JP6006259B2 - Removable antimicrobial coating composition and method of use - Google Patents

Description

  The present invention relates to US Provisional Patent Application No. 60 / 776,081, filed on February 23, 2006, and US Provisional Patent Application No. 60 / 831,983, filed July 19, 2006. Claims the benefit of the description.

  The present invention relates to a method for controlling microorganisms comprising the step of coating a surface with a removable antibacterial film-forming composition, a durable and easily removable antibacterial composition, and a method of applying said composition .

  The present invention relates to a method for providing microbial control in a location by contacting the location with a removable coating composition comprising at least one antimicrobial agent.

  A particularly relevant area for controlling microbial contamination is the field of food processing. Food pathogen contamination is one of the major public health problems in the United States and around the world. The current incidence of foodborne pathogenic diseases is unknown, but CDC reports that it is between 700 and 81 million a year, of which more than 325,000 are hospitalized and 5,000 deaths per year in the United States. Estimated. The cost of treating human disease in the United States due to foodborne pathogens is on the order of $ 1 billion annually. In addition to the severity of illness and death, contaminated food represents a huge economic loss for many food processing plants.

  Current stringent sanitary sterilization procedures at food processing plants are effective in reducing the incidence of food pathogen contamination, but have not prevented serious explosive outbreaks resulting in death and disability. These procedures are costly both in terms of effort and time spent in effectively implementing them and in terms of materials. Furthermore, a problem caused by food pathogen contamination is that it tends to be expensive, especially when a consumer recall occurs as a result.

  Poor hygienic sterilization of food contact surfaces, equipment, and processing environments contributes to the explosive outbreak of food-borne diseases, particularly those involving Listeria monocytogenes and Salmonella enterocolitis It was a factor. Improperly cleaned surfaces promote soil accumulation and, in the presence of water, contribute to the development of bacterial biofilms that can contain pathogenic microorganisms. Cross-contamination occurs when food passes over a contaminated surface or through exposure to aerosols or condensates derived from the contaminated surface (R.A.N. Chimielewski). ) And JF Frank, “Biofilm Formation and Control in Food Processing Facilities”, Comprehensive Reviews, Food Science 200, Food Science 2, 22-32; Boulange-Petermann, Laurence, Biofouling, 199 Year, No. 10, pp. 275-300). Factors such as food contact surface type and topography play a significant role in situations where surface contamination cannot be removed. A worn surface accumulates dirt and is more difficult to clean than a smooth surface. Surface defects further complicate the removal of dirt and pathogens, resulting in the growth of pathogens even after decontamination, potentially resulting in biofilm formation due to this growth (Baulang Peterman, Supra; DA Timperley, RH Thorpe and JT Holah, “Engineering in the Hygiene of the Food Industry. Involvement of Engineering Design in Food Industry Hygiene ", Biofilm-Science and Technology, pages 35-41, L. F. Melo et al. hers, 1992, Netherlands; JT Hora, RH Thorpe, J. Applied Bacteriology, 1990, 69, 599-608).

  In addition, pathogens within the biofilm are more resistant to disinfectants, which may help the survival of Listeria and other foodborne pathogens within the food processing environment (JF Frank, R., et al. RA Koffi, J. Food Protection, 1990, 53, 550-554; EP Krysinski, L. J. Brown J. Brown) and T. J. Marchisello, J. Food Protection, 1992, 55, 246-251). Therefore, appropriate control methods for biofilms are needed for safe food processing operations.

  Pathogen contamination is particularly a problem when food processing equipment is shut down or not temporarily operating or used. This is in fact a perfect time for biofilm formation, especially on parts of equipment where disinfectants are difficult to reach as described above. The work currently practiced to avoid contamination during such outages is potentially using disinfection, coatings and other harsh means or other solutions that often include components. Includes a multi-step approach for disinfection prior to resuming processing, including removal of any harmful disinfectant. These approaches are costly and their effectiveness may be questionable. Thus, there is a need for better ways of protecting against pathogen contamination during such outages. Moreover, in addition to the food industry, several other industries that can benefit from disinfectant compositions that have the ability to form durable and easily removable antimicrobial coatings that provide adequate protection Is also present. Proper protection is achieved by certain properties of the coating, such as excellent spreading and surface tension control.

  Excellent spreading on the surface of the liquid antibacterial formulation after application is beneficial in achieving a homogeneous and continuous film, especially when spraying or aerosolization is used as the application method. Excellent spreading properties can enhance the antibacterial properties of the antibacterial formulation by achieving full surface coverage without leaving uncoated gaps in the finished antibacterial film or coating. These gaps allow microbial growth. Antibacterial properties can be further enhanced by a reduction in surface tension that allows liquid antibacterial formulations to flow into surface defects known as masking microorganisms.

  U.S. Pat. No. 5,585,407 provides an aqueous coating composition that can be applied to a substrate to inhibit the growth of pathogens over an extended period of time. The coating comprises an acrylate emulsion polymer and an organoalkoxysilane and can be removed under alkaline conditions.

  US Pat. No. 5,017,369 provides a prophylactic treatment of mastitis in dairy cows during milking comprising coating the nipple of a cow with an aqueous composition containing an antimicrobial agent. The composition includes at least 2 wt% partially hydrolyzed polyvinyl alcohol, from about 0 wt% to about 10 wt% opacifier, from about 0.1 wt% to about 10 wt% antimicrobial agent, and at least 65 wt% water. . Water washing is used to remove the film from the nipple of the cow after milking.

  Thus, a durable but easy to remove film or coating that can be accompanied by a bactericide such as a quaternary ammonium compound or a phenolic compound on the surface of, for example, ceramics, glass, thermosetting synthetic resin, plastic, metal, etc. There is a need for disinfectant compositions that have the ability to form. There is also a need for disinfectant films or coatings that provide broad protection against pathogen contamination. Additionally, there is a need for a long lasting homogeneous and continuous film or coating that can be easily removed and applied to a variety of surfaces. Neither the above-described method nor the coating applied in the method provides a durable but easily removable coating composition for coating the surfaces described herein. Thus, the problem to be solved is a method for controlling microorganisms at a specific location using a coating composition comprising at least one antimicrobial agent, wherein the coating is durable, provides residual antimicrobial efficacy, and facilitates There is a lack of methods that can be eliminated.

  The present invention addresses the above-mentioned problems by the following methods and compositions.

One aspect of the present invention is a method for providing control of a microorganism in a location, comprising:
a) i) a water-soluble or water-dispersible film-forming agent;
ii) at least one antimicrobial agent; and iii) an inert solvent;
Providing a removable liquid coating composition comprising:
b) applying the composition in its place, thereby forming a coating; and
c) removing the coating with an aqueous solution at a temperature of about 15 ° C to about 100 ° C.

  In another aspect, the surface tension of the compositions described herein is less than 40 mN / m.

  In another aspect, the film former in the above method comprises one or more polyvinyl alcohols including polyvinylpyrrolidone, polyacrylic acid, acrylate copolymers, ionic hydrocarbon polymers and polyurethanes or combinations thereof and That copolymer.

  In another aspect, the coating formed by the methods herein provides at least 3-log microbial reduction when applied to a contaminated surface.

  In another aspect, the coating provides at least a 5-log microbial reduction when applied to a contaminated surface.

  In another aspect, the coating prevents growth of at least one type of microorganism at a location.

  In another aspect, controlling microorganisms at a location includes reducing microorganisms that are hidden in the biofilm.

  In another aspect, the coating formed by the method described above is substantially continuous and homogeneous.

  In another aspect, the coating formed by the above-described method has a thickness of about 0.3 microns to about 300 microns, and preferably has a thickness of about 0.5 microns to about 100 microns.

Another aspect of the present invention is:
i) a water-soluble or water-dispersible film-forming agent;
ii) at least one antimicrobial agent,
iii) inert solvents; and iv) optionally, plasticizers, surfactants, crosslinkers, colorants, solubilizers, rheology modifiers, antioxidants, pH adjusters, wetting agents, antifoaming agents, A removable food processing shutdown spray composition comprising one or more of a bulking agent, lubricant, processing aid, anti-discoloring agent, film performance enhancing substance or enzyme and is durable and above 15 ° C This is a spray composition for shutdown, which can be removed when it is subjected to an aqueous solution treatment.

  In another aspect, the compositions described herein include a surfactant that provides a surface tension of about 20 to about 50 mN / m. In another embodiment, the surfactant is an organosilicone. In another embodiment, the surfactant is at a concentration of about 0.01 wt% to about 1.0 wt% of the composition.

  In another embodiment, the composition includes a rheology control agent that provides shear thinning properties to the composition.

  In another aspect, the composition provides at least a 3-log microbial reduction when applied to a contaminated food processing surface. In another aspect, the composition is a disinfectant, sanitizer, preservative or physical barrier to contamination when applied to a contaminated surface, wherein the composition is subsequently contaminated with contamination. When applied to a coated surface, it has the ability of residual antimicrobial efficacy.

  In another aspect of the invention, the location is a tank, conveyor, floor, drain, cooler, freezer, refrigerator, equipment surface, wall, valve, belt, pipe, fitting, crack, building surface, kitchen surface, Inanimate surfaces found in food processing facilities, veterinary or animal care facilities, animal care equipment or animal husbandry or hatching facilities, hospital or surgical center walls, beds, equipment, medical clothing or shoes worn in hospitals or other medical environments One or more surfaces of the surface of the fibers including and other in-hospital surfaces.

  In another aspect of the invention, the location consists of one or more metals selected from the group consisting of aluminum, steel, stainless steel, chromium, titanium, iron, alloys and mixtures thereof.

  In another embodiment of the present invention, the location is a polyolefin including polymers of polyethylene, polypropylene, polystyrene, polymethacrylate, polymethyl methacrylate, acrylonitrile, butadiene, ABS, acrylonitrile butadiene; polyester including polyethylene terephthalate; And a surface comprising one or more plastic materials selected from the group consisting of polyamides including nylon; and combinations thereof.

In another aspect of the invention, the location is made of brick, tile, ceramic, porcelain, wood, vinyl, linoleum, carpet, paper, leather, combinations thereof, and the like.

  In another aspect of the invention, the location is an inanimate surface or a coated or painted surface consisting of a metal, mineral, polymer, plastic, fibrous substrate or nonwoven, or a mixture thereof.

  The present invention can be more fully understood from the following detailed description and the accompanying drawings.

  Where amounts, concentrations or other values or parameters are indicated as either preferred upper and lower preferred ranges, preferred ranges or lists, this is independent of whether the ranges are disclosed separately or not. Should be understood to specifically disclose all ranges consisting of any upper range limit or preferred value and any lower range limit or preferred value. When numerical ranges are listed herein, unless otherwise stated, the ranges are intended to include the endpoints and all integers and fractions within the ranges. It is not intended that the scope of the invention be limited to the specific values recited when defining a range.

  There has been a long-standing need for antibacterial agents with improved antibacterial efficacy and improved rate of action. The specific requirements for such agents will vary depending on the intended field of use (eg sanitizer, disinfectant, sterilant, aseptic packaging process, etc.) and applicable public health regulatory requirements. For example, “Destructive germicide and sanitary bactericidal action of the disinfectant, the official analysis method of the American Institute of Chemistry of the United States of America.” And as described in the applicable section, 15th edition, 1990 (EPA Guidelines 91-2), sanitizers can be used for multiple test organisms within 30 seconds at room temperature, 25 +/− 2 ° C. Should provide 99.999% reduction (5-log reduction). As used herein, the term “antibacterial” refers to killing a microorganism, blocking or preventing pathogen contamination (eg, forming a barrier), or inhibiting or preventing microbial growth. Or contain an agent that has the ability to trap and kill microorganisms or prevent biofilm formation. As used herein, the term “sanitizer” means an agent that reduces the number of pathogen contaminants to a safe level as judged by public health regulatory requirements. According to the official sanitizer test, a sanitizer is a chemical that kills 99.999% of specific test microorganisms in 30 seconds under test conditions (EPA Policy DIS / TSS-4: “Effective Data Requirements” : Pre-cleaned food-Increased disinfection for contact surfaces (Effects of Sanitizing Rise for Preferentially Cleaned Food-contact Sact 30), United States Environmental Protection Agency (Month 19) Day).

  As used herein, the term “disinfectant” means an agent that provides antibacterial activity. According to official disinfectant tests, disinfectants are chemicals that kill 99.9% of specific test microorganisms in 10 minutes under test conditions (“disinfectant germicide and cleansing action, US Official Analytical Chemistry Association Official Analytical Methods ", 960.09 and applicable section, 15th edition, 1990 (EPA Guidelines 91-2)). As used herein, the term “ppm” here means micrograms per gram.

The present invention relates to methods and compositions for controlling microorganisms. The method includes coating the surface with a removable antimicrobial film-forming composition. Specifically, the present invention is a method for providing control of a microorganism at a location comprising:
a) i) a water-soluble or water-dispersible film-forming agent;
ii) at least one antimicrobial agent; and iii) an inert solvent;
b) applying the composition in place to form a coating; and c) removing the coating with an aqueous solution at a temperature of about 15 ° C to about 100 ° C.

  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.

  The location of the present invention includes some or all of the target surface suitable for coating. Target surfaces include all surfaces that can potentially be contaminated with microorganisms, including surfaces that are usually difficult to apply a film or coating (such as surfaces that are difficult to reach). . Examples of target surfaces include equipment surfaces found in the food or beverage industry (e.g. tanks, conveyors, floors, drains, coolers, freezers, refrigerators, equipment surfaces, walls, valves, belts, pipes, drains, fittings, cracks, Combinations thereof); interior or exterior surfaces of seasonal real estate (eg walls, wooden frames, floors, windows), kitchens, such as buildings under construction, building surfaces including newly built residential buildings and villa surfaces (Sink, drain, countertop, refrigerator, cutting board), bathroom (shower, toilet, drain, pipe, bathtub), (especially for mold removal), deck, wood, siding and other residential exteriors, asphalt single-sparing, courtyard or Stone parts (especially for algae treatment); boats and boat equipment surfaces; waste disposal equipment, waste bins and dumpsters or Other debris removal equipment and surfaces; pipes and drains related to non-food industries; surfaces in hospitals, surgical or outpatient centers or veterinary surfaces (eg hospitals including medical clothing, shoes, and other hospitals or veterinary surfaces) / Walls, floors, beds, equipment, clothing in veterinary or other medical environments), emergency relief or other emergency service equipment and clothing; sawmill equipment, surfaces and wooden products; restaurant surfaces; supermarkets, food Equipment and surfaces in grocery stores, retail stores and convenience stores; equipment and surfaces in prepared food stores and food preparation surfaces; brewery and bakery surfaces; bathroom surfaces such as sinks, showers, counters and toilets; clothing and shoes Toys; school and gymnasium equipment, walls, floors, windows and other surfaces; sinks, counties Kitchen surfaces such as utensils; wooden or composite decks, pools, hot tubs, and hot spring surfaces; carpets; paper; leather; animal death, fur and skin; barns or poultry, cattle, dairy cows, goats, horses and pigs Includes livestock shed surfaces; and hatchery for poultry or shrimp. Additional surfaces include food products such as beef, chicken, pork, vegetables, fruits, seafood, combinations thereof, and the like.

  Additional locations suitable for use in the present invention include fibrous substrates, including fibers, yarns, fabrics, fabrics, nonwovens, carpets, leather or paper. Fibrous substrates are made of natural fibers such as wool, cotton, jute, sisal, seaweed, paper, coir and cellulose or mixtures thereof; or polyamide, polyester, polyolefin, polyaramid, acrylic and blends thereof; Alternatively, it is made of a blend of at least one natural fiber and at least one synthetic fiber. “Fabric” refers to natural or synthetic fibers consisting of fibers such as cotton, rayon, silk, wool, polyester, polypropylene, polyolefin, nylon and aramid such as “NOMEX®” and “KEVLAR®”. Means fabric or its blend. “Fiber blend” means a 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 can also be a blend of two or more natural fibers or a blend of two or more synthetic fibers. Nonwoven substrates include, for example, spunlace nonwovens, such as EI du Pont de Nemours and Company (Wilmington, DE, USA). Sontala and laminated non-woven fabrics, such as spunbond, meltblown, and spunbond non-woven fabrics available from

  Examples of surface materials include metals (eg steel, stainless steel, chromium, titanium, iron, copper, brass, aluminum and their alloys), minerals (eg concrete), polymers and plastics (eg 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. Further surfaces include brick, tile, ceramic, porcelain, wood, vinyl and linoleum.

  Equipment or surfaces that are protected with a temporary coating may or may not be used while protected. The target surface can be hydrophobic or hydrophilic. The antibacterial removable coating composition useful for the present invention can be used as an alternative to standard cleaning products (such as diluted quaternary aluminum compound solutions, peracid foams, etc.) and is in use or in use It can be used as a protective coating for non-equipment for routine hygiene sterilization as well as for longer term protection (weeks or months).

  Antibacterial removable coating compositions offer several advantages. The coating composition kills microorganisms (both loose microorganisms and biofilms) by preventing the formation of biofilms and trapping microorganisms underlying or attached to the coating Providing antibacterial efficacy in a number of ways, including inhibiting its growth or preventing its growth.

  The application of the coating composition can also reduce the use of water since the concentrate of antimicrobial agent is applied directly into the thin film, allowing the antimicrobial agent to be maintained on the substrate at a higher concentration for a longer time. Furthermore, labor can be reduced because the antimicrobial coating is applied once and removed in subsequent process steps. The coating composition can be improved by formulating the composition with a flow improver to coat surfaces that are difficult to reach. Thus, it is possible to apply antimicrobial agents to surfaces on or inside devices that are not accessible by the application of other conventional antimicrobial soluble coating solutions having a conventional shear-viscosity profile. Horizontal and vertical surfaces can be covered with a thin layer of antimicrobial protective coating without waste. By formulating a composition with appropriate fluidity improvement and degree of crosslinking, coating compositions with various coating properties can be prepared that vary in the degree of surface finish and protection and ease of removal.

  In one embodiment of the present invention, the antimicrobial removable coating composition useful for the present invention is applied to the device during a device shutdown, for example in the food, dairy or beverage industry. When the instrument is activated, the coating is removed by the methods described herein. In another embodiment, the antibacterial removable coating composition is used for cleaning surfaces such as food or beverage industry equipment surfaces for daily or weekly cleaning purposes. In yet another embodiment, the fruit surface can be coated with a removable coating composition to prevent the spread and cross-contamination of pathogens in food processing facilities. In yet another embodiment, hospital walls, beds and other hospital surfaces can be coated with antimicrobial, removable coating compositions useful for the present invention. In another embodiment, the drain is coated with a removable coating composition. In another embodiment, interior building surfaces, walls or other surfaces, such as new residential buildings, are coated to prevent or remove mold contamination.

  The coating composition provides several protection mechanisms against contamination from non-pathogenic bacteria such as pathogenic bacteria or dirt.

  First, as the fluid composition is applied, the antimicrobial agent in the coating formulation kills (or suppresses or prevents growth) cells floating or loosely adherent on the surface.

  Second, cells hidden by the biofilm on the surface are killed (or growth is inhibited or prevented) by diffusion of the antimicrobial agent from the fluid coating into the hydrated biofilm. As the antibacterial coating dries, the antibacterial agent is more likely to remain active due to the high water content retained at the interface between the biofilm and the antibacterial coating. Because the film is semipermeable, the antimicrobial agent migrates into the film, contributing to a more effective barrier and longer lasting activity. The antibacterial film thus formed constitutes an antibacterial agent tank and provides a much longer contact time than conventional sanitary cleaning liquids that typically drip within seconds or minutes.

  Third, floating cells that reach the antimicrobial coating from the outside after application of the antimicrobial coating will be killed (or growth is inhibited or prevented) by the antimicrobial agent. Again, the antimicrobial coating will act as an antimicrobial tank that maintains its microbicidal properties until the antimicrobial is exhausted from the coating. This mechanism will also prevent the biofilm from growing on the antimicrobial coating until the antimicrobial agent has been used up from the coating. The term “biofilm” means a group of microorganisms (one or multiple strains) surrounded by a matrix of extracellular polymers (ie exopolymers or glycocalyx). These extracellular polymers are typically polysaccharides, but can also contain other biopolymers, which can be attached to either inert or biological surfaces. Standard biofilm microorganisms are gram positive and / or gram negative bacteria that act as pathogens, indicator organisms and / or spoilage organisms.

  Fourth, the coating constitutes a physical barrier to microorganisms, dirt, fats and other materials. These solid contaminants will remain on the surface of the coating and will be washed away at the time of removal of the coating.

  A fifth protection mechanism occurs under circumstances where the coating captures microorganisms, thus making it impossible for the microorganisms to reach or penetrate the target surface and contaminate it. FIG. 1 illustrates the various protection mechanisms described above. The protection mechanisms can act individually or simultaneously in any combination depending on the environmental conditions.

  Long lasting activity while the coating is in place is particularly beneficial in a variety of applications. This residual gain is far superior to antibacterial agents such as rapidly dripping cleaning solutions or agents removed by surface contact or slight polishing after application. The coatings of the present invention can be tailored to specific fields of application due to variations in film flexibility, viscosity, strength and adhesion, and thus in many situations where no sustained activity (residual gain) has been previously available. To make lasting antimicrobial protection available.

Composition Components The following provides a detailed description of the film or coating components described herein.

Water-soluble or water-dispersible film-forming agent The water-soluble or water-dispersible film-forming agent can be at least one of any agent as described below that is durable and removable. The film or coating can be removed, for example, when subjected to aqueous treatment at temperatures above 15 ° C, preferably above 30 ° C. Examples include, but are not limited to, polyvinyl alcohol, polyvinyl alcohol copolymers, polyvinyl pyrrolidone, polyacrylic acid, acrylate copolymers, ionic hydrocarbon polymers and polyurethanes, or combinations thereof.

Polyvinyl alcohol and its copolymers Polyvinyl alcohol, also referred to as poly (vinyl alcohol), is made from polyvinyl acetate by hydrolysis. The physical properties of polyvinyl alcohol are controlled by molecular weight and degree of hydrolysis. The most commonly available grades graded by the degree of hydrolysis of polyvinyl alcohol are 87-89% grade (containing 11-13 mol% residual vinyl acetate units), 96% hydrolysis grade (4 mol) % Of residual acetate acetate units), and “completely hydrolyzed” and “superhydrolyzed” grades in which more than about 98% and 99%, respectively, are hydrolyzed. Lower degrees of hydrolysis (eg 74% and 79%) are also commercially available. Some preferred degrees of hydrolysis are greater than 85 mol% or greater than 92 mol%. The polyvinyl alcohol component of the present invention may also be a vinyl alcohol copolymer such as that obtained by hydrolyzing a vinyl acetate copolymer with a small amount (about 15 mol% or less) of other monomers. possible. Suitable comonomers are, for example, esters such as acrylic acid, methacrylic acid, maleic acid or fumaric acid, itaconic acid. Similarly, hydrocarbons such as alpha-olefins such as ethylene, propylene or octadecene, higher vinyl esters such as vinyl butyrate, 2-ethylhexoate, stearate, trimethylacetate or homologues thereof (Shell Chem. Copolymerization of “VV-10” type vinyl ester) and vinyl acetate sold by Co.) provides a copolymer that can be hydrolyzed to the appropriate polyvinyl alcohol copolymer. Other suitable comonomers are N-substituted acrylamide, vinyl fluoride, allyl acetate, allyl alcohol, and the like. Similarly, free unsaturated acids such as acrylic acid, methacrylic acid, monomethylmaleic acid and the like can act as comonomers.

  Because of the various grades known or commercially available in the literature, one skilled in the art will simply average out a range of 74-99% or more by simply blending known or commercial grades in any desired ratio. A polyvinyl alcohol solution having a degree of hydrolysis can be formulated. Thus, as used herein, the term “partially hydrolyzed grade of polyvinyl alcohol” should be understood to include both single grades and mixtures of multiple grades. The term “average degree of hydrolysis” means the degree of hydrolysis reached (with appropriate weighting based on percentage) by averaging the partially hydrolyzed grades in the mixture, if used. Or if a single grade is used, it means the average degree of hydrolysis of a single grade (eg "88% grade" can be the average in the range 87-89% within the same grade). Should be understood.

  The film flexibility, water sensitivity, ease of solvation, viscosity, film strength and adhesion of the polyvinyl alcohol film can be varied by adjusting the molecular weight and degree of hydrolysis. In one embodiment, the polyvinyl alcohol for use in the process of the present invention has a degree of hydrolysis of about 85% to greater than 99%. In another embodiment, the polyvinyl alcohol has a degree of hydrolysis of about 92% to greater than 99%. In one embodiment, the polyvinyl alcohol has a number average molecular weight (Mn) that falls within a range between about 4000 and about 200,000 or about 4,000 to about 186,000 or 30,000 to about 186,000. Have In another embodiment, the polyvinyl alcohol has a molecular weight that falls within the range of between about 70,000 and 130,000. In another embodiment, polyvinyl alcohols of various molecular weights can be blended to obtain the desired properties. In one embodiment, the polyvinyl alcohol is used at about 2% to about 30% by weight of the solution. In a more specific embodiment, polyvinyl alcohol is used at about 2% to about 15% by weight of the solution. In an even more specific embodiment, polyvinyl alcohol is used at about 3% to about 6% by weight of the solution.

Polyvinylpyrrolidone (PVP)
The film-forming composition of the present invention may contain PVP at a concentration of about 0.25 to about 50% by weight. Appropriate grades of PVP are available from International Specialty Products (Wayne, NJ, 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; about 240,000 to about 450,000. K-60 having a molecular weight range of: K-90 having a molecular weight range of about 900,000 to about 1,500,000; and K- having a molecular weight range of about 2,000,000 to about 3,000,000. 120 is included. As well as combinations of PVP and other film forming compounds, mixtures of PVP can be used.

  The amount of PVP used and the molecular weight distribution will affect the viscosity, coating and cost of the final product. The viscosity should preferably be between about 20 and about 1000 centipoise, more preferably between about 20 and 100 centipoise. Typically, lower molecular weight PVP will provide a less viscous product than higher molecular weight PVP at the same concentration. For a given concentration of PVP, the viscosity will increase as the molecular weight range increases. The present invention can be utilized with PVP having any of a number of molecular weight ranges. For example, the film-forming composition can utilize the PVP grades K-15, K-30, K-60, K-90, or K-120 described above. However, it is preferred to use PVP with a molecular weight distribution between about 15,000 and about 3,000,000. PVP having this molecular weight distribution typically provides a film-forming composition with a viscosity that is easily tunable and easily washed away from the surface with no visible signs of interaction with the painted surface. . In a preferred embodiment, PVP having a molecular weight distribution between about 15,000 and about 3,000,000 is present at a concentration between about 0.25 wt% and about 40 wt%. In another preferred embodiment, PVP having a molecular weight distribution between about 60,000 and about 1,200,000 is present at a concentration between about 2 wt% and about 30 wt%.

Polyacrylate The film-forming composition of the present invention can also include an acrylate emulsion polymer. Preferred acrylate polymers are those composed of one or more copolymers of ethylenically unsaturated comonomers. Monomers useful within the compositions of the present invention include one or more ethylenically unsaturated polar or nonpolar, non-ionized monomers and at least one ethylenically unsaturated carboxylic acid. Monomers can contain more than one site of ethylenic unsaturation and suitable carboxylic acids preferably contain more than one carboxyl group. Suitable ethylenically unsaturated acids include acrylic acid, methacrylic acid, butenoic acid, maleic acid, fumaric acid, itaconic acid and cinnamic acid and dimer acids such as acrylic and methacrylic dimer acids and combinations of the foregoing. Ethylene unsaturated polar or non-polar, non-ionizable monomers include ethylene unsaturated esters, ethylene unsaturated nitriles, ethylene unsaturated alcohols, aryl vinyl compounds and arylalkyl vinyl compounds. Based on commercial availability, acrylate polymers are preferably C1-C6 in combination with acrylic or methacrylic acid, cyanoacrylates and methacrylates (eg acrylonitrile) and other known acrylic, vinyl and diene monomers. Copolymers of acrylates and methacrylates such as alkyl acrylates or methacrylates. The acrylate polymer component may optionally contain one or more metal salt complexing agents that are effective as crosslinkers. When such a complexing agent is present, it combines with pendant carboxyl groups on the acrylate polymer to form a crosslinked polymer that is more water resistant than a comparable non-crosslinked acrylate polymer. Suitable metal salt complexing agents include those containing zinc such as, for example, zinc ammonium carbonate. Other useful complexing agents include various known metal salts including, for example, zirconium, calcium, magnesium and transition metals. Typical complexing agents include polyvalent metal complexes such as zinc ammonium carbonate, ethylenediamine calcium ammonium carbonate, zinc ammonium acetate, zinc ammonium acrylate, zinc ammonium maleate, zinc ammonium aminoacetate and calcium aniline ammonium and above. Combinations are included.

  Commercially available carboxylated acrylate polymer emulsions can be used alone or in combination with each other in the film-forming composition of the present invention. Suitable commercial emulsions include those with metal complexing agents as described above as well as those without added metal complexing agents. Suitable metal-free emulsions include “Rhoplex” NT2624 (Rohm and Haas Company, Philadelphia, Pa.); “Esi-Cryl” 20/20 (emulsion) • Systems (Emulsion Systems, Valley Stream, NY, USA); “Syntran” 1905 (Interpolymer, Canton, Mass., USA) Commercial materials such as those that are possible are included. Commercial emulsions that include zinc complexing agents suitable for inclusion in the compositions of the present invention include "Duraplus" I and "Rhoplex" B-825 (both from Rohm and Haas), "Conlex "V (Morton International, Chicago, IL, USA) and" Esi-Cryl "2000 (Emulsion Systems, Valley Stream, NY, USA) Is included. Other metal-containing and metal-free acrylate emulsions as known to those skilled in the art can be used.

  The acrylate polymer component is preferably prepared as an emulsion and in the film-forming composition of the present invention ranges from about 0.25 to 30 wt% and more preferably from about 2 to 20 wt% based on the total weight of the composition. Present at a concentration of.

Ionic Hydrocarbon Copolymers Ionic hydrocarbon copolymers useful for the present invention include α-olefin polymers having the general structural formula RCH═CH 2, where R is hydrogen. And alkyl radicals having 1 to 8 carbon atoms (the olefin content of the polymer is at least 50 mol% based on the polymer), and α, β-ethylenically unsaturated having 1 or 2 carboxyl groups It is a radical selected from the class consisting of carboxylic acids (the acid monomer content of the polymer is 0.2 to 25 mol% based on the polymer). This type of polymer is described in US Pat. No. 3,264,272, which is specifically incorporated herein by reference.

Polyurethane dispersion:
A polyurethane dispersion or solution means an aqueous dispersion or aqueous solution of a polymer containing a urethane group. By cross-linked polyurethane dispersoid is meant an aqueous dispersion of a polymer containing urethane groups and crosslinks as understood by those skilled in the art. Depending on the degree of cross-linking, the polyurethane may be an aqueous solution (no or low cross-linking) or an aqueous dispersion.

  Cross-linked polyurethane dispersions are described in US Patent Application Publication No. 2005/0215663, which is specifically incorporated herein by reference. These polymers can incorporate hydrophilic functional groups to the extent required to maintain a stable dispersion of the polymer in the aqueous solution. These polymers can also incorporate ionic and nonionic functional groups to the extent required to maintain a stable dispersion of the polymer in water. Alternatively, these polymers can be obtained by emulsifying the hydrophobic polyurethane in water using a suitable external emulsifier, surfactant, etc. and / or by forming an oil-in-water dispersion using strong shear forces. It can be prepared.

  In general, the stability of a crosslinked polyurethane in an aqueous vehicle is achieved by incorporating an anionic, cationic and / or nonionic component into the polyurethane polymer that facilitates stabilization of the crosslinked polyurethane in an aqueous system. The The amount of cross-linking is selected to provide the desired water resistance. An external emulsifier can also be added to stabilize the polyurethane. Combinations of incorporated anionic, cationic and / or nonionic constituents and / or external emulsifiers can also be used.

Antimicrobial Agents Useful for the present invention can be either inorganic or organic agents or mixtures thereof. The present invention is not limited to the selection of any particular antimicrobial agent, provided that the antimicrobial agent is chemically compatible with the other components in the composition. Any known water-soluble or water-dispersible antibacterial agent, such as fungicides, antiseptics, disinfectants, sanitizers, bactericides, algicides, antifouling agents, preservatives and combinations of the foregoing and the like Can be included in the composition of the present invention. The types of suitable antibacterial agents are described below.

  As used herein, the term “inorganic antibacterial agent” is a general term for inorganic compounds containing metals or metal ions, such as silver, zinc, copper, etc., which have antibacterial properties. The term “organic antimicrobial agent” as used herein is for natural extracts, low molecular weight organic compounds and high molecular weight compounds that all have antimicrobial properties and generally contain nitrogen, sulfur, phosphorus, or similar elements. Is a general term. Examples of useful natural antibacterial agents include chitin, chitosan, antibacterial peptides such as nisin, lysozyme, wasabi extract, mustard extract, hinokitiol, tea extract and the like. High molecular weight compounds with antibacterial properties include (E.R. Kenawy) and Y.A.-G. Mammud (Y.A.-) as is known in the art. G. Mahmud), "Biologically active polymers, 6: Synthesis and antimicrobial activity of some linear copolymers with quaternary ammonium and phosphonium groups (6: Synthesis and antimicrobial activity of). some linear copolymers with quarter ammonia and phosphonium groups ", Macromolecular Bioscience (2003), No. 3 (2) 107-116) having, for example, an ammonium base, phosphonium base, sulfonium base or similar onium salt, phenylamide group, diguanide group attached to a linear or branched polymer chain such as a phosphonium salt-containing vinyl polymer Is included.

  Examples of useful low molecular weight antibacterial agents include chlorhexidine, chlorhexidine gluconate, glutaral, halazone, hexachlorophene, nitrofurazone, nitromelsol, thimerosol, C1-C5-paraben, hypochlorite, clofcarban, chlorophene, phenol Ingredients, mafenide acetate, aminacrine hydrochloride, quaternary ammonium salts, chlorine and bromine releasing compounds (eg alkali and alkaline earth hypochlorite and hypobromite, isocyanurates, chlorinated derivatives of hydantoin, sulfamides, amines, etc. ), Peroxides and peroxyacid compounds (eg, peracetic acid, peroctanoic acid), protonated short chain carboxylic acids, oxychlorocene, metabromosaran, merbromine, dibromosaran, glyceryl laurate, sodium and / or The zinc pyrithione, trisodium phosphate, and the like (dodecyl) (diethylenediamine) glycine and / or (dodecyl) (aminopropyl) glycine. Useful quaternary ammonium salts include N-C10- containing water solubilizing anions such as halides such as chlorides, bromides and iodides; heterocyclic imides such as sulfates, methosulfates and imidazolinium salts. C24-alkyl-N-benzyl quaternary ammonium salts are included. Useful phenolic fungicides 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 antibacterial agents known to be effective in preventing the visible growth of white mold colonies include, for example, 3-iodo-2-propynylbutyl carbamate, 2- (4-thiazolyl) benzimidazole, Included are diiodomethyl-p-tosylsulfone, tetrachloroisophthalonitrile, zinc complexes of 2-pyridinethiol-1-oxide (including their salts) and combinations of the foregoing.

  Coating compositions containing antimicrobial agents provide protection against a variety of microorganisms. The term “microorganism” is derived from phylogenetic domains of bacteria and archaea, as well as unicellular (eg yeast) and filamentous (eg mold) fungi, unicellular and filamentous algae, unicellular and multicellular parasites, viruses, virino and viroids. Intended to encompass any living thing.

  In one embodiment, the coating composition protects against gram positive or gram negative bacteria. Gram-positive bacteria that are inhibited or killed by the coating include Mycobacterium tuberculosis, M. et al. M. bovis, M.M. M. typhimurium, M. et al. Bovis strain BCG, BCG sub-strain, M. M. avium, M. Intracellularular, M. et al. Africanum, M. africanum Kansashi, M.M. M. marinum, M.M. M.ulcerans, M.M. M. avium subspecies paratuberculosis, Staphylococcus aureus, S. S. epidermidis, S. epidermidis. E. S. equi, Streptococcus pyogenes, S. S. agalactiae, Listeria monocytogenes, L. L. ivanovii, Bacillus anthracis, B. B. subtilis, Nocardia asteroides, and other Nocardia species, the Streptococcus viridans group, the Peptococcus species, the Peptococcus species Actinomyces israelii) and other Actinomyces species, including, but not limited to, Propionibacterium acnes and Enterococcus species. Gram-negative bacteria that are inhibited or killed by the coating include Clostridium tetani, C.I. C. perfringens, C.I. Botulinum, other Clostridium species, Pseudomonas aeruginosa, other Pseudomonas species, Campylobacter species, Vibrio cholerae E, Vibrio cholerae E P. pleuropneumoniae, Pasteurella haemolytica, P. pneumoniae. P. multocida, other Pasteurella species, Legionella pneumophila, other Legionella species, Salmonella typhi, other Salmonella species, Shigella or c Other Brucella species, Chlamydia trachomatis, C.I. C. psittaci, Coxiella burnetti, Escherichia coli, Neiseria meningitidis, N. et al. N. gonorrhea, Haemophilus influenzae, H. et al. H. ducreyi, other hemophilus species, Yersinia pestis, Y. Y. enterolitica, other Yersinia species, Escherichia coli, E. coli. E. hirae and other Escherichia species, as well as other Enterobacteriaceae, Brucella abortus and other Brucella species, Burkholderia cepacia, B. Pseudomallei, Francisella tularensis, Bacteroides fragilis (Bacteroides fragilis), Fusobacterium nuclei (Prosto), Proctorum ) Species and Proteus species, but are not limited to these. In another embodiment, the coating is Alternaria alternata, Aspergillus niger, Aureobasidium pullulans, Cladosporum cladosporoids, Drechlera australiensis, Gliomastyx cererias, Monilia grisea, Penicillium commune, Pima homme ti), Pitomisesu-Karutarumu (Pithomyces chartarum) and scores Recoba Shijiumu & Humicola (Scolecobasidium humicola) (but not being limited thereto, including a) provides protection against fungi.

Enzymes Enzymes useful for the present invention include enzymes that have beneficial effects such as cleaning, destaining and biofilm degradation. These enzymes include one or a mixture of deacetylases, amidases, cellulases, esterases, glycosidases, xylanases, amylases, transaminases, laminarinases, beta galactosidases, beta mannosidases, pullulanases, phosphatases, proteases, lipases and peroxidases. included.

Surfactant:
Compositions useful for the present invention can also contain one or more surfactants. While not being bound by theory, it is believed that the surfactant will help wet the surface to be coated and assist in even coverage with the film. Surfactants are also thought to help foam by the film at the time of removal, thus helping to remove the film and clean the protected surface. Suitable surfactants have a preferred hydrophilic-lipophilic balance (HLB) of about 9 to about 17. Suitable surfactants include amphoteric surfactants such as Amphoteric N from Tomah Products; silicone surfactants such as BYK348 available from BYK-Chemie (BYK-Chemie GmbH) Wesel, Germany); fluorinated surfactants such as Zonyl® FS300 (DuPont, Wilmington, Del.); And nonylphenoxy polyethoxyethanol surfactants such as Dow (But not limited to) Triton N-101 (Midland, MI, USA) available from (Dow). Other suitable surfactants include ethoxylated decyne diols such as Surfynol 465 available from Air Products & Chemicals (Allentown, PA, USA); alkyl Aryl polyethers such as Triton CF-10 available from Dow; octylphenoxypolyethoxyethanol such as Triton X-100 available from Dow; ethoxylated alcohols such as Shell (Hague, the Netherlands, The Netherlands) )) Neodol 23-5 or Neodol 91-8 available from; Tegitol 15-S-7 available from Dow, Stepan Steol-4N, 28% sodium laureth sulfate, manufactured by Stepan Company (Northfield, IL, USA), a sorbitan derivative, such as Uniqema (New Castle, Delaware, USA) , DE, USA)) Tween 20 or Tween 60, and quaternary ammonium compounds such as benzalkonium chloride.

  Other suitable surfactants include organosilane surfactants such as Silwet® L-77 from Setra Chemical Company (Mephis, TN, USA), Dow Corning (R) Q2-5211, manufactured by Dow Corning Silicones (Midland, MI, USA), or Siltech Corporation (Toronto, ON, Canada) , Canada)) Silsurf® A008.

  A preferred range for the use of the surfactant is from about 0.001 to about 1 wt% of the formulation, more preferably from about 0.01 to about 0.2 wt%.

solvent:
Inert solvents useful for the present invention include water. Additional solvents preferably include monoalcohol monofunctional and polyfunctional alcohols 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 higher glycols, polyglycols, polyoxides, glycol ethers and propylene glycol ethers. Additional solvents include alkali acids of free acids and sulfonated alkylaryls such as toluene, xylene, cumene and phenol or phenol ether or diphenyl ether sulfonate; alkyl and dialkylnaphthalene sulfonate and alkoxylated derivatives.

Additional components Additional components that can be added to the coating composition include colorants, rheology modifiers, crosslinkers, plasticizers, surfactants, solubilizers, antioxidants, pH adjusters, wetting agents. Anti-foaming agents, bulking agents, lubricants, processing aids, anti-discoloring agents and additional performance enhancing agents. Wetting agents reduce the surface tension of the formulation, which wets the surface and spreads on the surface, potentially dirt, solid materials, microorganisms, biofilms, surface contaminants, fats and surfaces Allow entry into, below and around the gap.

Colorant:
Colorants useful for the present invention include dyes and pigments such as food grade pigments.

  Dyes useful for the present invention include both water-soluble and water-insoluble dyes. Water-soluble dyes can be easily formulated in the aqueous system of the present invention. Water insolubility can be included in the oil phase and dispersed or suspended in the antimicrobial coating composition useful for the present invention. Dyes useful for the purposes of the present invention are typically organic compounds that absorb visible light and result in a detectable color appearance. For example, fluorescent dyes can be used to visualize the film with ultraviolet light.

  For food processing industries, including restaurant surfaces and for fruits, in one embodiment of the present invention, it is generally accepted because it is typically approved for use as a direct food additive. FD & C approved dyes can be used. Dyes that are standardly useful in the present invention are colorants approved for use in foods, drugs, cosmetics and medical devices.

  The colorants currently used and their current status are described below. Permitted in foods (1) The colorant to be certified is FD & C Blue No. 1, FD & C Blue No. 1 2, FD & C Green No. 3, FD & C Red No. 3, FD & C Red No. 40, FD & C Yellow No. 5, FD & C Yellow No. 6, Citra Thread No. 2 and Orange (B), (2) Colorant exempted from certification is Anato Extract, Theta Apo 8 'Carotenal, Canthaxanthin, Caramel, Theta Carotene, Carrot Oil, Cochineal Extract (Carmine) , Cornendos palm oil, dried beet (powdered beet), dried algal food, ferrous gluconate, fruit juice, indigo fruit extract, grape skin extract, paprika, paprika oleoresin, riboflavin, saffron, synthetic iron oxide, marigold extract , Titanium dioxide, toasted partially defatted cottonseed flour, turmeric, turmeric oleoresin, ultramarine blue and vegetable juice. The colorant permitted in the drug (including the colorant permitted in the food) and subjected to the certification is FD & C Red No. 4. D & C Blue No. 4 4. D & C Blue No. 4 9, D & C Green No. 5, D & C Green No. 6, D & C Green No. 8, D & C Orange No. 4. D & C Orange No. 4 5, D & C Orange No. 10, D & C Orange No. 11, D & C Red No. 6, D & C Red No. 7, D & C Red No. 17, D & C Red No. 21, D & C Red No. 22, D & C Red No. 27, D & C Red No. 28, D & C Red No. 30, D & C Red No. 31, D & C Red No. 33, D & C Red No. 34, D & C Red No. 36, D & C Red No. 39, D & C Violet No. 2, 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). It is. In addition, candaxanthin, beta-carotene, chlorophyllin and other pigments are also known.

For a more detailed list and / or discussion of approved pigments, see D.C. M.M. M. Marmion, “Handbook of US Colorants, Foods, US Colorants, Food, Drugs, Cosmetics and Medical Devices Handbook,
Drugs, Cosmetics and Medical Devices, "John Wiley & Sons Inc., New York (1991), and" US Code of Federals ". ) ", Volume 21, Parts 70-82.

Rheology modifier:
The compositions useful for the present invention contain one or more rheology modifiers or rheology agents that are used to enhance or thicken the viscosity and to adhere the aqueous treatment or coating composition to the surface. You can also. Adhesion allows the composition to remain in contact with transient and resident microorganisms for longer periods of time, promoting microbiological efficacy and combating waste due to excessive dripping. The rheology modifier can be a film-forming element or can interact with the film-forming agent to form a barrier that provides additional protection. Useful soluble or water dispersible rheology modifiers can be classified as inorganic or organic. Organic thickeners can be further divided into natural polymers and synthetic polymers, which can be further subdivided into synthetic natural-based polymers and synthetic petroleum-based polymers.

  Inorganic thickeners are generally colloidal magnesium aluminum silicate (VEEGUM®), colloidal clay (bentonite) or silica (CAB-O-SIL (which has been spun or precipitated to produce particles with a large surface to size ratio). Registered trademark))). Useful natural hydrogel thickeners are primarily plant-derived leachates. For example, tragacanth, karaya and acacia gum; and extracts such as carrageenan, locust bean gum, guar gum and pectin; or pure culture fermentation products such as xanthan gum may all be useful in the present invention. Chemically, these materials are all salts of complex anionic polysaccharides. Applicable synthetic natural-based thickeners are cellulose derivatives that provide a family of substances in which free hydroxyl groups on a linear anhydroglucose polymer are etherified or esterified and dissolve in water to provide a viscous solution. is there. This group of materials includes alkyl and hydroxyl alkyl celluloses, specifically methyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, hydroxybutyl methyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, hydroxypropyl cellulose and carboxymethyl cellulose. Another preferred group of thickeners include polyacrylates such as patented Acusol thickeners (eg, Acusol 823, Rohm and Haas, Philadelphia, PA, USA), and Carbopol thickeners such as Carbopol 934. Or Carbopol Aqua-30 Polymer (BF Goodrich, Cleveland, Ohio, USA). Polyacrylate thickeners can be used at concentrations up to about 3 wt% of the weight of the film-forming element. It is also possible to utilize a thickener mixture that can have a total amount of about 3 wt% or less, depending on the thickener utilized and the desired viscosity of the final product.

  Other potential thickeners for this area of use include dextrin, corn starch and hydrous magnesium silicate, such as Laponite XLG (Southern Clay Products, Inc., Gonzales, Texas, USA). , TX, USA)).

Cross-linking agent:
The present invention may optionally include a cross-linking agent. Advantages of using a cross-linking agent with the film-forming composition include affecting mechanical film properties such as tack and mechanical strength and coating solubility. In the present invention, the cross-linked film produced a mechanically much stronger film. Furthermore, cross-linking reduces stickiness and prevents soil and microorganisms from physically adhering to the polymer film, which may be desirable for some applications. In the present invention, the cross-linking had a beneficial effect on the release of the antimicrobial agent from the film. The degree of cross-linking is adjusted to achieve the desired combination of properties.

  Suitable crosslinking agents for use with polyvinyl alcohol and copolymers thereof include aldehydes (eg formaldehyde, glyoxal, glutaraldehyde), boric acid, sodium tetraborate, metal ions (eg Zn, Fe, Al, Ni, Ions of V, Co, Cu, Zr, Ti, Mn), organometallic compounds (eg, organic titanates such as DuPont Tyzor®, organic Cr (III) complexes such as DuPont Quilon®), Siloxane (eg, tetraethoxysilane, polydimethylsiloxane), isocyanate (eg, block type, water-soluble or dispersed type), epoxide (eg, diglycidyl ether), dicarboxylic acid (eg, oxalic acid, maleic acid, fumaric acid, Phthalic acid), urea base Other crosslinking agents (eg, Sunrez 700), but are not limited thereto. Divalent and trivalent metal cations (eg, Fe (II), Fe (III), Al (III) are preferred because they provide the formation of coordination linkages between PVOH polymer chains at the time of film drying. In this way, it is possible to add a cross-linking agent to the film-forming liquid in a “one pot” mixture, suitable for efficient cross-linking of the polymer without precipitating other components such as particle rheology control agents. Care must be taken to select the concentration.

  In most cases, the crosslinker will be mixed with the 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. In the case of aldehydes, isocyanates, siloxanes, diglycidyl ethers and dicarboxylic acids, it is possible to additionally use heat and acid or metal catalysts.

  The concentration of the cross-linking agent in the formulation can be from zero to an upper limit determined by the stability limit of the formulation where precipitation begins to occur or by the inability to efficiently remove the resulting film. The preferred crosslinker concentration can vary greatly depending on the type of crosslinker used and is typically less than 25 wt% of the polymer content, more preferably less than 10 wt% of the polymer content.

Plasticizer:
For the flexibility and integrity of the protective film, it is important that the resulting film is plasticized. Film plasticization was achieved for the purposes of the present invention by incorporation of a suitable plasticizer such as polyethylene glycol or glycerol. Other plasticizers suitable for the present invention include, but are not limited to, solvents, polyols, polyethylene glycol and sorbitol having an average molecular weight of 200-800 g / mol. Glycerol is easily metabolized by microorganisms, potentially resulting in the growth of pathogens, so PEG is preferred over glycerol.

  The inclusion of a plasticizer also allows the film to retain the slightly tacky surface feel. As the plasticizer level increases, the resulting film will also exhibit an increased degree of tack. Such stickiness may be desired to be at a low level to trap airborne particles and dirt or other materials. However, if the plasticizer level is too high, the coating will be too sticky and will exhibit low resistance to accidental mechanical removal, for example by wiping. A preferred plasticizer amount is from about 1.0 wt% to about 20 wt%, more preferably from about 5 wt% to about 8 wt% of the weight of the film-forming element.

Additional performance enhancers:
In addition to the components described above, the compositions of the present invention can also include one or more performance enhancing additives, “performance enhancing substances”. These include flash rust rust inhibitors that include any of a number of organic or inorganic materials used in aqueous systems to prevent the formation of rust on contact with the material and metal. One example is sodium benzoate.

  Another optional performance enhancing additive is one or more of a series of antifoams recommended for aqueous systems to prevent undesirable foaming of the product during application. Too much foam can break the required continuous film formation of the product, resulting in product failure. Similarly, a masking composition, such as Drewplus L475 from Ashland Chemical, Inc. Drew Industrial Division (Covington, KY, USA). It may also be advantageous to add foam control products to help in processing.

  An additional optional performance enhancing additive is an antioxidant to extend the shelf life of the coating formulation. One example is butylated hydroxytoluene. Additional additives include fragrances.

  A blowing agent can additionally be added to create bubbles in the applied coating. Air bubbles can be used to facilitate application and / or to allow for longer contact times with the surface, such as by preventing dripping from an inclined surface and / or to treat a certain surface area or volume. It can function as an opacifier to reduce the amount of coating formulation required.

  Application indicators can be added as well. Some of them have been mentioned above, but also include pigments, dyes, fluorescent dyes or bubbles generated during application.

  Small amounts (typically less than 1 weight percent) of these additional materials can be added with appropriate adjustment of water or other components. It should be understood that mixtures of any one or more of the optional components described above can be utilized as well.

  For locations comprised of fibrous substrates, any performance enhancing component is an agent that provides a surface effect. Such surface effects include no ironing, easy ironing, shrinkage control, wrinkle prevention, permanent press, humidity control, flexibility, strength, anti-slip, antistatic, fraying prevention, hairball prevention, stain prevention , Stain removal, stain prevention, stain release, water repellency, oil repellency, deodorization, antibacterial or sun protection.

Application of antibacterial coating composition:
The film or coating can be applied to the target surface or location by any means including injection. The film or coating is applied to achieve a continuous and / or homogeneous layer on the target surface. Coating systems routinely used for paints and coatings, such as but not limited to brushes, rollers, paint pads, mats, sponges, combs, manual pump dispensers, compressed air spray guns, airless Spray guns, electric or electrostatic atomizers, shoulder spray applicators, cloth, paper, feathers, styluses, knives and other applicator tools can be used for coating. If dipping is used as a method for applying the coating, no special equipment is required. For fibrous substrates such as fabrics and carpets, consumable, foam, flex-nip, nip, pad, kiss roll, beck, skein, winch, liquid jet, The coating can be applied by overflow flood, roll, brush, roller, spray, dipping, dipping, and the like. The coating can also be applied using conventional Beck dyeing procedures, continuous dyeing procedures or threadline application.

  The coating system may be one or more components and may include a catalyst.

  In one embodiment of the invention, an electrostatic sprayer can be used to coat the surface. The electrostatic sprayer imparts energy to the aqueous coating composition via a high potential. This energy helps 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. in Korea and Spectrum in Houston, TX, USA. . Generally, the coating is cured or dried for more than approximately 5 minutes to form a film. However, the coating may also exhibit antibacterial effects within a shorter time frame, such as after 30 seconds. The coating may be removed prior to drying or at any time thereafter, depending on the desired application. Drying time will depend in part on a number of factors including environmental conditions such as humidity and temperature. The drying time will also depend on the thickness of the coating applied.

  In another embodiment of the invention, an airless spray gun can be used to coat the target surface. Airless spray guns use high fluid pressure and special nozzles rather than compressed air to convey and atomize the liquid. Liquid is typically supplied to the airless gun by a fluid pump at a pressure in the range of 500-6500 psi. When the paint exits the fluid nozzle at this pressure, it expands slightly and atomizes into very small droplets without impact with the atomizing air. The high velocity of the exiting paint propels the droplet toward the target surface. The fluid nozzle on the airless gun is substantially different from the fluid nozzle on the air atomizing gun. The selection of an appropriate nozzle will determine the amount of paint to be delivered and the applied fan pattern. The size of the airless nozzle orifice determines the quantity of paint to be sprayed. Airless fluid delivery is high, 700-2000 mL / min. The recommended gun distance is 12 inches from the target, and 5-17 inch fan patterns are possible, depending on the nozzle type. Thus, a nozzle 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 produce little turbulence that can bounce off liquids from “hard to reach” areas such as those found in food processing equipment and hatcheries. The high flow rate makes airless advantageous under cleaning and disinfection situations where an antimicrobial coating must be applied on a large surface area and multiple surfaces.

  The thickness of the applied and dried film will depend on various factors. These factors include film former concentration, rheology control additive and / or other additive concentrations, as well as application temperature and humidity. Film thickness and film homogeneity are similarly at least in part, such as fluid delivery, spray orifice diameter, pneumatic pump or piston pump pressure in the case of airless applications, and distance from spray applicator to target surface, etc. It depends on the parameters of the applicable equipment. Thus, the liquid formulation can be tailored to produce the desired film thickness. The atomization of the coating solution is selected in such a way that a thin film is uniformly applied to the target part.

  Generally, the coating is cured or dried for about 5 minutes to about 60 minutes to form a film. When applied, the composition will form a film or coating by evaporation of the inert solvent. Evaporation of the solvent can occur by drying the coating in situ or by heating or alternatively spray drying with unheated air. However, the coating can be effective as an antimicrobial agent within a shorter time frame, such as after 30 seconds. The coating can be removed before it dries or at any time thereafter, depending on the desired application. Drying time will depend in part on a number of factors including environmental conditions such as humidity and temperature. The drying time will also depend on the thickness of the coating applied. 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.

Film or coating thickness:
The thickness of the film or coating applied on the target surface affects the time required for removal and the amount of biocide per unit area applied to the surface. The greater the thickness of the film, the longer the time interval before the film must be reapplied to maintain the desired antimicrobial properties. Thinner films are more easily and quickly removed by flushing. Thus, it is important to apply the formulation in a manner that results in a film thickness that allows both easy removal of the coating and long lasting antimicrobial properties. As mentioned above, 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.

Film removal:
The present invention relates to a film that can be removed when it is determined appropriate by the user. The time of removal is i) the desired minimum contact time to allow the desired antimicrobial activity, typically expressed as the amount of dead or inactivated microorganisms in the starting population, or (ii) ) Can be determined by either the need or desire to remove the coating from the surface before initiating subsequent work or process steps. The coating can be removed at any time, such as after drying, but the thickness of the film, the concentration of the antimicrobial agent, and the particular application will determine the appropriate point of removal. For example, the user may wish to return the processed equipment to normal operation after a shutdown period. For example, fruits need to be washed before eating. When the biocide in the film is exhausted, the film can be removed and a new coating layer can be applied. For example, the drain can be processed periodically, such as daily, weekly, or biweekly. Antimicrobial activity can be measured as early as 30 seconds after application of the film, or after hours, days, weeks, months or even years. Therefore, the timing of removing the coating depends on the field of application of the coating.

  Film removal can be achieved by dissolution or dispersion of the resulting coating. This can be achieved by applying an aqueous solution on the coating. In one embodiment, the temperature of the solution is in the range of about 15 to 100 degrees Celsius. In another embodiment, the temperature of the solution is from about 30 degrees Celsius to about 80 degrees Celsius. Application of solution or water can be achieved by simple washing or spraying on the surface. Coating removal can also be accomplished using a pressure washer that facilitates removal by additional mechanical force. Decoating can also be accomplished by washing with water in conjunction with a cloth or sponge. In addition, mild additives including commonly used acids or bases, chelating agents, or detergents can be used to mix with aqueous solutions to assist in solubilizing or dispersing the film forming or water dispersing agent. it can. Alternatively, as in the drain, the film can be broken down by repeatedly washing the drain down with water and / or other components. Similarly, the film can be peeled away from the surface, removed by polishing or brushing from the surface, or by other mechanical removal mechanisms.

  Except for intentional removal by the operator, removal may include removal by automated or robotic systems, and by liquid or wear, for example, in liquid or continuous contact with the coating over time in pipes or drains. Unintentional removal by continuous or periodic application of mechanical forces is also included.

Other terms:
For clarity, terms used herein are understood as described herein or as such terms would be understood by one of ordinary skill in the art of the invention. Should. Additional explanations for certain terms used herein are as follows:

Aqueous solution:
The aqueous solution used for coating removal is any solution containing 60-100 wt% water with the remaining components dissolved. Dissolved components include, but are not limited to, solvents such as alcohols, solubilizers, surfactants, salts, chelating agents, acids and bases.

Durable:
The term durable within the context of the present specification relates to the dry coating material remaining on the surface until its removal can be deliberately initiated or made. Use conditions are environmental conditions that prevail for the application field of the invention while the coating remains on the target surface, which may include accidental contact with water at temperatures below 40 degrees Celsius. .

Continuous:
The term continuous or substantially continuous means within this context a coating that covers a target surface that is free of coating defects such as uncoated parts, indentations and holes.

Homogeneous:
The term homogeneous or substantially homogeneous within this context means a coating with negligible thickness variation across the coating surface. A coating that is not homogeneous or substantially non-homogeneous will not provide uniform antimicrobial and removal properties across the surface to which the coating is applied.

Residual antimicrobial efficacy:
The term “residual antimicrobial efficacy” (or self-cleaning properties) refers to the properties of a coating formed as described herein that remains active even after repeated challenge with pathogenic bacteria. Yes. According to the present invention, a reduction of at least 3-log units is achieved after each inoculation over at least two inoculation cycles of at least 10 ⁶ cells per square inch. The test method used to determine the residual antimicrobial efficacy is described in Example 16.

Contact time for antimicrobial coating:
Depending on the specific requirements for the antibacterial formulation, the contact time may be determined according to the “disinfectant germicidal and cleansing action, American Official Analytical Chemistry Association Official Analytical Method” section 960.09 and the applicable section, Fluctuates as described in the 15th edition, 1990 (EPA Guideline 91-2). Where the intended field of use of the present invention is as a sanitizer, the composition is 99.999% within 30 seconds at room temperature (25 +/− 2 ° C.) for multiple test organisms. Reduction (5-log reduction) should be provided). On the other hand, if it is intended to use the present invention as a disinfectant, the composition should provide a 99.9% reduction (about 3 logs reduction) within 10 minutes. If the intended field of application is to be utilized as a residual antimicrobial activity, the present invention can have a contact time of more than 10 minutes with a microorganism.

Physical barrier A physical barrier is defined as a film formed from the film-forming composition. The resulting film seals the treated surface against contamination from the surrounding environment such as dirt, fat, dust, microorganisms. These contaminations will remain on the surface of the coating and will be washed away at the time of removal of the coating.

  All methods and compositions disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. While the methods and compositions of the present disclosure have been described with respect to various aspects of the present invention and preferred embodiments, those skilled in the art will have described herein without departing from the concept, spirit, and scope of the present invention. It will be apparent that changes can be made in the compositions and methods and method steps or sequence of methods present. More specifically, it is evident that some chemically related agents may be substituted for the agents described herein to achieve the same or similar results. It becomes. Such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and concept of the invention as defined by the appended claims.

  The invention is further defined in the following examples. These examples illustrate some preferred embodiments of the present invention, but are given for illustrative purposes only. From the foregoing discussion and these examples, one of ordinary skill in the art can determine the basic features of the present invention and adapt it to various applications and conditions without departing from the spirit and scope thereof. it can.

Abbreviations and other terms:
In the following examples, “degrees Celsius” is abbreviated as “° C.”.
ATCC-American Type Culture Collection BHI-Brain Heart Infusion
BHT-Butylated hydroxytoluene CFU-colony forming unit Conc. -Concentration cP-Centipoise DI-Deionized L-Liter LB-Luria Bertani Bros M-Mole / L MW-Molecular weight NA in grams / Mole-Not applicable ND-Undecided PBS-Phosphate buffered saline solution (Buffer): 10-fold stock solution at pH 6.8; NaCl (80); KCl (2.0); NaH ₂ PO ₄ (14.4); KH ₂ PO ₄ (2.4) (g / 800 mL)-Polyethylene glycol PVOH-Polyvinyl alcohol QAC-Quaternary ammonium compound RAC-Removable antimicrobial coating RPM-Rotational speed SS316-Stainless steel, type 316 (ASTM standard)
UHMWPE-Ultra high molecular weight polyethylene wt%-Weight percent ZOD-Diffusion zone

  All chemicals were obtained from Sigma-Aldrich (St. Louis, MO, USA) unless otherwise specified. Laponite® was obtained from Rockwood Additives Ltd. (Widnes, UK). Pseudomonas F-Agar is a product of Fisher Scientific (Pittsburgh, PA, USA); yeast extract, brain heart infusion (BHI), trypsin soy agar, trypsin soy broth. And Oxford Medium Base from Difco Products (Franklin Lake, NJ, Becton Dickenson, Franklin Lakes, NJ, USA); Dextrose and Magnesium Sulfate Heptahydrate (JT Baker) (Phillipsbu, New Jersey, USA) g, NJ, USA)); Elvanol (R) (71-30 and 52-22), polyurethane (RCP31374), Zonyl (R) surfactant and titanium dioxide are available from DuPont (Wilmington, Delaware, USA) Obtained from Kollicoat®-IR was obtained from BASF (Ludwigshafen, Germany). Silwet® L-77 was obtained from GE Silicones (Wilton, CT, USA). BYK (R) 425 was obtained from Big Chemie (Big Chemie, Wesel, Germany). DowCorning® Q2-5211 and Antifoam C were obtained from Dow Corning® Silicone (Midland, Michigan, USA). Silsurf® A012 was obtained from Siltec Corporation (Toronto, Ontario, Canada). Sil-co-sil® was obtained from US Silica® Company (Berkeley Springs, WV, USA). Chikasan, Carrageenan and Guar 8/22 were supplied by TIC Gums (Belcamps, MD, USA). Alcogum® L1228, L15, L520 and L251 rheological additives are obtained from Alco Chemical® (Chattanooga, TN, USA) and after the addition of the antimicrobial composition Neutralized at the time of formulation according to the supplier's regulations. Viskalex® HV100 and HV30 were obtained from Ciba® (Basel, Switzerland).

General method:
Test Methods for Antibacterial Efficacy in Solution The biocidal or antibacterial efficacy in solution can be determined by assays generally known in the art, as described in the following examples.

Test Method for Antibacterial and Antifungal Efficacy of Coatings by Diffusion Zone Test To evaluate the antibacterial and antifungal efficacy of antibacterial coatings, a diffusion zone (ZOD) test was utilized as described below.

Stainless steel cut coupons (1 inch x 3 inches) were dipped into the RAC formulation and allowed to dry completely overnight. An overnight culture of Staphylococcus aureus ATCC 6358 was prepared by taking a single colony from a refrigerated stock plate in a sterile inoculation loop and inoculating into 25 mL trypsin soy broth in a 250 mL sterile Erlenmeyer flask. . The cultures were incubated overnight at 30 ° C. with shaking at 150 RPM. By growing stock plates (malt extract agar) for 2 weeks at 25 ° C. and flooding the plates with 15 mL of filter sterilized saline solution (0.85% Nacl plus 0.05% Triton X-100) Fungal spores (Aspergillus niger and Penicillium expansium) were prepared. The plate was then scraped with a sterile plastic cell scraper, the liquid was pipetted off, vortexed and filtered through 3-4 layers of sterile cheesecloth. The spore suspension CFU was determined by fixing a serial dilution on a malt extract agar plate. Coated cut coupons were placed on an LB agar plate (plate center) for 60 minutes to allow the soluble components of the coating to diffuse into the agar. Soft agar (PBS buffer or 0.7 wt% agar in water) was prepared and aliquoted into 5 mL aliquots in sterile plastic centrifuge tubes and kept at 50 ° C. in a water bath until use. After 60 minutes, the cut specimen was removed by lifting it straight up with sterile forceps, taking care not to slip the cut specimen across the surface of the agar. Any coating pieces left on the surface of the agar were also removed with sterile forceps. Each soft agar tube is inoculated with 100 μL of a 1:10 dilution of the overnight bacterial culture prepared above. If fungal spores were used in the test, the spores of about 10 ³ cells / mL was inoculated into soft agar. The tube was rocked to gently mix the agar, and then the agar was poured onto the surface of the LB agar plate holding the coated cut coupons. The plate was swirled to completely cover the surface with soft agar. Soft agar solidified almost immediately. Bacterial inoculation plates were incubated overnight at 35 ° C. and incubated for 2 days at 25 ° C. with fungal inoculation plates. All plates were photographed to record the zone of inhibition provided by the antimicrobial agent that diffused from the antimicrobial coating into the agar. The area of this diffusion zone (ZOD) was analyzed with image analysis software ((ImageJ, version 1.36b, National Institutes of Health) and normalized by the area of the cut specimen used.All agar diffusion studies Had a control coupon that was coated with a formulation lacking antimicrobial agent.

  Determination of rheological properties: The rheological properties of the liquid antibacterial formulation were assessed using a rheometer that performs up and down flow curves. The rheometer used was Brookfield HAV-III + (Brookfield Engineering, Middleboro, Mass., USA) with Couette configuration, adapter for small samples, spindle SC4-21 and sample chamber 13RP. Met. The temperature was kept at 25 ° C. with a thermostat bath. Samples were loaded by pouring or scooping into a Brookfield sample holder. The program included a 5 minute pre-shear time at a pre-shear rate of 250 l / sec followed by a 10 minute rest time. Viscosity measurements were made at 0.1, 0.5, 5, 50, 100, 200, 100, 50, 5, 0.5, 0.1 RPM. The viscosity measurement interval was 2 minutes.

Example 1
Polyvinyl alcohol (PVOH) (DuPont Elvanol®, grade 71-30, molecular weight of about 94,000, degree of hydrolysis 99.0-99.8%; DuPont, Wilmington, Del., USA) as a film former did. A PVOH stock solution was prepared by mixing Elvanol® grade 71-30 powder in 90 ° C. deionized water to produce a 3-8 wt% solution. The mixture was stirred with a magnetic stir bar for about 20 minutes until the polyvinyl alcohol was completely dissolved. The mixture was allowed to cool to room temperature.

  Benzalkonium chloride (QAC) as a variable amount of active biocide, poly (ethylene glycol) (PEG) with a molecular weight of about 300 grams / mole as a film plasticizer, polyoxyethylene sorbitan laurate interface as a wetting agent A blend base solution was prepared by mixing activator and butylated hydroxytoluene (BHT) as antioxidant and a polyvinyl alcohol stock solution. The QAC used was mainly a mixture of C12 and C14 analogs of Sigma-Alkyldimethylammonium Chloride (Sigma-Aldrich) but also contained small amounts of lower and higher analogs.

  The formulation base solution was then mixed with additional additives to obtain the final spray formulation. These additives include cross-linking agents such as ferric chloride and ferrous chloride, rheology control improvers such as synthetic laminated silicates (Laponite®) and colorants such as food colorants and titanium dioxide. And contained opacifier. A liquid film forming mixture was prepared as schematically shown in Table 1. In the following examples, the mixture is referred to by the formulation number.

Example 2
This example demonstrated that the coating was substantially continuous and homogeneous.

  Films were prepared from the liquid mixture schematically shown in Example 1. This was done by spraying the liquid on a cut coupon (22 mm x 60 mm) or immersing the cut coupon in the solution. To spray the liquid, a standard pump fire spray bottle was filled with the liquid and sprayed onto the cut specimen. In most cases, stainless steel was cut and used as the specimen material. When a spray was used, the coupon was cut vertically and oriented with respect to the horizontal vertical food equipment surface to be treated with the antimicrobial formulation. For both dipping and spraying, the coupons were then dried in a vertical orientation at room temperature for at least 2 hours, typically overnight. After adding a trace amount of fluorescent dye (rhodamine 123) to the film-forming composition, the thickness of a part of the film was measured using a confocal laser scanning microscope. A Zeiss LM510 confocal microscope with Carl Zeiss LSM-5 image analysis software (Carl Zeiss MicroImaging, Thornwood, NY, USA) was used.

  It was found that the formulation with 4.0 wt% PVOH had a thickness of about 20 micrometers. The resulting film became thinner as the PVOH concentration was lowered. FIG. 2 shows a cross section of formulation # 2 through the depth of the film coating in two orthogonal planes. A high degree of homogeneity within the thickness of the film and the absence of structural film defects (eg, holes, cracks, indentations, air inclusions, etc.) could be clearly observed. For protective functionality, high homogeneity of the film is extremely important. Structural film defects or significant thickness variations can result in parts that are less protected from pathogen contamination.

  Different film textures were prepared depending on the formulation. Formulation # 14a spray resulted in a rubbery and flexible film after drying. In contrast, the spray of Formulation # 16 resulted in a very stiff and hard film after drying. The texture could be used according to the needs of the workers.

  The dripping of the film-forming liquid from the vertical surface after spraying is accomplished by adding 0.5-1.5 wt% colloidal synthetic laminated silicate (Laponite® RD) as a thixotropic rheology control modifier. Could be prevented.

Example 3
This example demonstrates that the solubility of the coating depends on the concentration of the crosslinker.

  The formulation can be adjusted to allow the film to be easily removed over a wide water temperature range. Film formulations can be developed to allow the film to dissolve at either low or high water temperatures. For example, films formed from Formulations # 2 and # 10 can be easily wiped mechanically with a cotton ball and easily dissolved after rinsing with either 20 ° C or 98 ° C water. It was. The film formed from formulation # 14a could be easily wiped mechanically and dissolved easily in 98 ° C. water, but not easily dissolved in 20 ° C. water. In order to achieve stability in cold water, a crosslinking agent had to be added to the mixture. At concentrations of liquid formulations between 0.1-1 wt%, both Fe (II), chloride and Fe (III) -chloride were suitable crosslinkers.

Example 4
Two plastic cover slips (type Thermonox® # 1749442, 22 mm × 60 mm; Nalge Nunc International, Rochester, NY, USA), 1.0 g / Soaked in a 4 wt% PVOH solution containing L benzalkonium chloride biocide. Two additional cover slips were immersed in a 4 wt% PVOH solution without benzalkonium chloride as a control. The coverslip was placed in a 50 mL centrifuge tube and allowed to air dry overnight.

A culture of Listeria welshimeri (ATCC 35897) was prepared by growing single cell colonies in 25 mL BHI (37 g / L) in a 125 mL shake flask at 30 ° C. with shaking at 150 RPM. Incubated overnight. The cell concentration of this overnight culture was approximately 1 × 10 ⁹ cells per mL. The culture was diluted 100-fold with Welshimer medium (see Table 2 for medium composition) to obtain a cell concentration of about 1 × 10 ⁷ cells / mL. The cut specimen was placed in a 50 mL centrifuge tube and cell suspension (10 mL) was added to the tube. Due to the high cell concentration, the cell suspension was completely opaque in the 50 mL tube. The tube was covered gently with a cap and incubated at 22 ° C. with shaking at 150 RPM.

  After 24 hours, the liquid with the biocide QAC-containing coupon turned completely transparent to the human eye, indicating significant cell lysis. In contrast, fluid with cut coupons that lacked QAC was still completely opaque, indicating some significant lack of cell lysis.

Example 5
One stainless steel coupon (format 22 mm x 60 mm x 1 mm) was coated with formulation # 22 by dipping and allowed to air dry. As a control, a second coupon was left uncoated. Two cut specimens were placed in a 50 mL centrifuge tube.

By growing single cell colonies in 25 mL BHI as described above, A culture of L. welshimeri (strain DUP-1074) was prepared. The cell concentration of this overnight culture was about 1 × 10 ⁹ cells per mL. The culture was diluted 10,000 times with modified well simmer medium to obtain a cell concentration of about 1 × 10 ⁵ cells / mL. This cell suspension (25 mL) is added to each cut specimen in a 50 mL centrifuge tube, and the tube is placed horizontally in an incubator shaker and shaken at 25 ° C. while shaking at 150 RPM. It was.

Samples (500 μL) were removed from each tube after 10 and 240 minutes. Make serial dilutions of each sample, plate 100 μL of each dilution onto a standard LB agar plate (Teknova, Inc., Hollister, Calif., USA) Incubated at 33 ° C. The number of CFU was counted after 24 hours. In samples taken after 10 minutes, no significant cell loss was observed (compared to the control). However, the viable cell concentration decreased from 4.7 × 10 ⁴ cells / mL to only 30 cells / mL after 240 minutes, representing a significant 3.2 log reduction in cell viability.

Example 6
Experiments were conducted to see if the surface sprayed with the antimicrobial film coating could delay the onset of biofilm formation. Stainless steel cut specimens (SS316, 22 mm x 60 mm x 1 mm) were sprayed with formulations # 14a, # 16 and # 17 in a vertical position or left untreated. The coupons were air dried overnight in a vertical position.

  From a single colony grown overnight in 30 mL of standard M9 medium (see Table 3) with shaking at 150 RPM, Pseudomonas fluorescens (ATCC 700830, Manassas, VA, USA) Manassas, VA, USA)) cultures were prepared. 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). Diluted cultures in LB medium (10 mL) were added to each centrifuge tube. The tube was covered gently with a cap and incubated at 30 ° C. with shaking at 150 RPM. The medium was changed daily with 10 mL fresh diluted LB medium.

Table 4 shows that the medium was changed every day. 1 schematically illustrates biofilm control properties of selected antimicrobial PVOH films challenged with P. fluorescens (approximately 1 × 10 ⁶ cells / mL). Biofilm growth was delayed for all formulations. In formulation # 14a, no biofilm was observed after 2 days.

Example 7
The release of QAC from the sprayed PVOH film was demonstrated by release experiments. The film was sprayed onto a stainless steel coupon, submerged in deionized water, and samples were removed over time to determine the released QAC. The concentration of QAC released was determined by HPLC method adapted from literature (RC Meyer, J. Pharm. Sci. 1980, 69, 1148-1150) .

  FIG. 3 shows the weight fraction of QAC released from films sprayed with formulations # 19, # 20 and # 21 over time. These three formulations differed only in the amount of crosslinker added to the formulation. The film thickness of the sprayed film was about 7.0 μm as judged by a micrometer gauge. The total QAC available in the film was calculated from the concentration and film volume within the liquid formulation. The semi-log graph shows the fraction of QAC released over a period of up to 7 days. A very fast initial release of QAC can be observed for all three film types. Adding iron salt to the formulation increases the amount of QAC released from the film. Adjustment of the amount of cross-linking agent in the liquid formulation provides a means of controlling the release profile over time and allows controlled and sustained release of the antimicrobial agent.

Example 8
An aqueous solution (25 wt%) of benzalkonium chloride (QAC) was added to a 10 wt% aqueous solution of polyvinylpyrrolidone (PVP K-120 in water; International Specialty Products, Wayne, NJ, USA). The final concentration of PVP was 5 wt%, and the most contracted concentration of benzalkonium chloride was 1 wt%. Using this PVP film-forming solution, cut specimens were treated to prevent biofilm formation.

L. An overnight culture of Wellsimeli single in 25 mL TSB / YE medium (trypsin soy broth plus 0.6 wt% yeast extract) in shake flasks to a density of 1 × 10 ⁹ cells per mL Grown from colonies (30 ° C. with shaking at 150 RPM). The cap of the sterile centrifuge tube was removed in the Biohood and each PVC coupon that had been thoroughly sprayed with 70 wt% ethanol was placed in the centrifuge tube. The cap was kept away from the tube so that the cut specimen could be air dried. For biofilm formation experiments, L. An overnight culture of Wellsimeli was diluted 1: 100 in modified wellsimmer medium (eg, 20 tubes per cut specimen required 2 mL overnight culture and 200 mL modified wellsimmer medium). A portion of this solution (10 mL) was added to each centrifuge tube. The tube was loosely covered with a cap and incubated at 22 ° C. on a shaker with shaking at 150 RPM. The medium was replaced every other day with fresh modified well-simmered medium.

  For the experiments summarized in Table 5, a specified time to form a biofilm (see Table 5), PVC (polyvinyl chloride) cut specimen (22 mm x 60 mm; lid for PVC flexible plate cut specimen) , Becton Dickinson) Growing Well Simeri. When the biofilm was formed, the cut specimen was treated with the PVP film forming solution by coating 100 μL of the PVP film forming solution on both sides thereof. The PVP film was cut and allowed to stay on the coupon for the specified processing time. At the end of the treatment time, each coupon was gently rinsed with sterile PBS to remove loosely adhering cells and the cell viability of the biofilm was determined as described below. Each treatment was performed in duplicate.

  To determine cell viability, the biofilm was removed from the coupon by scraping the coupon with a sterile object (eg, plastic, metal or wood). Both sides of the cut specimen were scraped and the film was resuspended in 10 mL of PBS buffer. To homogenize the cell suspension, the suspension was mixed by vortexing. Serial dilutions of cell suspension (1:10 in PBS buffer) were prepared and 100 μL aliquots were spread on Petri dishes containing either LB or modified Oxford agar. Plates were allowed to incubate overnight at 30-37 ° C. and colonies were counted the next day.

Example 9
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.

  2 days on a PVC cut specimen as described in Example 8. Well-simeli biofilms were grown and then biofilm cut coupons were treated with PVP film-forming solution as described in Example 8. The PVP film forming solution was left in contact with the biofilm for 3 hours. At the end of the treatment time, the cell viability of the biofilm was determined as described in Example 8. Each treatment was performed in duplicate. A PVP film with 0.01 wt% benzalkonium chloride produced a 7.7 log reduction in CFU / mL.

Example 10
Polyvinyl alcohol (PVOH) (molecular weight 100,000, degree of hydrolysis> 99%, Sigma-Aldrich) was dissolved in water. Sodium dichloroisocyanurate was added to the PVOH solution to achieve a final film-forming composition of 0.1 wt% sodium dichloroisocyanurate, 5 wt% PVOH, and 100% sufficient deionized water. This composition was used to coat PVC coupons coated with Listeria Welsimelli biofilm (prepared as described in Example 8) two days after production. After 3 hours contact time, cell viability was determined as described in Example 8. PVOH coating with sodium dichloroisocyanurate produced a 7.3 log reduction in CFU per mL.

Example 11
Polyurethane dispersions were synthesized as described in US Patent Application Publication No. 2005/0215663, paragraphs 212-217 (see also paragraphs 154-187 for abbreviations). The preparation produced a 30 wt% polyurethane water dispersion.

  The polyurethane dispersion was diluted to 10 wt% with ethanol. A polyurethane film-forming composition was prepared by adding a 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 100 wt% sufficient deionized water. The coating was applied to the surface of the PVC coupon as described in Example 8, and the coupon was air dried and placed in a sterile centrifuge tube.

Pseudomonas aeruginosa (ATCC 27853) cultures are grown overnight (at 30 ° C. with shaking at 150 RPM) from a single colony in 25 ml M9 medium in shake flasks to a density of 1 × 10 ⁹ cells per ml It was. The culture was then diluted 1: 100 in 0.1 × LB medium (eg: 20 tubes per cut specimen, 2 mL overnight culture plus 200 mL of 1/10 strength LB medium was required. ) A aliquot of this solution (10 mL) was added to each centrifuge tube to partially submerge the centrifuge tube. Tubes were loosely covered with caps and incubated for 24 hours at 30 ° C. with shaking at 150 RPM.

  At the end of the treatment time, each centrifuge tube was gently rinsed with sterile PBS to remove loosely adhered cells and the cell viability of the biofilm was determined. Each treatment was performed in duplicate.

  Cell viability was determined as described in Example 8 except that Pseudomonas F agar was used in a Petri dish. In this treatment, an 8 log reduction in CFU / ml was observed, and there was no visible biofilm formation, whereas uncoated cut specimens had visible biofilm formation. Was not.

Example 12
Two pipes (PVC-1120, J-M Manufacturing, Livingston, NJ, USA) were cut open in the longitudinal direction to obtain a half-pipe. . The pipes were combined and taped again using standard Scotch® duct tape (3M, St. Paul, Minn., USA). The pipe geometry is shown in Table 6. Using the Wagner Spray System (Wagner Power Painter, model 0500139, Wagner Spray Tech Corp., Plymouth, MN, USA) The pipe was coated with Formulation # 91 by spraying for 10 seconds with a spray nozzle coaxially centered on one end of the horizontally oriented pipe.

  Formulation # 91 had the following composition: Elvanol® grade 71-30 (5.0 wt%); benzalkonium chloride (0.63 wt%); Silwet L-77® (0 BYK®-425 (0.1 wt%): erythrosine B (0.05 wt%) and 100 wt% sufficient amount of deionized water.

  The coverage of the coating was observed visually, which was easily achieved because the coating was colored and had a high contrast to the white background of the pipe. Full coverage of the upper and lower halves of the pipe was achieved to a certain depth as summarized in Table 6. As presented in the table, even a small gap between the two half pipes was completely covered with the coating to a certain depth in the pipe. This example illustrates that the present invention can also be used to coat partially closed, concave or hard to reach surfaces such as pipes and drains.

Example 13
This example illustrates how a rheology modifier provides a removable antimicrobial coating composition with shear thinning behavior. Such behavior allows easy (excellent sprayability), efficient (no dripping) and effective (homogeneous antimicrobial activity) application of the composition to the surface. This example also illustrates that the antimicrobial efficacy can be fully retained after the addition of the rheology modifier.

  The composition used in this example is based on a PVOH solution in water (5 wt%) and a series of selected additives. The order of addition and formulation method (mixing, scale, etc.) will vary for a particular formulation.

Here, the viscosity is reported in centipoise (cp) units at shear rates of 5 and 190S- ¹ . High viscosity means less waste due to dripping. The ratio of the two viscosities is a measure of the shear thinning effect. Higher ratios indicate better shear thinning and better sprayability.

  The formulation itself was used to assess the antibacterial activity of a composition containing a rheology modifier by the diffusion zone (ZOD) test described above using Staphylococcus aureus ATCC 6358. The rheology modifier tested was found to either contribute positively to the antimicrobial activity of the coating or to be neutral.

  The composition in this example is based on a solution of PVOH (5 wt%, Elvanol® 71-30) in a sufficient amount of 100 wt% deionized water, benzalkonium chloride (0.6 wt%), Silwet ( It was obtained by adding (registered trademark) L-77 (0.15 wt%), BYK (registered trademark) 425 (0.1 wt%) and erythrosine B (0.05 wt%). In the second formulation step, a rheology modifier was added (see Table 7).

Example 14
This example illustrates that rheology agents can be used to provide shear thinning for coating formulations based on polyvinyl alcohol grades with different degrees of hydrolysis. This example also illustrates that shear thinning (viscosity ratio) can be adjusted by varying the level of rheology modifier added to the formulation. The rheological agent used in this example is Alocgum® L251.

  The composition in this example was charged with water (100 wt% total of all ingredients) into a flask with a magnetic stir bar, then 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 w%, Elvanol® water 71-30 ) And indigo carmine dye (0.03 wt%).

Example 15
This example illustrates the use of a coating formulation according to the present invention to prevent fungi from growing on the surface.

  Grow stock plates (malt extract agar) for 2 weeks at 25 ° C. and flood the plates with 15 mL of sterile filter saline solution (0.85% NaCl plus 0.05% Triton® X-100) Fungal spores (Aspergillus niger and Penicillium expansium) were prepared by harvesting spores at The plate was then scraped with a sterile plastic cell scraper, the liquid was pipetted off, vortexed and filtered through 3-4 layers of sterile cheesecloth. 400 microliters of the coating formulation was spread on a 1 inch x 1 inch stainless steel cut specimen with a sterile pipette tip.

  The coating formulation of this example is 5 wt% Elvanol® 71-30, 0.2 wt% PEG (M˜300), 0.2 wt% benzalkonium chloride, 0.1 wt% Silwet ( (Registered trademark) L-77, 0.05 wt% BYK (registered trademark) 425, 0.01 wt% erythrosine B, and 100 wt% sufficient amount of deionized water. The coating formulation # 115 used for the negative control experiment was identical to formulation # 109 except that no benzalkonium chloride was added.

  The surface was completely covered and the coating was completely dried in a vertical flow biofood (3-4 hours or overnight). A 10 mL spore suspension aliquot was centrifuged and the supernatant was discarded. Spores were resuspended in the same volume of Czapak Dox broth. 100 microliters of this inoculum was added to each cut coupon and allowed to dry for 5 minutes. Cut coupons were placed on a water agar plate with the coated side up and incubated at room temperature in a desiccator filled with water on the bottom for 2-4 weeks and observed daily for fungal growth.

  Table 9 shows that no fungal growth was observed for coating formulation # 109, while there was an excess of uncoated cut coupons or cut coupons coated with a coating formulation lacking the QAC active ingredient Exemplifies that it has demonstrated fungal growth.

Example 16
This example illustrates the use of a coating formulation according to the present invention to enable long-term antimicrobial efficacy. This example also demonstrates the continuous antimicrobial efficacy after multiple re-inoculations of the antimicrobial coating with microorganisms. This example also demonstrates the residual antimicrobial efficacy of a coating formed from the formulation. This example also illustrates that the antibacterial coating is effective against Gram positive bacteria (Staphylococcus aureus) and Gram negative bacteria (Klebsiella pneumoniae) organisms.

  In order to test the effect of numerous bacterial contaminations on the efficacy of the antimicrobial coating, the following method was used. Test microorganisms included Staphylococcus aureus ATCC 6358 and Klebsiella pneumoniae ATCC 4352. Remove a single colony from the refrigerated stock plate by loop and inoculate selected microorganisms overnight by inoculating 25 mL trypsin soy broth or other liquid medium in a sterile plastic Erlenmeyer flask with 250 mL Cultures were prepared. The flask was incubated overnight at 30 ° C. with shaking at 150 RPM. Thereafter, 0.4 mL of the coating formulation was spread on a 1 inch × 1 inch stainless steel (SS316) cut specimen with a sterile pipette tip. The entire surface was covered and the coating was completely dried (3-4 hours or overnight) in a vertical flow biohood. In addition to the antimicrobial agent-containing formulation, as a control, a formulation lacking the antimicrobial agent was also cut and coated with coupons. The overnight culture was then diluted 1:10 with phosphate dilution buffer. At this point, 5 percent sterile fetal calf serum can be added to the culture as an additional challenge to the coating. 10 microliters of this 1:10 dilution was used each time to spot the specimen surface by spotting with at least 20 locations with a pipette tip and waiting for 5 minutes. Thereafter, two coupons and two control coupons for each coating formulation were placed in a sterile 50 mL plastic centrifuge tube containing 20 mL of Letheen neutralizing broth. The tube was sonicated for 10 seconds and shaken for 10 minutes (200 RPM at 25 ° C.). These samples were then serially diluted and fixed on LB agar plates for colony forming unit (CFU) determination. Plates were incubated overnight at 35 ° C. and the next day colonies were counted. The remaining coupons were incubated at room temperature in a desiccator with the bottom filled with water. After 1 hour, all remaining cut specimens are inoculated with 10 microliters of diluted culture as described above. After 5 minutes, two coupons are removed for each formulation and processed as described above. The process is repeated 2-3 hours after the initial inoculation of the coupon.

The coating formulation # 119 used in this example was 5 wt% Elvanol® 71-30, 0.2 wt% PEG (molecular weight about 300), 0.05 wt% benzalkonium chloride,. It consisted of 1 wt% Silwet® L-77, 0.01 wt% indigo carmine dye and 100 wt% sufficient amount of deionized water. Tables 10 and 11 show that no viable cells from the two organisms used were recovered for the cut coupons coated with Formulation # 119, while coated with the same formulation lacking QAC. was more from coupons, i.e. 10 more than ^six cells shows that was recovered.

Example 17
This example illustrates the use of a surfactant to achieve spreading of the formulation into the film after application to the surface.

  In this example, organosilicone (Silwet® L-77) is used as a surfactant. The formulation of this example is 5 wt% polyvinyl alcohol (Elvanol® 52-22), 0.2 wt% PEG (molecular weight about 300), 0.05 wt% benzalkonium chloride, 0-1 wt% Consisting of varying concentrations of Silwet® RL-77 (see Table 12) and 100 wt% sufficient amount of deionized water.

  The surface tension of the sample was measured at a temperature of 26.3 ° C. using a Klaus K11 tensiometer (Krüss GmbH, Hamburg, Germany) with a wet length of 40.2 mm.

  A 100 μl drop of each sample was pipetted onto a clean test surface of stainless steel (SS316) and ultra high molecular weight polyethylene (UHMWPE). Both SS316 and UHMWPE are key materials for the manufacture of industrial equipment such as equipment used for food processing. The droplets were spread for 5 minutes after being applied to the surface. A digital photograph of the test surface was taken, and the coating spread area of the droplets on the test surface was measured by image analysis (ImageJ software, version 1.36b, National Institutes of Health). The spread area of the drop was used as a measure of the spread efficacy of each formulation. Table 12 reports the results for the two surface materials and the tested formulations.

  By adding 0.001 wt% of organosilicone surfactant and resulting surface tension of 35.9 mN / m, an improvement in spreading on SS316 was already observed. Compared to the formulation without added surfactant, the spread area increased by 16% for SS316.

  A more significant increase in the spread area was seen when the surface tension was reduced to 22.5 mN / m or less using an organosilicone concentration of at least 0.3 wt%. Under these conditions, the spread area increased by over 160% for SS316 and over 220% for UHMWPE when compared to formulations without added surfactant.

Example 18
This example illustrates the use of small bubbles in the antimicrobial coating as a temporary opacifier. For some of the intended uses of the present invention, it is not always preferred that the coating has a permanent color. For example, for wall coatings, color coatings or opaque coatings can be considered a bad taste, and transparent antimicrobial coatings may be preferred instead. The exclusion of permanent colorants or opacifiers has the disadvantage that the operator applying the coating cannot obtain feedback on what part of the surface to be coated has already been coated. To overcome this drawback, the following embodiments of the present invention can be applied. That is, at least one blowing agent can be added to create small bubbles in the film created on the target surface. The bubbles act as opacifiers, turning the newly applied film white. An anti-foaming agent is also added to the formulation to prevent air bubbles from being taken into the dry film. Anti-foaming agents help break up bubbles while the film is still wet and produce a clear coating after drying.

  Formulation # 134 used in this example is 7 wt% Elvanol® 52-22, 0.2 wt% PEG (molecular weight about 300), 0.05 wt% benzalkonium chloride,. It consisted of 2 wt% Silwet® L-77 and 100 wt% sufficient amount of deionized water. Formulation # 134a used in this example was identical to Formulation # 134, except that the formulation contained 120 ppm of Antifoam C emulsion active ingredient.

  Surfactants Benzalkonium Chloride and Silwet® L-77 foam both of the above-described formulations, and a high volume / low pressure (HVLP) spray gun (Devilbiss GTI spray gun: Air Cap # 2000; 1.5 mm fluid chip; EI DuPont Company, spray booth, Canada, Ajax, Ontario, Fairfall Street 377, Room 112 (EI DuPont Company spray boot, Room 112, 377 Fairy Street, Ajax, ON, Bubbles (> 1,000,000 per square meter) were visible in the film obtained directly after spraying the formulation onto the surface with Canada)). The spray conditions were as follows: application of 2-3 layers resulting in a total film of 5-20 microns at 5-25 ° C, 30-60% relative humidity. The bubbles were counted visually using a 4 inch × 4 inch square and reported as bubbles per square meter. The bubbles gave the film a white appearance after spraying. Many of the bubbles disappeared as the film dried. For formulation # 134 lacking Antifoam C, approximately 15,000 bubbles / square meter remained. However, for Formulation # 134a, only 100-500 very small bubbles per square meter were obtained after the film dried (see Table 14).

Example 19
This example illustrates the effect of film thickness on antimicrobial properties. Antibacterial efficacy was measured by the diffusion zone (ZOD) method using Staphylococcus aureus ATCC 6358. The composition of coating formulation # 134 is described in Example 18. A thicker film resulted in a larger diffusion zone and thus improved biocidal properties of the coating.

Figure 2 illustrates the mechanism by which a coating composition provides protection. The arrows indicate the transfer of the biocide active component into the pathogen contaminated area above and below the antimicrobial coating. The coating composition also provides a physical barrier to soil and other solid contaminants. Figure 2 shows a cross-sectional view of an antimicrobial coating. Shown here are the xz cross section (top) and the yz cross section (bottom) of the same film through a polymer film formed from formulation # 2. The film was visualized by confocal laser scanning microscopy after addition of a trace amount of fluorescent dye (Rhodamine 123) to the film-forming composition. FIG. 4 shows the release of quaternary ammonium compounds (QAC) over time from films sprayed from three liquid compositions of the present invention on stainless steel cut coupons, then dried and submerged in water.

Claims (3)

i) a water-soluble or water-dispersible film-forming agent;
ii) at least one or more antimicrobial agents;
iii) Provide a surface tension of 20-50 mN / m, and 0.01 wt% to 1.0 wt% of the composition
Surfactant, contained at a concentration of%;
iv) an inert solvent; at least one rheology modifier in an amount to adjust the and v) a shear thinning of 1.1 or more viscosity ratio, the viscosity ratio, 5S on viscosity at a shear rate of 190S ^-1 A removable food processing shutdown spray composition comprising a rheology modifier that is a ratio of viscosities at a shear rate of ^-1 , wherein the composition was applied to a contaminated food processing surface The above composition, which provides a coating that is durable in case and removable when subjected to aqueous treatment above 15 ° C.   2. The composition of claim 1, wherein the composition provides at least 3-log microbial reduction when applied to a contaminated food processing surface.   The film forming agent is one or more polyvinyl alcohols or copolymers thereof, including polyvinyl pyrrolidone, polyacrylic acid, acrylate copolymers, ionic hydrocarbon polymers, and polyurethanes or combinations thereof; At least one antibacterial agent is an antibacterial agent, fungicide, fungistatic agent, fungicide, fungicide, antiseptic, disinfectant, sanitizer, bactericidal agent, algicidal agent or antifouling agent Item 3. The composition according to Item 1 or 2.

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