amorphous polymer. Those of ordinary skill in the field are able to easily determine the amount of such comonomers.
  • the role of the solvent in coating applications is typically to dissolve the polymer (F) in order to allow the application of the composition onto the surface if the article to finally obtain a coating upon evaporation of the solvent.
  • solvent (S) is thus intended to denote a solvent suitable for dissolving polymer (F) as defined above.
  • solvent (S) is typically an organic solvent selected from the group consisting of:
  • alcohols such as methyl alcohol, ethyl alcohol and diacetone alcohol
  • ketones such as acetone, methylethylketone, methylisobutyl ketone, diisobutylketone, cyclohexanone and isophorone
  • - linear or cyclic esters such as isopropyl acetate, n-butyl acetate, methyl acetoacetate, dimethyl phthalate and y-butyrolactone
  • - linear or cyclic amides such as N,N-diethylacetamide, N,N- dimethylacetamide, dimethylformamide and N-methyl-2-pyrrolidone, and
  • the fluoroalkyl ether is preferably a C4-12 compound.
  • CF3CH2OCF2CF2H AE-3000, tradename, manufactured by Asahi Glass Company, Limited
  • C4F9OCH3 Novec- 7100, tradename, manufactured by Sumitomo 3M Limited
  • C4F9OC2H5 (Novec-7200, tradename, manufactured by Sumitomo 3M Limited) and C6F13OCH3 (Novec-7300, tradename, manufactured by Sumitomo 3M Limited) may, for example, be mentioned.
  • the perfluorinated polyether is preferably a low molecular weight perfluoropolyether (PFPE) having a boiling point in the range from 55°C to 135°C, such as commercially available products under the tradename Galden®SV80, manufactured by Solvay Specialty Polymers Italy.
  • PFPE low molecular weight perfluoropolyether
  • the present invention provides a composition (C) comprising at least one polymer (F-1) and a fluoroalkyl ether.
  • the present invention provides a composition (C) comprising at least one polymer (F-1) and a perfluorinated polyether.
  • the present invention provides a composition (C) comprising at least one polymer (F-2) and a ketone.
  • composition (C) the proper amount of said solvent (S) in composition (C) in order to achieve dissolution of the fluorinated polymer [polymer (F)] and suitable evaporation of the same when composition (C) is applied onto the at least one surface of the article to provide a coated article.
  • compositions (C) including at least one polymer (F) and a solvent (S) are prepared having the total solid content (TSC) in the range from 0.05 to 10.0, preferably from 0.1 to 5.0, are prepared.
  • TSC total solid content
  • the polymer coating composition (C) may further include at least one additive (A).
  • the additive (A) is selected from fillers, thickeners, pigments, antioxidants, additives to improve aging resistance and stabilizers.
  • composition (C) comprises a filler as additive (A), wherein the filler may be selected from organic filler materials, inorganic filler material, or combinations thereof.
  • inorganic filler material examples include calcium silicates such as, e.g., wollastonite; barium sulfate; calcium carbonate; mica; talc; silica; iron oxide; titanium dioxide; carbon black; phthalocyanines; chromium oxide; and combinations thereof.
  • calcium silicates such as, e.g., wollastonite; barium sulfate; calcium carbonate; mica; talc; silica; iron oxide; titanium dioxide; carbon black; phthalocyanines; chromium oxide; and combinations thereof.
  • the inorganic filler used in the composition (C) of this invention is silicon dioxide, and even more preferably it is precipitated silica.
  • precipitated silica it is meant herein a silica that is typically prepared by precipitation from a solution containing silicate salts (such as sodium silicate), with an acidifying agent (such as sulphuric acid).
  • silicate salts such as sodium silicate
  • acidifying agent such as sulphuric acid
  • Precipitated silica used in this invention may be prepared by implementing the methods already described in EP396450A, EP520862A, EP670813A, EP670814A, EP762992A, EP762993A, EP917519A, EP1355856A, W003/016215, W02009/112458, WO2011/117400, WO2013/110659, WO2013/139934, W02008/000761.
  • Non-limiting examples of precipitated silica which could be used in the present invention are for instance Tixosil® 365 and Zeosil® 1085 GR, all commercially available from Solvay.
  • composition (C) comprises a stabilizer as additive (A), wherein the stabilizer may conveniently be a light stabilizer, particularly a UV stabilizer.
  • the UV stabilizer used in the composition (C) of this invention is selected from the group consisting of T1O2, ZnO, hydroxybenzophenone, hydroxyphenylbenzotriazole, oxalanilide, phenyl ester, benzoxazinone, cyanoacrylate, formamidine, benzylidene malonate and hydroxyphenyltriazine and combinations thereof, and even more preferably is a cyanoacrylate.
  • the ratio between the polymer (F) and the at least one additive (A) is in the range from 1:1 to 20:1.
  • composition (C) comprises:
  • an additive (A) which is preferably an inorganic filler, more preferably a precipitated silica.
  • composition (C) comprises:
  • an additive (A) which is preferably an inorganic filler, more preferably a precipitated silica, wherein the ratio between the polymer (F-1) and the at least one additive (A) is in the range from 5: 1 to 20: 1.
  • composition (C) comprises:
  • an additive (A) which is preferably a UV stabilizer, more preferably a cyanoacrylate.
  • composition (C) comprises:
  • a solvent (S) which is preferably a perfluorinated polyether
  • an additive (A) which is preferably a UV stabilizer, more preferably a cyanoacrylate, wherein the ratio between the polymer (F-2) and the at least one additive (A) is in the range from 1:1 to 10:1.
  • the polymer coating composition (C) is prepared by dissolving polymer (F) in a solvent (S) optionally followed by the addition of at least one additive (A).
  • Composition (C) comprising polymer (F), solvent (S) and additive (A) has a TSC in the range comprised between 0.05 to 15 %.
  • Dissolution of polymer (F) in solvent (S) is preferably carried out under stirring at room temperature, more preferably at a temperature in the range from 10 to 30°C.
  • step c) of the method of the present invention composition (C) obtained in step b) is at least partially applied onto at least one portion of the at least one surface of the article to be coated by a technique selected from casting, spray coating, rotating spray coating, roll coating, doctor blading, slot die coating, gravure coating, inkjet printing, spin coating and screen printing, brush, squeegee, curtain coating, vacuum coating and dip coating.
  • the article After the application of the polymer coating composition (C) onto the at least one portion of at least one surface of the article, the article is subjected to drying to obtain the removal of the solvent and to provide the article provided with a polymer coating layer.
  • Drying may be performed either under atmospheric pressure or under vacuum. Alternatively, drying may be performed under modified atmosphere, e.g. under an inert gas, typically exempt notably from moisture (water vapour content of less than 0.001% v/v).
  • modified atmosphere e.g. under an inert gas, typically exempt notably from moisture (water vapour content of less than 0.001% v/v).
  • the drying temperature will be selected so as to effect removal by evaporation of solvents (S) from the coating.
  • step c) may be repeated, typically one or more times, by applying the composition (C) provided in step b) onto the surface of the article assembly provided in step a).
  • drying is performed by a multi-step procedure including drying under atmospheric pressure and C have a thickness of between 0.5 pm and 5 pm.
  • step d) of the method of the present invention the coated article obtained in step c) is exposed to sanitisation or sterilisation means.
  • Suitable sanitisation or sterilisation means are selected from one or more of: radiation means; chemical means; and/or heat means.
  • the means of sanitisation or sterilisation include, gamma radiation, electron beam radiation, ethylene oxide, steam, autoclave, dry-heat, ozone, bleach, glutaraldehyde, formaldehyde, ortho-phthalaldehyde, hydrogen peroxide, x-rays, subatomic particles and/or UV radiation.
  • the sanitisation or sterilisation means used in step d) of the method of the invention are selected from dry/low-temperature means, more preferably from UV radiation and ozone.
  • step d) the coated article provided in step c) is exposed in step d) to an ultraviolet light source and/or to an ozone source for generating ozone for a time sufficient to sanitize or sterilize the coated article.
  • composition (C) comprising
  • an additive (A) which is preferably an inorganic filler, more preferably a precipitated silica said article can be advantageously sanitized or sterilized with ozone without affecting the tensile properties provided by the polymer coating.
  • an additive (A) which is preferably a UV stabilizer, more preferably a cyanoacrylate is advantageously sanitized or sterilized with UV radiation without affecting the colour properties of the coated article.
  • the present invention provides for a sanitized or sterilized coated article obtainable by the method of the invention.
  • Polymer (F-1) Hyflon® AD-60, commercially available from Solvay Specialty Polymers Italy S.p.A.
  • Polymer (F-2) SOLEF ® 21510 VDF/HFP polymer having a melt flow index of 2.3 g/10 min as measured according to ASTM D1238 (190°C, 5 Kg).
  • Solvent (S-1) NovecTM7300, commercially available from 3M.
  • Solvent (S-2) Galden®SV80, commercially available from Solvay Specialty Polymers Italy S.p.A.
  • Solvent (S-3) Methylethyl ketone (MEK), commercially available from Merk.
  • Filler (A-1) ZEOSIL®1085GR: Precipitated Si0 2 commercially available from Solvay.
  • UV exposure was made by Helios Quartz UV equipment, at 254nm, 100% lamp opening; Lamp type: Zp; Exposure time: 9 min.
  • Fluoropolymer compositions were each manufactured by dissolving, under stirring, at 25 °C, polymer (F-1) in solvent (S-1). Each fluoropolymer composition was kept stirred until complete dissolution of the polymer in the solvent. The obtained compositions had solids content %wt/wt on total composition: 0.1; 1.0; 5.0 respectively.
  • Fluoropolymer compositions were each manufactured by dissolving, under stirring, at 25 °C, polymer (F-1) in solvent (S-2). Each fluoropolymer composition was kept stirred until complete dissolution of the polymer in the solvent.
  • the obtained compositions had solids content %wt/wt on total composition: 0.1; 1.0; 5.0 respectively.
  • Fluoropolymer compositions were each manufactured by dissolving, under stirring, at 25 °C, polymer (F-2) in solvent (S-3). Each fluoropolymer composition was kept stirred until complete dissolution of the polymer in the solvent. The obtained compositions had solids content %wt/wt on total composition: 1.0; 5.0 respectively.
  • the obtained compositions had total solid content %wt/wt on total composition: 0.107; 1.07; 5.35 respectively.
  • a blank composition was manufactured as described in Example 1 and 2, by dispersing, under stirring, at 25° C, filler (A-1) in solvent (S-1).
  • the obtained composition had total solid content %wt/wt on total composition: 0.35.
  • compositions were manufactured by dispersing under stirring, at 25° C, filler (A-2) in solvent (S-3).
  • the obtained compositions had solid content %wt/wt on total composition: 0.5; 5.0 respectively.
  • Fluoropolymer compositions were manufactured as described in Example 1, and subsequently added and dispersed filler (A-2), keeping the ratio (F)/(S) between solids in the range: 1:1 to 9:1.
  • the obtained compositions had total solid content %wt/wt on total composition: 10.
  • Example 8 Coating of textile substrate - Tensile properties
  • 8x8cm specimen of Tyvek textile was dip-coated by immersing in each compositions of Examples 1 , 2 and 5, repeated for at least 6 specimen for each composition, air dried and finished at 140°C/2min in vented oven. Average dry pick up, with standard deviation ⁇ 2%, was recorded.
  • Example 9 Coating of plastic substrate - Tensile properties
  • 8x8cm specimen of PC was dip-coated by immersing in each compositions of Example 1 , repeated for at least 4 specimen for each composition, air dried and finished at 140°C/2min in vented oven. Average dry pick up, with standard deviation ⁇ 0.3%, was recorded.
  • Example 10 Coating of plastic substrate - Yellow Index after UV exposure
  • 8x8cm specimen of PPSU was coated by dipping, or casting on both sides, by composition of Example 6, followed by drying at room temperature and annealing at 140°C.

Abstract

The present invention relates to protective coatings for medical devices, equipment and PPE that are resistant to sanification and sterilization technologies, imparting durability and promoting safe use and re-use of the same.

Description

METHOD FOR SANITIZING OR STERILIZING THE SURFACE OF AN ARTICLE HAVING A FLUOROPOLYMER COATING
Cross-reference to related applications
[0001] This application claims priority to European application number 21159664.8 filed on February 26, 2021 , the whole content of this application being incorporated herein by reference for all purposes. Technical Field
[0002] The present invention relates to protective coatings for medical devices, equipment and PPE that are resistant to sanification and sterilization technologies, imparting durability and promoting safe use and re-use of the same.
Background Art
[0003] Sterilization and sanitization are techniques used to, respectively, eliminate or reduce the microorganisms that are in or on a material. During sterilization process all microorganisms, harmful or not, are killed. During sanitization the number of microorganic pathogens is reduced to a level where they can’t be harmful.
[0004] Sterilization is mostly used in health care centers on medical instruments, such as surgical tools. Such tools have to be sterilized since they are used on different patients. Thus, sterilization prevents the transfer of diseases, bacteria, or viruses from one patient to another.
[0005] Sanitization is mainly intended as cleaning and disinfection in non healthcare settings for surface and textile in indoor environments in the context of environmental contamination and pathogens persistence on different surfaces.
[0006] Conventional sterilization processing procedures for medical instruments or devices involve high temperature (such as steam) or toxic gasses (e.g., chlorine dioxide, hydrogen peroxide, nitric oxide, nitrogen dioxide, ozone, and ethylene oxide).
[0007] Steam pressure sterilization has been the time-honoured method of sterilization. It is fast and cost effective. However, the autoclave destroys heat-sensitive instruments and devices. Ethylene oxide sterilization is used to cold sterilize heat-sensitive instruments and devices. However, ethylene oxide requires long sterilization and aeration periods, since the molecule clings to the surface of instruments. This necessitates the use of containment rooms, monitoring systems, and room ventilators.
[0008] A more efficient, safer, and less expensive sterilization agent is ozone (O3). Ozone can easily be generated from oxygen, especially hospital grade oxygen.
[0009] Ozone gas generators may also be used in sanitization processes in healthcare and non-healthcare indoor environments, as described for example in JP2004130006A.
[0010] It is well established that some ionizing radiation sterilization sources, such as ultraviolet (UV) light, may be used to kill or reduce pathogens.
[0011] EP 1973578 relates to methods for producing sanitary health care environments, such as the operating room or other ambulatory treatment facilities, by utilizing ultraviolet irradiation and ozone to destroy viruses, bacteria, and fungus.
[0012] Coating the surface of medical devices, equipment and personal protective equipment (PPE) with polymers has become a common practice.
[0013] Numbers of polymer-based coatings materials and process can be found to repel bacteria and prevent biofilm building, and virus as well.
[0014] However, materials coated with polymers can be sensitive to sterilization procedures, which may damage the coating by causing it to delaminate from the surface of the device or equipment, or may alter the chemical properties of materials in the coating. In particular, these type of polymer coatings are affected by one or more cycles of sanitization technologies, which may cause significant polymer chain scission and a substantial reduction in molecular weight, with a consequent substantial change in polymer properties, negatively affecting the medical device or equipment after sanitizing.
[0015] There is a need for protective coatings for medical devices, equipment, PPE that are resistant to the different sanitization technologies (gas, vapor, irradiation e.g. ozone/UV) to be usable and safe re-usable. Summary of invention
[0016] Accordingly, the Applicant faced the problem of providing a polymer suitable for coating the surfaces of an article such as medical device, equipment or PPE, said polymer being such to provide a durable protective coating towards dry/low-temperature sanitization methods of medical devices to promote safe reuse.
[0017] Surprisingly, the Applicant found that when certain fluoropolymers are used as coating for surfaces made of different materials, said problem can be solved.
[0018] Thus, in an aspect, the present invention relates to a method for sanitizing or sterilizing the surface of an article contaminated with pathogens selected from viruses, bacteria, and fungus, said article having a polymer coating, the method comprising the following steps: a) providing an article having at least one surface onto which a polymer coating is to be applied; b) providing a polymer coating composition [composition (C)] for application onto the article; and c) applying the composition (C) obtained in step b) onto the at least one surface of the article provided in step a) to obtain a coated article; then d) exposing the coated article to sanitisation or sterilisation means, wherein the polymer coating composition (C) comprises: i) at least one fluoropolymer [polymer (F)] selected from the group consisting of:
- polymers (F-1) comprising recurring units derived from: • perfluorodioxoles of formula (I):
Figure imgf000005_0001
wherein Ri, R2, R3 and R4, equal to or different from each other, are independently selected from the group consisting of -F, a C1-C6 fluoroalkyl group, optionally comprising one or more oxygen atoms;
• at least one fluorinated monomer selected from the group consisting of:
- C2-C8 perfluoroolefins such as tetrafluoroethylene (TFE) and hexafluoropropylene (HFP);
- C2-C8 hydrogenated fluoroolefins such as vinyl fluoride (VF1), 1 ,2- difluoroethylene and trifluoroethylene (VF3); and
- chloro- and/or bromo- and/or iodo-C2-C6 fluoroolefins such as chlorotrifluoroethylene (CTFE);
- polymers (F-2) comprising:
• recurring units derived from C2-C8 perfluoroolefins such as tetrafluoroethylene (TFE) and hexafluoropropylene (HFP); and
• recurring units derived from C2-C8 hydrogenated fluoroolefins such as vinylidene fluoride (VDF), vinyl fluoride (VF1), 1,2-difluoroethylene and trifluoroethylene (VF3); ii) a solvent (S) iii) optionally, at least one additive (A).
[0019] In a second aspect, the present invention provides for sanitized or sterilized coated articles obtainable by the above method.
Description of embodiments
[0020] In the context of the present invention, the use of parentheses “(...)” before and after symbols or numbers identifying formulae or parts of formulae has the mere purpose of better distinguishing that symbol or number with respect to the rest of the text; thus, said parentheses could also be omitted.
[0021] In the context of the present invention, the term “weight percent” (wt %) indicates the content of a specific component in a mixture, calculated as the ratio between the weight of the component and the total weight of the mixture. When referred to the recurring units derived from a certain monomer in a polymer/copolymer, weight percent (wt %) indicates the ratio between the weight of the recurring units of such monomer over the total weight of the polymer/copolymer. When referred to the total solid content (TSC) of a liquid composition, weight percent (wt %) indicates the ratio between the weight of all non-volatile ingredients in the liquid.
[0022] In the context of the present invention, the term “article contaminated with pathogens” indicates any object having at least a surface that can be suitably coated by a polymer coating composition (C) that needs to be sterilized due to the presence, at least onto the external surface, of pathogens such as viruses, bacteria, and fungus. An article may include, for example, without limitation, medical devices, equipment or PPEs.
[0023] The articles can be formed by a variety of elements and having at least different types of basic materials, such as plastics, metals, glasses, ceramic, textiles, etc.
[0024] As a result, the polymer coating composition (C) can be used on a variety of surfaces.
[0025] As used herein, a “medical device” is to be intended in a broad sense as including any instrument, apparatus, machine, appliance, implant, or other similar or related article, including any component or part, which is intended for use in the cure, mitigation, treatment, or prevention of disease, of a human or animal.
[0026] Typical examples of plastic materials for medical devices are polymers such as polyurethanes and their copolymers, or block polyetheramides or other polymeric materials including polyvinyl chloride, polyamide, silicone, block copolymers styrene-ethylene / butylene-styrene (SEBS), block copolymers of styrene isoprene-styrene (SIS), copolymers in Block of styrene-ethylene / propylene-styrene (SEPS), ethylene-vinyl acetate copolymers (EVA), polyethylene (PE), metallocene catalyzed polyethylene, and copolymers of ethylene and propylene or mixtures thereof.
[0027] The term “equipment” is to be intended as any patient- care equipment (such as respirators, diagnostic equipment, shunts, body scopes, wheel chairs, beds, etc.), or surgical and diagnostic equipment.
[0028] The term “personal protective equipment (PPE)” is likewise broad and in principle can include any objects that are used for personal protection or for survivability in hostile or aggressive environments, for example, rubber shoes or objects selected from the group consisting of breathing masks, protective breathing masks, breathing tubes, protective goggles, diving regulators, snorkels, mouthpieces, and protective clothing.
[0029] As used herein, a “textile” is any woven or non-woven fabric or article, or garment including, but not limited to, all types found in the consumer and industrial markets including, but not limited to, those made of cotton, poly cotton blends, wool, aramids, polyurethanes, olefins, polyactids, nylons, silk, hemp, rayon, flax, jute, acrylics, polyesters, those made from many other synthetic or natural fibers and mixtures thereof.
[0030] In addition, the polymer coating composition (C) can be used to effectively reduce the microorganisms population of health care surfaces and equipment.
[0031] As used herein, the phrase “health care surface” refers to a surface of an instrument, a device, a cart, a cage, furniture, a structure, a building, or the like that is employed as part of a health care activity. Health care surfaces are found in hospital, surgical, infirmity, birthing, mortuary, and clinical diagnosis rooms. These surfaces can be those typified as “hard surfaces” (such as walls, floors, bed-pans, etc.), or textiles (such as surgical garments, draperies, bed linens, bandages, etc.).
[0032] In step b) of the method of the invention, a polymer coating composition (C) is provided, said composition (C) comprising: i) at least one fluoropolymer [polymer (F)j selected from the group consisting of:
- polymers (F-1) comprising recurring units derived from: • perfluorodioxoles of formula (I):
Figure imgf000008_0001
wherein Ri, R2, R3 and R4, equal to or different from each other, are independently selected from the group consisting of -F, a C1-C6 fluoroalkyl group, optionally comprising one or more oxygen atoms;
• at least one fluorinated monomer selected from the group consisting of:
- C2-C8 perfluoroolefins such as tetrafluoroethylene (TFE) and hexafluoropropylene (HFP);
- C2-C8 hydrogenated fluoroolefins such as vinyl fluoride (VF1), 1 ,2- difluoroethylene and trifluoroethylene (VF3); and
- chloro- and/or bromo- and/or iodo-C2-C6 fluoroolefins such as chlorotrifluoroethylene (CTFE);
- polymers (F-2) comprising:
• recurring units derived from C2-C8 perfluoroolefins such as tetrafluoroethylene (TFE) and hexafluoropropylene (HFP); and
• recurring units derived from C2-C8 hydrogenated fluoroolefins such as vinylidene fluoride (VDF), vinyl fluoride (VF1), 1,2-difluoroethylene and trifluoroethylene (VF3); ii) a solvent (S) iii) optionally, at least one additive (A).
[0033] By the expression “at least one fluorinated monomer, it is hereby intended to denote a polymer comprising recurring units derived from one or more than one fluorinated monomers. In the rest of the text, the expression “ fluorinated monomers” is understood, for the purposes of the present invention, both in the plural and the singular, that is to say that it denote both one or more than one fluorinated monomers as defined above. The prefix "per" in the expression "perfluorodioxoles” and in the term “ perfluoroolefin” means that the monomer can be fully or partially fluorinated.
[0034] The polymers (F-1) more preferably comprise recurring units derived from at least one perfluorodioxole of formula (I):
Figure imgf000009_0001
Figure imgf000009_0002
wherein Ri, F¾, F¾ and R4, equal to or different from each other, are independently selected from the group consisting of -F, a C1-C3 perfluoroalkyl group, e.g. -CF3, -C2F5, -C3F7, and a C1-C3 perfluoroalkoxy group optionally comprising one oxygen atom, e.g. -OCF3, -OC2F5, -OC3F7, -OCF2CF2OCF3; preferably, wherein RI=R2= -F and R3=R4 is a C1-C3 perfluoroalkyl group, preferably R3=R4= -CF3 or wherein RI=R3=R4 = -F and R2 IS a C1-C3 perfluoroalkoxy, e.g. -OCF3, -OC2F5, -OC3F7, and tetrafluoroethylene (TFE).
[0035] The perfluorodioxoles class having structure (I) preferably used in the present invention are mentioned in EP 633256; still more preferably 2,2,4- trifluoro-5-trifluoromethoxy-1,3-dioxole (TTD) is used.
[0036] The polymer (F-1) more preferably comprises recurring units derived from at least one perfluorodioxole of formula (I) as defined above wherein RI=R3=R4 = -F and R2 = -OCF3 or wherein RI=R2= -F and R3=R4= -CF3 and recurring units derived from tetrafluoroethylene (TFE).
[0037] Non-limitative examples of suitable polymers (F-1) include, notably, those commercially available under the trademark name HYFLON® AD from Solvay Specialty Polymers Italy S.p.A. and TEFLON® AF from E. I. Du Pont de Nemours and Co.
[0038] The polymers (F-2) preferably comprise recurring units derived from vinylidene fluoride (VDF) and recurring units derived from at least one C3- Ce perfluoroolefins, such as hexafluoropropene (HFP). [0039] Non-limitative examples of suitable polymers (F-2) include, notably, those commercially available under the trademark name Solef®from Solvay Specialty Polymers Italy S.p.A..
[0040] The polymer (F) is typically manufactured by suspension or emulsion polymerization processes.
[0041] Polymer (F) can either be semi-crystalline or amorphous.
[0042] The term “semi-crystalline” is intended to denote a polymer (F) which possesses a detectable melting point. It is generally understood that a semi-crystalline polymer (F) possesses a heat of fusion determined according to ASTM D 3418 of advantageously at least 0.4 J/g, preferably of at least 0.5 J/g, more preferably of at least 1 J/g.
[0043] The term “amorphous” is hereby intended to denote a polymer (F) having a heat of fusion of less than 5 J/g, preferably of less than 3 J/g, more preferably of less than 2 J/g as measured by Differential Scanning Calorimetry (DSC) at a heating rate of 10°C/min according to ASTM D- 3418-08.
[0044] The amount of one or more comonomers in polymers (F-1) and (F-2) is to be such to bring either to semi-crystalline or to amorphous polymer. Those of ordinary skill in the field are able to easily determine the amount of such comonomers.
[0045] The role of the solvent in coating applications is typically to dissolve the polymer (F) in order to allow the application of the composition onto the surface if the article to finally obtain a coating upon evaporation of the solvent.
[0046] Within the present invention, solvent (S) is thus intended to denote a solvent suitable for dissolving polymer (F) as defined above. To this aim, solvent (S) is typically an organic solvent selected from the group consisting of:
- fluoroalkyl ethers,
- perfluorinated polyethers,
- alcohols such as methyl alcohol, ethyl alcohol and diacetone alcohol,
- ketones, such as acetone, methylethylketone, methylisobutyl ketone, diisobutylketone, cyclohexanone and isophorone, - linear or cyclic esters such as isopropyl acetate, n-butyl acetate, methyl acetoacetate, dimethyl phthalate and y-butyrolactone,
- linear or cyclic amides such as N,N-diethylacetamide, N,N- dimethylacetamide, dimethylformamide and N-methyl-2-pyrrolidone, and
- dimethyl sulfoxide.
[0047] The fluoroalkyl ether is preferably a C4-12 compound. As commercially available products, for example, CF3CH2OCF2CF2H (AE-3000, tradename, manufactured by Asahi Glass Company, Limited), C4F9OCH3 (Novec- 7100, tradename, manufactured by Sumitomo 3M Limited),
C4F9OC2H5 (Novec-7200, tradename, manufactured by Sumitomo 3M Limited) and C6F13OCH3 (Novec-7300, tradename, manufactured by Sumitomo 3M Limited) may, for example, be mentioned.
[0048] The perfluorinated polyether is preferably a low molecular weight perfluoropolyether (PFPE) having a boiling point in the range from 55°C to 135°C, such as commercially available products under the tradename Galden®SV80, manufactured by Solvay Specialty Polymers Italy.
[0049] In a preferred embodiment, the present invention provides a composition (C) comprising at least one polymer (F-1) and a fluoroalkyl ether.
[0050] In another preferred embodiment, the present invention provides a composition (C) comprising at least one polymer (F-1) and a perfluorinated polyether.
[0051] In another preferred embodiment, the present invention provides a composition (C) comprising at least one polymer (F-2) and a ketone.
[0052] The skilled in the art, depending on the boiling point of the at least one solvent (S), will select the proper amount of said solvent (S) in composition (C) in order to achieve dissolution of the fluorinated polymer [polymer (F)] and suitable evaporation of the same when composition (C) is applied onto the at least one surface of the article to provide a coated article.
[0053] In a preferred embodiment according to the present invention, compositions (C) including at least one polymer (F) and a solvent (S) are prepared having the total solid content (TSC) in the range from 0.05 to 10.0, preferably from 0.1 to 5.0, are prepared. [0054] The polymer coating composition (C) may further include at least one additive (A).
[0055] Typically, the additive (A) is selected from fillers, thickeners, pigments, antioxidants, additives to improve aging resistance and stabilizers.
[0056] In a preferred embodiment of the present invention, composition (C) comprises a filler as additive (A), wherein the filler may be selected from organic filler materials, inorganic filler material, or combinations thereof.
[0057] The non-limiting examples of inorganic filler material include calcium silicates such as, e.g., wollastonite; barium sulfate; calcium carbonate; mica; talc; silica; iron oxide; titanium dioxide; carbon black; phthalocyanines; chromium oxide; and combinations thereof.
[0058] More preferably, the inorganic filler used in the composition (C) of this invention is silicon dioxide, and even more preferably it is precipitated silica.
[0059] By "precipitated silica" it is meant herein a silica that is typically prepared by precipitation from a solution containing silicate salts (such as sodium silicate), with an acidifying agent (such as sulphuric acid).
[0060] Precipitated silica used in this invention may be prepared by implementing the methods already described in EP396450A, EP520862A, EP670813A, EP670814A, EP762992A, EP762993A, EP917519A, EP1355856A, W003/016215, W02009/112458, WO2011/117400, WO2013/110659, WO2013/139934, W02008/000761.
[0061] Non-limiting examples of precipitated silica which could be used in the present invention are for instance Tixosil® 365 and Zeosil® 1085 GR, all commercially available from Solvay.
[0062] In a preferred embodiment of the present invention, composition (C) comprises a stabilizer as additive (A), wherein the stabilizer may conveniently be a light stabilizer, particularly a UV stabilizer.
[0063] More preferably, the UV stabilizer used in the composition (C) of this invention is selected from the group consisting of T1O2, ZnO, hydroxybenzophenone, hydroxyphenylbenzotriazole, oxalanilide, phenyl ester, benzoxazinone, cyanoacrylate, formamidine, benzylidene malonate and hydroxyphenyltriazine and combinations thereof, and even more preferably is a cyanoacrylate.
[0064] Non-limiting example of cyanoacrylate which could be used in the composition (C) in the present invention is a compound of formula (C6H5)2C=C(CN)C02C2H5, commercially available under the tradename UV-3035.
[0065] Preferably, in composition (C), the ratio between the polymer (F) and the at least one additive (A) is in the range from 1:1 to 20:1.
[0066] In an embodiment according to the present invention, composition (C) comprises:
- at least one fluoropolymer (F-1);
- a solvent (S), which is preferably a fluoroalkyl ether; and
- an additive (A), which is preferably an inorganic filler, more preferably a precipitated silica.
[0067] According to a preferred embodiment of the present invention, the composition (C) comprises:
- at least one fluoropolymer (F-1);
- a solvent (S), which is preferably a fluoroalkyl ether; and
- an additive (A), which is preferably an inorganic filler, more preferably a precipitated silica, wherein the ratio between the polymer (F-1) and the at least one additive (A) is in the range from 5: 1 to 20: 1.
[0068] In another embodiment according to the present invention, composition (C) comprises:
- at least one fluoropolymer (F-2);
- a solvent (S), which is preferably a perfluorinated polyether; and
- an additive (A), which is preferably a UV stabilizer, more preferably a cyanoacrylate.
[0069] According to a preferred embodiment of the present invention, the composition (C) comprises:
- at least one fluoropolymer (F-2);
- a solvent (S), which is preferably a perfluorinated polyether; and - an additive (A), which is preferably a UV stabilizer, more preferably a cyanoacrylate, wherein the ratio between the polymer (F-2) and the at least one additive (A) is in the range from 1:1 to 10:1.
[0070] The polymer coating composition (C) is prepared by dissolving polymer (F) in a solvent (S) optionally followed by the addition of at least one additive (A).
[0071] Composition (C) comprising polymer (F), solvent (S) and additive (A) has a TSC in the range comprised between 0.05 to 15 %.
[0072] Dissolution of polymer (F) in solvent (S) is preferably carried out under stirring at room temperature, more preferably at a temperature in the range from 10 to 30°C.
[0073] In step c) of the method of the present invention, composition (C) obtained in step b) is at least partially applied onto at least one portion of the at least one surface of the article to be coated by a technique selected from casting, spray coating, rotating spray coating, roll coating, doctor blading, slot die coating, gravure coating, inkjet printing, spin coating and screen printing, brush, squeegee, curtain coating, vacuum coating and dip coating.
[0074] After the application of the polymer coating composition (C) onto the at least one portion of at least one surface of the article, the article is subjected to drying to obtain the removal of the solvent and to provide the article provided with a polymer coating layer.
[0075] Drying may be performed either under atmospheric pressure or under vacuum. Alternatively, drying may be performed under modified atmosphere, e.g. under an inert gas, typically exempt notably from moisture (water vapour content of less than 0.001% v/v).
[0076] The drying temperature will be selected so as to effect removal by evaporation of solvents (S) from the coating.
[0077] Optionally, step c) may be repeated, typically one or more times, by applying the composition (C) provided in step b) onto the surface of the article assembly provided in step a). [0078] In a preferred embodiment of the present invention, drying is performed by a multi-step procedure including drying under atmospheric pressure and C have a thickness of between 0.5 pm and 5 pm.
[0079] In step d) of the method of the present invention, the coated article obtained in step c) is exposed to sanitisation or sterilisation means.
[0080] Suitable sanitisation or sterilisation means are selected from one or more of: radiation means; chemical means; and/or heat means. The means of sanitisation or sterilisation include, gamma radiation, electron beam radiation, ethylene oxide, steam, autoclave, dry-heat, ozone, bleach, glutaraldehyde, formaldehyde, ortho-phthalaldehyde, hydrogen peroxide, x-rays, subatomic particles and/or UV radiation.
[0081] Preferably, the sanitisation or sterilisation means used in step d) of the method of the invention are selected from dry/low-temperature means, more preferably from UV radiation and ozone.
[0082] In a preferred embodiment of the present invention, in step d), the coated article provided in step c) is exposed in step d) to an ultraviolet light source and/or to an ozone source for generating ozone for a time sufficient to sanitize or sterilize the coated article.
[0083] The Applicant has surprisingly found that when an article having at least a portion of at least a surface that is least partially coated with a composition (C) comprising
- at least one fluoropolymer (F);
- a solvent (S); and
- an additive (A), which is preferably an inorganic filler, more preferably a precipitated silica said article can be advantageously sanitized or sterilized with ozone without affecting the tensile properties provided by the polymer coating. [0084] The Applicant has also surprisingly found that when an article having at least a portion of at least a surface that is least partially coated with a composition (C) comprising
- at least one fluoropolymer (F);
- a solvent (S); and - an additive (A), which is preferably a UV stabilizer, more preferably a cyanoacrylate is advantageously sanitized or sterilized with UV radiation without affecting the colour properties of the coated article.
[0085] In a second aspect, the present invention provides for a sanitized or sterilized coated article obtainable by the method of the invention.
[0086] Should the disclosure of any patents, patent applications, and publications which are incorporated herein by reference conflict with the description of the present application to the extent that it may render a term unclear, the present description shall take precedence.
[0087] The invention will be now described in more details with reference to the following examples whose purpose is merely illustrative and not limitative of the scope of the invention.
[0088] Raw materials:
[0089] Polymer (F-1): Hyflon® AD-60, commercially available from Solvay Specialty Polymers Italy S.p.A.
[0090] Polymer (F-2): SOLEF® 21510 VDF/HFP polymer having a melt flow index of 2.3 g/10 min as measured according to ASTM D1238 (190°C, 5 Kg).
[0091] Solvent (S-1): Novec™7300, commercially available from 3M.
[0092] Solvent (S-2): Galden®SV80, commercially available from Solvay Specialty Polymers Italy S.p.A.
[0093] Solvent (S-3): Methylethyl ketone (MEK), commercially available from Merk.
[0094] Filler (A-1): ZEOSIL®1085GR: Precipitated Si02 commercially available from Solvay.
[0095] Filler (A-2): UV-3035: cyanoacrylate UV absorber of formula
(C6H5)2C=C(CN)C02C2H5), commercially available from BASF.
[0096] General procedure: Ozone treatment
[0097] Coated specimen were exposed to Ozone at the following conditions: Cycle exposure time: 20min, 8ppm. Set of cycles: 6 or 20. Exposure pause: 40min, complete change air in the chamber removing O3 (<=00.1 ppm). Both sides of samples exposed. Visual aspect is unchanged. [0098] General procedure: Tensile properties
[0099] Before and after O3 exposure, tensile properties of the specimen were measured by Instron 4302 Dynamometer, at 23°C according to ASTM D638 type V, Grip distance= 25.4mm, Lo=21.5mm, speed= 1-50mm/min.
[00100] General procedure: Yellow Index after UV exposure
[00101] UV exposure was made by Helios Quartz UV equipment, at 254nm, 100% lamp opening; Lamp type: Zp; Exposure time: 9 min.
[00102] Yellow Index (Yl) of samples of examples 10 and 11 were measured before and after UV exposure using a Gardner Colorimeter, according to ASTM E313-00.
[00103] Example 1
[00104] Fluoropolymer compositions were each manufactured by dissolving, under stirring, at 25 °C, polymer (F-1) in solvent (S-1). Each fluoropolymer composition was kept stirred until complete dissolution of the polymer in the solvent. The obtained compositions had solids content %wt/wt on total composition: 0.1; 1.0; 5.0 respectively.
[00105] Example 2
[00106] Fluoropolymer compositions were each manufactured by dissolving, under stirring, at 25 °C, polymer (F-1) in solvent (S-2). Each fluoropolymer composition was kept stirred until complete dissolution of the polymer in the solvent. The obtained compositions had solids content %wt/wt on total composition: 0.1; 1.0; 5.0 respectively.
[00107] Example 3
[00108] Fluoropolymer compositions were each manufactured by dissolving, under stirring, at 25 °C, polymer (F-2) in solvent (S-3). Each fluoropolymer composition was kept stirred until complete dissolution of the polymer in the solvent. The obtained compositions had solids content %wt/wt on total composition: 1.0; 5.0 respectively.
[00109] Example 4
[00110] Fluoropolymer compositions were each manufactured , under stirring, at 25° C, as described in Example 1, and subsequently filler (A-1) was added and dispersed respectively to system (F-1 )-(S-1 ), keeping the ratio between solids (F)/(A)= 14.3/1. The obtained compositions had total solid content %wt/wt on total composition: 0.107; 1.07; 5.35 respectively.
[00111] Example 5 - Comparative
[00112] A blank composition was manufactured as described in Example 1 and 2, by dispersing, under stirring, at 25° C, filler (A-1) in solvent (S-1). The obtained composition had total solid content %wt/wt on total composition: 0.35.
[00113] Example 6 - Comparative
[00114] (A-2) compositions were manufactured by dispersing under stirring, at 25° C, filler (A-2) in solvent (S-3). The obtained compositions had solid content %wt/wt on total composition: 0.5; 5.0 respectively.
[00115] Example 7
[00116] Fluoropolymer compositions were manufactured as described in Example 1, and subsequently added and dispersed filler (A-2), keeping the ratio (F)/(S) between solids in the range: 1:1 to 9:1. The obtained compositions had total solid content %wt/wt on total composition: 10.
[00117] Example 8 - Coating of textile substrate - Tensile properties
[00118] 8x8cm specimen of Tyvek textile was dip-coated by immersing in each compositions of Examples 1 , 2 and 5, repeated for at least 6 specimen for each composition, air dried and finished at 140°C/2min in vented oven. Average dry pick up, with standard deviation±2%, was recorded.
[00119] The results of tensile properties of coated textiles and non coated textile (comparative) before and after ozone treatment are shown in Table 1.
Table 1
Figure imgf000018_0001
Figure imgf000019_0001
[00120] The results show that when a textile specimen is coated with a coating composition according to the present invention, the tensile properties of said specimens remain substantially unchanged after the sanitization treatment, while in the absence of the coating, the tensile properties of the specimens are evidently worse. [00121] Example 9 - Coating of plastic substrate - Tensile properties [00122] 8x8cm specimen of PC was dip-coated by immersing in each compositions of Example 1 , repeated for at least 4 specimen for each composition, air dried and finished at 140°C/2min in vented oven. Average dry pick up, with standard deviation±0.3%, was recorded.
[00123] The results of tensile properties of coated plastic specimens and non- coated plastic specimens (comparative) before and after ozone treatment are shown in Table 2.
Table 2
Figure imgf000020_0001
[00124] The results show that when a plastic specimen is coated with a coating composition according to the present invention, the tensile properties of said specimens remain substantially unchanged after the sanitization treatment, while in the absence of the coating, the tensile properties of the specimens are evidently worse.
[00125] Example 10 - Coating of plastic substrate - Yellow Index after UV exposure
[00126] 8x8cm specimen of PPSU, repeated for at least 4 specimen for each composition, was coated by dipping, or casting on both sides, by composition of Example 6, followed by drying at room temperature and annealing at 140°C. [00127] The same coated sample, and each repetitions, was subsequently coated by dipping in composition of Example 1, followed by drying at room temperature and final annealing at 140°C.
[00128] Average dry pick up, with standard deviation±0.6%, was recorded.
[00129] Example 11 - Coating of plastic substrate - Yellow Index after UV exposure
[00130] 8x8cm specimen of PSU, or PPSU, or PC was dip-coated by immersing in each compositions of Example 7, repeated for at least 4 specimen for each composition, air dried and finished at 140°C/2min in vented oven. Average dry pick up, with standard deviation±2%, was recorded.
[00131] The results of yellow index measurement of coated plastics of Examples 10 and 11 and non-coated plastic (comparative) before and after ozone treatment are shown in Table 3.
Table 3
Figure imgf000021_0001
[00132] The results show that the treatment of plastic specimens with a coating composition according to the present invention allows to avoid coloration of the specimen subjected to UV treatment.

Claims

Claims
Claim 1. A method for sanitizing or sterilizing the surface of an article contaminated with pathogens selected from viruses, bacteria, and fungus, said article having a polymer coating, the method comprising the following steps:bacteria, and fungus, the method comprising the following steps: e) providing an article having at least one surface onto which a polymer coating is to be applied; f) providing a polymer coating composition [composition (C)] for application onto the article; and g) applying the composition (C) obtained in step b) onto the at least one portion of the at least one surface of the article provided in step a) to obtain a coated article; then h) exposing the coated article to sanitisation or sterilisation means, wherein the polymer coating composition (C) comprises: i) at least one fluoropolymer [polymer (F)] selected from the group consisting of:
- polymers (F-1) comprising recurring units derived from:
• perfluorodioxoles of formula (I):
Figure imgf000022_0001
wherein Ri, R2, R3 and R4, equal to or different from each other, are independently selected from the group consisting of -F, a C1-C6 fluoroalkyl group, optionally comprising one or more oxygen atoms;
• at least one fluorinated monomer selected from the group consisting of:
- C2-C8 perfluoroolefins such as tetrafluoroethylene (TFE) and hexafluoropropylene (HFP); - C2-C8 hydrogenated fluoroolefins such as vinyl fluoride (VF1), 1 ,2- difluoroethylene and trifluoroethylene (VF3); and
- chloro- and/or bromo- and/or iodo-C2-C6 fluoroolefins such as chlorotrifluoroethylene (CTFE);
- polymers (F-2) comprising:
• recurring units derived from C2-C8 perfluoroolefins such as tetrafluoroethylene (TFE) and hexafluoropropylene (HFP); and
• recurring units derived from C2-C8 hydrogenated fluoroolefins such as vinylidene fluoride (VDF), vinyl fluoride (VF1), 1,2-difluoroethylene and trifluoroethylene (VF3); ii) a solvent (S) iii) optionally, at least one additive (A).
Claim 2. The method according to claim 1 wherein polymer (F-1) comprises recurring units derived from at least one perfluorodioxole of formula (I):
Figure imgf000023_0001
wherein Ri, R2, R3 and R4, equal to or different from each other, are independently selected from the group consisting of -F, a C1-C3 perfluoroalkyl group, e.g. -CF3, -C2F5, -C3F7, and a C1-C3 perfluoroalkoxy group optionally comprising one oxygen atom, e.g. -OCF3, -OC2F5, -OC3F7, -OCF2CF2OCF3; preferably, wherein RI=R2= -F and R3=R4 is a C1-C3 perfluoroalkyl group, preferably R3=R4= -CF3 or wherein RI=R3=R4 = -F and R2 IS a C1-C3 perfluoroalkoxy, e.g. -OCF3, -OC2F5, -OC3F7, and tetrafluoroethylene (TFE).
Claim 3. The method according to claim 1 wherein polymer (F-2) comprises recurring units derived from vinylidene fluoride (VDF) and recurring units derived from at least one C3-C8 perfluoroolefins, such as hexafluoropropene (HFP).
Claim 4. The method according to anyone of the preceding claims wherein the solvent (S) is an organic solvent selected from the group consisting of:
- fluoroalkyl ethers, - perfluorinated polyethers,
- alcohols such as methyl alcohol, ethyl alcohol and diacetone alcohol,
- ketones, such as acetone, methylethylketone, methylisobutyl ketone, diisobutylketone, cyclohexanone and isophorone,
- linear or cyclic esters such as isopropyl acetate, n-butyl acetate, methyl acetoacetate, dimethyl phthalate and y-butyrolactone,
- linear or cyclic amides such as N,N-diethylacetamide, N,N- dimethylacetamide, dimethylformamide and N-methyl-2-pyrrolidone, and
- dimethyl sulfoxide.
Claim 5. The method according to anyone of the preceding claims wherein composition (C) comprises at least one polymer (F-1) and a solvent (S) selected from a fluoroalkyl ether and a perfluorinated polyether.
Claim 6. The method according to anyone of the preceding claims wherein composition (C) comprises at least one polymer (F-2) and a solvent (S) that is a ketone.
Claim 7. The method according to anyone of the preceding claims wherein composition (C) further comprises at least one additive (A) selected from fillers, thickeners, pigments, antioxidants, additives to improve aging resistance and stabilizers such as UV stabilizers, preferably selected from fillers and UV stabilizers.
Claim 8. The method according to claim 7 wherein the filler is precipitated silica and the UV stabilizer is a cyanoacrylate.
Claim 9. The method according to claim 8 wherein composition (C) comprises:
- at least one fluoropolymer (F-1);
- a solvent (S), which is preferably a fluoroalkyl ether; and
- an additive (A), which is preferably an inorganic filler, more preferably a precipitated silica, wherein the ratio between the polymer (F-1) and the at least one additive (A) is in the range from 10:1 to 20: 1.
Claim 10. The method according to claim 8 wherein composition (C) comprises:
- at least one fluoropolymer (F-2);
- a solvent (S), which is preferably a perfluorinated polyether; and - an additive (A), which is preferably a UV stabilizer, more preferably a cyanoacrylate, wherein the ratio between the polymer (F-2) and the at least one additive
(A) is in the range from 1:1 to 10:1.
Claim 11. The method according to anyone of the preceding claims wherein sanitisation or sterilisation means are selected from one or more of: radiation means; chemical means; and/or heat means, preferably the means of sanitisation or sterilisation are selected from the group consisting of gamma radiation, electron beam radiation, ethylene oxide, steam, autoclave, dry-heat, ozone, bleach, glutaraldehyde, formaldehyde, ortho-phthalaldehyde, hydrogen peroxide, x-rays, subatomic particles and/or UV radiation, more preferably selected from ozone and UV radiation.
Claim 12. The method according to anyone of the preceding claims wherein an article having at least a portion of at least a surface that is least partially coated with a composition (C) comprising
- at least one fluoropolymer (F);
- a solvent (S); and
- an additive (A), which a precipitated silica is sanitized or sterilized with ozone.
Claim 13. The method according to anyone of the preceding claims wherein an article having at least a portion of at least a surface that is least partially coated with a composition (C) comprising
- at least one fluoropolymer (F);
- a solvent (S); and
- an additive (A), which a cyanoacrylate is sanitized or sterilized with UV radiation.
Claim 14. The method according to anyone of the preceding claims wherein the article is selected from the group consisting of medical devices, equipment and PPEs.
Claim 15. A sanitized or sterilized coated article obtainable by the method according to anyone of claims 1 to 14.
PCT/EP2022/054583 2021-02-26 2022-02-23 Method for sanitizing or sterilizing the surface of an article having a fluoropolymer coating WO2022180133A1 (en)

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Citations (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0396450A1 (en) 1989-05-02 1990-11-07 Rhone-Poulenc Chimie Silica beads, process for their preparation and their use for reinforcing elastomers
EP0520862A1 (en) 1991-06-26 1992-12-30 Rhone-Poulenc Chimie Process for the preparation of precipitated silica, precipitated silicas thus obtained, and their use in the reinforcement of rubbers
EP0633256A1 (en) 1988-12-13 1995-01-11 Beecham Group Plc Benzopyran and related compounds
EP0670813A1 (en) 1993-09-29 1995-09-13 Rhone-Poulenc Chimie Precipitated silica
EP0670814A1 (en) 1993-09-29 1995-09-13 Rhone-Poulenc Chimie Precipitated silica
EP0762992A1 (en) 1995-03-29 1997-03-19 Rhone-Poulenc Chimie Novel method for preparing precipitated silica, novel aluminium-containing precipitated silicas, and use thereof for reinforcing elastomers
EP0762993A1 (en) 1995-03-29 1997-03-19 Rhone-Poulenc Chimie Novel method for preparing precipitated silica, novel aluminium-containing precipitated silicas, and use thereof for reinforcing elastomers
EP0917519A1 (en) 1997-05-26 1999-05-26 Rhodia Chimie Fällungskieselsäure
US20020051730A1 (en) * 2000-09-29 2002-05-02 Stanko Bodnar Coated medical devices and sterilization thereof
WO2003016215A1 (en) 2001-08-13 2003-02-27 Rhodia Chimie Method of preparing silicas, silicas with specific pore-size and/or particle-size distribution and the use thereof, in particular for reinforcing polymers
EP1355856A1 (en) 2000-12-28 2003-10-29 Rhodia Chimie Method for preparing precipitated silica containing aluminium
JP2004130006A (en) 2002-10-15 2004-04-30 Fuji Electric Systems Co Ltd Ozone sterilization method, and its apparatus
EP1691858A1 (en) * 2003-12-12 2006-08-23 C.R.Bard, Inc. Implantable medical devices with fluorinated polymer coatings, and methods of coating thereof
WO2008000761A1 (en) 2006-06-27 2008-01-03 Rhodia Operations Precipitated silica for paper application
EP1973578A2 (en) 2006-01-14 2008-10-01 Optimus Services, LLC Use of ultraviolet germicidal irradiation in health care environments
WO2009112458A1 (en) 2008-03-10 2009-09-17 Rhodia Operations Novel method for preparing precipitated silica, precipitated silica having particular morphology, grading and porosity, and use thereof particularly for reinforcing polymers
WO2011117400A1 (en) 2010-03-25 2011-09-29 Rhodia Operations Novel method for preparing precipitated silicas containing aluminium
WO2013110659A1 (en) 2012-01-25 2013-08-01 Rhodia Operations Precipitated-silica production method
WO2013139934A1 (en) 2012-03-22 2013-09-26 Rhodia Operations Method for the production of precipitated silica, comprising a membrane concentration step
EP3766942A1 (en) * 2018-03-16 2021-01-20 Daikin Industries, Ltd. Coating film and coated article

Patent Citations (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0633256A1 (en) 1988-12-13 1995-01-11 Beecham Group Plc Benzopyran and related compounds
EP0396450A1 (en) 1989-05-02 1990-11-07 Rhone-Poulenc Chimie Silica beads, process for their preparation and their use for reinforcing elastomers
EP0520862A1 (en) 1991-06-26 1992-12-30 Rhone-Poulenc Chimie Process for the preparation of precipitated silica, precipitated silicas thus obtained, and their use in the reinforcement of rubbers
EP0670813A1 (en) 1993-09-29 1995-09-13 Rhone-Poulenc Chimie Precipitated silica
EP0670814A1 (en) 1993-09-29 1995-09-13 Rhone-Poulenc Chimie Precipitated silica
EP0762992A1 (en) 1995-03-29 1997-03-19 Rhone-Poulenc Chimie Novel method for preparing precipitated silica, novel aluminium-containing precipitated silicas, and use thereof for reinforcing elastomers
EP0762993A1 (en) 1995-03-29 1997-03-19 Rhone-Poulenc Chimie Novel method for preparing precipitated silica, novel aluminium-containing precipitated silicas, and use thereof for reinforcing elastomers
EP0917519A1 (en) 1997-05-26 1999-05-26 Rhodia Chimie Fällungskieselsäure
US20020051730A1 (en) * 2000-09-29 2002-05-02 Stanko Bodnar Coated medical devices and sterilization thereof
EP1355856A1 (en) 2000-12-28 2003-10-29 Rhodia Chimie Method for preparing precipitated silica containing aluminium
WO2003016215A1 (en) 2001-08-13 2003-02-27 Rhodia Chimie Method of preparing silicas, silicas with specific pore-size and/or particle-size distribution and the use thereof, in particular for reinforcing polymers
JP2004130006A (en) 2002-10-15 2004-04-30 Fuji Electric Systems Co Ltd Ozone sterilization method, and its apparatus
EP1691858A1 (en) * 2003-12-12 2006-08-23 C.R.Bard, Inc. Implantable medical devices with fluorinated polymer coatings, and methods of coating thereof
EP1973578A2 (en) 2006-01-14 2008-10-01 Optimus Services, LLC Use of ultraviolet germicidal irradiation in health care environments
WO2008000761A1 (en) 2006-06-27 2008-01-03 Rhodia Operations Precipitated silica for paper application
WO2009112458A1 (en) 2008-03-10 2009-09-17 Rhodia Operations Novel method for preparing precipitated silica, precipitated silica having particular morphology, grading and porosity, and use thereof particularly for reinforcing polymers
WO2011117400A1 (en) 2010-03-25 2011-09-29 Rhodia Operations Novel method for preparing precipitated silicas containing aluminium
WO2013110659A1 (en) 2012-01-25 2013-08-01 Rhodia Operations Precipitated-silica production method
WO2013139934A1 (en) 2012-03-22 2013-09-26 Rhodia Operations Method for the production of precipitated silica, comprising a membrane concentration step
EP3766942A1 (en) * 2018-03-16 2021-01-20 Daikin Industries, Ltd. Coating film and coated article

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