US20080026026A1 - Removable antimicrobial coating compositions and methods of use - Google Patents

Removable antimicrobial coating compositions and methods of use Download PDF

Info

Publication number
US20080026026A1
US20080026026A1 US11/710,290 US71029007A US2008026026A1 US 20080026026 A1 US20080026026 A1 US 20080026026A1 US 71029007 A US71029007 A US 71029007A US 2008026026 A1 US2008026026 A1 US 2008026026A1
Authority
US
United States
Prior art keywords
coating
composition
agent
film
antimicrobial
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US11/710,290
Other languages
English (en)
Inventor
Helen Lu
Christian Hoffmann
Christian Lenges
Barry Stieglitz
Lynn Leger
Judith VanGorp
Shaun Malone
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lanxess Corp
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to US11/710,290 priority Critical patent/US20080026026A1/en
Assigned to E. I. DU PONT DE NEMOURS AND COMPANY reassignment E. I. DU PONT DE NEMOURS AND COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: LEGER, LYNN, MALONE, SHAUN F., LU, HELEN S. M., LENGES, CHRISTIAN PETER, STIEGLITZ, BARRY, VAN GORP, JUDITH JOHANNA, HOFFMANN, CHRISTIAN
Publication of US20080026026A1 publication Critical patent/US20080026026A1/en
Assigned to THE CHEMOURS COMPANY FC, LLC reassignment THE CHEMOURS COMPANY FC, LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: E. I. DU PONT DE NEMOURS AND COMPANY
Assigned to JPMORGAN CHASE BANK, N.A. reassignment JPMORGAN CHASE BANK, N.A. SECURITY AGREEMENT Assignors: THE CHEMOURS COMPANY FC LLC, THE CHEMOURS COMPANY TT, LLC
Priority to US15/095,450 priority patent/US20160286796A1/en
Assigned to THE CHEMOURS COMPANY FC, LLC reassignment THE CHEMOURS COMPANY FC, LLC RELEASE BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: JPMORGAN CHASE BANK, N.A.
Assigned to LANXESS CORPORATION reassignment LANXESS CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: THE CHEMOURS COMPANY FC, LLC
Assigned to THE CHEMOURS COMPANY FC, LLC reassignment THE CHEMOURS COMPANY FC, LLC RELEASE BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: JPMORGAN CHASE BANK, N.A., AS ADMINISTRATIVE AGENT
Abandoned legal-status Critical Current

Links

Images

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/70—Web, sheet or filament bases ; Films; Fibres of the matrix type containing drug
    • A61K9/7015—Drug-containing film-forming compositions, e.g. spray-on
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02—Amines; Quaternary ammonium compounds
    • A01N33/12—Quaternary ammonium compounds
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
    • A23B2/00—Preservation of foods or foodstuffs, in general
    • A23B2/70—Preservation of foods or foodstuffs, in general by treatment with chemicals
    • A23B2/725—Preservation of foods or foodstuffs, in general by treatment with chemicals in the form of liquids or solids
    • A23B2/729—Organic compounds; Microorganisms; Enzymes
    • A23B2/762—Organic compounds containing nitrogen
    • 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
    • A61L2/00—Disinfection or sterilisation of materials or objects, in general; Accessories therefor
    • A61L2/16—Disinfection or sterilisation of materials or objects, in general; Accessories therefor using chemical substances
    • A61L2/23—Solid materials, e.g. granules, powders, blocks or tablets
    • A61L2/232—Solid materials, e.g. granules, powders, blocks or tablets layered or coated
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/008—Temporary coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1625—Non-macromolecular compounds organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1668—Vinyl-type polymers
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs

Definitions

  • This invention relates to a method for controlling microorganisms comprising coating a surface with a removable, antimicrobial film-forming composition, durable and readily removable antimicrobial compositions, and methods of applying said compositions.
  • the present invention relates to a method for providing control of microorganisms at a locus by contacting said locus with a removable coating composition comprising at least one antimicrobial agent.
  • Microbial contamination of food represents one of the major United States and worldwide public health problems.
  • the actual incidence of microbial food-borne illness is unknown, but the CDC estimates it to be between 7 to 81 million illnesses per year, with over 325,000 hospitalizations, and 5,000 deaths in the U.S. annually.
  • the costs of human illness in the U.S. due to food-borne pathogens are in the billion of dollars annually.
  • contaminated food represents a huge economic loss for many food-processing plants.
  • Factors such as the type of food contact surface and topography, play a significant role in the inability to decontaminate a surface. Abraded surfaces accumulate soil and are more difficult to clean than smooth surfaces. Surface defects further complicate the removal of soil and microbes, resulting in microbial growth even after attempts at decontamination and, potentially, biofilm formation due to said growth.
  • microbes within a biofilm are more resistant to disinfectants, which may assist the survival of Listeria and other food-borne pathogens in the food processing environment (J. F. Frank, R. A. Koffi, J. Food Protection, 1990, 53, 550-554; E. P. Krysinski, L. J. Brown, and T. J. Marchisello, J. Food Protection, 1992, 55, 246-251).
  • disinfectants may assist the survival of Listeria and other food-borne pathogens in the food processing environment.
  • Microbial contamination is of particular concern when the food processing equipment is either shut-down or temporarily not in operation or use. This is in fact an opportune time for biofilm formation, especially on parts of equipment that are hard to reach with disinfectants, as described above.
  • practices to avoid contamination during such shutdown periods involves multi-step approaches for disinfection prior to restart-up of processing, including disinfecting, coating, and removing any potentially harmful disinfectant with other solutions that often include other harsh means or components. These approaches are costly and may be of questionable efficacy.
  • a method to better address protection against microbial contamination during such shutdown periods are costly and may be of questionable efficacy.
  • a disinfectant composition capable of forming a durable, yet easily removable, antimicrobial coating that provides the appropriate protection.
  • the appropriate protection is achieved by certain characteristics of the coating, such as good spreading and surface tension control.
  • Good spreading of the liquid antimicrobial formulation onto the surface after application is beneficial in achieving a homogeneous and continuous film, especially when spraying or aerosolizing is used as the application method.
  • Good spreading properties can enhance the antimicrobial properties of an antimicrobial formulation by achieving complete surface coverage without leaving uncovered gaps in the created antimicrobial film or coating. These gaps allow for growth of microorganisms.
  • Antimicrobial properties can further be enhanced by the reduced surface tension by allowing the liquid antimicrobial formulation to flow into surface imperfections known to harbor microorganisms.
  • U.S. Pat. No. 5,585,407 provides water-based coating compositions that can be applied to a substrate to inhibit growth of microbes for extended periods of time.
  • the coating comprises an acrylate emulsion polymer and an organoalkoxysilane and can be removed under alkaline conditions.
  • U.S. Pat. No. 5,017,369 provides a prophylactic treatment of mastitis in a cow between milkings comprising coating the cow teats with an aqueous composition comprising an antimicrobial agent.
  • the composition comprises at least 2 wt % partially hydrolyzed polyvinyl alcohol, from about 0 wt % to about 10 wt % of an opacifier, about 0.1 wt % to about 10 wt % of an antimicrobial agent, and at least 65 wt % water.
  • a water wash is used to remove the film from the cow teat prior to milking.
  • the problem to be solved is the lack of a method for controlling microorganisms at a particular locus with a coating composition, comprising at least one antimicrobial agent, wherein said coating is durable, provides residual antimicrobial efficacy and is readily removable.
  • the present invention addresses the problems identified above with the following methods and compositions.
  • An aspect of this invention is directed to a method of providing control of microorganisms at a locus comprising
  • the surface tension of the liquid coating composition described herein is below 40 mN/m.
  • the film-forming agent in the above method is one or more polyvinyl alcohols and copolymers thereof, including polyvinyl pyrrolidones, polyacrylic acid, acrylate copolymers, ionic hydrocarbon polymers, and polyurethanes or combinations thereof.
  • the coating formed by the methods herein provides a reduction of microorganisms of at least 3-log when applied to a contaminated surface.
  • the coating provides a reduction of microorganisms of at least 5-log when applied to a contaminated surface.
  • the coating prevents growth of at least one type of microorganism at a locus.
  • control of microorganisms at a locus comprises a reduction of microorganisms harbored in a biofilm.
  • the coating formed by the method above is substantially continuous and homogenous.
  • the coating formed by the method above has a thickness of about 0.3 to about 300 microns, preferably, it has a thickness of about 0.5 to about 100 microns.
  • a removable food-processing shut-down spray composition comprising:
  • compositions described herein comprise a surfactant that provides a surface tension of about 20 to about 50 mN/m.
  • the surfactant is an organo-silicone.
  • the surfactant is at a concentration of about 0.01 wt % to about 1.0 wt % of the composition.
  • the composition comprises a rheology control agent that provides shear thinning properties to the composition.
  • the composition provides a reduction of microorganisms of at least 3-log when applied to a contaminated food processing surface.
  • the composition is a disinfectant, sanitizer, preservative, or physical barrier to contamination when applied to a contaminated surface and wherein said composition is capable of residual antimicrobial efficacy when applied to a contaminated surface that is subject to subsequent contamination.
  • the locus is the surface of one or more: tanks, conveyors, floors, drains, coolers, freezers, refrigerators, equipment surfaces, walls, valves, belts, pipes, joints, crevasses, a building surface, kitchen surface, an inanimate surface found in a food processing facility, veterinary or animal care facility, animal care equipment, or animal husbandry or hatchery facility, the surface of a hospital or surgery center wall, bed, equipment, textile worn in a hospital or other healthcare setting, including scrubs, shoes, and other hospital surfaces.
  • the locus is composed of one or more metals selected from the group consisting of aluminum, steel, stainless steel, chrome, titanium, iron, alloys and mixtures thereof.
  • the locus is the surface comprises one or more plastic material selected from the group consisting of polyolefins, including polyethylene, polypropylene, polystyrene, polymethacrylate, polymethylmethacrylate, polymers of acrylonitrile, butadiene, ABS, acrylonitrile butadiene; polyesters, including polyethylene terephthalate; and polyamides, including nylon; and combinations thereof.
  • polyolefins including polyethylene, polypropylene, polystyrene, polymethacrylate, polymethylmethacrylate, polymers of acrylonitrile, butadiene, ABS, acrylonitrile butadiene
  • polyesters including polyethylene terephthalate
  • polyamides including nylon
  • the locus is made of brick, tile, ceramic, porcelain, wood, vinyl, linoleum, carpet, paper, leather, combinations thereof, and the like.
  • the locus is an inanimate surface comprised of metals, minerals, polymers, plastics, fibrous substrates or non-wovens, or mixtures thereof, or coated or painted surfaces.
  • FIG. 1 shows mechanisms by which the coating composition provides protection. Arrows indicate migration of biocidal active component into microbially-contaminated regions above and below the antimicrobial coating.
  • the coating composition also provides a physical barrier to soil and other solid contaminants.
  • FIG. 2 shows cross-sections of an antimicrobial coating. Shown are x-z-cross-sections through the polymer film formed from Formulation #2 (top), and y-z-cross-sections of the same film (bottom). The film was visualized by confocal laser-scanning microscopy after addition of traces of a fluorescent dye (rhodamine 123) to the film-forming composition.
  • a fluorescent dye rhodamine 123
  • FIG. 3 shows the release of a quaternary ammonium compound (QAC) over time from films sprayed from three liquid compositions of the invention on stainless steel coupons, then dried and submerged into water.
  • QAC quaternary ammonium compound
  • antimicrobial agents having improved antimicrobial efficacy and improved speed of action.
  • the specific requirements for such agents vary according to the intended application (e.g., sanitizer, disinfectant, sterilant, aseptic packaging treatment, etc.) and the applicable public health requirements.
  • sanitizer should provide a 99.999% reduction (5-log order reduction) within 30 seconds at room temperature, 25.+ ⁇ 0.2.degree. C, against several test organisms.
  • antimicrobial as used herein includes agents capable of killing microorganisms, blocking or preventing microbial contamination (such as a forming a barrier), or suppressing or preventing growth of microorganisms, trapping microorganisms for killing, or preventing biofilm formation.
  • sanitizer as used herein means an agent which reduces the number of microbial contaminants to safe levels as judged by public health requirements.
  • a sanitizer is a chemical that kills 99.999% of the specific test microorganisms in 30 seconds under the conditions of the test (EPA policy DIS/TSS-4: “Efficacy data requirements—Sanitizing rises for previously cleaned food-contact surfaces”, United States Environmental Protection Agency, Jan. 30, 1979).
  • disinfectant as used herein means an agent which provides antimicrobial activity. According to an official disinfectant test, a disinfectant is a chemical that kills 99.9% of the specific test microorganisms in 10 minutes under the conditions of the test. (Germicidal and Detergent Sanitizing Action of Disinfectants, Official Methods of Analysis of the Association of Official Analytical Chemists, paragraph 960.09 and applicable sections, 15th Edition, 1990 (EPA Guideline 91-2)).
  • ppm as used herein means micrograms per gram.
  • the present invention relates to a method and composition for controlling microorganisms. Said method comprises coating a surface with a removable, antimicrobial film-forming composition. Specifically, the invention relates to a method of providing control of microorganisms at a locus comprising
  • the coating can be removed with an aqueous solution at a temperature of about 15° C. to about 100° C., or more preferably at a temperature of about 30° C. to about 80° C.
  • a locus of the invention comprises part or all of a target surface suitable to be coated.
  • Target surfaces include all surfaces that can potentially be contaminated with microorganisms, including surfaces typically difficult to apply a film or coating to (such as hard-to-reach surfaces).
  • Examples of target surfaces include equipment surfaces found in the food or beverage industry (such as tanks, conveyors, floors, drains, coolers, freezers, refrigerators, equipment surfaces, walls, valves, belts, pipes, drains, joints, crevasses, combinations thereof, and the like); building surfaces, including buildings under construction, new home construction, and surfaces in or on seasonal properties like vacation home surfaces (such as walls, wood frames, floors, windows), kitchens (sinks, drains, counter-tops, refrigerators, cutting boards), bathrooms (showers, toilets, drains, pipes, bath-tubs), (especially for mold removal), decks, wood, siding and other home exteriors, asphalt shingle roofing, patio or stone areas (especially for algae treatment); boats and boating equipment surfaces; garbage disposals, garbage cans and dumpster
  • Additional loci suitable for use in the present invention comprise fibrous substrates and include fibers, yarns, fabrics, textiles, nonwovens, carpets, leather, or paper.
  • the fibrous substrates are made with natural fibers such as wool, cotton, jute, sisal, sea grass, paper, coir and cellulose, or mixtures thereof; or are made with synthetic fibers such as polyamides, polyesters, polyolefins, polyaramids, acrylics and blends thereof; or blends of at least one natural fiber and at least one synthetic fiber.
  • fabrics is meant natural or synthetic fabrics, or blends thereof, composed of fibers such as cotton, rayon, silk, wool, polyester, polypropylene, polyolefins, nylon, and aramids such as “NOMEX®” and “KEVLAR®.”
  • fabric blends is meant fabric made of two or more types of fibers. Typically these blends are a combination of at least one natural fiber and at least one synthetic fiber, but also can be a blend of two or more natural fibers or of two or more synthetic fibers.
  • Nonwoven substrates include, for example, spunlaced nonwovens, such as SONTARA available from E. I. du Pont de Nemours and Company (Wilmington, Del., USA), and laminated nonwovens, such as spunbonded-meltblown-spunbonded nonwovens.
  • surface materials are metals (e.g., steel, stainless steel, chrome, titanium, iron, copper, brass, aluminum, and alloys thereof), minerals (e.g., concrete), polymers and plastics (e.g., polyolefins, such as polyethylene, polypropylene, polystyrene, poly(meth)acrylate, polyacrylonitrile, polybutadiene, poly(acrylonitrile, butadiene, styrene), poly(acrylonitrile, butadiene), acrylonitrile butadiene; polyesters such as polyethylene terephthalate; and polyamides such as nylon).
  • Additional surfaces include brick, tile, ceramic, porcelain, wood, vinyl, and linoleum.
  • Equipment or surfaces protected with a temporary coating can be in use or not in use while protected.
  • the target surface can be hydrophobic or hydrophilic.
  • the antimicrobial, removable coating composition useful for the invention can be used as a replacement for standard sanitation products (such as diluted quaternary ammonium compound solutions, peracid foams, and the like), and can be used for daily sanitation as protective coatings for equipment in use or not-in use as well as for longer term protection (weeks or months).
  • the coating composition provides antimicrobial efficacy in a number of ways, including, but not limited to killing (both loose microorganisms and biofilms), reducing the growth of, or preventing the growth of microorganisms, by preventing the formation of biofilms, and by trapping microorganisms in, beneath or attached to the coating.
  • the coating composition also reduces water usage because a concentrate of antimicrobial agent is directly applied in a thin film, and the antimicrobial agent can be maintained in higher concentrations and for longer periods of time at the substrate. In addition, labor can be reduced because the antimicrobial coating is applied once and removed in a later process step.
  • the coating composition can be modified by formulating the composition with flow modifiers to coat hard-to-reach surfaces. This enables application of the antimicrobial agent to surfaces on or in equipment otherwise not accessible by application of conventional antimicrobial solutions with traditional shear-viscosity profiles. Horizontal and vertical surfaces can be covered with a thin layer of protective coating without waste of antimicrobial agent. By formulating compositions with appropriate flow modification and degree of cross-linking, coating compositions with various coating properties can be prepared that will vary in the degree of surface finish and protection as well as ease of removal.
  • the antimicrobial, removable coating composition useful for the invention is applied to equipment, for example, in the food, dairy, or beverage industries, during shutdown periods of the equipment. When the equipment is started up, the coating is removed by a method described herein.
  • the antimicrobial, removable coating composition is used for sanitation of surfaces, such as surfaces of equipment of the food or beverage industry, for daily or weekly sanitation purposes.
  • fruit surfaces can be coated with the removable coating composition to prevent microbial spread and cross-contamination in food processing facilities.
  • hospital walls, beds, and other hospital surfaces can be coated with the antimicrobial, removable coating composition useful for the invention.
  • drains are coated with the removable coating composition.
  • building surfaces such as in new home construction, walls or other surfaces are coated for prevention of mold contamination or mold removal.
  • the coating composition offers several mechanisms of protection towards contamination of microbial or non-microbial origin, such as soiling.
  • planktonic or loosely adhering cells on the surface are killed (or growth is reduced or prevented) by the antimicrobial agent in the coating formulation.
  • the antimicrobial agent is likely to remain active because of the high water content retained at the interface between biofilm and antimicrobial coating. Due to the film being semi-permeable, the antimicrobial agent is mobile within the film contributing to a more effective barrier and longer lasting activity.
  • the antimicrobial film thus formed constitutes a reservoir of antimicrobial agent providing much longer contact time than conventional sanitary rinse solutions that typically drip off within seconds or minutes.
  • biofilm refers to a collection of microorganisms (either one species, or multiple species) surrounded by a matrix of extracellular polymers (i.e., exopolymers or glycocalyx).
  • extracellular polymers are typically polysaccharides, but they can contain other biopolymers as well, and they can be attached to either an inert or living surface.
  • Typical biofilm microorganisms are Gram positive and/or Gram negative bacteria, acting as pathogens, indicator organisms, and/or spoilage organisms.
  • the coating constitutes a physical barrier for microorganisms, soil, fat and other matter. These solid contaminants will remain on the surface of the coating and will wash off at the time of removal of the coating.
  • FIG. 1 illustrates various protection mechanisms described above.
  • the protection mechanisms can operate individually, or simultaneously in any combination, depending on environmental conditions.
  • the long lasting activity while the coating is present on the locus is especially beneficial in a variety of applications.
  • This residual benefit is far superior to antimicrobial agents such as a rinse solution that drips off quickly, or an agent that is subject to removal by touching or minor abrasion of the surface after application.
  • antimicrobial agents such as a rinse solution that drips off quickly, or an agent that is subject to removal by touching or minor abrasion of the surface after application.
  • the variation of film flexibility, viscosity, strength, and adhesion of the coating of the present invention permits it to be tailored to specific applications, thus making sustained antimicrobial protection available in numerous situations where such sustained activity (residual benefit) was not previously available.
  • the film-forming water soluble or water dispersible agent can be at least one of any agent, as described below, that is durable and removable.
  • the film or coating is removable, for instance, when subjected to an aqueous solution treatment above 15° C., preferably above 30° C.
  • examples include, but are not limited to, polyvinyl alcohols, polyvinyl alcohol copolymers, polyvinyl pyrrolidones, polyacrylic acid, acrylate copolymers, ionic hydrocarbon polymers, and polyurethanes, or combinations thereof.
  • Polyvinyl alcohol is made from polyvinyl acetate by hydrolysis.
  • the physical properties of polyvinyl alcohol are controlled by the molecular weight and the degree of hydrolysis.
  • the most commonly available grades of polyvinyl alcohol, ranked by degree of hydrolysis are an 87-89% grade (containing 11-13 mole % residual vinylacetate units), a 96% hydrolysis grade (containing 4 mole % residual vinyl acetate units), and the “fully hydrolyzed” and “superhydrolyzed” grades, which are about 98% and greater-than-99% hydrolyzed, respectively.
  • Lower degrees of hydrolysis e.g. 74% and 79%) are also commercially available.
  • the polyvinyl alcohol component of the present invention can also be a copolymer of vinyl alcohol, such as one obtained by hydrolyzing a copolymer of vinyl acetate with small amounts (up to about 15 mole %) of other monomers.
  • Suitable co-monomers are e.g. esters of acrylic acid, methacrylic acid, maleic or fumaric acids, itaconic acid, etc.
  • copolymerization of vinyl acetate with hydrocarbons e.g.
  • alpha.-olefins such as ethylene, propylene or octadecene, etc.
  • higher vinyl esters such as vinyl butyrate, 2-ethyl hexoate, stearate, trimethyl acetate, or homologues thereof
  • W-10 type of vinyl esters sold by Shell Chem. Co.
  • suitable comonomers are N-substituted acrylamides, vinyl fluoride, allyl acetate, allyl alcohol, etc.
  • the free unsaturated acids such as acrylic acid, methacrylic acid, monomethyl maleate, etc. can act as comonomers.
  • partially hydrolyzed grade polyvinyl alcohol should be understood to include both a single grade and a mixture of grades, and the term “average degree of hydrolysis” should be understood to refer to the degree of hydrolysis arrived at by averaging (with appropriate weighting on the basis of proportions) the partially hydrolyzed grades in the mixture, if a mixture is used, or the average degree of hydrolysis of a single grade, if a single grade is used (an “88% grade”, for example, may be the average of a spectrum ranging from 87 to 89% within the same grade).
  • Variation of film flexibility, water sensitivity, ease of solvation, viscosity, film strength and adhesion of the polyvinyl alcohol film can be varied by adjusting molecular weight and degree of hydrolysis.
  • the polyvinyl alcohol for use in the process of this invention has a degree of hydrolysis from about 85% to greater than 99%.
  • the polyvinyl alcohol has a degree of hydrolysis from about 92% to greater than 99%.
  • the polyvinyl alcohol has a number-averaged molecular weight (Mn) that falls in the range of between about 4,000 to about 200,000, or about 4,000 to about 186,000, or 30,000 to about 186,000.
  • the polyvinyl alcohol has a molecular weight that falls in the range of between about 70,000 and 130,000. In another embodiment, the polyvinyl alcohol of various molecular weights can be blended to give the desired properties. In one embodiment, the polyvinyl alcohol is used at about 2% to about 30% by weight of the weight of the solution. In a more specific embodiment, the polyvinyl alcohol is used at about 2% to about 15% by weight of the weight of the solution. In an even more specific embodiment, the polyvinyl alcohol is used at about 3% to about 6% by weight of the weight of the solution.
  • the film-forming composition of the present invention can contain PVP at a concentration of about 0.25 to about 50% by weight.
  • Suitable grades of PVP are available from International Specialty Products (Wayne, N.J., USA). Such grades include: K-15, having a molecular weight range of about 6,000 to about 15,000; K-30, having a molecular weight range of about 40,000 to about 80,000; K-60, having a molecular weight range of about 240,000 to about 450,000; K-90, having a molecular weight range of about 900,000 to about 1,500,000; and K-120, having a molecular weight range of about 2,000,000 to about 3,000,000. Mixtures of PVP's can be employed, as can combinations of PVP and other film-forming compounds.
  • the amount and molecular weight distribution of the PVP used will influence the viscosity, coverage, and cost of the final product.
  • the viscosity should preferably be between about 20 to about 1000 centipoise, and more preferably between about 20 to 100 centipoise.
  • lower molecular weight PVP will give a less viscous product than a higher molecular weight PVP at the same concentration.
  • concentration of PVP As the molecular weight range increases, the viscosity will also increase.
  • the present invention can employ PVP having any of a number of molecular weight ranges.
  • film-forming compositions can utilize the PVP grades K-15, K-30, K-60, K-90, or K-120 described above.
  • PVP polyvinyl urethane
  • PVP having this molecular weight distribution typically gives a film-forming composition with a viscosity, which can be easily adjusted and washes off a surface easily with no visible signs of interaction with a painted surface.
  • PVP with a molecular weight distribution between about 15,000 and about 3,000,000 is present at a concentration of between about 0.25% and about 40% by weight.
  • PVP with a molecular weight distribution between about 60,000 and about 1,200,000 is present at a concentration of between about 2% and about 30% by weight.
  • the film-forming compositions of the invention can also include an acrylate emulsion polymer.
  • Preferred acrylate polymers are those composed of one or more copolymers of ethylenically unsaturated comonomers.
  • the monomers useful in the compositions of the invention comprise one or more ethylenically unsaturated polar or non-polar, non-ionizing monomers and at least one ethylenically unsaturated carboxylic acid.
  • the monomers can include more than one ethylenically unsaturated sites and the suitable carboxylic acids preferably include one or more carboxyl groups.
  • Suitable ethylenically unsaturated acids include acrylic, methacrylic, butenoic, maleic, fumaric, itaconic, and cinnamic acids as well as dimer acids such as acrylic and methacrylic dimer acids and combinations of the foregoing.
  • Ethylenically unsaturated polar or non-polar, non-ionizing monomers include ethylenically unsaturated esters, ethylenically unsaturated nitriles, ethylenically unsaturated alcohols, aryl vinyl compounds and arylalkyl vinyl compounds.
  • the acrylate polymers are preferably copolymers of acrylic acid esters and methacrylic acid esters, such as C1 to C6 alkyl acrylates or methacrylates, in combination with acrylic or methacrylic acid, cyanoacrylates and methacrylates (e.g., acrylonitrile) and other known acrylic, vinyl and diene monomers.
  • the acrylate polymer component can optionally contain one or more metal salt complexing agents effective as cross-linking agents. When present such complexing agents bond with the pendant carboxyl groups on the acrylate polymers to form a cross-linked polymer, which is more water resistant than a comparable acrylate polymer which is not cross-linked.
  • Suitable metal salt complexing agents include those containing zinc such as zinc ammonium carbonate, for example.
  • Other useful complexing agents include known salts of various metals including zirconium, calcium, magnesium and the transition metals, for example.
  • Exemplary complexing agents include polyvalent metal complexes such as ammonium zinc carbonate, ammonium calcium ethylenediamine carbonate, ammonium zinc acetate, ammonium zinc acrylate, ammonium zinc maleate, ammonium zinc amino acetate and ammonium calcium aniline and combinations of the foregoing.
  • carboxylated acrylate polymer emulsions can be used either alone or in combination with one another in the film-forming compositions of the invention.
  • Suitable commercial emulsions include those with a metal complexing agent as described above as well as those without added metal complexing agents.
  • Suitable metal free emulsions include commercially available materials such as those available under the trade names of “Rhoplex” NT 2624 (Rohm and Haas Company, Philadelphia, Pa.); “Esi-Cryl” 20/20 (Emulsion Systems, Valley Stream, N.Y., USA); and “Syntran” 1905 (Interpolymer of Canton, Mass., USA).
  • Other metal containing and metal free acrylate emulsions can be used, as known by those skilled in the art.
  • the acrylate polymer component is preferably prepared as an emulsion and is present in the film-forming composition of the invention at a concentration ranging from about 0.25 to 30 wt %, and more preferably from about 2 to 20 wt % based on total weight of the composition.
  • Ionic hydrocarbon copolymers useful for the present invention include a polymer of an ⁇ -olefin having the general formula RCH ⁇ CH 2 where R is a radical selected from the class consisting of hydrogen and alkyl radicals having from 1 to 8 carbon atoms, the olefin content of said polymer being at least 50 mol % based on the polymer, and an ⁇ , ⁇ -ethylenically unsaturated carboxylic acid having 1 or 2 carboxylic groups, the acid monomer content of said polymer being from 0.2 to 25 mol % based on the polymer.
  • R is a radical selected from the class consisting of hydrogen and alkyl radicals having from 1 to 8 carbon atoms
  • R is a radical selected from the class consisting of hydrogen and alkyl radicals having from 1 to 8 carbon atoms
  • the olefin content of said polymer being at least 50 mol % based on the polymer
  • a polyurethane dispersion or solution refers to an aqueous dispersion or solution of a polymer containing urethane groups.
  • a cross-linked polyurethane dispersoid refers to an aqueous dispersion of a polymer containing urethane groups and cross-linking, as those terms are understood by persons of ordinary skill in the art.
  • the polyurethane may be an aqueous solution (no cross-linking or low cross-linking) or an aqueous dispersion.
  • Cross-linked polyurethane dispersions are described in the U.S. Patent Application 2005/0215663, herein incorporated specifically by reference.
  • These polymers can incorporate hydrophilic functionality to the extent required to maintain stable dispersion of the polymer in an aqueous solution.
  • These polymers can also incorporate ionic and nonionic functionality to the extent required to maintain a stable dispersion of the polymer in water.
  • these polymers can be prepared by emulsification of hydrophobic polyurethanes in water with the aid of suitable external emulsifiers, surfactants and the like, and/or utilizing strong shear forces to form an oil-in-water dispersion.
  • the stability of the cross-linked polyurethane in the aqueous vehicle is achieved by incorporating anionic, cationic and/or non-ionic components in the polyurethane polymer, which facilitates stabilizing the cross-linked polyurethane in aqueous systems.
  • the amount of cross linking is chosen to give the desired water resistance.
  • External emulsifiers can also be added to stabilize the polyurethane. Combinations of incorporated anionic, cationic and/or non-ionic components, and/or external emulsifiers can also be used.
  • the antimicrobial agent useful for the invention can be either an inorganic or organic agent, or a mixture thereof.
  • the invention is not to be limited to the selection of any particular antimicrobial agent, and any known water-soluble or water-dispersible antimicrobial may be included in the compositions of the invention such as antimicrobials, mildewcides, antiseptics, disinfectants, sanitizers, germicides, algicides, antifouling agents, preservatives, and combinations of the foregoing and the like provided that the antimicrobial agent is chemically compatible with other components in the composition. Suitable classes of antimicrobial agents are described below.
  • inorganic antimicrobial agent used herein is a general term for inorganic compounds which contain a metal or metal ions, such as silver, zinc, copper and the like which have antimicrobial properties.
  • organic antimicrobial agent used herein is the general term for natural extracts, low molecular weight organic compounds and high molecular weight compounds all of which have antimicrobial properties and which generally contain nitrogen, sulfur, phosphorus or like elements. Examples of useful natural antimicrobial agents are chitin, chitosan, antimicrobial peptides such as nisin, lysozymes, wasabi extracts, mustard extracts, hinokitiol, tea extracts and the like.
  • High molecular weight compounds having anti-microbial properties include those having an ammonium salt group, phosphonium salt group, sulfonium salt group or like onium salts, a phenylamide group, diguanide group attached to a straight or branched polymer chain, for example phosphonium salt-containing vinyl polymers, as are known in the art (E.-R. Kenawy and Y. A.-G. Mahmoud “Biologically active polymers, 6: Synthesis and antimicrobial activity of some linear copolymers with quaternary ammonium and phosphonium groups” in Macromolecular Bioscience (2003), 3(2), 107-116).
  • Examples of useful low molecular weight antimicrobial agents include chlorhexidine, chlorhexidine gluconate, glutaral, halazone, hexachlorophene, nitrofurazone, nitromersol, thimerosol, C1-C5-parabens, hypochlorite salts, clofucarban, clorophen, phenolics, mafenide acetate, aminacrine hydrochloride, quaternary ammonium salts, chlorine and bromine release compounds (e.g.
  • alkali and alkaline earth hypochlorites and hypobromites isocyanurates, chlorinated derivatives of hydantoin, sulfamide, amine, etc.), peroxide and peroxyacid compounds (e.g. peracetic acid, peroctanoic acid), protonated short chain carboxylic acids, oxychlorosene, metabromsalan, merbromin, dibromsalan, glyceryl laurate, sodium and/or zinc pyrithione, trisodium phosphates, (dodecyl)(diethylenediamine)glycine and/or (dodecyl)(aminopropyl)glycine and the like.
  • peroxide and peroxyacid compounds e.g. peracetic acid, peroctanoic acid
  • protonated short chain carboxylic acids oxychlorosene, metabromsalan, merbromin, dibromsalan,
  • Useful quaternary ammonium salts include the N—C10-C24-alkyl-N-benzyl-quaternary ammonium salts which comprise water solubilizing anions such as halide, e.g., chloride, bromide and iodide; sulfate, methosulfate and the like and the heterocyclic imides such as the imidazolinium salts.
  • halide e.g., chloride, bromide and iodide
  • sulfate, methosulfate and the like and the heterocyclic imides such as the imidazolinium salts.
  • Useful phenolic germicides include phenol, m-cresol, o-cresol, p-cresol, o-phenyl-phenol, 4-chloro-m-cresol, chloroxylenol, 6-n-amyl-m-cresol, resorcinol, resorcinol monoacetate, p-tert-butylphenol and o-benzyl-p-chlorophenol.
  • Useful antimicrobial agents known to be effective in preventing the visible growth of mildew colonies include, for example, 3-iodo-2-propynl butylcarbamate, 2-(4-thiazolyl)benzimidazole, diiodomethyl-p-tolylsulfone, tetrachloroisophthalonitrile, the zinc complex of 2-pyridinethiol-1-oxide (inciuding salts thereof) as well as combinations of the foregoing.
  • the coating composition comprising the antimicrobial agent offers protection against diverse microorganisms.
  • microorganism is meant to include any organism comprised of the phylogenetic domains of bacteria and archaea, as well as unicellular (e.g. yeasts) and filamentous (e.g. molds) fungi, unicellular and filamentous algae, unicellular and multicellular parasites, viruses, virinos and viroids.
  • the coating composition protects against Gram positive or Gram negative bacteria.
  • Gram positive bacteria which are inhibited or killed by the coating include, but are not limited to, Mycobacterium tuberculosis, M. bovis, M. typhimurium, M. bovis strain BCG, BCG substrains, M. avium, M. intracellulare, M. africanum, M. kansasii, M. marinum, M. ulcerans, M. avium subspecies paratuberculosis, Staphylococcus aureus, S. epidermidis, S. equi, Streptococcus pyogenes, S. agalactiae, Listeria monocytogenes, L.
  • Gram negative bacteria which are inhibited or killed by the coating include, but are not limited to, Clostridium tetani, C. perfringens, C.
  • the coating provides protection against fungi, including but are not limited to, Alternaria alternata, Aspergillus niger, Aureobasidium pullulans, Cladosporium cladosporioides, Drechslera australiensis, Gliomastix cerealis, Monilia grisea, Penicillium commune, Phoma fimeti, Pithomyces chartarum , and Scolecobasidium humicola.
  • Enzymes useful for the present invention include those that have beneficial effects such as cleaning, destaining, and biofilm degradation. These enzymes include one or a mixture of: deacetylase, amidase, cellulase, esterase, glycosidase, xylanase, amylase, transaminase, laminarinase, beta-galactosidase, beta-mannosidase, pullulanase, phosphatase, protease, lipase, and perioxidase.
  • compositions useful for the present invention can also contain one or more surfactants. While not being bound by theory, it is believed that a surfactant will aid wetting of the surface to be covered and will aid even coverage by the film. The surfactant is also believed to aid foaming by the film when removed, thereby aiding removal of the film and washing of the protected surface. Suitable surfactants have a preferred hydrophilic-lipophilic balance (HLB) of from about 9 to about 17.
  • HLB hydrophilic-lipophilic balance
  • Suitable surfactants include, but are not limited to: amphoteric surfactants, such as Amphoteric N from Tomah Products; silicone surfactants, such as BYK 348 available from BYK Chemie (BYK-Chemie GmbH, Wesel, Germany); fluorinated surfactants such as Zonyl® FS300 from DuPont (DuPont, Wilmington, Del., USA); and nonylphenoxypolyethoxyethanol based surfactants, such as Triton N-101 available from Dow (Midland, Mich., USA).
  • amphoteric surfactants such as Amphoteric N from Tomah Products
  • silicone surfactants such as BYK 348 available from BYK Chemie (BYK-Chemie GmbH, Wesel, Germany
  • fluorinated surfactants such as Zonyl® FS300 from DuPont (DuPont, Wilmington, Del., USA)
  • nonylphenoxypolyethoxyethanol based surfactants such as Trit
  • surfactants include ethoxylated decynediols such as Surfynol 465 available from Air Products & Chemicals (Allentown, Pa., USA); alkylaryl polyethers such as Triton CF-10 available from Dow; octylphenoxy polyethoxy ethanols such as Triton X-100 available from Dow; ethoxylated alcohols such as Neodol 23-5 or Neodol 91-8 available from Shell (The Hague, the Netherlands); Tergitol 15-S-7 available from Dow, Steol-4N, a 28% sodium laureth sulfate from Stepan Company (Northfield, Ill., USA), sorbitan derivatives such as Tween 20 or Tween 60 from Uniqema (New Castle, Del., USA), and quaternary ammonium compounds, such as benzalkonium chloride.
  • ethoxylated decynediols such as Surfynol 465 available
  • Suitable surfactants include organo-silicone surfactants such as Silwet®L-77 from Setre Chemical Company (Mephis, Tenn., USA), DowCorning® Q2-5211 from DowCorning Silicones (Midland, Mich., USA), or Silsurf® A008 by Siltech Corporation (Toronto, ON, Canada).
  • the preferred range for use of the surfactant is from about 0.001 to about 1 wt % of the formulation, and more preferably from about 0.01 to about 0.2 wt %.
  • Inert solvents useful for the invention include water. Additional solvents include mono alcohols monofunctional and polyfunctional alcohols, preferably containing from about 1 to about 6 carbon atoms and from 1 to about 6 hydroxy groups. Examples include ethanol, isopropanol, n-propanol, 1,2-propanediol, 1,2-butanediol, 2-methyl-2,4-pentanediol, mannitol and glucose. Also useful are the higher glycols, polyglycols, polyoxides, glycol ethers and propylene glycol ethers.
  • Additional solvents include the free acids and alkali metal salts of sulfonated alkylaryls such as toluene, xylene, cumene and phenol or phenol ether or diphenyl ether sulfonates; alkyl and dialkyl naphthalene sulfonates and alkoxylated derivatives.
  • sulfonated alkylaryls such as toluene, xylene, cumene and phenol or phenol ether or diphenyl ether sulfonates
  • alkyl and dialkyl naphthalene sulfonates alkoxylated derivatives.
  • Additional components that can be added to the coating composition include colorants, rheology modifiers, cross-linking agents, plasticizers, surfactants, solubilizing agents, antioxidants, pH adjusters, wetting agents, antifoaming agents, extenders, lubricants, processing aids, color fastness agents, and additional performance-enhancing agents.
  • Wetting agents lower the surface tension of the formulation to allow it to wet the surfaces, spread on the surfaces and potentially penetrate into, under, and around soils, solid matter, microorganisms, biofilms, surface contaminations, fat and surface crevices.
  • Colorants useful for the present invention include dyes and pigments such as food grade pigments.
  • Dyes useful for the invention include both water soluble and water insoluble dyes.
  • Water soluble dyes can be formulated easily in the aqueous systems of the invention.
  • Water insoluble dyes can be included in an oil phase that can be dispersed or suspended in the antimicrobial coating compositions useful for the invention.
  • Useful dyes for the purpose of this invention are typically organic compounds that absorb visible light resulting in the appearance of a detectable color. Fluorescent dyes can also be used, for example, for purposes of visualizing a film by ultraviolet light.
  • FD&C approved dyes can be used since these materials are typically approved for use as direct additives for food stuffs.
  • the dyes typically useful in this invention are colorants approved for use in foods, drugs, cosmetics and medical devices.
  • annatto extract (2) exempt from certification: annatto extract, theta-apo-8′-carotenal, canthaxanthin, caramel, theta-carotene, carrot oil, cochineal extract (carmine), corn endosperm oil, dehydrated beets (beet powder), dried algae meal, ferrous gluconate, fruit juice, grape color extract, grape skin extract, paprika, paprika oleoresin, riboflavin, saffron, synthetic iron oxide, tagetes meal and extract, titanium dioxide, toasted partially defatted cooked cottonseed flour, turmeric, termeric oleoresin, ultramarine blue, and vegetable juice.
  • D&C Yellow No. 7 D&C Yellow No. 8
  • D&C Yellow No. 10 D&C Yellow No. 11, and Ext. D&C Yellow No. 7.
  • cantaxanthin, beta carotene, chlorophyllin, and other colors are known.
  • the composition useful for the invention can also contain one or more rheology modifiers, or rheology agents, employed to enhance viscosity, or thicken and cause the aqueous treatment or coating composition to cling to the surface. Clinging enables the composition to remain in contact with transient and resident microorganisms for longer periods of time, promoting microbiological efficacy and resisting waste because of excessive dripping.
  • the rheology modifier can be a film former or act cooperatively with a film-forming agent to form a barrier that provides additional protection.
  • Water soluble or water dispersible rheology modifiers that are useful can be classified as inorganic or organic.
  • the organic thickeners can further be divided into natural and synthetic polymers with the latter still further subdivided into synthetic natural-based and synthetic petroleum-based.
  • Inorganic thickeners are generally compounds such as colloidal magnesium aluminum silicate (VEEGUM®), colloidal clays (Bentonites), or silicas (CAB-O-SIL®) which have been fumed or precipitated to create particles with large surface to size ratios.
  • Natural hydrogel thickeners of use are primarily vegetable derived exudates. For example, tragacanth, karaya, and acacia gums; and extractives such as carrageenan, locust bean gum, guar gum and pectin; or, pure culture fermentation products such as xanthan gum are all potentially useful in the invention. Chemically, all of these materials are salts of complex anionic polysaccharides.
  • Synthetic natural-based thickeners having application are cellulosic derivatives wherein the free hydroxyl groups on the linear anhydro-glucose polymers have been etherified or esterified to give a family of substances which dissolve in water and give viscous solutions.
  • This group of materials includes the alkyl and hydroxylalkylcelluloses, specifically methylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, hydroxybutylmethylcellulose, hydroxyethylcellulose, ethylhydroxyethylcellulose, hydroxypropylcellulose, and carboxymethylcellulose.
  • Another preferred group of thickeners include polyacrylates such as the proprietary Acusol thickeners, (e.g.
  • a polyacrylate thickener can be used at concentrations of up to about 3 wt % of the film former weight. Mixtures of thickening agents can also be employed where the total amount can be up to about 3 wt % depending on the thickeners used and the desired viscosity of the final product.
  • thickeners for this application include dextrin, cornstarch and hydrous magnesium silicates, such as sodium magnesium silicate sold under the trade name Laponite XLG (Southern Clay Products, Inc., Gonzales, Tex., USA).
  • the present invention may optionally include cross-linking agents.
  • Advantages of using cross-linking agents with the film-forming composition include influencing the mechanical film properties, such as tackiness and mechanical strength, as well as solubility of the coating.
  • cross-linked films yielded much more mechanically robust films.
  • cross-linking decreases tackiness and prevents soil and microorganisms from physically adhering to the polymer film, which may be desirable for certain applications.
  • cross-linking had a beneficial impact on release of the antimicrobial agent from the film. The degree of cross-linking is adjusted so to achieve the desired combination of properties.
  • Cross-linking agents suitable for use with polyvinyl alcohol and copolymers thereof include, but are not limited to: aldehydes (e.g. formaldehyde, glyoxal, glutaraldehyde), boric acid, sodium tetraborate, metal ions (e.g. ions of Zn, Fe, Al, Ni, V, Co, Cu, Zr, Ti, Mn), organometallic compounds (e.g. organic titanates such as DuPont Tyzor®, organic Cr(III) complexes such as DuPont Quilon®), siloxanes (e.g., tetraethoxysilane, polydimethylsiloxane), isocyanates (e.g.
  • aldehydes e.g. formaldehyde, glyoxal, glutaraldehyde
  • boric acid sodium tetraborate
  • metal ions e.g. ions of Zn, Fe, Al, Ni, V,
  • bi- and trivalent metal cations are preferred because they provide the formation of a coordinative linkage between the PVOH polymer chains upon film drying. This allows the cross-linker to be added to the film-forming liquid in a ‘one-pot’ mixture. Care must be taken to choose an adequate concentration in order to efficiently cross-link the polymer without precipitating other ingredients such as particulate rheology control agents.
  • cross-linking agent will be mixed with other ingredients using standard mixing techniques.
  • the cross-linking reaction can optionally be carried out in the presence of a catalyst, as is well known to those skilled in the art.
  • a catalyst as is well known to those skilled in the art.
  • aldehydes isocyanates, siloxanes, diglycidyl ether, and dicarboxylic acid
  • heat and an acid catalyst or metal catalyst can be used additionally.
  • the cross-linking agent concentration in the formulation can be zero to an upper limit which is either determined by the stability limit of the formulation where precipitation starts to occur, or the inability of the resulting film to be removed efficiently.
  • the preferred cross-linking agent concentration can depend strongly on the type of cross-linking agent used and is typically below 25 wt % of the polymer content, more preferably below 10 wt % of the polymer content.
  • plasticizing agent such as polyethylene glycol or glycerol.
  • plasticizers suitable for the invention include, but are not limited, to solvents, polyols, polyethylene glycols of and average molecular weight between 200 and 800 g/mole and sorbitol. PEG is preferred over glycerol since glycerol is easily metabolized by microorganisms potentially resulting in microbial growth.
  • a plastisizer generally also allows the film to retain a slightly tacky surface feel. As the plastisizer level increases, the resulting film will also exhibit an increasing degree of tackiness. Such tackiness can be desirable at low levels in order to capture airborne particles and soil or other materials. If plastisizer levels are too high, however, the coating becomes too tacky and will show low resistance to accidental mechanical removal, by wiping, for example.
  • the preferred plasticizer amount is from about 1.0 wt % to about 20 wt % of the weight of the film former, and more preferably from about 5 wt % to about 8 wt %.
  • composition of the present invention can also comprise one or more performance enhancing additives, “performance enhancers”.
  • performance enhancers include flash rust inhibitors, which include any of a number of organic or inorganic materials used in a water-based system to prevent rust from forming on contact with the material and bare metal.
  • flash rust inhibitors include any of a number of organic or inorganic materials used in a water-based system to prevent rust from forming on contact with the material and bare metal.
  • flash rust inhibitors include any of a number of organic or inorganic materials used in a water-based system to prevent rust from forming on contact with the material and bare metal.
  • One example is sodium benzoate.
  • Another optional performance enhancing additive is one or more of an array of defoamers recommended for water-based systems, to prevent unwanted foaming of the product during application. Too much foam can disrupt the required continuous film formation of the product and result in product failure. It can also be advantageous to add a foam control product, to aid in mixing and processing the masking composition, such as Drewplus L475 from Ashland Chemical, Inc. Drew Industrial Division (Covington, Ky., USA).
  • Additional optional performance enhancing additives are antioxidants to increase the shelf life of the coating formulation.
  • One example is butylated hydroxytoluene.
  • Additional additives include fragrances.
  • Foaming agents can additionally be added to create gas bubbles in the applied coating.
  • Gas bubbles can function as an opacifying agent to facilitate the application and/or to allow for longer contact time with a surface e.g. by preventing dripping from an inclined surface and/or to reduce the amount of coating formulation needed to treat a certain surface area or volume.
  • Application indicators may also be added. Some of these are described above, but include pigments, dyes, fluorescent dyes or gas bubbles generated during application.
  • an optional performance-enhancing ingredient is an agent that provides a surface effect.
  • Such surface effects include no iron, easy to iron, shrinkage control, wrinkle free, permanent press, moisture control, softness, strength, anti-slip, antistatic, anti-snag, anti-pill, stain repellency, stain release, soil repellency, soil release, water repellency, oil repellency, odor control, antimicrobial, or sun protection,
  • the film or coating can be applied to the target surface or locus by any means, including pouring.
  • the film or coating is applied to achieve a continuous and/or homogenous layer on a target surface.
  • Coating systems routinely used for paints and coatings such as, but not limited to, brushes, rollers, paint pads, mats, sponges, combs, hand-operated pump dispensers, compressed air operated spray guns, airless spray guns, electric or electrostatic atomizers, backpack spray application equipment, clothes, papers, feathers, styluses, knives, and other applicator tools can be used for coating. If dipping is used as a method to apply the coating, no special equipment is required.
  • the coating can be applied by exhaustion, foam, flex-nip, nip, pad, kiss-roll, beck, skein, winch, liquid injection, overflow flood, roll, brush, roller, spray, dipping, immersion, and the like.
  • the coating can also be applied by use of the conventional beck dyeing procedure, continuous dyeing procedure or thread-line application.
  • the coating system may also be one more components, and may include a catalyst.
  • electrostatic sprayers can be used to coat the surface. Electrostatic sprayers impart energy to the aqueous coating composition via a high electrical potential. This energy serves to atomize and charge the aqueous coating composition, creating a spray of fine, charged particles. Electrostatic sprayers are readily available from suppliers such as Tae In Tech Co, South Korea and Spectrum, Houston, Tex., USA. Generally, the coating is allowed to set or dry for about greater than 5 minutes in order to form the film. However, the coating may be antimicrobially effective in a shorter time-frame, such as after 30 seconds. The coating may be removed before it is dried or anytime thereafter depending on the desired use. The drying time will be partially dependent on a number of factors, including environmental conditions such as humidity and temperature. The drying time will also depend on the thickness of the applied coating.
  • an airless spray guns can be used to coat the target surface.
  • Airless spray guns use high fluid pressures and special nozzles, rather than compressed air, to convey and atomize the liquid.
  • the liquid is supplied to an airless gun by a fluid pump at pressures typically ranging from 500 to 6500 psi.
  • the high velocity of the exiting paint propels the droplets toward the target surface.
  • the fluid nozzle on an airless gun differs substantially from the fluid nozzle on an air atomized gun. Selection of the proper nozzle determines how much paint is delivered and the fan pattern of application.
  • the size of the airless nozzle orifice determines the quantity of paint to be sprayed.
  • Airless fluid delivery is high, ranging from 700-2000 mL/min.
  • Recommended gun distance is 12 inches from the target, and depending upon the nozzle type, a fan pattern of 5 to 17 inches is possible.
  • nozzles can be selected for each application based on the size and shape of the target surface and the thickness of the coating to be applied.
  • Airless guns create little air turbulence that can repel the liquid from “hard to reach areas”, such as would be found in food processing equipment, hatcheries etc.
  • the high flow rate makes airless advantageous in cleaning and disinfecting situations, where the antimicrobial coating is to be applied over a large surface area and multiple surfaces.
  • the thickness of the applied and dried film will depend on a variety of factors. These factors include the concentration of the film forming agent, the concentration of rheology control additives and/or other additives, as well as the application temperature and humidity. Film thickness and film uniformity also depend, at least in part, on parameters of the application equipment, such as fluid delivery, spray orifice diameter, air pressure or piston pump pressure in the case of airless application, and the distance of the spray applicator to the target surface. Therefore, the liquid formulation may be adjusted to yield the desired film thickness.
  • the atomization of the coating solution is chosen such that a thin film is applied homogeneously to the target area.
  • the coating is allowed to set or dry for about 5 to about 60 minutes in order to form the film.
  • the present composition when applied onto a surface, will form a film or a coating by evaporation of the inert solvent.
  • the solvent evaporation could occur by allowing the coating to dry in place, or alternatively by blowing dry with heated or unheated air.
  • the coating may be effective as an antimicrobial agent in a shorter time-frame, such as after 30 seconds.
  • the coating may be removed before it is dried or anytime thereafter depending on the desired use.
  • the drying time will be partially dependent on a number of factors, including environmental conditions such as humidity and temperature. The drying time will also depend on the thickness of the applied coating.
  • the coating is preferably used at a thickness of about 0.3 to about 300 microns. In a more specific embodiment, the coating is used at a thickness of about 0.5 to about 100 microns. In an even more specific embodiment, the coating is used at a thickness of about 1.0 to about 30 microns.
  • the thickness of the film or coating applied onto the target surface influences the time needed for removal and the amount of biocide per unit area applied to the surface. Thicker films increase the time interval until the film has to be re-applied to maintain the desired antimicrobial properties. Thinner films will be easier and faster to remove by rinsing. It is thus important to apply the formulation in a fashion that results in a film thickness that allows both easy removal of the coating and long-lasting antimicrobial properties.
  • the film or coating has a thickness of about 0.3 to about 300 microns. In a more specific embodiment, the film or coating has a thickness of about 0.5 to about 100 microns. In an even more specific embodiment, the film or coating has a thickness of about 1.0 to about 30 microns.
  • This invention is directed to films that can be removed at a time determined appropriate by the user.
  • the time of removal can be determined by either (i) the desired minimum contact time to allow for the desired antimicrobial activity, typically expressed as amount of killed or inactivated microorganisms out of a starting population or (ii) the need or desire to take the coating off the surface before starting a subsequent operation or process step.
  • the coating can be removed at any time, such as after drying, the film thickness, concentration of antimicrobial agent, and specific use determines the appropriate time for removal. For instance the user may wish to put treated equipment back into normal operation after a period of operational shutdown. Fruit, for example, will require washing prior to eating.
  • the film Upon exhaustion of the biocide in the film, the film could be removed and a fresh coating layer could be applied.
  • drains can be treated periodically such as daily, weekly or biweekly.
  • Antimicrobial activity can be measured as early as after 30 seconds, hours, days, weeks, months, even years after application of the film. Therefore, timing of removing the coating is a function of the application for which the coating is employed.
  • Film removal can be achieved by dissolution or dispersion of the resulting coating. This can be achieved by the application an aqueous solution onto the coating. In one embodiment, the temperature of the solution is in the range of about 15 degrees Centigrade to about 100 degrees Centigrade. In another embodiment, the temperature of the solution is from about 30 to about 80 degrees Centigrade.
  • the application of the solution, or water can be achieved by a simple rinse or spray onto the surface. Coating removal can also be achieved by use of a pressure washer, facilitating removal by additional mechanical forces. Coating removal can also be achieved by washing with water together with a cloth or sponge.
  • mild additives can utilized or mixed with the aqueous solution to help solubilize or disperse the film-forming or water-dispersible agents, including commonly used acids or bases, chelators or detergents.
  • the film can be degraded, such as in a drain, by repeated washing of water and/or other components down the drain. The film can also be removed by peeling it off a surface, being abraded or brushed from the surface, or other mechanical mechanisms of removal.
  • removal also includes the removal by an automated or robotic system and the non-intentional removal by a liquid continuously or periodically contacting the coating over time, e.g. in a pipe or drain, or by continuous or periodical application of mechanical forces, such as wear.
  • An aqueous solution used for coating removal is any solution containing 60 to 100 wt-% water, the remaining components being dissolved components.
  • Dissolved components can include but are not limited to solvents such as alcohols, solubilizing agents, surfactants, salts, chelators, acids and bases.
  • Durable in this context relates to the dried coating matter remaining on the surface until its removal is purposely initiated or allowed to occur.
  • Use conditions are the environmental conditions prevalent during the period the coating remains on the target surface for the application areas of this invention and can include inadvertent contact with water of a temperature below 40 degrees Centigrade.
  • Continuous, or substantially continuous, in this context refers to a coating that covers the target surface without uncovered areas, coating defects, such as craters and holes.
  • Homogeneous, or substantially homogenous in this context refers to a coating with only negligible thickness variations across the coating surface. Coatings that are not homogeneous or not substantially homogenous will not provide even antimicrobial and removal properties across the whole surface the coating is applied to.
  • residual antimicrobial efficacy (or self-sanitizing properties) describes the property of coatings formed as described herein which remain active even after repeated challenges with microbes. According to this invention, at least a 3-log unit reduction is achieved after each inoculation over at least 2 inoculation cycles of at least 10 6 cells per square inch. The test method used to determine residual antimicrobial efficacy is described in Example 16.
  • the contact time would vary, as set out in Germicidal and Detergent Sanitizing Action of Disinfectants, Official Methods of Analysis of the Association of Official Analytical Chemists, paragraph 960.09 and applicable sections, 15th Edition, 1990 (EPA Guideline 91-2). If the intended application of the present invention is use as a sanitizer, then the composition should provide a 99.999% reduction (5-log order reduction) within 30 seconds at room temperature (25+/ ⁇ 2° C.) against several test organisms. On the other hand, if the intention is to use the invention as a disinfectant, then the composition should provide a 99.9% reduction (3-log order reduction) within 10 minutes. If the intended application is to be applied as a residual antimicrobial activity, then the present invention would be allowed to have greater than 10 minute contact time with microorganisms.
  • a physical barrier is defined as the film formed from the present film forming composition.
  • the resulting film seals the treated surface from contamination from the surrounding, such as soil, fat, dust, microorganisms etc. These contaminants will remain on the surface of the coating and will wash off at the time of removal of the coating.
  • PBS phosphate buffered saline solution (buffer)-10 ⁇ stock solution contains (g/800 mL): NaCl (80); KCl (2.0); NaH 2 PO 4 (14.4); KH 2 PO 4 (2.4) at pH 6.8
  • PVOH polyvinyl alcohol
  • UHMWPE ultra-high molecular-weight polyethylene
  • Laponite® was obtained from Rockwood Additives Ltd. (Widnes, UK).
  • Pseudomonas F-Agar was obtained from Fisher Scientific (Pittsburgh, Pa., USA); yeast extract, Brain Heart Infusion (BHI), Tryptic Soy Agar, Tryptic Soy Broth, and Oxford Medium Base were from Difco products (Becton Dickenson, Franklin Lakes, N.J., USA); dextrose and magnesium sulfate heptahydrate were from JT Baker (Phillipsburg, N.J., USA); Elvanol® (71-30 and 52-22), polyurethane (RCP 31374), Zonyl® surfactants and titanium dioxide were from DuPont (Wilmington, Del., USA).
  • Kollicoat®-IR was obtained from BASF (Ludwigshafen, Germany).
  • Silwet®L-77 was obtained from GE Silicones (Wilton, Conn., USA).
  • BYK® 425 was obtained from BYK Chemie (BYK-Chemie GmbH, Wesel, Germany).
  • DowCorning® Q2-5211 and Antifoam C were obtained from DowCorning® Silicones (Midland, Mich., USA).
  • Silsurf® A012 was obtained from Siltech Corp. (Toronto, ON, Canada).
  • Sil-co-sil® was obtained from U.S. Silica® Company (Berkeley Springs, W. Va., USA).
  • Ticaxan, Carrageenan, and Guar 8/22 were supplied by TIC Gums (Belcamps, Md., USA).
  • Alcogum® L1228, L15, L520 and L251 rheology additives were obtained from Alco Chemical® (Chattanooga, Tenn., USA) and were neutralized as specified by the supplier upon formulation after addition to antimicrobial compositions.
  • Viskalex® HV100 and HV30 were obtained from Ciba® (Basel, Switzerland).
  • Biocidal or antimicrobial efficacy in solutions can be determined by assays generally known in the art and as described in the following Examples.
  • ZOD zone-of diffusion
  • Stainless steel coupons (1 inch ⁇ 3 inch) were dipped into RAC formulations and allowed to dry completely overnight.
  • An overnight culture of Staphylococcus aureus ATCC 6358 was prepared by taking with a sterile inoculating loop a single colony from a refrigerated stock plate and inoculating into 25 mL of tryptic soy broth in a 250 mL sterile Erlenmeyer flask. The culture was incubated overnight at 30° C. while shaking at 150 RPM.
  • Fungal spores Aspergillus niger and Penicillium expansium ) were prepared by growing stock plates (malt extract agar) for 2 weeks at 25° C., and harvesting spores by flooding plates with 15 mL of filter-sterilized saline solution (0.85% NaCl plus 0.05% Triton X-100). Plates were then scraped with a sterile plastic cell scraper, the liquid was pipetted off, vortexed and filtered through 3-4 layers of sterile cheesecloth. Spore suspension CFU was determined by plating serial dilutions onto malt extract agar plates.
  • Coated coupons were placed on the surface of LB agar plates (center of plate) for 60 minutes, allowing soluble components of the coating to diffuse into the agar.
  • a soft agar (0.7 wt-% agar in PBS buffer or water) was prepared, aliquoted into 5 mL portions in sterile plastic centrifuge tubes and held at 50° C. in a water bath until use. After 60 minutes, the coupons were removed by lifting straight up with sterile forceps, taking care not to slide the coupons across surface of agar. Any coating pieces that are left on the surface of the agar were also removed with sterile forceps. Each soft agar tube is inoculated with 100 ⁇ L of a 1:10 dilution of the overnight bacterial culture prepared above.
  • the soft agar was inoculated with approximately 10 3 spores/mL when fungal spores were used in the test.
  • the agar was mixed gently by rocking tube and then agar was poured onto surface of LB agar plates which held coated coupons. Plates were swirled to completely cover surface with soft agar. The soft agar solidified almost immediately.
  • Bacterial inoculated plates were incubated overnight at 35° C. and fungal inoculated plates were incubated at 25° C. for 2 days. All plates were photographed to record the zone of inhibition provided by the antimicrobial that diffused from the antimicrobial coating into the agar.
  • ZOD zone of diffusion
  • rheological properties of liquid antimicrobial formulations was assessed using a rheometer, running ascending and descending flow curves.
  • the rheometer used was a Brookfield HADV-III+ (Brookfield Engineering, Middleboro, Mass., USA) with a couette geometry, small sample adapter, spindle SC4-21 and sample chamber 13RP. The temperature was kept at 25° C. with a thermostat bath. Samples were loaded by pouring or scooping into the Brookfield sample holder.
  • the program contained a pre-shear time of 5 min. at a pre-shear shear rate of 250 1/s, followed by a rest time of 10 min. Viscosity measurement were taken at: 0.1, 0.5, 5, 50, 100, 200, 100, 50, 5, 0.5, 0.1 RPM. The viscosity measurement interval was 2 min.
  • PVOH Polyvinyl alcohol
  • DuPont Elvanol® grade 71-30, MW approximately 94,000, degree of hydrolysis 99.0-99.8%; DuPont, Wilmington, Del., USA
  • PVOH stock solutions were prepared by mixing Elvanol® grade 71-30 powder into deionized water of 90° C. to yield a 3 to 8 wt % solution. The mixture was stirred using a magnetic bar stirrer for approximately 20 minutes until the polyvinyl alcohol was completely dissolved. The mixture was allowed to cool to room temperature.
  • Blend base solutions were prepared by mixing the polyvinyl alcohol stock solutions with varying amounts of benzalkonium chloride (QAC) as active biocide, poly(ethylene glycol) (PEG) of MW ⁇ 300 grams/mole as film plasticizer, polyoxyethylene sorbitan laurate surfactants as wetting agent(s), and butylated hydroxytoluene (BHT) as antioxidant.
  • QAC benzalkonium chloride
  • PEG poly(ethylene glycol)
  • BHT butylated hydroxytoluene
  • the QAC used was a mixture of mostly C12 and C14 analogues of alkylbenzyldimethyl-ammonium chloride (Sigma-Aldrich) but also contained small amounts of lower and higher analogues.
  • the blend base solution was then mixed with additional additives to yield the final spray formulation.
  • additives included cross-linkers such as ferric and ferrous chloride, rheology control modifiers such as synthetic layered silicate (Laponite®), and colorants and opacifying agents, such as food colorants and titanium dioxide.
  • cross-linkers such as ferric and ferrous chloride
  • rheology control modifiers such as synthetic layered silicate (Laponite®)
  • colorants and opacifying agents such as food colorants and titanium dioxide.
  • Liquid film-forming mixtures were prepared as outlined in Table 1. The mixtures are referenced in the subsequent examples by formulation number.
  • Films were prepared from the liquid mixtures outlined in Example 1. This was done by either spraying the liquids onto coupons (22 mm ⁇ 60 mm) or by dipping coupons into the solutions. To spray the liquids they were filled into standard pump-action spray bottles and sprayed onto coupons. In most cases stainless steel was used as the coupon material. When spraying was used coupons were oriented vertically to model vertical food equipment surfaces to be treated with an antimicrobial formulation. For both dipping and spraying, coupons were then allowed to dry in vertical orientation at room temperature for at least 2 hours, typically overnight. The thickness of some films was measured using confocal laser-scanning microscopy after adding trace amounts of a fluorescent dye (rhodamine 123) to the film forming composition. A Zeiss LM 510 confocal microscope with Zeiss LSM-5 image analysis software (Carl Zeiss MicroImaging, Thornwood, N.Y., USA) was used.
  • Formulations with 4.0 wt-% PVOH were found to have a thickness of approx. 20 micrometers. Lower PVOH concentrations yielded thinner films.
  • FIG. 2 shows cross sections of Formulation #2 through the depth of the film coating in two perpendicular planes.
  • High degree of uniformity in film thickness and absence of structural film defects can clearly be observed. High film uniformity is of high importance for protection functionality. Structural film defects or significant thickness variations could result in some areas remaining inefficiently protected from microbial contamination.
  • Dripping of the film-forming liquid from vertical surfaces after spraying could be prevented by addition of 0.5-1.5 wt % of colloidal synthetic layered silicate (Laponite® RD) as a thixotropic rheology control modifier.
  • colloidal synthetic layered silicate Lignonite® RD
  • the formulation can be adjusted to allow easy removal of the film over a wide range of water temperatures.
  • Film formulations can be developed to allow the film to be soluble in either cold or hot water temperatures.
  • films formed from Formulation #2 and #10 could easily be wiped off mechanically using a swab and could readily be dissolved after either a rinse of 20° C. or 98° C. water.
  • Films formed from Formulation #14a could easily be wiped off mechanically and dissolved easily in 98° C. water but did not readily dissolve in 20° C. water.
  • a cross-linker had to be added to the mixture.
  • Both Fe(II)-chloride and Fe(III)-chloride were suitable cross-linkers at concentrations between 0.1 and 1 wt % of the liquid formulation.
  • Two plastic cover slips (type Thermanox® #174942, 22 mm ⁇ 60 mm; Nalge Nunc International, Rochester, N.Y., USA) were dipped into a 4 wt % PVOH solution containing 1.0 g/L of benzalkonium chloride biocide. An additional two cover slips were dipped into a 4 wt % PVOH solution without benzalkonium chloride as control. The cover slips were placed into 50 mL centrifuge tubes and allowed to air-dry over night.
  • a culture of Listeria welshimeri was prepared by growing a single cell colony in 25 mL BHI (37 g/L) in a 125 mL capacity shaker flask and incubated overnight at 30 C while shaking at 150 RPM. The cell concentration of this overnight culture was approximately 1 ⁇ 09 cells per mL. The culture was diluted 100-fold with modified Welshimer's medium (see Table 2 for medium composition) to provide a cell concentration of approximately 1 ⁇ 10 7 cells/mL. The coupons were placed in 50 mL centrifuge tubes and the cell suspension (10 mL) added to the tubes. Due to the high cell concentration the cell suspension was completely opaque in the 50 mL tube. Tubes were loosely covered with caps and incubated at 22° C. while shaking at 150 RPM.
  • a culture of L. welshimeri (strain DUP-1074) was prepared by growing a single cell colony in 25 mL of BHI as outlined above. The cell concentration of this overnight culture was approx. 1 ⁇ 10 9 cells per mL. The culture was diluted ⁇ 10,000 with modified Welshimer's medium to provide a cell concentration of approximately 1 ⁇ 10 5 cells/mL. This cell suspension (25 mL) was added to each coupon in 50 mL centrifuge tubes and the tubes were horizontally placed into an incubator-shaker and shaken at 25° C. while shaking at 150 RPM.
  • a culture of Pseudomonas fluorescens was prepared from a single colony grown overnight in 25 mL of standard M9 medium (see Table 3) at 30° C. while shaking at 150 RPM. The overnight culture was then diluted 100-fold with a solution of diluted LB medium (1.0 part LB diluted with 9 parts deionized water and filter sterilized). The diluted culture in the LB medium (10 mL) was added to each centrifuge tube. Tubes were loosely covered with caps and incubated while shaking at 150 RPM at 30° C. on. The medium was replaced each day by 10 mL fresh diluted LB medium.
  • Table 4 outlines biofilm control properties of selected antimicrobial PVOH films challenged with P. fluorescens ( ⁇ 1 ⁇ 10 6 cells/mL) and daily change of medium. The growth of biofilms was delayed with all formulations. With Formulation #14a no biofilm was observed after 2 days. TABLE 3 M9 growth medium used Ingredient amount per (sterile solutions) liter Supplier 20% Glucose 2.5 mL J T Baker, Philipsburg, NJ, USA 10% Bacto TM 0.2 mL Difco, Sparks, yeast extract MD, USA 1.0 M MgSO 4 *7H 2 O 2 mL J T Baker, Philipsburg, NJ, USA 1.0 M CaCl 2 0.1 mL Sigma-Aldrich, St. Louis, MO, USA
  • FIG. 3 shows the weight fraction of QAC released from the films sprayed with Formulations #19, #20 and #21 over time. These three formulations differed only in the amount of the cross-linker added to the formulation.
  • the film thickness for the sprayed films was approximately 7.0 ⁇ m as determined by a micrometer gage.
  • the total QAC available in the film was calculated from the concentration in the liquid formulation and the film volume.
  • the semi-logarithmical graph shows the released fraction of QAC over time up to 7 days. A very fast initial release of QAC can be observed for all three film types.
  • the addition of iron salt to the formulation increases the amount of QAC released from the film. Adjusting the amount of cross-linker in the liquid formulation provides a means of controlling the release profile over time, allowing a controlled and sustained release of the antimicrobial agent.
  • aqueous solution 25 wt %) of benzalkonium chloride (QAC) was added to a 10 wt % aqueous solution of polyvinyl pyrrolidone (PVP K-120 in water; International Specialty Products, Wayne, N.J., USA) solution.
  • PVP K-120 polyvinyl pyrrolidone
  • the final concentration of PVP was 5 wt % and the final concentration of benzalkonium chloride was 1 wt %.
  • This PVP film-forming solution was used to treat coupons for prevention of biofilm formation.
  • L. welshimeri An overnight culture of L. welshimeri was grown from a single colony in 25 mL TSB/YE medium (Tryptic Soy Broth plus 0.6 wt % yeast extract) in a shaker flask (30° C. with shaking at 150 RPM) to a density of 1 ⁇ 10 9 cells per mL.
  • TSB/YE medium Tryptic Soy Broth plus 0.6 wt % yeast extract
  • welshimeri was diluted 1:100 in the modified Welshimer's medium (for example: for 20 tubes/coupons, 2 mL of overnight culture plus 200 mL of modified Welshimer's medium was required). A portion of this solution (10 mL) was added to each centrifuge tube. The tubes were covered loosely with caps and incubated at 22° C. on a shaker while shaking at 150 RPM. The medium was replaced every other day with fresh modified Welshimer's medium.
  • modified Welshimer's medium for example: for 20 tubes/coupons, 2 mL of overnight culture plus 200 mL of modified Welshimer's medium was required. A portion of this solution (10 mL) was added to each centrifuge tube. The tubes were covered loosely with caps and incubated at 22° C. on a shaker while shaking at 150 RPM. The medium was replaced every other day with fresh modified Welshimer's medium.
  • the L. welshimeri was grown on PVC (polyvinyl chloride) coupons (22 mm ⁇ 60 mm; Lid for Flexible Plate PVC coupons, Becton Dickenson) for a specified time (see Table 5) to form a biofilm.
  • PVC polyvinyl chloride
  • the coupon was treated with the PVP film-forming solution by coating 100 ⁇ L of the PVP film-forming solution onto each side of the coupon.
  • the PVP film was allowed to remain on the coupon for a specified treatment time.
  • each coupon was gently rinsed with sterile PBS to remove loosely adhering cells, and cell viability of the biofilm was determined as described below. Each treatment was carried out in duplicates.
  • the biofilm was removed from the coupons by scraping the coupons with a sterile object (for example, plastic, metal or wood). Both sides of the coupon were scraped and the film was re-suspended in 10 mL of PBS buffer. The suspension was mixed by vortexing to homogenize the cell suspension. Serial dilutions (1:10 in PBS buffer) of the cell suspensions were prepared, and 100 ⁇ L aliquots were spread onto Petri plates containing either the LB or the Modified Oxford Agar. The plates were incubated at 30-37° C. overnight, and colonies were counted the following day.
  • a sterile object for example, plastic, metal or wood
  • a film-forming solution of PVP K-120 and benzalkonium chloride was prepared such that the final concentration of PVP was 5 wt % and the final concentration of benzalkonium chloride was 0.01 wt %. This solution was used to treat biofilm coupons as described in Example 8.
  • the L. welshimeri biofilm was grown on PVC coupons as described in Example 8 for 2 days after which the biofilm coupon was treated with the PVP film-forming solution as described in Example 8.
  • the PVP film-forming solution was allowed to remain in contact with the biofilm for three hours.
  • the cell viability of the biofilm was determined as described in Example 8.
  • Each treatment was carried out in duplicate.
  • the PVP film with 0.01 wt % benzalkonium chloride yielded a 7.7 log reduction in CFU/mL.
  • Polyvinyl alcohol (PVOH) (MW 100,000, >99% hydrolyzed, Sigma Aldrich) was dissolved in water.
  • Sodium dichloroisocyanurate was added to this PVOH solution to achieve a final film-forming composition of 0.1 wt % sodium dichloroisocyanurate, 5 wt % PVOH, and the balance to 100% of DI water.
  • This composition was used to coat a PVC coupon which was covered by a 2 day old Listeria welshimeri biofilm (prepared as described in Example 8). Cell viability was determined as described in Example 8 after three hours of contact time.
  • the PVOH coating with sodium dichloroisocyanurate yielded a 7.3 log reduction in CFU per mL.
  • Polyurethane dispersion was synthesized as described in US2005/0215663 paragraphs 212 through 217 (see also paragraphs 154 through 187 for abbreviations). The preparation yielded a 30 wt % aqueous dispersion of polyurethane.
  • the polyurethane dispersion was diluted to 10 wt % with ethanol.
  • a polyurethane film-forming composition was prepared by adding aqueous benzalkonium chloride solution to the diluted polyurethane dispersion.
  • the final film-forming composition was 5 wt % polyurethane, 0.5 wt % benzalkonium chloride, 25 wt % ethanol and the balance to 100 wt % of Dl water.
  • the coating was applied to the surface of PVC coupons as described in Example 8, and the coupons were air dried and placed in sterile centrifuge tubes.
  • An culture of Pseudomonas aeruginosa was grown overnight from a single colony in 25 mL of M9 Medium in a shaker flask (30° C. while shaking at 150 RPM) to a density of 1 ⁇ 10 9 cells per mL.
  • the culture was then diluted 1:100 in 0.1 ⁇ LB medium (for example: for 20 tubes/coupons, 2 mL of overnight culture plus 200 mL of one-tenth strength LB medium was required). A portion of this solution (10 mL) was added to each centrifuge tube to partially immerse the coupon.
  • the tubes were covered loosely with caps and incubated at 30° C. for 24 hours while shaking at 150 RPM.
  • each coupon was gently rinsed with sterile PBS to remove loosely adhering cells, and cell viability of the biofilm was determined.
  • Each treatment was carried out in duplicates.
  • Formulation #91 had the following composition: Elvanol® grade 71-30 (5.0 wt %); benzalkonium chloride (0.63 wt %); Silwet L-77® (0.15 wt %); BYK®-425 (0.1 wt %); erythrosine B (0.05 wt %) and the balance to 100 wt % of DI water.
  • Pipe properties and penetration of coating formulation Pipe properties and coating results Pipe #1 Pipe #2 Inner diameter (mm) 51 71 Wall thickness (mm) 4 6 Length (mm) 800 700 Material PVC PVC Pipe orientation during spraying horizontal horizontal Penetration length to yield complete 390 430 coating on top half of pipe (mm) Penetration length to yield complete 700 550 coating on bottom half of pipe (mm) Penetration length to yield complete 700 320 coating in gaps between half-pipes (mm)
  • This example illustrates how rheology modifiers provide a removable antimicrobial coating composition with a shear thinning behavior. Such behavior enables easy (good sprayability), efficient (no drip) and effective (homogeneous antimicrobial activity) application of the composition to the surface. The example also illustrates that the antimicrobial efficacy can be fully retained after the addition of a rheology modifier.
  • compositions used in this examples are based on a solution of PVOH (5 wt %) in water and a selection of additives. Addition order and formulation methods (mixing, scale etc.) vary for specific formulations.
  • the formulation itself was used to assess the antimicrobial activity of the composition containing the rheology modifier by means of the zone-of-diffusion (ZOD) test described earlier using Staphylococcus aureus ATCC 6358. It was found that the tested rheology modifiers were either neutral or contributing positively to the antimicrobial activity of the coating.
  • ZOD zone-of-diffusion
  • composition in this example was obtained by adding benzalkonium chloride (0.6 wt %), Silwet® L-77 (0.15 wt %), BYK®425 (0.1 wt %) and erythrosine B (0.05 wt %) to a solution of PVOH (5 wt %, Elvanol® 71-30) in the balance to 100 wt % of DI water.
  • a second formulation step the rheology modifiers were added (see Table 7). TABLE 7 Rheological properties of rheology modifiers in a composition containing 5 wt % PVOH in DI water and antimicrobial activity according to the ZOD method using Staphylococcus aureus ATCC 6358.
  • rheology agents can be used to provide shear-thinning properties to the coating formulation based on polyvinyl alcohol grades of different degrees of hydrolysis.
  • the example also illustrates that the degree of shear thinning (viscosity ratio) can be adjusted by varying the level of rheology modifier added to the formulation.
  • the rheology agent used in this example is Alcogum® L251.
  • composition in this example was prepared by loading water (total of all ingredients 100 wt %) into a flask with magnetic stir bar, followed by Silwet® L-77 (0.1 wt %), benzalkonium chloride (0.05 wt %), PEG (M ⁇ 300) (0.2 wt %), Alcogum® L251 (various levels in Table 8), PVOH (5 wt %, Elvanol® 71-30 in water) and indigo carmine dye (0.03 wt %).
  • This example illustrates the use of coating formulations according to this invention to prevent fungi from growing on surfaces.
  • Fungal spores Aspergillus niger and Penicillium expansium ) were prepared by growing stock plates (malt extract agar) for 2 weeks at 25° C., and harvesting spores by flooding plates with 15 mL of filter-sterilized saline solution (0.85% NaCl plus 0.05% Triton® X-100). Plates were then scraped with a sterile plastic cell scraper and the liquid is pipetted off, vortexed and filtered through 3-4 layers of sterile cheesecloth. 400 microliters of the coating formulation was spread onto 1 inch ⁇ 1 inch stainless steel coupons with a sterile pipet tip.
  • the coating formulation #109 of this example consisted of 5 wt % Elvanol® 71-30, 0.2 wt % PEG (M ⁇ 300), 0.2 wt % benzalkonium chloride, 0.1 wt % Silwet® L-77, 0.05 wt % BYK®425, 0.01 wt % erythrosine B and the balance to 100 wt % of DI water.
  • the coating formulation #115 used for the negative control experiments was identical to formulation #109 except that no benzalkonium chloride was added.
  • Table 9 illustrates that no fungal growth was observed for coating formulation #109 whereas uncoated coupons or coupons coated with a coating formulation lacking the QAC active ingredient showed excessive growth of fungi.
  • TABLE 9 Fungistatic activity of antimicrobial coating #109 and control experiments QAC Inoculum Coated with conc. Fungal growth after week Fungal strain (spores/mL) formulation (ppm) 1 2 3 4 Aspergillus niger 10 6 #109 2000 ⁇ ⁇ ⁇ Aspergillus niger 10 6 #115 0 +++ +++ +++ +++ Aspergillus niger 10 6 No coating 0 +++ +++ +++ +++ P. expansium 10 6 #109 2000 ⁇ ⁇ ⁇ ⁇ P. expansium 10 6 #115 0 +++ +++ +++ +++ P. expansium 10 6 No coating 0 ++++ +++ +++ +++ ⁇ indicates that no fungal growth was observed. +++ indicates excessive fungal growth.
  • This example illustrates the use of coating formulations according to this invention to allow antimicrobial efficacy over extended periods of time.
  • the example also demonstrates continued antimicrobial efficacy after multiple reinoculations of the antimicrobial coating with microorganisms.
  • the example also demonstrates the residual antimicrobial efficacy of coatings formed from the formulation.
  • the example also illustrates that the antimicrobial coating is efficacious against Gram-positive ( Staphylococcus aureus ) and Gram-negative ( Klebsiella pneumoniae ) organisms.
  • Microorganisms tested included Staphylococcus aureus ATCC 6358 and Klebsiella pneumoniae ATCC 4352.
  • An overnight culture of the selected microorganism was prepared by taking a single colony from a refrigerated stock plate by loop and inoculating 25 mL of tryptic soy broth or other liquid medium in a 250 mL sterile plastic Erlenmeyer flask. The flask was incubated overnight at 30° C. while shaking at 150 RPM. Then, 0.4 mL of coating formulation was spread onto a 1 inch ⁇ 1 inch stainless steel (SS316) coupons with a sterile pipet tip.
  • SS316 1 inch ⁇ 1 inch stainless steel
  • the tubes were sonicated for 10 seconds and shaked for 10 minutes (200 RPM at 25° C.). These samples were then diluted serially and plated onto LB agar plates for colony forming unit (CFU) determination. Plates were incubated at 35° C. overnight and colonies were counted the following day. The remaining coupons were incubated at room temperature in a dessicator with the bottom filled with water. After one hour, the remaining coupons are all reinoculated with 10 microliters of diluted culture as above. After 5 minutes, two coupons for each formulation are removed and treated as above. The process is repeated after 2 and 3 hours after the first inoculation of the coupons.
  • CFU colony forming unit
  • the coating formulation #119 used in this example consisted of 5 wt % Elvanol® 71-30, 0.2 wt % PEG (MW ⁇ 300), 0.05 wt % benzalkonium chloride, 0.1 wt % Silwet® L-77, 0.01 wt % indigo carmine dye and the balance to 100 wt % of DI water.
  • Tables 10 and 11 show that no viable cells of the two organisms used were recovered for the coupons coated with formulation #119 whereas the more the 10 6 cells were recovered from the coupons coated with the identical formulation lacking the QAC. TABLE 10 Effect of multiple inoculations with Staphylococcus aureus (ATCC 6358) on the efficacy of coating formulation #119 Sample QAC conc.
  • This example illustrates the use of surfactants to achieve that the formulation spreads out into a film after application to a surface.
  • an organosilicone (Silwet®L-77) was used as the surfactant.
  • the formulations of this example consisted of 5 wt % polyvinyl alcohol (Elvanol® 52-22), 0.2 wt % PEG (MW ⁇ 300), 0.05 wt % benzalkonium chloride, varying concentrations of Silwet®L-77 between 0 and 1 wt % (see Table 12) and a balance to 100 wt % of DI water.
  • the surface tensions of the samples were measured at temperature of 26.3° C. using a Kruess K11 tensiometer (Kruess GmbH, Hamburg, Germany) using a wetted length of 40.2 mm.
  • a 100 ⁇ L droplet of each sample was pipetted onto clean test surfaces of stainless steel (SS316) and ultra-high-molecular weight polyethylene (UHMWPE). Both SS316 and UHMWPE are key materials of construction of industrial equipment, such as equipment used for food processing. After application of the droplets to the surfaces the droplets were allowed to spread for 5 minutes. Digital photographs of the test surfaces were taken and the covered spreading area of the droplets on the test surfaces was measured by image analysis (ImageJ Software, version 1.36b, National Institute of Health, USA). The droplets' spreading area was used as a measure of the spreading efficacy of each formulation. Table 12 reports the results for two surface materials and the formulations tested.
  • This example illustrates the use of small gas bubbles in the antimicrobial coating as a temporary opacifying agent.
  • a permanent color of the coating For some of the intended uses of this invention it is not always desired to have a permanent color of the coating.
  • a colored or opaque coating could be considered unaesthetic and a transparent antimicrobial coating may be preferred instead.
  • Leaving out a permanent colorant or opacifying agent has the disadvantage that the operator applying the coating does not obtain feedback on what parts of the surface to be coated have already been covered.
  • the following embodiment of this invention can be applied.
  • At least one foaming agent can be added to create small gas bubbles in the film that is created on the target surface.
  • the gas bubbles act as an opacifying agent and turn the freshly applied film white.
  • at least one antifoaming agent is also added to the formulation. The antifoaming agent aids the breakdown of the gas bubbles while the film is still wet to yield a transparent coating after drying.
  • the formulation #134 used in this example consisted of 7 wt % Elvanol® 52-22, 0.2 wt % PEG (MW ⁇ 300), 0.05 wt % benzalkonium chloride, 0.2 wt % Silwet® L-77, and the balance to 100 wt % of DI water.
  • the formulation #134a used in this example was identical to formulation #134 except that it contained 120 ppm active ingredient of Antifoam C emulsion in the formulation.
  • the surfactants benzalkonium chloride and Silwet® L-77 caused both of the above formulations to foam and gas bubbles (>1,000,000 per square meter) were visible in the film obtained directly after spraying of the formulations on a surface using an high-volume/low-pressure (HVLP) spray gun (Devilbiss GTI spray gun; air cap #2000; 1.5 mm fluid tip; E.I. DuPont Company spray booth, Room 112, 377 Fairall Street, Ajax, ON, Canada.)
  • HVLP high-volume/low-pressure
  • the spray conditions were as follows: 2-3 coat application totaling 5-20 microns film at 5° C.-25° C., 30-60% relative humidity). Bubbles were counted visually using 4 inch ⁇ 4 inch square and are reported as bubbles per square meter.
  • the antimicrobial efficacy was measured by the zone-of-diffusion (ZOD) method using Staphylococcus aureus ATCC 6358.
  • ZOD zone-of-diffusion
  • the composition of coating formulation #134 is described in Example 18. Thicker films result in a larger zone-of diffusion and thus improved biocidal properties of the coating.
  • TABLE 14 Antimicrobial efficacy as a function of coating thickness for formulation #134.
  • Antimicobial efficacy was determined by zone of diffusion method using Staphylococcus aureus ATCC 6358.
  • Coating thickness Antimicrobial efficacy (ZOD) micrometers
  • coupon areas 8 1.89 12 2.12 15 2.33

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • General Health & Medical Sciences (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Plant Pathology (AREA)
  • Animal Behavior & Ethology (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Medicinal Chemistry (AREA)
  • Epidemiology (AREA)
  • Zoology (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Agronomy & Crop Science (AREA)
  • Dentistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Environmental Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Food Science & Technology (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Floor Finish (AREA)
US11/710,290 2006-02-23 2007-02-23 Removable antimicrobial coating compositions and methods of use Abandoned US20080026026A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US11/710,290 US20080026026A1 (en) 2006-02-23 2007-02-23 Removable antimicrobial coating compositions and methods of use
US15/095,450 US20160286796A1 (en) 2006-02-23 2016-04-11 Removable coating composition

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US77608106P 2006-02-23 2006-02-23
US83198306P 2006-07-19 2006-07-19
US11/710,290 US20080026026A1 (en) 2006-02-23 2007-02-23 Removable antimicrobial coating compositions and methods of use

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US15/095,450 Continuation US20160286796A1 (en) 2006-02-23 2016-04-11 Removable coating composition

Publications (1)

Publication Number Publication Date
US20080026026A1 true US20080026026A1 (en) 2008-01-31

Family

ID=38326198

Family Applications (3)

Application Number Title Priority Date Filing Date
US11/710,290 Abandoned US20080026026A1 (en) 2006-02-23 2007-02-23 Removable antimicrobial coating compositions and methods of use
US11/710,325 Expired - Fee Related US9668476B2 (en) 2006-02-23 2007-02-23 Removable antimicrobial coating compositions and methods of use
US15/095,450 Abandoned US20160286796A1 (en) 2006-02-23 2016-04-11 Removable coating composition

Family Applications After (2)

Application Number Title Priority Date Filing Date
US11/710,325 Expired - Fee Related US9668476B2 (en) 2006-02-23 2007-02-23 Removable antimicrobial coating compositions and methods of use
US15/095,450 Abandoned US20160286796A1 (en) 2006-02-23 2016-04-11 Removable coating composition

Country Status (7)

Country Link
US (3) US20080026026A1 (https=)
EP (1) EP1987106A2 (https=)
JP (1) JP5478074B2 (https=)
CN (1) CN103992676B (https=)
AU (1) AU2007221203B2 (https=)
CA (1) CA2635932C (https=)
WO (1) WO2007100653A2 (https=)

Cited By (48)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040143992A1 (en) * 2002-11-26 2004-07-29 Do Gi Hyeong Laundry drier control method
US20040166102A1 (en) * 2000-06-09 2004-08-26 Darouiche Rabih O. Combination of antimicrobial agents and bacterial interference to coat medical devices
US20070042924A1 (en) * 2005-04-29 2007-02-22 Dicosimo Robert Enzymatic production of peracids using perhydrolytic enzymes
US20070275101A1 (en) * 2006-02-23 2007-11-29 Lu Helen S Removable antimicrobial coating compositions and methods of use
US20090130157A1 (en) * 2005-12-14 2009-05-21 Ylitalo Caroline M Antimicrobial Adhesive Films
US20090155451A1 (en) * 2005-12-14 2009-06-18 Ylitalo Caroline M Antimicrobial coating system
US20100137472A1 (en) * 2008-12-01 2010-06-03 Becton, Dickinson And Company Antimicrobial coating compositions
US20100186674A1 (en) * 2009-01-26 2010-07-29 E. I. Du Pont De Nemours And Company Methods and compositions for treating fertilized avian eggs
US20100240799A1 (en) * 2007-06-13 2010-09-23 3M Innovative Properties Company Antimicrobial film-forming composition, antimicrobial film, and method of verifying the presence of an antimicrobial film
US20100286016A1 (en) * 2010-04-01 2010-11-11 KLC Brands, Inc. Non-V.O.C. sprayable gel to remove insect bodies-environmentally friendly
WO2011009083A1 (en) * 2009-07-17 2011-01-20 Carefusion 2200, Inc. Particles incorporating antimicrobial agents
WO2011017095A2 (en) 2009-07-27 2011-02-10 E. I. Du Pont De Nemours And Company Enzymatic in situ preparation of peracid-based removable antimicrobial coating compositions and methods of use
WO2011017097A1 (en) 2009-07-27 2011-02-10 E. I. Du Pont De Nemours And Company Removable antimicrobial coating compositions containing cationic rheology agent and methods of use
WO2011017090A1 (en) 2009-07-27 2011-02-10 E. I. Du Pont De Nemours And Company Removable antimicrobial coating compositions containing acid-activated rheology agent and methods of use
US20110081207A1 (en) * 2009-10-01 2011-04-07 Teledyne Scientific & Imaging, Llc System for mitigating marine bio-fouling of an underwater structure
US20110177148A1 (en) * 2009-07-27 2011-07-21 E. I. Du Pont De Nemours And Company Enzymatic in situ preparation of peracid-based removable antimicrobial coating compositions and methods of use
US20110206817A1 (en) * 2010-02-25 2011-08-25 Polyprotectechnologies Inc. Anti-microbial coated devices and methods for making same
US8309626B2 (en) 2010-07-13 2012-11-13 Rohm And Haas Company Microbiocidal coatings
WO2013101498A1 (en) * 2011-12-27 2013-07-04 3M Innovative Properties Company Burnishing methods and compositions
US20130310764A1 (en) * 2012-05-15 2013-11-21 Becton, Dickinson And Company Blood control iv catheter with antimicrobial properties
US8821455B2 (en) 2009-07-09 2014-09-02 Becton, Dickinson And Company Antimicrobial coating for dermally invasive devices
US20150359945A1 (en) * 2013-01-15 2015-12-17 Board Of Regents, The University Of Texas System Antimicrobial coatings
US9327095B2 (en) 2013-03-11 2016-05-03 Becton, Dickinson And Company Blood control catheter with antimicrobial needle lube
WO2016196112A1 (en) * 2015-05-29 2016-12-08 Zebrasci, Inc. Biopolymer-based emulsion lubricants for syringe barrels
US9579486B2 (en) 2012-08-22 2017-02-28 Becton, Dickinson And Company Blood control IV catheter with antimicrobial properties
US9670434B2 (en) 2012-09-13 2017-06-06 Ecolab Usa Inc. Detergent composition comprising phosphinosuccinic acid adducts and methods of use
US9675793B2 (en) 2014-04-23 2017-06-13 Becton, Dickinson And Company Catheter tubing with extraluminal antimicrobial coating
US9695323B2 (en) 2013-02-13 2017-07-04 Becton, Dickinson And Company UV curable solventless antimicrobial compositions
US9750928B2 (en) 2013-02-13 2017-09-05 Becton, Dickinson And Company Blood control IV catheter with stationary septum activator
US9752105B2 (en) 2012-09-13 2017-09-05 Ecolab Usa Inc. Two step method of cleaning, sanitizing, and rinsing a surface
US9750927B2 (en) 2013-03-11 2017-09-05 Becton, Dickinson And Company Blood control catheter with antimicrobial needle lube
US9789279B2 (en) 2014-04-23 2017-10-17 Becton, Dickinson And Company Antimicrobial obturator for use with vascular access devices
US9994799B2 (en) 2012-09-13 2018-06-12 Ecolab Usa Inc. Hard surface cleaning compositions comprising phosphinosuccinic acid adducts and methods of use
US10064273B2 (en) 2015-10-20 2018-08-28 MR Label Company Antimicrobial copper sheet overlays and related methods for making and using
US10093811B2 (en) 2016-07-11 2018-10-09 Spartan Chemical Company, Inc. Antimicrobial sacrificial floor coating systems
US10232088B2 (en) 2014-07-08 2019-03-19 Becton, Dickinson And Company Antimicrobial coating forming kink resistant feature on a vascular access device
US10376686B2 (en) 2014-04-23 2019-08-13 Becton, Dickinson And Company Antimicrobial caps for medical connectors
US10493244B2 (en) 2015-10-28 2019-12-03 Becton, Dickinson And Company Extension tubing strain relief
EP3546529A4 (en) * 2017-10-23 2020-01-29 LG Chem, Ltd. ANTIBACTERIAL POLYMER COATING COMPOSITION AND ANTIBACTERIAL POLYMER FILM
US10609933B2 (en) 2015-03-13 2020-04-07 Gea Food Solutions Bakel B.V. Method for cleaning and storing of a mould drum
US10759949B2 (en) 2016-07-11 2020-09-01 Spartan Chemical Company, Inc. Antimicrobial sacrificial floor coating systems
US10834922B2 (en) 2014-11-26 2020-11-17 Microban Products Company Surface disinfectant with residual biocidal property
US10842147B2 (en) 2014-11-26 2020-11-24 Microban Products Company Surface disinfectant with residual biocidal property
US10925281B2 (en) 2014-11-26 2021-02-23 Microban Products Company Surface disinfectant with residual biocidal property
US11033023B2 (en) 2014-11-26 2021-06-15 Microban Products Company Surface disinfectant with residual biocidal property
US11122806B2 (en) 2018-10-19 2021-09-21 Gold Bond Building Products, Llc Antimicrobial coating for building panel
US11503824B2 (en) 2016-05-23 2022-11-22 Microban Products Company Touch screen cleaning and protectant composition
US11865219B2 (en) 2013-04-15 2024-01-09 Ecolab Usa Inc. Peroxycarboxylic acid based sanitizing rinse additives for use in ware washing

Families Citing this family (71)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITMI20030643A1 (it) 2003-04-01 2004-10-02 Copan Innovation Ltd Tampone per il prelievo di campioni biologici
US8846154B2 (en) 2005-06-07 2014-09-30 S.C. Johnson & Son, Inc. Carpet décor and setting solution compositions
AU2007221030B2 (en) 2006-02-28 2013-02-14 Cellular Bioengineering, Inc. Polymer composition and method for removing contaminates from a substrate
CN101815435A (zh) * 2007-06-19 2010-08-25 细胞生物工程有限公司 处理微生物和/或传染原的方法
EP2162498B1 (en) * 2007-06-19 2011-04-13 Cellular Bioengineering, Inc. Method for protecting substrates and removing contaminants from such substrates
US9101131B2 (en) 2007-12-03 2015-08-11 Valent U.S.A., Corporation Seed treatment formulations
WO2009073164A1 (en) * 2007-12-03 2009-06-11 Valent U.S.A. Corporation Seed treatment formulations and methods of use
US20100003198A1 (en) * 2008-07-07 2010-01-07 Patrick John Stolmeier Antimicrobial Topical and Other Preparations Containing Fluorescent or Illumination Dye and Tracer Agents or Compounds
BRPI0921629A2 (pt) * 2008-10-31 2016-01-05 Dsm Ip Assets Bv composição de revestimento anti-incrustação compreendendo nanopartículas
WO2010078413A1 (en) 2008-12-31 2010-07-08 Apinee, Inc. Preservation of wood, compositions and methods thereof
GB0901966D0 (en) * 2009-02-05 2009-03-11 Danisco Composition
US8685476B2 (en) * 2009-03-19 2014-04-01 Mark L. Folkman Polysiloxane (silicone) treatment composition for suppression of mold and spoilage on animal feed and forage, and methods of using same
US20100239718A1 (en) * 2009-03-19 2010-09-23 Folkman Mark L Use of polydimethylsiloxane and/or siloxane (silicone) derived chemical compounds in the suppression of mold and spoilage on harvested forages
US20110177145A1 (en) * 2009-07-27 2011-07-21 E.I. Du Pont De Nemours And Company In situ preparation of peracid-based removable antimicrobial coating compositions and methods of use
CA2800901C (en) * 2009-07-31 2015-03-17 Mark L. Folkman Polysiloxane (silicone) treatment composition for suppression of mold and spoilage on animal feed and forage, and methods of using same
EP2332587A1 (de) * 2009-12-12 2011-06-15 Bayer MaterialScience AG Polyurethan-Dispersionen zur Versiegelung von Zitzen der Milchdrüse bei milchliefernden Tieren
IT1401447B1 (it) 2010-06-09 2013-07-26 Copan Italia Spa Metodo per il trasferimento quantitativo di analiti
KR101135006B1 (ko) 2010-07-23 2012-04-09 이명오 황토분말과 황마분말을 주요성분으로 함유하는 도료조성물
IT1403618B1 (it) * 2011-01-05 2013-10-31 Copan Italia Spa Procedimento per realizzare un dispositivo per il prelievo ed il trasferimento di campioni per biologia molecolare
US9528009B2 (en) 2011-04-15 2016-12-27 Craig Grossman Composition and method to form a self decontaminating surface
KR102008121B1 (ko) 2011-04-15 2019-08-06 얼라이드 바이오사이언스, 인크. 자가 오염제거 표면의 형성을 위한 조성물 및 방법
US11166458B2 (en) 2011-04-15 2021-11-09 Allied Bioscience, Inc. Wet wipes comprising antimicrobial coating compositions
US9878464B1 (en) 2011-06-30 2018-01-30 Apinee, Inc. Preservation of cellulosic materials, compositions and methods thereof
US9757603B2 (en) 2011-08-11 2017-09-12 Cbi Polymers, Inc. Polymer composition
JP2013177584A (ja) * 2012-02-07 2013-09-09 Nippon Soda Co Ltd 拭き取り可能な油汚れ防止用被覆剤
US20130255061A1 (en) * 2012-04-03 2013-10-03 Becton, Dickinson And Company Systems and methods for applying a novel antimicrobial coating material to a medical device
ITMI20121603A1 (it) 2012-09-25 2014-03-26 Copan Italia Spa Dispositivo e metodo per il prelievo ed il trasferimento di campioni di materiale biologico
US20140206767A1 (en) * 2013-01-22 2014-07-24 Miraculum Applications AB Product for mold prevention and treatment
US9532568B2 (en) 2013-01-22 2017-01-03 Miraculum, Inc. Product for mold prevention and treatment
US9353269B2 (en) * 2013-03-15 2016-05-31 American Sterilizer Company Reactive surface coating having chemical decontamination and biocidal properties
US11011283B2 (en) 2013-03-15 2021-05-18 General Cable Technologies Corporation Easy clean cable
JP6168691B2 (ja) * 2013-08-01 2017-07-26 日本曹達株式会社 拭き取り可能な油汚れ防止用被覆剤
US9474282B2 (en) 2013-12-13 2016-10-25 Tony John Hall Acid-solubilized copper-ammonium complexes and copper-zinc-ammonium complexes, compositions, preparations, methods, and uses
WO2015112195A1 (en) * 2014-01-22 2015-07-30 Miraculum Applications AB Product for mold prevention and treatment
WO2016093792A1 (en) * 2014-12-08 2016-06-16 General Cable Technologies Corporation Cables having an antimicrobial coating
CN104403459A (zh) * 2014-12-19 2015-03-11 常熟市方塔涂料化工有限公司 一种防水抗菌涂料
CA2987770C (en) 2015-06-08 2024-02-20 Myco Sciences Limited Antimicrobial and agrochemical compositions
US10555889B2 (en) 2015-07-01 2020-02-11 3M Innovative Properties Company Compositions for spore removal
CN105568771A (zh) * 2015-12-24 2016-05-11 浙江华川实业集团有限公司 一种抗菌能力强医用包装原纸及其制备方法
CN105780592B (zh) * 2016-03-18 2018-03-20 江苏金恒新型包装材料有限公司 一种用于香烟包装的哑光镭射材料的生产工艺
CN105780597B (zh) * 2016-03-18 2017-11-24 江苏金恒新型包装材料有限公司 一种用于食品包装的哑光镭射材料及其生产工艺
DE102017105970A1 (de) * 2017-03-20 2018-09-20 m-u-t GmbH Verfahren zur Reinigung einer Innenwandung eines Schlauches
IL304085B2 (en) * 2018-04-27 2025-09-01 Fresh Inset S A Preparations and articles containing complexes of 1-methylcyclopropane and alpha-cyclodextrin
IT201800006780A1 (it) * 2018-06-28 2019-12-28 Film polimerico amovibile e suo utilizzo in campo calzaturiero e nella lavorazione del pellame
JP7248234B2 (ja) * 2018-12-25 2023-03-29 ダイナガ株式会社 木材防護塗料の製造方法
US10995011B2 (en) * 2019-01-17 2021-05-04 Nano Sono Cooperation Ltd. Compositions of metal oxide semiconductor nanomaterials
US11730824B2 (en) 2019-01-17 2023-08-22 Nsc Nano Sono Cooperation Ltd. Drug-releasing compositions of metal oxide semiconductor nanomaterials and hemostatic polymers
US10998467B2 (en) * 2019-09-25 2021-05-04 Nano Sono Cooperation Ltd. Compositions of metal oxide semiconductor nanomaterials and hemostatic polymers
EP3962662B1 (en) * 2019-04-29 2025-08-27 Kiinns Foodtech Ltd. In situ liner production system and method
US12134709B2 (en) * 2019-07-09 2024-11-05 The Boeing Company Coatings for sterilization with UV light
RU2714240C1 (ru) * 2019-07-11 2020-02-13 Михаил Леонидович Галкин Способ хранения свежего охлажденного мяса свинины в постоянном магнитном поле
EP4099826A1 (en) 2020-02-03 2022-12-14 Fresh Inset S.A. Stable 1-methylcyclopropene compositions and uses thereof
US20210278343A1 (en) * 2020-03-06 2021-09-09 Mshield Holdings Inc. Tracking application coverage and degradation of antimicrobial chemical compositions
BR102020007311A2 (pt) * 2020-04-13 2021-02-17 Hermes Paulo De Amorim Filho composição para obtenção película de revestimento antiviral e antimicrobiana, a base de água
JP7515160B2 (ja) * 2020-06-30 2024-07-12 ウェトラブホールディング株式会社 抗菌性組成物
PE20231188A1 (es) 2020-08-26 2023-08-15 Ecolab Usa Inc Metodos y composiciones para procesar minerales de sulfuro
CN113712028A (zh) * 2020-10-21 2021-11-30 南京百思福医药科技有限公司 一种光致发光长效成膜消毒组合物及其制备方法与应用
BR102020024967A2 (pt) * 2020-12-07 2022-06-21 União Brasileira De Educação E Assistência - Mantenedora Da Pucrs Composição antimicrobiana para uso tópico e/ou externo
AU2022272311A1 (en) * 2021-05-12 2023-11-30 Cargill, Incorporated Method and system for contamination intervention
EP4337728A1 (en) * 2021-05-12 2024-03-20 Ludwig-Maximilians-Universität München Compositions and methods of reducing aggregation of molecules
WO2023012809A1 (en) * 2021-08-05 2023-02-09 Prerna Goradia A surface disinfectant formulation
US11969121B2 (en) * 2021-11-22 2024-04-30 Patricia Weeks Cookware lid and utensil holder device
US12217468B2 (en) * 2022-03-09 2025-02-04 The Boeing Company Systems and methods for sanitizing surfaces and devices and methods for detecting an antimicrobial coating
CN116213221A (zh) * 2022-12-21 2023-06-06 安徽同曦高科新材料股份有限公司 一种抗菌抗病毒不锈钢静电粉末喷涂工艺
CN116285455B (zh) * 2023-03-24 2024-04-23 广州卡帝斯科技有限公司 一种具有抑菌功能的汽车扶手箱储物盒及其制备工艺
WO2024249341A1 (en) * 2023-05-26 2024-12-05 Nabaco Inc. Sheen control of coated produce
CN121240779A (zh) * 2023-05-26 2025-12-30 纳巴科公司 改善的农产品阻隔涂层
CN117026674B (zh) * 2023-08-02 2026-02-10 中山大学 基于生物材料的高分子聚合物纸张涂层制备方法及系统
WO2025120351A1 (en) * 2023-12-05 2025-06-12 Rabdan Academy Water-based disinfectant formulation and process for preparation of said formulation
WO2025171191A1 (en) * 2024-02-06 2025-08-14 Nabaco Inc. Barrier coating for produce with better fungicide delivery and efficacy
CN117844561B (zh) * 2024-03-07 2024-05-17 感控卫士(山东)医疗科技有限公司 一种水溶性润滑防锈剂及其制备方法

Citations (53)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3264272A (en) * 1961-08-31 1966-08-02 Du Pont Ionic hydrocarbon polymers
US3657175A (en) * 1969-06-26 1972-04-18 Standard Brands Chem Ind Inc Carboxylic acid latices providing unique thickening and dispersing agents
US3993777A (en) * 1975-08-12 1976-11-23 Bio-Lab, Inc. Aqueous compositions to aid in the prevention of bovine mastitis
US4115292A (en) * 1977-04-20 1978-09-19 The Procter & Gamble Company Enzyme-containing detergent articles
US4384096A (en) * 1979-08-27 1983-05-17 The Dow Chemical Company Liquid emulsion polymers useful as pH responsive thickeners for aqueous systems
US4567221A (en) * 1983-03-31 1986-01-28 Kuraray Co., Ltd. Water resistant compositions
US4600761A (en) * 1985-04-04 1986-07-15 Alco Chemical Corporation Acrylic emulsion copolymers for thickening aqueous systems and copolymerizable surfactant monomers for use therein
US4743698A (en) * 1985-10-01 1988-05-10 Alco Chemical Corp. Acrylic emulsion copolymers for thickening aqueous systems and copolymerizable surfactant monomers for use therein
US4783340A (en) * 1987-04-29 1988-11-08 Ecolab Inc. Two-package co-sprayable film-forming sanitizer
US4792343A (en) * 1985-08-12 1988-12-20 Allied Colloids Limited Dispersing agents
USRE33156E (en) * 1984-08-23 1990-01-30 Desoto, Inc. Alkali soluble latex thickeners
US5017369A (en) * 1987-03-03 1991-05-21 Marhevka Virginia C Film-forming teat sealer for prevention of mastitis and use thereof
US5102936A (en) * 1989-10-21 1992-04-07 Hoechst Ag Copolymers based on ethylenically unsaturated monomers and containing urethane groups, processes for their preparation and their use
US5234974A (en) * 1990-07-26 1993-08-10 S. C. Johnson & Son, Inc. Alkali-soluble hydrophilic polymer coatings
US5294692A (en) * 1993-06-30 1994-03-15 National Starch And Chemical Investment Holding Corporation Associative monomers and polymers
US5398846A (en) * 1993-08-20 1995-03-21 S. C. Johnson & Son, Inc. Assembly for simultaneous dispensing of multiple fluids
US5585407A (en) * 1995-07-13 1996-12-17 Minnesota Mining And Manufacturing Company Water-based coatable compositions comprising reaction products of acrylic emulsion polymers with organoalkoxysilanes
US5604282A (en) * 1994-12-06 1997-02-18 Groco Specialty Coatings Company Strippable film coating composition
US5624634A (en) * 1991-10-17 1997-04-29 Solvay Interox Limited Peracid compositions for medical disinfection
US5817325A (en) * 1996-10-28 1998-10-06 Biopolymerix, Inc. Contact-killing antimicrobial devices
US5874164A (en) * 1988-03-14 1999-02-23 Nextec Applications, Inc. Barrier webs having bioactive surfaces
US5888501A (en) * 1994-07-26 1999-03-30 Auburn University Induced systemic resistance of plants to pathogenic microorganisms
US5990233A (en) * 1996-08-16 1999-11-23 National Starch And Chemical Investment Holding Corporation Rheology modifiers for use in aqueous compositions
WO1999060085A1 (en) * 1998-05-20 1999-11-25 Rhodia Inc. Liquid hard surface cleaner rinse
US6136776A (en) * 1997-04-01 2000-10-24 Dickler Chemical Laboratories, Inc. Germicidal detergent packet
US6228354B1 (en) * 1999-07-02 2001-05-08 Allegiance Corporation Water resistant film-forming antimicrobial skin-preparation
US6306810B1 (en) * 1998-08-12 2001-10-23 Reckitt Benckiser Inc. Hard surface cleaning and disinfecting compositions comprising fluorosurfactants
US6365169B1 (en) * 1999-09-30 2002-04-02 Solomon Rosenblatt Polymeric broad spectrum antimicrobial coatings
US6391840B1 (en) * 1999-04-12 2002-05-21 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Multiple component bleaching compositions
US20020086936A1 (en) * 2000-12-28 2002-07-04 Eoga Anthony B. Anti soiling coating composition and process for use thereof
US6437009B1 (en) * 2001-03-29 2002-08-20 Air Products And Chemicals, Inc. Low foam n-alkyltartarimide and n-alkylmalimide wetting agents
US20020185199A1 (en) * 2001-04-30 2002-12-12 Myers Frederick A. Antimicrobial coated metal sheet
US20030158459A1 (en) * 1998-06-30 2003-08-21 Tucker Mark D. Enhanced formulations for neutraliztion of chemical, biological and industrial toxants
US20030203991A1 (en) * 2002-04-30 2003-10-30 Hydromer, Inc. Coating composition for multiple hydrophilic applications
US6683036B2 (en) * 2000-07-19 2004-01-27 The Procter & Gamble Company Cleaning composition
US20040018787A1 (en) * 1996-08-07 2004-01-29 Hi-Tex, Inc. Treated textile fabric
US6749869B1 (en) * 1997-09-26 2004-06-15 Ecolab Acidic aqueous chlorite teat dip providing shelf life, sanitizing capacity and tissue protection
US20050008526A1 (en) * 2003-07-08 2005-01-13 The Procter & Gamble Company Liquid activator composition
US20050014427A1 (en) * 2003-07-17 2005-01-20 Nhk Teleflex Morse Co., Ltd. Shift operation apparatus for outboard motor, electronic remote control apparatus for medium-sized boat, and engine control apparatus
US20050064176A1 (en) * 2001-12-03 2005-03-24 Terry Richard N. Microbe-resistant medical device, microbe-resistant polymeric coating and methods for producing same
US20050139608A1 (en) * 2002-08-16 2005-06-30 Hans-Georg Muehlhausen Dispenser bottle for at least two active fluids
US20050175568A1 (en) * 2004-02-10 2005-08-11 The Procter & Gamble Company Conditioning compositions comprising hydrophobically modified crosslinked cationic thickening polymers
US6939554B2 (en) * 2002-02-05 2005-09-06 Michigan Biotechnology Institute Antimicrobial polymer
US20050215663A1 (en) * 2004-01-21 2005-09-29 Berge Charles T Inkjet inks containing crosslinked polyurethanes
US20050245671A1 (en) * 2002-06-25 2005-11-03 Woeng-Sig Moon Polymer resin formulation having anti-microbial or anti-cogulability and preparation method thereof
US20050250668A1 (en) * 2004-05-05 2005-11-10 Serobian Ashot K Rheologically stabilized silicone dispersions
US20060039953A1 (en) * 1998-09-25 2006-02-23 Leung Sau-Hung S Fast dissolving orally consumable films
US20060165742A1 (en) * 2001-10-18 2006-07-27 Karl Reizlein Powdery active ingredient formulations
US20060217515A1 (en) * 2005-03-22 2006-09-28 Biosafe Inc. Method of creating a sustained silicon-containing quaternary ammonium antimicrobial agent within a polymeric material
US20070275101A1 (en) * 2006-02-23 2007-11-29 Lu Helen S Removable antimicrobial coating compositions and methods of use
US20070275929A1 (en) * 2006-05-24 2007-11-29 The Dial Corporation Composition and method for controlling the transmission of noroviruses
US20080021113A1 (en) * 2004-09-10 2008-01-24 Reckitt Benckiser Inc. Organic Compositions
US20080138312A1 (en) * 2005-02-02 2008-06-12 Novapharm Research (Austalia) Pty Ltd Biostatic Polymer

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2342074A1 (fr) 1976-02-26 1977-09-23 Salkin Nicolas Produits de desinfection a remanence d'action
DE2723493B2 (de) 1977-05-25 1980-05-22 Unilease S.A., Luxemburg Verfahren zur Reinhaltung von verschmutzungsgefährdeten Oberflächen
FR2552097A1 (fr) 1983-09-15 1985-03-22 Lappartient Sa Peintures H Composition pour revetement de surface depouillable
JPH0688882B2 (ja) 1985-06-28 1994-11-09 ライオン株式会社 防かび剤組成物
JPH06346029A (ja) 1993-06-11 1994-12-20 Nitto Denko Corp 抗微生物性粘着シート
US5535950A (en) 1994-12-07 1996-07-16 Calmar Inc. Dual trigger sprayer
GB2297976A (en) 1995-02-01 1996-08-21 Reckitt & Colmann Prod Ltd Improvements in or relating to a bleaching process
EP0891708A1 (en) * 1997-07-17 1999-01-20 The Procter & Gamble Company Anti-microbic agent
FR2782840B1 (fr) 1998-08-25 2003-09-05 Commissariat Energie Atomique Circuit electronique et procede de realisation d'un circuit electronique integre comprenant au moins un composant electronique de puissance dans une plaque de substrat
DE29903267U1 (de) 1999-02-24 1999-05-12 Wereca GmbH, 06110 Halle Beschichtungsmittel zum temporären Schutz von Oberflächen
AU5303800A (en) * 1999-05-28 2000-12-18 Coating Systems Laboratories, Inc. Foot care compositions containing quaternary ammonium organosilanes
US6849328B1 (en) 1999-07-02 2005-02-01 Ppg Industries Ohio, Inc. Light-transmitting and/or coated article with removable protective coating and methods of making the same
AU5377701A (en) 2000-04-28 2001-11-12 Ecolab Inc Antimicrobial composition
WO2002087339A1 (en) 2001-04-30 2002-11-07 Ak Properties, Inc. Antimicrobial powder coated metal sheet
US6734153B2 (en) * 2001-12-20 2004-05-11 Procter & Gamble Company Treatment of fabric articles with specific fabric care actives
GB0301034D0 (en) * 2003-01-16 2003-02-19 Dupont Teijin Films Us Ltd Polymeric film and coating
US20060008585A1 (en) * 2004-06-14 2006-01-12 Cal-West Specialty Coatings, Inc. Masking solutions comprising siloxane-based surfactants for using in painting operations
WO2007070649A2 (en) 2005-12-14 2007-06-21 3M Innovative Properties Company Antimicrobial coating system
CA2636052A1 (en) 2006-02-23 2007-09-07 E.I. Dupont De Nemours And Company Removable antimicrobial coating compositions and methods of use
AU2007221030B2 (en) 2006-02-28 2013-02-14 Cellular Bioengineering, Inc. Polymer composition and method for removing contaminates from a substrate
JP5320008B2 (ja) 2007-10-05 2013-10-23 高知県 防汚・抗菌剤、防汚・抗菌性塗装材、防汚・抗菌剤組成物および防汚・抗菌処理方法

Patent Citations (54)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3264272A (en) * 1961-08-31 1966-08-02 Du Pont Ionic hydrocarbon polymers
US3657175A (en) * 1969-06-26 1972-04-18 Standard Brands Chem Ind Inc Carboxylic acid latices providing unique thickening and dispersing agents
US3993777A (en) * 1975-08-12 1976-11-23 Bio-Lab, Inc. Aqueous compositions to aid in the prevention of bovine mastitis
US4115292A (en) * 1977-04-20 1978-09-19 The Procter & Gamble Company Enzyme-containing detergent articles
US4384096A (en) * 1979-08-27 1983-05-17 The Dow Chemical Company Liquid emulsion polymers useful as pH responsive thickeners for aqueous systems
US4567221A (en) * 1983-03-31 1986-01-28 Kuraray Co., Ltd. Water resistant compositions
USRE33156E (en) * 1984-08-23 1990-01-30 Desoto, Inc. Alkali soluble latex thickeners
US4600761A (en) * 1985-04-04 1986-07-15 Alco Chemical Corporation Acrylic emulsion copolymers for thickening aqueous systems and copolymerizable surfactant monomers for use therein
US4792343A (en) * 1985-08-12 1988-12-20 Allied Colloids Limited Dispersing agents
US4743698A (en) * 1985-10-01 1988-05-10 Alco Chemical Corp. Acrylic emulsion copolymers for thickening aqueous systems and copolymerizable surfactant monomers for use therein
US5017369A (en) * 1987-03-03 1991-05-21 Marhevka Virginia C Film-forming teat sealer for prevention of mastitis and use thereof
US4783340A (en) * 1987-04-29 1988-11-08 Ecolab Inc. Two-package co-sprayable film-forming sanitizer
US5874164A (en) * 1988-03-14 1999-02-23 Nextec Applications, Inc. Barrier webs having bioactive surfaces
US5102936A (en) * 1989-10-21 1992-04-07 Hoechst Ag Copolymers based on ethylenically unsaturated monomers and containing urethane groups, processes for their preparation and their use
US5234974A (en) * 1990-07-26 1993-08-10 S. C. Johnson & Son, Inc. Alkali-soluble hydrophilic polymer coatings
US5624634A (en) * 1991-10-17 1997-04-29 Solvay Interox Limited Peracid compositions for medical disinfection
US5294692A (en) * 1993-06-30 1994-03-15 National Starch And Chemical Investment Holding Corporation Associative monomers and polymers
US5398846A (en) * 1993-08-20 1995-03-21 S. C. Johnson & Son, Inc. Assembly for simultaneous dispensing of multiple fluids
US5888501A (en) * 1994-07-26 1999-03-30 Auburn University Induced systemic resistance of plants to pathogenic microorganisms
US5604282A (en) * 1994-12-06 1997-02-18 Groco Specialty Coatings Company Strippable film coating composition
US5585407A (en) * 1995-07-13 1996-12-17 Minnesota Mining And Manufacturing Company Water-based coatable compositions comprising reaction products of acrylic emulsion polymers with organoalkoxysilanes
US20040018787A1 (en) * 1996-08-07 2004-01-29 Hi-Tex, Inc. Treated textile fabric
US5990233A (en) * 1996-08-16 1999-11-23 National Starch And Chemical Investment Holding Corporation Rheology modifiers for use in aqueous compositions
US6025431A (en) * 1996-08-16 2000-02-15 National Starch And Chemical Investment Holding Corporation Thickened personal care composition
US5817325A (en) * 1996-10-28 1998-10-06 Biopolymerix, Inc. Contact-killing antimicrobial devices
US6136776A (en) * 1997-04-01 2000-10-24 Dickler Chemical Laboratories, Inc. Germicidal detergent packet
US6749869B1 (en) * 1997-09-26 2004-06-15 Ecolab Acidic aqueous chlorite teat dip providing shelf life, sanitizing capacity and tissue protection
WO1999060085A1 (en) * 1998-05-20 1999-11-25 Rhodia Inc. Liquid hard surface cleaner rinse
US20030158459A1 (en) * 1998-06-30 2003-08-21 Tucker Mark D. Enhanced formulations for neutraliztion of chemical, biological and industrial toxants
US6306810B1 (en) * 1998-08-12 2001-10-23 Reckitt Benckiser Inc. Hard surface cleaning and disinfecting compositions comprising fluorosurfactants
US20060039953A1 (en) * 1998-09-25 2006-02-23 Leung Sau-Hung S Fast dissolving orally consumable films
US6391840B1 (en) * 1999-04-12 2002-05-21 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Multiple component bleaching compositions
US6228354B1 (en) * 1999-07-02 2001-05-08 Allegiance Corporation Water resistant film-forming antimicrobial skin-preparation
US6365169B1 (en) * 1999-09-30 2002-04-02 Solomon Rosenblatt Polymeric broad spectrum antimicrobial coatings
US6683036B2 (en) * 2000-07-19 2004-01-27 The Procter & Gamble Company Cleaning composition
US20020086936A1 (en) * 2000-12-28 2002-07-04 Eoga Anthony B. Anti soiling coating composition and process for use thereof
US6437009B1 (en) * 2001-03-29 2002-08-20 Air Products And Chemicals, Inc. Low foam n-alkyltartarimide and n-alkylmalimide wetting agents
US20020185199A1 (en) * 2001-04-30 2002-12-12 Myers Frederick A. Antimicrobial coated metal sheet
US20060165742A1 (en) * 2001-10-18 2006-07-27 Karl Reizlein Powdery active ingredient formulations
US20050064176A1 (en) * 2001-12-03 2005-03-24 Terry Richard N. Microbe-resistant medical device, microbe-resistant polymeric coating and methods for producing same
US6939554B2 (en) * 2002-02-05 2005-09-06 Michigan Biotechnology Institute Antimicrobial polymer
US20030203991A1 (en) * 2002-04-30 2003-10-30 Hydromer, Inc. Coating composition for multiple hydrophilic applications
US20050245671A1 (en) * 2002-06-25 2005-11-03 Woeng-Sig Moon Polymer resin formulation having anti-microbial or anti-cogulability and preparation method thereof
US20050139608A1 (en) * 2002-08-16 2005-06-30 Hans-Georg Muehlhausen Dispenser bottle for at least two active fluids
US20050008526A1 (en) * 2003-07-08 2005-01-13 The Procter & Gamble Company Liquid activator composition
US20050014427A1 (en) * 2003-07-17 2005-01-20 Nhk Teleflex Morse Co., Ltd. Shift operation apparatus for outboard motor, electronic remote control apparatus for medium-sized boat, and engine control apparatus
US20050215663A1 (en) * 2004-01-21 2005-09-29 Berge Charles T Inkjet inks containing crosslinked polyurethanes
US20050175568A1 (en) * 2004-02-10 2005-08-11 The Procter & Gamble Company Conditioning compositions comprising hydrophobically modified crosslinked cationic thickening polymers
US20050250668A1 (en) * 2004-05-05 2005-11-10 Serobian Ashot K Rheologically stabilized silicone dispersions
US20080021113A1 (en) * 2004-09-10 2008-01-24 Reckitt Benckiser Inc. Organic Compositions
US20080138312A1 (en) * 2005-02-02 2008-06-12 Novapharm Research (Austalia) Pty Ltd Biostatic Polymer
US20060217515A1 (en) * 2005-03-22 2006-09-28 Biosafe Inc. Method of creating a sustained silicon-containing quaternary ammonium antimicrobial agent within a polymeric material
US20070275101A1 (en) * 2006-02-23 2007-11-29 Lu Helen S Removable antimicrobial coating compositions and methods of use
US20070275929A1 (en) * 2006-05-24 2007-11-29 The Dial Corporation Composition and method for controlling the transmission of noroviruses

Cited By (95)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040166102A1 (en) * 2000-06-09 2004-08-26 Darouiche Rabih O. Combination of antimicrobial agents and bacterial interference to coat medical devices
US7941937B2 (en) * 2002-11-26 2011-05-17 Lg Electronics Inc. Laundry dryer control method
US20040143992A1 (en) * 2002-11-26 2004-07-29 Do Gi Hyeong Laundry drier control method
US7780911B2 (en) 2005-04-29 2010-08-24 E. I. Du Pont De Nemours And Company Biocidal compositions for producing peracids
US20070042924A1 (en) * 2005-04-29 2007-02-22 Dicosimo Robert Enzymatic production of peracids using perhydrolytic enzymes
US7550420B2 (en) * 2005-04-29 2009-06-23 E. I. Dupont De Nemours And Company Enzymatic production of peracids using perhydrolytic enzymes
US20090239948A1 (en) * 2005-04-29 2009-09-24 Dicosimo Robert Enzymatic Production Of Peracids Using Perhydrolytic Enzymes
US8063008B2 (en) 2005-04-29 2011-11-22 E. I. Du Pont De Nemours And Company Enzymatic production of peracids using perhydrolytic enzymes
US20090130157A1 (en) * 2005-12-14 2009-05-21 Ylitalo Caroline M Antimicrobial Adhesive Films
US20090155451A1 (en) * 2005-12-14 2009-06-18 Ylitalo Caroline M Antimicrobial coating system
US9247736B2 (en) 2005-12-14 2016-02-02 3M Innovative Properties Company Antimicrobial adhesive films
US8124169B2 (en) 2005-12-14 2012-02-28 3M Innovative Properties Company Antimicrobial coating system
US20070275101A1 (en) * 2006-02-23 2007-11-29 Lu Helen S Removable antimicrobial coating compositions and methods of use
US9668476B2 (en) 2006-02-23 2017-06-06 Lanxess Corporation Removable antimicrobial coating compositions and methods of use
US20100240799A1 (en) * 2007-06-13 2010-09-23 3M Innovative Properties Company Antimicrobial film-forming composition, antimicrobial film, and method of verifying the presence of an antimicrobial film
US8691887B2 (en) * 2008-12-01 2014-04-08 Becton, Dickinson And Company Antimicrobial coating compositions
US20100136209A1 (en) * 2008-12-01 2010-06-03 Becton, Dickinson And Company Systems and methods for applying an antimicrobial coating to a medical device
US20100137472A1 (en) * 2008-12-01 2010-06-03 Becton, Dickinson And Company Antimicrobial coating compositions
US20100135949A1 (en) * 2008-12-01 2010-06-03 Becton, Dickinson And Company Antimicrobial compositions
US20100186674A1 (en) * 2009-01-26 2010-07-29 E. I. Du Pont De Nemours And Company Methods and compositions for treating fertilized avian eggs
US8821455B2 (en) 2009-07-09 2014-09-02 Becton, Dickinson And Company Antimicrobial coating for dermally invasive devices
WO2011009083A1 (en) * 2009-07-17 2011-01-20 Carefusion 2200, Inc. Particles incorporating antimicrobial agents
US20110182959A1 (en) * 2009-07-27 2011-07-28 E.I. Du Pont De Nemours And Company. Removable antimicrobial coating compositions containing acid-activated rheology agent and methods of use
US20110177146A1 (en) * 2009-07-27 2011-07-21 E. I. Du Pont De Nemours And Company Removable antimicrobial coating compositions containing cationic rheology agent and methods of use
US20110177148A1 (en) * 2009-07-27 2011-07-21 E. I. Du Pont De Nemours And Company Enzymatic in situ preparation of peracid-based removable antimicrobial coating compositions and methods of use
US20160262385A1 (en) * 2009-07-27 2016-09-15 The Chemours Company Fc, Llc Removable antimicrobial coating compositions containing cationic rheology agent and methods of use
WO2011017090A1 (en) 2009-07-27 2011-02-10 E. I. Du Pont De Nemours And Company Removable antimicrobial coating compositions containing acid-activated rheology agent and methods of use
WO2011017097A1 (en) 2009-07-27 2011-02-10 E. I. Du Pont De Nemours And Company Removable antimicrobial coating compositions containing cationic rheology agent and methods of use
WO2011017095A2 (en) 2009-07-27 2011-02-10 E. I. Du Pont De Nemours And Company Enzymatic in situ preparation of peracid-based removable antimicrobial coating compositions and methods of use
US20110081207A1 (en) * 2009-10-01 2011-04-07 Teledyne Scientific & Imaging, Llc System for mitigating marine bio-fouling of an underwater structure
US8356959B2 (en) 2009-10-01 2013-01-22 Teledyne Scientific & Imaging Llc System for mitigating marine bio-fouling of an underwater structure
US9109292B2 (en) * 2010-02-25 2015-08-18 Polyprotec Technologies Anti-microbial coated devices and methods for making same
US20110206817A1 (en) * 2010-02-25 2011-08-25 Polyprotectechnologies Inc. Anti-microbial coated devices and methods for making same
US20100286016A1 (en) * 2010-04-01 2010-11-11 KLC Brands, Inc. Non-V.O.C. sprayable gel to remove insect bodies-environmentally friendly
US8309626B2 (en) 2010-07-13 2012-11-13 Rohm And Haas Company Microbiocidal coatings
WO2013101498A1 (en) * 2011-12-27 2013-07-04 3M Innovative Properties Company Burnishing methods and compositions
US9770580B2 (en) * 2012-05-15 2017-09-26 Becton, Dickinson And Company Blood control IV catheter with antimicrobial properties
US9352119B2 (en) * 2012-05-15 2016-05-31 Becton, Dickinson And Company Blood control IV catheter with antimicrobial properties
US20160206869A1 (en) * 2012-05-15 2016-07-21 Becton, Dickinson And Company Blood control iv catheter with antimicrobial properties
US20130310764A1 (en) * 2012-05-15 2013-11-21 Becton, Dickinson And Company Blood control iv catheter with antimicrobial properties
US9579486B2 (en) 2012-08-22 2017-02-28 Becton, Dickinson And Company Blood control IV catheter with antimicrobial properties
US9670434B2 (en) 2012-09-13 2017-06-06 Ecolab Usa Inc. Detergent composition comprising phosphinosuccinic acid adducts and methods of use
US11952556B2 (en) 2012-09-13 2024-04-09 Ecolab Usa Inc. Detergent composition comprising phosphinosuccinic acid adducts and methods of use
US9994799B2 (en) 2012-09-13 2018-06-12 Ecolab Usa Inc. Hard surface cleaning compositions comprising phosphinosuccinic acid adducts and methods of use
US11859155B2 (en) 2012-09-13 2024-01-02 Ecolab Usa Inc. Hard surface cleaning compositions comprising phosphinosuccinic acid adducts and methods of use
US12371639B2 (en) 2012-09-13 2025-07-29 Ecolab Usa Inc. Hard surface cleaning compositions comprising phosphinosuccinic acid adducts and methods of use
US11053458B2 (en) 2012-09-13 2021-07-06 Ecolab Usa Inc. Hard surface cleaning compositions comprising phosphinosuccinic acid adducts and methods of use
US9752105B2 (en) 2012-09-13 2017-09-05 Ecolab Usa Inc. Two step method of cleaning, sanitizing, and rinsing a surface
US11001784B2 (en) 2012-09-13 2021-05-11 Ecolab Usa Inc. Detergent composition comprising phosphinosuccinic acid adducts and methods of use
US10377971B2 (en) 2012-09-13 2019-08-13 Ecolab Usa Inc. Detergent composition comprising phosphinosuccinic acid adducts and methods of use
US10358622B2 (en) 2012-09-13 2019-07-23 Ecolab Usa Inc. Two step method of cleaning, sanitizing, and rinsing a surface
US20150359945A1 (en) * 2013-01-15 2015-12-17 Board Of Regents, The University Of Texas System Antimicrobial coatings
US9695323B2 (en) 2013-02-13 2017-07-04 Becton, Dickinson And Company UV curable solventless antimicrobial compositions
US11357962B2 (en) 2013-02-13 2022-06-14 Becton, Dickinson And Company Blood control IV catheter with stationary septum activator
US9750928B2 (en) 2013-02-13 2017-09-05 Becton, Dickinson And Company Blood control IV catheter with stationary septum activator
US9327095B2 (en) 2013-03-11 2016-05-03 Becton, Dickinson And Company Blood control catheter with antimicrobial needle lube
US9789280B2 (en) 2013-03-11 2017-10-17 Becton, Dickinson And Company Blood control catheter with antimicrobial needle lube
US9750927B2 (en) 2013-03-11 2017-09-05 Becton, Dickinson And Company Blood control catheter with antimicrobial needle lube
US12337073B2 (en) 2013-04-15 2025-06-24 Ecolab Usa Inc. Peroxycarboxylic acid based sanitizing rinse additives for use in ware washing
US11865219B2 (en) 2013-04-15 2024-01-09 Ecolab Usa Inc. Peroxycarboxylic acid based sanitizing rinse additives for use in ware washing
US10376686B2 (en) 2014-04-23 2019-08-13 Becton, Dickinson And Company Antimicrobial caps for medical connectors
US9675793B2 (en) 2014-04-23 2017-06-13 Becton, Dickinson And Company Catheter tubing with extraluminal antimicrobial coating
US11357965B2 (en) 2014-04-23 2022-06-14 Becton, Dickinson And Company Antimicrobial caps for medical connectors
US10589063B2 (en) 2014-04-23 2020-03-17 Becton, Dickinson And Company Antimicrobial obturator for use with vascular access devices
US9789279B2 (en) 2014-04-23 2017-10-17 Becton, Dickinson And Company Antimicrobial obturator for use with vascular access devices
US9956379B2 (en) 2014-04-23 2018-05-01 Becton, Dickinson And Company Catheter tubing with extraluminal antimicrobial coating
US11219705B2 (en) 2014-07-08 2022-01-11 Becton, Dickinson And Company Antimicrobial coating forming kink resistant feature on a vascular access device
US10232088B2 (en) 2014-07-08 2019-03-19 Becton, Dickinson And Company Antimicrobial coating forming kink resistant feature on a vascular access device
US11033023B2 (en) 2014-11-26 2021-06-15 Microban Products Company Surface disinfectant with residual biocidal property
US11134678B2 (en) 2014-11-26 2021-10-05 Microban Products Company Surface disinfectant with residual biocidal property
US10925281B2 (en) 2014-11-26 2021-02-23 Microban Products Company Surface disinfectant with residual biocidal property
US10834922B2 (en) 2014-11-26 2020-11-17 Microban Products Company Surface disinfectant with residual biocidal property
US11026418B2 (en) 2014-11-26 2021-06-08 Microban Products Company Surface disinfectant with residual biocidal property
US10842147B2 (en) 2014-11-26 2020-11-24 Microban Products Company Surface disinfectant with residual biocidal property
US11134674B2 (en) 2014-11-26 2021-10-05 Microban Products Company Surface disinfectant with residual biocidal property
US10609933B2 (en) 2015-03-13 2020-04-07 Gea Food Solutions Bakel B.V. Method for cleaning and storing of a mould drum
EP3267799B1 (en) * 2015-03-13 2020-06-10 GEA Food Solutions Bakel B.V. Method for cleaning and storing of a mould drum
US10143804B2 (en) 2015-05-29 2018-12-04 ZebraSci, Inc Biopolymer-based emulsion lubricants for syringe barrels
WO2016196112A1 (en) * 2015-05-29 2016-12-08 Zebrasci, Inc. Biopolymer-based emulsion lubricants for syringe barrels
US10064273B2 (en) 2015-10-20 2018-08-28 MR Label Company Antimicrobial copper sheet overlays and related methods for making and using
US10493244B2 (en) 2015-10-28 2019-12-03 Becton, Dickinson And Company Extension tubing strain relief
US11904114B2 (en) 2015-10-28 2024-02-20 Becton, Dickinson And Company Extension tubing strain relief
US11503824B2 (en) 2016-05-23 2022-11-22 Microban Products Company Touch screen cleaning and protectant composition
US12264261B2 (en) 2016-07-11 2025-04-01 Spartan Chemical Company, Inc. Antimicrobial sacrificial floor coating system comprising a nonionic/cationic wax mixture
US11274215B2 (en) 2016-07-11 2022-03-15 Spartan Chemical Company, Inc. Antimicrobial sacrificial floor coating systems
US11286393B2 (en) 2016-07-11 2022-03-29 Spartan Chemical Company, Inc. Antimicrobial sacrificial floor coating systems
US10759948B2 (en) 2016-07-11 2020-09-01 Spartan Chemical Company, Inc. Antimicrobial sacrificial floor coating systems
US10093811B2 (en) 2016-07-11 2018-10-09 Spartan Chemical Company, Inc. Antimicrobial sacrificial floor coating systems
US12312496B2 (en) 2016-07-11 2025-05-27 Spartan Chemical Company, Inc. Antimicrobial sacrificial floor coating systems
US10759949B2 (en) 2016-07-11 2020-09-01 Spartan Chemical Company, Inc. Antimicrobial sacrificial floor coating systems
EP3546529A4 (en) * 2017-10-23 2020-01-29 LG Chem, Ltd. ANTIBACTERIAL POLYMER COATING COMPOSITION AND ANTIBACTERIAL POLYMER FILM
US11578179B2 (en) 2017-10-23 2023-02-14 Lg Chem, Ltd. Antimicrobial polymer coating composition and antimicrobial polymer film
US12098100B2 (en) 2018-10-19 2024-09-24 Gold Bond Building Products, Llc Antimicrobial coating for building panel
US11731904B2 (en) 2018-10-19 2023-08-22 Gold Bond Building Products, Llc Antimicrobial coating for building panel
US11122806B2 (en) 2018-10-19 2021-09-21 Gold Bond Building Products, Llc Antimicrobial coating for building panel

Also Published As

Publication number Publication date
CN103992676B (zh) 2017-08-15
WO2007100653A2 (en) 2007-09-07
AU2007221203B2 (en) 2013-02-21
US20160286796A1 (en) 2016-10-06
CA2635932C (en) 2014-05-27
JP5478074B2 (ja) 2014-04-23
WO2007100653A3 (en) 2007-11-29
EP1987106A2 (en) 2008-11-05
US9668476B2 (en) 2017-06-06
US20070275101A1 (en) 2007-11-29
AU2007221203A2 (en) 2008-08-14
WO2007100653A8 (en) 2008-01-17
CA2635932A1 (en) 2007-09-07
JP2009527356A (ja) 2009-07-30
CN103992676A (zh) 2014-08-20
AU2007221203A1 (en) 2007-09-07

Similar Documents

Publication Publication Date Title
US9668476B2 (en) Removable antimicrobial coating compositions and methods of use
AU2007221204B2 (en) Removable antimicrobial coating compositions and methods of use
CA2764434C (en) Removable antimicrobial coating compositions containing cationic rheology agent and methods of use
EP2458989B1 (en) In situ preparation of peracid-based removable antimicrobial coating compositions and methods of use
US20110182959A1 (en) Removable antimicrobial coating compositions containing acid-activated rheology agent and methods of use

Legal Events

Date Code Title Description
AS Assignment

Owner name: E. I. DU PONT DE NEMOURS AND COMPANY, DELAWARE

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:LU, HELEN S. M.;MALONE, SHAUN F.;HOFFMANN, CHRISTIAN;AND OTHERS;REEL/FRAME:020132/0031;SIGNING DATES FROM 20070613 TO 20071031

AS Assignment

Owner name: THE CHEMOURS COMPANY FC, LLC, DELAWARE

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:E. I. DU PONT DE NEMOURS AND COMPANY;REEL/FRAME:035432/0023

Effective date: 20150414

AS Assignment

Owner name: JPMORGAN CHASE BANK, N.A., NEW YORK

Free format text: SECURITY AGREEMENT;ASSIGNORS:THE CHEMOURS COMPANY FC LLC;THE CHEMOURS COMPANY TT, LLC;REEL/FRAME:035839/0675

Effective date: 20150512

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION

AS Assignment

Owner name: THE CHEMOURS COMPANY FC, LLC, DELAWARE

Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:JPMORGAN CHASE BANK, N.A.;REEL/FRAME:040688/0754

Effective date: 20161209

Owner name: LANXESS CORPORATION, PENNSYLVANIA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:THE CHEMOURS COMPANY FC, LLC;REEL/FRAME:041036/0344

Effective date: 20160831

AS Assignment

Owner name: THE CHEMOURS COMPANY FC, LLC, DELAWARE

Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:JPMORGAN CHASE BANK, N.A., AS ADMINISTRATIVE AGENT;REEL/FRAME:045845/0913

Effective date: 20180403