WO2011005270A1 - Composition de peracide/peroxyde, procédé pour la fabriquer avec précision, et procédé pour une utilisation en tant que solution antimicrobienne de film d'évaporation et en tant que photosensibilisateur - Google Patents

Composition de peracide/peroxyde, procédé pour la fabriquer avec précision, et procédé pour une utilisation en tant que solution antimicrobienne de film d'évaporation et en tant que photosensibilisateur Download PDF

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WO2011005270A1
WO2011005270A1 PCT/US2009/057695 US2009057695W WO2011005270A1 WO 2011005270 A1 WO2011005270 A1 WO 2011005270A1 US 2009057695 W US2009057695 W US 2009057695W WO 2011005270 A1 WO2011005270 A1 WO 2011005270A1
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concentration
composition
hydrogen peroxide
microbicidal
microbicidal composition
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PCT/US2009/057695
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English (en)
Inventor
Jeffry Golden
Paul Brister
Joan Stader
Charles Martin
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Jeffry Golden
Paul Brister
Joan Stader
Charles Martin
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Application filed by Jeffry Golden, Paul Brister, Joan Stader, Charles Martin filed Critical Jeffry Golden
Priority to US13/383,067 priority Critical patent/US20130251590A1/en
Priority to AU2009349654A priority patent/AU2009349654A1/en
Priority to CA2767493A priority patent/CA2767493A1/fr
Priority to EP09847184A priority patent/EP2451483A1/fr
Publication of WO2011005270A1 publication Critical patent/WO2011005270A1/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
    • A61L2/18—Liquid substances or solutions comprising solids or dissolved gases
    • A61L2/186—Peroxide solutions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/02—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using physical phenomena
    • A61L2/08—Radiation
    • A61L2/10—Ultraviolet radiation
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
    • A61L2/22—Phase substances, e.g. smokes, aerosols or sprayed or atomised substances
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00—Disinfection, sterilisation or deodorisation of air
    • A61L9/14—Disinfection, sterilisation or deodorisation of air using sprayed or atomised substances including air-liquid contact processes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2209/00—Aspects relating to disinfection, sterilisation or deodorisation of air
    • A61L2209/20—Method-related aspects
    • A61L2209/21—Use of chemical compounds for treating air or the like
    • A61L2209/211—Use of hydrogen peroxide, liquid and vaporous
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00—Disinfection, sterilisation or deodorisation of air
    • A61L9/16—Disinfection, sterilisation or deodorisation of air using physical phenomena
    • A61L9/18—Radiation
    • A61L9/20—Ultraviolet radiation
    • A61L9/205—Ultraviolet radiation using a photocatalyst or photosensitiser

Definitions

  • the invention relates to a method for microbicidal treatment such as saniti/ation, disinfection, sterilization, and decontamination of a surface by use of such compositions as an anti-microbial thin film and also as a photosensitizer for light-activated killing. Further, the invention relates to a process for accurately making storage-stable embodiments of the anti-microbial compositions. This invention still further relates to aqueous anti-microbial compositions, made by the provided process, the compositions comprising peracetic acid, hydrogen peroxide, acetic acid, phosphate ester surfactant, water-soluble polymer containing lactam, and optionally, small amounts of minors and liltle or no additional stabilizer.
  • compositions comprising aqueous solutions of peracetic acid (peracetic acid) and hydrogen peroxide (HP) as microbicidal active ingredients are well known to have excellent microbicidal efficacy.
  • peracetic acid peracetic acid
  • HP hydrogen peroxide
  • Such compositions can be highly effective sporicidcs, disinfectants, bactericides, virucides, fungicides, tuberculocidcs, sanitizers, decontaminants, and mold killers.
  • Such compositions are applied onto surfaces as a wiped, sprayed, or brushed on liquid, as a sprayed, drifted, or electrostatically attracted aerosol, or by immersion such as dipping.
  • a surfeit of anti-microbial is applied to the surface to thoroughly wet the surface and maintain a wet surface for at least a required period of time, the contact time, to obtain a desired fractional reduction in the targeted microbial population.
  • the desired fractional reduction is commonly expressed as minus the logarithm of the ratio of the surviving microbial population and the initial microbial population and is referred to as the "logs of killing".
  • Regulatory approval of a product as a sanitizer, disinfectant, sterilant, or decontaminant and approval of efficacy claims made on the label for such a product generally involve the validated achievement of a required number of logs of killing within the contact time stated in the label claim for a specific organism or type of organism.
  • a commonly used approach to shorten the contact time is to use an antimicrobial composition with greater concentration of active ingredients so that the product of concentration (C) and contact time (T c ), the so-called >! CT C " product, is adequate to achieve the required logs of killing with a desired T 0 .
  • C concentration
  • T c contact time
  • use of compositions with greater concentration of active ingredients has the disadvantages of greater cost, greater corrosivity, greater release of volatile organic compounds, potential hazards, and/or toxicity, constraints on shipping, storage, and disposal, and additional hazard warnings and requirements for use of personal protection equipment.
  • compositions of Martin et al arc used typically with an application rate of about 40 to 150 ml/nr (that corresponds to u layer thickness of about 40 to 150 ⁇ m) for non-porous surfaces and up to about 300 ml W for porous surfaces such as textiles and carpets.
  • SST Surface Sterilization Test
  • a necessary condition for good microbicidal efficacy in an uncon fined space is that the inoculated surface is completely wet so that the microbicidal composition contacts the target microbes.
  • a surfeit of microbicidal composition is applied by common practice because application of a thinner film is likely to lead to film defects of imperfect wetting or dry spots resulting from surface tension effects or patches that day more quickly and so, the required CT 0 is not obtained in such places.
  • the method for microbicidal treatment of a surface of the instant invention applies to the case where the surface is in a space, either confined or not confined, an example of an unconfined space being the outdoors, and where the relative humidity, RH, is sufficiently less than 100% so that the applied thin layer significantly evaporates during the contact time.
  • compositions comprising peracetic acid, hydrogen peroxide, acetic acid, phosphate ester ' surfactant, and, optionally, water-soluble polymer that differed only by the choice of water-soluble polymer or the absence of water-soluble polymer, it has been shown by the instant invention that compositions comprising water-soluble polymer having a lactam, such as the compositions provided by Martin et al. result in superior microbicidal efficacy to compositions with other polymers or no polymer.
  • the combination of- phosphate ester anionic surfactant and water soluble polymer containing lactam in the microbicidal composition is found to be particularly well-suited to the method for microbicidal treatment with an evaporating film and outperforms other polymer and surfactant combinations.
  • US 6,436,445 to Hci et al teaches polymer thickeners, e.g., methyl cellulose and many related polymers, and synthetic petroleum-based water soluble polymers, which include PVP among many others.
  • US 5,294,644 to Login teaches use of lactams for complexing and for thickener for phosphate esters and for obtaining a highly polar and hydrophobic pyrrolidone moiety for anionic interactions, but not for improved microbicidal efficacy.
  • US 6,403,547 to Grippaudo et al teaches a process of cleaning carpets with a composition comprising pcroxygen bleach and an N-vinyl polymer (0.01 to 10% preferably 0.05-2%).
  • Grippaudo teaches a composition further with a surfactant, preferably an anionic surfactant (or a zwitterionic surfactant or a mixture thereof, most preferably a sarcosinate surfactant) and organic and inorganic acid, with preferred organic acids being acetic acid or citric acid or a mixture thereof and preferred inorganic acids being sulfuric acid or phosphoric acid or a mixture thereof. Particularly preferred inorganic acid is sulfuric acid. Typical levels of such acids, when present, are from 0.01 % to 1 .0% by weight, preferably 0.05% to 0.08%, and more preferably from 0.1 % to 0.5% by weight of the total composition.
  • a preferred peroxygen bleach is hydrogen peroxide.
  • Suitable preformed peroxyacids include diperoxydodecandioic (DPD ⁇ ).
  • DPD ⁇ diperoxydodecandioic
  • surfactants anionic, nonionic, zwitterionic, amphoteric, and cationic and mixtures thereof.
  • Suitable anionic surfactants include sarcosinate surfactants, alkyl sulfate surfactants, alkul sulphonate surfactants, alkyl glycerol sulfate surfactants, and alkyl glycerol sulphonate surfactants (but Grippaudo et al. does not mention alkyl ethoxylate phosphate esters).
  • US 6,462,008 B l to Ortiz teaches detergent compositions comprising photobleach delivery systems in which hydrophobic photobleaches arc combined with certain water-soluble polymers, which include copolymer of PVP and polyvinylimidazole (PVPVI), and most preferably PVP with an average molecular weight of from 20,000 to 60,000.
  • PVPVI polyvinylimidazole
  • US 6,472,360 to Beggs et al teaches a multi-part thickenable non-spray of at least two liquid partial compositions each having a viscosity of 20 mPa-s (cP) or less, one part containing peroxygen bleach, and after mixing, f ⁇ nal composition having a viscosity of 50 mPa-s (cP) or greater.
  • Alcohol alkoxylates have ethylene oxide (EO), propylene oxide ( PO), and butylenes oxide (BO) blocks, with straight chain primary aliphatic alcohol alkoxylates being particularly useful as sheeting agents.
  • EO ethylene oxide
  • PO propylene oxide
  • BO butylenes oxide
  • Alcohol ethoxylates found to be useful are those having the general formula R— (EO)m— (PO)n, wherein m is an integer of about 2- 10 and n is an integer from about 2-20.
  • R can be any suitable radical such as a straight chain alkyl group having from about 6-20 carbon atoms.
  • antimicrobial compositions having active oxygen compounds including hydrogen peroxide, isolated peracids, such as peracelic acid inter alia, and anionic surfactants including alkyl, aryl, or alkaryl phosphate esters inter alia, and further.
  • active oxygen compounds including hydrogen peroxide, isolated peracids, such as peracelic acid inter alia, and anionic surfactants including alkyl, aryl, or alkaryl phosphate esters inter alia, and further.
  • US 6,436,445 to Hei et al teaches the use of water soluble thickener, which may include PVP, although other polymers that have non-Newtonian viscosity are preferred in contrast to PVP that has Newtonian viscosity, to give viscous solutions.
  • PVP water soluble thickener
  • alkyl phosphate ester surfactant has some antimicrobial properties, there is no motivation to combine with water soluble polymer containing lactam for the purpose of obtaining improved microbicidal efficacy in an evaporating thin film treatment. Still further, when such compositions in the prior art are used for photoactive processes, the polymer taught as a thickener is specified as one of high molecular weight, which is not desirable for the microbicidal treatment method of the instant invention, nor is it desirable for the process to make a htorage stable composition or for the resulting composition of the instant invention.
  • an improved method for the antimicrobial treatment of a surface or object.
  • the anti-microbial liquid is applied with a wipe or comparable applicator that is wet with the composition and so forms an evaporating thin layer that completely wets the surface according to the instant invention, and the wiping dislodges or removes some of the microbes from the surface, the results of the combination of removal of microbes and microbicidal action is superior efficacy with a short T 1 . and a further reduction of the microbial population on the surface.
  • a wipe that is packaged as a pre-wetted wipe is particularly attractive for its convenience and the speed that it enables with the reduced T c .
  • the anli-microbial composition in the form of a ready-to-use (“RTU") solution is especially useful and desirable.
  • RTU Ready to use
  • anti-microbial compositions are desired for several reasons. These include convenience, ease of use, safety, ship-ability, and broader market applications. Because excellent microbicidal efficacy can be obtained with concentrations of active ingredients that are relatively small, namely, hydrogen peroxide less than 8 % weight by weight (w/w) and peracetic acid less than I % vv/w, RTU compositions comprise very dilute solutions of peracetic acid. Such very dilute solutions avoid the handling of more concentrated solutions to prepare a "Use Dilution" solution, and they are easier to store and transport. The very dilute solutions further avoid the common prohibition against shipping by air a concentrate that contains more than 8% hydrogen peroxide.
  • Very dilute RTU compositions are attractive because they pose low risk, greater ease of use, can be used in non-professional settings such as home use, and can be shipped without the constraints that may be applied to more concentrated compositions such as risk mitigation measures such as extensive personal protective equipment, spill containments and counte ⁇ neasures. mixing equipment and protected and ventilated storage locations that enable the storage, handling, and mixing of more concentrated compositions.
  • microbicidal compositions There are several desirable characteristics of microbicidal compositions that depend on the concentrations of the active ingredients of the composition and on the concentrations of additional components that are necessary to obtain the desired characteristics. Of particular interest are the following characteristics:
  • rheological properties such as ability to wet a surface, especially when applied as a thin film by spraying or wiping, e.g., with a wet wipe, spray-ability, ability to penetrate porous materials, and in regard to the instant invention, the ability to consistently and completely coat a surface for CT 0 enhancement as an evaporating thin film
  • compositions with hydrogen peroxide and peracetic acid can be categorized by their concentration of peracetic acid.
  • Relatively concentrated products have peracetic acid concentration greater than about 25 %, with about 30- 35% being typical. There are less concentrated products with peracetic acid concentration of about 15%. Still less concentrated are products with peracetic acid of about 5%.
  • all of these compositions may be called dilute solutions of peracetic acid, they are corrosive and are diluted still further with water to make "Use Dilution " solutions for their use as microbi ⁇ des.
  • Peracetic acid (also known as peroxyacetic acid) in aqueous solution is necessarily found as a component with hydrogen peroxide, and acetic acid.
  • Peracetic acid can be formed by reaction of acetic acid and hydrogen peroxide, which, in a reverse reaction are the products of hydrolysis of peracetic acid.
  • Peracetic acid and hydrogen peroxide can be very reactive with trace constituents even in very dilute solutions.
  • solutions of peracetie acid, hydrogen peroxide, acetic acid, and water can be prepared that have the constituent proportions that correspond to a chemical equilibrium between the formation and hydrolysis reactions, such solutions arc generally unstable, especially in the presence of trace amounts of contaminants in the solution or because of interaction between constituents of the solution and the container for the solution.
  • Concentrated peracetic acid solutions have low pH, i.e., abundant [H 1 ]. and so, chemical equilibrium or near equilibrium can readily be obtained for compositions for which the formation rate is in balance with the rates of hydrolysis and other destruction/loss reactions.
  • a very dilute peracetic acid solution or more
  • AJso reactions involving other ingredients to the composition, which are added to achieve certain desired properties, may greatly alter the reaction rates and the rate of approach to equilibrium.
  • Such ingredients include sequcstrants, stabilizers, chelators, which are added as stabilizers to one or more of the components used to make the dilute solution, anti- corrosives, surfactants (surface active agents), or rheological modi Here such as polymer, or they may be inadvertent additives as contaminants such a.s transition metals, halides, and organics.
  • the effect of one or more of these additional components can make unstable a very dilute peracetic acid solution that is initially prepared at or near equilibrium. The consequence is poor storage stability.
  • compositions comprising concentrates wherein component losses and degradation amount to an acceptably small fraction of the active ingredients, i.e., the ingredients that are the principal active microbicidal ingredients, (2) compositions that comprise binary components wherein ingredients that might react and lead to poor storage stability are put in separate components for mixture prior to use within the pot-life of the mixture, (3) the use of stabilizers and sequestrants to sufficiently overcome the effects or prevent reactions with trace components such as mono- and divalent metal ions and organic contamination that can react with the active ingredients or components necessary for equilibrium and adversely affect storage stability, and (4) use of very clean ingredients that have sufficiently low concentration of trace metals, organic contamination, salts, etc, so that reactions that lead to degradation occur acceptably infrequently so that the desired storage li fetime is achieved.
  • Another approach for storage stability is the addition of stabilizer, e.g., sequestrant that 'captures' trace quantities of metals and metallic ions.
  • Storage stability is commonly limited because of the degradation of the active ingredients by interactions with trace quantities of mono- and divalent ions, especially those of transition metals, by interactions with trace quantities of halides and/or with trace quantities of organic contamination, and also because of interactions of one or more of the components of the aqueous solution with the container for the composition.
  • One or more stabilizer compounds are commonly added to sequester the metallic species and an anti-corrosive compound may be added to reduce the interaction of the composition with its container. ' Several examples have been given above.
  • aliphatic alcohol ethoxylate wetting agent which has an EO number of greater than 4 in an amount from 0.1 to 5 % w/w (US 5.489,706 to Revell).
  • the sequestrant may also be an anti-corrosive compound. Further, an anti-corrosive compound commonly is also desirable so that the anti-microbial composition will not damage items that it contacts for microbicidal treatment.
  • compositions as an equilibrium or near-equilibrium solution with sufficiently small concentrations of active ingredients to reduce shipping constraints and to employ a sufficient amount of stabilizer to obtain storage stability (see for example, US 5.656.302 to Cosentino).
  • concentrations and storage stability are of special importance when such very dilute solutions are incorporated in products packaged as pre-vvetted wipes, which include pre-saturated wipes.
  • the minimum requirement for storage stability is a relative change of less than 10% in the concentration of the microbicidal active ingredients in the course of a year.
  • a larger change during the approved shelf-life of the product is permitted, e.g.. a relative change in peracetic acid of up to about 30% and relative change in hydrogen peroxide of up to about 10% in a year or longer, e.g., in three years.
  • compositions in the prior art and in commercially available products have a concentration of peracetic acid that typically is greater than 1 % w/w and contain stabilizer with concentration greater than about 0.5%.
  • inorganic phosphate US 5.077,008 to Kralovic. US 5,624,634 to Brougham, US 5,767,308 to Thiele.
  • polymeric molecularly dehydrated phosphates US 2,590,856 to Greenspan
  • pyro-phosphate US 4.320, 102 to Dalton).
  • ortho-phosphate, phosphonate, phosphonic acid (US 5,130,053 to Fcascy), including organic phosphonic acids (US 4,051 ,058 and 4,051 ,059 to Bowing, US 6,028, 104 to Schmidt) or their salts, an example being I -Hydroxy Ethylidene-l , l-Diphosphonic ⁇ cid (H EDP) CAS No. 2809- 21 -4, or ethylenediami netetracetic acid (EDTA) or its sodium salt, or pyridine carboxylatc (see for example, US 5,656,302 to Cosentino. Zhao, et al., and Dul'neva ct al.).
  • a Use Dilution comprising a 5-fold to 100-fold or greater dilution will have stabilizer concentration that is less than 0. 1 %.
  • a stabilizer concentration greater than about VA % may lead to an unacceptable amount of residue, in particular when the stabilizer is a phosphate or phosphonate compound that may have adverse environmental impact.
  • the prior art does not provide very dilute RTU compositions that are storage stable for one or more years and that have low stabilizer content, i.e., less than about % % w/w.
  • compositions comprising an aqueous solution of peracctic acid and hydrogen peroxide with anionic surfactant and water soluble polymer containing PVP with a lactam ("PVP/lactam").
  • the benefits include superior efficacy by comparison with compositions not containing anionic surfactant and PVP/lactam, good material compatibility, i.e., low corrosivity, and use as sterilant, disinfectant, saniti/er. and decontaininant.
  • the composition comprises a phot ⁇ sensitizer for light-activated killing of microbes and also an effective microbicide without the light activation.
  • a 6- fold dilution made by mixing one part of the concentrate with 5 parts of water results in a Use Dilution solution with about 4.2% active ingredients that has been shown to be a superior sterilant.
  • fungicide, mold-killer, photosensiti/er disinfectant, and photosensitizer sporicidal decontaminant As a concentrate nominally comprising about 24% hydrogen peroxide and 1 .2% peracctic acid, a 6- fold dilution made by mixing one part of the concentrate with 5 parts of water results in a Use Dilution solution with about 4.2% active ingredients that has been shown to be a superior sterilant.
  • fungicide, mold-killer, photosensiti/er disinfectant, and photosensitizer sporicidal decontaminant As a concentrate nominally comprising about 24%
  • the prior art does not disclose unambiguous equilibrium constant values and does not teach ingredient proportions for the reliable and consistent preparation of storage stable, very dilute RTU compositions. ⁇ n accurate value of the equilibrium concentration quotient K 0 for very dilute compositions was not known because compositions of the prior ail contain stabilizers and acid that apparently alter the equilibrium balance between peracetic acid formation and hydrolysis, so, the compositions of the prior art appear to have different values of K c (see, for example, US 5,767,308 to Thiele, Uul'neva et al., and Zhao et al).
  • Dilute aqueous peracetic acid solutions comprise mixtures of peracetic acid (CH 3 COOOH. a.k.a. PAA), water (H 2 O), acetic acid (CH 3 COOH, a.k.a. AcOH), and hydrogen peroxide (H 2 Oi. a.k.a. HP). Commonly, such solutions also contain a small amount of acid catalyst: the most common being sul furic acid.
  • the acetic acid + hydrogen peroxide react as a "forward" reaction (also, the "formation” reaction) with reaction rate K
  • the equilibrium constant Ko for the reactions is the product of the equilibrium concentration quotient, K 0 . and the activity constant quotient, Y M , i.e..
  • and k 2 can be defined that include the effect of dependence of the activity coefficients on concentration so that the ratio of the effective reaction rates is equal to the equilibrium concentration quotient, i.e., r Ic 2 [HP][AcOH] where [x] is the molar concentration of species "x", PAA means peracetic acid, HP means hydrogen peroxide, and K c will vary with the ionic strength of the solution.
  • equilibrium means that the ingredients to the reaction are in proportions so that the concentrations of the individual reactants do not change in time.
  • there are additional reactions so that ideal equilibrium is not achieved, or there are differences in concentration from equilibrium so that equilibration proceeds, but a condition of near-equilibrium exists for which the temporal changes are sufficiently slow that the composition meets practical use. storage, and regulatory requirements.
  • a storage stability challenge is posed by equilibrium or near- equilibrium very dilute aqueous compositions with a water mole fraction that is greater than or equal to about 0.91 and with peracetic acid concentration less than 1 % w/w and more concentrated dilute solutions for which the ratio of peracetic acid concentration and hydrogen peroxide is less than about 0. 15, because small changes or errors in the concentration of hydrogen peroxide and/or acetic acid can lead to large changes in the concentration of peracetic acid. Such errors in concentration may result from the difficulty of accurately measuring peracetic acid concentration in a very dilute solution having a concentration of hydrogen peroxide that is much greater than the concentration of peracetic acid.
  • Changes in concentration may result from degradation of one or more ingredients, especially the degradation of hydrogen peroxide by reactions catalyzed by transition metal ions or halide ions, and it may also result from a loss of water and other constituents from the composition, for example, by evaporation or permeation.
  • the peracetic acid is reactive and it is also susceptible to decomposition and reactions with the container and impurities.
  • the storage stability of such compositions has been elusive, especially for compositions containing little or no slabili7er. As a consequence, the prior art has not adequately provided such storage stable compositions and methods for their preparation.
  • Regulatory requirements for the storage stability of products comprising peracctic acid-hydrogen peroxide solutions constrain the concentration of the active ingredients to remain, for the duration of the shelf-life of the product, within a range that is defined by a lower certified limit and an upper certified limit. The value of the range depends on the jurisdiction of the regulatory agency. Typically, for compositions with hydrogen peroxide between about 1 % and 8 % vv/vv. the allowable range in hydrogen peroxide concentration may be ⁇ 10 % w/ w of the nominal value, and the allowable range for the pcracetic acid concentration may be in a range from 15 % to i-30% w/w of the nominal value.
  • compositions with peracetic acid concentration less than 1 % do not exhibit acceptable storage stability for one year or more.
  • An example of such a very dilute composition is provided by Cosentino (5,656,302. Table 1 ), which has an initial equilibrium concentration quotient K 0 of about 1 .4 and comprising about 0.055 % w/w peracetic acid, about 1 % w'w hydrogen peroxide, and about 5 % w/w of acetic acid, but this composition contains about 0.5% or greater concentration of phosphonic acid stabilizer and within a few days of mixture, the peracetic acid concentration is found to rise substantially and K 0 to rise to nearly 2.
  • Cosentino's example in his Table I does not represent a storage stable equilibrium, nor docs it have IC C of about 1 .4 at room temperature. Thus. Cosentino does not provide for a storage stable very dilute composition with little or no stabilizer and also having phosphate ester surfactant in combination with water soluble polymer containing lactam.
  • the prior art does not provide a process for making a composition with sufficient accuracy so that the concentrations in a composition produced in a batch can be selected and obtained so that upon transferring the batch material to product packages, for example, smaller containers, that the shift in composition can be offset with the effects of evaporation, permeation, and interactions of the composition with the container.
  • Prior art teaches formation of peracetic acid and water as products of the reaction of acetic acid and hydrogen peroxide or acetic anhydride and hydrogen peroxide. Once formed in aqueous solution, the equilihrium is a balance of the forward formation reaction and reverse reaction of hydrolysis of pcracetic acid.
  • Crommclynck (US 4,297,298) teaches a method of making a dilute, storage stable solution containing a rated concentration between I and 20% by weight of an aliphatic carboxylic peracid.
  • the composition made by preparing a concentrated solution of aliphatic peracid from the corresponding carboxylic acid or anhydride and hydrogen peroxide in a concentration of between 60 and 90% in the presence of the substantially minimal amount of strong acid catalyst necessary to obtain equilibrium of the system in a maximum period of 48 hours; and diluting the concentrated solution of aliphatic peracid, prepared in the preparing step, with a solution containing at least one of the reagents used in the said preparing step in an amount and concentration sufficient to bring the concentration of the aliphatic peracid at least to the rated concentration of the mixture.
  • This method involves very concentrated initial reagents and substantial dilution by which it is very difficult to accurately achieve peracetic acid concentration much less than I % w/w. Moreover, the concentrated initial reagents are not compatible with a prior addition of surfactant and polymer, and so the anti-corrosive benefit to reduce the interactions of hydrogen peroxide, acetic and peracetic acids with the blending vessel are not obtained.
  • Le Rouzic ct al (US 4,743,447) teaches very dilute compositions with 0.01 to 0.04 % peracetic acid. 1 -8 % hydrogen peroxide, preferably about 3 %, and an equilibrium amount of acetic acid (0.5 to 1 .5 %). These compositions are made by direct reaction of hydrogen peroxide and acetic acid. However, the accurate preparation of such compositions is problematic. Moreover, Le Rouzic teaches the optional use of a non-ionic surfactant, and so, a different equilibrium is to be expected for a composition containing anionic phosphate ester surfactant as for the compositions of the instant invention.
  • Brougham's prescription is to predetermine an equilibrating 'model' system and making measurements. This process does not provide for account of batching reactions other than the "forward" formation reaction and the "reverse” hydrolysis reaction. In particular, account is not made of the ancillary batching reactions of decomposition of peracetic acid to acetic acid and oxygen, degradation reactions between the ingredients and the containing vessel, and evaporation, and in particular at an elevated batch temperature. Thus, Brougham's process is not readily used to make a very dilute solution with high accuracy.
  • DaSilva et al (US 5,358,867) teaches a process for the accelerated production of stable very dilute peracetic acid solutions in equilibrium. DaSilva's process is an alternative to make dilute equilibrium, storage stable solutions of peracetic acid to the process wherein such compositions are made from mixtures of aqueous hydrogen peroxide and acetic acid, or by dilution of more concentrated peracetic acid solutions, which takes a long time because of the low concentrations of the active participating materials.
  • DaSilva the process can be accelerated by employing a two step procedure in which a concentrated peracetic acid solution is diluted with water and partially hydrolyzed in the first step, and then the hydrolysis reaction is quenched by addition of hydrogen peroxide in the second step.
  • the DaSilva process does not provide for account of the ancillary batching reactions.
  • Example 1 is a solution with about 2.2 % peracetic acid and an apparent K c of about 1.77
  • Example 2 is a solution with about 0.13 % peracetic acid and an apparent K t of about 3.773. No prescription is given to determine the specific equilibrium compositions, the value of K c , or to account for the ancillary batching reactions.
  • a peracetic acid solution can be prepared by any of the methods known in the art, which generally comprise reacting acetic acid or acetic anhydride solution with hydrogen peroxide, optionally at elevated temperature, and in the presence of strong acid catalyst, together with any desired stabilizers, such as dipicolinic acid and or an organic phosphonic acid such as ethyl enehydroxy-di phosphonic acid.
  • any desired stabilizers such as dipicolinic acid and or an organic phosphonic acid such as ethyl enehydroxy-di phosphonic acid.
  • Cosentino (US 5,656,302) teaches stable, shippable microbicidal compositions including between about 0.2 to 8% hydrogen peroxide, about 0.2 to 1 1 % peracetic plus acetic acid, 0 to about 1 .0% sequestrant such as organic phosphonic acid or its salt and water, and surfactant between 0 and about 1 % with the ratio of total acid to H 2 O 2 being between about 1 .0 and 1 1.
  • sequestrant such as organic phosphonic acid or its salt and water
  • surfactant between 0 and about 1 % with the ratio of total acid to H 2 O 2 being between about 1 .0 and 1 1.
  • SUMMARY OF THR INVENTION 100541 ⁇ method for the microbicidal treatment of a surface such as sanitation, disinfection, sterilization, and decontamination of a surface or object by use of an microbicidal composition
  • an microbicidal composition comprising a very dilute aqueous solution of peracetic acid, hydrogen peroxide, acetic acid, water soluble polymer containing lactam, phosphate ester surfactant, and little or no stabilizer, and according to the method enhanced microbicidal efficacy is obtained when the composition is applied onto a surface as a thin film wetting the surface and subsequently is an evaporating film so that a shorter contact time for a desired fractional reduction in microbial population is obtained because of the increase in the concentration of the microbicidal active ingredients as the water in the composition evaporates from the thin film.
  • the composition may be applied as a wiped, sprayed, or brushed on liquid, as a sprayed, drifted, or electrostatic
  • the method for the microbicidal treatment of a surface comprises the step of applying a very dilute peracetic acid solution as a microbicidal composition to form a thin layer that wets the said surface; and the additional steps of contacting the said surface with the said microbicidal composition for a contact time.
  • T c that is greater than about 20 % but less than or equal to 1 00% of the evaporation time, t e , of the thin layer.
  • the thin layer is evaporating; and after the contact time, the optional step of illuminating the wet said surface with light for photosensitized microbicidal effect; the optional step of rinsing the surface with clean water to substantially remove residue; the optional step of drying the said wet surface with a sterile wipe: and the optional step of air drying the said wet surface.
  • the invention is a process for accurately making a batch of a storage stable embodiment of the compositions for use in the above method of microbicidal treatment of a surface, whereby according to the process ingredients comprising a relatively concentrated solution of peracetic acid, hydrogen peroxide, and acetic acid, a relatively concentrated solution of hydrogen peroxide, glacial acetic acid, phosphate ester surfactant, water soluble polymer containing lactam, little or no additional stabilizer, and optionally small amounts of acid catalyst such as sulfuric acid and minors such as fragrance and colorants are combined in a specified order and in precise amounts to form a more dilute solution with peracetic acid at concentration greater than the desired final concentration of peracetic acid and reacted at elevated temperature to obtain with accuracy an equilibrium or near-equilibrium very dilute composition with concentrations of active ingredients that are storage stable within regulatory limits for more than one year.
  • ingredients comprising a relatively concentrated solution of peracetic acid, hydrogen peroxide, and acetic acid, a relatively concentrated solution of hydrogen peroxid
  • the target concentrations are selected, these being the concentrations of hydrogen peroxide, peracetic acid, polymer, and surfactant in the resulting composition at a selected batching temperature in the range of about 40° C" to about 55° C.
  • the peracetic acid stock solution comprising peracetic acid, hydrogen peroxide, acetic acid, acid catalyst, and water, the amount of glacial acetic acid of known concentration, the amount of an aqueous solution of hydrogen peroxide of known concentration, designated the hydrogen peroxide stock solution, the amounth of surfactant, polymer, and minors, and the amount of de-ionized/reverse osmosis filtered water to be added to the batch to obtain the target concentrations;
  • the instant invention provides the compositions made by the above process and comprising very dilute peracetic acid solutions that are storage stable R l ' U microbicidal compositions that can be used in the microbicidal treatment of a surface by the method of the instant invention. Further, the compositions made by the above process comprise photosensitizcr for light-activated anti-microbial efficacy.
  • the storage stable, very dilute RTU compositions so made can be used for microbicidal treatment by a variety of application methods such as liquid or aerosol spraying or misting, wiping, pouring, or by immersion of objects into the composition, or, still further, as a photosensitizcr, for application as a liquid or aerosol into a volume or onto a surface for subsequent illumination by light, especially ultraviolet light.
  • Anti-microbial uses include use as a sanitizer, disinfectant, sterilant. virucidc. fungicide, moldicide, bactericide, dccontaminant, and sporicide.
  • microbicidal compositions also may be used as ingredients in other products to obtain microbicidal efficacy for a liquid aqueous composition.
  • the storage stable, very dilute RI U compositions may be incorporated with application means such as the prc-wetted wipes, e.g., partially or fully prc-saturated wipes, carriers, or applicators, or added at the time of use to such application means.
  • the microbicidal composition can be useful for additional purposes such as cleaning, washing, deodorizing, and as preservative.
  • the composition also can be further diluted just prior to use as a sanitizer, sanitizer- cleaner, or other microbicidal application.
  • Desirable characteristics of the RTU solution include the following:
  • the composition can be applied by various means, for example, by aerosol spraying, pouring, painting, brushing, etc. or be applied with a wipe, such as a partially-saturated or saturated pre-wetted wipe, or a wipe wetted just prior to use. Further, the composition may be used as a microbicidal bath for immersion of objects to be treated, or used as a mist, fog, or aerosol spray to kill airborne microbes and/or be used as a fumigant.
  • Fig. I shows the evaporation time for a uniform liquid layer as a function of relative humidity for various initial layer thickness (bottom) 12.5 ⁇ m to (top) 75 ⁇ m, for air current conditions that are typical of a ventilated interior room (v ⁇ 0.3 m/s and X - 0.3 m);
  • F'g- 2 shows the evaporation time for a uniform liquid layer as a function of relative humidity for various initial layer thickness (bottom) 25 ⁇ m to (top) 100 ⁇ m, tor air current conditions that are typical of a container undergoing decontamination outdoors in a 7 mph wind (v ⁇ 3.2 m/s, X ⁇ 1.0 m);
  • Fig. 3 shows the concentration of hydrogen peroxide in the remaining liquid layer of the composition of Example 1 (initial concentration is 4.4 % w/w) as a function of the evaporated fraction of the initial layer, wherein the boxes are experimental measurements and the curve is a theoretical prediction;
  • FIG. 4 shows the ratio (solid curve) of the concentration of hydrogen peroxide in the remaining liquid layer and its initial concentration as a function of the evaporated fraction, (percent) and the ratio (dotted curve) of the concentration of peracetic acid in the remaining liquid layer and its initial concentration as a function of the evaporated fraction (percent), wherein the diamonds correspond to the experimental measurements of hydrogen peroxide;
  • Fig. 7 shows the log reduction plotted as a function of contact time (minutes) for B. sublilis spores dried on a glass Petri dish and treated with microbicide (comprising 4 % w/w hydrogen peroxide and 0.2 % w/w peracetic), wherein the dotted curve is a regression tit that includes the point at 5 minutes, which corresponds to the limit of detection (LOD - 7.28 logs reduction) and wherein the dashed line is a 2" order polynomial fit to the data points, each of which represents the mean of several tests;
  • Fig. 8 shows the log reduction of Bacillus atrophaeus spores (bar 1 ) 4.43 logs, resulting from a I minute contact time of the composition of Example 1 compared to compositions that differ by replacement of the PVP polymer containing lactam with (bar 2) 2.76 logs, PPG, (bar 3) 2.66 logs, PEG, and (bar 4) 2.78 logs, no polymer;
  • [0073J Fig. 9 shows the concentration quotient K 0 plotted as a function of the mole fraction of water X w .
  • the data points shown with "x" are experimentally measured values from the data of Revel] et al., Martin et al., and DaSilva et al. for X w ⁇ 0.91 , and the composition of the instant invention for X w > 0.91
  • curve 1 is a 4 th order polynomial fit to the data
  • curve 2 is a polynomial fit
  • curve 3 is a local polynomial regression to the data of Cosentino et al.
  • curve 4 is an extrapolation of the data of Sawaki et al.
  • Fig. 10 shows the concentration quotient for Cosentino * .. Table 1 dilute formulation seen to vary significantly with time, wherein the composition does not appear to be storage-stable;
  • Fig. 1 1 shows the concentration quotient for Coscntino's Table 2 formulation is seen to vary significantly with time, wherein the composition does not appear to be storage- stable:
  • Fig. 12 shows a plot of the concentration quotient K v vs water mole fraction X w for the compositions of Cosentino's Table 2 showing a significant monotonic decrease of KL 0 with increasing X w ;
  • Fig. 13 shows a plot of the measured concentration of pcracetic acid as a function of time for batches at various temperatures ((boxes) 23°, (diamonds) 45°, and (circles) 55° C) allowing determination of the equilibration times (7.5, 1 .3, and 0.77 days, respectively);
  • Fig. 14 shows the concentration of pcracetic acid as a function of time shown for two batches, each started with the same initial ingredients, wherein one batch (upper curve) was made and stored just above room temperature (23° C) and the other batch (lower curve) was made and stored at 45° C;
  • Fig. 1 5 shows the w/w concentrations of (upper curve) acetic acid, (middle curve) hydrogen peroxide, and (lower curve) pcracetic acid as functions of time (hours) during a batch process at a temperature of about 55" C, wherein the curves are calculated values and agree with measurement data with a standard deviation of about 3 %; and
  • Fig. 16 shows the predicted concentrations as a function of time shown for the post-batching equilibration and evolution of the batch of microbicidal composition at room temperature after batching for 60 hours at a temperature of about 55° C (as shown in Fig. 15), followed by a fast cool down with no added fragrance, and then storage in sealed containers.
  • RTU microbicidal compositions and Use Dilutions i.e., very dilute solutions that are made from more concentrated microbicidal compositions
  • Use Dilutions i.e., very dilute solutions that are made from more concentrated microbicidal compositions
  • the evaporation rates of the solutes, peracetic acid, hydrogen peroxide, and acetic acid are governed by Henry's Law, for which at the air-liquid interface of the solution the vapor pressure of a solute constituent is equal to the molar concentration of the constituent divided by the product of the relevant Henry's Law constant and the density of the solution (which density is close to I kg/liter for very dilute solutions), rather than Rauolt's Law. for concentrated solutions for which the vapor pressure is equal to the product of the saturation vapor pressure for a vapor of the constituent and the mole fraction of the solute in the solution.
  • the solute vapor pressures are small in a very dilute solution, so the solute evaporation rates are small, and the evaporation of a thin film of such a very dilute peracetic acid solution is dominated by the evaporation of water.
  • the saturation vapor pressures of acetic acid and peracetic acid are about two-thirds that of water for temperatures in the range ⁇ f 10°-50° C, and the saturation vapor pressure of hydrogen peroxide is an order of magnitude smaller, their vapor pressures given by Henry's Law for very dilute solutions are very much smaller.
  • the relative evaporation rates of the acetic acid and peracetic acid will be comparable to that of the water.
  • the evaporation time depends on the relative humidity, RH (in percent), the air speed over the liquid-air interface of the thin film, v°, the scale size for the air flow over the film, ⁇ " , the ambient temperature, T, and the initial thickness of the film, ⁇ () .
  • the scale length for the vapor concentration gradient can be calculated as a function of viscosity ⁇ . flow velocity v", mass density p u , of the atmosphere and the diffusion coefficient D of the evaporating species.
  • Boundary layer thickness c) ' and local vapor pressure of the evaporating species at the liquid film- atmosphere interlace provide a basis for calculating the concentration gradient Vc , which is such that
  • ⁇ . ⁇ Dp 1 , is the concentration boundary layer thickness [see, for example, ⁇
  • CusslerJ, and C 1 , - c «- is the difference of the vapor concentration c, at the liquid-atmosphere interface and- the concentration c a , in the atmosphere outside of the boundaiy layer.
  • v ins is the liquid molecular volume of species s, M.
  • a ' where A 1 , is the initial film thickness and t e is the evaporation time.
  • the concentration boundary layer thickness of ⁇ c is calculated as a function of characteristic scale length .V of the surface over which the laminar flowing atmosphere has a convecti ve velocity of v .
  • a typical velocity may be estimated as the resull of ventilation, density delects of suspended aerosol, or, more typically, buoyancy as a result of thermal gradient. In outdoor situations, a typical velocity may be estimated as the mean wind speed. [00901 The buoyancy velocity for a room of height H r and thermal difference AT is estimated as o h ⁇ 7" // (10) where g(dTfl)' is a "reduced gravity 1 ', and ventilation flow is assumed to be small. In a typical office, U, - 2.4 m. J7 ' ⁇ '/; 0 K, so v" ⁇ 0.3 m/s, i.e., the air current is about one foot per second.
  • c is the liquid solute concentration (typically in moles/kg) of solute species "s" and Kn is Henry's constant (e.g.. Ku ⁇ 745 mole/kg-bar for peracetic acid, Kn ⁇ 4900 molc'kg-bar for acetic acid, and K 11 - 1 . 1 x 10 5 mole/kg-bar for hydrogen peroxide).
  • the saturated vapor pressure is p ⁇ s Ton" (14)
  • t e can be calculated using Eqn. 18 for the evaporation of a microbicidal composition comprising 4% w/w hydrogen peroxide, 0.2 % vv/vv peracelic acid, and less than 5 % w/w acetic acid from a treated surface.
  • v" 0.3 m/s
  • RJtI - 50% then
  • Of particular interest are thin films with initial thickness ⁇ (t—O) in the range of about 12.5 ⁇ m to about 75 ⁇ m or in the range of about 50 ⁇ m to about 150 ⁇ m.
  • I he first range is typical of the layer applied by a pre-vvetted wipe such being especially useful for the disinfection or sanitizing of interior surfaces in healthcare, residential, commercial, and food preparation settings, and the like.
  • Fig. 1 initial thickness range.
  • t c shows the evaporation time, t c , for a uniform liquid layer as a function of relative humidity, RJf, for various initial layer thickness (bottom) 12.5 ⁇ m to (top) 75 ⁇ m, for air current conditions that are typical of a ventilated interior room (v ⁇ 0.3 rn/s and X ⁇ 0.3 m).
  • the second range of initial thickness is typical of the layer applied by spraying as an aerosol as being especially useful for larger scale indoor and outdoor applications such as mold remediation, decontamination of biological warfare and bio-terrorism agents, agriculture and food production settings, and the settings listed above.
  • Fig. 2. shows the evaporation time, t e , for a uniform liquid layer as a function of relative humidity, RH, for various initial layer thickness (bottom) 25 ⁇ m to (top) 100 ⁇ m, for air current conditions that are typical of a container undergoing decontamination outdoors in a 7 inpli wind (v ⁇ 3.2 rn/s, X - 1 .0 m).
  • ⁇ (t)j is a function that depends on the evaporated fraction of the initial layer
  • microbicidal compositions that are each a very dilute peracetic acid solution comprising about 0.23 % w/w peracetic acid, about 4.4 % w/w hydrogen peroxide, about 4.9 % w/w acetic acid, 0.1 % w/w phosphate ester surfactant, dc-ionized/reverse osmosis (DI'RO) filtered water, and 0.1 % W/ W polymer selected from the group of lactam containing polyvinyl pyrrolidone (P VP), polyethylene glycol (PEG), and polypropylene glycol (PPG), or with no polymer, minor amounts of stabilizer and sulfuric acid, and with a balance of water.
  • P VP polyvinyl pyrrolidone
  • PEG polyethylene glycol
  • PPG polypropylene glycol
  • Fig. 4 shows the ratio (solid curve, per Eqn. (20)) of the concentration of hydrogen peroxide in the remaining liquid layer and its initial concentration as a function of the evaporated fraction, ⁇ (percent), and the ratio (dotted curve, theoretical estimate) of the concentration of peracetic acid in the remaining liquid layer and its initial concentration as a function of the evaporated traction (percent).
  • the diamonds correspond to the experimental measurements of hydrogen peroxide. Measurement of the peracetic acid in the layer proved to be very challenging.
  • the T c necessary to achieve a desired log reduction, i.e.. microbicidal efficacy level, is reduced by a factor that is the inverse of the enhancement in comparison with the T c without the enhancement.
  • the log reduction in a microbial population by microbicidal treatment is proportional to CT C .
  • This is illustrated in Fig. 5, where the log reduction in E. coli on the bottom surface of a 14 mm diameter well of a polystyrene 24 well plate after a 30 second treatment by 40 ⁇ l. of microbicidal composition with PVP polymer, described above, at various dilutions to vary the concentrations of the active ingredients.
  • the initial film thickness of microbicide is approximately 150 ⁇ m. and lhe evaporation time is much greater than 5 minutes, so very little evaporation occurs and consequently, very little enhancement of active ingredient concentration occurs.
  • the abscissa shown in the figure is the weight/weight percentage of hydrogen peroxide in the composition.
  • the ratio of peracetic acid and hydrogen peroxide is 1 :20.
  • T c - 30 sec the treatment time
  • LOD 6.94 logs reduction
  • subtilis spores dried on a glass Petri dish and treated with the microbicidal composition with PVP polymer (the active ingredients comprising 4 % w ⁇ v hydrogen peroxide and 0.2 % w/w pcracetic)
  • the dashed line is a 2" d order polynomial fit to the data points, each of which represents the mean of several tests.
  • the dotted curve is misleading because the point at 5 minutes is at the LOD, and so distorts the curve. Instead, the dashed curve should be considered to be representative of the temporal dependence.
  • compositions for which the polymer and/or surfactant lead to a viscosity substantially greater than water will not flow and readily form a thin film.
  • the viscosity at about room temperature of the compositions of the instant invention is less than about 2 mPa-s (cP). and in a more preferred embodiment, the viscosity is less than about 1.5 mPa-s (cP), and in a still more preferred embodiment, the viscosity is less than about 1 .3 mPa-s (cP). By comparison, the viscosity of water at room temperature is about 1 .003 mPa-s (cP).
  • the spore challenge level was approximately 1 .9 to 2.2 x H) 7 spores and the nominal recovery was about 1 x 1 C) 7 spores.
  • Experimental controls included comparison test with neutralization, with no polymer, and with the various polymers, also phosphate buffered saline (PBS) controls, titer determination, and recovery fraction determination. The recovered samples were plated and enumerated on days 1 , 2 and 3.
  • Fig. 8 The log reduction of Bacillus atrophaeus spores by the microbicidal composition with PVP, (bar I ) 4.43 logs, is compared to compositions that differ by replacement of the PVP polymer containing lactam with PPG (bar 2). 2.76 logs, (bar 3) PEG, 2.66 logs, and no polymer (bar 4). 2.78 logs.
  • the microbicidal composition with PVP polymer containing lactam is found to be superior by about 1.6 logs.
  • the applicability of the method of microbicidal treatment of a surface in a confined space may be limited because the evaporation of an applied thin layer will slow and may essentially stop because of the increase in RH as water evaporates from the layer.
  • An example is given by decontamination or disinfection of a confined space for which the microbicidal composition is applied to the entire or the majority of the interior surface.
  • the application of the microbicidal composition forms a layer a thickness such that the desired T c is greater than about 20 % of the evaporation time t c , i.e.. T c Zt 1 . > 0.2, and in a more preferred embodiment, T c /t t . > 0.5.
  • an initial layer thickness in the range of about 10 ⁇ m to about 40 ⁇ m will have T 1 . in the range of about 1 .3 to about 7.5 minutes.
  • a layer with initial thickness of 10 ⁇ m to 25 ⁇ m will result in an enhancement factor for the log reduction in the range of about 1 .25 to about 1 .5.
  • a layer with an initial thickness of about 25 ⁇ m to about 40 ⁇ m will have t c in the range of about 2.5 to about 7.5 min, and so result in an enhancement factor for the log reduction in the range of about 1 .2 to about 4.
  • a layer with an initial thickness of about 50 ⁇ m will have t t . in the range of about 5.5 to about 9.5 min, and so result in an enhancement factor for the log reduction in the range of about 1 .7 to about 4.
  • the amount of microbicidal composition applied to the surface to form a layer of a desired initial thickness can be selected by adjusting the spray applicator spray parameters such as flow rate, droplet size, and distance between the sprayer nozzle and the surface to be treated, and, for hand pumped sprayers, additionally selecting the number of pump actuations.
  • the sprayer is a hand held, hand pumped aerosol sprayer that delivers about 25 ⁇ l to about 100 ⁇ l per pump actuation.
  • the amount of microbicidal composition applied to the surface can be selected by the choice of the saturation ratio, i.e., the ratio of the mass of the microbicidal composition to the mass of the wipe, the si/e of the wipe, the efficiency of transfer, which is the ratio of the mass of microbicide transferred to the surface and the mass of microbieide initially in the wipe, and the area to be treated. Further, as known in the art, the transfer efficiency further may depend on the • wipe material and its physical and chemical properties, morphology, which may depend on manufacturing method as well as its construction, and on its absorptive properties.
  • the saturation ratio is in the range of about 0.5 to about 10. In a more preferred embodiment, the saturation ratio is in the range of about 1 to about 3, and the efficiency of transfer is in the range of 40 % to about 75 %.
  • Another important use parameter is the ratio of treated area to wipe area. In a preferred embodiment, the ratio of treated area to wipe area is in the range of about 1 to about 4. The smaller value corresponds to thicker initial film thickness as is desirable for sporicidal disinfection treatment and longer T 0 , and the larger value corresponds to a thinner initial film thickness as is desirable for sanitizing treatment and shorter T 0 .
  • the microbicidal composition comprises hydrogen peroxide in concentration in the range of about 0.4 to 8 % by weight, peracetic acid in concentration in the range of about 0.02 to about 0.55 % by weight, acetic acid in concentration less that about 8 % by weight, phosphate ester surfactant in concentration in the range of about 0.01 to about 0.5 % by weight, water soluble polymer containing lactam in concentration in the range of about 0.01 to about 0.5 % by weight, less than 0.2 % by weight of stabilizers in the group consisting of inorganic phosphates, phosphonatcs, organic phosphonic acids or their salts, ethylenediaminetetracetic acid or its sodium salt, less than about 1 ppm of mono- and divalent metal ions, less than about 1 ppm of halitle ions, less than 0.5% by weight of minors selected from the group of fragrance
  • the microbicidal composition comprises hydrogen peroxide in concentration in the range of about 3.5 to 5 % by weight, pcracetic acid in concentration in the range of about 0. 15 to about 0.35 % by weight, acetic acid in concentration less that about 5.5 % by weight, phosphate ester surfactant in concentration in the range of about 0.05 to about 0.3 % by weight, water soluble polymer containing lactam in concentration in the range of about 0.05 to about 0.3 % by weight, less than 0.2 % by weight of stabilizers in the group consisting of inorganic phosphates, phosphonates, organic phosphonic acids or their salts, ethylenediaminetetracetic acid or its sodium salt, less than about 1 ppm of mono- and divalent metal ions, less than about 1 ppm of halide ions, less than 0.5% by weight of minors selected from the group of fragrance, colorant, and aesthetic enhancements, and a balance of water.
  • the polymer is a homopolyincr or copolymer of polyvinyl pyrrolidone and exemplary surfactants are anionic phosphate surfactants not limited to OC-40 manufactured by Hercules, Inc. of Wilmington, DE.
  • This family of surfactants is characterized by the R terminal lipophilic alkyl hydrocarbon chain in range of C9 thru C l 3, a hydrophilic PRO polyoxyethylene chain in a range of PEO-3 to PFO-9 and a Z terminal mono and diester phosphate.
  • the lactam-containing polymer and anionic surfactant are essential to obtain the desired characteristics of the composition, although they arc present in small percentage by weight.
  • ingredients arc selected so that the combination of anionic surfactant and lactam- containing polymer aid in providing microbicidal efficacy, especially for CT C enhancement in an evaporating thin film of the composition.
  • the anionic surfactant and polymer are further selected for their rheological properties so that the composition will form a good film when sprayed or applied by wiping, and yet, the polymer and surfactant do not greatly increase the viscosity or surface tension of the composition so as to preclude good transfer efficiency when applied as an aerosol spray, Further, the surfactant itself has some microbicidal efficacy and also has very good properties as an anti-corrosive, which is very important so that the composition has good material compatibility characteristics, i.e..
  • the polymer-surfactant interaction provides for effective dispersion in the pH range and has sequestrant properties that contribute to the equilibrium stability of hydrogen peroxide and peracetic acid.
  • the unique aqueous soluble polymer- surfactant interaction provides a film forming capability to the formulation and further provides an anti-corrosive effective on metal surfaces.
  • Another advantage of the polymer and surfactant combination is the essentially thorough sequestration of metals and metal ions so that the reactions of the metals and metal ions with the active ingredients are effectively eliminated so that, except for minor and acceptably small rates of degradation of the hydrogen peroxide, peracetic acid, and/or acetic acid, the metals and metal ions do not play a significant role in the chemistry, use. or efficacy of the composition.
  • the combination promotes stabilization of dielectric properties of the formulations when utilized in electrostatic spray applications.
  • the surfactant and polymer are each present in the microbicidal composition in concentration less than about 0.5 % w/w, acceptably little residue for most uses remains after evaporation of the composition.
  • the polymer has a molecular weight in the range of about 4000 to about 20,000, and is present in a by-weight concentration in the range of 0.05% to about 0.5%.
  • the surfactant is present in the range of about 0.05% to about 0.5%.
  • the concentration of polymer and surfactant arc each less than 0.3 % w/w.
  • the composition has a low corrosion rate on most materials.
  • the principal anti -corrosive in the composition is the anionic surfactant.
  • a preferred RTU embodiment with about 4.4 % w/w hydrogen peroxide, about 0.23 % w/w peracetic acid, about 4.9 % w/w acetic acid, about 0.
  • a typical initial immersion corrosion rate on reactive metals, copper for example is about 4 mils/cm 2 -yr. This corresponds to a material loss of about 4 ⁇ g/cm 2 per hour of immersion. Such a corrosion rate is sufficiently low so that this RTU microbicidal composition is not classed as a corrosive and subject to the Department of Transportation shipping constraints as a Class 8 UN/DOT material.
  • the method of microbicidal treatment by an evaporating thin film is well suited for the additional step of illumination with light for producing photochemical species and also obtaining direct photo-killing and inactivation of microbes.
  • This additional step is enabled in a preferred embodiment when the microbicidal composition is also a photosensitizer.
  • a photosensitize it is important that the anionic surfactant not merely be photoabsorptive, but that it is photoreactive and beneficially promote the formation of microbicidal species, for example, ions and radicals.
  • the anionic surfactant is photoreactive and is a phosphate ester.
  • the surfactant is an alkyl cthoxylate phosphate ester.
  • a light fluence greater than or equal to about 45 mJ/cm 2 of light in the visible and ultraviolet parts of the spectrum provides for sporicidal and disinfecting efficacy.
  • the light used for such photosensitized killing and photo-killing is in the spectral range of about 210 nm to about 400 nm. In this case, the destruction of Deoxyribonucleic acid (DNA) and/or Ribonuclei acid (RN ⁇ ) and other nucleic acid compounds results when the lluencc is greater than or equal to about 30 mJ/cm 2 .
  • DNA Deoxyribonucleic acid
  • RN ⁇ Ribonuclei acid
  • the light is greater than or equal to about 30 mJ/CTir in the spectral region of 210 nm to about 315 nm.
  • the microbicidal composition is a storage stable, very dilute peracetic acid solution.
  • the target concentrations are selected so that the composition will remain in compliance within regulatory limits, in spite of anticipated changes in [PAA] and [HP].
  • An example of such limits are the Upper Certified Limit and Lower Certified Limit that are specified for a product that is registered with the U.S. Environmental Protection Agency (US EPA) under the Federal Insecticide, Fungicide, and Rodcnticide Act.
  • [HP]/[PAA] is in a range of about 10 to about 30, and [PAA] « [AcOIJ], the peracetic acid can be susceptible to a substantial secular temporal change that leads to [PAA] being outside the regulatory permitted limits.
  • the change in [PAA] can result from equilibrium shift because of degradation and decomposition reactions, or other loss of hydrogen peroxide, acetic acid, or peracetic acid. It also can result from loss of water or other ingredients by evaporation or permeation into or through a container. Further, the change in equilibrium concentrations also may be the result of errors in manufacturing the target composition.
  • One approach to reduce degradation of hydrogen peroxide, peracetic acid, and acetic acid is to use ingredients that have low impurity content.
  • the use of water that has low content of mono- and di-valent metals, halides. and organics is essential as water is the majority ingredient of the very dilute solution.
  • the water is de-ionized and reverse osmosis filtered (DI/RO) water with mono- and di-valent metals in concentration below one part per million (ppm), and with species such as iron, copper, manganese, /inc ions and the like each preferably in concentration less than 100 parts per billion (ppb).
  • the other ingredients namely the peracetic acid stock solution, the glacial acetic acid, the hydrogen peroxide stock solution, the polymer containing lactam, the phosphate ester surfactant, and minor ingredients all have low concentrations, in a preferred embodiment less than about I O ppm, and in a more pre fared embodiment less than about 1 ppm. of impurities such as organics. halides, and mono- and di-valent metal ions.
  • impurities such as organics. halides, and mono- and di-valent metal ions.
  • the peracetic acid stock solution stabilizer is often present, and an acid catalyst is also typically present, for example, sulfuric acid in an amount up to about 1 % w/w.
  • an acid catalyst is also typically present, for example, sulfuric acid in an amount up to about 1 % w/w.
  • sulfuric acid in an amount up to about 1 % w/w.
  • a peracetic acid stock solution comprising about 15 % w/w peracetic acid, about 22 % ⁇ v/ ⁇ v hydrogen peroxide, and about 1 6 % w/w acetic acid, stabilizer, acid, and a balance of water
  • addition to a batch to make the microbicidal composition will result in the stabili/er and sulfuric acid being diluted by more than an order of magnitude to less than about 0.1 % w/w of the resulting composition.
  • stabilizer alone in such small concentration has not been sufficient to achieve storage stability of a very dilute peracetic acid solution.
  • Curve 1 is a 4 th order polynomial fit to the data.
  • Curve 2 is a polynomial fit and curve 3 is a local polynomial regression to the data of Cosentino et al.
  • Curve 4 is an extrapolation of the data of Sawaki et al.
  • the solution contains a w/w percentage of inert ingredients, I, the water concentration is related to the other constituents by
  • reducing the manufacturing time is desirable so that the resulting composition can be packaged sooner as a composition with constituent concentrations that are within the regulatory acceptable limits, and can have a longer shelf life before degradation and decomposition reactions make it unacceptable.
  • An additional advantage of reduced manufacturing time is that the manufacturing resources have a greater throughput. In particular, batching at sufficiently elevated temperature so that at least one or.
  • two batches per standard work week can be prepared, equilibrated sufficiently, analyzed to meet release criteria, and packaged impacts manufacturing capacity and economic return on capital investment favorably even though batching at elevated temperature requires a blending tank that is maintained at the elevated temperature and may also require a means for rapidly cooling the tank to further reduce the time between the start of the batch and packaging or storage.
  • a typical water evaporation rate, ⁇ , of a very dilute solution is on the order of about ⁇ ⁇ 0.5 - 1 ⁇ 10 "4 per hour. So. in 60 hours of batching, the evaporated water loss amounts to about one half percent.
  • blending tanks are made of Austenitic stainless steel, in a preferred embodiment, the alloy is type 3 16 stainless steel. It is also common practice to passivate the tank. e.g.. by rinsing the interior tank wall with nitric or citric acid and then rinsing the tank with DI/RO water, and then, still further, rinsing it with a dilute hydrogen peroxide solution, for example, a 4 % solution.
  • the polymer and surfactant are more easily dissolved and can, in the presence of metals and metal ions, especially mono- and di-valent species, in concentration less than about 1 ppm, in essence, thoroughly sequester metals and metal ions prior to the addition of the other ingredients so that the reactions of the metals and metal ions with the active ingredients are effectively eliminated and so that, except for minor and acceptably small rates of degradation of the hydrogen peroxide, peracetic acid, and/or acetic acid, the metals and metal ions do not play a significant role in the chemistry, use, or efficacy of the composition.
  • the degradation rate for hydrogen peroxide is about ⁇ h - 3 x 10 ⁇ 4 percent per hour. It is found that the degradation rates for peracetic acid. ⁇ p , and acetic acid. ⁇ v are comparable or less by a factor of a few, i.e., ⁇ p. ⁇ v ⁇ ] x ] (T 4 percent per hour.
  • Batches may also be prepared in plastic tanks that can be heated.
  • a plastic blending tank is made of high density polyethylene (HDPR), or polypropylene, or a combination of stainless steel, plastic, and/or compatible metals that are known in the art.
  • the piping, pump components, mixing blade, and other components that may contact the microbicidal composition must be made of compatible materials.
  • passivation of a plastic tank is not necessary, but the tank must be well cleaned, for example by thoroughly washing and then rinsing the tank with DI/RO water ⁇ or other low impurity water. However, interaction with the tank may still occur at elevated temperature.
  • a heated plastic tank may not be as durable as a metal tank.
  • the cost of a plastic tank may be much less than a comparable stainless steel tank. Small batches have conveniently been made in well cleaned HDPE plastic drums that are heated with thermostatically controlled electric blankets.
  • Fig. 13 shows a plot of the concentration of peracetic acid as a function of time for various batching temperatures ((boxes) 23°, (diamonds) 45°, and (circles) 55° C). Measurement of the decay rates allows determination of the equilibration times (7.5, 1 .3, and 0.77 days, respectively).
  • K c increases about 10 % as T decreases from 55 0 C and room temperature. Furthermore, by knowing K 0 , the equilibrium molar concentration o f acetic acid can be related to the concentrations of hydrogen peroxide and peracetic acid by Eqns. 29 and 35a to obtain,
  • the evolution of the batching process can be predicted for the batch preparation of the composition at a temperature T, by knowing good estimates of the reaction rates, degradation and decomposition rates, and the evaporation and/or permeation rates, and using the model of Eqns. 34, .
  • T temperature
  • These are typically HPLC that is calibrated by comparison with standard solutions and/or titranietric assays such as 2-step titration methods commonly practiced in the art. In our experience, these methods have accuracy in the range of about ⁇ 2 % to about -t 8 % w/w as practiced in the conditions of a "manufacturing facility" setting.
  • the starting or initial concentration of peracetic acid be greater than the target concentration by at least 15 % vv/vv, and that the initial concentrations of hydrogen peroxide and acetic acid be less than the target values.
  • the greater starting value of [P ⁇ ] also provides a margin for account of measurement errors.
  • the stock peracetic acid solution may be a source of sulfuric acid and stabilizer, and so it may be advantageous to use a greater starting value of [FAAJ so that these minor ingredients are provided in the step of adding the initial peracetic acid to the batch.
  • the starting value of [PAA] is at least 50 % greater than the target value, but less than about 6 times the target value.
  • the process accurately makes a batch of a storage stable microbicidal composition comprising a very dilute peracetic acid solution with the resulting composition having an equilibrium concentration quotient o f about
  • the target concentrations arc selected, these being the concentrations of hydrogen peroxide, peracetic acid, polymer, and surfactant in the resulting composition at a selected batching temperature in the range of about 40° C to about 55° C.
  • the following steps arc:
  • the polymer and/or the surfactant may each be mixed with a quantity of DI/RO filtered water, which may be at elevated temperature, for example, approximately the temperature of the batch process.
  • Such pre-mixing may lead to more ready pouring or pumping or other means of introduction of the polymer and/or surfactant to the batch, for example, reducing viscosity, or more convenient and thorough mixing.
  • the instant invention provides the compositions made by the above process and comprising very dilute peracetic acid solutions that are storage stable RTU microbicidal compositions that can be used in the microbicidal treatment of a surface by the method of the instant invention. Further, the compositions made by the above process comprise photosensitizer for light-activated anti-microbial efficacy.
  • Fig. 14 A comparison of predictive calculation and experimental measurement is shown in Fig. 14.
  • the concentration of peracetic acid as a function of time is shown for two batches, each started with the same initial ingredients.
  • One batch (upper curve) was made and stored just above room temperature (23 3 C).
  • the other batch (lower curve) was made and stored at 45° G.
  • Both batches were made in sealed HDPE containers, split into aliquots, and stored in sealed HDPE containers. Because the batching was performed in sealed containers, evaporation and water loss during the process were negligible.
  • the increase in concentration with time is likely the result of water loss by permeation and/or absorption into the container.
  • the difference in post-batching concentration of the two batches results from the increased decomposition of peracetic acid at elevated temperature and the difference in K c . which is a function of temperature.
  • the microbicidal compositions made by the batch process of the instant invention comprise, at about room temperature, hydrogen peroxide in concentration in the range of about 2.0 to about 6 % by weight, peracetic acid in concentration in the range of about 0.05 to about 0.74 % by weight, acetic acid, phosphate ester surfactant in concentration in the range of about 0.025 to about 0.3 % by weight, water soluble polymer containing lactam in concentration in the range of about 0.025 to about 0.3 % by weight, acid catalyst in concentration in the range of 0 to about 1 000 ppm by weight, less than 0.2 % by weight of stabilizers in the group consisting of inorganic phosphates, phosphonatcs.
  • organic phosphonic acids or their salts ethylenediaminetetracetic acid or its sodium salt, less than about 1 0 ppm by weight of mono- and divalent metal ions, less than about 1 ppm by weight of halide ions, less than 0.5% by weight of minors selected from the group of fragrance, colorant, and aesthetic enhancements, and a balance of water.
  • the combination of polymer and surfactant in the compositions of the instant invention provide, in the presence of metals and metal ions, especially mono- and di-valent species, in concentration less than about 1 ppm, essentially thorough sequestration of metals and metal ions so that the reactions of the metals and metal ions with the active ingredients are effectively eliminated and so that, except for minor and acceptably small rates of degradation of the hydrogen peroxide, peracetic acid, and/or acetic acid, the metals and metal ions do not play a significant role in the chemistry, use, or efficacy of the composition.
  • the initial starting concentration of peracetic acid is in the range of 0.75 to 1.15 % w/w so that after batching, the resulting post-batch composition has a concentration of peracetic acid in the range of 0. 17 to 0.29.
  • the starting concentrations of hydrogen peroxide and acetic acid are below the post-batching target levels in amounts commensurate with the predictions of the results of integration of Eqns. 34.
  • the surfactant is an alkyl ethoxylate phosphate ester.
  • the batching is carried out at a temperature in the range of 50° to 55° C, and the starting concentrations of 1 .09 % w/w pcraeetic acid, 4.07 % w/w hydrogen peroxide, 4.20 % w/w acetic acid, 0.1 % w/w of PVP polymer, 0.
  • 1 % w/w rridecyl alcohol ethoxylate phosphate ester surfactant about 50 -750 ppm of sulfuric acid, less than 200 ppm of stabili/.ers, and a balance of water having a low content of impurities, i.e., less than 1 ppm of organic compound impurities, halidcs, and mono- and divalent metal ions and metals.
  • the resulting composition has target concentrations values that will equilibrate at about room temperature, namely T - 2O 0 C, to 0.23 % vv/w peracetic acid, 4.4 % w/w hydrogen peroxide, and about 4.9 % w/w acetic acid.
  • fragrance amounting to about 0.1 to about 0.4 % w/w concentration may be added to the post-batching composition.
  • the fragrance is compatible, i.e., of low reactivity, with the constituents of the composition so that the fragrance is not functionally degraded nor is the storage stability of the resulting composition significantly reduced.
  • a batch of microbicidal composition was prepared by the process of the instant invention with 5 days of batching at 55° C and then storage in H DPE containers at room temperature.
  • the target concentrations were:
  • Hydrogen peroxide 4. 10 % w/w 4.50 % w/w 4.50 % w/w
  • Acetic acid 4.20 % w/w 4.80 % w/w 4.88 % w/w
  • the pH of the composition is about 2. 1 and the viscosity is 1.126 mPa-s (cP) at 20° C and 0.74 mPa-s (cP) at 40° C.
  • the viscosity of water is about 1.003 and 0.653 mPa-s (cP), respectively. So, the viscosity of the composition is only about 12% greater than water.
  • a batch was prepared with stalling concentrations of 1.003 % w/w peracetic acid, 4.262 % w/w hydrogen peroxide, and 4.58 % w/w acetic acid.
  • the concentrations of PVP polymer and phosphate ester surfactant each were 0.1 % w/w. After 60 hours of batching, the concentrations were 0.24 % w/w, 4.60 % w/w, and 5.19 % w/w, respectively.
  • Microbicidal efficacy tests have been performed with three lots of microbicidal composition prepared according to the process of the instant invention.
  • the nominal active ingredient concentrations were selected so that they would be representative of the lower half of the range between the certified limits for the composition of Example 1.
  • the hydrogen peroxide concentration was about 4.2 % w/w
  • the pcracetic acid concentration was 0.20 % w/w.
  • the tests comprised several tests according to the AOAC Official Methods of Analysis and as required by the US HPA Disinfectant Technical Science Section ( DlSTSS) Guidelines. At least one of the lots of the composition used in the tests listed below was more than 60 days old at the time of testing.
  • a .soil load typically, 5 % soil
  • neutralization controls to demonstrate the success and reliability of the catalase/thiosulfate neutralization of the active ingredients at the end of the contact time
  • experimental controls to determine recovered fraction of inoculum, titer concentration, and as applicable, to determine cytotoxicity, for example in the virucidal efficacy test.
  • the tests that have been successfully passed when the composition was used as a ready-to-use microbicide with the listed contact times are listed in Table IV, below.
  • VRE Enterococcits faecalis-V 'ancomycin Resistant
  • CA-MRSA Community Acquired- Staphylococcus aureus
  • PRSP Streptococcus pneumoniae- Penicilin Resistant
  • Norovirus F. CaI ici virus
  • Poliovirus type-1 Poliovirus type-1
  • the tested microbicidal composition is expected to have Use Sites that will include the following: Disinfectant for use on hard, non-porous surfaces m: Hospitals and Health Care Facilities such as Clinics, Dental Offices, Nursings, Laboratories, Nursing Homes, Physical Therapy, Physician's Offices. Radiology. Rehabilitation, and Transport Vehicles, Critical Care Areas such as Critical Care Unit (CCU), Emergency Room, Intensive Care Unit (ICU), Neonatal Intensive Care Unit (NICU). Operating Room, Pediatric Intensive Care Unit (PICXJ), Surgery, and Emergency Medical Services, and Other Sites such as Schools, Colleges, Correctional Facilities, Hospitality Establishments such as Hotels.
  • Hospitals and Health Care Facilities such as Clinics, Dental Offices, Detectives, Hospitals, Laboratories, Nursing Homes, Physical Therapy, Physician's Offices. Radiology. Rehabilitation, and Transport Vehicles, Critical Care Areas such as Critical Care Unit (CCU), Emergency Room, Intensive Care Unit (ICU), Neonatal Intensive Care Unit (NICU). Operating Room, Pediatric
  • Typical items that can be treated by the tested microbicidal composition include the following: Hospital. Healthcare, and Critical Use Sites: May be used on hard non- porous surfaces of autoclaves, bed railings, blood glucose monitors, cabinets, caits, chairs, counters, exam tables, gurneys, isolettes, infant incubators and care cribs.
  • IV Intravenous
  • PVC polyvinyl chloride
  • stethoscopes stretchers, tables, bathrooms, sinks, faucets, toilet seats and rims
  • towel dispensers hand railings, stall doors, bath tubs, showers, hampers, tiled walls, telephones, door knobs, vanities, floors, non-porous shelves, and display cases.
  • Hard non-porous exrival surfaces include the following: ambulance equipment, diagnostic equipment, dialysis machines, mammography equipment, patient monitoring equipment, respiratory equipment, ultrasound transducers and probes, patient support ami delivery equipment.
  • the microbicidal composition is compatible with and in typical use will not harm aluminum, low density polyethylene (LDPE).
  • LDPE low density polyethylene
  • HDPE high density polyethylene
  • vinyl painted surfaces
  • polycarbonate polypropylene
  • polyurethane varnish PV 7 C
  • silicone rubber stainless steel
  • medical tubing vinyl rubber, acrylic, brass, LCD screens, copper.
  • Corian®. glass, laminate flooring and eountertops nickel, polycarbonate, porcelain, glass, glazed tile, and many other materials.
  • compositions having lower concentrations of active ingredients than the composition of Examples I and 2 Tests with active ingredients being about 0.05 % w/w peracetic acid and hydrogen peroxide about 1.0 % w/w, which corresponds to a 4-fold dilution of the composition of Example 2. exhibited about 5.6 logs of killing of E. coli bacteria.
  • the compositions of the instant invention may be diluted prior to use as an effective anti-microbial solution.
  • microbicidal compositions of Examples 1 and 2 have been found to be excellent tor mold killing and mold remediation because they kill provide about 5 logs of killing of Aspergillus niger spores on porous surfaces such as textiles, nylon and polyolefin carpet, painted drywall, and painted/sealed masonry with a contact time of about 10 minutes and an application rate that is in the range of about 150 to about 300 rriL/m 2 as sufficient to thoroughly wet the surface and contaminated pores of lhe material.
  • compositions For killing mold, it is further found that use of the composition in a step of cleaning the contaminated surface and removing deposits of mold and infested material, followed by the application of the composition by aerosol spraying, wiping, pouring, or other means, results in effective mold remediation.
  • the compositions provide significant reduction in odors associated with mold, bacteria, and other microbial infestations.
  • the compositions when used as an aerosol spray, especially in conjunction with circulating or non-still air. dramatically remove undesirable odors.
  • Use of the compositions containing fragrance results provides the aesthetic appeal of air- freshening.
  • nucleic acid compounds which include Deoxyribonucleic acid (DNA) and Ribonucleic acid (RNA), are substantially destroyed by such photosensitized UV treatment.
  • the rapid and thorough killing and destruction of nucleic acid compounds arc desirable attributes for uses in response and remediation to biological contamination alter a bio-terrorism event or resulting from a natural disaster, such as a Hood, and for tactical use by military forces or emergency or law enforcement rcsponders. Effective killing is also obtained with the composition being used as a photosensitizer with a contact time of about 1 to about 3 minutes and the subsequent illumination by at least about 45 mJ/ciir fluence of visible light, although treatment without UV does not substantially destroy nucleic acid compounds.

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Abstract

L'invention porte sur un procédé pour le traitement microbicide d'une surface, tel qu'un nettoyage, une désinfection, une stérilisation et une décontamination d'une surface ou d'un objet, par l'utilisation d'une composition antimicrobienne comprenant une solution aqueuse d'acide peracétique et de peroxyde d'hydrogène avec de l'acide acétique, un polymère soluble dans l'eau contenant un lactame, et un agent tensio-actif phosphate ester et peu ou pas de stabilisant, et, selon le procédé, une efficacité microbicide améliorée est obtenue lorsque la composition est appliquée sur une surface en tant que film mince mouillant la surface, de telle sorte qu'un temps de contact plus court pour une réduction fractionnaire désirée dans la population microbienne est obtenu. De plus, des compositions comprennent un photosensibilisateur pour une efficacité antimicrobienne activée par la lumière.
PCT/US2009/057695 2005-01-11 2009-09-21 Composition de peracide/peroxyde, procédé pour la fabriquer avec précision, et procédé pour une utilisation en tant que solution antimicrobienne de film d'évaporation et en tant que photosensibilisateur WO2011005270A1 (fr)

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US13/383,067 US20130251590A1 (en) 2005-01-11 2009-09-21 Peracid/Peroxide Composition, Process for Accurately Making the Same, and Method for Use as an Evaporating Film Anti-Microbial Solution and as a Photosensitizer
AU2009349654A AU2009349654A1 (en) 2009-07-08 2009-09-21 Peracid/peroxide composition, process for accurately making the same, and method for use as an evaporating film anti-microbial solution and as a photosensitizer
CA2767493A CA2767493A1 (fr) 2009-07-08 2009-09-21 Composition de peracide/peroxyde, procede pour la fabriquer avec precision, et procede pour une utilisation en tant que solution antimicrobienne de film d'evaporation et en tant que photosensibilisateur
EP09847184A EP2451483A1 (fr) 2009-07-08 2009-09-21 Composition de peracide/peroxyde, procédé pour la fabriquer avec précision, et procédé pour une utilisation en tant que solution antimicrobienne de film d'évaporation et en tant que photosensibilisateur

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US8883848B2 (en) 2011-07-14 2014-11-11 Ecolab Usa Inc. Enhanced microbial peracid compositions and methods of use at reduced temperatures in aseptic cleaning
US8906963B2 (en) 2011-07-14 2014-12-09 Ecolab Usa Inc Deodorization of peracids
EP2886635A1 (fr) * 2013-12-20 2015-06-24 Chemische Fabrik Dr. Weigert GmbH & Co. KG Produit de désinfection
US9241483B2 (en) 2012-06-29 2016-01-26 Contec, Inc. Fast-acting disinfectant compositions for reducing or eliminating microbial populations
WO2017137408A1 (fr) * 2016-02-12 2017-08-17 Mavena International Ag Moyen de désinfection
WO2017137546A1 (fr) * 2016-02-12 2017-08-17 Sven Reichwagen Moyen de désinfection
EP3136861B1 (fr) 2014-04-28 2020-03-25 American Sterilizer Company Composition contenant du peroxide et agent animicrobien et procédés pour tuer des spores

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US6183807B1 (en) * 1998-08-20 2001-02-06 Ecolab Inc. Antimicrobial composition for cleaning and sanitizing meat products
US20060229225A1 (en) * 2005-01-11 2006-10-12 Clean Earth Technologies, Llc Peracid/peroxide composition and use thereof as an anti-microbial and a photosensitizer
US7247325B2 (en) * 2002-12-12 2007-07-24 K.T.& G. Corporation Crude drug compositions and the process for preparing them

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US6183807B1 (en) * 1998-08-20 2001-02-06 Ecolab Inc. Antimicrobial composition for cleaning and sanitizing meat products
US7247325B2 (en) * 2002-12-12 2007-07-24 K.T.& G. Corporation Crude drug compositions and the process for preparing them
US20060229225A1 (en) * 2005-01-11 2006-10-12 Clean Earth Technologies, Llc Peracid/peroxide composition and use thereof as an anti-microbial and a photosensitizer

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8883848B2 (en) 2011-07-14 2014-11-11 Ecolab Usa Inc. Enhanced microbial peracid compositions and methods of use at reduced temperatures in aseptic cleaning
US8906963B2 (en) 2011-07-14 2014-12-09 Ecolab Usa Inc Deodorization of peracids
US9084421B2 (en) 2011-07-14 2015-07-21 Ecolab Usa Inc. Deodorization of peracids
US9241483B2 (en) 2012-06-29 2016-01-26 Contec, Inc. Fast-acting disinfectant compositions for reducing or eliminating microbial populations
EP2886635A1 (fr) * 2013-12-20 2015-06-24 Chemische Fabrik Dr. Weigert GmbH & Co. KG Produit de désinfection
EP3136861B1 (fr) 2014-04-28 2020-03-25 American Sterilizer Company Composition contenant du peroxide et agent animicrobien et procédés pour tuer des spores
WO2017137408A1 (fr) * 2016-02-12 2017-08-17 Mavena International Ag Moyen de désinfection
WO2017137546A1 (fr) * 2016-02-12 2017-08-17 Sven Reichwagen Moyen de désinfection
CN108697080A (zh) * 2016-02-12 2018-10-23 丹托尔生物科技股份有限公司 消毒剂

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