CN101454406A - Removable antimicrobial coating compositions and methods of use - Google Patents

Abstract

This invention relates to a method of providing control of microorganisms at a locus comprising a) providing a removable liquid coating composition comprising: i) a film-forming water soluble or water-dispersible agent; ii) at least one antimicrobial agent; iii) an inert solvent; b) applying said composition to the locus whereby a coating is formed; and c) removing said coating with an aqueous solution at a temperature of about 15 DEG C to about 1000C.

Description

Removable antimicrobial coating compositions and using method

The rights and interests of the U.S. Provisional Application that the application requires to submit on February 23rd, 2006 U.S. Provisional Application is submitted to number on July 19th, 60/776,081 and 2006 number 60/831,983.

Technical field

The present invention relates to comprise method with the controlling microbial of removable antimicrobial film-forming composition coating surface, the competent and antimicrobial composition that can remove easily, and apply described method for compositions.

Background technology

The present invention relates to a kind of method, contact with the removable coating composition that comprises at least a biocide, in described playground, provide microbiological manipulation by making playground (locus).

The special field of being concerned about that controlling microbial is polluted relates to food-processing.The microbial contamination of food is one of main U.S. and whole world public health problem.And do not know the pathophorous actual sickness rate of microbial food thing, but CDC estimates that it is that 7 to 8,100 ten thousand examples are fallen ill in the U.S. every year, surpasses 325,000 routine being in hospital and 5,000 example death.Because the expense of American's disease of food transmission pathogenic agent is annual 1000000000 dollars.Except the loss of disease and death, food contamination means the tremendous economic loss of numerous food product source mill.

Strict health operation reduces the generation that food microorganisms pollute effectively in the current food processing plant, but does not prevent to cause the outbreak of dead and disabled serious outburst.Make peace with regard to the time and effort of effective enforcement operation with regard to material, these operations are expensive.In addition, it is expensive polluting by food microorganisms that caused problem tends to; If particularly these cause the human consumer to recall.

The bad health of food contacting surface, equipment and processing environment has been the foodborne disease outburst, particularly relates to the influence factor in Listeria monocytogenes (Listeria monocytogenes) and the Salmonellas enterocolitis (Salmonella enterocolitis).The clean surface promotes dirt to form irrelevantly, and in the presence of water, impels the bacterial biof iotalm growth that may contain pathogenic microorganism.When food through contaminated surface or be exposed to the aerosol that derives from contaminated surface or during phlegma, crossed contamination (R.A.N.Chmielewski and J.F.Frank take place, " BiofilmFormation and Control in Food Processing Facilities ", see ComprehensiveReviews in Food Science and Food Safety, 2003,2,22-32; Boulange-Petermann, Laurence.Biofouling, 1996,10,275-300).Play an important role can not purifying in the surface such as the factor of food contacting surface type and configuration.The surface of wearing and tearing is accumulated dirt and is difficult to cleaning more than smooth surface.Surface imperfection further make remove dirt and microorganism complicated, microorganism still grows after making great efforts to purify even cause, and possibly, owing to described growth forms microbial film.(Boulange-Petermann, the same; D.A.Timperley, R.H.Thorpe, and J.T.Holah " Implications of EngineeringDesign in Food Industry Hygiene ", see Biofilms-Science and Technology, 35-41, people such as LF.Melo (volume), Kluwear Academic Publishers, 1992, Holland; J.T.Holah, R.H.Thorpe, J.Applied Bacteriology, 1990,69,599-608).

In addition, the microorganism in the microbial film tolerates sterilizing agent more, and this may promote Lee Salmonella (Listeria) and the survival rate (J.F.Frank of other food transmission pathogenic agent in the food-processing environment, R.A.Koffi, J.Food Protection, 1990,53,550-554; E.P.Krysinski; LJ.Brown, and T.J.Marchisello, J.Food Protection, 1992,55,246-251).Therefore, the suitable microbial film control method of An Quan food-processing manipulation require.

When food processing plant cuts out or temporarily do not turn round or when using, microbial contamination receives publicity especially.In fact this is the biological film formed opportune time, particularly is difficult to when sterilizing agent contacts as mentioned above at some equipment unit.At present, the practice of avoiding polluting in this shut-down period process is included in the multistep sterilization method of restarting first being processed, comprises sterilization, is coated with and removes any potential deleterious sterilizing agent with other solution of device that often comprises other strictness or component.These methods are expensive and may have insecure effect.Therefore, there are needs in the method for better being devoted to protect at microbial contamination in this shut-down period process.In addition, except foodstuffs industry, existence may have benefited from some other industry of antiseptic composition, and described antiseptic composition can form the antimicrobial coatings that the durable of due care is provided but can removes easily.By some characteristic of coating, for example good distribution and surface tension control realize due care.

From the teeth outwards well distributed of liquid anitmicrobial formulation is being favourable obtaining aspect homogeneous and the continuous film after applying, and particularly is used as when applying method when spraying or atomizing.Do not stay under the situation in unlapped gap in antimicrobial membranes that forms or coating, by obtaining surface coverage completely, good distribution performance can improve the antimicrobial properties of antimicrobial formulation.These gaps allow microorganism growth.By reducing surface tension, the liquid anitmicrobial formulation is flowed in the known surface imperfection of concealing microorganism, can further improve antimicrobial properties.

U.S. Patent number 5,585,407 provide water base paint compositions, and it can be applied over base material to suppress the lasting time period that prolongs of microorganism growth.This coating comprises acrylic ester emulsion polymkeric substance and organoalkoxysilane, and can remove under alkaline condition.

U.S. Patent number 5,017,369 provide a kind of between milking the preventive therapy of mazoitis in the cow, comprise with the waterborne compositions coating cow teat that comprises biocide.Said composition comprises the polyvinyl alcohol of the partial hydrolysis of 2wt% at least, and about 0wt% is to the opalizer of about 10wt%, and about 0.1wt% is biocide and the water of 65wt% at least of about 10wt% extremely.Make to wash with water before milking and remove film from cow teat.

Therefore, for forming durable from the teeth outwards but there are demand in the film that can remove easily or the antiseptic composition of coating, described surface is the hard surface that is for example formed by pottery, glass, bakelite (formica), plastics, metal etc., described film can carry bacteriocidal substance, for example quaternary ammonium compound or phenolic compound.For microbial contamination being provided the sterilizing agent film or the coating that prolong protection have further demand.In addition, for can be applied over various surfaces can remove easily, there is demand in competent, homogeneous and continuous film or coating.Above method of using in the described method and coating all can not be provided for being coated with the durable of said surface but the coating composition that can remove easily.Therefore, the problem that solve is to lack a kind of usefulness to comprise the method for the coating composition of at least a biocide in specific playground controlling microbial, and wherein said coating is competent, remaining antimicrobial efficacy is provided and can removes easily.

Summary of the invention

The present invention is devoted to address the above problem in order to following method and composition.

One aspect of the present invention relates in the playground method that microbiological manipulation is provided of living in, comprises

A) provide removable liquid coating composition, comprising:

I) the water-soluble or water-dispersible agents of film forming;

Ii) at least a biocide; With

Iii) inert solvent;

B) described composition is applied over the playground, forms coating thus; With

C) about 15 ℃ to about 100 ℃ of described coatings of following water solution removal.

In yet another aspect, the surface tension of liquid coating composition described herein is lower than 40mN/m.

In yet another aspect, the membrane-forming agent in the aforesaid method is one or more polyvinyl alcohol and multipolymer thereof, comprises polyvinylpyrrolidone, polyacrylic acid, acrylate copolymer, ion hydrocarbon polymer and urethane or its combination.

In yet another aspect, when being applied over contaminated surface, the coating that is formed by described method makes microorganism be reduced by at least 3-log.

In yet another aspect, when being applied over contaminated surface, the coating that is formed by described method makes microorganism be reduced by at least 5-log.

In yet another aspect, this coating prevents that the microorganism of at least a type is in playground growth of living in.

In yet another aspect, playground microbiological manipulation of living in comprises the microorganism of concealing in the minimizing microbial film.

In yet another aspect, the coating that is formed by above method is successive and homogeneity basically.

In yet another aspect, the coating that is formed by above method has about 0.3 to about 300 microns thickness, and preferably it has about 0.5 to about 100 microns thickness.

Another aspect of the present invention is removable food-processing shut-down spray composition, comprising:

I) the water-soluble or water-dispersible agents of film forming;

Ii) at least a or multiple biocide;

Iii) inert solvent; With

Iv) Ren Xuan one or more softening agent, tensio-active agent, linking agent, tinting material, solubilizing agent, rheology modifier, oxidation inhibitor, pH regulator agent, wetting agent, antifoams, extender, lubricant, processing aid, laking agent, film properties toughener or enzyme

Wherein described composition is competent and removable when standing to be higher than 15 ℃ aqueous solution processing.

In yet another aspect, composition described herein comprises provides about 20 to about 50mN/m capillary tensio-active agents.In yet another aspect, tensio-active agent is an organo-siloxane.In yet another aspect, surfactant concentration is that about 0.01wt% of composition is to about 1.0wt%.

In yet another aspect, said composition comprises the Control of Rheological Property agent that the shear thinning performance is provided to composition.

In yet another aspect, when being applied over the food-processing surface of pollution, said composition makes microorganism be reduced by at least 3-log.In yet another aspect, when being applied over contaminated surface, said composition is sterilant, sterilizing agent, sanitas, or the physical barriers layer to polluting, and wherein when being applied over the contaminated surface of the follow-up pollution of experience, described composition can have residual antimicrobial efficacy.

In another aspect of the present invention, the playground is one or more surfaces: container, travelling belt, the floor, water shoot, water cooler, refrigerator, refrigerator, equipment surface, wall, valve, belt, pipeline, joint, the crack, building surface, the surface, kitchen, the inanimate surfaces that exists in the food processing plant, animal doctor or animal care facility, animal care equipment, or livestock industry or hatcher facility, hospital or Surgicenter wall, bed, the surface of equipment, the fabric that weares and teares in hospital or other healthcare environment, comprise rag, footwear, and other hospital surface.

In another aspect of the present invention, the playground comprises one or more metals that are selected from aluminium, steel, stainless steel, chromium, titanium, iron, alloy and composition thereof.

In another aspect of the present invention, the playground is the surface that comprises one or more plastic materials, described plastic material is selected from polyolefine, comprise polyethylene, polypropylene, polystyrene, polymethacrylate, polymethylmethacrylate, the polymkeric substance of vinyl cyanide, divinyl, ABS, acrylonitrile butadiene; Polyester comprises polyethylene terephthalate; And polymeric amide, comprise nylon; And combination.

In another aspect of the present invention, the playground is made by brick, ceramic tile, pottery, porcelain, timber, ethenoid resin, malthoid, carpet, paper, leather, its combination etc.

In another aspect of the present invention, the playground is by metal, mineral, polymkeric substance, plastics, fiber base material or non-woven fabric, or its mixture, or the inanimate surfaces of coating or painted surface formation.

The accompanying drawing summary

Can understand the present invention more fully by following detailed description and accompanying drawing.

Fig. 1 illustrates the mechanism that coating composition provides protection.Arrow represent that biocidal activity component migration enters on the antimicrobial coatings and under the microbial contamination zone.This coating composition also provides the physical barriers layer to dirt and other solid pollutant.

Fig. 2 shows the cross section of antimicrobial coatings.Show the x-z cross section (by last) of the polymeric film that forms by formulation #2 and the y-z cross section of same film (by down).In film-forming composition, add trace fluorescence dye (rhodamine 123) afterwards, estimate this film by confocal laser scanning microscopy.

Fig. 3 shows quaternary ammonium compound (QAC) from being sprayed on the stainless steel sample by three kinds of liquid compositions of the present invention, and dry then also water-immersed film is along with the release of time.

Describe in detail

When the form that lists limit preferred value and lower limit preferred value with scope, preferred scope or provides When amount, concentration or other value or parameter, it should be understood that concrete open by any a pair of any model Place all scopes that limit or preferred value and any scope lower limit or preferred value form, no matter each scope Whether disclosed separately. When in this narration number range, except as otherwise noted, this scope is intended bag Draw together its end points, and all integers and mark in this scope. When the scope of restriction, do not wish Scope of the present invention is limited in described particular value.

There is length for the antimicrobial that antimicrobial efficacy is improved and the speed of action is improved always The demand of phase. To the specific (special) requirements of this reagent according to the application of expection (for example disinfectant, bactericide, Go out natural disposition, aseptic packaging processing etc.) and suitable public health require and change. For example, as Germicidal and Detergent Sanitizing Action of Disinfectants, Official Methods of Analvsis of the Association of Official Analytical Chemists, 960.09 section and suitable chapters and sections, the 15th edition, propose in nineteen ninety (EPA Guideline 91-2), For some test organism, disinfectant should provide in 30 seconds under room temperature (25 ± 2 ℃) 99.999% minimizing (minimizing of 5-log magnitude). As used herein, term " antimicrobial " Comprise and to kill microorganism, block or prevent microbial contamination (for example forming the barrier layer) or press down System or prevent microorganism growth, catch microorganism and be used for killing or preventing biological film formed reagent. As used herein, term " disinfectant " expression requires to judge according to public health, with microorganism The pollutant number is reduced to the reagent of level of security. According to the test of official disinfectant, disinfectant be In 30 seconds, kill the chemicals (EPA of 99.999% fc-specific test FC microorganism under the test condition Policy DIS/TS S-4: " Efficacy data requirements-Sanitizing rises for Previously cleaned food-contact surfaces ", United States Environmental Protection Agency, on January 30th, 1979).

As used herein, term " bactericide " expression provides the reagent of antimicrobial acivity. Root According to official's bactericide test, bactericide is for killing 99.9% spy in 10 minutes under test condition The chemicals of location survey examination microorganism. (Germicidal and Detergent Sanitizing Action of Disinfectants, Official Methods of Analysis of the Association of Official Analytical Chemists, 960.09 sections and suitable chapters and sections, the 15th edition, nineteen ninety (EPA Guideline 91-2)). As used herein, the microgram number of the every gram of term " ppm " expression.

The present invention relates to control the method and composition of microorganism. Described method comprises with removable Antimicrobial film-forming composition coating surface. Particularly, the present invention relates to provide in that playground is of living in The method of microorganism control comprises

A) provide removable liquid coating composition, comprising:

I) the water-soluble or aqueous dispersion reagent of film forming;

Ii) at least a antimicrobial; With

Iii) atent solvent;

B) described composition is applied over the playground, forms thus coating; With

C) under about 15 ℃ to about 100 ℃, remove described coating with the aqueous solution.

Coating can be at about 15 ℃ to about 100 ℃, or more preferably from about 30 ℃ to about 80 ℃ of lower waters Solution is removed.

Playground of the present invention comprises and is suitable for part or all applied target surface. Order The mark surface comprises potentially all surfaces of microbial contamination, comprises usually being difficult to apply film Or the surface of coating (for example being difficult to arrive the surface). The example of target surface comprises the Foods or drinks worker Equipment surface (for example container, conveyer belt, floor, drainpipe, cooler, the refrigeration that exists in the industry Device, refrigerator, equipment surface, wall, valve, belt, pipeline, drainpipe, joint, crack, Its combination etc.); Building surface comprises the building in the construction, new housing construction body, and season In the joint property or the time the surface, for example vacation home surface (for example wall, wooden frame, floor, window), Kitchen (sink, drainpipe, cabinet top, refrigerator, chopping block), bathroom (shower, toilet, drainpipe, Pipeline, bathtub) (removing especially for mould), deck, timber, baffle plate and other house outside, Bituminized shingle roof, courtyard or stone zone (processing especially for algae); Ship and device by ship The surface; Refuse treatment plant, dustbin and rubbish heap or other rubbish are removed equipment and surface; With Pipeline and drainpipe that non-food stuff industry is relevant; In hospital, operation or the outpatient service in the heart the surface or beastly The doctor (is is for example worn and torn in wall, floor, bed, equipment, hospital/animal doctor or other healthcare environment on the surface Clothes, comprise rag, footwear and other hospital or animal doctor surface), first responder (first-responder) or other anxious service equipment and clothes of answering; Sawmill equipment, surface and wooden Product; The surface, restaurant; Supermarket, grocery store, retail shop and convenience store equipment and surface; Delicatessen equipment and surface and food preparation surface; Brewery and bakery surface; The surface, bathroom, For example sink, shower, cabinet and toilet; Clothes and footwear; Toy; School and gymnasium equipment, Wall, floor, window and other surface; Surface, kitchen, for example sink, cabinet, appliances; Wooden or composite platform, pond, heat channel and hot spring surface; Carpet; Paper; Leather; Spoil, Hair and skin; Granary or the corral for animals surface of poultry, ox, milk cow, goat, horse and pig for example; With poultry or shrimps hatchery. Other surface also comprises food, for example beef, poultry, pork, Vegetables, fruit, seafood, its combination etc.

Other playground that is suitable for using in the present invention comprise the fiber base material and comprise fiber, Yarn, fabric, textile, non-woven fabric, carpet, leather or paper. The fiber base material is by natural fibre Dimension is made, and described natural fiber is for example wool, cotton, jute, sisal hemp, sea grass, paper, coconut palm fibre Peacekeeping cellulose, or its mixture; Or made by synthetic fibers, described synthetic fibers are for for example poly-Acid amides, polyester, polyolefin, aramid, acrylic acid series and blend thereof; Or at least a The blend of natural fiber and at least a synthetic fibers. Natural or the synthetic textiles of " fabric " expression Or its blend, by such as cotton, viscose glue, silk, wool, polyester, polypropylene, polyolefin, Buddhist nun The dragon and such as

With

Aromatic polyamides fibrous. " knit The thing blend " fabric made by the fiber of two or more types of expression. Common these blends Be the combination of at least a natural fiber and at least a synthetic fibers, but also can be two kinds or many Plant the blend of natural fiber or the blend of two or more synthetic fibers. Nonwoven substrates comprises For example jet sprays the net non-woven fabric, for example available from E.I.du Pont de Nemours and Company The SONTARA of (Wilmington, DE, USA) and lamination non-woven fabric, for example spunbond-molten Spray-spunbonded non-woven.

The example of surfacing be metal (for example steel, stainless steel, chromium, titanium, iron, copper, brass, Aluminium and its alloy), mineral (for example concrete), polymer and plastics (for example polyolefin, for example poly-second Alkene, polypropylene, polystyrene, poly-(methyl) acrylate, polyacrylonitrile, polybutadiene, poly-(third Alkene nitrile, butadiene, styrene), poly-(acrylonitrile, butadiene), acrylonitrile butadiene; Polyester, PETG for example; And polyamide, for example nylon). Surface in addition comprise brick, Ceramic tile, pottery, porcelain, timber, vinyl and malthoid.

Can be in use or be protected during non-use with the equipment of stripping lacquer protection or surface. Target surface can be hydrophobic or hydrophilic. Can be used for the antimicrobial coating group of removing of the present invention Compound can be used as standard health product (such as the quaternary ammonium compound solution that dilutes, peracid foam etc.) Alternative, and can be used for daily hygiene with the form of protective coating, be used in use or Equipment during non-the use, and be used for long-term protection (several weeks or several months).

Use antimicrobial removable type coating composition that some advantages are provided. Coating composition is with many Mode provides antimicrobial efficacy, include but not limited to kill (loose microorganism and biomembrane), Reduce or prevent the microorganism growth, prevent that biomembrane from forming, and catch among the coating, the below or Be attached to its microorganism.

The application of coating composition also reduces water consumption because the concentrate of antimicrobial directly with Form of film applies, and antimicrobial can remain at the base material place higher concentration and when longer Between. In addition, because antimicrobial coatings applies once and removes in procedure of processing afterwards, institute Can reduce the labour. Coating composition can be by coming composition and the preparation of mobile modifier Modification, the surface that is difficult to arrive with coating. Like this can be with on the antimicrobial paint equipment Or among the surface, otherwise have the conventional antimicrobial molten of traditional shear viscosity scope by applying Liquid can not arrive. The horizontal and vertical surface can be with the protective coating of not wasting antimicrobial thin Layer is coated with. By the composition that preparation has suitably flow modification and the degree of cross linking, can prepare with In surface smoothness and protection and easily differently aspect the removal have being coated with of various coating performances The material composition.

In one embodiment of the invention, can be used for the antimicrobial coating of removing of the present invention Composition is applied over establishing in for example food, dairy or the beverage industry in equipment downtime process Standby. When device start, remove coating by method described herein. In another embodiment, Antimicrobial removable type coating composition is used for every day or weekly for example food or the drink of health purpose The surperficial health on the equipment surface of material industry. In another embodiment, the fruit surface can be used The removable type coating composition coating is used for preventing that microorganism is in the propagation of food processing facility and intersection Pollute. In another embodiment, hospital's wall, bed and other hospital surface can be with available In antimicrobial removable type coating composition coating of the present invention. In another embodiment, row Water pipe is coated with removable type coating composition. In another embodiment, new house knot for example Building surface in the structure body, wall or other surface coated are used for prevention mould contamination or mould Remove.

Coating composition provides some microorganisms for for example dirt or non-microorganism source to pollute Protection mechanism.

The first, when applying the fluid composition, lip-deep swim or the loose cell that adheres to is coated with Antimicrobial in the material preparation material is killed (or growth is reduced or prevents).

The second, the cell of being concealed by lip-deep biomembrane will be diffused into aquation by the fluid coating Antimicrobial killing in the biomembrane (or growth will be reduced or prevent). When antimicrobial coatings is done When dry, antimicrobial is retentive activity probably, because between biomembrane and antimicrobial coatings At the interface maintenance high water content. Because film is semi-permeable, thus antimicrobial can Mobile in the film, help more effectively barrier layer and lasting activity. Compare usually several seconds or The routine cleaning flushing liquor that drips off in a few minutes, the antimicrobial membranes that so forms consists of antimicrobial The reservoir of agent provides much longer time of contact.

The 3rd, apply after the antimicrobial coatings, it is thin to arrive from the outside swimming of antimicrobial coatings Born of the same parents will be killed by antimicrobial (or growth will be reduced or prevent). Again, antimicrobial coatings To play the antimicrobial reservoir, keep its microbial performance until exhaust from coating. This Mechanism will prevent that also biomembrane from growing at antimicrobial coatings, until antimicrobial is from being coated with Layer exhausts. Term " biomembrane " expression is by Extracellular Polymers (i.e. outer polymer or outward by polysaccharide) Many microorganisms (a kind of material or many kinds of substance) of matrix parcel. These Extracellular Polymers are common Be polysaccharide, but they can contain other biopolymer, and they can be attached to inertia Or active surface. Typical biomembrane microorganism has been pathogen, eucoen body and/or spoilage organisms Gram-positive (Gram positive) and/or gram-Negative bacillus (the Gram negative of effect Bacteria).

The 4th, coating consists of the physics barrier layer to microorganism, dirt, grease and other material. These solid pollutants will remain on the coating surface and will wash off when removing coating.

The 5th protection mechanism occurs in its floating coat and catches microorganism so that they can not arrive or The infiltration target surface also pollutes in the situation of this target surface. Fig. 1 for example understands above-mentioned various guarantors Protect mechanism. Protection mechanism can work separately or with any combination simultaneously, depends on environmental condition.

Activity is advantageous particularly in various application lastingly in the time of on coating is present in the playground . This residual benefit outclass the antimicrobial of the flushing liquor that for example drips off rapidly, perhaps After applying because contact surface or littler surface abrasion and removed reagent. The present invention is coated with Film pliability, viscosity, intensity and the fusible variation of layer allow it to be suitable for special application, Thus so that can before can not obtain therein the many of this lasting activity (residual benefit) Obtain lasting antimicrobial protection in the situation.

The component of composition

The detailed description of film described herein or coating ingredients below is provided.

Water-soluble or the aqueous dispersion reagent of film forming:

Water-soluble or the aqueous dispersion reagent of film forming can for durable with removable as described below What reagent at least a. For example be higher than 15 ℃ when experiencing, preferably be higher than 30 ℃ aqueous solution place During reason, film or coating are removable. Example includes but not limited to that polyvinyl alcohol, polyvinyl alcohol are common Polymers, polyvinylpyrrolidone, polyacrylic acid, acrylate copolymer, ion polymerized hydrocarbon thing and Polyurethane or its combination.

Polyvinyl alcohol and copolymer thereof

Polyvinyl alcohol is sometimes referred to as poly-(vinyl alcohol), is made by hydrolysis by polyvinyl acetate.The physicals of polyvinyl alcohol is by molecular weight and degree of hydrolysis control.The most frequently used grade by degree of hydrolysis fractionated polyvinyl alcohol is 87-89% grade (the remaining vinyl acetate unit that contains 11-13mol%), 96% hydrolysis grade (the remaining vinyl acetate unit that contains 4mol%), with be respectively about 98% " all-hydrolytic " grade and greater than " super hydrolysis " grade of 99% hydrolysis.Than low in hydrolysis degree (for example 74% and 79%) also is commercially available.Some preferred degree of hydrolysis are greater than 85mol%, or greater than 92mol%.Polyvinyl alcohol component of the present invention also can be the multipolymer of vinyl alcohol, is for example obtained by vinyl-acetic ester and a small amount of (about at the most 15mol%) other monomeric multipolymer hydrolysis.The comonomer that is fit to is the ester of vinylformic acid, methacrylic acid, toxilic acid or fumaric acid, methylene-succinic acid etc. for example.Equally, vinyl-acetic ester and hydrocarbon, alpha-olefin for example, for example ethene, propylene or vaccenic acid etc., with high-stage ethylene base ester, for example vinyl butyrate, caproic acid 2-ethyl ester, stearate, 3-acetic acid methyl ester, or its homologue (" VV-10 " type vinyl ester of being sold by Shell Chem.Co.) copolymerization generation that waits can be hydrolyzed to the multipolymer of suitable polyvinyl alcohol copolymer.The acrylamide that other comonomer that is fit to is the N-replacement, vinyl fluoride, allyl acetate, vinyl carbinol etc.Free unsaturated acid, for example vinylformic acid, methacrylic acid, monomethyl maleate etc. also can be used as comonomer.

Because the diversity of known or commercially available grade in the document, those skilled in the art can be simply is 74 to greater than 99% polyvinyl alcohol solution by prepare the average hydrolysis degree with the known or commercially available grade of any required ratio blend.Therefore, as using in this specification sheets, term " partial hydrolysis grade polyethylene alcohol " is understood to include the mixture of single-grade and each grade, and term " average hydrolysis degree " is if be interpreted as using mixture, the degree of hydrolysis that expression obtains by the partial hydrolysis grade in average (adopting according to the suitable weighting of ratio) mixture, if perhaps use single-grade, the average hydrolysis degree (for example " 88% grade " can be the mean value of 87 in the same levels to 89% scope) of expression single-grade.

Film snappiness, the water sensitivity of polyvinyl alcohol film, be easy to solvation, viscosity, film toughness and fusible variation and can change by regulating molecular weight and degree of hydrolysis.In one embodiment, the polyvinyl alcohol that uses in the inventive method has about 85% to greater than 99% degree of hydrolysis.In another embodiment, polyvinyl alcohol has about 92% to greater than 99% degree of hydrolysis.In one embodiment, polyvinyl alcohol has and falls into about 4,000 to about 200,000, or about 4,000 to about 186,000, or 30,000 number-average molecular weights to about 186,000 scopes (Mn).In another embodiment, polyvinyl alcohol has the molecular weight that falls into about 70,000 to 130,000 scopes.In another embodiment, the polyvinyl alcohol of various molecular weight can blend produce desired properties.In one embodiment, polyvinyl alcohol uses with the extremely about 30wt% of about 2wt% of solution weight.At one more in the special embodiment, polyvinyl alcohol with about 2wt% of solution weight to about 15wt% use.At one more in the special embodiment, polyvinyl alcohol with about 3wt% of solution weight to about 6wt% use.

Polyvinylpyrrolidone (PVP)

Film-forming composition of the present invention can contain concentration and be the PVP of about 0.25wt% to about 50wt%.The PVP that is fit to grade available from International Specialty Products (Wayne, NJ, USA).This grade comprises: K-15, molecular weight are about 6,000 to about 15,000; K-30, molecular weight are about 40,000 to about 80,000; K-60, molecular weight are about 240,000 to about 450,000; K-90, molecular weight are about 900,000 to about 1,500,000; And K-120, molecular weight is about 2,000,000 to about 3,000,000.The mixture of PVP can be used, the combination of PVP and other film forming compound can be used.

The amount of the PVP that uses and viscosity, coverage and the cost that molecular weight distribution will influence final product.Viscosity should be preferably about 20 to about 1000 centipoises and more preferably about 20 to 100 centipoises.Usually, compare with the higher molecular weight PVP of same concentrations, lower molecular weight PVP will produce more not heavy-gravity product.For given PVP concentration, along with molecular weight ranges raises, viscosity also will raise.The present invention can use the PVP with any molecular weight ranges numerical value.For example, film-forming composition can use above-mentioned PVP grade K-15, K-30, K-60, K-90 or K-120.But preferably use molecular weight distribution for about 15,000 to about PVP of 3,000,000.Have the film-forming composition that the PVP of this molecular weight distribution usually produces and have and to regulate easily and to wash off from the surface easily, and do not have the viscosity of visible interaction vestige with painted surface.In preferred embodiments, molecular weight distribution is about 15,000 to about PVP of 3,000,000 to exist to the concentration of about 40wt% with about 0.25wt%.In another preferred embodiment, molecular weight distribution is about 60,000 to about PVP of 1,200,000 to exist to the concentration of about 30wt% with about 2wt%.

Polyacrylic ester

Film-forming composition of the present invention also can comprise the acrylic ester emulsion polymkeric substance.Preferred acrylic ester polymer those that the multipolymer of one or more olefinic unsaturated comonomers forms of serving as reasons.The monomer that can be used for the present composition comprises the unsaturated polarity of one or more olefinics or nonpolar, unionized monomer and at least a ethylenically unsaturated carboxylic acids.Monomer can comprise more than a unsaturated site of olefinic, and the carboxylic acid that is fit to preferably includes one or more carboxyls.The ethylenic unsaturated acid that is fit to comprises vinylformic acid, methacrylic acid, butenoic acid, toxilic acid, fumaric acid, methylene-succinic acid and styracin and dimeracid, for example vinylformic acid and methacrylic acid dimeracid and above-mentioned combination.Unsaturated polarity of olefinic or nonpolar, non-ionized monomer comprise ethylenic unsaturated ester, olefinically unsaturated nitriles, olefinic unsaturated alcohol, aryl ethylene based compound and arylalkyl vinyl compound.According to commercially available, acrylic ester polymer is preferably the multipolymer of acrylate and methacrylic ester, for example vinylformic acid C1 to C6 alkyl ester or methacrylic acid C1 to C6 alkyl ester combine with acrylic or methacrylic acid, cyanoacrylate and methacrylic ester (for example vinyl cyanide) and other known acrylic acid series, vinyl and diene monomer.The acrylic ester polymer component can be chosen wantonly and contain effective one or more metal-salt complexing agents as linking agent.When the side on this complexing agent and acrylic ester polymer are provided was hung carboxyl bonding formation cross-linked polymer, it was more water-fast than uncrosslinked similar acrylic ester polymer.The metal-salt complexing agent that is fit to comprises those of the zinc that contains zinc carbonate ammonium for example.Other useful complexing agent comprises known various metal-salt, and described metal comprises for example zirconium, calcium, magnesium and transition metal.Exemplary complexing agent comprises the polyvalent metal complex compound, for example zinc carbonate ammonium, quadrol lime carbonate ammonium, zinc acetate ammonium, zinc acrylate resin ammonium, MALEIC ACID, ZINC SALT ammonium, Padil zinc ammonium and aniline calcium ammonium and above-mentioned combination.

The acrylate polymer emulsion of commercially available carboxylation can be used alone or in conjunction with each other in film-forming composition of the present invention.The commercial emulsion that is fit to comprise have metal chelating agent as mentioned above those and do not add those of metal chelating agent.The not containing metal emulsion that is fit to comprises the commercially available material, for example with trade mark " Rhoplex " NT 2624 (Rohm and Haas Company, Philadelphia, PA); " Esi-Cryl " 20/20 (Emulsion Systems, Valley Stream, NY, USA); " Syntran " 1905 (Interpolymer of Canton, MA, USA) those that obtain.The commercial emulsion that comprises the zinc complexing agent that is suitable for being included in the present composition comprises with trade mark " Duraplus " I and " Rhoplex " B-825 (Rohm and Haas), " Conlex " V (Morton International, Chicago, IL, USA) and " Esi-Cryl " 2000 (EmulsionSystems Ltd., Valley Stream, NY, USA) those that obtain.Understand as those skilled in the art, can use to contain other metal and metal-free acrylic ester emulsion.

The acrylic ester polymer component is preferably with emulsion form preparation, and with based on composition total weight, about 0.25 to 30wt% and more preferably from about 2 to 20wt% concentration range exists in film-forming composition of the present invention.

Ionic hydrocarbon copolymer

Can be used for the α that ionic hydrocarbon copolymer of the present invention comprises the alpha-olefin with general formula R CH=CH2 and has 1 or 2 carboxyl, the polymkeric substance of β-ethylenically unsaturated carboxylic acids, wherein R is the group that is selected from hydrogen and has the alkyl of 1 to 8 carbon atom, the olefin(e) centent of described polymkeric substance is 50mol% at least, based on this polymkeric substance, the acid mono content of described polymkeric substance is 0.2 to 25mol%, based on this polymkeric substance.Such polymkeric substance is at US 3,264, describes in 272, is introduced into as a reference especially at this.

Polyurethane dispersions

Polyurethane dispersions or solution represent to contain the aqueous dispersion or the solution of the polymkeric substance of carbamate groups.Crosslinked polyurethane dispersions represents to contain the aqueous dispersion of carbamate groups and crosslinked polymkeric substance, those terms of understanding as those of ordinary skills.According to degree of crosslinking, urethane can be the aqueous solution (uncrosslinked or low cross-linking) or aqueous dispersion.

Crosslinked polyurethane dispersions is described in US patent application 2005/0215663, is introduced into as a reference especially at this.These polymkeric substance can be introduced hydrophilic functional groups, reach to keep the required degree of polymkeric substance stable dispersion in the aqueous solution.These polymkeric substance also can be introduced ion and nonionic functional group, reach to keep the required degree of polymkeric substance stable dispersion in water.In addition, these polymkeric substance can pass through by means of the external emulsification agent that is fit to, tensio-active agent etc., and/or utilize strong shearing force to form oil-in-water dispersion, and the hydrophobic urethane of emulsification prepares in water.

Usually, by in polyether polyols with reduced unsaturation, introducing negatively charged ion, positively charged ion and/or the nonionic components that promotes crosslinked urethane stabilization in water-based system, realize crosslinked urethane stablizing in the water-based vehicle.Select crosslinked amount, obtain required water tolerance.Also can add the external emulsification agent and come stabilizing polyurethane.Also can use negatively charged ion, positively charged ion and/or the nonionic components of introducing, and/or the combination of external emulsification agent.

Biocide:

Can be used for biocide of the present invention and can be inorganic or organic additive or its mixture.The invention is not restricted to the selection of any specific antimicrobial, any known water-soluble or water dispersible biocide can be included in the composition of the present invention, for example biocide, mould inhibitor, sanitas, disinfectant, sterilizing agent, sterilant, algicide, stain control agent, rust-preventive agent and above-mentioned combination etc., condition be this biocide chemically with composition in other component compatibility.The proper classification of biocide is below described.

Term " inorganic anti-microbial agents " is to having the common name such as the mineral compound of metals such as silver, zinc, copper or metal ion of containing of antimicrobial properties as used herein.Term " organic biocide " is the common name that all are had antimicrobial properties and contain natural extract, low molecular weight organic compound and the high-molecular weight compounds of nitrogen, sulphur, phosphorus or analogous element usually as used herein.The example of available natural antimicrobial agent is chitin, chitosan, antimicrobial peptide, for example nisin, N,O-Diacetylmuramidase, Euterma Wasabi extract, mustard extract, chamenol, tea extract etc.High-molecular weight compounds with antimicrobial properties comprises as known in the art, has the ammonium salt group phosphonium salt group that is connected to straight chain or branched polymer chains, sulfonium group or class are saloid, the phenyl amide group, those of guanyl guanidine group, Han phosphonium salt vinyl polymer for example, (E-R.Kenawy and Y.A-G.Mahmoud " Biologically active polymers; 6:Synthesis and antimicrobial activity of some linear copolymers withquaternary ammonium and phosphonium groups ", MacromolecularBioscience (2003), 3 (2), 107-116).

The example of available lower molecular weight biocide comprises chlorhexidine, the chlorhexidine gluconate, glutaraldehyde, halazone, Hexachlorophene, nitrofural, Nitromersol, willow mercury (thimerosol), the C1-C5-p-Hydroxybenzoate, hypochlorite, Trifluoromethyldichlorocarbanilide (clofucarban), chlorine card phenol, resol, the mafenide acetic ester, acramine, quaternary ammonium salt, release chlorine and bromine compounds (for example basic metal and alkaline-earth metal hypochlorite and hypobromite, isocyanurate, glycolylurea, sulphonamide, the chlorinated derivatives of amine etc.), superoxide and peracetic acid compound (peracetic acid for example, it is sad to cross), protonated short chain carboxy acid, oxychlorosene, benzene spills orchid, mercurochrome, dibromsalan, lauric acid glyceryl ester, sulphur oxy picolinate sodium and/or zinc pyridinethione, tertiary sodium phosphate, (dodecyl) (diethylenediamine) glycine and/or (dodecyl) (aminopropyl) glycine etc.The available quaternary ammonium salt comprises N-C10-C24-alkyl-N-phenmethyl quaternary ammonium salt, and it comprises water soluble anion, for example halogenide, for example muriate, bromide and iodide; Vitriol, Methylsulfate etc. and heterocycle imide, for example imidazole salts.Available phenols sterilant comprises phenol, meta-cresol, ortho-cresol, p-cresol, adjacent phenyl-phenol, 4-chloro-m-cresol, roxenol, 6-n-pentyl-meta-cresol, Resorcinol, resorcinol monoacetate, p-tert-butylphenol and neighbour-phenmethyl-right-chlorophenol.Knownly preventing that effective available biocide comprises for example 3-iodo-2-propyl group butyl carbamate, 2-(4-thiazolyl) benzoglyoxaline, diiodomethyl-right-tolyl sulfone, daconil M, 2-pyridine mercaptan-1-zinc oxide complex compound (comprising its salt) and above-mentioned combination aspect the mold colony visible growth.

The coating composition that comprises biocide provides protection to various microorganisms.Term " microorganism " expression comprises by bacterium and primary territory and unicellular (for example yeast) and thread (for example mould) mushroom, unicellular and filamentous algae, unicellular and any organism of forming that many cells parasite, virus, virosome and viroid kind system grow.

In one embodiment, coating composition prevents Gram-positive (Gram positive) or gram negative bacillus (Gram negative bacteria).Suppress or the Gram-positive bacillus killed includes but not limited to mycobacterium tuberculosis (Mycobacterium tuberculosis) by coating, Mycobacterium bovis (M.bovis), mouse typhus mycobacterium (M.typhimurium), the Mycobacterium bovis strain is BCG, the BCG substrain, mycobacterium avium (M.avium), Mycobacterium intracellulare (M.intracellulare), African bacillus (M.africanum), Kan Sasishi mycobacterium (M.kansasii), Mycobacterium marinum (M.marinum), mycobacterium buruli (M.ulcerans), mycobacterium avium subspecies paratuberculosis, streptococcus aureus (Staphy lococcus aureus), staphylococcus epidermidis (S.epidermidis), streptococcus equi (S.equi), micrococcus scarlatinae (Streptococcus pyogenes), streptococcus agalactiae (S.agalactiae), Listeria monocytogenes (Listeria monocytogenes), sheep Listera (L.ivanovii), Bacillus anthracis (Bacillus anthracis), subtilis (B.subtilis), nocardia asteroide (Nocardia asteroids) and other Nocardia (Nocardia) species, viridans streptococci (Streptococcus viridans) family, Peptococcus (Peptococcus) species, Peptostreptococcus (Peptostreptococcus) species, actinomyces Israeli (Actinomyces israelii) and other actinomyces (Actinomyces) species, propionibacterium acnes (Propionibacterium acnes) and enterococcus spp (Enterococcus) species.Suppress or the gram negative bacillus killed includes but not limited to clostridium tetanus (Clostridium tetani) by coating, bacillus aerogenes capsulatus (C.perfrmgens), clostridium botulinum (C.botulinum), other Clostridium (Clostridium) species, Pseudomonas aeruginosa (Pseudomonas aeruginosa), other Rhodopseudomonas (Pseudomonas) species, campylobacter (Campylobacter) species, vibrio cholerae (Vibrio cholerae), the ehrlichiosis body belongs to (Ehrlichia) species, pleuropneumonia unwrapping wire genus bacillus (Actinobacilluspleuropneumoniae), pasteurella hemolytica (Pasteurella haemolytica), pasteurella multocida (P.multocida), other pasteurella (Pasteurella) species, legionella pneumophilia (Legionella pneumophila), other legionella (Legionella) species, salmonella typhi (Salmonella typhi), other salmonella (Salmonellla) species, Shigella (Shigella) species, Bacillus abortus (Brucella abortus), other Brucella (Brucella) species, chlamydia trachomatis (Chlamydia trachomatis), ornithosis virus (C.psittaci), Bei Shi Ke Kesi body (Coxiella burnetti), bacillus coli (Escherichia coli), Neisseria meningitidis (Neiserria meningitides), Diplococcus gonorrhoeae (N.gonorrhea), hemophilus influenzae (Haemophilus influenzae), haemophilus ducreyi (H.ducreyi), other hemophilus (Haemophilus) species, Yersinia pestis (Yersinia pestis), yersinia entero-colitica (Y.enterolitica), other Yersinia (Yersinia) species, bacillus coli (Escherichia coli), Hai Shi escherich's bacillus (E.hirae) and other Escherichia (Escherichia) species, and other enterobacteriaceae (Enterobacteriacae), Bacillus abortus (Brucella abortus) and other Brucella (Brucella) species, onion burkholderia (Burkholderia cepacia), pseudoglanders burkholderia (B.pseudomallei), soil draws hot francis fungus (Francisella tularensis), bacteroides fragilis (Bacteroides fragilis), fusobacterium nucleatum (Fusobacteriumnucleatum), Prey is irrigated bacterium (Provetella) species, ruminant is examined De Lishi body (Cowdriaruminantium), klebsiella (Klebsiella) species and proteus (Proteus) species.In another embodiment; coating provides the protection to following mushroom, includes but not limited to mutual lattice chain lattice spore (Alternaria alternate); black aspergillus (Aspergillus niger); aureobasidium pullulans (Aureobasidium pullulans); the dendritic branch of bud spore (Cladosporiumcladosporioides); Drechslera australiensis (Drechslera australiensis); cereal is glued whip mould (Gliomastix cerealis); grey beads mould (Monilia grisea); penicillium communne (Penicillium commune); excrement stem point mould (Phoma fimeti); paper shape marrow mould (Pithomyceschartarum) and Scolecobasidium humicola (Scolecobasidium humicola).

Enzyme:

Can be used for enzyme of the present invention comprise for example have clean, the advantageous effect of decolouring and microbial film degraded those.These enzymes comprise one of following or mixture: deacetylase, Ntn hydrolase, cellulase, esterase, Glycosylase, zytase, amylase, transaminase, laminarinase, beta-galactosidase enzymes, beta-Mannosidase, Starch debranching enzyme, Phosphoric acid esterase, proteolytic enzyme, lipase and peroxidase.

Tensio-active agent:

Can be used for composition of the present invention and can also contain one or more tensio-active agents.Though not bound by theory, it is believed that tensio-active agent will help the moistened surface that will be capped, and the even fraction of coverage that will promote film.Tensio-active agent also is considered to help film to bubble when being removed, and helps to remove film and the protected surface of washing thus.The tensio-active agent that is fit to has about 9 to about 17 preferred hydrophile-lipophile balance value (HLB).The tensio-active agent that is fit to comprises but is not limited to: amphoterics, for example available from the Amphoteric N of Tomah Products; Silicone surfactant is for example available from the BYK348 of BYK Chemie (BYK-Chemie GmbH, Wesel, Germany); Fluorinated surfactant, for example available from DuPont (DuPont, Wilmington, DE, USA)

FS300; With Nonylphenoxy polyethoxyethanols based surfactants, for example available from Dow (Midland, MI, Triton N-101 USA).Other tensio-active agent that is fit to comprises the ethoxylation acetylenediol, for example available from Air Products; Chemicals (Allentown, PA, Surfynol 465 USA); Alkyl aryl polyether is for example available from the Triton CF-10 of Dow; Octylphenoxy polyethoxy ethanol is for example available from the Triton X-100 of Dow; Ethoxylated alcohol is for example available from Neodol23-5 or the Neodol 91-8 of Shell (The Hague, Holland); Available from the Tergitol 15-S-7 of Dow, available from StepanCompany (Northfield, IL, Steol-4N USA), 28% Zetesol NL; Dehydrated sorbitol derivative is for example available from Uniqema (New Castle, DE, polysorbas20 USA) or polysorbate60, and quaternary ammonium compound, for example benzalkonium chloride.

Other tensio-active agent that is fit to comprises the organo-siloxane tensio-active agent, for example available from SetreChemical Company (Mephis, TN, USA)

L-77, available from DowCorningSilicones (Midland, MI, USA)

Q2-5211, or available from SiltechCorporation's (Toronto, ON, Canada)

A008.

The preferable range of the tensio-active agent that uses as formulation about 0.001 to about 1wt% and more preferably formulation about 0.01 to about 0.2wt%.

Solvent:

Can be used for inert solvent of the present invention and comprise water.Other solvent comprises single pure simple function and polyfunctional alcohol, preferably contain have an appointment 1 to about 6 carbon atoms and 1 to about 6 hydroxyls.Example comprises ethanol, Virahol, n-propyl alcohol, 1,2-propylene glycol, 1,2-butyleneglycol, 2-methyl-2,4-pentanediol, seminose alcohol and glucose.Equally usefully higher glycols, polyglycol, polyoxide, glycol ether and propylene glycol.Other solvent comprises free acid and such as an alkali metal salt and phenol or the phenol ether or the diphenyl ether sulfonate of the sulfonated alkyl aryl of toluene, dimethylbenzene, isopropyl benzene; Naphthene sulfonic acid alkyl ester and dialkyl and alkoxy derivative.

Annexing ingredient:

The annexing ingredient that can join in the coating composition comprises tinting material, rheology modifier, linking agent, softening agent, tensio-active agent, solubilizing agent, oxidation inhibitor, pH regulator agent, wetting agent, antifoams, extender, lubricant, processing aid, laking agent and additional properties toughener.Wetting agent reduces the surface tension of formulation, allows its wetted surface, from the teeth outwards diffusion and may be penetrated among dirt, solid matter, microorganism, microbial film, surface contamination, grease and the surface gaps, under and on every side.

Tinting material:

Can be used for tinting material of the present invention and comprise dyestuff and pigment, for example food grade pigment.

Can be used for dyestuff of the present invention comprises water-soluble and the water-insoluble dyestuff.Water-soluble dye can preparation easily in water-based system of the present invention.The water-insoluble dyestuff can be included in the oil phase, and described oil phase can be dispersed or suspended in and can be used in the antimicrobial coating compositions of the present invention.Be used for the object of the invention available dyestuff and be generally the absorption visible light, produce the organic compound of discernable color outward appearance.For example, also can use fluorescence dye in order to manifest film by UV-light.

For food-processing industry, comprise the surface, restaurant and, in one embodiment of the invention, can use common FD﹠amp for fruit; The dyestuff of C approval is because these materials go through usually as the direct additive of food.Usually can be used for dyestuff of the present invention is used for food, medicine, makeup and medical device for approval tinting material.

Tinting material and the state thereof that uses is as follows at present.The tinting material that allows in the food is (1) process check: FD﹠amp; C blue No. 1, FD﹠amp; C blue No. 2, FD﹠amp; Green No. 3 of C, FD﹠amp; Red No. 3 of C, FD﹠amp; Red No. 40 of C, FD﹠amp; C yellow No. 5, FD﹠amp; Yellow No. 6 of C, orange No. 2 and orange (B), (2) are inspection-free: carmine extract, θ-A Piao-8 '-Radix Dauci Sativae aldehyde, canthaxanthin, caramel, θ-carotene, carrot oil, cochineal extract (famille rose), maize missible oil, dehydration beet (sugar beet powder), dry algae meal, ferrous gluconate, fruit juice, the colored extract of grape, Pericarpium Vitis viniferae extract, paprika, paprika turps, riboflavin, Stigma Croci, synthetic iron oxide, Flower of Aztec Marigold meal and extract, titanium dioxide, the boiling cottonseed meal of the partially skimmed of baking, turmeric, turmeric rosin (termericoleoresin), ultramarine indigo plant and vegetables juice.The tinting material that allows in the medicine (comprising the tinting material that allows in the food) is (1) process check: FD﹠amp; Red No. 4 of C, D﹠amp; C blue No. 4, D﹠amp; C blue No. 9, D﹠amp; Green No. 5 of C, D﹠amp; Green No. 6 of C, D﹠amp; Green No. 8 of C, D﹠amp; C orange No. 4, D﹠amp; C orange No. 5, D﹠amp; C orange No. 10, D﹠amp; C orange No. 11, D﹠amp; Red No. 6 of C, D﹠amp; Red No. 7 of C, D﹠amp; Red No. 17 of C, D﹠amp; Red No. 21 of C, D﹠amp; Red No. 22 of C, D﹠amp; Red No. 27 of C, D﹠amp; Red No. 28 of C, D﹠amp; Red No. 30 of C, D﹠amp; Red No. 31 of C, D﹠amp; Red No. 33 of C, D﹠amp; Red No. 34 of C, D﹠amp; Red No. 36 of C, D﹠amp; Red No. 39 of C, D﹠amp; C purple No. 2, D﹠amp; C yellow No. 7, D﹠amp; C yellow No. 8, D﹠amp; C yellow No. 10, D﹠amp; C yellow No. 11 and Ext.D﹠amp; Yellow No. 7 of C.Other canthaxanthin, beta carotene, CHLOROPHYLLINE and other color are known.

For the more detailed tabulation and/or the argumentation of the color of ratifying, referring to D.M.Marmion, Handbook of U.S.Colorants, Foods, Drugs, Cosmetics and MedicalDevices, John Wiley ﹠amp; Sons Inc., New York (1991) and U.S.Code of FederalRegulations, title 21,70-82 section.

Rheology modifier:

Can be used for composition of the present invention and also can contain one or more rheology modifiers, or rheological reagent, be used for strengthening viscosity or thickening and initiation aqueous treatment or coating composition and be attached to the surface.Adhere to and make that composition keeps contact the longer time with that stay temporarily and resident microorganism, promote microorganism effect and prevention waste because of excessive drippage.Rheology modifier can be membrane-forming agent, or with the membrane-forming agent co-action, form the blocking layer that Additional Protection is provided.Water-soluble or the water dispersible rheology modifier of available can be categorized as inorganic or organic.Organic thickening agent can be further divided into natural and synthetic polymer, and the latter further is subdivided into synthesis of natural base and synthetic petroleum base.

Inorganic thickening agent is generally such as colloidal magnesium aluminum silicate

Colloidal clay (bentonite) or pyrolysis or precipitation form has the particulate silicon-dioxide of big surface to the size ratio

Compound.Available natural water gelling thickener is mainly vegetables deutero-exudate.For example, tragacanth, sterculia and Sudan Gum-arabic; With extractives such as carrageeman, Viscogum BE, guar gum and pectin; Or the pure culture tunning, for example xanthan gum all is potential in the present invention available.Chemically, all these materials are the salt of complex anion polysaccharide.Synthesis of natural base thickening material with application is a derivatived cellulose, and free hydroxyl group etherificate or the esterification on its neutral line anhydroglucose polymkeric substance produces water-soluble material family and produce viscous solution.This group material comprises alkyl and hydroxy alkyl cellulose, particularly methylcellulose gum, hydroxyethylmethyl-cellulose, Vltra tears, hydroxy butyl methyl cellulose, Natvosol, Type 3U, hydroxypropylcellulose and carboxymethyl cellulose.Another group preferred thickening comprises polyacrylic ester, for example (for example Acusol 823 for the Acusol thickening material of patent, Rohm and Haas, Philadelphia, PA, USA), with the Carbopol thickening material, for example Carbopol 934 or Carbopol Aqua-30 polymkeric substance (B F Goodrich, Cleveland, OH, USA).Polyacrylate thickeners can use with the concentration of about 3wt% at the most of membrane-forming agent weight.Also can use mixtures of thickening agents, wherein total amount can depend on the required viscosity of the thickening material and the final product of use up to about 3wt%.

The potential thickening material of other of this application comprises dextrin, W-Gum and hydrated magnesium silicate, for example with trade mark Laponite XLG (Southern Clay Products, Inc., Gonzales, TX, USA) sodium magnesium silicate of Xiao Shouing.

Linking agent:

The present invention can choose wantonly and comprise linking agent.Using the advantage of linking agent to comprise for film-forming composition influences the film mechanical property, for example viscosity and physical strength, and coating solvability.In the present invention, crosslinked film produces mechanically more firm film.In addition, crosslinked minimizing viscosity and prevent dirt and the microorganism physical attachment in polymeric film, this point may be an ideal for some is used.In the present invention, crosslinked have favorable influence to discharging biocide from film.Regulate degree of crosslinking to obtain required performance combination.

The linking agent that is fit to use with polyvinyl alcohol and multipolymer thereof includes but not limited to: aldehyde (for example formaldehyde, oxalic dialdehyde, glutaraldehyde), boric acid, sodium tetraborate, metal ion (for example ion of Zn, Fe, Al, Ni, V, Co, Cu, Zr, Ti, Mn), organometallic compound (for example organic titanate, for example DuPont

Organic C r (III) complex compound, for example DuPont

Siloxanes (for example tetraethoxysilane, polydimethylsiloxane), isocyanic ester (that for example seal, water miscible or decentralized), epoxide (for example diglycidylether), dicarboxylic acid (for example oxalic acid, toxilic acid, fumaric acid, phthalic acid), urea groups linking agent (for example Sunrez 700).Divalence and trivalent metal cation (for example Fe (II), Fe (III), A1 (III)) are preferred, because when film was dry, they formed coordinate bond between the PVOH polymer chain.Allow linking agent to join in the film forming liquid like this with the form of ' still ' mixture.Must careful select suitable concentration, so that cross-linked polymer effectively, not become fractional precipitation and do not make such as other of grain flow sex change control agent.

In most of the cases, will use the standard hybrid technology that linking agent is mixed with other composition.Crosslinking reaction can be chosen wantonly well known to a person skilled in the art in the presence of the catalyzer and carry out.Under the situation of aldehyde, isocyanic ester, siloxanes, diglycidylether and dicarboxylic acid, can use heating and acid catalyst or metal catalyst in addition.

The concentration of linking agent can be for zero to the upper limit in the formulation, and the described upper limit is by the limit of stability decision that wherein begins to take place sedimentary formulation, or by the limit of stability decision of the formulation that can not effectively remove the gained film.Preferred cross-linking agents concentration can depend on the linking agent type of use consumingly, and is usually less than the 25wt% of polymer content, is more preferably the 10wt% that is lower than polymer content.

Softening agent:

Importantly for the snappiness and the integrity of protective membrane, with the plasticising of gained film.For the purposes of the present invention, by introducing the softening agent that is fit to, for example polyoxyethylene glycol or glycerol realize the plasticising of film.Be suitable for other softening agent of the present invention and include but not limited to that solvent, polyvalent alcohol, molecular-weight average are 200 to 800g/mol polyoxyethylene glycol and Sorbitol Powder.PEG is better than glycerol, because glycerol is easily by the potential microbial metabolism that causes microorganism growth.

Comprising softening agent also allows film to keep the surface feel of slightly adherent usually.Along with level of plasticizer raises, the gained film will show that also sticky limit raises.This viscosity can it is desirable to be in low-level, carries particle and dirt or other material so that intercept and capture gas.If but level of plasticizer is too high, it is sticking that coating then became, and will show low tolerance to for example accidental machinery removal owing to wiping.The preferred plasticizer amount is that about 1.0wt% of membrane-forming agent weight is to about 20wt% and 5wt% about 8wt% extremely more preferably from about.

Other performance strengthens reagent:

Except said components, composition of the present invention also can comprise one or more performance-enhancing additive, " performance enhancers ".These comprise flash distillation rust-preventive agent, and it comprises that being used for aqueous based systems prevents any of many organic or inorganic materials of getting rusty when contacting with bare metal with material.An example is a Sodium Benzoate.

Another kind of optional performance-enhancing additive prevents to apply one or more of the undesirable blistered a series of defoamers of process product for recommending to be used for aqueous based systems.Too many foam may destroy required product continuous film formation and cause product to destroy.Equally maybe advantageously add the foam control product, help to mix and process this covering composition, for example available from AshlandChemical, Inc.Drew Industrial Division (Covington, KY, DrewplusL475 USA).

Other optional performance-enhancing additive is an oxidation inhibitor, is used for improving the preservation period of coating formulation.An example is a Yoshinox BHT.Other additive comprises spices.

Can add pore forming material in addition, in the coating that applies, to form bubble.Bubble can play opacifying agent, promotes to apply and/or for example longer by preventing to allow with the duration of contact on surface from the scarp drippage, and/or reduces the amount of the required coating formulation of some surface areas of processing or volume.

Also can add and apply indicator.Some still comprise pigment, dyestuff, fluorescence dye or apply the bubble that produces in the process as mentioned above.

Follow suitable adjusting water or other component, can add these other materials of a small amount of (being less than 1wt% usually).Should understand the mixture that also can use any or multiple above-mentioned optional components.

For the playground of being made up of fiber base material, optional performance enhancing ingredients is for providing the reagent of surface effects.This surface effects comprises does not has flatiron, be easy to flatiron, shrink control, wrinkle discharges, non-ironing, humidity control, pliability, intensity, antiskid, antistatic, wear-resistant light, anti pilling, anti-dyeing, dyeing are peeled off, pollution resistance, dirt are peeled off, water resisting property, oil-proofness, smell control, antimicrobial or solar protection.

Apply antimicrobial coating compositions:

Film or coating can comprise casting paint target surface by any method.Apply film or coating obtain successive and/or homogeneity on target surface layer.Coating system is generally used for paint and coating, can be used for coating such as but not limited to the spray gun of brush, roller, paint pads, felt, sponge, comb, manual pump dispenser, air-operated drive, airless sprayer, electric or electrostatic nebulizer, Backpack type spray equipment, cloth, paper, feather, syringe needle, cutter and other applicator instrument.If dip-coating does not need specific equipment as the method that applies coating.For fiber base material, for example fabric and carpet can apply coating by exhaust, foam, bending-pincers (flex nip), pliers, liner, the roller that coincide, cylinder, thread ball, winch, spouting of liquid, overflow dipping, roller, brush, cylinder, spraying, dip-coating, impregnating.Also can apply coating by using conventional cylinder formula staining procedure, continuous dyeing step or spinning tow.

Coating system also can be more component, and can comprise catalyzer.

In one embodiment of the invention, electrostatic atomiser can be used for coating surface.Electrostatic atomiser provides energy via high potential hydrotropisms coating composition.This energy is used for making water-based paint compositions atomizing and charged, forms one tiny charged particle.Electrostatic atomiser is easily available from for example Tae In Tech Co, South Korea, and Spectrum, Houston, TX, the supplier of USA.Usually, allow coating curing or drying, so that form film approximately greater than 5 minutes.But coating can be effectively antimicrobial after 30 seconds for example in the short period scope.Before drying or thereafter any time, can decoating, depend on required purposes.To depend in part on many factors time of drying, comprise envrionment conditions, for example humidity and temperature.Also will depend on the thickness of the coating that applies time of drying.

In another embodiment of the invention, can use airless sprayer to be coated with target surface.Airless sprayer uses high fluid pressure and special nozzle rather than pressurized air is carried and atomized liquid.Liquid offers no air gun by hydro-pump with common 500 to 6500psi pressure.When paint breaks away from fluid tip under this pressure, its slightly microdilatancy and be tiny drop not having to be atomized under the ballistic situation of atomizing air.The high speed that breaks away from paint is pushed drop to target surface.Fluid tip on the no air gun significantly is different from the fluid tip on the air atomizing rifle.Select the amount of suitable nozzle decision paint supply and the fan-shaped form that applies.The amount of the paint that the size decision of no gas jets mouth will spray.Airless body operational throughput height is 700-2000mL/min.The rifle of recommending and the distance of target are 12 inches, depend on bleed type, and 5 to 17 inches fan-shaped form is possible.Therefore, can be according to the size of target surface and shape and the coat-thickness that will apply, at the various selection nozzles that apply.No air gun forms air turbulence hardly, and described air turbulence can arrange liquid from for example there be " being difficult to arrive the zone " food processing apparatus, hatcher etc.High flow rate produces no gas advantage under the cleaning and disinfection situation, wherein antimicrobial coatings applies on high surface area and a plurality of surface.

Applying also, the thickness of exsiccant film will depend on various factors.These factors comprise the concentration of membrane-forming agent concentration, rheological control additive and/or other additive and apply temperature and humidity.Film thickness and film uniformity also depend in part on the parameter of applicator device at least, for example dose of fluid delivered, injection diameter, air pressure or do not have gas and apply piston pump pressure under the situation, and the distance of spraying applicator and target surface.Therefore, can regulate liquid formulations and produce the required film thickness degree.Select the atomizing of coating solution, make film paint target area equably.

Usually, allow coating curing or drying about 5 to about 60 minutes, so that form film.When on the paint surface, this composition will form film or coating owing to the evaporation of inert solvent.Solvent evaporation can pass through to allow the coating dried in place, or by carrying out with the air blow dried of heating or not heating.But coating can for example be effective as biocide after 30 seconds in the short period scope.Before drying or thereafter any time, can decoating, depend on required purposes.To depend in part on many factors time of drying, comprise envrionment conditions, for example humidity and temperature.Also will depend on the thickness of the coating that applies time of drying.Coating is preferably used to about 300 microns thickness with about 0.3.At one more specifically in the embodiment, coating is used to about 100 microns thickness with about 0.5.At one even more specifically in the embodiment, coating is used to about 30 microns thickness with about 1.0.

Film or coat-thickness:

Required time and the sterilization dose that is applied over surperficial per unit area are removed in the film or the coat-thickness influence that are applied on the target surface.Thicker film increases the intermittent phase, up to applying film again to keep required antimicrobial properties.Thin film is incited somebody to action easier and is removed by rinsing more quickly.Therefore importantly apply formulation, make film thickness allow easily decoating and make antimicrobial properties lasting with a kind of pattern.As mentioned above, film or coating have about 0.3 to about 300 microns thickness.At one more specifically in the embodiment, film or coating have about 0.5 to about 100 microns thickness.At one even more specifically in the embodiment, film or coating have about 1.0 to about 30 microns thickness.

Film is removed:

The present invention relates to can be at the film of the time removal of suitably being determined by the user.Can allow the required minimum duration of contact of required antimicrobial acivity by (i), be typically expressed as from initial population and kill or the amount of inactivation microorganism, or (ii) before beginning subsequent operations or procedure of processing, remove the demand of coating from the surface or require to determine the removal time.Though decoating at any time, for example after the drying, film thickness, concentrations of biocide and suitable removal time of specific end use decision.For example the user may wish after one section operation is shut down the device of handling to be put back in the normal running.For example fruit will require to be washed before edible.When the sterilant in the film exhausts, can remove this film and can apply new coating.For example, can periodically handle water shoot, for example every day, weekly or per two weeks.Can be after applying film 30 seconds, hour, day, week, month in addition year after measure antimicrobial acivity.Therefore, the time of decoating is to use the function of the application of this coating.

Film is removed and can be realized by dissolving or the coating of disperseing to obtain.This point can realize by apply the aqueous solution on coating.In one embodiment, the temperature of solution is about 15 degrees centigrade to about 100 degrees centigrade.In another embodiment, solution temperature is about 30 to about 80 degrees centigrade.Can be by simple rinsing or spraying apply solution or water from the teeth outwards.Coating removal also can pass through the applying pressure cleanser, is promoted to remove by other mechanical force and realizes.Coating removal also can wash together with cloth or sponge by water and realize.In addition, can use gentle additive or and aqueous solution, promote dissolving or disperse film forming or water-dispersible agents, comprise normally used acid or alkali, sequestrant or washing composition.In addition, for example the film in the water shoot can be by water and/or other component flush discharge pipe are degraded repeatedly.Film also can be by with its stripper surface, grind off or brush from the surface, or the removal mechanism of other machinery removes.

Except that deliberately removing by the operator, remove also comprise by automatization or robot system remove and since for example the liquid in pipeline or the water shoot along with the time contacts coating continuously or periodically, or owing to apply mechanical force continuously or periodically, what for example wearing and tearing caused removes unintentionally.

Other term:

For the sake of clarity, as used herein term be interpreted as described herein, perhaps this type of term that should understand as those of ordinary skills of the present invention.In addition, below provide the explanation of some terms as used herein:

The aqueous solution:

The aqueous solution that is used for coating removal is for containing 60 to 100wt% water, and all the other components are any solution of dissolved constituent.Dissolved constituent can include but not limited to solvent, for example alcohol, solubilizing agent, tensio-active agent, salt, sequestrant, bronsted lowry acids and bases bronsted lowry.

Lastingly:

Represent lastingly that in this article the exsiccant coated substance keeps deliberately being removed or allow to remove up to it from the teeth outwards.Working conditions for be held at coating protection on the target surface of Application Areas of the present invention during general envrionment conditions, and can comprise with the water chance that is lower than 40 degrees centigrade and contacting.

Continuously:

Continuously or basically represent coating coverage goal surface continuously in this article and do not have unlapped zone, coating defects, for example pit and hole.

Evenly:

Evenly or basically evenly be illustrated in whole coatingsurface in this article, coating only has insignificant variation in thickness.Inhomogeneous or be not basically uniformly coating can not on the whole surface that coating applies, provide antimicrobial uniformly and remove performance.

Remaining antimicrobial efficacy:

Term ' remaining antimicrobial efficacy ' (or from disinfectant properties) is even the coating performance of describing as said formation is still keeping active after the attack micro organisms repeatedly.According to the present invention, cultivate through per square inch at least 10 at each ⁶After at least 2 culture cycle of individual cell, obtain the minimizing of 3-log unit at least.Be used for measuring the method for testing of remaining antimicrobial efficacy in embodiment 16 descriptions.

The duration of contact of antimicrobial coatings:

Particular requirement according to antimicrobial formulation, duration of contact will be as Germicidal andDetergent Sanitizing Action of Disinfectants, Official Methods of Analysisof the Association of Official Analytical Chemists, 960.09 section and suitable paragraph, the 15th edition, the variation of being set forth among 1990 (the EPA Guideline 91-2).If predetermined being applied as sterilizing agent of the present invention, said composition should be at some mensuration bacterium so, provide 99.999% minimizing (minimizing of 5-log magnitude) in room temperature (25+/-2 ℃) in following 30 seconds.On the other hand, if the present invention is used as sterilant, said composition should provide 99.9% to reduce (minimizing of 3-log magnitude) in 10 minutes so.If predetermined being applied as remaining antimicrobial acivity, the present invention will allow and microorganism has duration of contact greater than 10 minutes so.

The physical barriers layer:

The physical barriers layer is defined as the film that is formed by this film-forming composition.Gained film phonograph seal surface treated is away from pollution on every side, for example dirt, grease, dust, microorganism etc.These pollutents will remain on the coatingsurface and will wash off when decoating.

All disclosed herein and claimed method and compositions can not have manufacturing and enforcement on the basis of undo experimentation according to present disclosure.Though according to the present invention and all respects of preferred embodiment the method and composition of present disclosure has been described, but conspicuously for those skilled in the art will be, under the situation that does not break away from design of the present invention, spirit and scope, can be changed each step of composition and method and said method or the order of each step.More specifically, it is evident that some chemically relevant reagent can replace reagent described herein, will obtain identical or similar result simultaneously.Conspicuous for those skilled in the art all this similar substitute and improve be considered within spirit of the present invention, scope and design that claims limit.

Embodiment

The present invention is described in further details in following examples.Represent certain preferred embodiments of the present invention though should understand, these embodiment only illustrate as an example and provide.From above-mentioned discussion and these embodiment, those skilled in the art can determine essential characteristic of the present invention, and in the case of without departing from the spirit and scope, can carry out each change of the present invention and modification, make it be adapted to various uses and condition.

Abbreviation and other term:

In following examples, " degree centigrade " be abbreviated as " ℃ ".

The ATCC-American type culture collection

The BHI-brain heart infusion

The BHT-Yoshinox BHT

The CFU-colony-forming unit

Conc-concentration

The cP-centipoise

DI-is deionized

The L-liter

LB-Luria Bertani substratum

The M-mol

The MW-molecular weight, gram/mole

NA-is inapplicable

The ND-undetermined

PBS-phosphate buffered salt solution (buffer reagent)-10 * liquid storage contains (g/800mL): NaCl (80); KCl (2.0); NaH ₂PO ₄(14.4); KH ₂PO ₄(2.4), under the pH6.8

The PEG-polyoxyethylene glycol

The PVOH-polyvinyl alcohol

The QAC-quaternary ammonium compound

RAC-can remove antimicrobial coatings

RPM-rev/min

The SS316-stainless steel, 316 types (ASTM standard substance)

The UHMWPE-ultrahigh molecular weight polyethylene(UHMWPE)

The wt%-weight percentage

The ZOD-diffusion zone

Except as otherwise noted, (St.Louis, MO USA) obtain all chemical reagent by Sigma-Aldrich.

(Widnes UK) obtains by Rockwood Additives Ltd..(Pittsburgh, PA USA) obtain pseudomonas F-agar (Pseudomonas F-Agar) by Fisher Scientific; (NJ USA) obtains for BectonDickenson, Franklin Lakes by Difco products for yeast extract, brain heart infusion (BHI), tryptic soy agar, tryptic soy substratum and Oxford medium base (Oxford Medium Base); (Phillipsburg, NJ USA) obtain by JT Baker for glucose and magnesium sulfate 7 hydrate;

(71-30 and 52-22), urethane (RCP 31374),

(Wilmington, DE USA) obtain by DuPont for tensio-active agent and titanium dioxide.

Obtain by BASF (Ludwi gshafen, Germany).

(Wilton, CT USA) obtain L-77 by GE Silicones.

425 are obtained by BYK Chemie (BYK-Chemie GmbH, Wesel, Germany). Q2-5211 and antifoams C by

(Midland, MI USA) obtain Silicones.

(Toronto, ON Canada) obtain A012 by Siltech Corp..

By U.S. (Berkeley Springs, WV USA) obtain Company.(Belcamps, MD USA) provide by TIC Gums for Ticaxan, carrageenin (Carrageenan) and Guar 8/22.

L1228, L15, L520 and L251 rheological additives are by Alco

(Chattanooga, TN USA) obtain, and being added into antimicrobial composition after when preparing the explanation according to supplier neutralized.

HVI00 and HV30 by

(Basel, Switzerland) obtains.

General method:

The testing method of the antimicrobial efficacy in solution:

Can determine killing livestock or antimicrobial efficacy in solution by the chemical examination with described in following examples generally known in the art.

The method of testing of the antimicrobial and antifungal efficacy of the coating by diffusion zone test:

For estimating the antimicrobial and antifungal efficacy of antimicrobial coatings, use diffusion zone as described below (ZOD) test.

Immerse stainless steel test piece (1 inch * 3 inches) in the RAC formulation and allow its complete drying to spend the night.By from the flat board that keeps in cold storage, extracting single bacterium colony with the aseptic inoculation ring, and it is inoculated in the 25mL tryptic soy substratum in the aseptic Erlenmeyer flask of 250mL into the bacterial classification that spends the night of preparation streptococcus aureus (Staphylococcus aureus) ATCC 6358.Follow the 150RPM shake, with this bacterial classification 30 ℃ of overnight incubation.By cultivating dull and stereotyped (malt extract agar) 2 weeks of storage at 25 ℃, and by gathering spore by flat board with 15mL filter sterilised salts solution (0.85% NaCl adds 0.05%Triton X-100) submergence, preparation fungal spore (aspergillus niger and Penicilllum expansum (Penicillium expansium)).Use the scraping of aseptic plastic cell scraper should flat board then, liquid is sopped up, rotates and filter via the aseptic cheese cloth of 3-4 layer.Measure spore suspension CFU by on the malt extract agar plate, applying serial dilution.The test piece of coating is placed on LB agar plate surface (dull and stereotyped center) 60 minutes, allows the soluble constituent of coating to diffuse in the agar.Preparation soft agar (the 0.7wt% agar in PBS buffer reagent or the water) is divided into 5mL part, and remains in 50 ℃ of water-baths up to use in the aseptic plastic centrifuge tube.After 60 minutes, shift out test piece, carefully test piece is not slided on agar surface by mentioning on straight with sterility forceps.Shift out any coating flat board of staying on the agar surface with sterility forceps equally.Inoculate each soft agar pipe with the 1:10 dilution of the bacterial cultures that spends the night for preparing more than the 100 μ L.When in test, using fungal spore, with about 10 ³Spore/mL inoculates this soft agar.By vibrating tube disturbance agar leniently, agar is poured on holds on the LB agar plate surface that is coated with test piece then.Rotate this flat board with the complete covering surfaces of soft agar.Soft agar almost solidifies immediately.35 ℃ of overnight incubation, the fungi inoculation is dull and stereotyped cultivated 2 days at 25 ℃ with the microbionation flat board.With all flat boards inhibition zone that record provides by the biocide that diffuses into agar from antimicrobial coatings of taking pictures.(National Institute of Health USA) analyzes the area of this diffusion zone (ZOD) for ImageJ, 1.36b version, and according to the area normalization of the test piece of using by image analysis software.All agar diffusion researchs have the contrast test piece with the formulation coating that does not have biocide.

The measurement of rheological:

Use rheometer, draw and rise and the katabatic drainage moving curve, estimate the rheological of liquid anitmicrobial formulation.(MA USA), has hummingbird geometry (coquettegeometry) to the rheometer that uses, small sample adapter, spindle SC4-21 and sample chamber 13RP for BrookfieldEngineering, Middleboro as Brookfield HADV-III+.With the thermostat container bath temperature is remained on 25 ℃.Load sample by being poured or scooped into the Brookfield sampling receptacle.Program comprises to be sheared shearing rate in advance with 250l/s and shears 5 minutes time in advance, is 10 minutes time of repose subsequently.With 0.1,0.5,5,50,100,200,100,50,5,0.5,0.1RPM carries out viscosity measurement.Viscosity measurement is spaced apart 2 minutes.

Embodiment 1

Polyvinyl alcohol (PVOH) (DuPont

Grade 71-30, MW is about 94,000, degree of hydrolysis 99.0-99.8%; DuPont, Wilmington, DE is USA) as membrane-forming agent.By in 90 ℃ of deionized waters, mixing

Grade 71-30 powder produces 3 to 8wt% solution and prepares the PVOH liquid storage.Use the bar magnet agitator to stir the mixture about 20 minutes, dissolve fully up to polyvinyl alcohol.Mixture is cooled to room temperature.

The benzalkonium chloride as active bactericide (QAC) by making polyvinyl alcohol liquid storage and different amounts, (PEG), be mixed with the blend base fluid as the polyoxyethylene sorbitan laurate tensio-active agent of wetting agent with as the Yoshinox BHT (BHT) of oxidation inhibitor as poly-(ethylene glycol) of the MW～300 gram/moles of film softening agent.The QAC that uses is as the main C12 and the C14 homologue (Sigma-Aldrich) of alkyl benzyl dimethyl-ammonium chloride and contain the mixture of a small amount of rudimentary and higher homologue.

The blend base fluid is mixed with other additive produce final spraying formulation.These additives comprise linking agent, for example iron(ic) chloride and iron protochloride, rheological control properties-correcting agent, for example layered silicate synthesis

And tinting material and opacifying agent, for example food colorant and titanium dioxide.Preparation liquid film forming mixture described in table 1.Mixture in the subsequent embodiment is with reference to the preparation item number.

Table 1: use PVOH

Grade 71-30) example of preparation film forming antimicrobial composition

Embodiment 2

This embodiment shows that coating is a successive and uniformly basically.

Prepare film by the liquid mixture described in the embodiment 1.By (22mm * 60mm) goes up spraying liquid or finishes this point in the solution by test piece is immersed in test piece.Be spraying liquid, their are injected standard pumping mode spray bottle and be sprayed in the test piece.In most of the cases, stainless steel is as the test piece material.When using spraying, test piece is arranged perpendicular to the vertical food apparatus of model surface, and handle with antimicrobial formulation on described surface.For dip-coating and spraying, allow test piece at room temperature vertical direction drying at least 2 hours then, usually dried overnight.In film-forming composition, add trace fluorescence dye (rhodamine 123) afterwards, use confocal laser scanning microscopy to measure the thickness of some films.Zeiss LM 510 confocal microscopes of use employing Zeiss LSM-5 image analysis software (Carl Zeiss Microlmaging, Thornwood, NY, USA).

The formulation that discovery has 4.0wt%PVOH has about 20 microns thickness.Low PVOH concentration produces thin film.Fig. 2 shows the cross section of the formulation #2 of the film thickness that is applied in two vertical surface coatings.Can clearly observe the high evenness in the film thickness and not have structural membrane defective (for example hole, crackle, pit, contained gas etc.).High film uniformity has high importance for defencive function.Structural membrane defective or significant variation in thickness may cause some zones still invalid to the protection of microbial contamination.

Different membrane structures prepare according to formulation.Spraying formulation #14a produces elastomeric after drying and the softish film.On the contrary, spraying formulation #16 produces the very film of inflexible and hard after drying.Can use described structure according to operator's demand.

The colloidal state layered silicate synthesis as thixotroping Control of Rheological Property properties-correcting agent by adding 0.5-1.5wt% (

RD) can preventing to spray afterwards, film forming liquid is dripped by vertical surface.

Embodiment 3

This embodiment shows that the coating solvability depends on crosslinker concentration.

Can regulate formulation makes can remove film easily in very wide water temperature range.Can research and develop the film formulation makes film to dissolve under cold or hot water temperature.For example, can use mop easily machinery wipe the film that forms by formulation #2 and #10, and it can dissolve after 20 ℃ or 98 ℃ of water rinses easily.The film that is formed by formulation #14a easily machinery is wiped, and is dissolved in easily in 98 ℃ of water, but can not be dissolved in easily in 20 ℃ of water.For obtaining cold water stability, linking agent must be joined in the mixture.Concentration is that 0.1 to 1wt% chlorination Fe (II) and chlorination Fe (III) of liquid formulations is suitable crosslinking agent.

Embodiment 4

With two plastic coverslip

The #174942 type, 22mm * 60mm; NalgeNunc International, Rochester, NY, USA) immersion contains in the 4wt%PVOH solution of 1.0g/L benzalkonium chloride sterilant.Two other cover glass immersed in the 4wt% PVOH solution that does not have benzalkonium chloride in contrast.Cover glass is placed in the 50mL centrifuge tube and it is dried spend the night.

By breeding single cell group among the 25mL BHI (37g/L) in 125mL volume vibrator flask, and in the 150RPM shake 30 ℃ of overnight incubation, and preparation Wei Shi Listera (Listeria welshimeri) (ATCC 35897) bacterial classification.The cell concn of this bacterial classification that spends the night is every mL about 1 * 10 ⁹Individual cell.Welshimer medium (referring to the media compositions of table 2) with modification dilutes 100 times of this bacterial classifications, provides about 1 * 10 ⁷The cell concn of cell/mL.Test piece is placed in the 50mL centrifuge tube and with cell suspending liquid (10mL) joins in this pipe.Because the cell concn height, cell suspending liquid is opaque fully in the 50mL pipe.Cover this pipe loosely and cultivation under 22 ℃ in the 150RPM shake with lid.

After 24 hours, have the liquid that contains sterilant QAC test piece and become human eye transparently fully, represent considerable cytolysis.On the contrary, the liquid with the test piece that lacks QAC is still opaque fully, and expression is without any significant cytolysis.

Table 2: the formulation that uses the Welshimer growth medium of modification

Embodiment 5

By dip-coating and dry, with stainless steel test piece of formulation #22 coating (specification 22mm * 60mm * 1mm).Second test piece keeps uncoated thing in contrast.The 50mL centrifuge tube is put in two test pieces.

By as mentioned above, in 25mL BHI, breed single cell group, the bacterial classification of preparation Wei Shi Listera (L.welshimeri) (strain is DUP-1074).The cell concn of this bacterial classification that spends the night is every mL about 1 * 10 ⁹Individual cell.Welshimer medium bacterial classification * 10,000 with modification provide about 1 * 10 ⁵The cell concn of individual cell/mL.This cell suspending liquid (25mL) is joined each test piece in the 50mL centrifuge tube, and each pipe flatly put into thermostat container-vibrator and with the 150RPM shake time at 25 ℃ of shakes.

Take out sample (500 μ L) from each pipe after 10 and 240 minutes.Each sample is carried out serial dilution, and with 100 each dilution of μ L be placed on standard LB agar plate (Teknova, Inc., Hollister, CA USA) goes up and 33 ℃ of cultivations.Count the CFU number after 24 hours.Do not observe significant cell in the sample that extracts after 10 minutes and reduce (comparing contrast).But viable cell concentrations is from 4.7 * 10 after 240 minutes ⁴Individual cell/mL is reduced to only 30 cell/mL, shows that cells survival significantly reduces 3.2log.

Embodiment 6

Experimentize and observe surface with the antimicrobial membranes paint spay-coating and whether can delay microbial film and begin formation.Spray stainless steel test piece (SS316,22mm * 60mm * 1mm), perhaps do not process in the vertical position with formulation #14a, #16 and #17.The test piece of handling is dried in the vertical position spends the night.

(ATCC 700830, Manassas, VA, bacterial classification USA) to prepare Pseudomonas fluorescens (Pseudomonasfluorescens) by the single bacterium colony that breeding is spent the night in 30 ℃ of following 25mL standard M9 substratum (referring to table 3) in 150 RPM shakes.Solution (with 9 parts of 1.0 parts of LB of deionized water dilution and the strainer sterilization) bacterial classification that will spend the night with dilution LB substratum dilutes 100 times then.Dilution bacterial classification in the LB substratum (10mL) is joined in each centrifuge tube.With lid cover this pipe loosely and in the 150RPM shake 30 ℃ of cultivations.Replace this substratum with the LB substratum of the new dilution of 10mL every day.

Table 4 is listed with Pseudomonas fluorescens (P.fluorescens) (～1 * 10 ⁶Individual cell/selected antimicrobial PVOH the film of mL) attacking and the every day of microbial film control performance substratum change.Adopt all formulations all to delay biomembranous growth.For formulation #14a, do not observe microbial film after 2 days.

Table 3: the M9 growth medium of use

Table 4: the microbial film control performance of using the selected antimicrobial PVOH film of Pseudomonas fluorescens (P.fluorescens) ATCC 700830 attacks

Embodiment 7

By the release of release experiment explanation QAC by the PVOH film of spraying.Film is sprayed in the stainless steel test piece, and dry air immerses in the deionized water, and extracts sample in time and measure the QAC that discharges.The concentration of the QAC that discharges is by document (R.C.Meyer, J.Pharm.Sci.1980,69, the HPLC method mensuration of 1148-1150) transforming.

Fig. 3 shows the QAC weight fraction in time that is discharged by the film with formulation #19, #20 and #21 spraying.These three kinds of formulations are difference aspect the cross-linked dosage in joining formulation only.The thickness of the film of spraying is about 7.0 μ m, is measured by micrometer gauge.Calculate the total QAC of available in the film by concentration in the liquid formulations and membrane volume.Semilogarithmic plot shows the QAC mark that discharged until 7 days in time.Can observe very fast initial Q AC for three kinds of all film types discharges.In formulation, add molysite and improved the QAC amount that discharges by film.The cross-linked dosage of regulating in the liquid formulations provides the sustained release curve time dependent method, allows control and continues to discharge biocide.

Embodiment 8

The aqueous solution (25wt%) of benzalkonium chloride (QAC) is joined polyvinylpyrrolidone (the PVP K-120 in the water; International Specialty Products, Wayne, NJ is in 10wt% aqueous solution USA).The ultimate density of PVP is 5wt%, and the ultimate density of benzalkonium chloride is 1wt%.This PVP film-forming soln is used for handling test piece and is used to prevent that microbial film from forming.

Bacterial classification to the density of spending the night of the single breeding colony Wei Shi Listera (L.welshimeri) in the 25mL TSB/YE substratum (the tryptic soy substratum adds the 0.6wt% yeast extract) from vibrator flask (at the 150RPM shake, 30 ℃) is every mL 1 * 10 ⁹Individual cell.Aseptic centrifuge tube is uncovered in biohood, and centrifuge tube is put in each the PVC test piece that thoroughly sprays with 70wt% ethanol.Lid is taken off from pipe, test piece is dried.Form experiment for microbial film, the bacterial classification that spends the night of 1:100 dilution Wei Shi Listera (L.welshimeri) in the Welshimer of modification substratum (for example:, require the 2mL bacterial classification that spends the night to add the Welshimer substratum of 200mL modification) for 20 pipe/test pieces.This solution of portion (10mL) is joined in each centrifuge tube.Cover this pipe loosely and cultivation under 22 ℃ on vibrator in the 150RPM shake with lid.Every other day replace this substratum with new modification Welshimer substratum.

For the experiment of summing up in the table 5, at PVC (polyvinyl chloride) test piece (22mm * 60mm; The lid of flexible sheet PVC test piece, Becton Dickenson) go up and breed Wei Shi Listera (L.welshimeri) preset time (referring to table 5) formation microbial film.When microbial film forms,, handle this test piece with the PVP film-forming soln by the PVP film-forming soln of coating 100 μ L on each face of test piece.Make the PVP film remain on the predetermined process time in the test piece.At the treatment time end, remove the loose cell that adheres to each test piece of aseptic PBS rinsing leniently, and the biomembranous cell survival rate of mensuration as described below.Each processing is carried out in duplicate.

For measuring cell survival rate, by removing microbial film from this test piece with sterile object (for example plastics, metal or timber) scraping test piece.The two sides of scraping test piece and with film resuspending in the PBS of 10mL buffer reagent.Mix this suspension with the homogenizing cell suspending liquid by eddy current.The serial dilution (1:10 in the PBS buffer reagent) of preparation cell suspending liquid, and 100 μ L aliquots containigs are coated on the culture dish flat board that contains LB or modification Oxford agar.Should flat board 30-37 ℃ of overnight incubation, and at subsequently several days counting bacterium colonies.

Table 5: use the fungicidal activity of the test piece of PVP and QAC processing to Wei Shi Listera (Listeriawelshimeri).

Embodiment 9

The film-forming soln of preparation PVP K-120 and benzalkonium chloride makes that the ultimate density of PVP is 5wt%, and the ultimate density of benzalkonium chloride is 0.01wt%.This solution is used for handling the microbial film test piece, as described in example 8 above.

Wei Shi Listera (L.welshimeri) microbial film was bred 2 days in the PVC test piece, as described in embodiment 8, handle this microbial film test piece afterwards with the PVP film-forming soln.PVP film-forming soln and microbial film were kept in touch three hours.At the treatment time end, measure biomembranous cell survival rate as described in example 8 above.Each processing is carried out in duplicate.PVP film with 0.01wt% benzalkonium chloride produces 7.7log aspect CFU/mL reduces.

Embodiment 10

With polyvinyl alcohol (PVOH) (MW 100,000,〉99% hydrolysis, Sigma Aldrich) water-soluble.Dichloroisocyanuric acid sodium is joined the final film-forming composition that obtains the DI water of 0.1wt% dichloroisocyanuric acid sodium, 5wt% PVOH and surplus to 100% in this PVOH solution.The PVC test piece of using the said composition coating to cover by 2 Tian Weishi Listeras (Listeria welshimeri) microbial film (preparation as described in example 8 above).Measure cell survival rate after three hour duration of contact as described in example 8 above.PVOH with the dichloroisocyanuric acid sodium coating is producing the 7.3log minimizing aspect the CFU of every mL.

Embodiment 11

Synthesis of polyurethane dispersion described in 212 to 217 sections of US2005/0215663 (also referring to 154 to 187 sections abbreviation).This preparation produces the 30wt% polyurethane aqueous dispersion body.

With ethanol polyurethane dispersions is diluted to 10wt%.By preparation polyurethane film-forming composition in the polyurethane dispersions that the benzalkonium chloride aqueous solution is joined this dilution.Final film-forming composition is 5wt% urethane, 0.5wt% benzalkonium chloride, 25wt% ethanol and the surplus DI water to 100wt%.As described in example 8 above coating is applied over PVC test piece surface, and with this test piece dry air and being placed in the aseptic centrifuge tube.

By single breeding colony Pseudomonas aeruginosa (Pseudomonas aerugmosa) bacterial classification (ATCC27853) to the density in the 25mLM9 substratum in the vibrator flask (30 ℃, simultaneously at the 150RPM shake) is every mL1 * 10 ⁹Individual cell.

1:100 dilutes this bacterial classification (for example: for 20 pipe/test pieces, require the 2mL bacterial classification that spends the night to add the LB substratum of 200mL 1/10th concentration) in 0.1 * LB substratum then.This solution of portion (10mL) is joined partially submerged test piece in each centrifuge tube.Cover this pipe loosely and in the 150RPM shake, descend cultivation 24 hours with lid at 30 ℃.

At the treatment time end, remove the loose cell that adheres to each test piece of aseptic PBS rinsing leniently, and measure biomembranous cell survival rate.Each processing is carried out in duplicate.

Measure cell survival rate as described in example 8 above, except in the culture dish flat board, using pseudomonas F (Pseudomonas F) agar.The 8log that observes in this processing aspect the CFU/mL reduces; In the test piece of handling, do not observe the visible microbial film in addition and form, and uncoated test piece has the formation of visible microbial film.

Embodiment 12

With two pipes (PVC-1120, J-M Manufacturing, Livingston, NJ USA) vertically cuts open and obtains pipe half.The use standard

(MN USA) should manage and tied together with belt once more the pipeline band from the outside for 3M, St.Paul.The pipe geometry provides in table 6.Use Wagner fog system (Wagner power varnishing machine, 0500179 type, Wagner Spray TechCorp., Plymouth, MN, USA), by system's nozzle being arranged in coaxially the Guan Yiduan of horizontal alignment and spraying 10 seconds, #91 is coated with stringing with formulation.

Formulation #91 has following composition:

Level 71-30 (5.0wt%); Benzalkonium chloride (0.63wt%);

(0.15wt%);

(0.1wt%); Erythrosin B (0.05wt%) and surplus are to the DI water of 100wt%.

The fraction of coverage of visual observation coating can realize when coating is colored and has high-contrast for the white background of pipe easily.Realize the first half of pipe and the covering fully of Lower Half, until the certain thickness described in the table 6.As shown in form, in addition the small gap between two semicanals that wherein cover fully with coating also in pipeline up to certain thickness.This embodiment illustrates that the present invention also can be used for the surface that coated portion is airtight, spill or be difficult to arrive, for example pipeline and water shoot.

Table 6: the perviousness of pipe performance and coating formulation

Embodiment 13

How present embodiment explanation rheology modifier provides the antimicrobial coating compositions removed with shear thinning behavior.This behavior easily (good sprayability), efficiently (do not drip) and effectively (uniformly antimicrobial acivity) composition is applied over the surface.This embodiment also illustrates after adding rheology modifier can keep antimicrobial efficacy fully.

The composition that uses in the present embodiment is based on the selection of (5wt%) solution of the PVOH in the water and additive.For specific formulation, order of addition(of ingredients) is different with compound method (mixing, scale etc.).

At this, we report 5 to 190s ^-1Viscosity under the shearing rate is unit with centipoise (cP).High viscosity is represented because the waste of drippage is less.The ratio of two viscosity is measuring of shear thinning effect.Mean shear thinning preferably and good sprayability than ratio.

By means of the test of described diffusion zone (ZOD) early of using streptococcus aureus (Staphylococcus aureus) ATCC 6358, formulation itself is used for estimating the antimicrobial acivity of the composition that contains rheology modifier.The rheology modifier that it is found that test is a neutral, perhaps promotes the antimicrobial acivity of coating energetically.

By with benzalkonium chloride (0.6wt%), L-77 (0.15wt%),

425 (0.1wt%) and Erythrosin B (0.05wt%) join PVOH (5wt%, 71-30) obtain composition among this embodiment at surplus to the solution in the DI water of 100wt%.In second preparation steps, add rheology modifier (referring to table 7).

Table 7: contain the rheological of rheology modifier in the composition of the 5wt%PVOH in the DI water and according to the antimicrobial acivity of the ZOD method of using streptococcus aureus (Staphylococcus aureus) ATCC 6358

The area of+expression diffusion zone (ZOD) is equal to or greater than the area of the coating test piece of using in the experiment.ND represents " undetermined ".NA represents " inapplicable ".

Embodiment 14

This embodiment illustrates that rheological agent can be used for providing the shear thinning performance for the coating formulation based on the polyvinyl alcohol of different degree of hydrolysis grades.This embodiment also illustrates the degree that can join the horizontal adjustment shear thinning (viscosity ratio) of the rheology modifier in the formulation by change.The rheological agent that uses among this embodiment is L251.

By water is added the flask that has magnetic stirring bar, add subsequently

L-77 (0.1wt%), benzalkonium chloride (0.05wt%), PEG (M～300) (0.2wt%),

L251 (each level in the table 8), PVOH (5wt% in the water,

71-30), prepare the composition (summation of all the components is 100wt%) among this embodiment with Indigo Carmine A red (0.03wt%).

Table 8: contain 5wt%PVOH

Waterborne compositions in the rheological property of rheology modifier

NA represents " inapplicable ".

Embodiment 15

This embodiment illustrates that use coating formulation according to the present invention prevents that fungi from breeding from the teeth outwards.

Store dull and stereotyped (malt extract agar) 2 weeks by cultivating at 25 ℃, and by (0.85% NaCl adds 0.05% with 15mL filter sterilised salts solution X-100) wash this flat board and gather spore, preparation fungal spore (aspergillus niger and Penicilllum expansum).Use the scraping of aseptic plastic cell scraper should flat board then, liquid is sopped up, rotates and filter via the aseptic cheese cloth of 3-4 layer.With aseptic transfer pipet tip 400 microlitre coating formulations are coated in 1 inch * 1 inch stainless steel test piece.The coating formulation #109 of this embodiment is by 5wt% 71-30,0.2wt%PEG (M～300), 0.2wt% benzalkonium chloride, 0.1wt%

L-77,0.05wt%

425,0.01wt% Erythrosin B and surplus to the DI water of 100wt% is formed.The coating formulation #115 that is used for negative control experiment is identical with formulation #109, except not adding benzalkonium chloride.

Complete covering surfaces and make coating complete drying (3-4 hour or spend the night) in vertical mobile biohood.The 10mL aliquots containig of centrifugal treating spore suspension, and abandon supernatant liquor.Spore is resuspended in the Czapek Dox substratum of equal volume.This bacterial classification of 100 microlitres is joined in each test piece and dry 5 minutes.Test piece is placed on the water agar plate, make coating towards last, and in the water-filled moisture eliminator in bottom, at room temperature cultivate 2-4 week, observe fungal growth every day.

Table 9 explanation does not observe fungal growth to coating formulation #109, and uncoated test piece or with the test piece demonstration fungi hypertrophy of the coating formulation coating that does not have the QAC activeconstituents.

Table 9: the antifungal activity of antimicrobial coating #109 and control experiment

-expression does not observe fungal growth.+++expression fungi hypertrophy.

Embodiment 16

This embodiment illustrates that use allows antimicrobial efficacy to prolong in time according to coating formulation of the present invention.This embodiment proves also with microorganism and repeatedly inoculates after the antimicrobial coatings that antimicrobial efficacy still continues.This embodiment also proves the remaining antimicrobial efficacy of the coating that is formed by formulation.This embodiment illustrates that also antimicrobial coating is effective at Gram-positive (streptococcus aureus (Staphylococcus aureus)) and Klebsiella pneumoniae (Klebsiella pneumomae) organism.

For testing the influence of repeatedly bacterial contamination combating microorganisms coating effect, use following method.The microorganism of test comprises streptococcus aureus (Staphylococcus aureus) ATCC 6358 and Klebsiella pneumoniae (Klebsiella pneumomae) ATCC 4352.By from the flat board that keeps in cold storage, extracting a single bacterium colony, circulation and inoculation 25mL tryptic soy substratum in 250mL aseptic plastic Erlenmeyer flask, the bacterial classification that spends the night of the selected microorganism of preparation.Follow the 150RPM shake, with this flask 30 ℃ of overnight incubation.With aseptic transfer pipet tip the 0.4mL coating formulation is coated in 1 inch * 1 inch stainless steel (SS316) test piece then.Cover whole surface and make coating complete drying (3-4 hour or spend the night) in vertical mobile biohood.Except that containing antimicrobial formulation, also be coated with test piece thing in contrast with the formulation that does not have biocide.Dilute the bacterial classification that spends the night with phosphoric acid salt diluent buffer reagent 1:10 then.Can join in the bacterial classification 5% aseptic foetal calf serum as the other attack to coating this moment.By with the transfer pipet tip at least 20 position drops and wait for 5 minutes, use the such 1:10 diluent of 10 microlitres to pollute the test piece surface at every turn.Then, two test pieces of each coating formulation and two contrast test pieces are placed on contain among the 20mL Letheen and the aseptic plastic 50mL centrifuge tube of substratum in.To manage sonic treatment 10 seconds and shake 10 minutes (25 ℃, 200RPM).These samples of serial dilution and being placed on are used for colony-forming unit (CFU) and measure on the LB agar plate then.Should flat board 35 ℃ of overnight incubation, and at subsequently sky counting bacterium colony.All the other test pieces are at room temperature cultivated in the water-filled moisture eliminator in bottom.After one hour, use the bacterial classification of as above 10 microlitres dilution all to inoculate all the other test pieces.After 5 minutes, shift out two test pieces of each formulation and as above processing.Cultivate test piece first and repeated afterwards this step in 2 and 3 hours afterwards.

The coating formulation #119 that uses among this embodiment is by 5wt%

71-30,0.2wt%PEG (Mw～300), 0.05wt% benzalkonium chloride, 0.1wt%

L-77,0.01wt% Indigo Carmine A red and surplus to the DI water of 100wt% is formed.Table 10 and 11 shows for the test piece with formulation #119 coating, is not recovered to the viable cell of two kinds of organisms of use, and is recovered to above 10 from the test piece with the identical formulation coating that does not have QAC ⁶Individual cell.

Table 10: repeatedly cultivate influence to coating formulation #119 effect with streptococcus aureus (Staphylococcus aureus) (ATCC 6358)

Table 11: repeatedly cultivate influence to coating formulation #119 effect with Klebsiella pneumoniae (Klebsiella pneumomae) (ATCC 4352)

Embodiment 17

This embodiment illustrates and uses tensio-active agent to realize that formulation launches to become film after being applied over the surface.

In this embodiment, organo-siloxane

L-77) as tensio-active agent.The formulation of this embodiment is by the 5wt% polyvinyl alcohol

52-22), 0.2wt% PEG (MW～300), 0.05wt% benzalkonium chloride, 0 to 1wt% different concns

L-77 (referring to table 12) and surplus to the DI water of l00wt% is formed.

At 26.3 ℃, use the 40.2mm wet length, with Kruess K11 tonometer (KruessGmbH, Hamburg, Germany) surface tension of mensuration sample.

100 μ L drops of each sample are drawn on the cleaning test surfaces of stainless steel (SS316) and ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE).SS316 and UHMWPE are the key structure materials of industrial equipments that for example is used for the device of food-processing.Drop is applied to after the surface, makes drop diffusion 5 minutes.The test surfaces numeral is taken pictures, and (National Institute of Health USA) measures the covering diffusion area of drop on test surfaces for ImageJ software, 1.36b version by image analysis.The diffusion area of drop is measured as the diffusion effect of each formulation.The two kinds of surfacings of table 12 report test and the result of formulation.

Causing surface tension by the organo-siloxane tensio-active agent that adds 0.001wt% is 35.9mN/m, and the diffusion of having observed on SS316 improves.When comparing, increase by 16% for the SS316 diffusion area with the formulation that does not add tensio-active agent.

When using that the organo-siloxane concentration of 0.3wt% makes surface tension be reduced to 22.5mN/m at least or when lower, observing diffusion area increases more significantly.When comparing, under these conditions, increase above 160%, and increase above 220% for the UHMWPE diffusion area for the SS316 diffusion area with the formulation that does not add tensio-active agent.

Table 12: in the antimicrobial coating formulation, add

The L-77 tensio-active agent is to the influence in SS316 and lip-deep surface tension of UHMWPE and diffusibility

Embodiment 18

This embodiment explanation uses small bubbles as interim opacifying agent in antimicrobial coatings.Be used for intended purpose more of the present invention, always do not wish that coating has permanent color.For example, for the coating of wall, coloured or opaque coating may be considered to inaesthetic, and as an alternative, transparent antimicrobial coatings may be preferred.Omit permanent tinting material or opacifying agent and have such shortcoming: the operator who applies coating can not obtain the feedback what part on the surface that will be coated with has been capped.For overcoming this problem, can use following embodiment of the present invention.Can add at least a pore forming material to form small bubbles in the film that on target surface, forms.Bubble plays opacifying agent and makes the film that newly applies become white.For preventing that bubble incorporation from advancing in the dry film, also at least a antifoams is joined in the formulation.Antifoams helps bubble to decompose, and film is still moist, to produce Clear coating after drying.

The formulation #134 that uses among this embodiment is by 7wt%

52-22,0.2wt%PEG (Mw～300), 0.05wt% benzalkonium chloride, 0.2wt%

L-77 and surplus to the DI water of 100wt% is formed.The formulation #134a that uses among this embodiment is identical with formulation #134, except it contains the activeconstituents of 120ppm antifoams C in formulation.

The tensio-active agent benzalkonium chloride and

The foaming of the above-mentioned formulation that L-77 causes and bubble (every square metre〉1,000,000) using heavy body/low pressure (HVLP) spray gun (Devilbiss GTI spray gun; Air cap #2000; 1.5mm fluid tip; E.I.DuPont Company spray booth, Room 112,377Fairall Street, Ajax, ON, Canada) spraying in the film that directly obtains after the formulation from the teeth outwards is visible.The spraying condition is as follows: 2-3 time coating applies, and amounts to the 5-20 micron membranes, and 5 ℃-25 ℃, 30-60% relative humidity.Use 4 inches * 4 inches visual counting bubbles of square, and report with the form of every square metre of number of bubbles.Bubble makes film produce white appearance after the spraying.Numerous air-bubble disappears along with the film drying.For the formulation #134 that does not have antifoams C, the rest is about 15,000 bubbles/square metre.But, only obtain every square metre of 100-500 minimum bubble (referring to table 14) after the film drying for formulation #134a.

Table 14: separately bubble in film after the firm spraying and the dry coating

Embodiment 19

This embodiment illustrates film thickness combating microorganisms Effect on Performance.Use streptococcus aureus (Staphylococcus aureus) ATCC 6358 to measure antimicrobial efficacy by diffusion zone (ZOD) method.The composition of coating formulation #134 as described in example 18 above.Cause diffusion zone bigger than thick film, and therefore improve the biocidal properties of coating.

Table 14: as the antimicrobial efficacy of the function of the coat-thickness of formulation #134.Use streptococcus aureus (Staphylococcus aureus) ATCC 6358 to measure antimicrobial efficacy by the diffusion zone method.

Claims (39)

1. the method for microbiological manipulation is provided in the playground, comprises

A) provide removable liquid coating composition, it comprises:

I) the water-soluble or water-dispersible agents of film forming;

Ii) at least a biocide; With

Iii) inert solvent;

B) described composition is applied over the playground, forms coating thus; With

C) about 15 ℃ to about 100 ℃ of described coatings of following water solution removal.

2. the process of claim 1 wherein that the surface tension of liquid coating composition is lower than 40mN/m.

3. the process of claim 1 wherein that described composition is applied to the playground by spraying or atomizing.

4. according to the process of claim 1 wherein that described membrane-forming agent is one or more polyvinyl alcohol and multipolymer, polyvinylpyrrolidone, polyacrylic acid, acrylate copolymer, ion hydrocarbon polymer and urethane or its combination.

5. according to the method for claim 4, wherein said polymkeric substance is polyvinyl alcohol and multipolymer thereof.

6. the method for claim 1, wherein said playground is the surface of following one or more: container, travelling belt, the floor, water shoot, water cooler, refrigerator, refrigerator, equipment surface, wall, valve, belt, pipeline, joint, the crack, building surface, the surface, kitchen, the inanimate surfaces that exists in the food processing plant, animal doctor or animal care facility, animal care equipment, or livestock industry or hatcher facility, hospital or Surgicenter wall, bed, the surface of equipment, the fabric that weares and teares in hospital or other healthcare environment, comprise rag, footwear, and other hospital surface.

7. the method for claim 6, wherein said surface comprises one or more metals that are selected from aluminium, steel, stainless steel, chromium, titanium, iron, alloy and composition thereof.

8. the method for claim 6, wherein said surface comprises one or more plastic materials, be selected from polyolefine, comprise polyethylene, polypropylene, polystyrene, polymethacrylate, polymethylmethacrylate, vinyl cyanide, divinyl, ABS, acrylonitrile butadiene; Polyester comprises polyethylene terephthalate; And polymeric amide, comprise nylon; With its combination.

9. the method for claim 6, wherein said surface are brick, ceramic tile, pottery, porcelain, timber, ethenoid resin, malthoid, carpet, paper, leather, its combination etc.

10. the process of claim 1 wherein that described playground is an inanimate surfaces, comprise surface metal, mineral, polymkeric substance, plastics, fiber base material or non-woven fabric or its mixture or coating or paint.

11. the process of claim 1 wherein that the described aqueous solution is basically by water; Water and acid; Or water and alkali; Or water and washing composition composition.

12. the method for claim 5, wherein said polyvinyl alcohol have the average hydrolysis degree of 70-96mol%.

13. the method for claim 5, wherein said polyvinyl alcohol have the average hydrolysis degree of 85-90mol%.

14. according to the method for claim 4, it is about 4 that wherein said membrane-forming agent has, 000-186,000 molecular weight.

15. the process of claim 1 wherein that described inert solvent is a water.

16. the process of claim 1 wherein that described liquid coating composition further comprises one or more softening agent, tensio-active agent, linking agent, tinting material, solubilizing agent, rheology modifier, oxidation inhibitor, pH regulator agent, wetting agent, antifoams, extender, lubricant, processing aid, laking agent and film properties toughener or one or more enzymes.

17. the method for claim 6, wherein said playground are the food processing apparatus surface.

18. the method for claim 17, wherein said food-processing surface are following one or more surface: container, travelling belt, floor, water shoot, water cooler, refrigerator, apparatus surface, wall, valve, belt, pipeline, joint, crack or its combination.

19. the process of claim 1 wherein that described playground is a food surfaces, comprises one or more of beef, poultry, pork, vegetables, fruit and seafood.

20. the process of claim 1 wherein that described coating is the blocking layer to microbial contamination.

21. the process of claim 1 wherein that described at least a biocide is one or more antiseptic-germicides, fungus killing agent, mycostatic agent, fungicide, mould inhibitor, sanitas, Disinfectant, sterilizing agent, sterilant, algicide or stain control agent.

22. the process of claim 1 wherein that described biocide is one or more quaternary ammonium compounds or its mixture.

23. the process of claim 1 wherein that described removal is by spraying or washing described playground and carry out.

24. the process of claim 1 wherein that when being applied over contaminated surface coating provides the microorganism minimizing of 3-log at least.

25. the method for claim 24, wherein when being applied over contaminated surface, coating provides the microorganism minimizing of 5-log at least.

26. the process of claim 1 wherein that coating prevents that the microorganism of at least a type from growing in described playground.

27. the process of claim 1 wherein that the control in described playground comprises the microorganism of concealing in the minimizing microbial film.

28. the process of claim 1 wherein that described coating is basic successive and homogeneous.

29. the method for claim 28, wherein said coating have about 0.3 to about 300 microns thickness.

30. the method for claim 29, wherein said coating have about 0.5 to about 100 microns thickness.

31. removable food-processing shut-down spray composition comprises:

I) the water-soluble or water-dispersible agents of film forming;

Ii) at least a or multiple biocide;

Iii) inert solvent; With

Iv) Ren Xuan one or more softening agent, tensio-active agent, linking agent, tinting material, solubilizing agent, rheology modifier, oxidation inhibitor, pH regulator agent, wetting agent, antifoams, extender, lubricant, processing aid, laking agent and film properties toughener or enzyme;

Wherein when standing to surpass 15 ℃ aqueous solution processing, described composition is persistent and removable.

32. comprising, the composition of claim 31, wherein said composition provide about 20 to about 50mN/m capillary tensio-active agents.

33. the composition of claim 32, wherein said tensio-active agent are organo-siloxane.

34. the composition of claim 32, wherein said surfactant concentrations are that about 0.01wt% of composition is to about 1.0wt%.

35. the composition of claim 31, wherein said composition comprise the Control of Rheological Property agent that the shear thinning performance is provided to composition.

36. the composition of claim 31, wherein when being applied over the food-processing surface of pollution, described composition provides the microorganism minimizing of 3-log at least.

37. the composition of claim 31, wherein when being applied over contaminated surface, described composition is Disinfectant, sterilizing agent, sanitas or the physical barriers layer to polluting, and wherein when being applied over the contaminated surface that stands follow-up pollution, described composition can have remaining antimicrobial efficacy.

38. according to the composition of claim 31, wherein said membrane-forming agent is one or more polyvinyl alcohol and multipolymer thereof, comprises polyvinylpyrrolidone, polyacrylic acid, acrylate copolymer, ion hydrocarbon polymer and urethane or its combination.

39. the method for claim 31, wherein said at least a biocide are antiseptic-germicide, fungus killing agent, mycostatic agent, fungicide, mould inhibitor, sanitas, Disinfectant, sterilizing agent, sterilant, algicide or stain control agent.

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