AU2012393508B2 - Cationic micelles with anionic polymeric counterions compositions, methods and systems thereof - Google Patents

Abstract

The invention relates to polymer-micelle complex. The polymer-micelle complexes include a positively charged micelle selected from the group consisting of a monomeric quaternary ammonium compound, a monomeric biguanide compound, and mixtures thereof. The positively charged micelle is electrostatically bound to a water-soluble polymer bearing a negative charge. The polymer does not comprise block copolymer, latex particles, polymer nanoparticles, cross-linked, polymers, silicone copolymer, fluorosurfactant, or amphoteric copolymer. The compositions do not form a coacervate, and do not form a film when applied to a surface.

Description

The invention relates to polymer-micelle complex. The polymer-micelle complexes include a positively charged mi celle selected from the group consisting of a monomeric quaternary ammonium compound, a monomeric biguanide compound, and mixtures thereof. The positively charged micelle is electrostatically bound to a water-soluble polymer bearing a negative charge. The polymer does not comprise block copolymer, latex particles, polymer nanoparticles, cross-linked, polymers, silicone copolymer, fluorosurfactant, or amphoteric copolymer. The compositions do not form a coacervate, and do not form a film when applied to a surface.

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2012393508 09 Dec 2016

CATIONIC MICELLES WITH ANIONIC POLYMERIC COUNTERIONS COMPOSITIONS, METHODS AND SYSTEMS THEREOF

BACKGROUND OF THE INVENTION

1. The Field of the Invention [0001] The present invention relates to polymer-micelle complexes.

2. Description of Related Art [0001a] Any discussion of the prior art throughout the specification should in no way be considered as an admission that such prior art is widely known or forms part of common general knowledge in the field.

[0002] Cleaning product formulations, including those which contain common antimicrobial agents such as quaternary ammonium compounds and biguanides such as chlorhexidine and alexidine, rely on surfactants and mixtures of surfactants to deliver cleaning (detergency) and antimicrobial efficacy. A key aspect of these processes is the interaction of the surfactants and antimicrobial agents with the solid surfaces of the materials being cleaned, as well as the surfaces of microorganisms, together with the effects of the formulations on the air-water interface (surface tension). Reduction of the surface tension of aqueous formulations, which is directly related to the effectiveness of the wetting of solid surfaces and hence the detergency and antimicrobial processes, can be manipulated through the use of mixtures of surfactants, as is known in the art.

[0003] At a molecular level, surfactants and surfactant mixtures in aqueous media exhibit the ability to adsorb at the air-water, solid-water, and oil-water interfaces, and this adsorption is hence responsible for a wide range of phenomena, including the solubilization of oils in the detergency process, the changes in the properties of solids and dispersions of solids, and the lowering of the surface tension of water. Adsorption of surfactants at interfaces is generally known to increase with surfactant concentration up to a total surfactant concentration known as the critical micelle concentration (CMC). At the CMC, surfactants begin to form aggregates in the bulk solution known as micelles, in equilibrium with the monomeric species of surfactants which adsorb onto the interfaces. [0004] The details of the structures and sizes of the micelles, as well as the properties of the adsorbed layers of surfactants or surfactant mixtures, depend on the details of the molecular shape and charges, if any, on the hydrophilic “headgroups” of the surfactants. Strongly charged headgroups of surfactants tend to repel each other at interfaces, opposing the efficient packing of the surfactants at the interface, and also favoring micelle structures that are relatively small and spherical. The charged headgroups of many surfactants, such

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PCT/US2012/063433 as foe quaternary ammonium compounds, will also introduce a counterion of opposite charge, for example a chloride or bromide ion, into femufetfens.

IWtIS] It is known that the nature of the counterion can affect the repulsion between charged surfactants In micelles and adsorbed layers through a partial screening of the headgroup charges from one· another in surfactant aggregates like micelles, ft is also well known that addition of simple electrolytes, such as sodium chloride, into aqueous solutions can also be used to increase the screening of'like headgroop charges from each other, and thus is a common parameter used to adjust the properties of surfactant micelles, such as size and shape, and to adjust the adsorption of surfactants onto surfaces, fofelfe Addition of significant amounts of simple electrolytes into many formulations, such as hard surface spray cleaners or nonwoven wipes loaded with'.a cleaning lotion, ia undesirable due to residues left behind upon .drying of the formulations, Au alternative method to adjusting the properties of such formulations, including foe wetting of solid surfaces and the antimicrobial.activity, is to include.significwt.amounts of volatile organic, solvents such as lower alcohols or glycol ethers. Volatile organic solvents, however, am. coming under increasing regulation due to their 'potential health effects, and are not preferred by the significant fraction of consumers who desire efficacious cleaning and. disinfecting products with a minimum of'chemical actives, including vblatiles. Ih the healthcare industry, efficacious formulations comprising quaternary ammonium compounds and lower alcohols are known, but are viewed, as haying shortcomings interms of the potential for irritation of confined patients. Such products, pose similar risks to cleaning and clinical personnel who. may be exposed to such products on a daily. basis.

Them is an increasing interest from consumers, and a known need in foe: healthcare and housekeeping industries, to reduce the number of microorganisms on fabrics while using familiar equipment such as washing machines. Concentrated products are required for such an application, due to the high dilution level of fee product in fee rinsewater, typically by a factor -of about 600 times dilution. In the case of formulations comprising quaternary ammonium compounds, high concentrations of the quaternary ammonium compounds in the concentrate are needed in order to ensure an adequate amount of adsorption occurs in a kineticallv relevant time onto the microbes under dilution use conditions. As detailed above, if is desirable, yet very difficult, to manipulate (he., reduce) the CMC of tbs quaternary ammonium compound in such an application. Thus very high concentrations of quaternary' ammonium compounds, which tend to be

2012393508 03 Jan 2018 hazardous to the skin and eyes, are used in the concentrates, in combination with high temperatures and long exposure times.

[0008] Thus, there is an ongoing need for methods and compositions offering fine control of the properties of surfactant aggregates comprising cationic species, especially antimicrobial species such as quaternary ammonium compounds and biguanides.

[0008a] It is an object of the present invention to overcome or ameliorate at least one of the disadvantages of the prior art, or to provide a useful alternative.

BRIEF SUMMARY OF THE INVENTION [0008b] According to a first aspect the present invention provides a composition comprising: a polymer-micelle complex comprising: a positively charged micelle, wherein said positively charged micelle comprises a water-soluble cationic material selected from the group consisting of a monomeric quaternary ammonium compound, a monomeric biguanide, and mixtures thereof, said micelle is electrostatically bound to a water-soluble polymeric counterion bearing a negative charge;

wherein said polymeric counterion does not comprise a block copolymer, latex particles, polymer nanoparticles, cross-linked polymers, silicone copolymer, fluorosurfactant, or amphoteric copolymer;

wherein said composition does not form a coacervate, and wherein said composition does not form a film on a surface; and wherein said composition does not comprise a polyelectrolyte complex.

[0008c] According to a second aspect the present invention provides a composition comprising: a polymer-micelle complex comprising: a positively charged micelle, wherein said positively charged micelle comprising a water-soluble cationic material is selected from the group consisting of a monomeric quaternary ammonium compound, a monomeric biguanide, and mixtures thereof, said micelle is electrostatically bound to a water-soluble polymeric counterion bearing a negative charge;

wherein the polymeric counterion is selected from a copolymer of a polysaccharide and a synthetic monomer; and wherein said polymeric counterion does not comprise a block copolymer, latex particles, polymer nanoparticles, cross-linked polymers, silicone copolymer, fluorosurfactant, or amphoteric copolymer;

and wherein said composition does not comprise a polyelectrolyte complex.

[0009] Described herein is a composition comprising a polymer-micelle complex comprising a positively charged micelle comprising a water-soluble cationic material

2012393508 09 Dec 2016 selected from the group consisting of a monomeric quaternary ammonium compound, a monomeric biguanide compound, and mixtures thereof. The micelle is electrostatically bound to a water-soluble polymer bearing a negative charge. The water-soluble polymer bearing a negative charge comprises a hybrid copolymer derived from a synthetic monomer or monomers chain terminated with a hydroxyl-containing natural material synthesized with a free radical initiator. The polymer does not comprise block copolymer, latex particles, polymer nanoparticles, cross-linked polymers, silicone copolymer, fluorosurfactant, or amphoteric copolymer. The complex advantageously does not form a coacervate, and does not form a film on a surface (e.g., a durable film remaining after application of the composition to the surface).

[0010] Also described herein is a composition comprising a polymer-micelle complex comprising a positively charged micelle comprising a water-soluble cationic material selected from the group consisting of a monomeric quaternary ammonium compound, a monomeric biguanide compound, and mixtures thereof. The micelle is electrostatically bound to a water-soluble polymer bearing a negative charge. The water-soluble polymer bearing a negative charge comprises a hybrid copolymer derived from a synthetic monomer or monomers chain terminated with a hydroxyl-containing natural material synthesized with a free radical initiator. The polymer does not comprise block copolymer, latex particles, polymer nanoparticles, cross-linked polymers, silicone copolymer, fluorosurfactant, or amphoteric copolymer. The composition advantageously does not form a coacervate, and does not include alcohols (e.g., particularly lower alcohols) or glycol ethers.

[0011] Further described herein is a composition comprising a polymer-micelle complex comprising a positively charged micelle that is electrostatically bound to a watersoluble polymer bearing a negative charge. The water-soluble polymer does not comprise block copolymer, latex particles, polymer nanoparticles, cross-linked polymers, silicone copolymer, fluorosurfactant, or amphoteric copolymer. The composition advantageously does not form a coacervate and does not form a film on a surface. In addition to the polymer-micelle complex, the composition further comprises an oxidant.

[0012] In another embodiment, the composition includes an oxidant, which may be selected from the group consisting of: hypohalous acid, hypohalite or sources thereof;hydrogen peroxide or sources thereof, peracids, peroxyacids peroxoacids, or sources thereof ;organic peroxides or hydroperoxides, peroxygenated inorganic compounds;solubilized chlorine, solubilized chlorine dioxide, a source of free chlorine,

2012393508 09 Dec 2016 acidic sodium chlorite, an active chlorine generating compound, or a chlorine-dioxide generating compound, an active oxygen generating compound, solubilized ozone, N-halo compounds, and combinations thereof.

[0013] In another embodiment, the positively charged micelle comprises a monomeric quaternary ammonium compound. In another embodiment, the positively charged micelle further comprises a nonionic surfactant. In another embodiment, the nonionic surfactant comprises an amine oxide. In another embodiment, the positively charged micelle comprises a monomeric biguanide compound. In another embodiment, the monomeric biguanide compound is selected from the group consisting of chlorhexidine, alexidine, and combinations thereof.

[0014] In another embodiment, the composition is free of iodine, iodine-polymer complexes, nanoparticles of silver, nanoparticles of copper, nanoparticles of zinc, triclosan, p-chloromethyl xylenol, monomeric pentose alcohols, D-xylitol and its isomers, D-arabitol and its isomers, aryl alcohols, benzyl alcohol, and phenoxyethanol.

[0015] In another embodiment, the composition further comprises a water-immiscible oil that is solubilized into the positively charged micelle. In another embodiment, the composition is free of water-miscible alcohols and glycol ethers.

[0016] In another embodiment, the water-soluble polymer bearing a negative charge is selected from the group consisting of a copolymer of a polysaccharide and a synthetic monomer, copolymers comprising maleic acid, a copolymer of dimethylacrylamide and acrylic acid, a copolymer of acrylic acid and styrene, a copolymer of sulfonated styrene and maleic anhydride, and combinations thereof.

[0017] In addition, described herein is a method for cleaning a surface. The method comprises contacting a surface with a composition comprising a polymer-micelle complex. The polymer-micelle complex includes a positively charged micelle electrostatically bound to a water-soluble polymer bearing a negative charge. The positively charged micelle comprises a water-soluble cationic material selected from the group consisting of a monomeric quaternary ammonium compound, a monomeric biguanide compound, and mixtures thereof. The water-soluble polymer bearing a negative charge does not comprise block copolymer, latex particles, polymer nanoparticles, crosslinked polymers, silicone copolymer, fluorosurfactant, or amphoteric copolymer. The composition advantageously does not form a coacervate, and does not form a film on a surface.

2012393508 09 Dec 2016 [0018] Also described herein is a method for treating a surface. The method comprises mixing a first composition comprising a water-soluble polymer having a negative charge with a second composition comprising a positively charged micelle. The water-soluble polymer bearing a negative charge does not comprise block copolymer, latex particles, polymer nanoparticles, cross-linked polymers, silicone copolymer, fluorosurfactant, or amphoteric copolymer. The positively charged micelle comprises a water-soluble cationic material selected from the group consisting of a monomeric quaternary ammonium compound, a monomeric biguanide compound, and mixtures thereof. The method further comprises contacting the composition resulting from mixing of the two parts with a surface so as to treat the surface.

[0019] Described herein is a method for treating bacterial endospores, fungal spores, or viruses. The method comprises contacting the endospores, spores, or viruses with an aqueous composition that comprises a polymer-micelle complex comprising a positively charged micelle that is electrostatically bound to a water-soluble polymer bearing a negative charge. The positively charged micelle comprises a water-soluble cationic material selected from the group consisting of a monomeric quaternary ammonium compound, a monomeric biguanide compound, and mixtures thereof. The water-soluble polymer bearing a negative charge does not comprise block copolymer, latex particles, polymer nanoparticles, cross-linked polymers, silicone copolymer, fluorosurfactant, or amphoteric copolymer. The composition does not form a coacervate.

[0020] Also described herein is a method for killing bacteria arising from germination of bacterial endospores or fungi arising from germination of fungal spores. The method comprises contacting the endospores with an aqueous composition that comprises a polymer-micelle complex comprising a positively charged micelle that is electrostatically bound to a water-soluble polymer bearing a negative charge. The positively charged micelle comprises a water-soluble cationic material selected from the group consisting of a monomeric quaternary ammonium compound, a monomeric biguanide compound, and mixtures thereof. The water-soluble polymer bearing a negative charge does not comprise block copolymer, latex particles, polymer nanoparticles, cross-linked polymers, silicone copolymer, fluorosurfactant, or amphoteric copolymer. The composition does not form a coacervate.

[0021] Further described herein is a system comprising a dual chambered device comprising a first chamber, a second chamber, a first composition in the first chamber, and a second composition in the second chamber. The first composition comprises a water7

2012393508 09 Dec 2016 soluble polymer bearing a negative charge that does not comprise block copolymer, latex particles, polymer nanoparticles, cross-linked polymers, silicone copolymer, fluorosurfactant, or amphoteric copolymer. The second composition comprises a positively charged micelle comprising a water-soluble cationic material selected from the group consisting of a monomeric quaternary ammonium compound, a monomeric biguanide compound, and mixtures thereof. The system provides the ability to mix the first and second compositions (e.g., prior to application) to result in a mixed composition for application in which the micelle is electrostatically bound to the water-soluble polymer to form a polymer-micelle complex. The resulting mixed composition advantageously does not form a coacervate, and does not form a film on a surface.

[0022] Also described herein is a system comprising a dual chambered device comprising a first chamber, a second chamber, a first composition in the first chamber, and a second composition in the second chamber. The first composition comprises a watersoluble polymer bearing a negative charge that does not comprise block copolymer, latex particles, polymer nanoparticles, cross-linked polymers, silicone copolymer, fluorosurfactant, or amphoteric copolymer. The second composition comprises a positively charged micelle comprising a water-soluble cationic material selected from the group consisting of a monomeric quaternary ammonium compound, a monomeric biguanide compound, and mixtures thereof. The system provides the ability to mix the first and second compositions to result in a mixed composition for application in which the micelle is electrostatically bound to the water-soluble polymer to form a polymer-micelle complex. The resulting mixed composition advantageously does not form a coacervate, and does not form a film on a surface. The resulting composition does not include alcohols or glycol ethers.

[0023] Also described herein is a system comprising a dual chambered device comprising a first chamber, a second chamber, a first composition in the first chamber, and a second composition in the second chamber. The first composition comprises a watersoluble polymer bearing a negative charge that does not comprise block copolymer, latex particles, polymer nanoparticles, cross-linked polymers, silicone copolymer, fluorosurfactant, or amphoteric copolymer. The second

7a

Dec 2016 composition comprises a positively charged micelle comprising a water-soluble cationic material selected from the group consisting of a monomeric quaternary ammonium compound, a monomeric biguanide compound, and mixtures thereof. At least one of the first or second compositions further comprises an oxidant. The system provides the ability to mix the first and second compositions (e.g., prior to application) to result in a mixed composition for application in which the micelle is electrostatically bound to the watersoluble polymer to form a polymer-micelle complex. The resulting mixed composition (Τ') advantageously does not form a coacervate, and does not form a film on a surface.

CG

O\ [0024] Further features and advantages of the present invention will become apparent

CG

CM to those of ordinary skill in the art in view of the detailed description of preferred

O embodiments below. -7

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PCT/US2012/063433

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS F Definitions ffid2$] Before describing the present invention in detail, it is to be understood that this invention Is not limited to particularly exemplified systems or process'parameters feat may, of course, vary. It is also to be understood font the terminology used herein is for the purpose of describing particular embodiments of the invention only, and is not intended to limit the scope of the foventtoo in any manner, (0026] All publications, -patents and patent applications cited herein, whether supra or infra, are hereby incorporated by reference in their-entirety to the- same extent as if each individual publication, patent or patent application was specifically and individually indicated to he incorporated by reference.

|0O2?] The term '“comprising” which Is synonymous with “including,” “containing.,” or “characterized by,” Is inclusive or open-ended and does not exclude additional, unrecited elements or method steps.

The term “consisting essentially of’ limits the scope of a claim to the specified materials or steps “and those that· do not materially aifect the basic and novel charaotefistiefs)” of the claimed invention., pi>j The term “consisting of’ as used herein, excludes -any element, step, or ingredient not specified. in the claim, [0030] It mbst. be noted that, as used in this specification and ths appended claims». the singular forms MT MM and “the” include plural referents unless the content clearly dictates otherwise. Thus, for example, reference to a “surfactant” includes one, two or more such surfactants.

fwti The term water-soluble polymer as used herein means a. polymer which gives an optically clear solution free of precipitates at a concentration of 0,001 grams per 100 grams of water, preferably 0.01 grams/100 grams of water, more preferably 0,1 grams/100 grams of wafer, and even mom preferably I gram or more per NX) grams of water, at 25 NT [0032( As used herein, foe terra “substrate” is intended to include any material that Is used to clean an article or a surface. Examples of cleaning substrates include, but are not limited to nonwovens, sponges, films and similar materials which can he attached to a cleaning implement, such as a floor mop, handle, or a hand held cleaning tool, such as a toilet cleaning device.

WO 2014/070201

PCT/US2012/063433 (W33) As used herein, the terms ’‘nonwoven’* or nonwoven web means a web having & structure of individual fibers or threads which are interlaid, but not In an identifiable manner as in a knitted web.

(M341 As used herein, the term “polymer” as used in reference to a substrate (e.g., a non-woveu substrate) generally includes,. but b not limited to, homopoiymers, copolymers, such as for example, block, graft, random and alternating copolymers, terpoiymets, etc. and biends and modifications thereof. Furthermore, unless otherwise specifically limited, the term ‘‘polymer” shall include all possible geometrical configurations of the molecule. These configurations include, but am not limited to isotaetie, syndloiactio and random symmetries.

|β®3·§] Unless defined otherwise, all technical and scientific terms used herein have the same- meaning as commonly understood by one of ordinary skill in the att to which the invention pertains. Although a number of methods and materials similar or equivalent to those described herein can be used in the practice 'of the present invention, the preferred materials and methods are described herein.

fn the application, effective amounts are generally those' amounts listed as tite .ranges or levels of ingredients in the descriptions, which follow hereto. Unless otherwise stated, amounts listed ih percentage Cbviba’s”} are In wt% '{based on 100 weight% active) of the particular material present. ih the referenced composition, -any remaining percentage being water or .an aqueous- carrier sufficient to. account for 100% of the composition, unless otherwise noted. For very low weight percentages, the term “ppm” corresponds to pads per -million on a weight/weight basis may be used, noting that 1-.0 wtH corresponds to 10,000 ppm.

B„ Introduction (0037) The present inventors have now determined that the use of water-soluble polymers comprising groups which bear or are capable, of bearing -an electrostatic charge as counterions (polymeric counterions) for micelles comprising at least one ionic surfactant selected such that the net electrostatic charge on the micelle is opposite to that of the polymeric, counterion can yield, simultaneously, very fine control of the interactions between the headgroups of the ionic surfactant as well as the adsorption of the ionic surfactant at the air-liquid and solid-liquid interface when corn-positions are adjusted such, that precipitates or coacervates are completely absent from at least some embodiments of the compositions.

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PCT/US2012/063433 [S938] Surprisingly, such compositions m which micelles with polymeric counterions exist as soluble, thermodynamically stable aggregates exhibit very high adsorption activity at both the «ir-liquid and solid-liquid Interfaces. Such characteristics completely eliminate the need to adjust formulations such that they change their solubility, forming eoacervates or precipitates, in order to deliver adsorption of useful amounts of ionic surfactant and polymer to these interfaces. The micelle-polymer complexes formed when a watersoluble polymer comprising groups which bear or -are capable of bearing an electrostatic charge opposite to that of a micelle are usually found to be somewhat larger than the micelles alone. The addition of a water-soluble polymer bearing electrostatic charges opposite to that of at least one surfactant in aqueous solutions often can reduce the CMC of the given surfactant by a significant fraction, which can also have the effect of reducing the-cost of certain formulations.,

101)39] Fine control of surfactant interactions within micelles via -addition of oppositely charged polymers according to the invention has· also beeo found to increase the oil solubilization ability of the micelles to. -an unexpected degree. Without befog bound by theory, it is believed that this effort is due to the uniquely high counter Ion charge density carried by the charged polymer, which is distinctly different from regular counter ion effect provided by typical salting out electrolytes. This Is thought to increase the .degree of' Counter lots association of charged, polymers compared to regular electrolytes, even at very low polymer concentrations, which its turn promotes increases in micellar sire and an increase in oil solubilization efficiency. The inventors have discovered- that the oil solubilization boosting effect develops only if the. interactions are fine-tuned such that the system is felly free of coacervate yet. is near the water soluble/coacervate phase, boundary.

Formulations comprising mixed micelles of a cationic germicide (quaternary ammonium compound or a water-soluble salt of a biguanlde such as -chlorhexidine or alexidine), optionally a second surfactant such as as amine oxide, and a water-soluble polymer bearing an anionic charge can be made with control of the size and Pel electrostatic charge. It is believed, without being hound by theory, that tire anionic polymers act as polymeric counterions to the cafiomeally charged micelles, either increasing the -size of these micelles or collecting groups of these micelles into soluble, thennodynamically stable aggregates which have enhanced activity at solid surfaceaqueous solution, interfaces, including the surfaces of microorganisms such as bacteria, viruses, fungi, and bacterial spores. This reduces or even eliminates the need for the

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PCT/US2012/063433 presence of an alcohol fo -enhance or “potetfoate” the antimicrobial performance of the cationic biocide.

[0043] in -one embodiment, the compositions can comprise alcohol In another embodiment, the compositions can be completely free of water-miscible lower alcohols. Similarly, the compositions can comprise water-miscible glycol ethers or be completely free of the materials, sometimes referred to as “co-solvents” or “co-surfactants”. Compositions free of the lower alcohols or glycol ethers not only, can provide acceptable antimicrobial performance at lower cost, but also reduce irritation to patients and healthcare workers, while providing formulations which can be considered mom environmentally friendly or sustainable due to lowered total actives levels and lack of volatile organic compounds. Those embodiments ihst are free of alcohols or cosolvents are especially suited as sanitizing cleaners, disinfecting cleaners or treatments for pets in home or veterinary applications.

[01)42] Surprisingly, the compositions, even without alcohol, show inactivation of nonenveloped viruses -such as rhinov-irus, even though cationic biocides are typically not considered as. active against .such microorganisms. it is believed, without being bound by theory, that the- interfacial activity of the micelles with polymeric counterions is so significant that the'viral proteins are. disrupted, denatured or otherwise damaged such that the viral particles are rendered noiwnfective, even when they are exposed to significant dilutions such as those, during the microbiological test -protocols. Surprisingly., the compositions, even without alcohol, exhibit activity against mycobacteria, (bacteria responsible for tuberculosis), which am. heretofore known to be relatively resistant to the actions of cationic- germicides in aqueous formulations lacking a co-solvent or alcohol. Such resistance Is thought to be due to the thick, waxy outer membranes characteristic of this type of bacteria.

[1)1)43] The compositions may be useful as ready to use cleaners, and may be applied via spraying or -pouring, but may also he delivered by loading onto nonwc»ven substrates to produced pre-moistened wipes. The compositions may also he provided as concentrates that are diluted by the consumer (e.g., with tap water). Such concentrates may comprise a part of a kit for refilling a container (also optionally included within such a kit), such as an. empty trigger sprayer. The eornpositions may also be provided as concentrates for ssngfouse (unit dose) products for cleaning floors, -windows, counters, etc. Concentrated dishwashing lipoids that provide antibacterial performance upon very high dilutions may be formulated, as may concentrates which can deliver sanitization of laundry via addition

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PCT/US2012/063433 ίο ordinary washloads.. Such compositions and results may be achieved without inclusion of triclosan. Such concentrated products also can provide protection against the growth of biofihns and associated outgrowth of molds in drain tines' associated with automatic dishwashers, laundry washing machines, and the like, reducing undesirable odors which are sometimes encountered by consumers.

(0044) Concentrated forms of the formulations may also he provided which may be diluted by the consumer to provide solutions that ere then used. Concentrated forms suitable for dilution. via automated systems, in which the concentrate i s diluted with water, or in which two solutions are combined in a given ratio to provide the final use formulation are possible.

The formulations may be in the form of gels delivered to a reservoir or surface with a dispensing device. They may optionally be delivered, in single-use pouches comprising. a soluble film.

The superior wetting,. spreading, and. cleaning performance of the systems make them especially suite hie for delivery from .aerosol packages comprising either -single or dual chambers.

The compositions arc useful in providing a reversal in the native surface charge (I.e.., seta potential) of bacterial endospores and other microorganisms from anionic (negative) to cationic (positive), or at. least, to less'anionic as a result of contact with the compositions. Such a change in. charge .increases the electrostatic binding of the microorganisms to cleaning implements, such as pre-moistened nonwoven wipes, which typically have a native- anionic (negative)- charge-, hence improving the removal of the microorganisms from surfaces being -cleaned. Because the compositions-provide robust adsorbed layers of germicidal materials such as quaternary' ammonium compounds and biguanides, they are able to kill bacteria which arise from foe germination of endospores under favorable environmental conditions. Such compositions may thus find utility in various applications including combating weaponized spores such as ffocP/fo /fofomcfo Low residue treatment solutions tor surfaces which .may be infrequently cleaned and which may be subject to outgrowth of bacteria or molds from contamination by air-borne spores can be produced with the compositions. In other words, foe compositions do not result in the formation of a durable film on a surface after application. Simple rinsing is sufficient to remove any residue, and even without rinsing, those embodiments or me invention that do exhibit a residue do not form macroscopic durable films. Thus, any

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PCT/US2012/063433 remaining residue does not constitute a film, but is easily disturbed, destroyed, or otherwise removed.

The invention also contemplates use of the polymer»m.icelie complexes for delivering improved sanitization of surfaces and protection of treated surfaces through the same mechanism of enhanced adsorption of cationic biocides such as quaternary ammonium salts and biguanides onto living bacteria, bacterial endospores, fongai spores, and viruses. Examples of antimicrobial activity .exhibited by the inventive compositions include, but are not limited to killing, of living bacteria, killing of bacteria upon germination from bacterial endospores-, killing of living fungi, killing of fungi upon germination from spores, damage to the proteins or lipids- of viral capsids resulting. in decreased or inhibited iniectivity to a target host, adsorption onto the proteins of viral capsids resulting in blockage of the protein from a target site in a host, or increased binding of a bacterial eodo&pore, a. fungal spore, or a virus to a non-animate surface resulting in a decrease in physical transmission to a host which in turn decreases the transmission of disease of the host or addition contamination of other surfaces. Depending on application use, the surface may be hard, sob, animate- (e.g,, skin), non-animate, or other type surface.

IIEBeimfrioa of Dost and F/rfoet Parameters

As will fee shown m the examples below, very tine control of the interactions between micelles comprising an ionic surfactant- arid water-solhhie polymers bearing electrostatic charges opposite to that of the .micelles, end hence functioning ..as -polymeric counterions to the micelles, eon be achieved through manipulation of the relative number of charges due to ionic- surfactants In the system and those charges due to the watersoluble polymer.

[bhSbi Mixtures of surfactants, including mixtures of ionic and nonionic surfactants, may be employed. A convenient way to describe the not charge on the micelles present in the formulations of the instant invention is to calculate the total number of equivalents of the charged headgroups of the surfactants; both anionic and cationic, followed by a determination of which type of charged headgroup is in excess in the-formulation.

|W511 Surfactants bearing two opposite electrostatic charges in the formulations, such as carboxy-betaines and sulfo-betaines, act as “pseudo-nomobic’'' surfactant's in the compositions of the instant invention, since the net charge, on them will be sero. 'Thus, the calculation of Dost will not involve -the concentration of such psendo-nonionic surfactants. Similarly, phosphatidyl choline, an edible material which is a major component of the

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PCT/US2012/063433 surfactant commonly referred to as lecithin,, contains both an aniouicaily charged phosphate group and a cation toady charged choline group In its headgroup region, and thus would be treated as pseudo-nonlonic in the inventive compositions. On the other hand, a material such as phosphatidic acid, which contains only an. anionieally charged phosphate group as its headgroup, would contribute to the calculation of Dnet. as described below.

|WS2] Some surfactants, such as amine oxides, may be uncharged (nonionic) over a wide range of pH values, but may become charged (e.g>, cationically in the ca.se of amine oxides) at acidic pH values, especially below about pH 5. Although snob components may not. contain two permanent and opposite electrostatic charges, applicants have found that they may be treated explicitly as nonionic surfactants in the inventive formulations, As taught herein, inventive compositions which are free of coacervates and precipitates that comprise mixed' micelles of an amine oxide and a cationic germicide. such as a quaternary ammonium compound and a water-soluble polymer' bearing anionic charges may he readily formed through adjustment of the P/Ctoet parameter, the Dost parameter, and/or the presence of adjuvants such as electrolytes, without regard'to the precise value bi any catipnic charge, present on-fee amine, oxide, [WS3] Two parameters can be defined for any mixture of surfactants comprising hcadgroups bearing, or capable.or bearing, anionic of cationic charges ormixtures of both, said parameters being D anionic and Deatibme.

D anionic, will be defined as ~

D aniohic ~ (4) x(Eq anionic)

D cationic will be defined asD cationic nd) x dy cationic) [WS4| A final parameter expressing the net charge on the micelles is Dnet, which is simply the sum of the parameters D anionic and D cationic, i.e..

Duet 0 cationic + D anionic in the. expressions above, Eq anionic is the sum of the total number of equivalents or charges due. to the headgroups of all anionic surfactants present, For a formulation comprising a single surfactant with a headgroup bearing or capable of bearing an anionic charge:

Eq anionici (C aruonicj x Q anioniC|)/M anieuicj wherein C anionic^ is the concentration of a surfactant with anionic hsadgroups in grams/per 100 grams of the formulation or use composition, Q anionic > is. a number

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PCT/US2012/063433 representing the number of anionic charges present on the surfactant, which may be viewed as having the units equivalents per snob, and M anionic? is the molecular weight of the surfactant in grams/mole.

fSBSb) For a formulation comprising two different surfactants with anionic he-adgronps, the parameter Eq anionic would he calculated as the sum:

Eq anionic- ™ Eq anionic? t· Eq anionic^ ™ (C anionic? x Q aaionici)/M anionic? * (C anionic^ x Q anionicsXM anionic^ (0057) Commercially available surfactants are often mixtures of materials due to the presence of a distribution In the number of, for example, methylene groups in the hydrophobic “tai ls” of the surfactant. It is also possible that a distribution in the number of charged “headgroups”' per molecule could exist In practical work with commercial materials, it may also be acceptable to use an “average’'’ molecular 'weight of an “average” number of anionic, (or cationic) charges per molecule quoted by the manufacturer of the surfactant In the calculation of D anionic '(of D cationic), it may also he acceptable to use values of the Eq anionic (or Eq cationic) derived from direct analysis of a surfactant raw materfaf (0058) In the expressions above, Eq cationic is the sum of the total number of equivalents or charges due to the headgroups of all cationic surfeeffots present. For a formulation'comprising .a single surfactant with aheadgroup hearing or capable of bearing a cationic charge:

Eq cationic? ~ (C cationic? x.Q cationic? )/M-cationic?

wherein C cationic? is the concentration of a surfactant whh cationic headgroups in. grams/per 100 grants of the tbrmulation or use composition,· Q cationic? is a numberrepresenting the number of cationic charges present on the -surfactant, which may be viewed as having the units equivalents per mole, and M cationic? Is the molecular weight of the surfactant in. gmm.s/mole. In cases where the lormnlation comprises more than one surfactant with cationic headgroups, the summation, of the equivalents of cationic headgronps would.be performed-as in the case of the anionic surfactants described above, [OOSffl As an example, consider a formulation comprising a mixture of a single anionic surfactant and a single nonionic surfactant, but lacking a cationic surfactant. Furthermore, consider the anionic surfactant is present at a concentration of 2 wt% or 2 grams/100 grams of the formulation, has one group capable of developing an anionic charge per molecule, and has a molecular weight of 20.0 grams/mole.

Then Eq anionic ™ (2 x 1)/200 -0,0.1 equivalentsrfOOg in the formulation.

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Then, B aniomc ™ (-Ί) x. (0,01)- -0.01,

And D cationic - 0.

Thus, Duet - (0 - 0,01) - -0.01,

As a second exampb, consider a fbrmulation comprising a mixture of a single anionic surfactant, a single nonionic surfactant, and a single cationic surfactant which Is a germicidal quaternary ammonium compound.. Furthermore, consider the anionic surfactant is present at a concentration of 2 wt% or 2 grams/100 grams· of die formulation, has one group capable of developing an anionic charge per molecule, and has a molecular weight, of 200 grams/mole. Furthermore, consider' the cationic surfactant is present in &e formulation at a concentration 0.1 wt% or 0.1 grams/100 grams of the formulation, has one group capable of developing a cationic charge per molecule, and has a molecular weight of 300 gramsAnole.

Then Eq anionic ™ (2 ,x 1)/200 - 0..01 equivalents/! 00 g in the formulation.

Assd Bq cationic (0.1 x 1)/.300 - 0,00033 equivalents/ 100 g in the formulation.

Then, D anionic ““ (-1) x (OBI) -0,01,

And D cationic' - fl) x (0,00033) - 40.00033,

Thus, BnA - -40.00033 3- (-0,01) - -0.00067,

This negative -value clearly indicates that the number of anionically charged headgroups .in the mixed micelles comprising the anionic, nonionic, and cationic surfactants present, in the formulation exceed that of the cafionically charged headgroups, (0001.( A second parameter which can be used to describe the instant invention and the interactions between a polymeric counterion and surfactant micelles bearing a net charge is the ratio WDnet. P is the number of charges (in equivalents) due to the polymeric counterion present per 100 grams of the formulation and can be calculated as follows;

P - (C polymer x F polymer x Q polymer x Z)/M polymer, where C polymer is the concentration of the polymer in the formulation in grants/100 grams of formulation, F polymer Is the weight fraction of the monomer unit bearing or capable of bearing a charge with respect to the total polymer weight and thus ranges from 0 to 1, Q polymer is the number of charges capable of being developed by the monomer unit capable of hearing a charge and can be viewed as having the units .equivalents per mole, Z is an integer indicating the type of charge developed by the monomer unit, and is equal to +1 when the monomer' unit can develop a cationic charge or is equal to -1 when

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PCT/US2012/063433 the monomer unit can develop an anionic charge, end M polymer is the molecular weight of the monomer unit capable of developing a charge, in gpanis/moie.

[0002-1 For example, consider a formulation comprising polyacrylic acid homopolymer (PAA) as a water-soluble polymeric counterion. PAA is capable of developing 1 anionic charge per acrylic acid monomer unit (which has a molecular weight of 72 grams/mole), and hence Q polymer^:::: 1 and Z -1. In addition, the pojymer is a homopoiymer, so F polymer ~ 1. If the PAA is present in the formulation at a .concentration of 0.1 grams/100 grams of the formulation, the value of P would he calculated as follows:

F - (0.1 x 1 x 1 x - I )/72 ' -0.00139.

(0063) Using the Dnet value of -0.00707 calculated in the example described above for a mixture of an. anionic, cationic, and nonionic surfactant, the ratio P/Unet would he •calculated as:

F/Dnet = (0.00139)/(-0.00967) = *0444 [00641 This positive· value of Pfofoet not only indicates the ratio of the charges due. to the polymeric counterion and the· net charge on the mixed micelles, but also indicates, since it Is a positive number, that the charge on the polymeric counterion and the net. charge on tbs mixed micelles are the same, both being anionic. In this esse, there would he no net. electrostatic interaction between the polymeric counterion -and. the mixed micelles expected, and hence -the example would not be within the scope of the instant invention, which requires that the polymeric counterion must be of opposite .charge to that of the headgrbnps of the surfactant or mixture of surfactants comprising the micelle,

HWI Now consider another example in which the formulation comprises, a. mixture of a single anionic surfactant, a single non ionic -surfactant, and a single cationic surfactant and a single cationic surfactant w hich Is a germicidal quaternary ammonium compound. Furthermore, consider the anionic surfactant is present at a concentration of 0.2 wi% or 0.2 grams/100 grams of the formulation, has one group capable of developing an anionic charge per molecule, and .has a molecular weight of 200 gmms/mole. Furthermore, consider the cationic surfactant is present in the formulation at a concentration t ,0 wl% or 1.0 -grams/100 grams of the formulation, has one group capable of developing a cationic charge per molecule, and has a molecular weight of 300 gtsms/mofc.

Then Bq anionic = (0.2 x 1)/200^:!!: 0.001 equivalents/!00 g in the formulation. And Eq cationic - (B0 x .1)/300 ~ 0.00333 equivalents/ BOO g in the formulation.

Then, D anionic = (-.1) x (0.001)-= »0.001.

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And D cationic - (1) x (0,00333)^:t:: /-0,00333, [0066) Thus, Dnet - +0.00333 T (-0.001) ^::: +0.00233, This positive value clearly indicates that the number of eationically charged headgreups in the mixed micelles comprising the anionic, nonionic, and cationic surfactants present in the formulation exceed that of the anionically charged hsadgtoups. Such mixed micelles would be suitable for interaction with a polymeric counterion bearing anionic charges.

Continuing this example, now consider that the formulation also comprises a polyacryiic acid homopoiyfoer (FAA) as a water-soluble polymeric counterion. PAA is capable of developing 1 an ionic charge per acrylic acid monomer unit (which has a molecular weight of 72 gmms/mole), and hence Q polymer1 and £--1. In addition, the polymer is a-homopolymer, so F polymer ~ 1. If the PAA is present in the formulation at a concentration of '0.1 grams/190 grams of the formulation,. the value of P would' be. calculated as follows;

P = (0. { x .1 x 1 x -3.)/72 - 41,00/139.

Thus, for this formulation, P/Dnet would he calculated as;

P/Bnet - (-0.00139)/(+0.00233) « - 0.5966.

(W6S) This negative value of P/Unes indicates that the. charges on the polymeric counterion .(PAA) and the mixed micelles are opposite to one another, indicating that there Pw be an electrostatic interaction between the FA A and. the micelles, and hence the composition may he within the scope-of the instant invention. Of course, the value-of P/Bnet also indicates foe ratio of-the charges due to the .polymeric counterion and the net charge on the mixed micelles, |00Of Alternatively, if foe number of equivalents of charged groups present per gram of polymer is available from the manufacturer, or can be derived font the synthetic route used to create the polymer, or can he derived from analysis of the polymer, then F may also be calculated based on that information.

(0070) For example, P ^::s (C polymer x Bq polymer x £), where Cpoiymer and .2 are defined as above, and Bq polymer is foe number of equivalents of groups per gram of polymer with a charge consistent with the value of 2 used. For example, if a watersoluble polymer that is described as having 0.0139 equivalents per gram of polymer (actives) of an anionlsaliy charged monomer, sod this polymer is used in a formulation at a. concentration of 0.1 grams/lOO grams of foe formulation, F is calculated as follows:

P-(0T x 0.0139 x-1)- 0.00139,

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PCT/US2012/063433 [W71] This value of to wife the sums Dnet value used m the example above in which the micelles comprising an anionic surfactant, a nonionic surfactant and a cationic surfactant which is a quaternary ammonium compound, may then be used to calculate the ratio fi/Dnet:

P/Dnet - (-0.00139)/+-00213) - - 0.596+ which yields the same result as described above.

|9+7+l In the case of copolymers comprising more than one monomer of like charge or capable of developing a like charge, then the P value calculated for the formulation would be the sum of the P values calculated for each of the appropriate monomers comprising the polymer used.

[W73| Finally, in practical work, the absolute value of P/Bnet is an indicator of which charges are in excess and which are in deficiency in. formulations of the instant invention. When the absolute value of P/ftoct is greater than. 0 but. less then .1, the number of charges due to groups on the polymeric counterion is less than the net number of charges due- to the headgroups- of the ionic surfactant or 'surfactants, comprising the micelles, i.e. the polymeric-counterion is in deficiency. When the absolute value of WDoet is greater than 1, the polymeric counterion is in excess, and of course^, when the absolufo value of P/Dnet “ i, the number of charges. due· to the hcadgronps of the-polymeric, counterion equals the net number of charges of the ionic surfactant or surfactants Comprising the micelles.

{·¥. Suitable Polymers jWMf Many -polymers are suitable for use a.s polymeric counterions in the instant invention, in one embodiment, the polymers are waisr-sotohte as defined herein. The polymers -may be· homo.polyrn.ors or copolymers, and they may be linear' or branched. Linear polymers may be preferred in at least some embodiments, Copolymers may be synthesized by processes expected to lead to statistically random· or so-called gradient type copolymers, to contrast, water-soluble block copolymers are not suitable, since these types of polymers may form aggregates or micelles, in which the more hydrophobic block or blocks comprise the core of the aggregates or micelles and the more hydrophilic block comprises a “corona” region in contact with water. It is thought that these self-assembly -processes compete with the electrostatic interactions required for a water-soluble polymer to serve as a polymeric counterion with ordinary surfactant micelles. Although mixtures of water-soluble polymers are suitable in at least some embodiments of the presentinvention, fee mixtures selected should not comprise block copolymers capable of forming so-called “complex coacervate” micelles- through self-assembly, since this micelle

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PCT/US2012/063433 formation process also competes with the interaction of the water-soluble polymer as a polymeric counterion to ordinary surfactant micelles. When the polymers are copolymers, the ratio of the two or more monomers may vary over a wide range, as long as water solubility of the polymer is maintained, (W7S| in an embodiment, the polymers should be.water soluble, as defined herein, and therefore, should not be latex particles or microgels of any type. In such eHifeodimenb the polymers should not he cross-linked through the use of monomers capable of forming covalent bonds between independent polymer chains, and the compositions and formulations- should be free of cross-1 inks ng agents added expressly for this purpose. .1( is believed that polymer aggregates (hat may be “swollen’* by water in the form of'microgels or polymers that form cross-linked networks will not have the appropriate foil mobility of the polymer chains needed for therh to fhnetion- as polymeric counterions with respect to ordinary surfactant, micelles. Polymer-particles which can serve as stmefurants for an aqueous composition through the formation of fibers or threads .are not suduble as the water-soluble polymers for similar reasons. Similarly, latex particles are believed to not be suitable because-many of the individual polymer chains in such particles are. In foci, confined to the particle·-interior and are not readily available- for interaction with the aqueous phase- Latex-particles also lack the chain mobility required io function as counterions to ordinary surfactant micelles.

The random copolymers may* comprise one or more monomers bearing the same charge or capable of developing the same charge and one or more monomers which ate nonlonic, i.e., .not capable of bearing a charge. Copolymers may be synthesized by graft processes, resulting in “comb-like” structures.

[Oilfol Preferred copolymers include so-called “hybrid” materials from Akzo Nobel such as Alcoguard® H 5240. These materials are described as comprising polysaccharides and synthetic monomers which can function in the same manner as acryiate/maleate copolymers (i.e., a water-soluble polymer with anlonicaliy charged .groups) in cleaning formulations. Hybrid polymers such as those described in US Pat. No. 8,058,8.37 are preferred in formulations where the overall sustainability of the formulation is of concern to the end user. Such hybrid polymers are derived from synthetic monomers chain terminated with a hydroxyl-containing natural material, such as a polysaccharide, using free radical initiators.

[(MI78J Various anionic polymers available from Afczo Nobel under the tradenames Ateoguafo®, Akospcvsetey and Aquafreai®· are suitable for use. 'For example.

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Alcosperse® 747, a random. copolymer, Aquatreat®· ARM, an acrylic acid homopolymer, and Aicoguard® 52.40, a random graft copolymer, all of which contain carboxylic acid groups, arc additional examples of anionic polymers that may be employed. Afoogcard® 2300 Is a random copolymer of the nonionic monomer dimethybcryiamide and the anionic monomer acrylic acid. AlcosperseS> 4bS is a pcly(acrylic add) homepoiymer; Versa-TL® 4 (Ates Nobel) is another example of a suitable anlonie polymer. This material is described as a random copolymer of sulfonated styrene and maleic anhydride. Another example of a suitable anionic polymer Is poly (d-scryfoifodcfo-msthy 1-1prcpangsfofonfo acid), also known as poly AMPS.

in one embodiment, the compositions are tree of copolymers comprising at least one monomer bearing or capable of developing as anionic charge and at least owe •monomer hearing or capable of developing a cationic charge. Such copolymers, sometimes referred Io as - “amphoteric” copolymers, are believed Io not .function as well or at all as polymeric counterions to micelles bearing a net electrostatic charge for at least two reasons. First, the'proximity of both types (anionic and· cationic) of charges along the polymer chains, if msdomly distributed, interferes with the efficient, pairing of a given type of charge on the polymer chain with the headgroup of a surfactant of opposite charge in a micelle. Second, such copolymers 'have the potential for electrostatic interactions of tbs anionic charges on a. given polymer chain with the carionie- charges on another polyhrer-chain. Such interactions: could, lead. to the formation of polynter aggregates or complexes in a process that is undesirably competitive with -the interaction of the -polymer with micellar aggregates..

[DOW] The water-soluble polymers may include natural or sustainable materials bearing anionic groups, including inulm. derivatives (example Carboxyline CM1 or 'Dequest PB), anionically modified starches with tbs proviso that they exhibit water solubility without cooking to achieve water solubility’, water-soluble salts of alginic acids, anionically modified cellulosic materials such as carboxymethyl cellulose, modified proteins, and the likeNoa-limhing examples of monomers bearing or capable of bearing, an anionic charge are acrylic acid, methacrylic acid, vinyl sulfonate, acrylamide propyl methane sulfonic acid (AMPS), it&conic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, pyromeffitle acid, methallyi sulfonate, sulfonated styrene, crotonic acid, aeonitie acid, eyanoacrylic acid, methylene malonic acid, vinyl acetic acid, allyl acetic acid, .ethylidineacetic acid, propylidineacetk acid, angelic acid,, cinnamic acid, styrylacrylic-add, cilmccfoc acid, giutaconle acid, phenylacrylic tscld, acryioxyptopriome

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PCT/US2012/063433 acid, vinyl benzoic acid, N-vinylsuccihamide acid, mesacohic acid, methaeroyl alanine, aerylohydroxyglycine, sulfoethyl acrylate, styrene sulfonic acid, 3-{vinyloxy}propa«e-lsulfonic acid, ethyelenesulfbnic acid, vinyl sulfuric-acid, 4-vinylphenyj sulfuric acid, vinyl phosphonie acid, maleic anhydride, and mixtures thereof. Suitable monomers may include acid-functional ethylenically unssturated monomers capable of polymerization or copolymerization via processes including free radical polymerization, ATRP and RAFT polymerization conditions that are expected to produce statistically random or gradient copolymers with ethylenically unsaturated monomers which are incapable of developing a charge, the so-called. nonionlc monomers, [0081] Non-limiting examples of monomers which are nonionic, not bearing, or not capable of bearing an electrostatic charge include the alkyl esters of acrylic acid or methacrylic acid, vinyl alcohol, vinyl methyl ether, vinyl ethyl ether,· ethylene oxide, propylene oxide, and mixtures thereof, Other examples include acrylamide, dimethyiacrylamide, and. other alkyl acrylamide derivatives. Other' suitable monomers may include ethoxylated esters of acrylic .acid- or methacrylic acid, the related tristyryl phenol ethoxylated: esters of acrylic acid, methacrylic acid or mixtures thereof; Other examples- of 'nonionic monomers include saccharides such as hexoses and. pentoses, ethylene glycol, alkylene glycols, branched polyols, and mixtures thereof, [8882] In some embodiments, water-soluble polymers comprising monomers which bear N-halo· groups, 'for example;, N~C1 groups, are not present It is believed that interactions between polymers comprising such groups, as polymeric counterions to micelles leads to either a degradation of the surfactants'themselves and/or a degradation of the polymers through the enhanced local concentration of the polymers at the micelle surfaces, fhW3] When the compositions comprise surfactant micelles with, for example, a net cationic charge and a water-sofubie polymer or mixture of polymers· bearing or capable of bearing anionic charges, then the compositions may be free of any additional polymers bearing a cationic charge, i.e., a charge opposite to that of the first water-soluble polymer bearing or capable of bearing anionic charges. The presence of a first water-soluble polymer bearing an anionic charge and a second water-soluble polymer bearing a cationic charge in foe same, formulation is believed to give rise to the formation of complexes between the two polymers, i.e.„ so-called polyelecbolyte complexes, which would undesirably compete with the formation of complexes between foe micelles 'bearing the cationic charge and the polymer bearing foe anionic charge.

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However, compositions comprising surfactant micelles bearing a net electrostatic charge and a water-soluble polymer bearing or capable of bearing an electrostatic charge opposite to that of the surfactant micelles may comprise additional polymers which do not bear charges, that is, nonionic polymers. Such nonionic polymers may be useful as adjuvants for thickening, gelling, or adjusting the rheological properties of the compositions or for adjusting the aesthetic appearance of the formulations through the addition of pigments or other suspended particulates. it should be noted, however, that in many cases, the polymer-micelle complexes of die instant invention, when adjusted to certain total actives concentrations, may exhibit selfethickemug” properties and not explicitly require an additional polymeric thickener, which is desirable from a cost standpoint.

V. Suitable Snrfeefeats (dWSl in onp embodiment, the compositions am free of nomonie surfactants which comprise blocks of hydrophobic and hydrophilic groups, such as. the Piuromcs®. it is believed that the.micellar structures formed with such large surfactants, in which the hydrophobic blocks assemble into the core -regions of the micelles· and the hydrophilic blocks are present·, at the -micellar surface would interfere with -the polymeric counterion interactions wife an additional charged, surfactant. Incorporated into a mixed middle, and/or also represent a shorn competitive- micelle.- assembly mechanism, in a manner similar to that of the use of block copolymers used as polymeric eounteriohs, which are also preferably not present [DbShi A very wide range of surfactants and mixtures of surfactants may be used, including anionic, nonionic and cationic surfactants and mixtures -thereof. As alluded to above 'in the description of Dost and P/Ffeeh it will he apparent feat'mixtures of differently charged surfactants may be employed. For example, mixtures of cationic and anionic surfactants, mixtures of cationic and nonionic, mixtures of anionic and nonionic, and mixtures of cationic, nonionic and anionic may be suitable for use.

Examples of cationic surfactants include, but are not limited to monomeric quaternary ammonium compounds, monomeric biguanide compounds, and combinations thereof Suitable exemplary quaternary ammonium compounds are available from Stepan Co under fee tradename BW® (e.g., BTC® 1010, BTC® 1210, BTC® 818, BTC® 8358). Any other suitable monomeric quaternary ammonium compound may also be employed* BTC® 1010 and BTC® 1210 are described as didecyl dimethyl ammonium chloride and a mixture didecyl dimethyl ammonium chloride and n-alkyl dimethyl benxyl

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PCT/US2012/063433 ammoniun? chloride, respectively. Examples of monomeric biguanide compounds include, but are not limited to shlorhexidine, alcxidine and salts thereof |W§Sj Examples of anionic surfactants include, but are not limited to alkyl sulfates, alkyl sulfonates, alkyl ethoxysul&tes, fatty acids and fatty acid salts, linear alkylbenzene sulfonates (LAS and HLAS), secondary alkane sulfonates (for example Uostapus<' SAS30), methyl ester sulfonates (such as Sfepan~Mild€· PCL from Stepan Corp), alkyl snlfosaccinates, and alkyl amino acid derivatives. Rh&mnolipids bearing mt ionic charges may also be used, for example, in formulations emphoizing· greater sustainability, since they are not derived from petroleum-based materials. An example of such a rhamnolipid is JSR 425, which is supplied as an aqueous, solution with 25% actives, from Jenil BiosurfactantCo., LLC (Saukville, Wl„ USA).

So-ealfod “extended chain surfactants” are preferred in some formulation's, Examples ofthese anionic surfactants are described in US Pat. Pub. No. -2006/0211543 , [OWl Non-limiting examples of nonionic surfactants Include -alkyl amine oxides (for example Awsonyx® 1,0 from Stepan .Corp.) alkyl amidoamine oxides (for example Ammonyx® LMDO from Stepan Corp.), alkyl phosphine oxides, alkyl polyglneosides and alkyl poiypentosides, slkyl poly(glycerol esters)· and aikyi polyCglyeerol ethers), and aikyi and alkyl 'phenol ethoxyiafos of ail -types and mixtures thereof. Sorbifan esters and ethoxylated sorbi'tan e«s am also· useful nonionic surfactants.. Other useful non.ionic surfactants include, but am not limited to, tatty acid amides, fetty acid monoethanolamides,· fatty acid· dsethanobsnides, and fatly acid isqprppanoi&mides, [tWlj l.n one embodiment, a phospholipid suffect&nt may he included. Lecithin Is an example of s phospholipid.

fofofo In one embodiment synthetic zwitteriohic surfeetets may be present. Nonlimiting examples include N-alkyl betaines (for example Amphosoi® LB from Stepan Corp.), alkyl sulfo-betaines and. mixtures thereof.

In one embodiment, at least some of the surfactants may he edible, so long as they exhibit water solubility or can form mixed micelles with edible nonionic surfactants. Non-limiting examples of such edible surfactants include casehs or lecithin or mixtures thereof.

|W4) In one embodiment, the surfactants may be selected based on green or natural criteria. For example, there is an increasing desire to employ components that are naturally-derived,. naturally-pressed, and biodegradable, rather than simply being recognized as safe. For example, processes such as ethoxylatibn may be undesirable

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PCT/US2012/063433 where if is desired to-provide· a green or natural product, as such processes can. leave residual compounds or impurities behind. Such “natural surfactants” may he produced using processes perceived to be more natural or ecological, such as distillation, condensation, extraction, steam distillation, pressure cooking and hydrolysis to maximize the purity of natural ingredients. Examples of such “natural surfactants” that may be suitable for use are described in U.S, Patent Nos. 7,608,573, 7,618,931, 7.629,305, 7,939,486, 7,939,488, all of which are herein incorporated by reference.

VI, Suitable Adjuvants [06931 A wide range of optional adjuvant or mixtures of optional adjuvants may be present For example, builders and chelating agents, including but not limited to BDTA salts, GLD.A, MSG, gluconates, 2-hydroxyaclds and derivatives, -glutamic- acid and derivatives, trimeihylglycine, etc. may he included.

Amino acids and mixtures of amino acids may be present, as either racemic mixtures or as Individual components of a single chirality. jD097j Vitamins or vitamin precursors, for example-retinal,.may be present |0P98 j Sources of soluble zinc, copper, or silver ions may be present, as the simple inorganic- salts or salts of chelating agents, inc lading, but not limited to, EDTA, GLDA, MGBA, citric acid, etc.

[O| Dyes' and colorants may fee present, Polymeric thickeners, when used as taught above, may he present (bhlitoj Buffers, Including but 'not llsrbted to, carbonate, phosphate,- silicates, -borates,'and combinations thereof may be present. Electrolytes such as alkali metal salts, for example including, but not limited to, chloride salts (e,g., sodium chloride, potassium chloride), bromide salts, iodide salts, or combinations thereof may be present [WtWj Waler-miscible solvents may be present in some embodiments. Lower alcohols (e.g., ethanol), ethydene glycol, propylene glycol, glycol ethers, and mixtures thereof with water miscibility at 23^CC may be present in some embodiments. Other embodiments will include no lower alcohol or glycol ether 'solvents. Where such solvents are present, some embodiments may mclutte-fhem in only small amounts,, for example, of not more than. S% by weight, not more than 3% by weight,, or not more than 2% by weight. (ihFWJ Water-immiscible' solvents may fee- present, 'feeing solubilized into the micelles.

(061.G3) Wafer-immiscible oils may be present, being solubilized Into the micelles. Among these oils are those added as fragrances.. Preferred oils are those that are from

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PCT/US2012/063433 naturally derived sources, including 'the wide variety of so-called essential oils derived from a variety of botanical sources. Formulations intended io provide antimicrobial benefits, coupled wdh improved overall sustainability may advantageously comprise quaternary ammonium compounds or wafer soluble salts of chlorhexidine or alexidine in combination with essential oils such as thymol and the like, preferably In the absence of water-miscible alcohols.

[99199] fa one- embodiment, the corn-position may farther include one or more oxidants. Examples of oxidants include, but are not limited to hypohafous acid, hypohalite and sources thereof (e.g., alkaline metal salt and/or alkaline earth metal salt of hypochlorous or hypobromous sold), hydrogen peroxide and sources thereof (e.g., aqueous hydrogen peroxide, perborate and its salts, percarbonate and its salts, carbamide peroxide, metal peroxides, or - combinations thcreoife peraeids, peroxy-acids, peroxoacids (e.g, peracetic acid, pereitric acid, diperoxydodecancic acid, peroxy amido phthalamide, peroxomonosulfotnc acid, or peroxodisulfamic acid) and sources thereof (e,g., salts (e.g., alkali metal salts) of peraeids or salts of peroxyaeids such as peracetic acid., percifric acid, dipcroxydodecanoic acid sodium potassium peroxysnliate, or combinations thereof), organic peroxides and hydroperoxides (e.g. benzoyl peroxide) peroxvgenatbd inorganic compounds (e.g. perchlorate and its salts, permanganate and Its salts and periodic acid and its salts), solubilized chlorine,· solubilized chlorine dioxide, a source of free chlorine, acidic sodium chlorite, an active chlorine generating compound, or a chlorine-dioxide generating compound, an active oxygen generating compound, solubilized ozone, N-halo compounds, or combinations of any such oxidants. Additional examples of such oxidants are disclosed in fe'.S·. Patent No, 7,517.,569 and U.S. Publication No. 201 i/0236582, each of which is herein incorporated fey reference in its entirety.

[901951 Water-soluble hydrotropes, sometimes referred to as monomeric organic electrolytes, may also be present. Examples include xylene sulfonate salts, naphthalene sulfonate salts, and cumene sulfonate salts.

[99M9[ Enzymes may be present, particularly when the - formulations are tuned for use as laundry detergents or as cleaners for kitchen and restaurs®) surfaces, or as drain openers or drain maintenance products.

[99197) Applicants have found that a wide range surfactant mixtures resulting in a wide range of Dnef values may be used. In many cases, the surfactants' selected may be optimized for the solubilization of various water-immiscible materials, such as fragrance oils, solvents, or even the oily soil to be removed from a surface with a cleaning operation.

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In foe cases of the design sf products which deliver an antimicrobial benefit in the absence of a strong oxidant such ss hypochlorite, a. germicidal quaternary ammonium compound o? a salt of a monomeric biguanide such as chiorhexidine or alexldine are often incorporated, and hence are incorporated into-micelles with polymeric counterions. The fine control oyer the spacing between the cationic headgroups of the germicidal quaternary ammonium compound or biguanide which is achieved via the incorporation of a polymeric counterion can .result in a significant reduction in the amount of surfactant needed to solubilize an oil, resulting in cost reductions and improvement in foe overall sustainability of the .formulations.

fotlitfy 1« contrast to what is described in the art, applicants have also found that the magnitude and precise value of P/Dnet heeded to ensure the absence of precipitates and/or coacervate phases cart vary- widely, depending on the nature of the polymeric counterion and the surfactants selected to form the-mixed mtecltes. Thus, since -there is. great ..flexibility in the selection of foe polymeric counterion for a given surfactant mixture to achieve--a particular .goal, applicants have adopted» systematic, but simple approach for quickly “scanning through” ranges of P/Dnfy in order to Identify and to compare, formulations eomprisfog: polymeric counterions,.

fotWfy The formulations comprising the mixed micelles of a net charge and .a water-soluble polymer bearing charges opposite to that of the micelles, are useful as ready to use surface cleaners delivered via pre-moistened nonwoven substrates (e.g., wipes), or as sprays in a variety of packages familiar to consumers.

fob-fob) Concentrated forms of the formulations may. also bs developed which maybe diluted by the. consumer to provide solutions that are then used. Concentrated forms that suitable for dilution vis. automated systems, in which the concentrate is diluted with water, or in which two solutions are combined in a given ratio to provide the final use formulation are possible, [Will] The formulations may he in the form, of gels delivered to a reservoir or surface with a dispensing device. They may optionally be delivered in single-use pouches comprising a soluble film.

foM 12] The superior wetting, spreading, and cleaning performance of the systems make them especially suitable for delivery from aerosol packages comprising either single or dual chambers.

fofofodl When the compositions comprise chlorhexidine or alexldine salts as a cationicaliy -charged surfactant, foe compositions may he free of iodine or iodine-polymer

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PCT/US2012/063433 complexes, nanopartieles of silver, copper or zinc, triclosan, p-ehteromethyl xylenol, monomeric pentose alcohols, D-xyhtol and its isomers, D-arabitol end. its isomers, aryl alcohols, benzyl alcohol, and phenoxyethanol.

VH, Suitable Heawpven Substrates

100114] Many of the compositions are useful as liquids or lotions that may he used In combination with nonwoven substrates te produce pre-moistened wipes. Such wipes may he employed as disinfecting wipes or for floor cleaning in combination with various tools configured to attach to the wipe.

in one embodiment, the cleaning pad of the present invention comprises a nonwoven substrate or web. The cleaning substrates can be provided dry, pre-moistened, or impregnated with, cleaning composition, but dry-to-the-tooch. 'in one aspect, dry cleaning substrates cab he provided with dry or 'substantially dry cleaning or disinfecting agents coated on.or In the multicomponent multiloba! fiber layer, in addition, the cleaning substrates can he: provided. In a pre-moistened and/or saturated condition.. The wet cleaning substrates can be maintained over time in a sealable container such as, for example, within a bucket with an attachable lid, sealable plastic pouches- or bags', canisters^ jars, tubs and'so forth,

VH1 Examples

How Farrids Size and Zeta [email protected] Were Measured

The diameters of the aggregates with the polymeric counterions (in nanometers) and their zeta potentials were measured with a Zetasizer ZS (Malvern Instruments). This instrument utilizes dynamic light scattering (DLS, also known as Photon Correlation spectroscopy) to determine the diameters, of colloidal particles m the range from 0.1 to 10000 nm.

[001.17) The Zetasizer ZS instrument offers a range of default parameters which can be used in the calculation of particle diameters from the raw data (known as the correlation function or autocorrelation function). The diameters of the aggregates reported herein used a simple calculation model, in which the optical properties of the aggregates were assumed to be similar to spherical particles of polystyrene latex particles, a common •calibration standard used for more complex DLS experiments. In addition, the software package supplied with, the Zetasizer provides automated analysis of the quality of the measurements made, in the form, of “Export Advice”. The diameters described herein (specifically what is known as the “Z” average particle diameter) were calculated from taw data that met “Expert Advice” standards consistent with acceptable results, unless

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PCT/US2012/063433 otherwise noted. In other words, the simplest set of default measurement conditions and calculation parameters were used to calculate the diameters of all of the aggregates described herein, in order to facilitate direct comparison of aggregates based on a variety of-polymeric counterions and surfactants, and avoiding the. use of complex models of the scattering which could complicate or prevent-comparisons-of the diameters of particles of differing chemical composition. Those skilled in the art will appreciate the particularly simple approach taken here, and realize that it is useful in comparing and characterizing complexes of micelles and water-soluble polymers, independent of the details of the types of polymers and surfactants utilized to form the complexes.

(WO d] This instrument calculates the zeta. potential of colloidal particles from measurements of the electrophoretic mobility, determined via a Doppler laser velocity •measurement. There exists a relationship between the electrophoretic mobility (a measurement of the velocity .of a charged colloidal particle moving in an electric field) and the zete potential (electric charge, expressed In units of 'millivolts),. As in the particle size measurements, to facilitate direct comparison of aggregates based on a variety of polymeric counterions and surfactants, d'io simplest set of default measurement conditions were Used, i.e,, tits, aggregates wem assumed: to behave as pelysAfcns latex -particles, and the Smoluchowski model relating tbs electrophoretic mobility and the zeta' potential was used'.in all calculations. Unless. Otherwise noted, the mean zeta potentials described herein were calculated from raw data that met “Expert .Advice” standards consistent. with acceptable results. Aggregates bearing a. net cationic (positive) charge· will exhibit positive values of the zeta. potential (in mV), while those bearing a. het anionic (negative) charge will exhibit .negative values, of the zeta potential. (b mV),

Example 1

Ready to Use Disinfecting Spray Cleaner Formulation tea? s «ιοο eu I '< i, I'cum.d \oeU\ . Woo .nA V .Pv- $ ^iS‘4\.ng(K

Counterion (00110) The interaction between mixed micelles comprising an amine oxide and two different germicidal. quaternary ammonium compounds and an anionic -polymeric counterion can bs readily illustrated by comparing the diameters of the mixed micelles (as measured by DLS) in the absence and presence of the -polymeric counterion. The aqueous control formulations' were prepared by mixing the germicidal quaternary ammonium raw material (supplied as aqueous solutions, Stepan Corp.) with the amine oxide .raw material (supplied as an aqueous solution, Stepan. Corp.) to form, a mixed surfactant stock solution.

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PCT/US2012/063433

Appropriate mnonnts of the surfactant stock solution, meneethanoiamine (to adjust pH above 9..0) and water were mixed to form the final control formulation containing the mixed micelles. in the case of the formulations comprising foe polymeric counterion, the same mixed surfactant stock solution, menoethanolamme, Aleosperse® 747 (supplied as an aqueous solution, Akzo Nobel), and water were mixed in appropriate amounts to yield the final formulations with different PZDnet values, hut with the same mixed micelle compositions. The formulations, all of which were clear solutions free of eoacervate or precipitates, are summarized in Table hi. The measured values of the Z-average diameters and the acts potentials of the aggregates are summarized in Table 1.2.

Table U

Iksrt»- uiatioK Nssue	.Akxisjxif.se A AC whA	Amt se Oxicfe, A:(nri:i>Kyx A16, wite	stefstedd&i Qast, BTC® .tow, ά%	Gsrinwkik BTC® Ufih wi®	5 Moncjsh ; audandn : e wt% :	P/Dne r	EAei
Al		0,23'	0,30			0,1.	0 ..................	0.00090 4
A2		0.25	-	0.30		0.1	0	0.0010
AS	0.02	0.27	0.36			0.5	-0,1	0,(50099 4
A4	0.05	0.23	0J6			0,1	0,25	0,00099 4
A5	0.02	0.25		0.36		o.l	-03	0.001
Ab	0,05 _______________	(5.23		0.30		0,1	(5,25	0,001

[00120] Alcosperse®' 74? (Akzo Nobel) acrylic acid: styrene random copolymer supplied as aqueous solution (40 % actives) with Z ·· -.1 and Eq polymer 0.005054 equivalenls/grsm of polymer actives, [00121] BTC® 1010 quaternary ammonium germicide (Stepan Co.) supplied as aqireous solution (80 % actives) described as bidecyl dimethyl ammonium chloride, average molecular weight ~ 302 grums/meie, Q = k [00(22] BTC® 1210 quaternary'· ammonium germicide (Stepan Co.) .supplied as aqueous solution (80 %-actives) described as a mixture of didecyl dimethyl ammonium

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PCT/US2012/063433 chloride and n-alkyl (50% Cl4, 40% 02.. 103406) dimethyl benzyl ammonium chloride, average molecular weight 360.5 grams/moie, Q^:;ri ,

Table 1.2

F«3ft5ut&doa Name	PAteet	Z average dhsineier, ntn	'Mean -2CM petes&b ε?5 V	Cormnei-sis
Al	0	1.032	4.1(),6	Micellar aggregate control
A2	0	1.006	+32,6	Micellar aggregate control
A3	-0..1	76.08	456.8	With polymeric counterion
A4	- 0.25	33.19	451.8	With polymeric counterion
AS	- 0.1	79.14	+50.0	With polymeric counterion
Ah	-0,25	92.57	-50.5	With polymeric counterion

[00133| The results in Table 1.2 indicate that the .micellar aggregate controls at WDnet ~ 0 were around 1 nm in diameter, which is an expected size range for micellar aggregates of Ionic surfactants in aqueous solutions. These results suggest that the default parameters selected for calculation of the diameters from· the D'LS measurements, as described above, were· reasonable, and. thus could, be used for comparing changes in diameter due to. the interactions between the micellar aggregates -and the polymeric counterions, [(10124] Since· these aggregates comprised mixed micelles of an amine oxide surfactant, which is expected to be uncharged at the high pH of the formulation and a cationic -germicidal quat,· a positive mean zeta potential Is expected and is: observed for the two control systems comprising the two distinct germicidal quaternary ammonium compounds.

[Ml 25| The addition of the water-soluble mt ionic polymer Alcosperse 74? to the formulations at P/Dnet values of- 0.1 and - 0.25 yielded clear solutions that were free of coacervate. The strong electrostatic interactions between the polymer and the mixed micelles result in the formation of stable aggregates that are much larger in average diameter than the micellar controls, but which are still small enough to exhibit colloidal stability and a clear appearance. Increasing (be absolute value of P/Dnet from 0.1 to 0.25 corresponds to moving closer to the lower boundary of the coacervate region for mixed, micelles of ibis composition and at this total surfactant concentration, and hence the average diameters measured increase somewhat.

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PCT/US2012/063433

In order te test whether these larger aggregates comprising mixed micelles and the polymeric counterion were stable structures, repeated measurements of the aggregate diameters were made· on undisturbed samples held in cuvettes in the instrument, every 5 minutes over foe course of shout one hour. Thus, any growth in the aggregates, which might he a precursor to coacervate or precipitate formation and which would he fess obvious than foe haziness of samples detected visually, would be detectable from a trend In the Z-average diameters over time. No such trends were detected for samples A3 through A6. All of these samples exhibited, relative -standard deviations of the Z-average diameters of fess than '1% from the 11 sequential measurements made. The Z-average diameters for these samples, based on 11 measurements each, ate those reported in Table

A >.«u.

|W127) Since the aggregates with-die polymeric counterions were formulated· atari absolute value of P/Dnet < .1.0, the number of cationic charges provided by ihe gcfm.lc.idal quaternary ammonium compound in the mixed micelles exceeds that of the anionic charges provided by the anionic polymer, and the stable colloidal aggregates formed would be. expected to bear- a net cationic charge and hence a positive seta potential. Table 1.2 shows that the aggregates formed with, the -polymeric counterion· have mean seta potential values that are positive, -even somewhat greater than the micelles alone, consistent with 'the formation of distinct,· tunable aggregates· which cannot be formed without the use of a polymeric counterion, that is, that cannot be formed at the same total surfactant concentration and the same mixed micelfe compositions when the. .native counterions of the-cadooic: surfactant (the germicidal quaternary ammonium compound),· here· chloride ions, are the. only ones present A conservative estimate of the precision of ail of the zeta potential measurements referenced herein is about 10% of the reported mean value.

Example 2

Ready to Use Disinfecting Cleaner Lotion Suitable for Delivery from· a Nonwoven Wipe Mean Diameter and Zeta Potential- of Surfactant Micelles Without and With Polymeric 'Counterion - At low Y values

A 'series of formulations were prepared in foe stene manner as its Example· 1, at a lower relative concentration of the germicidal quaternary ammonium compound in ihe mixed surfactant aggregates. Formulations using those mixed micelle compositions are suitable for use as lotions which can be loaded onto nonwoven wipes and provide

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PCT/US2012/063433 convenient disinfection of hard surfaces combined with good cleaning of greasy soils, all without the requirement for the addition of volatile organic solvents such as lower alcohols or glycol ethers. The formulations comprising the polymeric counterion were clear and free of coacervate when the absolute value of F/lOnet was less than 0.30, according to aa inspection of a series of samples covering a range of this parameter between 0 and 0.5 at this total surfactant, concentration and micelle composition.

Table 2.1

Fwrti- afeidoa Name	FT yreer ; Andes	i.ses'iiiicjdsj Oast, BTC® 1016. 'MA	Germicidal BTC® 1210, wtA	MotiiXit Aetod's	, : i r® 1 parameter i
A ί c>'ispers si A 747 vXA	O.xiae. AsissKssys: + LO,
A?		2.05	oas		0,1	0	-[0,00090 4
A§		2.05	--	<06	OT	0	+0,00
> \ ............. i	0.002	2,05	0.36		0,1	<01	-•<00099 4
AW	0,02	2,05	0,3 b		0.1	A;	+0.00099 4
All	0.02	2,05:	»»	0,06	0,1	-0,1	-5-0,001
A12	0.05	2,05	--	0.56	Oo	--0,25	-0.001

Table 2.2

Fort»- ukiU-.'n Nam«	P/Dfjei	X average feneter, S!R	Mesa -.+ ·-·. + :++. spV	Cof-SRiSKiS
A7	0	2,505 + -5, 2 preps)	2-6,91.	Micellar aggregate control.
AS	0	2.417+-6,2 preps)	Not measured	Micellar aggregate control
A9	-0.01	3,266 (n-3)	+9.31	With polymeric counterion
A10	-0.1	5.203 +“3)	+7,99	With polymeric counterion
All	-0T	3.114 (n--3)	+4,18	A oh cob, ό?!)? ---55 h
A12	-0.25	3,680 (ή”3)	+4.00	With, polymeric counterion

1W12-9) The results in Table 2,2 show that, at this total surfactant concentration and mixed micelle composition, the mixed micelles are somewhat larger than those formulated

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PCT/US2012/063433 with the same quaternary ammonium compound and amine oxide as shown in Table LL Without being bound by theory, it is believed that as the relative amount of quaternary' ammonium corn-pound in the mixed micelles decreases, an effective dilution of the charged quaternary ammonium compound headgronps in the micelles occurs due to the additional number’s of amine oxide molecules, which allows greater average spacing between the charged qrjatematy ammonium compound headgronps and a growth in the average micelle diameter. Also, due to the lower average number of quaternary ammonium compound molecules present'in the mixed aggregates, the measured mean zets potential is reduced, but is confirmed to be positive, i.e., cationic, as expected.

[W138| The results in Table 2.2 also indicate that, the addition of an anionic polymeric counterion at P/Dnet values that do not cause formation of eoacervates results in aggregates-which are. significantly larger than the micellar controls, but- still small enough to exhibit colloidal stability. The relative standard deviations cf the 'measured fo average diameters of each of the formulations were again found to be less than 1.6%, even when multiple preparations of the same compositions were prepared on different boys, .and hence the differences' in diameter between the control formulations -and those comprising the polymeric counterions may be considered detectable and significant [0013!j The results in Table 2.2 also indicate that the aggregates formed with the addition of the anionic polymeric counterion,, at absolute -values of P/Dnot less than 1 ..0, exhibit a positive (Cationic) zeta potential, as expected.

[00132] Thus, the addition of a polymeric counterion yields stable, soluble aggregates with a tenable size and charge which can be adjusted through the mixed micelle composition and. the P/Doci value.. As shown elsewhere herein, such aggregates' exhibit surprisingly good antimicrobial performance, across a range of microorganism^., without requiring volatile organic materials such as -alcohols or glycol, ethers to boost or “potentiate” the-action of the quaternary ammonium compound. It is believed, without being hound by theory, that the aggregates comprising polymeric counterions can more readily act at the solid-liquid interface, including that of microbes,, enhancing the delivery of the germicidal quaternary ammonium eomporetd and thus enhancing antimicrobial efficacy, l-xample 3

Ready to Use Disinfecting Cleaner .Lotion Suitable for Delivery from a Nonwoven Wipe Meso Diameter and 2eta Potential of Surfactant Micelles Without and With Polymeric Counterion - At absolute values of P/Dnet > I

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PCT/US2012/063433 (W1331 A series of formulations were prepared in foe some manner as in Example 1, at a constant mixed micelle composition and Dnet -value which are suitable for use as lotions which can be loaded onto nonwoven wipes or used as a ready to use spray cleaner with excellent bard surface wetting properties in foe absence of volatile organic solvents such as alcohols or glycol ethers. The formulations comprising the polymeric counterion were cleat and free of coacervate at absolute values of P-'Bnet greater than '1.3, determined by an inspection of a series of samples covering a wide range of foe absolute value of P/Dnet between 0 and 2.0 at the total surfactant concentration. The addition of foe anionic polymeric counterions io the mixed micelles containing a quaternary ammonium compound provides a mechanism to tune foe solubilization efficiency of water-immiscible oils, through adjustment of both Dnef and foe absolute value of P/Bnet.

Table 3.1

F-unP' visitor.	Polymer Atosspme	Affine Axide,	Oerrsicidal Qeat,	>..ίίΐΐο«κ;;.		AD set	D »<-;
T-iame	® 74 7	.Aiwnefw':·;'®	BTC® W Kf		y
AB		0.785	0522		05	0	4-0.00033 7
AB	05	08$	0522	0.2 ...........	85	5.50	40.00033 7
........ A15	0.1	............ 0.785	0.1.22		05	-1.50 ..................	+0.000,33 7

Tifole 3.2

Forsn- aifoon Naim?	WB ίϊΝ	Z «v er yw dissietxr.	Mesa xesa poteahaL ®Y	Cerasnsats,
AB	0	2,22:	+734	h to ' to’-to ,· i '
AB	-1,50	9,102 (n~5)	- 2.31	Wlfo polymeric counterion
A.15	A.SO	0532 to 4, 2 preps)	A 15	With ooivmcric counterion ......

(00.134] The results shown in Table 3.2 show that, at absolute values of 'P/Dnet greater than 1.0 and outside foe region in which coacervates are formed for this system, stable soluble aggregates are formed with foe addition of the anionic polymeric counterion. The aggregates have somewhat larger Z-average diameters relative to micellar

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PCT/US2012/063433 aggregate controls formed in the absence of the polymeric counterion. Addition of a significant amount of limonene, which is both a model fragrance oil component -as well as a model hydrocarbon solvent, to the aggregates comprising the polymeric counterions is readily achieved at the same F/Dnet value as in the absence of the limonene. Thus, the aggregates comprising the mixed surfactant and the polymeric counterion are capable of solubilizing water-insoluble materials such as limonene. It is believed, without being hound by theory, that the solubilization of limonene m the aggregates with the polymeric counterions is possible because the aggregate structures maintain a property of ordinary mixed micelles, i.e., a non-polar interior in which water-insoluble materials may be solubilized, even in the presence of the -polymeric counterions.

Example 4

Dilutable Disinfecting Formulations

Z-Average Diameter with and without Polymeric Counterions of Diluted Formulations |W135] The addition pf polymeric counterions to formulations corn prising mixed micelles of a.germicidal quaternary ammonium compound. and another surfactant provides concentrates which, can. be diluted either manually or via the use of an automated, dilution apparatus to provide economical disinfecting solutions. The enhanced wetting propertiesof the formulations comprising the polymeric counterions, in the absence of volatile organic materials such as lower alcohols or glycol ethers, provide excellent performance with a. minimum of residues, which is of concern^ tor example, in floor, cleaning of health care facilities -and the like..

fWlM] In the- first step, the appropriate F/Dnet range for the concentrated formulations was determined, with different germicidal quaternary 'ammonium compound and an amine oxide snr&c-tant mixture. The concentrates also comprised telrapoiasshun ethylenediamine tetraacetate, a common chelant and buffer useful in controlling the effects of common tap water used as a diluent, and NaCl as an electrolyte. Multiple concentrated formulations which were clear and free of coacervate am identified through the adjustment of F/Dnet and NaCl level. Formulations suitable for dilution at a rate of 1:250 by volume are then identified through visual inspection. Formulations which appeared to yield- clear, soluble solutions free of coacervate phase when diluted were then analyzed via DtS to confirm that the aggregates comprising polymeric counterions formed by a simple dilution process had diameters in the range expected to provide colloidal-stability, i.e., Z-average diameters less titan 5tXI nm., as measured -as described herein. The anionic polymeric

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PCT/US2012/063433 counterion in these examples Is Versa-TL® 4 (Akze Nobel), described by the supplier as a random copolymer of sulfonated styrene and maleic anhydride, which is supplied as an aqueous solution at 25% actives at pH 7.0, which means the anionic sulfonate groups are present in the salt form, and that the maleic anhydride has been hydrolyzed to maleic acid via reaction with water, and the acid groups are present in the ionized (salt) form, The nominal molecular weight of the -polymer is described as· 20,000 daitons. The total number of anionieally charged groups oh this-polymer yields 0,006427 moles of anionic groups/gram of polymer solids, and this was used in the calculation of the P/Dnet values hsted below.

Table 4.1 - Concentrate Formulations at Constant Y “0,5

Rii-so ylsiiof·	Ρ<ΗΫΪίϊ£ r	Affisae Oxide,	Gemiic ids!	vte :::Y feta'i	% TOT	TsCT.....	P/bnet	Cksf, Stable	Claai- dihrted
Nsiiie	V ' i so® s wtte	Anenony xte LO,' asm	Quat, §358 -mA	Q«at telCS teW, wTA	A,	Ateo ................		CTiKeis irate? YZN	solutesT YZNor ate teste?
ΛΙ6	...............	4.08	6.4	-	1.0	5.0	0	Y	Y
A17	-	4.07	-·	6.4	1,0	5,.0 to	0	¥	V
ATI	0.:137	4.03	6,4	-	TO	--0,05	Y	N
A10	. 0.275	4,03	6,4		1.0	5.0	-0T0	Y	N
A20	0.412	4.08	0.4		TO	5.0	-0,15	Y	N
All	0.5-50	4,03	6,4	-	TO	5.0	-0.20	Y	N
A22	0.033	4.03	6.4	-	1,.0	5,0	A S S	Y	N
A23	1.375	4.08	6,4	-	TO	5,0	a-5	Y	-
A24	275	OS	6.4	-	TO	5.0	- TO	Y
A2S	3.44	4,03	6.4		1.0	5.0	- 1.2.5	N	-
A26	0.137	4,08	6.4		--	5.0	- 0.0:	\	-
A27	0.273	4.08	6.4	-	-	5.0	-0..T	X !	:
A28	0,412	4.08		-	-	5,0	-0.1;	X
A20	0,530	4.08	6.4	-	-	5.0	~ 0.20	\
A30	0.063	4.07		6.4	TO	5.0	0.025	¥	¥
A3.I	0,137	4.07	-	6,4	1.0	5,0	- 0.05	Y	Y
A32	0.275	4.07	V	6.4	TO	5.0	-OTO	Y	N

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A33	0,412	4,07	-	6.4	1-0 .................		- 0.15	V	A
A34	0,550	4,07	-	6.4	1.0	5,0	- 0,20	Y	A
A35	0.068	4,07		6,4	-	5.0		A	V.
							0,025
A36	O.137	_...... 4.0?		6,4		5.0	- 0.05		-
A3?	0473	4.07		6,4		5,.0	-040	A
ASS	0.412	4.07	-	6,4		5,0	- 0. IS	A
A.fo	0,550	4.07		6.4	-'·	5,6	- 0.20	N
				..................1.................			I

[80137] The results la Table 4.1 illustrate that multiple concentrate formulations which .are clear and free of coacervate (A'18 through A24) comprising the anionie polymeric counterion are possible, even, up to absolute- values of P/Dnet -~ 1.0, when .sufficient total eidcbolyie (NaCl and KJSDTA) is present Formulations A16 and A17> ®wb-ich P/Dnet ™ 0 acted as micelle controls. It Is believed, without being bound by-theory, that the' interactions betweeb the polymeric counterion and the mixed micelles comprising quaternary ammonium compound and amine oxide can be adjusted through the .addition of ordinary electrolytes like NaCl and KfoDTA, which partially screen the charges on the soluble polymeric counterions from the opposite charges on the mixed micelles, and/or compete with the polymeric counterions for the oppositely charged quaternary 'ammonium compound molecules in the -mixed micelles. When the absolute value of the P/Bnet parameter is at or near 1.0, the number of anionic charges present are exactly or nearly sufficient to completely neutralize the cationic charges due. to the .germicidal quaternary ammonium compound, which would be expected to lead to the formation of coac-ervates or precipitates. Surprisingly, however, the absolute value of P/Dnet alone is not a reliable guide for avoiding coacervates or precipitates in the formulations, instead, for a given desired PBnet value, a given mixture of germicidal quaternary' ammonium compound and another, uncharged surfactant such as an amine oxide, the concentration of electrolyte or mixture of electrolytes needed to prevent the formation of coacervates or -precipitates' can be readily, and systematically determined.

[06138! Formulations A26 through 27. for example, can be compared with· A18 through A21, all of which cover a range of the absolute- value of P/Dnet values less than fob which Is of interest for lower total actives and hence lower cost. Formulations A26

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PCT/US2012/063433 through A2A have an insufficient total electrolyte level das to the elimination of K^EDTA without an increase in the NaCI concentration, and hence are not dear solutions which would not be suitable candidates for a concentrated formulation, [901.391 Similarly, Formulations A30 through Α34» in which a different ge.miis.idal quaternary ammonium compound is used, are- acceptable concentrate candidates, By comparison, formulations A35 through A39, in which the total electrolyte concentration was again. reduced via elimination of KUBOTA,. are not acceptable concentrate candidates, since none of them were clear solutions, hut in fact exhibited cloudiness due to the presence of coacervates and/or precipitates.

P8H4I) In a second step, the behavior upon dilution in water of the stable concentrates was evaluated. A sample of the concentrate (40 microliters) was added fc 9,96 ml of-water of coafrshed hardness (representing the 1:250 fold dilution .rate of interest for this application) in a capped vial and mixed via manual, agitation for -a few seconds,. The dilafed samples wem -visually evaluated for cloudiness, haziness, or the presence of precipitates immediately. Formulations A30 and A3!, are examples of concentrates which, upon dilution, form dear solutions that are- free of coacervates or precipitates. D.LS was then used to confirm the presence of stable aggregates comprising the mixed micelles and the polymeric counterion, In comparison to mixed micelles comprising the same quaternary ammoosn® -.compound and asnine oxide .surfactant without the polymeric counterion.

Table 4.2 - Chamcterization of Diluted Formulations Prepared from Concentrates

Form» wisiioK Nar«<:	WDnet	2 a - is dswfe:«!» ................	Mean Ma poieoiish mV	Ctsnvwss
Al? '	0	5,14.1 (fH)	*12.5	Control - no polymeric counterioi , ' trd water : 1:33 ddcucns
A.31	- h.(fr	167.7 yr A)	+44.5	With polymeric counterion diluted 1:250 in hard water ~ : ·, ->t Όο ; o
Α3Ί	- 0.05	17S.7 ;> A		With poly nodi, counterion diluted ,t :250 tn deionised water
A30	- 0.025	136,8 (n~5)	'·	With polymeric counterion ~ ddhuT'd 1:2>t'· m lend waferfresh sample
A30	· 0,025	140.0 (irfe)		With polymeric counterion ~ diluted 1:250 in hard water aged 6 hours'

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^Synthetic hard water used for dilution contained calcium and magnesium ions- in a. 3:1 mole ratio at a total concentration of 150 ppm.

[WMI] The results in Table 4.2 indicate that the Z-avemge diameter of the micelles in the control sample is significantly less than that of the formulations comprising the same cationic micelles and the anionic polymeric counterion, It should be noted that, successful DLS analysis of the micelle control formulation required that it be diluted only by a factor of 25, in order to ensure an adequate and reproducible level of scattering. The amount of scattering from colloidal particles in the DLS experiment is a function of the average diameter of the particles to the sixth power, or proportional to (diameter)⁰. Thus, small increases in the average diameter result in very large increases is the amount of .scattered light, which in tura allows the detection and analysis of Iss-gcr particles at much lower coneehtratiohs than smaller particles.. That expected trend is consistent with the measured diameters of the aggregates formed, upon dilution of formulations A3d and Alt. The results else indicate that the quality of the water d id not have a large effect pn the Zaverage diameter of the -aggregates of formulation 31 formed -upon dilution.

In Table 4,2, “fresh sample” means that the first DLS analysis of the .diluted sample was conducted within 10 minutes of the initial dilution step. Multiple .replicate measurements of the some sample (typically 4 or 5, as indicated}- were usually made. Replicates could typically be ohteined. within 2-3 minutes of each other. The stability of the .aggregates formed upon dilution of Formulation A30 was also checked, by aculyAng the same sample that was allowed to age· .6 hours, in the instrument. The results indicate that co significant change in the Z average diameter of the aggregates, in the- diluted sample was observed, indicating that stable structures are formed immediately upon dilution of the concentrates, without need of any special processing other than simple mixing.

(00143( The results in Table 4.2 also indicate that the xeta potential of the diluted sample of the control micelles is positive (cationic), as expected. Since the absolute value of P/Dnet for Formulation A31 is 0.05, Le., significantly less than 1.0, thexeta potential of the stable, soluble aggregates formed upon dilution is expected to be positive (cationic), and the measured result confirms this, at +44.5 mV.

(001441 The results in Table 4.1 and 4,2 also indicate that systematic adjustment of the P/Dnef parameter and the electrolyte level (and, if desired, the mixed micelle

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PCT/US2012/063433 composition) may be used, with initial visual inspection, to teumfy concentrates wmeh, upon significant dilution, deliver stable, soluble aggregates comprising mixed micelles of a. germicidal quaternary ammonium compound and a second surfactant and an atnontc polymeric counterion, in a solution free of coacervates or precipitates.

Example 5

Formulations Suitable for Delivery from Nonwovens Control of Micelle Interactions with Polymeric Counterions Over Wide Range of P/Dnet Hie pH of the aqueous formulations comprising mixed micelles with a cationic charge and an anionic polymer may be adjusted over a wide range, providing the polymeric counterion maintains its solubility in water at the pH of interest.

}W?45j Thus, a series of aqueous formulations in which the pH was adjusted to about pH 7,6 were made in order to confirm tbs absence of coacervate formation across dm P/Dnet range of interest.

(661461 Samples Were prepared by making the following stock'solutions; (I) 0,33 wt% MEA and 0.52 vA% glycolic acid at a pH of 6.9- '(2) .1.2 wt% BTC® 1010 and 6.8 wtbo Ammonyx®Ί.0 at natural pH, and (3) l.S wt% AlCesperse® 74? adjusted to pH 6,2 with glycolic acid. The MEA/glycoOe acid stock was then diluted in the proper amount of water followed by addition of the BTC® 10.1 0/Ammonyx® CO stock and finally the. Aicosperse® 747 stock. Final pH was measured and found to be between 7.6 and 7,3 for Otesc formulas.

Table 5,1 - Compositions suitable for delivery from nonwpvens

Fterimsteiioa Aam-S;	BTC® Kite	AiimiiXiyx® 1,0 YVite	Alcospeete® 747 v4%	MCA vfoA	OlyculSc aciti wt%	pH
1C	036	2,05	0.005	03	036	7.0
B2	0,36	2,05	0.01	03	036	7,6
B3	036	2,05	0,02	0.1	036	7.6
B4	0,36	2.05	0.025	03	036	7,6
B5	036	2.05	0.03	03	1 C>	7.0
B6	036	2,05	0.05	03	ό 16	foi? : 6 A:: .........1........,
B?	0,36	2.05	03 J 03	036
B8	036	2.05	0,2	03	036	73
B9	036	2,05 i 0.25 .................................i....................................	03 ..............	036	7.5
B10	036	2.05	03	03	036	7.4

...

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.811	0.76	2,05	0.32	0.1	0,16	7.4
B12	0,36	3 <	0,34	9,1	0T6	7.4
BI3	0,36	2,05	0.35	0.1	0,16	7.1
BI 4	0.36	2.05	0.37	0,1	0.16	7.4
BI 5	0,36	2,05	0.30	0.1	0.16	7,3
BI 6	0,36	2.05	0.49	0.1	0, lb	·-} ·> Z <ηΊί

Table 5.2 - Characterisation of Cationic Micelles with Anionic Polymeric Counterions at pH 7.3 to pH 7..6

'Formulation Name	P/D .net	Z average diameter, nm
BI	4),025	2.998
02	<95	3.197
133	-0J	3,613
.84	<125	3,036
85	<15	4.999
86	-0,25	5.199 ................................. ......................:
87	0.5	7.85
B8	-1,0	12.76
89	_________________________ 6.25	23.96
BIO	-1.5	............................... ..................... 26.62
811	-1.6	29,47
........................ 812	.................. 6,7	20.84
813	-LS	36,15
814	6,9	23.97
815	2.0	25.66
BI6	2,5	36,62

[<KH4?1 The visual inspection of the formulations in Table 5,1, comprising cationic mixed micelles and an anionic polymeric counterion indicate that clear, stable solutions were produced across a range of the absolute value of P/Dnet from less than to significantly greater than 1.0. In order to confirm the absence of small amounts of coacervate phase, the Z-average diameters of the series of samples were also measured. The results in Table 5.2 indicate that-the binding of the anionic polymeric counterion to

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PCT/US2012/063433 the cationic mixed micelles results in aggregates that are all larger than mixed micelles of the same composition without the polymeric counterion. The Z«average diameters of the micelles with polymeric counterions were small enough to exhibit excellent colloidal stability, be,, the diameters found were < 500 nm, and more preferably <100 as.

Example 6

Stability 'of Size of Cationic Micelles with Anionic Polymeric Counterions at P/Dnet >i (OK) The absence of coacervate or precipitate phases from formulations comprising micelles with polymeric counterions may, in general, be readily determined by visual examination of samples made on the scale as small as about 10 to 15 mi in capped test tubes. As taught herein, cationic mixed mteeOes with an anionic polymeric counterion also exhibit the important, property of solubilization of water-insoluble oils when coacervate or precipitate phases are absent, and this solubilization may also be evaluated through visual inspection of samples. The absolute value·of tbs P/Dstet parameter csnoot be used alone to determine formulations which are free- of coacervates or precipitates, but instead must be considered together with the mixed micelle composition and tbs type of water-soluble polymer selected for use as a polymeric counterion. In order to avoid coacervate and procipifate phases, the polymeric counterion must he soluble in aqueous compositions at the pH of the desired final .formulation. The solubility of polymeric counterions in aqueous compositions may also be readily evaluated through visual inspection techniques. Thus, for example, the .solubility in water of Aicosperse^ 747, a random copolymer, Aocatragt®. All-4, an. acrylic acid hpfnopolymer, and Aicoguatd^ 524b, a. random graft copolymer, all of which contain carboxylic acid groups, may he compared over a range of pH values and .any polymer which-does not exhibit the necessary solubility at the pH of interest may be. avoided.

Formulations comprising cationic micelles and anionic polymeric counterions that arc free of coacervate and precipitates with, the- absolute value- of the Ρ/Dnet parameter >1. can also be readily identified, for example, formulation Bit) in Example 5. in addition to the visual inspection of this sample, which indicated It to be free of coacervates or precipitates, HLS was used to monitor the Z-average diameter of these aggregates upon overnight aging to confirm their stability, he,, as an alternative method of ensuring that the aggregates remained free of coacervates, (MW)) Thus, formulation B10 was placed in a sealed cuvette and a measurement of the Z-average diameter was taken every 30 minutes over a. 13.5 hour period, with the

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PCT/US2012/063433 temperature controlled at 2S°C. Such a procedure. may be readily accomplished with the Malvern Zeta Sizer used, and those skilled in the art will, realize .that equivalent measurements may be made with other instruments. The results of this experiment are shows is Table 6,

Table 6

Z average diameter of Aggregates Comprising Cationic Mixed Micelles and Anionic Polymeric counterion Formulation BIO Stared. Overnight

Age of Sample, hours	Z~aver»ge diameter, nm
0	24,6 1
0.5	23.86
1	23.61
L5	23.77
................. 2 ..............	23.33
2.5	23.36
$	23.47
.-:.5	25 66
4	23.71
4.5	23.81
5	24.64
S4	24.44
6	24,2.2
6.5	24,36
T	23.33
7.5	23.54 ............................................... ........................
§ ί 25.47 ........... :____________________ ___________________________________
8.5	24.37
9	23.15
9.5	24.33
10	23.87
11X5	.24.13
11	23.34

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11.5	233
12	23 /«
123	23.8
13	23,87
13.5	2531
Overall mean Z~
average diameter,
mn	22 8
Relative Standard Deviation of Diameter, %	1.73

ΗΜ.Π51| The- results in Table b indicate that.the Z-average diameter of Formulation Bi 0 appears stable, hs., with a relative-standard deviation of less than 2% over a 13.5 hour period, confirming conclusions made with visual inspection of the sample. The resultsalso indicate that stable-formulations five of coacervate and precipitates with the absolute value of F/Dnet > t_s comprising cationic micelles and anionic polymeric Counterions may be made.

Example 7

Formulations· Suitable For Delivery from Nonwovsns-pr as Disinfecting Spray -Cleaners Acidic pH

Formulations comprising mixed micelles of a germicidal quaternary' ammonium compound -and an amine oxide may also comprise adjuvants or buffers which can be used to adjust the pH. In these examples, monoethanolamine (MBA) was used to Increase the pH of the formulations, and glycolic acid was used to decrease the pH of the formulations. Decreasing tbs pH of such formulations may be desirable for increasing certain aspects of cleaning performance, for example, the dissolution of hard water spots from sinks, tiles, dishes, etc. The inactivation of certain viruses and bacteria is also known io improve when the pH is decreased below pH 7, to the acid pH range. Certain other aspects of cleaning performance of amine oxides, such as residue deposition on bas'd surfaces which results in filming or streaking, and decreased ability to solubilize greasy soils tend to be exacerbated as the pH of the formulations Is decreased, especially below pH 7, Surprisingly, the use of anionic polymeric counterions in formulations comprising

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PCT/US2012/063433 germicidal quaternary ammonium compound and amine oxides improves the wetting properties of the formulations on a range of surfaces, while decreasing residue formation. Thus, the addition of volatile cosolvents to die acidic formulations to improve performance properties may be avoided when polymeric counterions are utilized.

|'CWtS3] In this example, the water soluble polymer (Alcoguard® 2300 from Akzo Nobel) was a random copolymer of the nonionic monomer dimethyiacrylamide (95 mcle%) and the anionic monomer acrylic acid (5 moie%), which thus provides 0,00600 moles of anionic groups per gram of polymer actives. This polymer Is soluble in water at. both low pH, e.g., pH 2.0, and high pH, e.g,. pH 10, and can thus be employed as the anionic polymeric counterion to mixed micelles of the germicidal quaternary ammonium compound BTC® 1010 (MW 362 gOnol) and the amine oxide Ammonyx® LO.

[00364] Visual inspection and DLS were used, to determine foe formation of stable aggregates, the compositions of which are summarized in Table 7.1. In Tabic 7.2, the Z* average diameters are .summarized, and'indicate, the aggregates' formed as much larger than .mixed micelles of the 'germicidal quaternary ammonium compound and amine oxide in the absence of tbs polymeric counterion. P/Dnet was calculated based on characteristics of the polymerand BTC 1010 quaternary' ammonium compound.

Table 7.1 - Compositions

Formulation Name	BTC® 1010 wt%	.Ammonyx® LO wt%	Alcognard® 23θθ wl%	MLA wt%	Glycolic ik-d Wt%	pH
ci.	036	0.23	1.1.7	0.1	0	9,4
C2	0,36	033	1.01	0.15	0	9.2
CT	636	0.23	1,01	0,012	0.05	4.74
Of	036	0.23	0.72	0,009	0.0;	437
C5	030	0,23	(5.23	0,028	0,0 s	5.4
C6	036	0.23	5 0;	3 50	0.5	935
C7	036	(5,23	1.05	0.012	0.1	4.73 ................... 43
€8	036 _	0,23	(5.73	0,009	03
C9	036	0.23	0,23	0,003	0.5	3,4

Table 7.2 - Characterization of Compositions

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Formulation Name	P/Duel	Z averagediameter, run	Comments
Ci	1,5	26,33	Visually clear
C2 ...	•>1.3	25.98	Visually clear
C3	-1,3	30.91	VHuc® dear
C4	-TO	24.88	Visually Near
Cf	-0.3	15.13	VCrsa® Hear
C6	-I.3	28,93	Visually dear
€7	-ϋ	. f	Visually Near
O	-Ί.0	31,11	Visually clear
C9	-0.3	16.51	Visually clear

Example 0

Formulations Suitable For Delivery from. Nonwovens or as Disinfecting Spray Cleaners Acidic pH ^OOISSJ This- example shows some additional acidic formulations .using mixtures of arginine, -an amino acid, and glycolic acid to adjust the pH,

1001661 Visual inspection and DLS were used to determine the formation of stableaggregates, the compositions of which are summarized in Table 8,1. ip Table 8.2, the'Zaverage diameters .are summarised, and. indicate the -aggregates formed as- much larger than mixed micelles of fee germicidal quaternary ammonium compound and amine oxidein fee absence of fee polymeric counterion. P/Dnef was calculated based on characteristics of fee polymer and BTC® HI 10 quaternary ammonium compound.

Table 8Π - Compositions

Formulation	BTC®	Ammonvx® = Alcoguatd®	Arginine	I Glycolic	pH
Name	1019	1,0 v.4%	I 2309	wf®	i acid.
	wt%		: w!%		Wt%:
CIO	0.37	0.23 1 0.088 :	0,174		5
Ci I	0.35	0.21	ί 0.22 ....:....................................__	0.174	1 0,097	5
02	0.4	0.24	; 0,45	0,174	j 0.105	5
C13	0,34	0.21	i 0.67	0.174	90,112	5

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04	0.34	0,21	0,92	0,173	0.12?	4 5
A;?		034	0,21	1.43	0.174	0,08	5
CIS		0.35	0,2.2	1.37	0.174	0.08	5
cr?		0.34	0.22	1.55	0,174	0,00	5

Table 8.2 - Characterization of Compositions

Formulation Name	P/Dnet	z sveniga diameter, run	Comments
CIO	-(.3	13.51	Visually dear
Cl I	c' ·>„	17,15	Visually clear
02	§	17.5b	VONiy clsar
(.'13	-0,75	22,01	Visually dear
04	C ,0	30.70	Visually dear
0 5	-1.05	25.78	Vteuslly Neer
CIO	-1.8	30.41	Visually etear
07	-<.·,. A.»,-	29.31	Visually clear •

[00157] Spores (or more· properly, endospotcs) are. .a type of dormant cell produced by many types of bacteria, such .as .fibeh'to and Cfes/Hdnm, In response to. stressful emdronmental conditions. Tlx? exterior coats of spores, which are responsible for the resistance to extreme conditions.,'are mold-layer structures composed primarily of crosslinked polypeptides. When a spore encounters an environment favorable- for growth of vegetative cells, the spore coat also allows access to nutrients and water to the spore, and the production of a vegetative cell, in a germination process, [IWISS] The compositions of the polypeptides, proteins, and other minor materials that make up the eoat of TtezdCx Sw/A/A spores, for example, result in foe spore exhibiting s net anionic charge (negative zeta potential) when foe spores are dispersed in water at neutral pH, i.e., pH 7. Polypeptides in aqueous solutions will exhibit a net charge as a function. of pH of the solution that Is determined by the relative numbers of anionically and cationically charged amino acids in the polypeptide chain. At a pH corresponding to the isoelectric point of a polypeptide, foe net charge on the polypeptide is zero, due to the presence of equal numbers of eadonieally charged and aniosic&lly charged

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PCT/US2012/063433 amino acids. The net charge on the polypeptide at pH values greater than the isoelectric point will thus be negative (anionic), and will be positive (cationic) at pH values below the isoelectric point. The isoelectric points (or point of zero charge) of various .foam'/».? spores have been found to he between about pH 3 and pH 4, Thus, the zeta potential of foe spores used herein was found to be cationic (positive) when the spores were dispersed in water adjusted to around pH 2, i.e,, well 'below the known isoelectric point.

(bhlSfol spores exhibit average diameters of around WOO nm (1 micrometer), and can thus act. as charged scattering particles when dispersed in aqueous media. Measurements of foe zeta potential of spores are thus readily accomplished using foe approach of laser Doppler velocity determination. that is implemented in modem instruments, such as the Malvern Zeta Sizer. Those skilled in the art will realize that an appropriate concentration of spores for such measurements of tire zeta potential of the spores can readily he determined, using dilutions of standard· dispersions of spores which are commercially available, Typically, foe spore concentrations in these standard dispersions are expressed as spotes/mi or colony forming units/nd of the dispersions. Applicants have found foat reproducible measurements of foe zeta potential of ffofo/fos spores can easily be made at spore concentrations of around I to 3.3 x 10* spores/mlSuch concentrations are readily made by dihdfoo of commercially available stocks with concentrations of 1 x 10* sporcs/mh [OtO] Spores contaminating surfaces such as towels, other laundry, or hard surfaces, such as boors, walls, medical equipment, food preparation or service Counters·, etc- will germinate and grow, producing increasing numbers of organisms on foe surface, when the environment becomes favorable, for example* when foe surface, becomes soiled or contaminated with materials that are suitable nutrients for the microorganisms. Germicidal quaternary' ammonium compounds or biguanides have little effect on dormant spores, but if they are present on foe surface of foe spores in sufficient concentration, they may kill foe organism at foe initial stage· of germination when foe environmental conditions otherwise become favorable.

(0(1161) Exposure of spores io solutions comprising micelles with a net cationic charge due to a germicidal quaternary ammonium compound or a monomeric biguanide can result in foe adsorption of some quaternary ammonium compound or biguanide onto foe spore surface, just as would be foe case with any other solid surface, as described above. The amount of adsorption of the quaternary ammonium compound or biguanide will increase as the total concentration of foe quaternary ammonium compound or

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PCT/US2012/063433 biguanide in solution increases, op to about the critical micelle concentration, at which it will become constant and maximum. 'Ihe presence of cationic sites (due to cationicaliy charged amino acids and other materials comprising fee spore coat) on the spore surface will be expected to oppose and limit die adsorption. of cationic quaternary ammonium compound or biguanide.

Adsorption of the quaternary ammonium compound or biguanide will he favored at the anionic sites on the spore surface. If the medium surrounding the spore is suddenly changed, for example by fee addition, of an organic soil load which could servo as a nutrient source to fee spores and thus favor germination, then the adsorbed quaternary ammonium compound or biguanide, like any other surfactant, will re-equilibrate with, the surrounding medium, resulting in desorption of at least some of the quaternary ammonium compound or biguanide from the .spore surface,.thus decreasing its antimicrobial efficacy during fee subsequent germination of the spore.

As is shown below, the compositions of the instant, invention, in which micelles with a· net cationic charge am paired with g -water-soluble polymer of anionic charge, while remaining soluble and free of coacervates or precipitates, have fes advantage of fine control of the adsorption and description of cationic, surfactants, including the germicidal quaternary ammonium compound and biguariides, which CM he. exploited to provide better antimicrobial efficacy against the proliferation of bacteria on surfaces due to the germination of spores.

Example §

Demonstration of the Adsorption of Germicidal .Quaternary Ammonium Compounds onto Spore 'Surfaces from Mixed Micelles and Mixed Micelles with Polymeric Counterions (Micelle-Polymer Complexes)

The zeta potentials of Stfe/fed spores suspended in water at pH 7, the mixed -micelles without the polymeric counterion (P/Dnet -^= 0), or mixed micelles interacting with an anionic polymeric counterion were measured using the Malvern Eetasizer. The presence of monoeihanolamine in fee formulations ensured that the pH was >9.0, which Is well above the estimated isoelectric point of the spores, thus ensuring that the spores would exhibit a relatively strongly anionic (negative) zeta potential.

A commercially available stock .suspension of Bsfefeis Stferite spores was used to make all samples on a given day. Samples were analyzed within four bourn of preparation. Thirty micro liters of the stock spore suspension (1 x 10” cfu/ml) were mixed

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PCT/US2012/063433 with 870 mscrchters of water (pH 7) to give a control sample containing about 3.3 X KF cfu/ml. The entire sample was loaded into a disposable capillary call for measurement of the zete potential, of the spores, as described generally above, In the ease of the formulations, thirty microliters of the stock spore suspension was mixed with 270 pi of the fon.nuia.tion, allowed to equilibrate '10 minutes, and then 600 μ! of deionized water was added to again yield a spore suspension of about 3.3 x 10^υ cfo/rnl This sample preparation method was also followed in the comparison of the germicidal activity via the spiral plating method used in the next example below.

Table 0.1 - · Compositions

Formuiatio n Name	Polymer Alcosperse ® 747 Wi%	Amine Oxide, • Amrnonyx ® to.	Germicidal Quap BTC® IOW,wt%	Monoethanol xocoe wtef	P/Dstel
......... of
0	1.8	0.2	0.5	0
D2	0.00255	IA	0.2	0.1	MA
03	(1202	1,8	0,2	0,1	-2.0

Table 9.2

Zeta -potential of Rixh&s fftbO/A spores (3.3 XMC6 cfu/ntl) in-water and in Formulations of various P/Dcet

Spore·, treatment	Absolute vales, P/B .net	Mean Zeta potential, m.V
Control - spores only in deionized water	N/A	-45.3
Spores in D.1	0	-420.5
Spores in D2.	0,05	+12,4
Snores in ,D3: .....................'.....................	2,0	.C-. .Λ .............. ..............

[oofhbi 'the results m Table 0.2 indicate that the zeta potential cf the batch of spores used on this day exhibited an anionic (negative) zeta potential, as expected. Exposure cf the spores to formulation D.1, the mixed micelles comprising the· germicidal quaternary ammonium compound .and amine oxide in the absence of a polymeric counterion, causes a large shift in the'zete potential of the spores in the cationic direction, and in feci completely reverses the zeta potential of the -spores to +20.5 mV.

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PCT/US2012/063433 (WI§?1 This change can be explained by the adsorption of the germicidal quaternary ammonium compound onto the spore surface, causing a compensation of the negatively charged surface sites, which would ieave only cationic-ally charged surface sites available to contribute to the zeta potential. It is also possible that overcompensation of the negative sites on the spores could be achieved through the adsorption of multiple layers of quaternary ammonium comptnmd molecules, causing an additional shift in the zeta. potential of the spore in the same cationic direction. The results -also show that exposure of the spores to formulation D2 results in a shift of the zeta potential in the cationic direction. Since the absolute value of P/Dhet is. less than I.0, the aggregates (complexes) formed by the interaction of the -polymeric counterion and the mixed micelles have the cationic charges due to the quaternary ammonium contpcmnd in excess, and fans 'have a cationic charge, as shown above. The shift in the zeta potential of the spores caused by exposure to formulation B2. clearly indicates. adsorption of the germicidal -quaternary ammonium compound, i.e ,, the presence of the-polymeric counterion does not interfere with the adsorption process. Since the magnitude of the shift of the zeta potential is somewhat smaller far .exposure to formulation D2 compared to Di, It is believed, without being bound by theory, that the adsorption of some of tbs anionic polymeric counterion onto the spores also occurs, changing the- overall chemistry of the adsorbed layer [001 Surprisingly, exposure of the spores to formulation D3 also, causes a significant shift of the zeta potential in the cationic direction, to a value duly slightly below 0, Thus, even when the absolute value of PTfeel is much greater than i, indicating an excess of the anionic charges, due to the polymeric counterion over that of the cationic charges due to the germicidal quaternary «ammonium compound in the aggregates farmed, significant adsorption of the germicide onto the spore surfaces still occurs. Thus, delivery of an adsorbed layer of germicidal quaternary ammonium compound onto the spores, which will be available to kill the bacteria -upon germination, can be accomplished across a broad range of the absolute' value of P/Dnet,. which in tore allows adjustment of the formulations for other properties, such as oil solubilization, greasy soil removal during a cleaning process, and -aesthetic properties such as lack of filming .or streaking on solid surfaces,.

Example Id

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Antimicrobial Activity of Mixed Micelles Compared to Mixed Micelles with Poiymeric Gonnterions (Micelle-Polymer Complexes) Against fiocii/m'-S’nhPlfe spores [00ibfo A simple method was developed to demonstrate the utility of formulations comprising mixed micelles of a germicidal quaternary ammonium compound with a water-soluble anionic polymeric counterion (micelle-polymer complexes) in killing bacterial spores placed in an environment favorable for germination.

[00Π0] Serial dilution of concentrated cell suspensions followed by plating on a solid growth medium is a common way to determine the viable cells, or colony forming units (CFtJ), in a the suspension. The CFU multiplied by the relevant dilution factor relate back to the viable microbes in the original suspension. Those skilled in the art recognize that the automated spreading of a spore suspension in a spire! formation from near the center to foe periphery of a circular plate containing solid microbial growth medium (agar medium described in detail here) simultaneously accomplishes dilution and a way to determine theCPU/ml of the microbial suspension through deposition over an ever lengthening. ares of the solid medium. Standard recognition software can visualize colonics on the solid medium and calculate foe ChU/re i of the original suspension based on the distance, and number of colonies' relative to the center- of the plate.. Such an approach is implemented with eororocreiahy available equipment, such as foe Autoplater Model APSO0O (Advanced Instruments) used in the following examples, [00171] -Spores· which have been treated with the inventive compositions will be killed upon germination, when they are deposited onto the growth medium due to a combination of the presence of some residual, amount of the aqueous formulation and the quaternary ammonium molecules which are strongly adsorbed onto the surface of foe spore. The spiral plating of the spore suspension accomplishes an exponentially increasing amount of dilution of foe spores in a spire! pattern on foe growth medium. Thus, the concentration of the aqueous .formulation deposited with foe spores is exponentially decreased by dilution with foe growth medium. In addition, the chemistry of foe aqueous environment surrounding the spores changes dramatically towards one rich in. .nutrients such as proteins. Thus, foe quaternary ammonium molecules and any other surfactants adsorbed on foe surface' of the spore will reroqushbrete with foe surrounding growth medium through desorption (partial or complete) from the spore surface, and/or a displacement from the spore surface through the adsorption of other materials present in the growth medium. In other words, the spiro! plating method exposes foe spores suspended in the inventive compositions to an exponentially increasing “organic load”.

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PCT/US2012/063433 which is well-known, in the art. to Interfere with and or prevent the antimicrobial action of common germicides such as quaternary ammonium compounds .or bignanides.

[M172) When suspensions of spores in fee inventive compositions are deposited on growth medium via the spiral plat tog technique, fee spores ..nearest the center of the spiral pattern will be more likely to he- killed upon germination by fee adsorbed germicidal quaternary ammonium compound or higuanide·, and feus there will be no colonies observed after incubation in this region. Thus, instead of fee expected. spiral pattern in which there are torse numbers of colonies cro wded together nearest the center of the plate, there will he a circular “hole” In the pattern due to the killing of fee spores upon germination, Farther away from the central starting point of fee spiral, where the huge dilution has decreased the ability of fee· adsorbed biocidal species to kill the spore upon germination as described above, viable colonies will appear and continue In a spiral to the outer .edge of the plate, 'Thus,. the diameter' of fee circular hole- In the spiral pattern is .larger for formulations which provide, more killtog of spores upon germination under favorable conditions, (00173) The equipment used for fee splml plating of fee suspensions of tire treated spores yields a pattern in which the central hole has a diameter of about 2 cm when a high concentration of spores feat are viable (in a control experiment, for example) are present at the start of the spiral pattern. if the treatment of fee spores results in killing upon gemination of all of the spores, then the maximum diameter of the hole is-about 8'-cm, Thus, -values of the diameter of fee central hois- between about 2 cm and 8 cm, herein called fee -germicidal zone diameter, represent varying degrees of effectiveness of'the treatment of fee spores for prevention of-fee contamination.of a surface by the germination of spores under extremely favorable conditions, with larger values of fee diameter indicating better effectiveness, Such testing methods are feus a- good indication of the efficacy of the inventive compositions under various real life use conditions where various organic loads may be present Or applied.

!.wm) The treatment formulations, and dilutions of them., were placed in fee wells of a 76 well plate, 10 mlcrolitem of fee- standard spore suspension were added and allowed io age for if) minutes, followed by fee addition of 266 pi of sterile water, and then 20 pi of fee spore suspensions were then spire! plated onto the pistes containing growth media. The spore concentrations treated were all the same, about 1 xltT, which is similar io fee number of spores nested with fee compositions in fee determination of fee changes in the

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PCT/US2012/063433 zeta potential of the spores described above. The plates were incubated overnight at 37%, followed by a measurement of the diameter of the germicidal zone diameter.

[00175) Formulations comprising mixed micelles of the germicidal quaternary ammonium compound STO .1010 and an amine oxide were made as described above, over a range of P/Dnet values, using the anionic water-soluble polymer Alcosperse® 747 as the 'polymeric counterion. Formulations El through E5 contained the same quaternary ammonium compound concentration, while formulation E6 contained a significantly lower quaternary ammonium compound concentration. The relative amounts of quaternary¹ ammonium compound and amine oxide in the mixed micelles, however, was the same. The compositions are shown in 'Fable 10- .1.

Table 10. .1- Compositions for Testing Effects of Treatment of TEmE&v Sff&E/ff spores

Formulation Name	Polymer Alcosperse ® 747 wt%	Amine Oxide, Ammouyx Φ LO, wt%	Germicidal Quat. ETC® 1010, wt%	Monoefoan olamine vffff	F/D .net
El	0	LS	C‘; .........j	0,1	0
E2	.0,00255	it	0.2	05	•Ό.05
E3	0.0255	1,8	.............................. 0,2	........................ 04 ..............................	-05
E4	0.O5I	IT	0,2	0.1	5.0
15	0..102	I s	0.2	0.1	-2.0
E6	0	0,222	0,025	05	0

To Covet a large range of concentrations Of foe germicidal quaternary ammonium compound in the -treatment of the spores, formulations El through Ed were used neat (dilution factor ~1), and at various dilutions (dilution factors 0,5 to 0,03125, or 2x to 32x times dilution of the original formulation). The results obtained with foe spiral plating test are summarized in Table W.2

Table 10.2

- Spiral plate results Effects of Fomntiations on Viability of TOG/Eb 5255/5 spores

Fomas Luion Name	Dilution Factor Prior to Spore Exposure
1 ] 0,5 1 .....	0,25 10525 i 0,0625 ..................1............... J	0,03125 ..............................	/'Absolute value. P/Dnet
	Spiral Plate Germicidal Zone diameter, cm

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El	s	7.5	5,7	4,8	3.7	2	0
E2	7.9	7,4	5.6	S	4	i ··> : .«·	0.05
E3	7	7	6,4	4.7	4		2	0.5
E4	§	7	b	S	3.7		2	1,0
ES	S	7,5	5.8	5	3,5		2	2.0
E6	4.6	2.5	2	•x ,Z.	2	2	0
............... —ZL.

[S0177] The results in. Table 10.2 show that Formulations E2 through ES (all of which contain the same quaternary ammonium compound concentration) all exhibit excellent performance in killing the spores upon germination, as does the control formulation El, when used nest (dilution fector 1),..yielding germicidal zone diameters of 7 to 8 cm. Dilution of formulations El through E5 by 32x (factor 0.03125) results in zone diameters of 2 cm, Indicating no. significant effect, ou-the growth of the spores when they are placed oh the growth media. Surprisingly; formulatiqns in. which.the absolute value of P/Dnet are 1, (indicating an equal number of anionic .charges due. to the polymeric counterion and the cationic charges due to the germicidal quaternary .ammonium compound) or even 2 (indicating. an excess in the number .of anionic charges, due io the polymeric Counterion over the cationic charges due to the- germicidal quaternary ammonium compound) exhibit killing performance comparable to that of the control formulation across a. range of dilutions in this tesf. confirming the robustness of the adsorption of the germicidal quaternary ammonium compound onto the. spore, surfaces, and in. line with tbs effects of the formulations as measured by the changes in the zete potential of the spores, ss described above.

(00170] Control Formulation Ed included no polymeric counterion. Formulation E6, when diluted 2x (factor 0.5) contains 0.0125 % quaternary ammonium compound, and shows only a small amount of germicidal activity, as shown by a. germicidal zone diameter of 2.5 cm. Formulations· E2 through E5_S when diluted 1.6x (factor 0.0625), also contain 0.0125% quaternary ammonium compound. However, due to the presence of the polymeric counterion fo these inventive compositions, the germicidal activity is significantly better than in foe case of formulation E6. The germicidal zone diameters measured for treatment of spores with E2 through B5, at the dilution factor of 0.0625, are all significantly greater than that of formulation E6 at the dilution. factor of 0.5, indicating the significant benefit of the presence of the anionic polymeric counterion in ensuring the

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PCT/US2012/063433 kill of spores during germination under favorable conditions, Applicants speculate, without being bound by theory, that the presence of the anionic polymeric counterion along with the germicidal quaternary ammonium compound in the adsorbed layers formed on the spore surfaces decreases the tendency of the germicidal quaternary ammonium compound to desorb from the spore surface, upon dilution of the spores in the growth medium andfor decreases fee tendency of other surface-active molecules In fee growth medium from competitively displacing the germicidal quaternary-ammonium compound from the surface of the spore® thus providing improved germicidal performance of the inventive formulations compared to fee control, formulation containing mixed micelles without a polymeric counterion.

Example Π

Antimicrobial Activity of Mixed Micelles Compared to Mixed Micelles wife Polymeric Counterions {Micelle-Polymer Complexes) Against Eccd/i® SPEh/G spores feOlTP) Some additional inventive formulations were developed covering a range of P/Dnet values and tested for activity -against fee growth of spores in the .same manner as described in 'Example 10. A comparison wife fee activity of the control formulation B6 was also' made, for the reasons described in. Example 10,

Table .11.1.- Compositions for Testing Effects of Treatment o f Eccj&v GdVEA spores

Formfeatio n Name	Polymer AleosperSe A 74 ?'	Amine Oxide, Ammonyx. 40 CO, wt%'	Germicidal Quat, BTC® 1010, wt%	Monnefean datum® wdEs	F/D net
Pi	..... 0.00255	0.,2	t>	0.1	-0.05
F2	0,0051	0.2	ES	0,1	--0,1
F3	0.0102	0,2	1,8	0.1	-0,2
F4	0.0153	0.2	ES	0 1	-0.3
ES	0,0204	0,2 .......	1.8	0.1	-0.4
F6	0.0450	0.2	ES	Od	-0.9
E6	0	0,226 ______	0,025 ............ .................	0..1.	0

Table i 1.2 Spiral plate results - Effects of Formulations on Viability of tefe Sx6E/A spores

Dilution 'Factor Prior to Spore Exposure |

I 10.5 | 0.25 10.125 I 0.0625 | 0.03125 ί Absolute value,

Formulation

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[W18GJ The results in Table 11.2 again indicate that formulations of the instent invention exhibit .excellent germicidal performance, killing spores placed in an extremely favorable environment. In addition, the formulations show better performance at dilutions of i&c (factor 0.0625) than the control, which delivers the same total quaternary ammonium corn-pound concentration of control formulation E6 at a 2x dilution (factor 0,S).. The similarity in killing performance of the inventive compositions-across s range of the absolute. value of P/Dnet shows that optimization of other parameters of foe· formulations, such as cost, cleaning performance or kinetics, or surfbee residue aesthetics can be adjusted via P/Dnet while, maintaining foe mifimierobi&l properties of the formulations, due to foe fine control of the interactions of foe surfactants in the mixed micelles that can be .achieved with foe use of a water-soluble, polymeric counterion of charge opposite io font of foe net charge of foe mixed micelles.

Example 12

Antimicrobial Mixed Micelles with Polymeric Counterions (Micelle-Polymer Complexes) Delivered from a Nonwoven (00.1.6.1) Formulations comprising polymer micelle complexes comprised of mixed micelles of a-germicidal quaternary ammonium compound and an amine oxide and anionic water soluble polymers increase the antimicrobial efficacy of a formula delivered by a nonwoven wipe. In this example polymer micelle complexes formulated over a range of P/Dnet values ate shown fo outperform mixed micelles in foe VIM hucmafo'oal Standard Practice for Evaluation of Pre-Saturated or Impregnated Towelettes for Hard Surface Disinfection, Test Method E 2352 (henceforth referred fo as the toweiette test) against Paenrkmones. This example also demonstrates flexibility in c .- ,v of -polymer

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PCT/US2012/063433 chemistry and the compatibility' of mlcelle-polymer complexes with solvents and silver ions, [00182] Compositions and WDoet values of the foundations are shown in Table 12 J, Formulations we prepared fey first mixing BTC® 1010 (Stepan Co,) and Ammonyx® LO (Stepan Co,) in the specified asn cents with water, thus forming the mixed micelles. The pH was then adjusted using MEA and glycolic acid in the specified amounts. The specified amount of anionic polymer (Afcosperse® 747» Aicogusrd® H5240 or Alcoguafo® 2300, all from Also Nobel) were then added to form the micellepolymer complexes. Fropylene glycol n-hutyl ether (DowanoP⁸* PnB, Bow Chemical Co.) was added to. formulation 0.3 to demonstrate compatfofifey with, solvents. Silver dihydrogen citrate (Tinosan® SBC, Cifea) was added to formulation G6 at a raw material concentration of 0.123 wt% (equal to 3: ppm silver ions) to demonstrate compatibility with silver ions. The formulations form stable aggregates, characterized by DLS analysis as described in examples i-O'and were visually clear, [88183] Moist towefettes were prepared for ASTM Test Method E 2362 by applying foe appropriate formulation to a roil of the towefettes. The mass· of foe liquid formulation-added-to the rolls-of foweiettes was 4.5 times the mass of the- dry towefettes. Toweietfes used in this example were-nonwoven, 40' gsrn material purchased from N.R, Spnntech Industries Ltd. The moist towefettes were allowed to equilibrate- at room

Table .12.2 - Antimicrobial activity of formnlaiions delivered from nonwovens. | Formulation Name [ Towelette 60 carrier [

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PCT/US2012/063433 test against Pso&fomomr - 3

	Fail
G2	Pass
03 | Pass
04	Pass
05	Pass
G6	Pass

[<101041 Comparing formulations Oi and G2 show that addition of a small amount of anionic polymer to form micelle-polymer complexes characterized by P/Dnet ~ -075 increases the antimicrobial. qffieacy against PMWonmmx? enough to generate a 'passing result. Formulation. G3 shows that the microefficacy of formulation G2 is preserved when 2 wt% of PnB is added to the· formulation, which may be desirable, for robustness of the fohnula as well as· a variety of -aesthetic benefits. Formulations <34 and G5 demonstrate that a wide range of Water soluble polymers are suitable for forming the micelle-polymer complexes. Formulation 04 also shows that micelle-polymer complexes formulated st an absolute value of P/Dnef greater than 1.0 are. capable of boosting· antimicrobial- activity relative to-that of mixed micelles without the polymeric counterions as well. This result is particularly surprising considering that the cationic charge on the germicidal micelles -is widely accepted to he the driving force for adsorption of the active ingredients onto microbes. Finally, formulation G6 demonstrated, the Compatibility of the micelle-polymer complexes with silver tons.

Example 13

Kinetic Benefits of Antimicrobial Mixed Micelles with Polymeric Counterions (MicellePolymer Complexes) Delivered from a Nonwoven

Two of the formulations described in Example 12 were tested at I minute contact times against 5?apdp4ococcns /few· and using the ASTM

International, Standard Practice for Evaluation of Pre-Saturated or Impregnated Towolettes for Hard Surface Disinfection, Test Method E 2362. These· formulas' demonstrate passing antimicrobial efficacy at contact times considered to be extremely short for quaternary ammonium compound-based formulas.-Formula GI, a mixed micelle

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PCT/US2012/063433 control which delivers the same concentration of germicidal quat without the polymene counterion, is not capable of passing the towelette test, at 3 minute contact times (see example .12).

[001.86]

Table B.l - Antimicrobial activity of formulations delivered from no.nwove.as.

Formulation Name	Towelefte 60 carrier test against S'wp&y&weem· Aiifte.vs - 1 minute contact time	Toweletfe 60 carrier test against Psosfoswsos -1 minute contact time
G2	Pass	Psss
G6	Pass	Pass

Example .14

Dilutable fonndlations of Antimicrobial Mixed Micelles with Polymeric Counterions (Micelle»Folymer-Complexes) on Laundry [99187] Dilutable formulations· which way claim' sanitization of laundry are governed hv the documedt EPA DIS/TSS-13 ^Laundry .Additives - Disinfection and Sanitization”, Such 'formulations must be. demonstrated to reduce the levels of bacteria (both G« + and Gram *) by at least 99.95¾ in a specific test protocol known as the ‘Tetroecl and Clark.Laundry Additives Method (sanitizing level/’,

I06M8I This example demonstrates the delivery of antimicrobial efficacy benefits using dilutable- formulations, comprising polymer-micelle complexes comprising: mixed micelles of a germicidal quaternary ammonium compound and an amine oxide and muonic water soluble polymers- In this -formulation B'I33®^: 81.8 and Ammonvx® DO are mixed in water at the given concentrations, and then Alcoguard 5240 is added and mixed well. The formulation Is visibly clear in the concentrated form and when diluted in hard water as per the laundry sanitizer test protocol.

Table .14.1 - Composition of formulations for a dilutable laundry sanitizer

Form a laf ion	Polymer	Amine	Germicidal	| F/D net	Latmdr
Name	Alcoguard ® 5240 wt%	Oxide, Ammonyx A DO,	Quat, E1C® 818, wt%		y Sanifiza boa Test 1/5 84 dilution

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| Hi	0346	3,02	II ,7	0,025	Pass
s H2 !...................	0 ΐ ...... a	0	U.7	Q	Fail

(001S9] Formulation Hl is capable of passing the laundry sanitization test mentioned above against foigfefecoiwiw Bare®? and Hfefofe Pmnmonm at a 4 minute contact time when diluted 1 part to 584 parts in hard water. The extreme dilution ratio and high bacterial loads make this test method exceedingly difficult, to pass with quaternary ammonium chemistries· such as .formulation Η2»

Example 15

Oil Solubilization .'Enhancement wife Polymer-Micelle Complexes Formed with an anionic polymeric counterion and mixed micelles.

(<501W] Consumers, of aqueous based liquid cleaners frequently prefer fragranced formulations with excellent: oily soil removal, while still, demanding low residue on •cleaned surfaces. The key to successfully satisfying this consumer demand is that the total concentration of solubilizer compounds he· sufficiently high to fully incorporate the oily fragrance .and any nonaqueous solvent compounds used to ensure excellent oily sod cleaning according to consumer preferences, while minimizing the total concentration to lessen the visual residue left on the Cleaned surfaces, especially in the 'absence of a rinsing step. Applicants discovered that the interaction between mixed micelles comprising an amine oxide and germicidal quaternary ammonium compound and -an anionic polymeric counterion according to one embodiment of the Invention enables a. unique and surprising oil solubilization boosting effect, to satisfy these consumer preferences. In other words, similar results can be achieved with significantly less solubilizer when employing the inventive complexes.

The oil solubilization boosting effect of the polymer on the· mixed micelles is readily illustrated by comparing the lowest' total solubilizer concentration needed to solubilize 0.3wt% limonene used as a model oily compound, such that the compositions are visibly clear, fee of excess oil, precipitate and coacervate, in the absence and presence of the polymeric counterions. In this example, tne total sulubihzer concentration is the sum of the concentrations of the polymer, the germicidal quaternary ammonium compound BTC® 1010, and the nontonic surfactaut Ammonyx® LO. The compositions are shown in -Table 15,1,

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Table 15.1

Example	P/Dnet	3 A \ .ov,.	Asnreonyx® s Ako-sperreA	Limonene wAf
LO wt%	-405
A	0	0,05	>1.2 .....:.........	0	94
12	Q	0,1	1,275	0	0.3
73	1)	045	T35	0	0.3
$3»	TAI	0,05	9,595	0,90	0.5
IS ...	-0,01	0.1	0.754	t .93	0.3
	•ATI	94 5	9.981	,. k>	0.3

MBA	3fi s -i.i'r
Wt%	total solubilizer need wt%
04	>1,25
04.	1,375 ........
p.	LS
A	0.946
1 5 [ % 5	0454
[ \Λ ί-	:481

(0(0 §2] In this, example, the P/Dnet parameter was fixed at a relatively low absolute value, in order to teimmize the cost of the polymer added to the formuiatlom Throe different concentrations of S'fG® .10.1.0 were investigated. Tbs lowest total solubilizer requited in'foe absence of polymer was .determined at various concentrations by making a series of formulations in which the concentration of the Ammonyx® LO was- increased until the .formulation was completely clear, corresponding to foil solubilization of the. limonene oil. Solubilization of the limonene was not achieved in the series, of -samples made that ended with foe control formulation Π, which was a cloudy dispersion. Solubilization of foe- limonene could be achieved when the concentration of 'foe BTC® .10.(0 cationic germicidal surtbetant..was increased somewhat, and If enough Ammonyx® LO was added, to give foe final total solubilizer levels shown for formulations J2 and TT (W193) The same procedure was. used to detemtine foe minimum total solubilizer requirement -in foe presence of polymeric counterions, at a fixed F/Dnet- 0.01 ratio. Appropriate amounts of foe surfactant stock solution,· monoethanolamine (to adjust pH above 9.0), limonene, cod water were mixed to form foe final control formulation containing foe mixed micelles. In foe case of formulations comprising the polymeric counterion, the same mixed· surfactant stock solution, monoefoanolamine, limonene, and Aicosperse® 465 poly (acrylic acid) homopolymer supplied as an aqueous solution, Akzo Nobel), and water were mixed in appropriate amounts to yield the final formulations with foe fixed P/Dtist values, and increasing levels of Ammonyx® LO were added, thus varying the mixed micelle compositions, until a clear solution, indicating complete solubilization of fee'limonene, was obtained.

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PCT/US2012/063433 (001^41 Comparing the optimized compositions in Table 15.1., it is apparent that the formulations with polymeric counterions (14,. 55 and 56) require lower total solubilizer concentrations, demonstrating s significant oil solubilization boosting effect resulting from the polymer-mixed miceiie interaction. 'For example, formulation 55 requires only 0.854¾ total solubilizer to felly solubilize the limonene into a clear solution free ofeoacervates or precipitates, while formulation J2, which has the same concentration of the germicidal quaternary ammonium compound, requires a much higher total solubilizer level, 1.375%, to fully solubilize the same concentration of limonene.

jfeOlfos] Another unique- aspect of the effect of the presence of fee polymeric counterion is the remarkably low Alcosperse® 465 polymer concentration, in the ppm range, feat is needed for fee solubilization boosting. Thus, in .formulations such as hard surface cleaners feat may not be rinsed after use, very low levels of the polymeric counterion can .dramatically also lower the- total, levels of surfactant needed to deliver a water-insoluble oil such as limonene, contributing to significant cost savings as well as a reduction or elimination of consumer-perceptible residues on- surfaces cleaned, wife the formulations.

Example 16

Oil Solubilization Enhancement

108196] The enhancement or boosting of the solubilization of water-insoluble Oils ptay be obtained with a wide variety of water-soluble polymers., over a wide .range of P/Dnet values, offering considerable flexibility m meeting different antimicrobial performance, aesthetic or cost targets.

|00197] 011 solubilization optimization is carried oat In the presence of 0.3 wife limonene model oil by, in a series of samples, simultaneously Increasing the absolute value of P/Dnet and the concentration of fee nonionic amine oxide surfactant at a fixed cationic surfactant concentration until solutions which are clear, free of precipitate, coacervate and excess oil are obtained. Optimized compositions are feus tbs ones font turn clear at foe lowest added amine oxide surfactant concentration. The minimum total solubilizer values are feus the sum of fee BTC® 1010. Ammonyx® LG, and polymer (if present) in foe final formulations feat yield complete oil solubilization.

jfeliW] Appropriate amounts of BTC® 1010, Ammonyx® LO, monoefeanoi&mine (to adjust pH above 9,0). limonene, and wafer were mixed to form two series of samples in which fee Ammonyx® LO level was increased at fixed BTC® 1010 concentrations until

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PCT/US2012/063433 final control formubtfons K4 and K5, containing the mixed micelles «hd the solubilized limonene were obtained..

|WO9] In foe case of formulations comprising the polymeric counterion, the same surfactants. monoethanolamiae., limonene, and Alccspcrss® 747 (supplied as an aqueous solution, Akzo Nobel), and water were mixed in appropriate amounts to yield series of samples in which the mixed micelle compositions were changed by increasing, amounts of Ammonyx® LO, at several different, fixed P/Dnet values. Tha optimized compositions, ah of which are clear and free of eoacervate, precipitate and excess oil, are- summarized in Table 16-1.

Table '

			A: v 74? pm-	Limonene svtes	MEA wifo	Mis® sAabil .. ., ,v.· V'.-< ,‘Jl·
mtc tefo	W wiSS
K1 control	o·	04	1.275	0	03	04	< .·?. .·
K2	-0.]	0/1	1.09	510	0.3	04	1341
K3	A	0.1	0.91	510	03	04	L061
A4		04	0.91	510	0.3	04	1.061 1,577
K5 control	0	0.2	.1,275	0	03	04
K6	A	0,2	1.091	1020	0.3	04	. 1,393
K.7	A	0.2	0,545	1020	0,3	04	0347

|W2Wj The results in Table '16.1 show that inventive formulations K2> K3. and K.4 achieve complete limonene solubilization at lower total solubilize? levels than formulation K.1, indicating an enhancement or “boosting” of the 'solubilization of the water-insoluble oil when the water-soluble anionic copolymer is used as foe polymeric counterion for the mixed micelles bearing, a net cationic charge. Surprisingly, the oil. solubilization boosting can be achieved over a wide range of foe absolute value of P/Dnet, he,, oil solubilization enhancement can hs achieved with a wide range of compositions of mixed micelles due to the fine control over the interactions between the cationic and nonfonic-surfactants in foe mixed micelles that is possible through the use of foe anionic polymeric counterion.

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Similarly, formulations K6 and K? exhibit lower minimum total solubilizer concentrations than formulation K5.

Example I?

Antimicrobial Compositions Containing a Monomeric Siguanide, Chlorhexidine Gluconate [¢6201) The cationic germicide present in the mixed micelles may be a monomeric, biguanide salt, such as chlorhexidine gluconate (CHG). CHG was supplied as 20% solution in water, from S.igma»Aldrich, CHG has two cationic charges per molecule and a molecular weight of 897.8 g/mole, The mixed, micelles may also comprise nonionic surfactants. The compositions summarized in Table 17.1 comprise two nonionic surfactants, Snrfouic® LI2~8 {an alcohol etboxylate, from Huntssnan Corp), and Gluoopon^ 325% (an alkyl gluc-oside, from BASF Corporation) in the mixed micelles with the CHG, -Since the CHG .concentration is the same in formulations LI, L2 and L3, the value of Eq cationic will also he the same and is calculated as· follows:

Eq cationic “ 2 x 0.015 x 1/897,8 ~ 334 x i0‘^J eqnlvalents/WOg of formulation. And, since-there is no anionic surfactant present in the formulation, then

Draft =^:: D cationic ™ % x 0-.0000.334™ + 3.34 x 10^;> [00302] The water-soluble polymer used in this example as the polymeric counterion is poly{2-acjyiam.ido-2-methyl«Lpropanesulfonic.· acid}.» or polyAMPS, It has 1 anionic charge per monomer unit, which has a molecular weight of 207,25 g/mole. In formulation LI, polyAMPS is present at a concentration of 0.003'S vrfH or 0,0035 gram/100 grams of the formulation.

F is thus calculated as :

F - 0.0035 xlxlxfr 1)/207,25 - -0.0000168878.

Thus, P/Dnet - -0.0000168878/ 4· 334 x 10-5 - - 0.5053 [00203] The values of F and IVDnst for the other formulations are- summarized in Table 17.1

Table 17.1

		composition, wt %
ingredient	1., 1	L2 j	L3
CHG	0.015	0.015 |	0.015
FuriomCB 1....1'.G 8	035	0.016 1	0.01.6
Giucoponft- 325N	0 5	0.03? 1	0.037

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pofy(2~acry.iamido-'2~ methyl-i- e ??»< c	0.0035	0.014	0.035
DowsrmFM D.8	3.2
Bowanor''5 sfr-B	0.7
Monoeihanolam .ine	0.5
NaCl		0.6	0.6
Fragrance oil	0.3 ;
P«	11.	4	7
D net	3.3415 x I05	3.3415 x )05	3.3415 x IO5
F	4 ,68878 x!0'?	-6.75513 x Ifr	-0,0001689
I1 IWf	-0,5.053.9606	-2,021584238	-5.0530606

The negative values of P/Dnet for the formulations in Table 17.1 indicates that the polymer and mixed micelles are of opposite charge, and hence within the scope-of the. .instant invention, Ih.e formulations also illustrate that fragrance oil' may be solubilized Ip the mixed micelles, that the formulations may comprise water-soluble glycol -ethers or not, and that (he pH and electrolyte .levels of the formulations may be varied with appropriate adjuvants such as'monoethanol.ami.ns and sodium chloride. .Formulation LI is useful as a ready to use hard surface cleaner, while- formulations L2 and L3 are useful as lotions for -pre-moistehed wipes or as hand sanitizers.. Dowanol™ BB. and .Dowanol™ PnB are glycol ether solvents from DOw' Corporation. Fragrance oil was a lemon fragrance from Firmenieh.

[W20S] Without departing from the spirit and -scope of this invention, one of ordinary shill can make various changes and modifications to the invention to. adapt it to various usages and conditions. As such, these, changes -and modifications are properly, equitably, and intended to be, within the foil range of equivalence of the following claims.

2012393508 03 Jan 2018

Claims (13)

1. A composition comprising: a polymer-micelle complex comprising: a positively charged micelle, wherein said positively charged micelle comprises a water-soluble cationic material selected from the group consisting of a monomeric quaternary ammonium compound, a monomeric biguanide, and mixtures thereof, said micelle is electrostatically bound to a water-soluble polymeric counterion bearing a negative charge;

wherein said polymeric counterion does not comprise a block copolymer, latex particles, polymer nanoparticles, cross-linked polymers, silicone copolymer, fluorosurfactant, or amphoteric copolymer;

wherein said composition does not form a coacervate, and wherein said composition does not form a film on a surface; and wherein said composition does not comprise a polyelectrolyte complex.

2. The composition of claim 1, wherein the polymeric counterion is a copolymer of acrylic acid and styrene.

3. The composition of claim 1, wherein the polymeric counterion is a copolymer of a polysaccharide and a synthetic monomer.

4. The composition of claim 1, wherein the polymeric counterion is a copolymer of maleic acid and sulfonated styrene.

5. The composition of claim 1, wherein the polymeric counterion is a copolymer of a dimethylacrylamide and acrylic acid.

6. The composition of claim 1, wherein the polymeric counterion is a copolymer of acrylic acid and maleic acid.

7. The composition of claim 1, wherein the polymeric counterion is a copolymer of sulfonated styrene and maleic anhydride.

8. The composition of any one of claims 1 to 7, wherein the composition comprises a surfactant.

9. The composition of any one of claims 1 to 8, wherein the composition comprises a buffer.

10. The composition of any one of claims 1 to 9, wherein the composition comprises a fragrance.

11. The composition of any one of claims 1 to 10, wherein the composition comprises a dye.

2012393508 03 Jan 2018

12. The composition of any one of claims 1 to 11, wherein the composition comprises a colorant.

13. A composition comprising: a polymer-micelle complex comprising: a positively charged micelle, wherein said positively charged micelle comprising a water-soluble cationic material is selected from the group consisting of a monomeric quaternary ammonium compound, a monomeric biguanide, and mixtures thereof, said micelle is electrostatically bound to a water-soluble polymeric counterion bearing a negative charge;

wherein the polymeric counterion is selected from a copolymer of a polysaccharide and a synthetic monomer; and wherein said polymeric counterion does not comprise a block copolymer, latex particles, polymer nanoparticles, cross-linked polymers, silicone copolymer, fluorosurfactant, or amphoteric copolymer;

and wherein said composition does not comprise a polyelectrolyte complex.