WO2014070201A1 - 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

GATEO IC MICELLES WITH ANIONIC POLYMERIC COUNTERMMS COMPOSITIONS; METIIOBS A 1> SYSTEMS THE O

BACKGlOi!NB OF THE I mNTION

! , Use FfeM of the f nvettriors

|0§0I| The present itrventloo relates to polymer-micelle complexes,

2. Description si Related Art

[0002J Cleaning product formulations, including loose which contain common antimicrobial gge s such as y&teraary anrmonmm compounds and biguanides such as c orhextdhie and alexidine, rely on surfac an and mixtures of sor&eiaets to deliver eleanirsg (deisrgency) end aetlnderobial efficacy, A key aspect of these processes is the Interaction of the serihetants and tmtlrmeroblal agents with the solid snrfaees of the materials being clearred, as weli ss the surfaces of microorganisms, together wit the effects of the fo mulatio s on the alo-waier interface (surface tension). Redaction of the surface tension of aqneons fbrrnulatloes, winch is directly related to the effectiveness of the wetting of solid sorfaces and hence the dehn-genoy and antimicrobial processes, cars be manipulated through the rise of .mixtures of surfaetaets, as is known in the art.

| ®@3f At PKiieeiiiat level, surfactants and surfactant mixtures in aq eous, media exhibit the ability to adsorb ai the air-water, solid- ater, and - shwa;er interfaces, and this adsorption is hence responsible for a wide range of phenomena, Ineiedlrs the solubilization of oils in fire 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 generall known to irserease with surfactant eoircentration up to total surfac ant concentration known as the critical micelle concentration. (CIVIC), At the CMC, urfactants begin to term aggregates in the bulk solution known as micelles, in equilibrium with the monoroeric species of surfactants which adsorb onto die interfaces. i§ The details of the structures and slees of the micelles, as weli as the properties of the adsorbed layers of surfactants or soriaetani mixtures, depend on the details of the molecular shape and charges, If sa , on t e hydropailie "headgroups" of the snrte.ctan.ts. Strongly charged headgroirps of surfactants tend to repel each other si Interfaces, apposing h efficient packing of the surfactants at the interface, and also favoring micelle structures thai are relet; vely small and spherical. The charged headgroups of many surfactants, seed as the quaternary mmonium compounds, will also introduce a counterion of opposite charge, for example a chloride or bromide sou, into formulations.

£0005} It Is known that the nature of the counterion can afreet the repulsion between charged surfactants in mi elles and adsorbed layers through a partial scfseak of the headgroup charges from one another In surfactant aggregates like micelles. It 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 headgroup 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.

|OO 6| Addition of significant amounts of simple electrolytes into many formulations, such as hard surface spra cleaners or nonwoven wipes loaded with a cleaning louoo, Is undesirable doe to residues left behind upon drying of the tbn dahons. An alternative method to adjusting the properties of such formulations, including the wetting of solid surfaces and the antirnka-obad activity. I to include significant amounts of volatile organic solvents such as lower alcohols or glycol ethers. Volatile organic solvents, however, are coming under Increasing regulation due to their potential health effects, and are not preferred b the significant fraction of consumers who desire eOlcaeicos cleaning and disinfecting products with a mlnlmnm of chemical actives, including volati!es. Its the healthcare industry, efficacious formulat ons comprising quaternary ammonium compounds and lower alcohols are known, but are viewed as having shortcomings in terms of the potential for irritation of confined patients. Such p od cts pose similar risks to cleaning and clinical personnel who may be exposed to such products on a daily basis.

[000? I There is an increasing interest from consumers, and a known need in the healthcare and housekeeping industries, to reduce the number of microorganisms on fabrics while using f miliar equipment such as washing machines. Concentrated products arc required for soeh au application, due to the high dilution level of the product in the rinsewater, typically by a .factor of about 600 times dilution. In the ease of formulations comprising quaternary ammonium compounds, high eoncen /atkms of the quaternary ammon m compounds In the concemrate are needed in order to ensure an adequate amount of adsorption occurs in a kinetically relevant time onto the microbes under dilution, use conditions. As detailed above. It is desirable, yet very difficult, to manipulate the., reduce) the CMC of the quaternary ammonium compound in such ars application. Thus very high concentrations of quaternary ammonium com u ds_* which, tend to be azardous to the skin ard ayes, are used in the co»$ ½rates, in combination with high temperatures and long e p sure imes,

0OOS| Thus, them is an ongo ng need for methods and compositions offering i e control of the properties of surfactant aggregates comprising cationie species, especially antimicrobial spooks s sch as quaterna y ammonium com ounds and hig anides.

BRIEF SUMMARY OF THE INVENTION

fWM | One aspect of he invention is directed so a composition comprising a polymer- micelle complex comprising s positively charged mkelte comprising a water-soluble estiomc material selected from the group consisting of a monomerie quaternary amm ni m compound, a nton m dc biguanide compou d, and mixtures thereof. The micelle is electrostatically bound to a water-soluble polymer bearing a negativ.e charge. The -water-sokble polymer bearing a negative charge comprises a hybrid copolymer derived f om a synthetic monomer o monomers chain terminated vyitb. a hydroxy I- containing natural material synthesized with a free radios! initiator. The polymer does uo comprise block copolymer, hue--: particles, pol mer nanopartides, cross-linked l e s, silicone copolymer, fluo sm&oiant, or amphoteric copolymer. The complex advantageously does not form a eoacervate, and does not form a film on a surface (e. g., a durable film remaining after application of the composition to the surface),

piilttj Anorher embodiment of the invention is directed to a composition comprisin a polymer-micelle complex comprising a positively charged micell comprising a water- soluble eatlouie material selected from the group coexisting of a monomerie quaternary ammoniu c m und, a monomeric biguamd© compound, and mixtures thereof. The micelle is eiectrmstat.isa bound to a water-soluble polymer bearing a .negative charge. Use water-soluble polymer hearing a negative charge comprises a hybrid copolymer derived from a symbolic monomer or monomers chain terminated with a hydroxy!- eoptainiog natural material symth smad with a free radical initiator. The polymer does not comprise block copolymer, latex particles, polymer nanopartides., eross«l ked polymers, silicone copolymer, fhtorosurfeetaot, or amphoteric copolymer. The composition advantageously does not form a coaeervate, a d does not inemde alcohols (e.g., particularly l we alcohols) or glycol ethers,

f®M!| Another embodiment of the in vention Is directed to a composition comprising a olyme ies I is complex comprising a positively charged micelle that is electrostatically ^•fco nd to a water-soluble polymer bearing a negative charge. The waler-solubie polymer does not comprise block copolymer, latex particles, polymer oanopartloles, cross-linked polymers, silicone copolymer, fiuorosur&c ant, or amphoteric copolymer. The composition advantageously does not form a csoaoervate and does not form a fifes oo a. surface, in addition to the po!ymer--mk;etle complex, die c m osi i n further com rises s oxidant

. 121 in another embodiment, t e composition includes m oxidant, h ch may be selected from the group consisting of: hypobalous seid, hypohaiite or sor.sroes the?eof;hydrogen peroxide or sources thereof, petaeids, peroxyacids peroxoaeids, or sources thereoi;orgamc peroxides or hydroperoxides, psro ygenated inorganic componnds;solubiozed chlorine, soiubUized chlorine dioxide, a source of free chlorine, acidic sodkm chlorite, m active chlorine generating compound, or ch rine-riioxide generating compound, an ac ive oxygen generating compound, solubliked ozone, N^«h¾.lo compounds, sod combinations- ther of,

[0 )13] In. an ther embodiment, the positively charged micelle comprises a tnonotneric_: quaternary ffisimoni m compound. In another embodiment, the^' positively charged micelle iurther comprises a ooniooie surfactant In another embodiment, the oooi.on.ic xur&el&n comprises an si oxide. Its another em odimen ,, the positively char ed .micelle comprises 8 O'ionorneric biguanlde ooinpoHttd, In another embodiment, the onomerie bigaaoide compound is selected from the group consisting of ch!orhexidhre, alexkhne, sod combinations thereof.

| 014 Its soother embod men , the composition is tree of iodine, iodine-polymer complexes, tranonarticles of silver., stsnopartieles of copper, oa opsstides of 5- inc. o/ieiosan, p~cMoro eihy! xylenoh monomeric pentose alcohols. D-¾yh^'tol and its isomers, D-atabitol and Its is mer, my I alcohols, berszyl alcohol, and phenoxyethauol,

[§01 S| Its snother embodiment, the composition further comprises a water-immiscible oil that is soiubilms ioto the positively charged rnkelle, in another embodiment, th composition is free of ster-toiscible alcohols and glycol ethers,

|0 ) In another embodiment, the water-soluble polymer bearing a negative charge is selected from the group consisting of a co lyme of a polysaccharide and a. synthetic monomer, copolymers comprising rna!eic sold, a. copolymer of dhrsethykcrylatnlde and acrylic acid, a copolymer of acrylic acid and s-rytene, a copolymer of sulfona ed styrene and rn&leie arshydrlde, md combinations thereof.

1_.801?] in another em od ment, the invention is directed to a method for cleaning a surface. The method comprises contacting a surface with a composition comprising a polymer-micelle complex. The po!ymer-raicell complex ioclrtdes a positively charged micelle electrostatically bourn! to a water-soluble polymer bear- as a negative charge. The positively charged micelle comprises a water-soluble estionio material selected from, the group consisting of a mooomerie quaternary ammonium compound, a mononierie biguam^'de compound, a no mixtures thereof. The water-soluble pol ymer bearing a negative charge does not comprise block copolymer, ex particles, lymer nanopaslieks, crass- linked polymers, silicone copolymer, fl orosuffecu¾t. or amphoteric copolymer. The- composition advantageously does not form a coaeervate, and does not tbrm a b t ; on surface.

|¾81.8| Another etnbodlmem of the invention i directed to a method for treating a surface. The method comprises mixing a first composition comprising a water-soluble polymer having & negative charge with a second composition c mp s ng a positively charged micelle. The water-solnhle polymer bearing a negative charge does not comprise block copolymer, iaiex particles, polymer nanopardoks, cross-linked polymers, ah k one copolymer, loorosurtactant, or amphoterio copolymer. The positively charged mk.dk^> comprises a water-Soluble cation Is material selected from the group consisting of a monomelic quaternary ammonium compound, a monomeric biguanide compound, and mixtures thereof. The method further comprises contacting the composition respiting from, nrixing of the two parts with surface so as to beat the surface..

flKflv] Another embodiment of the invention Is directed to a method for treating bacterial endospores, fungal spores, or viruses-. The method comprises contacting the endos-pores, spores, or viruses with an aqueou composition that comprises a poiymer- mieehe complex comprising a positively charged micelle thai is electrostatically bound to a waiemsoiubk polymer bearing a negative charge. The positively charged miee!k comprises a water-soluble eationk material selected from the group consisting of a mouomeric quaternary ammonium compound, a monomer!© biguanide compound, and mixtures thereof. The water-soluble polymer bearing a negative charge does not comprise block copolymer, latex particles, polymer nanopanieies, cross-linked polymers, silicone copolymer,. fleorosoriactant, or amphoteric copolymer. T^'he composition does net form a coacervate.

Another embodiment of the kvemloo is directed to 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 tnicells that is eiecti statlcaily bound to a water-soluble polymer hearing a negative har e, ^'The positively charged micede com rises a water-sokhle cationic material selected from the group consisting of a oaomerie quaternar ammonium compound, a mo om n biguanlde compound, and m x u es thereof The ater-sokbk polymer bearing a ne a ive charge does not comprise biock copolymer, latex particles, polymer rranopsrtkles, cross-linked polymers, silicone copolymer, floorosarmetaray or amphoteric copolymer. The composition does oi form a coseerv&te.

| 02-11 Another aspect of the invention- is d e ted to a. system comprising a dual chambered device comprising a first chamber, a second chamber, a first composition In the first chamber, arid a second composit n in the second chamber. The first composition comprises a water-soluble polymer bearing a negative cbargo that does not comprise biock copolymer, ktex particles, polymer nanopartlcles, cross-linked polymers, silicone copolymer, iiuorosariaetaat, or amphoteric copolymer, The second composition comprises a osi ive charged micelle comprising a ateosolabk catiook materkl selected from the gronp consisting of a monomer!c quaternary ammooiam compound, a monomark igusnide compound, sod mix ai es thereof. The system provides the ability to mix the first and second compositions (e.g., prior to application} to result Its a mixed composition for application m whkh. the micelle is electrostatically bound to the water-- soluble polymer to form a polymer-rnkclie com lex. The resulting: mixed composition, advantageously does not form a coaoervate, and does not k¾ a film on a surface.

Another embodiment of the invention is directed to a system, comprising a d i chambered device comprising a first chamber, a second chamber, ¾. first cam-position m the first chamber, and second composition In the second chamber. The first composition comprises. s water-sokibis polymer bearing a negative charge that does not comprise block copolymer, latex, particles, polymer nanopartleles, cross-linked polymers, silicone copolymer, iuorosariactant, or amphoteric copolymer. The second c m os tion comprises a positively charged micelle comprising a water-soluble cadonlc material selected from the group consisting of a monomerie quaternary mnmonlurn com ound, a rnooomerie bigo&nids compoand, and ndxiures 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-mieelk com lex. The resulting mixed composition advantageously does not form a coacer vste₃ and does not form a film on a surface. The resulting composition does not include alcohols or glycol ethers. {Wt \ nodser aspect of ihe invention is directed to a system comprising a dual chambered device comprising s first chamber, a second chamber, a first composition in the first chamber, and a se ond composition in the second chamber. The first composition comprises a water-soluble polymer bearing a egative charge that does not comprise block copolymer, latex par e -.;, polymer nanopardcies, cross-linked polymers, silicone copolymer, iksorosrsrtaetaot, or amphoteric copolymer. The second composition comprises a positively charged micelle comprising a wster-solnble catioolc m&tsrlsl selected from the group consisting of a monomelic qu ternary ammonkmi compound, a mooomerie bsgyarnde com ound_s and m xtures thereof At least one of the first or second compositions further consprlses an oxidant. The system provides the ability to mix the first and second compositions (e.g., prior to apphcaiiors) to res id ι in a mixed composition for application in which the micelle is electrostatically bound to the water-soluble polymer to form s poiymerookeb^'e complex. The rssohing mixed composition advantageously does not form a cn cer ate and d:oes not form film on a surface.

!¾!!24] Farther features and advstit&ges_. of the present invention wii! become apparent to those of ordinary skid Is the art in view of the detailed description of preferred embo iments below.

DETAILED PESCMFTION OF TME F EF B.REB EMBODIMENTS it Bdlatttow

imtS] Before describing the present invent on in detail, it is to be understood that this iiwerstion is not limited to particularly exemplified systems or process^' parameters that may, of course, vary. It is also to be understood that the terms oology used herein Is for the purpose of describing particular embodiments of the invention only, and is not intended to limit the scope of the Invention in an manner,

p§26] All publications, -pa ents and patent applications cited herein, whether supra or infra, are hereby incorpo ated by reference in their entirety to the- same extent as if each individual publication patent or atera application was specifically and individually indicated to he incorporated by reference.

0 7j I^'he tsrm ^''^com r sing'' which is syoonyrnoos with "ijjei&d g, "containing,^{5 *} or "characterized byf is inclusive or · --poo -v robe and does not exclude additional, uarecited elements or method steps.

H §] The term ^{^}consisting essentially of limits the scope of a claim to the- specified materials or steps "and those that do not materially affect the basic and novel eharaeterist Csf ' of the claimed invention,

|^'fS2 | The term "co sist g of used herein, excludes any element, step, or ingredient not specified la the claim.,

[003f | It most be noted that, as irsed in this specification and the appended claims the singular forms ^SV " s and '"foe" include plural referents unless the conten clearly dictates otherwise. Thus, for example, reference to a ^Sisoriactanf' includes one, two or snore such surfactants.

flMBlf l¾e tes n water-soluble polymer as used herein means a. poly user which gives an optically clear solution ee of precipitates at a concentration of 0.001 grams per 100 grams of water, preferably 0.0 grams/100 grams of water, more preferably 0, 1 grams/1 0 grams of water, and even more preferably 1 gram or more per 100 grams of water, at 25

^'x:.

®32f As used herein, the term "substrate'⁵ Is intended to include any material that is used to clean an article or a sortsce. Examples of cleaning sobslrales include, bat are not limited to nonwovsns, sponges, films and similar materials which can be attached to a cleaning implement, such as a floor mop, handle, or a hand held cleaning tool, such as. a toilet cleaning device. 03J As used .herein, t e terms "nomvoveo" or no« oven web" means a web having a str c ure of kdivkfeal fibers or threads which are kterl&! , but not in art identifiable manne as m & knitted web.

\M$4] As used herein, the term " ol mer^* as used In reference to a substrate (e.g., a non-woven substrate) generally Inclu e , hut is not limited to, homopolymers, copolymers, such as for example, block, graft, random sod alternating copolymers, terpolyrners, etc. md blends and modifications thereof Furthermore, unless otherwise specifically limited, the term "polymer" shall include all possible geometrical eonf!gurstioiis of die molecule. These configurations include, but are limited io isotaetle, syitdloisctic and random symmetries,

f©®35] Unless defined otherwise, ail technical and scientific terms used herein have th same- meaning as commonly understood by one of ordinary skill In the a to which the invention pertains. Although a number of methods and materials similar or equivalent to those described herein cm he used in the practice^' f the present invention, the preferred materials and methods are described herein,

| MI3&| In the application, effective amounts are generally those amounts listed as the .ranges or levels of ingredients in the descriptions, which follow hereto. Unless otherwise stated, amounts listed in ercentage f*wtHV) ere In t% (based on 100 weight% active) of the particular material present in the referenced composition, any remaining percentage being water or an aqueous carrier suffic ent to account tor 100% of the composition., unless otherwise noted. For very low weight percentages, the term "p n ^s corresponding to parts per million tm a weight/weight hasls may be used, noting that 1.0 wt% corresponds to 10,000 ppm.

I.L Inlrodnetkm

[11137] ^'The present inventors have now determined t gt the use of wster-soluble polymers comprising groups which hear or are capable of bearing an electrostatic charge a eoonterfons (polymeric counterfoils) for micelles comprising at least one ionic surfactant selected snzh that the net electrostatic charge on the m icelle i opposite to i &t of the polymeric connterion cars yield, simniraoeously, very line control, of the Interactions between the headgroups of the ionic surfactant as well as die adsorption of the ionic surfactant at the air-liquid and solid-liquid interface when compositions are adlusted such that precipitates or eoacerv&tes are completely absent from at least some embodiments of the compositions. [§8381 Surprisingly, such compositions which micelles with polymeric counterforts exist as soluble, thermodynamlcaliv stable aggregates exhibit ver high adsorption activity at both the sdr-liqiad ami solid-liquid interfaces. Such characteristics completely eliminate the need to adjust formulations such that they change their solubility, forming eoaoervaies or precipitates, in order to deliver adsorption of useful amounts of ionic surfactant and pol r to these huerfaces. The r lcelle-polyurc complexes formed when a water- sokble polymer comprising groups which bear or are capable of bearing an electrostatic charge opposite to that of a mieeik are usually fbasd to he somewhat larger than, the micelles alone. The addition of a water-solu k polymer bearing electrostatic charges opposite to that of at least one surfactant in aqueous solutions often can reduce the CMC of he given surfactant by a significant fraction, which can also have the effect of reducing the cost of certain formulations.,

@39] Fine control of surfactant interactions within micelles via addition of oppositely charged polymers according to the inven o has also been found to increase the oil solubilization ability of the micelles to an unexpected degree. Without be ng bound b theory, it is believed that this effect is doe to the uoiqnely 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 Ion association of charged polymers com ared to regular electrolytes, e en at very low polymer concentrations, which in turn promotes Increases in nneellar size and an increase in oil socializ tion efficiency. The inventors have discovered Phat the oil solubilization boosting effect develops only if the- interactions are ftne ned soeh that the system is fu!iy free of coacervate yet is nea the watet soluble/eoacervaie phase boundary; 1 0 01 Fonmslations comprising mixed micelles of a cafionk germicide (quaternary ammonium compound or a water-soluble salt nf a biguanibe such as ehlorhexidine or aiexidinej, optionally a second surfactant such as an amine oxide, and a water-soluble polymer bearing an anionic charge can be made with control of the si e and net electrostatic charge. It is believed, without being bound by theory, that the anionic polymers act as polymeric eonoterions to the cationka!!y charged micelles, either increasing the size of these micelles or collecting groups of these micelles into soinb!e, thermodynsmic&ily stable aggregates which have enhanced activity at solid surface™ aqueous solution interfaces. Including the surfaces of microorganisms such as bacteria, viruses, fungi, aod bacterial spores. This reduces or even eliminates the need for the resence of y- akohoi as enhance or ^H - euierte ~ the aotinkerobial performance of the eationk bioekle.

j$043| In one embodiment, the e-omposhio^s can comprise alcohol In another embodiment, the compositions can be completely fee of watermksclb!e lower alcohols. Similarly* the compositions can comprise waten-nvlseible glycol ethers or be completely free of the r-mn-nak. soerethnes referred to as 'ko-solvents" or 'ko-surfactantsk €ompo$ k∞s free of the lower alcohols or glycol ethers not only cars provide acceptable antimicrobial performance at lower cost bat also reduce Irritation to patients nd healthcare workers, while providing forrmbations which can be considered more environmentally ifkndly or sustainable due to lowered total actives levels and lack of volatile organic compounds. Those embodiments that are tree of alcohols or cosolverris are especially suited as sanitizing cleaners, disinfecting d alers of treatments for pets in borne or veterinary applications.

|O042] Surprisingly, the com ositk^s, even without alcohol show inaetivatiop of non- enveloped viruses sack ss rhinovlras. even t g cationle biocldes are typically not considered a active agains such microorganisms. It is believed, withont being beuae by theory, that the interfaeial activity of the micelles with polymeric countenons Is so signifkapt that the viral proteins are disrupted, denatured or otherwise damaged sack that the viral particles are rendered on-infective, 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 takn alosis), which are heretofore known to be relatively resistant to the actions of eationk germicides m aqueous formulations lacking a co-solvent or aleohok Seek resistance is thooght to be dee to the thick, waxy outer mem brakes characteristic of this type of bacteria.

|CH 3| The compositions may be sef l as ready to use cleaners, and may be applied via spraying or peering, but .may also be delivered by loading onto nonwoven substrates to produced pre-m olstened wipes. The compositions ma also be provided as concentrates that are diluted by the consumer (e.g., with tap water). Such concentrates may comprise a part of a kit tor refilling a container (also optionally included wit in such a kit), such as so. empty trigger sprayer. The compositions may also be provided as concentrates for single-- use (unit diose) products for cleaning floors, windows, counters, etc. Corseentraied dishwashing liq ids that provide antibacterial perionnapce upon very high dilations may be tornTu!ated, as may concentrates which can deliver sanitkation of laundry vis addition io ordinary washloads.. Such comp sitions md osy Its may be achieved without inclusion of tridosan. Saeh co ce rated products also can provide protection against the growth of biofilms ami associated out row h of molds in drain line associated with automatic dishwashers, laundry washing machines, a id the like, reducing undesirable odors which are sometimes encountered by consumers.

f¾M4f Co c ntrated fbyms of the formulations may also be provided which may be diluted by me consumer to provide solutions thai are then used, Coneentraied forms suitable for dilation via amo aicd systems, io which the concentrate ?s diluted with water, or in which two solutions are combined In a givers ratio to provide the final use formulation are possible,

j¾045| The formulations may be in tire form of gels delivered to a reservoir or surf ce with a dispensing device. They may optionally be delivered Irs siugk-use pouches com risin a soluble film..

\ 6 The superior wetting, spreading, sad cleanin performance of the systems make them especially stntable for delivery from aerosol packages comprising either single o dual chambers.

[0047] The compositions are useful in providing a reversal its the native surface charge (i.e.., se a potential) of bacterial enriospores and other microorganisms from anionic (negative) to eationk (positive}, or a least to less anionic as a result of contact with the compositions. Saeh a change in charge Increases the electrostatic binding of the microorganism s to cleaning Implements such as pre-moistened ooowoven 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 ammon um compo nds and biguanides, they are able to kill bacteri which arise f om tne germination of endospore under favorable environmental conditions. Such compositions may thus find utility In various applications including combating weaponteed spores such as BacUI Amkracis. Low residue treatment solutions for 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 oduced with the compositions. In other words, the compositions do not result in the formation of a dura le film, on a surface after application. Simple rinsing i sufficient to remove any residue, and even without rinsing, those embodiments of the invention that do xhibit a residue do not form macroscopic durable films. Thus, any remaining resid e does no c sole a tuny bat is easily disturbed, destroyed, or otherwise removed.

|S S The invention also contemplates use of the poiynsewmkelle complexes for deli er g improved samtixaikm of surfaces mid protection of treated surfaces through the same mec an sm of enhanced adsorption of caiionic bioei es such as quaternary ammonium salts and biguanides onto living bacteria, bacterial eodospores, fongul spores, and viruses, Examples of antimicrobial activity exhibited by the Inventive compositions kcla e, but are not limited to killing of hving bacteria, killing of bacteria upon germination fr m bacteria! endospores, killing of ^'living fun i, killing of fungi upon germination from spores, damage to the proteins or lipids of viral capsids resulting in decreased or inhibited infectivity to a target host, adsorption onto the proteins o viral capsids resulting in blockage of the protein from a target site in a host, or increased binding of a bacterial ePdospore, a frmgaJ spore, or a virus to a nomanirnate surface resulting in a decrease in. physical transmission to a host which in lum decreases the transmission of disease of the host or addition contamination of other surfaces. Depending on application use, the surface may be hard, soft, animate (e.g., skin), non-animate, or other type smiace.

liLBeimtion of Ittjet smd P/Bnei Parameters

111114 1 As will be shown in the examples below, very fine ec trol of the interactions between micelles comprising m ionic surfactant and water-soluble polymers bearing electrostatic charges^' opposite to that of the micelles, and hence functioning as polymeric

micelles, can he achieved through manipulation of the reladve numbe of charges due to !onie surfactants in the system and those charges due to the water- soluble polymer.

βδ5§) Mixtures of surfactants, including mixtures of ionic and .oonlonic surfactants, may be employed. A co venient wa to describe the net charge on the micelles present In the formulations of the instant invention is to calculate the total number of equivalents of the charged beadgroaps of the surfactants, boil's anionic and cationic, followed by a determination of which type of charged headgroup I s in excess in the■ formulation.

[0( 51 Surfactants bearing two opposite electrostatic charges in the formulations, such as carboxy-hetalnes and sillftwbetaines, act as "pseodo-nonionie" sur&eiants in. the compositions of the instant invention, since the net charge on them will be isero. Thus, the calculation of Dnet will not involve the concentration of such pseedo-oonionk surfactants. Similarly, phosphatidyl choline, an edible material which is a major component of the surfkc&mt commonly referred to as ieeithiri,. c tsts as both an snio cft!i charged phosphate groap and a satiomca!Jy charged choline group In its ^'h«adgro up region, aad thus would be treated as pse do-¾O . «ie in the inventive compositions. On the other hand, a material such as h s ide acid, which contains only as anionieally charged phosphate roup as its headgroup, would contribute to the- catena ion of Dnet, as described below.

|1 IS2] Some surfactants, such as amine oxides, may be uncharged (nonionic) over a wide range of pH vakes, bat may become charged (e.g., calionkaOy in the case of am me oxides) at acidic pE vskes, especially below about hi 5. Although mch components may not eorstairj. two permanent sad opposite electrostatic charges, applicants have found that they may be treated explicitly as nons^'c-mc- surfactants in the inventive formulations. As taught herein, inventive compositions which are free of eoaeervates and precipitates thai comprise mixed .micelles of an amine oxide and a cationic germicide such as a qu ternar ammonium com_.pou¾d and a water-soluble polyme bearing anionic charges may be readily formed through djnsP'ne ii of the P/Dnet parameter, the Drier parameter, and/or the presence of adjnvaats such as electrolytes, without regard to the precise value of any cationic charge present on the amine oxide,

!§§53J Two parameters cars be defined for any mixture of surfactants comprising headgroups bearing, or capable . or bearing, anionic or cationic charges or mixtures of both, said parameters being D anionic and D cationic.

D anionic will be defined as - anionic ^:;: (-1 ) x (Eq anionic)

D cationic will be defined as -

D cationic ^~ (-H ) x (Eq cationic)

[005 1 A fiuai a am te expressing the net charge on the micelles is Dnet, which is simpl the sum of the parameters D anionic and D cation! e_s i.e.,

Dnet ^ D cationic + D anionic

In the expressions above, Eq anionic- is the sum of the total number of equivalents or charges due to the beadgroaps of all anionic sarfaeinnts present. For a formul t on comprising a single surfactant with a headgroup bearing or capable of bearing an anionic charge:

Eq anion c_! = (C anionics x Q monki V anionic;

wherein C anmnic; is the concentration of a surfactant with anionic headgronps in grams/per 100 grams of the formulation or use composition, Q anionics is a numbe represe t the number of anionic charges present an the surfactant, which rosy be viewed as having the units, eq alen s per mole, aad M anionic; is the molecular weight of the surfa an in grams/mole..

|W$g| For a formulation comprising two different surfactants with anionic headgroaps, the parameter Eq anionic would he calculated as the s m:

Eq anionic Eq anionic; ^■>· Eq nionic;_? -

(C anionic; x Q am mcj M amonk._: ÷ (C anion a:. > a Q anionk₂}/M anionic^ |<H)$?| Commercially available surfactants are often mlxtares of materials d e to the presence of a distribution in the camber of for example, .methylene groups the hydrophobic 'tails" of the s rfactant It is also possible that a distribution in the um er of charged 'Iveadgfoups" per molecule could exist la practical work with commercial materials, it may also be acceptable to rise &n "average" rnoleeeiar weight of an "average" number of anionic, (or c&tiotiie) charges per molecule quoted by ibe manufacturer of the surfactant, ?n d>e ealcnkiioa of 0 anionic (or D eationic), it .may also he acceptable to ass values of the Eq arnonk (or Eq eationic) derived from direct analysis of a surfactant raw material

[0058] in the expressions above, Eq cationk is the sum of the total number of equivalents or charges dee to e headgronps of ail cationk surfactants present. Fo a formulation comprising a single surfactant with a beadgroap hearing or capable oi bearing a cationk charge::

Eq cationiCi = (C eatlonki s Q cadonlck/M cationk;

wherein C catiooici is the concentration of a surfactant with cationk headgroups In grams/per 100 g ams of the formulation or ase composition, Q eationic; is a number representing the number of ea ionic charges present on the surfactant which may be viewed as having the units equivalents per mole, and M cationk; is the molecular weight of the surfactant in grams/mole, I s cases where the fbnrtnlation comprises more than one surfa ant with eationic headgroaps, the summation of the equivalents of eationic hea.dgro ps would be performed as in the ease of the anionic surfact nts described above. |tM15f J As an example, consider a formulation eonrpnslng a mixture of a single anionic surfactant and a single nonlonk surfactant, hat lacking a eationic surfactant Furthermore, consider the anionic surfactant is present at a eoneentmtkn of 2 t% or 2 grams/iOO grams of the formulation, has one rou capable of developing an anionic charge per moiecule, and has a molecular weight of 200 grams/mok.

Then Eq anionic (2 x l) 20G == 0,0] equivalents/! O g in the formulation. Then, B ismk ^« (-1 ) x. (0.01) - -0.01 ,

And D csikmlo ~ 0.

Thus, Dnei === (0 - 0,01) ^{« «}0.0! ,

|^"0O §i As a second example, soasidet a formulation comprising a mi ture of a single anionic surfactant, a single acnio c surfactant, and a single catiook surfactant which is a germicidal quaternary ammonium c m ound. Furthermore, consider the anionic surfactant is present at a concentration of 2 t% or 2 grs s/100 grams of the fonnaladon, has one group e table of developing an anionic charge per molecule, and as a molecular weight of 200 grams/mole. Furthermore, consider the cationk surfactant is present In die formulation at a concentration 0.1 wt% or 0.1 grams/100 grams of the formulation, has one group capable of developing & cationic charge per molecule, and has a .molecular Wei ht of 300 grains/mole.

Then Eq anionic - (3 x l)/2O0 ^«= 0..01 eqoi.valenis/100 g in the formulation.

A d Bq oadonic - (0.1 x l)/30 ^ 0.00033 equivalents/ 100 g In the formulation.

Then, D anionic - {-!) (0.01) = -0-01.

And D cationic - (I) x (0,0003a) - +0.00031

f¾us, Dn«t - t-0.00033 + (-0,01) - -0.00067,

This negative value clearly indicates that the number of anionicaliy charged headgroups in the mixed micelles comprising the anionic, nonioaic, and cationic surfactants present, in the formulation exceed that of the cationkal!y charged headgroups.

SI.| A second parameter which can fee used to describe the instant invention and the interactions between polymeric oouu erion and surfactant micelles bearing a net charge is the ratio P/Onet, P is the number of charges (in equi valents) due to the polymeric connter n present per 100 grams of the formulation and can be calcokied as follows;

P ~ (C polymer x f polymer x Q olymer x Z) M polymer,

where C polymer is the concentration of the polymer in the formulation in grams/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 i m ranges from 0 to 1, Q polymer is the number of charges capable of being developed by the monomer unit capable of bearing a charge and can be viewed as having d e unds equivalents per mole, Z is an integer indicating the type of charge developed by the monomer unit, nd is equal to 4-1 when the monome unit can develop a cationic charge or is equal to ~l when the mo ome m%it can develop an anionic charge and. M polymer b the molecular weight of the monomer unit capable of developing a charge, k grams/moie.

i® >2] For example, consider a formulation comprising polyacrvl acid homopofymesr (FAA) as a wateo-solubk polymeric coonterion. FA A .is capable of developing 1 anionic charge per acrylic acid mon mer unit (which has a molecular weight of 72 grams/mole},, and tecs Q polym r - 1 d Z = -1. in addibon, the -pojy er is a hotnopoiymer, so F polymer - 1 , If the FAA is present h\ the formulation at a concentration of 0, 1 gram 100 grams of the forrrsrFiat o, the value of F would be ca!cmsied as follows:

P - i0. ί x 1 x 1 x - 1 }/72 ^· -0.0 139,

fbt]63 Using the Dnet value of -0,00967 eakukkd it? the e ample described a o e for mixture of an anionic, eationie, and noniouic surfactant, die ratio P/Dnet w ld be eaietsiakd as:

FfD t ~ (41.001 39}/k0.00967) - +0.144

[§§6 ] This positive- value of IbfJuet not oak indicates the ratio of the charges due to the polymeric coun erion sod the net charge on the mixed micelles, but also kdicsk , since, it is a positive m iber, that the charge on polymeric; eoanterion and the net charge on the mixed micelles arc the same, both being ardooie, k this ease, there would be no net eketrostaue mteraetion between the polymeric counteridn and the mixed micelles expected, md hence the example would not be within the sco e of the instant: invention, which requires tha the polymeric ooankrlon miist be of opposite charge to thai of the headgroeps of the surfactant, or mixture of serfee ants comprising the micelle, |0SN¾1. Now consider another e am le in which the formulation comprises, a. mixture of a single aiuooic surfactant, a single nokonic surfactant, aod a single eationlc surfactant and a single eationk surfactant which Is a germicidal uaterna ammonium compound. Fenhermore, consider the anionic sarfeetam 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 grams/mole. Furthermore, consider the cariomc surfactant Is present ia the formulation at a concentration L0 wi% or 1.0 grams/100 grams of the formulation, has ooe group capable of developing a cationic charge per molecule, and has a rnokeokr weight of 300 gmrns/mole.

Then Eq anionic - (0,2 x 1 }/200 - 0,001 equivalents/ 100 g in the formulation.

And Eq catioaic (1.0 x i )/300 - 0.00333 ui len s 100 g its the formulation.

Thee. D anionic · (-1) x (0.0 1 ) - 41.00 F And D catkmfc - (1 ) x (0,00333) - -0.00.333,

\m \ Thus, Dnet - +0-00333 (-0.001) ^« 40.00233, This osi ve va¾s cteari indicates that the number of eaiionkaUy charged headgroups In the mixed mice ties comprising the anionic, oornoine. and eatlonic surfactants present In the formul ion exceed that of the snionkally charged haadgronps. Such mi ed micelles would be suitable for interac ion with a ol meric cmmterioo bearing snionk charges.

f§ ?i Continuing this e am le, now consider that the formulation also comprises a polyaerylle acid ho nopolyme (PAA) as a ster-soloble polymeric counterlors. PAA is capable of developing 1 aa ion c charge per acrylic acid monomer unit (which has a molecular weight of 72 pms/wole), a&d hence Q polymer ^:::: 1 md Z^∞ - I . In addition, fee polymer s a bomopoiymer, so F polymer ^::: I . if the PAA s present in the formu on at a concentration of 0.1 grams/] 0-0 grams of the f unda io , She vaiae oi^' P would be calculated s follows;

P ····· (0 1 x 1 x 1 x - i ;·? - -0.00139,

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

P/Dnet - (-0,00130)/( 0.00233) ^« - 0.5906.

[ΘΘ&8] This negative value of P Drset mdicaies that the charges on the polymeric connterion (PAA) and the mixed micelles are opposite ¾o one a other, indicating that there may be an electrostatic interaction between the PAA and the micelles, and hence the composition may he within the scope of the instant invention. Of course, the value of P Dnet also indicates the ratio of the charges due to the polymeric eouaterion and the net charge on the mixed micelles,

|0tl 9! Alternatively, if the num er of equivalents of charged groups present per gram of polymer is available from the m nufacturer, or can be derived from the synthetic route used to create the polymer, or can be derived from analysis of the polymer, then P may also be calculated based on that Information.

|00?0 For example, P ^» (C polymer x Eq polymer x Z), where Cpolymer and Z sm defined as above, and Eq polymer is ti¾e umber of eqniva nts of groups per gram of polymer with a charge consistent with the value of Z used. For example, if a water- soluble polymer tha i described as having 0.01 39 equivalents per grant of polymer (actives) of an anion aiiy charged monomer, and this polymer is used in a formulation at concentration of 0.1 grams/100 grams of the .formulation, P is calculated as follows:

P ~ (0.1 x 0.0139 x } - - 0.00139. F?1J This value of P, with the sss e Dn t value msd In the example above m which the micelles comprising an aai mc s rfsciant, a nomonic surfactant and a estionie surfeetam which is a quaternary ammon um om ou d, may then be used to calculate the ratio P/Dnet:

P Dnet - (^«0.00139)/ HO.{X)233) - - 0.5966,

which yields the same result as described above.

@72) the esse of copolymers comprising more than o e monomer of like charge or capable of developing a like charge, then the P value calculated for the fonnu^'lsiion would be the sum of the P values calculated for each of the appropriate monomer comprising the polymer used..

|W73| Finally, m practical work, the absolute value of P/^'Dnet s m indicator of which charges ate in excess d which at¾ deficiency in. formtdatiom of th instant Invention, When the absolute value of P/Dnet is greater t .0 but isss than i , the aumber of charges due to groups on the polymeric eountsrkm is less than the net number of charges diss to the headgroups of the onic surfactant or swiaetant comprising the micelles, i.e. fee polymeric connfexlon is in deficiency.. When the absolute value of F/Dnet is greater than 1, the polymeric coanterion is in excess, sad of coarse, when the bs lute value of P/Duet - 1. the number of charges due to the headgroops of the polymeric eounteriou equals the net number of cha ges of the io ho surfactant or surfactants comprising the mlcehes. fW f Many polymers are suitable for use as polymeric eounierions in the instant Invention.. In one embodiment, the polymers are water-soluble as defined herein. The pol mers may be homopolymers or copolymers, and they ma 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. In 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 Che more hydrophihe block comprises "c ona" 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 co nterion with ordinary surfactant micelles. Although mixtures of water-soluble polymers are suitable in at least some embodiments of the present invention, fee mixtures selected should not comprise block copolymers capable of forming so-ea!led ''c lex coaeervate'" micelles through self-assembly, since this micelle forma ion process also competes with hs Interaction of the water-soluble polymer as a polymeric counterion to ordinary surfactant micelles. Wheo the polymers are copolymers, the ratio of the two or more monomers ma vary over a wide range, as long as water solubility of ths polymer is mainta ned

|007S| I an embodiment, the ol me s should be water soluble, as defined hereby and therefore, shou d not be latex particles or tuierogels of any type. In such embodiments the polymers should not he crossdlnked through the use of monomers capable of forming covalent bonds between independent polymer chains, and the compositions and formulations should be tree of cross-linking agents added expressly for this piapose. H is believed that polymer aggregates that may be "s llen ' by water In the ibrm o mleroge or polymers thai form cross-linked networks will not have the appropriate Mi mobility of the polymer chams needed for them to Ihnotfen as polymeric eounterions with respect to ordinary surfactant micelles. Polymer particles which can serve as stmctcrants for an aqueous composition through the formation of fibers or threads arc not suitable as the water-soluble polymers for similar reasons. Similarly, latex, psrt les are belie ved to not be snitable because many of die individual polymer ch&ms-- in such particles are. In fact, confined to the particle interior and are not readily available or interaction with the aqueous phase, Lansx particles also lack the chain mobility required to function: as eounterions to ordinary soriaetsnt micelles, f uff%] Ths r ndom copolymers ma comprise one or more monomers bearing the same charge or capable of developing die same charge and one or more monomers which are noniouie, he,, not capable of bearing a charge. Copolymers may he synthesized by graft processes, resulting in "eomb-!ike" structures.

Preferred copolymers include so-called ^hyb id'^' materials from Akm Nobel such as Alcoguard® H 5240, These materials are described as comprising polysaccharides and synthetic monomers which can function in the same manner as aerylgts/ sleate copolymers (i.e., s water-soluble polymer with anionieally charged groups) in cleaning formulations. Hybrid^' polymers such as those described in US Pat, No, 8_sOSS.S37 are preferred in formulations where the overall susiaiuabihfy of ths formulation is of concern io the end user. Such hybrid polymers are derived from synthetic monomers chain terminated with a hydroxyl-eontaining natural material, such as a polysaccharide, using tree radical Initiators.

[0078] Various anionic polymers available from Akzo Model under the tradenames Aicoguard®, Aieospecse¾y and Aqua rear® am suitable for use. For example. Akosperse® ?4^'?, a . andom copolymer, Aa aireafr® A ~4, an acrylic acid horaopo!ymer, &nd Akoguard® 5240, a andom graft copolymer, ail of which contain carb xyhc acid grou s, as¾ additions^'! exa ples of anionic polymers thai ma be employed. A!coguatd® 2300 is a random co olymer of the nonionic monomer d¾ttsihyl&crylaffiide and the anionic monomer acrylic- acid. AkospfcrseS? 46S is a poly(acry!ic acid) honsopolymer. Versa- L® 4 (Akzo Nobel) is another example of a suitable anionic polymer. This materia! is described as a random copolymer of sulfonated styrene and aiek anhydride. Another example of a sui able anio ic ol mer is oiy(2-¾oryiamido^«-2~me hy!" ! ^» propanesulfonk sck1)_s also known as poly AMPS.

In one embodiment, the compositions are .ties of copolymers comprising at least one monomer hearing or capable of developing an anionic charge and at least one •monomer hearin or capable of developing a eationie charge. Such copolymers, sometimes referred to as "amphoteric" copolymers, arc believed to no function as wed or si all as polymeric eouoi^rioos to micelles bearing a n t electrostatic charge tor at least two reasons. First, the proximity of both types (anionic: and canonic) of charges along the polymer chains, if randomly disirihmed. Interferes with the efficient pairing of a given type of charge on (he polymer chain with the hsadgroup of a surfactant of opposite charge in s micelle, Second, such copolymers have the pot ntial for electrostatic iti ersciions of me anionic charges on given polymer chain with the oatknic charges on another polymer:^■ chain, Sach interactions: co ld lead t the formation of polymer aggregates or complexes in process that is undesirably competitive with the Interaction of the polymer with mieeflar aggregates..

[tlOSO] The water-soluble polymers may lochtde naiaral or sastthnabk materials heading anionic g oups, Including mulct derivatives (example Carboxyline CM! or Bequest FB), anionkally modified starches with the proviso that they exhibit waier solubility without cooking to achieve water solabiHty, a er-s luble salts of al inic acids, aniosical y modified eelkiosk materials suc as carboxy ethyl cellulose, modified proteins, and the Hke oiwhmking examples of monomers hearing or capable of bearing an anionic charge are acrylic acid, mediacrylic acid, vinyl sulfonate, acrviamkio propyl methane sulfonic acid (AMPS), itaoorae acid, ma!eic acid, fumarie acid, phihalk acid, iso- phthallc acid, pyro e! tk acid, methai!yi sulfonate, sulfonated siyrerie. crotoale acid, aeonitie acid, cyanoacrylk acid, methylene maloak acid, vinyl acetic acid, ally! acetic acid, ethylidlneaeetic acid, propyl id ineaee k acid, angelic acid, c-innam - acid, styryl acrylic acid citracoolc a.cid, glu aconk acid, phenyiacrylk acid, scryioxypropriomc acid, virryi e zo acid, -vinyisuccmamide ac d, mes&come acid, methacroy! alanine, aeryloimdroxyglyeine, sulfoeihyl acryfate, siyrene ulfonic acid, 3*{viay foxy }propane~ Ί. ^« sulfonic acid, etfcyetenestilihrk acid, vinyl s lfwrie-acid, 4-vmylphenyl sulfuric cid, vinyl p os onic acid, maidc anhydride, and .mixtures thereof. Suitable monomers ma inelade acid^unetion et ylenicslly unsaturated T.oouomers capable of polyraeiixation or copoiymerization via processes i cluding free radical polymerization, ATRP and RAFT polymerization co ditions that are expected to produce statistically random or gradient copolymers with edvykmcally unsaturated monos&ers which are Incapable of developing a charge, the so-cal!ed nonionic monom rs,

| >81i o«~Hm &g examples of monomers which are nonlonk, mi bearing, or not capable of bearing m electrostatic charge include the alky! esters of acrylic acid or meihaerylie acid, vinyl alcohol, vimy! methyl ether, vinyl ethyl ether, ethylene oxide, propylene oxide, and mixtures thereof. Other exam les include acsykrcids, dimethyiseryiamide, and other alkyl serylamide derivatives. Other^' suitable monomers ma include ethoxylated esters of acrylic acid or rnethseryl acid, the related tristyryl phenol ethoxyiaied esters of acrylic acid, methaeryllc acid or mixtures thereof. Other examples of ^'nonionic monomers nclude s ccha ides such as hexoses and pentoses, ethylene glycol alkylene glycols, branched polyols, and mkrarerlhereof.

[tM Sl] In some embodiments, water-soluble polymers comprising monomers which bear N~hal groups,, for example, N~€S. groups, are not present. It is believed ihsfc interaetioos between polymers comprising sm groups as polymeric coanterions to micelles leads to either a degradation of the surfactants themsekes and/or a degradation of the polymers through the enhanced local concentration of the ol mers the micelle surfaces,

|00S3| When the compositions comprise surfactant micelles with, for example., a net cationie charge and a water-soluble polymer or mixture of polymers hearing or capable of hearing anionic charges, then the compositions may he ree of any additional polymers bearing a cationie charge, i.e. , a charge opposite to that of the first warer-solabk polymer bearing or capable of bearing anionic charges. The presence of a first aier-sohrb!c polymer bearing an anionic charge and a second water-soluble polymer bearing a cadonic charge in the same formulation is believed to give rise to the formation of complexes between the two polymers, i.e., so-called poly electrol te complexes, which wo ld undesirably compete with the formation of complexes between the micelles bearing die cationie charg and the polymer bearing the anionic charge. |®684| Howe er, compositions comprising surfactant micelles bea i a net electrostatic charge and a water-soluble polymer bearing or capable of bearing an electrostatic charge opposite to thai of the surfactant micelles may comprise additional polymers which do not bear charges, that s, noniooic polymers, Such nonionfc polymers may be useful m adjuvants for thickening, gelling, or adjus ing the theological properties of the compositions or for adjusting he aesthetic a ea nce of the formulations through the addition of pigments or other suspended particulates, it should be noted, however, that many cases, the polymer-micelle c m lexes of the instant invention, hen adjusted to certain total actives concentrations, may exhibit 'h dMhiokenin " properties arid not explicitly requir an additional polymeric thickener, which is desirable from a cost standpoint.

V. Suitable -S»r¾*ta»ts

( 0851 *n on? embodiment, the compositions are free of not onie surfactants winch comprise blocks of hydrophobic sod. hytirophllio groups, such as the Plumules®, It is believed that the mieeikr structures formed with such large surfactants, in which the hydrophobic blocks assemble into the core regions of the micelles and the hydrophillc blocks are present at the micellar surface would interfere with the polymeric eouaisrion Interactions with so additional charged^ .surfactant, incorporated into a mixed micelle, and/or also represent a more competitive micelle assembly mee.bani.sm, in a mann r similar to that of dm axe of block copolymers used as polymeric eoontstions, which are also pxderably not present.

A very wide range of surfactants and mixtures of surfactants may be used_* Inclu ing an ic, noolonie and eabonlc serfsci&nis and mixtures thereof As alluded to above In the description of Dnet and P/Dneh it will be apparent that ixtures of differently charged surfactants may be employed. For example, mi tur s of catlotuc and anionic surfactants, mixtures of ca.tio.nic and nonkmic, m x ur s of anionic and nooiotbc, and miliums of caiionky nouionic and anionic ay be suitable for use.

|Q^@S?1 Examples of eationie surfactants include, bat are not limited to monomenc quaternary ammonium compounds, monomenc bigoanlde compounds, and combinations thereof Suitable exemplary quaternar anaooolum compounds are available from Siepsn Co under the tradename BTC® (e.g., ΒΤΟ 1010, BTC® 1210, BTC® 8 I S, BTC® S3S8). Any other suitable monomelic uaterna ammonium compound may also be employed, BTC® 1010 and BTC® 1210 are described as didecyl dimethyl mmonium chloride and a mixture didecyl dimethyl ammo ium chloride and nmlkyi dimethyl benzyl ammonium chloride, respectively. Examples of monomerie blgnanid compounds include, hut are not limited to ehlorhexidine, alexidlne and satis thereof.

i$m%\ Examples of anionic snriaeiaras include, but are not limited to alkyf sulfates, alkyi siilf riates, alkyl eiboxysalfates, fatty acids sad fatty acid salts, tinea? alkyibeoxerse sulfonates (LAS and Hi. AS.), secondary slksne sulfonates (for example Bes ow® SAS- 30), methyl ester sulfonates (such as Sie a -M t- PCL from Stepau Corp), alkyl suifosuccinates, and alkyl amino acid derivatives. harnnollpids bearing anionic charges may also be used, for example, it; formulat ons emphasizing greater sustalnabiiity, since they are not derived from petroleum-based .materials. An example of such a rhanmoHpi is JBR 425, which is supplied as an a ue us solut on with 25% actives, f m Jenil Biosurfa ani Co., LLC (Ssukvsiie, Wk USA).

[00B | So-called ''extend d chain surractmitkf am preferred Irs some formulations. Examples of these mkmic surfactants are described in US Pat. Pub. No, 2006/021 1593. O0f$j oo lmlting examples of nonionic satiact&ats Include alkyi amine oxides (for example Ammonyx® 1,0 from Stepao Corp,) alkyl amkloamine oxides (for example Am onyx® LMDO ixopt Siepan Corp.), alkyl phosphine oxides, aikyi poiygieeosides sad alkyl poiypentosidss, alkyi poly(giycerof esters) a d alkyl poiyiglyeerol ethers), and alkyl and alkyi ph nol ethoxvlates of all types and mixtures thereof. Sorbltan esters and eihoxylsted se-rbi^'ten esters are also useful no ionk surfactants.. Other useful noniomc surfactants include, but ate not limited to, fatty acid amides, ferity acid monoethauolamides, fatby acid dlelhanoiamidex, and fatty acid Isopropa-ootaosides, j¾H f Irs. one embodiment, a phospholipid stn'&etant m y be mehaied. Lecithin is an example of a phospholipid,

!§§§2| In one embodiment, syathetie xwittenonic surfactants may be present. ^"Non- limiting examples include N~alkyl beiaiaes ii r example Amphosoi® LB from Stepan Corp.), alkyl suffo-beiaioes and mixtures thereof.

[tMM>3] In one mbodiment, at least some of the surfactants may be edible, so long as they exhibit water solubility or can fbrrn mixed micelles with edible nonloaic surfactants. Non-limiting examples of such edible surfactants include casein or lecithin or mixtures thereof

in one embodiment, the surfactants may be selected based on green or natural criteria. For xample, there is an increasing desire to employ components that arc naturally-derived, naPuaily-proeessed. and biodegradable, rather than simply being recognized as safe. For example, processes seek as el soxylation may be undesirable where ¾ is desired to provide a green or natural product, as such rocesses can. leave residual com ound or impurities behind. Such "natural surfactants^ may be produced usin processes perceived to be more natural or ecological, uch as distillation, conde sation, extraction, steam distillation, pressure cooking a id hydrolysis o m& biize the purity of nateal ingredients, Examples of such "natural s rt¼cte.ts' that may be suitable for use are described in U.S. Patent Nos, 7,608,5 /3, 7,618,93 h 7,6-29,305, 7,939,486, 7,939,488, all of which are herein, incorporated by reference,

Vl. Saiiafete Adjvvftste

f00 S^'| A wide range of optional adjuvant or mkmtes of optional adjuvants ma be present, For example, builders and chelating agents, including bat not limited to EDTA salts, GLDA, MSG, gluconates, 2-bydroxyaclds and derivatives, -glutamic- acid and derivatives, rimethy [glycine., stc. may be included.

|00§6] Amino acids and mixtures of amino acids may be present, as either raeemie mixt res or as individual components ofa single chiraliiy,

§97J Vitamins or vitam In precursors, for example retinal, may be present, fdl)98f Sources of soluble zinc, copper, or silver ions may be present, as the simple inorganic salts or salts of chelating agents, me fading, but not limited to, EDTA, GLDA,

MGDA, citric acid, etc.

[0Θ$9| Dyes and colorants ma be present. Polymeric thickeners, when used as taught above, may be present.

ytC j Buffers, including but not limited to, carbonate, phosphate, silicates, borates, and combinations thereof may he present. Heettolytes such as alkali metal salts, for example including, but not limited to, chloride salts {e.g,, sodium chloride, potassium chloride), bromide sabs, Iodide salts, or combinations thereof may be present

( eiMJ Water-mi scibie solvents may be present in some embodiments. Lower alcohols (e.g., ethanol), ethylene glycol, propylene glycol, glycol ethers, and mixture thereof with water misclbility si 2S^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 include them in only small amounts, for example, of not more than S% by weight, not more th&n 3% by weight, or not more that; 2% by weight.

Wate -imm!selbb solvents may be present, being solubihzed into the m celles.

f©0t§3) Waierdmmlselbie oils may be present, being solubillzed into the micelles. Among these oils ape those added as fragrances. Preferred oils are those that are f om naturally deri ed sources, including the wide variety of so-called essential oils derived from & variet of botanical sources. Fonrmladoos teuded to provide antimicrobial benefits, coupled with Improved overall xustainabilky may advantageously comprise quaternary ammonium compounds or water soluble salts of ehiorhexldine or aiexidme in combination with essenlial oils such ax thymol anil the like, preferably In the absence of water-mi seiihie alcohols.

£001 §4f In o e embodiment, the^' composition may farther include one or more oxidants, Examples of oxidants nclu e* bet are not limited to bypoh&lous acid, hypofralite d sources thereof (e.g., alkal ne metal sab and/or alkaline earth metal salt of ypochlorous or hypohromons acid), !vydcogen peroxide and sources the eof (e.g., queous hydrogen peroxide, perborate and its sal s, percarbonate and Its salts, carbamide peroxide, metal peroxides, or combinations thereof), per&cids, peroxy acids, peroxoaeids (e.g. peraeetic acid, pereib ¾ acid, diperoxydodeeanoic acid, peroxy amido plrihsiamide, peroxo onosidfooie acid, or perax disulfamic acid) and sources thereof (s,g., salts (e.g., alkali metal salts) of peracids or salts of peroxyaelds such as peraeetic acid, petcdric acid, dipsroxydodecanok acid sodium potassium peroxystdfate, or combinations thereof), organic peroxides and hydroperoxides (e.g, benzoyl peroxide) peroxygenated inorganic compounds (e.g. perehloraie and its salts, ermanganate and its salts and periodic acid and its salts), solubi!bied chlorine, soiubiliml 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-ha!o: compounds, or combinations of any such oxidants. Additional examples of such oxidants are disclosed in U.S, Patent Mo, 7,5 17,568 and U.S. Publication No, 201 .1/0236582, each of which is herein incorporated by reference in its entirety.

MSJ.®5] Water-soluble rydrotropes, sometimes referred to as monornerie orgastic electrolytes, may also be present. Examples include xylene salibnate salts, naphthalene sulfonate salts, and crmiene sulfonate salts.

flRfi ] Enayoms may be present, particularly when e- formulations ar« tuned for use as laundry detergents or as cleaners for kitchen and restaurant surfaces, or as drain openers or drain maintenance products.

|001O?1 Applicants have found lhat a wide range surfactant mixtures reselling in a wide range of Dne values may be used, in many cases, the surfactants selected may be optimised for the solubilization of various waterdmmlseibie materials, such as fragrance oils, solvents, or even the oily soli to be removed from a surface with a cleaning operation. In the cases of the design of products which deliver m antimicrobial benefit is the absence of a stroE g oxidam ch as hypochlorite, a germicidal uaternary ammoni m compound or a salt of a monornerle bi_.go.msde such as ehlorhsyidfoe or alexidine arc often incorporated, and m&Q are Incorporated into micelles with polymeric counterioo . The fine control over the spacing between the catiomc headgroups of the germicidal qu ernar ammonium compound or biguardde which is achieved via the incorporation of a polymeric eounmrion can .resdt hi a. si nificant reduction in the amount of surfactant needed to soi bili¾e an oil, resulting in cost redactions and improvement in foe overall susialnabl!lty of the fonnu!atioas.

|00198| in contest to what is described in the an, app!ioa s have also found thai the mag i ude and precise value of f/Dnet needed to ensure the absence of precipitates and/or eoaceryale phases can var widely, de endin on the nature of the polymeric coun e foil and the sur&e ants selected to form the mixed micelles. Thus, si e tPete s great flexibility in the selection of the polymeric coanterion Ibr a given surfactant mixtu e to achieve a particular goaf applicants have adopted a syste na ie, bur slsisple approach for quickly "scanning through" .ranges of IkDnef in order to identify, a d to compare, formulations comprising: polymeric co n erions.

|0®!O ) The formulations comprising the mixed micelles of a se charge and a waier-seiable polymer hearing charges opposite to that of the micelles are usefoi as ready io use surface cleaners delivered via pre-s-nqistensd noowoven substrates (e.g., wipes), or as sprays in a variety of packages familiar to consumers.

ikkl f hi Concentrated forms of the formulations may also be de veloped which may be diluted by the consumer to provide solutions that are then used. Concentrated fonns that suitable for dilution vis automated s s ems, in -which the concentrate Is diluted with w fer, or in which two solutions are combined in a given ratio to provide the final use formulation are possible,

[001111 The fonmslations may be in the orm of gels delivered to a reservoir or surface with a dispensing device. They may optionall be delivered In single-use pouches comprising a soluble film.

!f!!Hi:!J 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.

100113] When the compositions comprise chlorhexidine or alexidiue salts as a egtio oa!b charged surfactant, the composltlosis may be free of iodine or iodine-polymer complexes sanopsrtk-tes of silver, copper or zmc, trkka&n, p-c loromsf yl xylenoL monomeric pentose alcohols, D-xyHrol and its isomers, D-arabitol and its isomers, aryl. alcohols, benzyl alcohol and pbenoxyethanol, flMH f n of the compositions are useful as liquids or lotions that may be used in combination; with norrwoven substrates to produce pre~ruol stoned wipes. Such wipes may be employed as disinfecting wipes or for floor cleaning in combination with various tools configured to attach to he wipe.

00115! te one embodiment, the clea ing pad of the present invention comprises a nonwoven substrate or web. The cleaning substrates can be provided dry, premiokiened, or impregnated with cleaning composition, but dry o-the-touch, in one aspect, dry cleaning substrates can be provided with dry or substantially dry cleaning or disinfecting agents coated on. or in the midticomponeni multiloba! tlber layer. In addition, the cleaning substrates can be provided in a prc-moistened and/or saturated condition. The wet cleaning substrates ca fee maintained over time in a sealabk container such as, for example, within a bucket with an attachable l d, scalable plastic pouches or bags, canisters, jars, tubs and so forth,

VIII, Examples

Mow artiek Sks and; Zeta Fnteatkk Were Pleasured

Si ^'f The diameters of the aggregates with the polymeric counterlons (in nanometers) and t e r zeta potentials were measured with a Xetasiaer ZS (Malvern instruments). This instrument utilizes dynamic light scattering (DLS, aise known as Photon Correlation spectroscopy) to determine the diameters of colloidal particles in the range Iron) 0.1 to 10000 nn .

|@ :11 | The Zstasker ZS instrument offers a range of default parameters which can he 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 ¾ which the optical properties of the aggregates were assumed to be si ikr 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 Zetasker provides automated analysis of the quality of the meas ments made, in the form of "Expert Advice". The diameters described herein (specifically what is known as the "Z" average particle diameter) were calculated .from raw data that met '^'"Expert Advice^"1 standards consistent with acceptable results, unless otherwise noted, I other words, the s m lest set of default measurem nt conditions md calculation parameters were used to calculate die diameters of all of the aggregates described herein, m order to facilitate direct comparison, of aggregates based on a variety of polymeric connterions and surfactants, and avoiding the use of complex aiodeis of the scattering which could com lic e or prevent comparisons of the diameters of particles of differing chemical composition. Those skilled in d^ye art will appreciate the particularly sunpie approach taken here, ami realize that It Is useful in comparing and char cterin complexes of micelle arid water-soluble polymers, independent of the details of the types of polymers and surfactants utilized to form the complexes.

ftKil l Sf This instrument calculates the zsta. potential of colloidal particles from measurements of the sleetrophoretic mobility, determined via a Doppler laser velocity easu ement. There exists a relationship between the slecirophoretie mobility (a measurement of the velocity of s charged colloidal panicle m vi g In an electric Held) and the zeta 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 coan¾¾rIons and s rfactaBts, the simplest set of default aieasnremeni conditions were used, Le,, the. aggregates were assumed: to behave as polystyrene latex particles, and the Smoluehowski model relating- the eisctrophoretic mobility and the: e¾ potential was used In all caienlstlons. Unless otherwise noled., the mean zeia potentials described herein were calculated fro taw data that met "Expert Advice" standards consistent with acceptable results. Aggregates bearing act cationie (positive) charge will exhibit positive values of the zeta potential (fn mV), while those bearing a. net anionic (negative) charge will exhibit negative values of the .reia potential (iu mV),

Exstnple !

Ready to Use Disinfecting Spray Cleaner Formulation Mean Diameter artd Zeis Potential of Surfactant Micelles With and Without Polymeric

Counterion

The iateraodon between mixed micelles comprising an amine oxide and two different germicidal, quaternary ammonium compounds and aa anionic polymeric connteriors cm he readily illustrated by comparing the diameters of the mixed micelles (as measured by DLS) in the absence and presence of the polymeric countersom The a ueous control formulations^' were repa ed by mixing the germicidal quaternary ammonium raw material (supplied as aqueous soluti ns; Stepan Corp.) with, the amine oxide raw material (supplied as an aqueous solution., Stepan Corp.) to form a mixed surfactant stock solution. Appropriate amounts of the surfactant stock so Piorp moooetl molamlrie (to adjus pH above 9,0} arsd water were mix d to form the fins! control formulstlon containkg ihe mixed micelles. In the case of l te formulation comprising be polymeric c mmiss on, the stuns mixed surf ctan stock solution, monoetl oianBrse, Alcosperse® 747 (su plied as an aqueous ol tion Ateo Nobel), and water were mixed appropriate amounts to yield the final formulations with differem P/Dnet values, but with tits same mixed micelle compositions. The formulations, all of which e e clear solutions fee of cos ervate or precipitates, are summarised m Table 1 .1. l te measured values of the Z^«sverage d ame ers and the ¾eta potentials of ihe aggregates are summarised m Table L2.

Table I J

t'csusr- Pc;hmer Amiise Gsoniaidiii Moo<>e :> !'■·)¾:

yiipiiVfi Alcosperse Omte, Q ·)¾;. aaoiamin !

Name 45^' 747 Aiis i-oayx BK« BTC¾

¾ % 1010. ¾fii ! 21¾ ¾

A.I 0,23 0,30 <u O 0.00099

4

A2 0.23 0.36 0.1 0 0.0010

A3^: 0.02 0,23 0.3b 0.1. • 0J 0.00099

4

A4 0,05 0.23 036 0, 1 0.00099

0,25 4

AS 0.02 0.23 - 0.36 0.1 - 0, 1 0.001

A.6 0,05 0.23 0.36 o;i 0,001

0.25 fSlM2tl] AleosperseS¹ 74? (Ak£o Nobel) acrylic acidrstyrsne random copolymer supplied as aqueous solution (40 % actives) with 7, ··" - I md Eq polymer ^ 0.005054 eqmva!enis/gram of polymer actives,

|^'00121| BTC® 1010 quaternary ammonium germicide (Stepa Co,) supplied as aqueous solution (80 % actives) described as didecyl dimethyl ar nonimn chloride, average molecular weigh ^!!; 362 grams/mole, ~ ] .

[801221 BTC® 1210 quaternary smmonium germicide (Stepan Co.) supplied as aqueous solution (10 % acti es) described as a mixture of didecyl dimethyl ammon m c¾Io«de md n~alky! (50% C14_; 40% CI 2, !0%C16) dimethyl ben yl ammonium chloride, average molecular weight 360.5 grams m le. ,

Table 1.2

Formulation Meaxt seta Cofnssra-iis

Name goi silais crs^'Y

A i 0 S .032 - 6 Mi cellar aggregate control

A2 0 1.006 ÷32.6 Mieeiiar aggregate control

A3 •- 0..1 76.08 S6.S With polymeric counterion

A4 - 0.25 §3.1 +51.8 With polymeric eounierion

A 5 - 0.1 79.14 -i-50.0 With polymeric ooimterbsi

A6 - 0.25 92.57 -50.5 With poiyrnerk couii erion

[001231 The results in Table 1 ,2 Indicate that the micellsr aggregate controls at Dne - were around 1. nm In diameter, which is m expected size mt%$& for mteeilar aggregates of i nic surfactants aqueous solutions. These results suggest .hat the de&nh parameters selected for calc lati n of the diameters from- Ore DLS measurements, as described above., were reasonable, a»d thus could, he used lor comparing changes in diameter due to. the inte actions between the micella? aggregates and 1¾« polymeric couaterions,

|O0124| Since these aggregates, comprised mixed micelles of an amine oxide surfactant which is expected t he uncharged at the high pH of the form daiion and a eationic germicidal qw&t, a positive mean zsta potential is expected and is observed for the two control systems comprising the two distinct germicidal quaternary ammonium c mpounds.

[ β125^'| e addition of the water-soluble anionic polymer Aleosperse 747 to the formulations at P/Daet al es of - 0, 1 and - 0.25 yielded clear solutions that were free of coacervate. Hie strong electrostatic in erac ions between the polymer and the mixed micelles result in the format n of stable aggregates that are m larger k average diameter than the micel!ar controls, but which are still small enongh to exhibit colloidal stability and a clear appearance. Increasing the absolute value of P/Dnet from 0 J to 0.25 cosrespends to moving closer to the lower boundary of the coacervate region for mixed micelles of this composition and at this total siniaetasd concentration, and hence the average diameters measured increase somewhat. fOOl ] In order to test whether these larger aggregates com risin mixed micelles and the polymeric eoaaterion were stable struc ures, repeated aieasiaerneats of the aggregate diameters were made on κ ύη%® &ά samples held In cuvettes m the instrument, every 5 mirmtes ve fee course of about one hour. Tr s, any growth in the aggregates, whkh m ght he & precursor to coacervate or precipitate formation and whkh would he less obvious than the haziness of samples detected visually, would be detectable from, a trend in the -avemge diameters over time. Mo such treads were detected for samples A3 through Λ6. All of these samples exhibited relative standard deviations of the Z-average diameters of less than 1% from the 1 1 sequential meas ements maele, The Zmverage diameters for these sam les, based on 1 1 measurements each, are those reported m Table 1.2.

|ί>θϊ2?1 Since the aggregates with the polymeric eonnterioas were formulated a aa absolute value of f/Dnet < 1 .0, the number of estioaio charges provided b i¾e germicidal quaternary mmonium compound in the mixe micelles exceeds that of the anionic charges provided by the anionic polymer, rid the stable colloidal a gregates formed would be expected to bea a net eationie charge and hence s positive zeta petential. Table 1.2 shows that the aggregates formed with the olymeric eo nterioa have .mean seta potential valises that are positive, eveo somewhat greater time the micelles alone, consistent with the torraation of distinct, tunable aggregates which car ot be f med without the irss of a polymeric comttetiom that is, t at eaeeot be formed ¾t the same total anrfaetani eoncentratloa and the same mixed micelle compositions when Ih rrative coo eriarss of the cationlc: surfactant (the germicidal quaternar amm nium com o nd.),- her chloride ions, are the only ones present, A conservative estimate of the precision of ml of the se potential measuremems referenced hereto is about 10% of the reported, mean value.

Exam le 2

Ready to Use Disinfecting Cleaner Lotion Suitable for Delivery from a Noowoven Wipe Mean Diameter and Zeis Poten ial of Sar ca t Micelles Without and With Polymeric

Coynienoa --- At lo w Y values

£00128 J A series of formulations were prepared in the same ma n as hi Example 1, at a lower relative coaeeotratlon of the germicidal quaternary anrmoaium compound hi the mixed surfactant aggregates. Formulations using these mixed micelle csmpositloas a e suitable far use as lo ioea which caa be loaded onto nonwovea wipes and provide convenent disinfection of hard surfaces combi ed with good c!eaamg of greasy soils, all without the rc^tre e&t for the addition of olatle organic solvents such as lower alcohols or glycol ethsrs. The forrmdsiions om rsing the polymeric cotmterion were clear md fee of coacervate whers the absolute val¾s of F/ oes. was bss than 0.39, according to m Inspection of a serks of sam les covering a range of this parameter between 0 md 0,5 ai this total surfactant cot>cerstraion md micelle cons ostion.

Table 2.1

Table 2.2

FormPDrsst Z a srsgt +«·;·:;.+·;·. M * 2£is potential, CofiiKi-SKis

ulations ;rsV

asxie

.47 0 2.SQ5 itr-5, 2 -09! kel!ar aggregate coouol preps)

AS 0 3,117(0 6.3 Not measured Micsllar aggregate control preps)

A9 -0.0! 3,266 (n-3) +9.31 ith polymeric eourtterion

AID -0.1 3.298 (o-3) +7.99 With poiys r conrdenoc

All -0,1 3,114(B-3) +4,18 With polymeric coantsrion

AI2 -0.25 3.680 (o- s +4.69 With polymeric countefion

|0β1291 The results in Table 2,2 show that, at this total surfactant concsntratiors and mixed rrs elie com os ion the mixed raicellss are some hat krgcr than those formulated wi the same quaternary ammonium com und and ami e oxide as shows n Table L I . Without be n bound by theory, it is believed that as the relative amount of quaternary amm niu compound in She mixed micelles decreases, an effect ve dilution of the charged quaternary amm ium com ound headgrcups in the micelles occurs due to the additional um e s of amine oxide molecules, which allows greater average spacing between the charged aternary amm maiSJ compound headgrcups 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 neao zeta potential is reduced, but is confirmed to be positive, i.e., eatiomc, as expected.

[001301 The results in. Table 2.2 also Indicate that the addition of an anionic polymeric eoursicrloc at P/Dnet values that do not cause formation of coaeervales results hi aggregates which are significantly larger than the tnicellar controls, bu still small enough to exhibit colloidal stability. The relative standard deviations of the measured Z- 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 pre ared on differen days, and hence the differences in i meter between the control formulations d those com rising the polymeric eounterious may be considered detectable and signif cant

[001311 The results In Table 2:2 also indicate thai the aggregates formed with the addition of the anionic polymeric coanterion, at absolute values of F/^'Dnet less than 1 ,0, exhibit a positive (eatlonie) xeta potential, as expected,

[00132] Thus, the ddi ion of a polymeric countsrion yields stable, soluble aggregates with a tunable size and charge which can be adjusted through the mixed micelle composition and the P/Dnet value. As shown, elsewhere herein, such aggregates exhibit surprisingly good antimicrobial performance, across a range of rnferoorga«ism¾. without requiring volatile organic materials such as alcohols or glycol ethers to boost or "potsntiats" the action of the quaternary ammonium compound. It is believed, without being bound by theory, that the aggregates comprising polymeric coemptio s can more readily act at the solid-liquid interlace, includiog that of microbes, enhancing the delivery of the germicidal quaternary ammonium compcamd and thus snhaucing amlmicrooiai efficacy.

xample 3

Ready to Use Disinfeedng Cleaner Lotion Suitable for Delivery from a Noowoven Wipe Mean Diameter and Zeta Potential of Surfactant Micelles Without an.d With Polymeric

Counterion - At absolute values of Ψ/Dmi > 1 f MH33] A se s of fo mktbns were re ared in the same manner as in Example L at a constant mixed micelle com osition and Duet -value which arc s table for use as lotions which ears be loaded onto nonwoven wipes or sed as a ready use spray deader with exc llent hard surface wetting properties in the absence of oiarlk organic solvents such as alcohols or glycol ethers, ^'The iornmiauor;s comprising the polymeric co« e.rio& were clear and tree of eoaoervate at absolute values of PBsei greater ibm 1 , determ e by an inspeciofi of a seeks of samples covering a wide range of the abs lute value of P/Daet between 0 and 2.0 at the total surfactant coimentfation. ^'The addition of the anionic polymeric counterions to the mixed missiles coniammg a q aternary ammonium compound provides a msehsnssrn to tune the sobAi!iaatioo efficiency oi waer-immiscibk oils, through aojhisment of both Dnet and the absolute value of P/Dnet.

Table 3.1

Table 3.2

^'Form- Mean sx-a Crs!?,;neaii

rcsae-n am iSesaiaL ¾V

AB 0 2,221 ÷7 4 Mkeifar aggregate control

A1 -130 102 (η··3· -231 With polymeric eoanlerion

A1S «1.50 9.732 (n-4.2 31.1 With polymeric counlerion preps) flMI!34] The results shown in Table 3.2 show that, at absolute values of FDnet greater ih 1.0 and outside the region in which coaeervaies are formed for this system, stable soluble aggregates are formed with she addition of the anionic- polymeric counterion. The aggregates have somewhat larger 2-average diametes relativ to mieeilar aggregate controls formed in the absence of the polymeric couaterion. Addition of a significant amount of !imonene., which is both a model fragrance oil component as well as a model hydrocarbon solved, to the aggregates com risi g the polymeric counterions is readily achieved at the same P/Dnei w! e as in the a sence of the limonene. Thus, the aggregates comprising the mixed surfactant nd the polymeric coemsrion are capable of solabili¾ing waier-½soksbte matesiafs mcb as Hmonene. It is believed, without being bound by theory_s that e soksblliKsilon of limonene m the aggregates wit the olymeric counterions is possible because the aggregate structures maintain a property of ord nar mixed nbceiles, i.e., a non-polar interior in which w&ter-lusolnble materials may be soieb!!ked, even in the presence of the polymeric counterions. i M le 4

Dilatable Disinfecting Formulations

Z-Average Diameter with nd without Polymeric Coantersons of Dilated Forum laiious |t¾135] The addition of polymeric counterions to iormaiadoos comprising mixed micelles of a germicide! qu terna y ammonium compound and aaoiher surf ctant provides concentrates which, can be dilated either manually or via rise se of an automated dilation apparatus to provide economical disinfecting solutions, The enhanced wetting properties of the formulations comprising the polymeric eoUBterions, in the absence of volatile organic materials such as lower alcohols or glycol et e s, provide excellerst performance with s minimum of residues, which is of c ncern, for example, in floor cleaning of health care facilities and fhe like.

fihJ h] In the first, step, the appropriate P/Dnet range for the concentrated fornmiatlons was determined, with different germicidal quaternary ammonium compound and an amine oxide surfactant mixture. The concentrates also comprised telrapotasslum eihy!enediarnlrse tetraacetate, a common ehe-!ant and buf er useful in controlling the effects of common tap water used as a diluent, and aCl as an electrolyte, Multiple concentrated formulations which were clear and free of coscervaie arc identified trou the adjustment of P/Dnet and Nad level. Formulations suitable for dilution at a rate of 1 :250 by volume are then identified through visual Inspection. Formulations which appeared to yield cleat; soluble solutions free of eoaeervate phase when diluted were then analyzed via DLS to confirm thai 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 than 500 nan as measured as described herein. The anionic polymeric cotsnterkwi m these examples Is Vsrss-TL® 4 (Akzo obel), described by the su lier as random co ol me of sulfonated styrene md m&kk anh dride, which s supplied as an aqueous solution at 25% actives si pH 7,0, which means the anionic sulfonate groups are present in the salt form, and thai t e m&kk anhydride has ee; hydrol ed to m&l&k acid via reaction with water, a d the acid groups are sent in the soaked (salt) form, ^'The nomina molecular weight of the polymer is described as 20,000 d&itons. The total n mber of amonk&lly charged rou s oo this polymer yields 0.00642? moles of anionic groupsgram of polymer solids, and this a used in the calculation of the OVDnet values listed below.

'Fable 4.1 - Concentrate I¾rmuMk>m si Constant Y ^:;:;0,5

A33 0.412 4.0? 6.4 J .0 5.0 - 0J5 Y 114

A34 0,550 4,0? - 6.4 1.0 5,0 - 0.20 Y N

A35 0.068 4.07 6,4 5.0

0,025

A36 0.B7 4.0? - 6.4 - 5.0 ^■· 0,05 N -

A3? 0.275 4.0? - 6.4 5.0 - 0.10 N -

ASS 0.412 4,0? - 6.4 5.0 - OA S N

.439 0.550 4.0? 6.4 5.0 - 0.20 N

|0#!3?1 The esults in Table 4.1 iikss rnte that mulilp . concentrate formulations h ch .®re clear md free of coaceryate (A 18 through A24) com rising the anionic polymeric ca Merlon are possible, eyes, up to absohrte values of IVDnet ^~ 1.0₅ when suffici t total elec rolyte (NaCi and K EDTA) is present. Fenerations A16 and A 17, b which P/Daet ^~ 0 acted as micelle controls. I Is believed, without being bound by theory, that the interactions between the polyiseric cour terion sad the mixed micelles comprising quaternary ai o i am compound md m oxide cm be adjusted through the .addition of ordinary electrolytes lsk¾ Ns€l and ₄EDTA, which partially screen the charges ort the soluble polymeric eoitn enons from the opposite charges cat the mixed micelles, and/or compete with the olymeria countenons for the oppositely charged quatemary^'smmonium compound molecules in the -mixed micelles.. When the absolute value of the P/^'Dnet param er s at or ne r 1.0, the number of anionic charges resent are exactly or nearl sufficient to comp et l neu alize the ea lome charges due to the germicidal uat rnar amfflOSi» compound_., which would be expected to lead to the formation of eoaeervates or precipitates, S¾rpri.siagly„ however, the absolute value of 0/Doet alone is not a reliable guide for avoiding eoacervat.es or precipitates in the formulations, instead, for a given desired F/Dnet value, a given mi u e 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 s stematicall determined.

(001381 F rmations A26 through 29. for e m le, can be compared with AI S through A21, ail of which cover a range of the absolute- value of F Dnet values less than 1 ,0, which is of interest for lower total actives and hence lower cost. Formulations A26 through A29. have m insufficient total electrolyte el dua to he aHminstloti of 4E.DTA without a ) increase its the NaCl coceentratkm, and hence are not clear solutions which would not be suitable can idates for a concentrated fom&siatioo.

Similarly, Pormidalions A30 through A34, Irs which a different gs.mik.kkl quaternary ammonium compound s used, are acceptable concentrate candidates. By comparison, formulations A35 through A39, tn which the total electrolyte concentration w s a ain reduced via elimmatiori of K BDTA, are no cceptable concentrate candidates, since aone of them were clear solutions, hut in tact exhibited cloudiness dae to ie presence of eoaeervams and/or precipitates,

&I 01 In a second ste , the behavior u n dilation wafer of the stable concentrates was evaluated. A sample of the concentrate (40 microliters) was sdded to 9.96 ml of water of eemrolkd hardness (re resentin the 1 :250 fold dilation rate of interest for this application) its a capped vial and n itted ia manual agitation for a few seconds. The dilated samples were visually evaluated tor cloudiness, h r e , or the presence of prsdpiPstes immediately. Formulations A30 artd A31 are examples of concentrates which, upon dilation, f m clear solutions that are free of coaeervates or preeipkates, DLS was then esed to confirm the presence of stable aggregates comprising the mixed micelles and the polymeric eounterloo. In comparison to mixed micelles comprising the same qua ernary ammonium compound and amine oxide samadant wi out the polymeric counterlon.

Table 4.2 - Characterisation of Diluted Formulations Prepared from Concentrates

FormP/Dnst 2 avsr-jgs Mean .se s Conunersts

ulation poteatisi,

:.« Y

A 17 ^' 0 5.141 (n-4) ^•M .5 Control - no polymeric

eoanterion - domed in hard water ( 1 :25 diksikm)^*

A31 - (LOS 167.7 or 51 +44,5 With polymeric coc erion - dilcted 1 :250 In ^"hard water - fresh sample ^*

A3 ! - 0.05 178.7 (rr-S) With polymeric eounteno¾ - dilated 1 :250 m deiontee water

A30 - 0.025 136,8 (mk>) With polymeric counterioa ~

diluted 1 :250 in hard water - f esh sample'^'

A30 - 0,025 140.0 (rr-5) With polymeric eoanterion - dilated 1 :250 In hard water - aged 6 hoars ^' * Synthetic hard ater used for dilution co taine calc um and magnes um ions in a 3: 1 mole ratio at a total concentration of 150 ppm.

[OOI !I The res lts in Table 42 indicate Chat the ^avera e 4i&m tet of the micelles In the control sample is significantly less than hat of the ibnsu ions comprising the same eationk micelles d the anionic polyms.de coanterion. It should be no ed tha successful DLS analysis of ths micelle control, formulation required that It be dilutee only by a factor of 25, in order to ensure adequate m reproducible level of scattering. The amount of scattering from colloidal particles in e DLS experiment is a fu c ion of the average diameter of the particles to the sixth power, or proportional to (diameter)⁰. Tims, small increases In the average diameter result in ver large increases in the amount of scattered light, which in tuns allows the detection and analysis of larger panicles at much lower concentrations than smaller art cles. That ex ec ed trend is consistent ith the measured diameters of the .a gre a es formed upon dilation of formulations A3Q and All , The results also indicate that the quality of the water did not have a large effect n the Z~ average diameter of the aggt'egates of formulation 31 formed upon dl lotion,

[001 2] in Table 4,2, "fresh sam le" means that ths first DLS analysis of the diluted sample was conducted within 10 inu es of the initial dilution step. Multiple replicate measurements of the same sample (typically 4 or 5, as Indicated) were usually made. Replicates could typically be obtained within 2-3 minutes of each other. The stability of the aggregates formed upon dilution of Formulation A30 was also cheeked by osl mg the same sample thai was allowed to age 6 hoars in the instrument. The res lts indicate that no significant change m the Z average disnteter of the aggregates: in the dikued sample was observed, indicating that stable structures am fonned immediately upon dilation of the concentrates, without need of any special processing other than simple mixing,

001 31 The results in Table 4.2 also indicate that the eta potential of the diluted sample of the control micelles is positive (eationic), as expected. Since the absolute value of !VDnet for Formulation A3 ! is 0.0 , Le._s signlficaatly less than 1 .0, the 2eta potential of the stable, soluble aggregates formed upon dilution is expected to be positi ve (eat!ornc), and the measured resuk confirms this, at ÷44.5 rrfvy

f K)144] The results in Table 4.1. and 4.2 also indicate that systematic adjustment of the MXnet parameter and the electrolyte level (and, if desired, the mixed micelle composition) m&y be used, w h Initial visual ins c ion, to kks ti concentrates which. upon significant dilation_* deliver stable, soluble aggregates comprising mixed micelles of a_. germicidal quaternary ammonium compound attd a second surfactant and an arnomc polymeric coueiedon, in a solution free of coacervaies or p eci ita es,

Etauttple 5

Formulations Suitable I r Delivery from Nonwovens Control of Mkeile Interactions with Polymeric Coanterions Over Wide Range of P/Dnet The pH of the aqueous formulations com r si g mi ed mke!ies wit a csdonlc charge aad an anionic polymer may be adjosied over a wide range, providing the polymeric counienon maintains its solubility in water ai the pR of InteresT

|08S4S| Thus, a series of aqueous forandations io which the pll was adjusted to about pM 7,6 e e made in order to confirm the absence of coseervsie form.ari.oc across the P Diset range of interest.

|ΘΘ146) Samples wem prepared by making die following stock solutions: ( I) 0,33 t% EA and 0.S2 wt% g!yeolic acid at a pi of 6. , (2) 1.2 wt% BTC® 1010 and 6 J wt% Ammonyx® LO at natnral pH, and (3) l.S wt% Alcosperse* 24? adjusted to pE 6.2 with glycolic acid. The EA/glycoik acid stock was then dilated in the proper amount of water followed by addition of the BTC® iO I O/Arnrnony¾® LO stock and finally the A!cosperse® 747 stock. Fina pll was measured and found to be between 7 A and 7,3 ίοτ these formulas,

Table 3 J - Compositions suitable for delivery from nonwovens

Fermu!&tiosi BTC® Afianonyx® Akos e ss® Olvccac pH Mams o e LO wi¾ 747 wt% acid, ¾ΐ%

B! 0.36 2,05 0.005 0.1 0.16 7,6

B2 036 2.05 0.01 0,1 0.16 7,6

B3 0,36 2.05 0,02 0.1 0, 16 7.6

.84 0,36 2.05 0.025 0, 1 0.16 7.6

BS 0,3d 2.05 0.03 0. 1 0.16 7.6

B6 0.36 2.05 0.05 0.1 0.16 7,5

7 0,36 2.05 0,1 0, 1 0.16 7,5

B8 0.36 2.05 0.2 0. 1 0.16 7.5

89 0.36 2.05 0.25 0.1 0.16 7,5

B IO 0A6 2.05 0,3 0.1 0,16 7.4 .81! 036 2.05 0.32 0.1 0.16 7.4

BI2 0.36 2.05 034 0.1 0.16 7.4 f^'3 036 2.05 0.3S 0.1 0.16 7,4

B14 0.36 2.05 0.3? Ο,ί 0.16 7.4

015 0.36 2,05 0.39 0.1 0.16 7,3

B16 036 2.05 0.49 0.1 0.16 73

C aracteristics of Cstlonk- Mice!ks with A onic Polymeric Counterfort at pB 73 to pH 7,6

CK114?j The visual inspection of the fomju kms m Table 5 ,1, com rising e&lianie mixed micelles md a anionic olymerc oouMerion indicate i &t clear, stable solutions were produced across a range of the absolute value of PDnet from less that* to signifcantly greater ihm 1.0. In order to confirm the absence of small amounts of eoaeervaie phase, the Z-average diameters of the series of samples were also measure . The results in Table S.2 Indicate ifea the binding of the anionic polymeric countertao to the c&ikmie raked rrd&eiles result k aggregates t at are ail larger than mixed micelles of the same composition without the olym ric counierlors. The Z-average diameters of Che micelles with pohyreerk eounterions were small enough to exhibit excellent colloidal stability, he.., the diameters found were < SOO era, aed more preferably <100 em.

Example 6

Stability of Size of Catioree Micelles with Anionic Polymeric Coenieric s at P/Drset >1 | S14S| The a sence of eoacervaie or precipitate phases from formulations comprising micelles with polymeric eo oterions may, in general, be readily de ermi ed by visual examination of samples m de or? the scale as small us shorn, 10 to 15 ml in capped test tabes. As taught herein., cationk mixed micelles with anionic polymeric eounterion also exhibit dte important property of solu il zation of waterAasoieble oils w en ooaeervate or precipitate phases are abserP, and tins solubilization may also he evaluated through visual Inspection of samples. The absolute value of the P/Doet parameter cannot be used alone to determine formulations ^"which are free of eoaeervates or precipitates, but instead must be considered together with s e mixed micelle c mposition and the type of water-soluble polymer selected for use as a polymeric couetsr!oo. in order to avoid eoseervate and precipitate phases, the polymeric eounterion must be soluble aqueous compositions at the H of the desired final .formulation. The solubility of polymeric countsrions in aqueous compositions may also be readily evaluated thoug visual inspection techniques. Thus, for example, the .solubility in water of Al.cosperse® 747, a random copolymer, Aeaatreat®. AR-4, an servile acid homopolymer, and Akogaard® 5240, a random graft copolymer, all of which contain carhoxyiic acid groups, may be compared over a range of pH values and any polymer which does not exhibit the necessary solubility at the pH of interest may he avoided,

(001.491 Formulations com r sing cstiopic micelles ari anionic polymeric coutttcrions drat am free of eoacetvate and precipitates with the absolute value of the P/Dset parameter >! can also be readily identified, for example, formulation BIO in Example 5, In additioe to h visual inspection of this sample, which indicated it to be free of eoaeervates or precipitates, DLS was used to monitor the Z-average diameter of these aggregates upon overnight aging to confirm their stability, i.e., as an alternative method of ensuring that the aggregates remained f ee of coaeervates.

30!5§) Thus, !brmulatioe B 10 was placed le a sealed cuvette and a measurement of the Z-average diameter was takers every 30 minutes over a 13.5 hour period, with the temperature controlled si 2S°C. Such a rocedu e »y be readily accomplished with t Mal ern Zets Steer & asd those skilled in the art will rsaltee thai e uivalent measurements may be mad« with other instrumea The results of this experiment a e shown Irs T&bte 6.

Table 6

Z average diameter of Aggregates Comprising Cstlonlc Mined Micelles and Aniorsic

Polymeric countenon

Formulation BIO Stored Overnight

1 1.5 23.6

12 2S ?¾

1 2.5 23.3

13 23 *?

13.5 26.01

O erall mean Z~

average diameter.

2S.U

«I.3 ve ta dard

Devistkm of

Diameter, % 1.-73

|001£3 I The results in Table 6 indicate that he Z-average diameter of Formulation Bi 0 a ears stable, i.e., with a r la ve .s andard deviation of less than 2% over a 13,5 horn period, c &Snam c nclus ons made with isual ins ect on of the sample. The results also indicate that stable . formulations free of coaeervste md precipitates with the a solute value of P/Dnet > l„ comprising catlonie micelles nd amo c polymeric eouaterions may be made.

Exam e 7

Formulations Suitable For Delivery from Noow ens or as Disinfecting Spray Cleaners

Acidic pH

|fl§IS2] Formulations comprising mixed micelles of a germicidal u ernar mmoni m com ound and -an. amine oxide rosy also comprise adjuvants or heifers w ich can be used to adjust the pH. In these examples, monoetbanolamioe (MEAs was osed to increase the pH of t e fotmaiatious, and glycoik .acid was used to decrease the pi! of the formulations. Decreasing the pH of such formulations may he desirable for increasing cerhiio aspects of cleaning performance, for example, the dissolution of hard water spots torn sinks, hies, dishes., etc. The inactivatioo of certain viruses ami bacteria is also known io improve when the pR is decreased below pH ?, to the acid pH rasuge. Certain other aspects of cleaning performance of am ne oxides, sack as residue deposition on hard surfaces which results in filming or streaking, and decreased ability to solabiltee greasy soils tend to he exacerbated as the pH of the formulations is decreased, especially below pH ?. Surprisingly, the use of anionic polymeric counterioes in formulations co prisin germicidal quaternary smmoafem compound and amine oxides improves the ettin properties of the formulations on a range of surfaces, while decreasing residue formation. Thus_* the addition of volatile con ents to t e acidic fbrm latioas to improve performance properties may be avoided when polymeric coimierioo* are utilized.

f§0!S3] In is example, the water soluble polymer f Aioogtrard® 2300 from Afczo Nobel) was a andom copolymer of the no onk monomer dis^tbylacryiamide (95 moie%) and the anionic mosiomer acrylic acid (5 moie%), w ich thus provides 0,00600 moles of anionic grou s per grarn of polymer actives. This polymer is soluble in water at both lo pfi, eg., pli 2- , d high. p!:L e.g.. pE 10, arsd can thus be employed as the anionic polymeric eountsrion. to mixed micelles of the germicidal quaternary ammon um comp und BTC-Φ 1010 ( W ~ 362 g moi) and the amine oxide Anvmonyx® LO.

1S ] Visual inspection sad BLS were used to determine the formation of stable aggregates, the compositions of which are s mmarized in Table 7.1. In Tabic 7.2, the Z~ average diameters, are . summ rized, and indicate the aggregates formed as much larger than .mixed micelles of the germicidal quaternary ammonium compound and amine oxide in the absence of the polymeric coanicrion. F/Dne was calculated based on characteristics of the polymer and BTC 1010 quaternary snnnotbara compound.

Table 7, i - Compositions

Formulation B^' Ci⁾ Alcognard® MEA Glycohe pH

Name i Oi O LO r% 2300^" w % acid,

i% Wt% wt%

CI. 0.36 0.23 L!7 0.1 0 9,4

C2 0.36 0,23 1.01 0.1 1 0 9.2

C3 0.36 0.23 1 .01 0.012 0.01 4.74

C4 0.36 0.23 0.78 0.009 0,01 4.87

C5 0.36 0,23 0,23 0.028 0.01 5.4

C6 0.36 0.23 1.0 ! 3.56 0.1 9.35

C7 0.36 0.23 1.01 0.012 0.1 4.73

C8 0,36 0.23 (⁾.?§^' 0,009 0.1 4,3 f 0.36 0.23 0,23 0,003 0.1 5,4

Table 7.2 - C aracterkaiiofi of Composition* Formulation P/Daef Z average Commens

Name diameter,

n

CI ^■ .5 26,33 isual dear

C2 33 25.98 isual ste

C3 -13 ^"30.9! Visually dear

C4 3,0 24.88 Visually desr

cs -03 15.13 Visually dear

C6 -! .3 28.93 Visually vlessr

C7 •3.3 64.1 Visually efear

CS 3.0 31. 1

C9 -0 16.51 Visually ce r

Ex m le 8

Formulations Suitable For Delivery fom Nonwove s or as Disinfecting Spray Clearssrs

Acidic pH

|001$5| This example shows some additional acidic formulations sir.ig mixtures of asi ine, an nn acid, and- glycolic acid to adjust the pH,

[8156 isual inspection nd DLS were used to determine the formation of stable aggregates, the compositions of which are s mmarized in T3.-38,1. la Table 8.2, the 2- average diameters are s mm ised, and indicate the aggregates forms d as much larger th naked micel s of the germicidal quaternary ammonium compound sad amine oxide in the absence of the polymeric eo enori. pD. et as calculated bassol o characteristics offhs polymer and BTOS> 1010 uaternar a amnsum compound.

Table 8,1 - Compositions

Formulation BTC® Alcogasrd® Agl ne Glycolic pH Name iOIO BOO^' wt% acid.

wt% wt%

CIO 0.37 0.23 0.088 0.174 0.08 5

CI I 0.35 0.2) 0.22 0.174 0.097 5

C12 0.4 0.24 0.45 0,174 0.105 5

CI 3 034 0.2 i 0.6? 0.174 0,112 5 C ! 4 0.34 0.21 032 0. 33 0.127 4.5

CI S 034 0.21 1 .43 0374 0.08 5

C 6 (US 0.22 137 0.174 0.08 5

CI 7 034 0.22 1 ,55 0374 o.os 5

- Chamcter-ization of Compositions

Po^pul ti n ?/Dnet Z average Comments

Name diameter, mi

C!O -03 13. 1 Visually dear

CI 1 -035 1 7.15 Visually sl r

C12 -03 17.56 V sua^y ci&sr

CI 3 -0.75 2231 Vis ally efesr

CI 4 3 ..0 30.79 Visually eisar

CIS 3.95 25.78 VssnsOSy dear

316 3.8 39.4.1 Visually dear

C I 7 .· r 29. 1 Visually dea

|00 S7| Spores (or mora properly, endospores) are a type of dormant cell produced by many types of bacteria, such as B etiim and Clostridium, res onse to stressful ei¾wo.omenta] conditions. The exterior coats of spores, which are responsible for the re-sisssnee to extreme conditions, ^'are muitM&yer structures composed primarily of cross- linked polypeptides. When a spore encounters e vironment favorable for growth of vegetative cells, the spore coa also allows access to nutrients and water to the spore, a d ite production of a vegetative cell la a geraOnatioa process.

01SS| The com osit ons of the polypeptides, proteins, sad other minor m te ials that make ap the coat of Ba illm Zubtilis spores, for example, residi the s ore exhibiting a net anionic charge (negative .¾e†a potential) when the spores are dispersed in water- ai neutral p¾ i.e., pi! 7. Polypeptides in aqneous solutions will exhibit a e cha ge as a functio of pH of the solution that is de ermin d by the relative num e s of amonioaily and cationically char ed Smin© acids in the polypeptide chain. At a pH corresponding to the isoelectric int of a polypeptide, rise net charge on the polypeptide is ze o, due to the presence of equal numbers of cahonicahy charged and aniaiiicatly charged amino acids. The net charge on rise polypeptide at pH values greater ihm the isoelectric pai t will t m be negative (anionic-), sod will he positive (cationfc) at pH values below the isoelectric point. The isoelectric points, (or point of zero charge) of various Baciiius spores have beers found to lie between about pE 3 and pH 4 , Thus, the zeta potential of the spores used herdo way tbursd to he oationlo (positive) when the spores were dispersed in water adjusted to around pH 2, i.e., wed below the known isoelectric point

i%%t$9] B i!hs spores exhibit average diameters of mx d 1000 u (1 micrometer), and cars thus act. as charged scattering ar icles when dispersed In aqueous media. Measurements of the zeia potential of spores are thus readily accomplished using the approach of laser Doppler velocity determination ih&t is implemented in modem instruments, such as the Malvern Zeis S!zer. Those skilled In the art will realize that an appropriate eonoerihatioo of spores for such measurements of the set potential of th spores cars readily be determined, using dilatio s of standard dispersions of spores which are commercially available_* Typically, the spore concentrations in these standard dispersions axe expressed as spores/mi or colony orming^' isnlts/rnl of the dispersions. Applicants have found that reproducible measurements of the xsta potential of Ba k s spores can easily be made at spore concentrations of around I to 3. x 10 ^: spores/rol Such concentrations are readily made by dilution of coaunereiaily available stocks with concentrations of I χ 10⁴ spores/ml.

[Mlfifl] Spores cont minating surfaces see a towels, other laundry, or hard surfaces, such, as floors, walls, medical equipment, food preparation or service counters, etc. will germinate and grow, producing increasing nutnbs s of organisms on the surface, wheiB the erwironroen becomes favorable, for example, when the surface becomes soiled or contaminated wife materials that are suitable nutrients for the microorganisms. Germicidal quaternary ammonium com o n s or higuamdes have little effect on dormant spores,, but If they are pr sent on the surface of the spores in sufficient concentration, they may kill the organism at the initial stage o germination when the environmental conditions otherwise become favorable.

f 08161] Exposisre of spores to solutions comprising micelles with a net catloolc charge due to s germicidal quaternary atnsio iiuro compound or a monomerie biguanide can result in the adsorption of some quaternary ammonium corapormd or biguanide onto the spore surface, joss as would be the 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 the quaternar ammonium compound o biguanide ί« solution incre ses, up to about the critical micelle concentration, at wh ch it will become constant d maximum. The esence of eatlonic s tes (due to c&tiomcaily charged s ina acids gnd offe materials comprising the spore cost) o the spore surface will be expected to oppose arid limit the adsorption of anionic quaternary ammonium compound or bigaaidde.

(00162] Adsorption of the quaternary ammonium ompo d or biguaaide wii! be favored at the anionic sites on the spore surface. If the medium surrounding the spore is sud enly changed, for example by the addition of an organic sod load which could serve as a nutrient source to the spores and t us favor germination, then the adsorbed q aternary ammonium comp und or biguanide, like any other sortac ani, will re-equilibrate with the surrounding medium, resulting in desorpt n of at least some of the quaternary ammonium c m und or bigaanide from the spore ur c , . thus decreasing its antimicrobial efficacy during the subsequent gernrinallon of the spore,

|m¾S3] As is s own belo , he compositions of tin; instant invention, in which micelles wi h a net cs!ionfc charge are paired i h s - ater-sokhle polymer of anionic charge, white mma lsg sol able and free of eoacervates or precipitates, have the advantag of ine control of the adsorption and desorption of p ion ic surfactants,nc uding the germicidal quaternary ammonium compound and biguanides, whkh can he exploited to provide better antimicrobial efficacy against the proliferation of hastens on surfaces doc to the germination of snores.

Exam le §

Demonstration of the Adsorption of Germicidal Quaternary Ammonium Compounds onto Spore Surfaces from Mixed Micelles and Mixed Micelles with Polymeric Counierions

(Msoeils-Poiymer Complexes)

1)fl!64] The zeia potentials of Bacillus Subiuis spores suspended in water at p l ?. the mixed micelles without the polymeric coanterion (F Dnet = 0), or m xed micelles Interacting with an anionic polymerse couoierioo were meas red using the Malvern Xetasteet, The presence of monoethanokmlne In the 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.

|##ίδ5| A eommerelaiiy available stock suspension of Bttciiius Su&i!is spores w s used to make all samples on a given day. Samples were analyzed within four hours of preparation. Thirty microliters of the stock spore suspension (I x 10^" efu/ml) were mixed with 870 microliters of water (pH 7) to give a control sample con a n n about 3.3 X 10" cfu/mt. The entire sample as loaded into a disposable capillary cell for meas rement of the ze&s potenf of the spores, as described generally above. In the case of die formulations, thirty microliters of the stock spore sus ension as mixed with 27 pi of the formulation allowed to equilibrate 10 minutes, and then 600 μ.Ι of deiomzed water was added to again yield a spore suspension of about 3.3 x 10° eiu/rnl This sample preparation method was also fowsd the corn pari eo of the germkktef activity via the spiral plating method used in the next e am le below.

Table 9 1 - Compositions

Formuktio Polymer Amine Germicidal Monoethano P/Dnet n Name Alcospetse Oxide, Qnat, amine wi%

® 74'? An rnonyx ^■BTC®

t% LO, 1010, wt%

wt%

01 0 1.8 0.2 0.J 0

D2 0.00255 1 ,8 0.2 0.1 41.05

D3 0, 102 1 ,8 0.2 0J -2.0

Table 9.2

Xeta poimtkl of Ba&Ihis S btiUs spores (3.3 Χ Ιϋ 6 ehibnl) In wster md in Pormula.iio.ns of various P/Dnet

Spore treatment Absolute value, oan eia

P D nut potential m V

Control - spores N/A -46.3

o¾f in ddonlze

water

Spores in 01 0 ^•20.5

Spores in D2 0.05 : 12

Spores in .03 2,0 -2.9

[0 166] The results hi Table 9.2 indicate that the eeta potential of the batch of spores used on this day exhibited m anionic (negative) zsta potential as expected. Exposure of the spores lo formulation Dl _s the mixed tnicellss comprising he germicidal quaternary ammonium compound rod amine oxide in the absence of a polymeric coimteriom eatsses a large shift in Che zeia potential of the spores in the cationie direciiom and in f ei completely reverses; the seta potential of the spores to +20.5 mV. |Ο0ί§7| This change cm be explained by the adsorption of the germ cidal quaternary ammonium comp und onto the spore surface, closin a compensation of the negatively charged surface sites, which wo ld leave only eatioofcally charged surface sites ava lable to contribute to the zela 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 c mpound molecules,, causing an additional shift in the s ta potential of the spore in the s me oationlc direction. The results also show that exposure of the spores to formulation D2 results in a shift of the xe potential in the cationic direction. Since the absolute value of P/Doet is less than 1.0_S lbs aggregates (complexes) formed by the interaction of the polymeric counterion and the mixed micelles have the cstiomc- charges dee to the quaternary aimnoaium c m ound in excess, nd thus have a. catiomc charge, as shown abo e. The shift in the zets tent al of the spores caused by exposure to formulation 02 clearly indicates adsorption of the germicidal ■quaternary snsraoninm compou d, he,, the re enc of the polymeric co nterion does not interfere with the adsorpt on process. Since d e magn ude of the s ift of the xeta potential is somewhat smaller for exposure to ibrmdstion .02 .compared to Di, It is believed, without being bound by theory, that the adsorption of some of the anionic polymeric co nterlou onto the spores also occurs, changing the overall chemistry of the adsorbed layer,

fOOMtf Surprisingly, ex o u e of the spores to formulation .03 also causes a significant shift of the :seta potential in the cadonic direction, to a value only slightly below 0, Thus, even when the absolute value of P/Dnet Is Touch greater than 1, indicating an excess of the anionic charges due to the polymeric eot tsrlon over that of the eationie charges due to the germicidal quaternary ammonium compound in the aggregates formed, 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 he accomplished across a broad range of the absolute value of P/Dnet which in tuns allows adjustment of the formulations or other properties, such as oil solubilization, greasy soli removal during a cleaning process, and aesthetic properties such as lack of filming or streaking on solid surfaces.

Exam le Id Antimicrobial Activity of Mixed Micelles Compared to Mixed Micelles with Polymeric Counterions (Micelle-Polymer Complexes) Against B c ius-Sabtiiis spores

A simple method was developed to demonstrate the utility of form lations comprising mixed micelles of a germicidal quaternary ammonium compound with a water-so!u k anionic polymeric connterion (mlcelleqaolynaer complexes) In killing bacterial spores placed in m environment favorable for germination.

0!7 | Se l dilation of concentrated ceil sirspenslons followed by plating on a solid growth medium is a common way to determine the viable ceils, or colony forming units (CPU). In a the suspension. The CPU multiplied by the relevant dilution factor relates baok i the viable microbes in the original suspension. Those skilled in the art fseognke hat the automated spreading of a s ore suspension in & spiral formation from near the center to the periphery of a circular plats containing solid microbial growth, medium (agar medium described hi detail here) simultane sly accomplishes dilution and a w y to determine the CPU /ml of the microbial suspension through deposition over an ever lengthening, area of the solid medium. S and rd recognition software eats visualize colonies on the solid medium and calcula e the CfU/rai of the or ginal suspension based on the distance_, and somber of colonies ela ive to the center of the plate, Such an approach Is implemented with commercially available equipment; such as the Antoplater Model APSOOi) (Advanced instrumen s) nssd in the fxdlowdng examples,

|0C ¾ 71 Spores which, have beers treated with the inventive compositions will be killed upon germination when they are deposited onto the growth medium, due to a c mbination of the presence of some residual amou t of the aqueous formulation and the quaternary mm nium molecoks which are strongly adsorbed onto the surface of the spore, t he spiral plating of die spore sus ension accomplishes an exponentially increasing amount of dilution of the spores in a spiral pattern on the growth medium. Thru;, the concentration of the aqueous formulation deposited with the spores is exponentially decreased by dilution with the growth medium. In addition, the chemistry of the a ueous environment sonoanding the spores changes dramadcaby towards one rich in .nutrients such as proteins. Thus, the quaternary amm nium molecules and any other suf&ctaotx adsorbed on the surface of the spore will re-equilibrate with the sumrnuding growth medium through desorptlon (partial or complete) from the spore surface, and/or a displacement from the spore surface through the adsorption of oilier materials present In the growth medium. In other words, the spiral plating method exposes the spores suspended in the inventive compositions to as exponentially increasing "organic loadT wh ch Is well-kno n m she art to interfere t and or revent t e antimicrobial action of common getmkides suc as quaternary a m nium compounds or big eanides.

|@ I72| When suspensions of spores in the inventive compositions re deposited on grow med u via. he s iral plating teohniipae, the spores rsearast the center of the spiral pattern will be more likely to b killed apon germination by t e adsorbed germicidal quaternary ansmoa um coBt imd or blguanlde, and thus there will be B colonies observed after incubation so this region. Thus, msimd of the expected spiral, partem in which there are large numbers of colonies crowded together nearest the center of t e pl&fce, there will be a circular "hole"' m the attern d e to the killing of die spores upon germination. Farther away from the cetstral starting point of the spiral, where the h e dilution has decreased the ability of the adsorbed bioeldal species to kid the spore upon germination as described above, viable colonies will ^'a pearand confess m a spiral to the c ter edge of the plate, This, the diameter of the circular hole its the spiral pattern is larger ibr formulations which provide m r killing of s ores u on germ mat ion unde favorable conditions,

0 173f The equipment used for the spiral plating of the suspensions of the treated spores yields a pattern In which the central hole has a diameter of about 2 cm when a high concentration of spores that are viable (m a control exp riment, for example) are resent at the start of the spiral pattern. If the treatment of the spores results i killing, upon: germination: of all f t the spores, then the maximum diameter of the hole Is about 8 em, ^'Tims, values of the diameter of the central hole be ween about 2 cm and S cm, herein called the germicidal diameter, represent varying degrees of effectiveness of the treatment of the spores for prevention of the con amination . of a surface by the genrnnation of spores under extremely favorable conditions, with larger values of the diameter indicating better effecti eness. Such testing methods are thus a good indication of the efficacy of the mveotive compositions under various real life use conditions where various organic loads may be present or applied,

|θβ!?4] The treatment formulations, md dilutions of them, wore placed in the wells of a 96 well plate, 10 mkro!iters of the standard spore suspension were added and allowed to age for 10 minutes, followed by the addition of 200 μ] of sterile water, and then 20 ui of the spore suspensions were then spiral plated onto the plates containing growth media. The spore concentrations treated were all the same, shout 1 i O" which is similar to the number of spores treated with the compositions in the determination of the changes in the zeta oten ial of he spores described above. The plates were incubated overrsighi at 37*12, followed by a measurement of the diamete of the gersrskkW z ne diameter.

!?5) Formulations comprising mi ed micelles of the germicidal quaternary ammoniu compound BT€S> 101 md an am me oxide were made as described above, over a range of iP/Dnst values, using the a o ic waier-solab!e polymer Aicosperse® 74? as the polymeric com¾ierioa. Formulations El through E5 c-OBia ed the same quaternary ammon um compound concentration, while formula o E6 contained a significantly lower quaternary ammonium compound concentration. The relative amounts of quaternary ammonium compound and amfe oxide in the mixed micelles, however, was the same. The compositions are shown in Table 10.1 .

Table 10. .!- ^'Com osi ions^' for Testing Effects of Trea men {ifBaefiks Stibii!b spores

Foromiatioo Polymer Amine Germicidal onoetbsn P/fi net Name Alcosperse Oxide, Quat, oiamme

& 747^' A mm.au y B 1 Oh wt%

wt% OD LO, wi% 1010, wt¾

El 0 1 ,8 0.2 0,1 0

12 0,00255 1 .8 0.2 0, 1 -0.05

E3 0.0255 L8 0,2 0. 1 -0.5

.E4 0.051 1 ,8 0.2: 0/1 -0.0

E5 0.102 l .S 0.2 0.1 -2.0

E6 0 0,22 0.025 021 0

To cover a large ra e of concentrations of the germicidal quaternary ammonium compound in the treatment of the spores, tbrmolahons E l through B6 were used eat (dilution factor -!), and at vanous clile soos (OOuOon meters 0.5 to 0,O3 i 25, or 2x to 32x times dilution of the original formulation). The resul s obtained with the spiral plating test are summarized in Table 10.2

Tabic J 0.2

- Spiral plate results - Effects of Form ulations on Viability acill Subiiib spores;

Dilution Factor Prior to Snore Exposure

Fonrudatioo 1 0.5 0.25 0. 125 0.062$ 0.03125 Absolute value. Name F/Dnet

Spiral Elate Germicidal Zone diameter, cm

|0§IT7| The results in Table 10.2 show thai Eosmalatlons E2 through E5 (all of which contain the same quaternary ammonium com o nd concentration) all exhibit excellent erform nce in kihing the spores upon germina on, as does the co trol fomralation EL when used ea (dilution factor 1% yielding germicidal zone diameters of 7 to 8 cm. Dilation of formulations E l through E5 by 32x (factor 0.03125) results in zo diameters of 2 cm, Indicating no significant effect on the growth of the spores when they are placed n the g owth media. Surprisingly, formulations in which the absolute valise of P/I3net are E (mdksting an equal number of anio ic .charges due to the polymeric eoanis.rion and the cationie charges d e to die germicidal quaternary ammonium compound) or even 2 (indicating, an excess itx the .number .of anionic charges due to the polymeric ooant rion over the eat ionic charges d sc to the germicidal quaternary ammonium compound) exhibit kilting performance comparable to that of the control formulatio across a. range of dilutions in this test, confirming the robustness of the ad.»rption of the germicidal quaternary ammonium compound onto the spore sarfsces, and in line with the effects of the formulations as measu ed by the changes in the∞ta potential, of the spores, as described above,.

| #f?S] Control Formulation Eh included no polymeric eounteriom Formulation Eh, 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 ¾one diameter of 2.5 cm . ronrndatsoos E2 through b¾_s wrseu diluted l.ox (.factor 0..OP2 ). also contain 0.0125% quaternary ammon m compound. However, due to the presence of the polymeric coonterson in these inventive compositions, the germicidal activity is significantly better than in rise ease of form elation E6. Tne germicidal o e diameters measured for treatment of spores with E2 through B5, at the dilution factor of 0.062S, a all significantly g eater than that of formulation E6 at the dilation factor of 0.5. indicating the significant benefit of the presence of the anionic polymeric coonterion In ensuring the kill of spores during germlasrioo under favorable conditions. Ap l ca s speculate, w h ut being bound by theory, that the presence of the anionic polymeric eoimtenoo along with the germicidal quaternary ammonl n compound h the adsorbed layers formed on the sp re surfaces decreases the teiideoey of f « germicidal quaternary ammonium compound to desorb ro the spore surface, upon dilation of the spores in the growth medium sod/or decreases the tendency of other surface-aetrve molecules in the growth medium f om competitively displacing the germicidal quaternary -ammomnm compound from the surface of the spo es, thus vidin improved germicidal performance of the inventive formulations compared to the control formulation co ammg mixed micelles without a polymeric eounterion.

Exa le 11

Antimicrobial Activity of Mixed Micelles Compared to Mixed Micelles with Polymeric Connterions ( lpelle-Poiymer Complexes) Aga nst Baciiius S htiih spores 0 179} Some additional inventive formulations were developed covering a range of P/Dnet values and tested for activity against the growth of spores in the same manne as described in Example 10. A c mpar son with the activity of the control form lation E6 was also ade, for the reasons described in ..Example 10.

Table 1 1 .1 - Compositions for Testing Effects of Treatment of BaciUtis Snlni!is spores

Table 1 1 .2 Spiral plate results ···^■ Effects of Formulations on Viability of Bacillus SuhiUis spores

Dilution Factor Prior to Spore Exposure

formulation i i 0.5 I 0.25 ( . 12 1 0.0025 ! 0.03125 Absolute value,

[CMHSs^'Jj The results in Table U .2 again indicate thai formulations of the in nt mv&Aioa exhibit excellent germicidal perfbroiarsee, killing spores placed in an extremely favorable environment hi addition, t e fornicat ns show better _.performance at dilutions of 16x (f tax- 0.0625) than the eoetrol. which delivers the total q aternary ammoelam compound concentration o cont ol, formulation E6 al a 2x diforioa actor .S). The similarity in killing erformance of the inventive compositions -across a range of the absolute, value of P/Drset shows that optimlzatioo of other parameters of the icrrmharions. such as cost, cleaning perfona^pe or kinetics, or sarisce residue aesthetics cm be adjusted -vis P/Dnsi. while maintaining the antimicrobial properties of the formulations, dm to the fine control of the Interactions of the surfactants in the mixed mkeiies that cm be achieved with the se of & water-soluble. r»ly erie eounterion. of charge opposite to that of the net charge of the m ed micelles.

Exam le 12

Antimicrobial Mixed Micelles with Polymeric Coaateriooa ί Micelle-Polymer Complexes)

Delivered from a Nonwovec

00181.1 Formulstiom comprising polymer micelle complexes c mprised of mixed micelles of a- ermicidal quaternary aramoniw com ound and an amiss oxide and anionic water soluble polymers increase the antimicrobial efficacy of a bnmda delivered by a soewoven wipe. In this example polymer micelle complexes formulated over a range of P D«et values arc shown to outperform mixed micelles in the AST Irstematiorsai, Standard Practice for Evaluation of Ihre-Ssierated or Impregnated To eiettes for Bard Surface Disinfection. Test Method E 2362 (henceforth, referred to as the towelett® test) against Pseudcrmorm. ^'This example also demonstrates flexibility in choice of polymer chemistry and the compatibility of rmcslfe-polysior complexes with solvents and silver ions,

[09182] Compositions and F/^'Dnet valises of the brrmdatioos g e shows* m Table 2, 1. Formulations we prepared by first rak ng BTC® 1010 (Slepan Co,.) and Ammonyx® LO (Stepasi Co,) tho specified amounts with water, t as fomtmg the mixed mkelies. The pH was then adjusted using MEA aod glyoolic acid In the specified amounts. The specified arrsorsfb of anionic polymer iAIcosperse® 747, Aicogaard® 145240 or Alcoguard® 2300, all from Afczo Nobel) were than added to form the micelle- polymer complexes. ropykoe glycol n-b sty! ether (DO SB ™ POB, DOW Chemical Co.) was added to formtdaiion 03 to demonst a e eon^mtibility with solvents. Silver dihydrogen citrate (Tinosarr® S0C_} Ciba) was added ιο tbraudaiion G6 at a raw mate i l concostratiors of 0.123 wt% {equal to 3; ppm silver loos) to de«loas¾-&ts eorrjpatiblhty with silver ions. The foraralations form stable aggregates, elmtactsr½ed by DLS analysis as described la examples 1-6^' and were visually clear,

imi ] Moist towefeties were prepared for ASTM Test Method E 2362 by applying th appropriate formulation to a roil of the toweiettss. The mass of the liquid formaiabon added to the rolls of towebites was 4.5 times the mass of the dry towdettes, Towelebe nssd in this example were rsoawoverp 40 gsm material purchased .from N.R, Spijatee ladastr s Ltd. ^'The moist towebttes were allowed to equilibrate at room isaspsrabae for at least 24 hoars.

Table 12 J - Compositions suitable for delivery from n Bwovess

Table 12.2 - Arsbrakmbial activity of formalaiioa delivered from aonwovens.

[ Formulation Name [ Tows bits 60 carrier 1

[00184| Comparing i nnui&tions G i and G2 show h&i addition of a s all amount, of anion c polymer to form micel!eHpofymer complexes characterized by P/D.aet™^: -0,05 Increases the ¾niiMiero ial efficacy against Pse domomx ©nough to generate a ^' ass n result. For alatlon G3 shows that the nheroeiilcaey of formulation G2 is preserved when 2 wt¾ of PnB is added to the- formulation, which may be desirable for robustness of the formula as well as a variety of aesthetic benefits. Fo mulat ons G4 and G5 demonstra that a wide range of water soluble polymers are suitable for forming dm micelle-polymer complexes. Foomoiatkai 04 also shows thai mieeHe-polymer completes formulated at an absolute value of P/Dne greater than Li) are. capable of boosting amimiorobial activity relative ro that of mixed micelles wit ou the polymeric couuterions as well. This result Is particularly surprising considering that the eatiordc charge on the germicidal micelles Is widely accepted to be the dri ing force for adsorption of the active Ingredients onto microbes. Finally, formulation G6. demonstrated the compatibility of the micelle-polymer complexes with silver ions.

Kinetic Benefits of Antimicrobial Mixed Micelles with Polymeric Counterkms (Micelle- Polymer Complexes) Delivered from & N on woven IhhlhSJ Two of the formulations described in Example 12 were tested at i minute contact times apinst

Aure ami Psetukmonas using the ASI^' Internationa!,. Standard lhaetke for Evaluation of Fre-Satamted or Impregnated Towelettes for Hard Surface Disinfection, Test Method £ 2362. These formulas demonstrate passing antimicrobial efficacy at contact times considered to be extremely short for uaternary ammonium com ou d -based formulas.- Formula G i, a mixed micelle control which el vers the same concentration of gw cidai qn&t it o!.it the polymeric cou terioru s not capa le of assi the towektte test at 3 minute contact times (see example 1 ),

imm\

Table 13. ! - Antimicrobial activity of formulations delivered iVora norovovens.

Form lation Name To eleiie 60 carrier Towelette 60 carrier test ag&insi s ns against

Ps omo s - i

Aureus --- ! :minute urinate contact time

contact time

G2 Pass Pass

G6 Pass Pass

Exam le !4

Dilutable formulations of Antimicrobial Mixed Micelles with Polymeric Counicrions

(Micelle-Polymer Complexes) on Laundry f®M§?| Dilutable Ibnmu'arions which rnay claim^' samtfeation of laundry are governed by the document EPA DIS/TSS-1 "Laundry Additives - Disiniecuon. and Sasdtizatiosf \ Such formuiadons must be demonstrated to redaoe the fevs!s of bacteria (both. Gram + and G m ~> by at least 99,9% in a specific test, rotocol known as the "Pettocci and Clark. Laundry Additives Method (sanitizing !eveiy\

P¾l§81 This example demonstrates the delivery of antirnkrobkl efficacy enefits usin dilutable formulations comprising polymew ice le complexes comprising; mixed micelles of a germicidal quaternary snvmonhrm compound and an amine oxide a d anionic water soluble polymers. In. this formulation ΒΤ€ 8 IS 6 Am onyx® DO are mixed in ^•water at the given concentrations, and then A ognard 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 sa¾itl¾sr test protocol.

Table 14.1 - Composition of formulations tor a dilutable laundry saodker

Fonmdation Polymer Amine Germicidal P/D net Lairnd

Name Alcomi rd Oxide. Oc-a.. BTC® y

® 5240 Arum on x 818, w% Sanitiza wt% DO. wt% tion

Test - 1/584 dilution H I 0.146 3.02 j 1 1 ,7 -0.02$ Pass

H2 0 0 ! 1 1.7 0 Fail

Formnladon HI capable of passing the laundry ssniluatton test mentioned above against Siaphyfa xx - Aureus am! Klesiei Pneumonia a a 4 minute contact time hen diln ed ! part to 584 parts in hard water. The ex.treme dilution ratio and high bacterial loads m ke t is test method exceedingl difficult to pass with quaternary ammonium chemistries such ss formulation H2.

Emm pie IS

Oil Soluhill at!O Enhancement with Polymer-Micelle Com lexes Formed with an anionic polymeric coimterion and mixed mkei!es.

|0O! Consmners of aqueous based liquid cleaners frequently prefer ifagranced fonrniiaiioas with excellen oily soil removal,, while still, demanding low residue on cleaned snr&ees. The key to successfully satisfying this consumer demand is that the total ooneeniratiort of sohfbiiker com u ds be sufficiently high to ftdfy incorporate the oily fragrance and any nonaqueous solvent compounds used to ensirre excellent oily soil c leasing according to consumer preferences, while inimizing the total concentration to lessen the visual residne left on the cle ned surfaces, especially in the absence of a rinsing siep. Applicants discovered that the interaction between mixed micelles comprising an amine oxide and germicidal quaternary ammonium compound m4 -an anionic polymeric counterion according to one embodiment of Use In vention enables a unique and surprising oil solubilization boosting effec to satisfy these consumer preferences. In other words, similar results can he achieved with significantly less sokbi!izer when em loy n the inventive complexes.

ftM119.1| The oil solubilization boosting effec t of the polymer on the mixed micelles is readily illustrated b comparing the lowest total sola litesr concentration needed to solnbiiixe 0,3wt% liroooene used as a model oily compound, suets that the compositions are visibly clear, free of excess oil precipitate and eoacervate, in the absence and presence of the polymeric conn erions. In this example, the total solublMzer concentration is the sum of the eoneentrsdons of the polymer, the germicidal usternary ammonium compound BTC® 1010, and the nonlonic surfactant Ammonyx® CO, The compositions axe shown in Table 15.1, Table 15,1

P/Dnet ΒΤ€ !0Ι0ννΐ% Aieo persea^j EA MiamuaTi

LO wt¾ 465 wt% wr% total solabiliser eed wt%

Ji 0 0,05 ·· ; :: 0 03 0.1 >L2S

J2 0 0.1 1.275 0 0.3 0.1 1 ,3 /5

J3 0 (115 1 ,35 0 0,3 0.1 1,5

J4 0,05 0.596 0.95 0.3 0, 1 0.640

J 5 41,01 0.1 0.754 1.93 0.3 0.1 0,854 6 -0.01 G. f S 0.98 ! 2.89 0.3 0.1 i . m f 00192] la this example, the F/Dnet parameter was fixed ax a relatively low absolute value, m order to minimize ike cost of the polymer added to the formulation Throe dif&rent concentrations of Wt^'C®. 1010 wots investigated. The lowest to l seiabiiizer required la the absence of polymer was determined at various concentrations by makin a series of fonntilaiians which the concentration of the Amr5)o«y ® LO was increased until the formulation as completely cleat, correspond g; to hall solu lization of the ilmonene oil. Sokmlh^atiou of the limonene was .not achieved in the series of samples made that ended with the control formulation .11., which was a cloudy dispersion. Solu il zation of the llmonene could be achieved when the concentration of the ETC® l OfO catlonlc germicidal surfactant was irai osaed sonnswh t, and if enough Aama^nyx® LO was added, to give the final total solubili sr levels shown lor fou d ti s J2 and . [§§195] The same procedure was used to detetad.no the mittimusi? total solabiHser requirement tit the presence of polymeric coontetioas at a fixed P/Dnet ^::; - 0.01 ratio. Appropriate amounts of the s rfactot stock so tion,- monoethanolaimine (to adjust pH above 9.0), !imoneoe, d water were mixed to form the final control formeiatloo containing the mixed micelles, in the ease of fonoolations comprising the polymeric couatenos, the same mixed suriactaat stock solutiou, moooeth&aolaaiine, ii oneoe, aed Aleosperse® 465 (a poly (acrylic acid) homopolvmei- supplied as m aeoirs solution., Akzo Nobel), a«d water were mixed in appropriate mounts to yield the final for al tions with the fixed P/Dnet values_* sad increasing levels of A mo ivx® LO were added, thus varying the mixed micelle compositions, until a clea solution, indicating complete solubilization of the hsnoneoe. w¾s ohtamed. (001941 Comparing the optimised compositions in Table .15.1., it is a arent that the formulations with polymeric cou erions (J4_S. .15 and j^'6) re u re lower total sokbiiixef cemeentrations. demo&st a†¾ a significant oil so!a iii tton boosting effect resulting from the polymer-mked mic«iis interaction. For example, formulation J5 re u es only 0.854% total sohmihzer to fully sorobilixe the limonene mto a clear solution tree of coaeervates of precipitates, w lfc formulation 12, which has the *>&m«s concentration of the germicidal quaternary ammonium com ound, re uires a much higher total solebiiizer level, 1 375%, to fully solubilize the same eoocem ation of limonene.

|00I | Ano he uni ue- as ect of the effect of the presence of the polymeric coonteriofi is the remarkably lo AlcosperseSD 455 polymer concentration, in the ppm rsrjge, that is needed for the SOlubiibmiion boosting. This, in formulations such s hard surface cleaners tha may not be rinsed after use, very low hswte of the polymeric cotmterioe. can dramatically also low the total, levels of surfactant needed to deliver a w8 er »solu ie oil such as innonCBe, contributing to significant cost savings as well as a reduction or eihmination of oonsnrner-perceptlbie residues on surfaces cleaned with the ferrmhations.

Oil Solubilization Enhancement

The enhancement or boosting of tire sohrbi!kation of water-insoluble oils may be obtained with a wide variety of water-soluble polymers,, over a wide range of F/Dnet values, offering considerable flexibility in meeting different arrtitnlerobial performance, aesthetic or cost targets.

S1§7| Oil solubilization optimization is carried oat in the presence of 0.3 wt% Hmouene mode! oil by, in a series of samples, simultaneously Increasing the absolute value of F/Dnet and she concentration of the sronlonic amine oxide surfactant at a fixed catk k surfactant concentration until solutions which are clear, free of precipitate, eoacervate and excess o!i are obtained. Optim zed compositions are thus the ones that turn clear at the lowest added amine oxide sar acteat concentration. The minimum total solnbilizer values are thus the sum of the BTOS? 1010_., Αηηηοηνχ LO, and polymer (if present) in the final tbrrmdstions thai yield complete oil solubilization.

!¾§!§§] Appropriate amounts of 8TC® 1010, ArmnorsyxS; LO, monoethnnoiamine (to adjust ρΗ above 9,0), limonene, and water were mixed to form t o series of samples in which the Αηηηοηνχ LO level was Increased at fixed BTCXD 1010 concentrations until final control formulations I and 5_< containing the m ed mtc tes and the solobiihsed hmonene are obtained.

In the case of fesrans iom comprising The polymeric counieriom the same su&csnts, monoe&anoiamine, limonene, and Akosperse® 747 (supplied as an que us soi tksn, Akzo Nobel), md water were mixed m appropriate amounts- to yield series of samples in which the mixed micelle compositions ere changed b inoreashrg .amounts of Ammonvx® LO_s &t several different, fixed F/D t values. The opimised compositions, alii of which are clear and frse of ooseervsts, prseipitaie and excess oil, ae summarised in Table 16 J.

Tabic 16.1

P-i>,,_: Bit:® Aicos eiKfit- L im os srse MEA

LO 747 pp;is Wt% total wi%

eed

VA%

l 0,1 1.275 0 0.1 1 ,426 control

2 -0.1 o;i 1,09 516 0.3 0,1 1.241 3 ~1 0J 0.91 510 0,3 0.1 1.061

K4 0 ! 0.91 510 0.3 0.1 1.06!

K5 0 0.2 .1.275 0 0,3 0.1 1.577

^•control

6 -1 0.2 1.091 1020 0.3 0,1 1.393 7 0.2 0.545 1020 0.3 0.1 0.847

\®®Zm] The results in Table 16.1 show thatmvemive formulations 2₅ 3. and K4 achieve complete hmosiere s lu lizaton si lower total soiabnizer levels than formulation Κ.Ϊ, indicating enh&rteeroent or '"boosting" of the solubihzalioo of the water-drssolabie oil whets the water-soluble anionic copolymer is used as the polymeric- coimtetion for the mixed micelles bearing a o eabonk charge, Sorprl singly, the oil sotsbiHzatlon boosti g can be achieved over a wide ran e of the absolute value of P/Dne be,, oil solubilization e anceme t can he achieved with a. wide range of compositions of isked micelles dee to the fine control over i¾« interactions between the cationic and nonlonlc sarfaciaats in the mixed micelles that is possible through the use of the anionic polymeric counterion. Smilarly, formulations K5 and 7 ex ibit lower minimum total soto lker sone &imlGns thm formulation 5.

Exam l 1

Antimicrobial Compostions Coatammg a Mooonsenc Biguarhde, Chlorhexidine

Gluconate

028 ] The caliomc germicide present n the mixed i ce!les may be a mooomerio i uisiside salt, such as chlorhexidine gluconate (CHG). CHG was supplied as 20% solution In water, from Sigrna-Aldrieh. CHG has two oatiorac charges per moieeole md a moleeeiar weight of 7.S g/mole, The mixed micelles m y also comprise omomc s fectams. The compositions sirmmariiied m Table 17.1 comprise two ao kmie surfactants, SarfoBki¾ L12-S (an alcohol etboxylste, from Hunsman Carp), ssd G¼cofxm<D 32SN (as alky! gs coside, from BASF Corporation) k. the mixed micelles with the CHG, Sioee the CHG cooceotrntion is tire same In orrauktions LL L2 arrd L3, the value of Eq catkkc will ls be the same md is c lculated as lo s

Eq eationie 2 x 0.015 x 1/897,8 ^ 334 χ iO^ equivaleots/lOOg of formi atio?i. And., since there is no ao rdc surfact nt present k the frsmudaikm, then

Dost == D cationk: - Ή x 0,0000334- + 3.34 χ 1 ^"·

§2§2 The water-sokh!e polymer osed s this example as the polymeric eountenon is p l {2~¾ci temldo-2-Tn®thyl-l- o a¾es lo lc acid), or^' poly AMPS, it has I arriorne charge per morojsser unit, which has & molecula weight of 207,25 g/mole. in formulation LP poly AMPS is preseot at a eoocersteatlon of 0.0035 wt% or 0,0035 gras i/1 0 rams of the formulation.

P is thm calculated s ;

P - 0.0035 x!xixGi)/207.25 - - .OOOG36iSS?S.

Thu:>. PDrust^ "-0.0000168878/ ·^♦· 3.34 x 10-5 -~ 0.5053

002i31 The val es of P and PDnet for the other ibrroolatiosis are summaized in

Table 17.1

Table 17.1

|O02#4| The negative al e of P/ ne* for the formulations in Table 17.1 indicates that the polymer nd mixed tnsodies ars of opposite charge, d hence M the scope of the Instant mvs tkst The fonmdations also iHesiraie tha fragrance oil may e so^'lubiisesdi 'n the m xed rrhedles, thai the forrmd sons m com rise afer-soluble glycol ethers or no and that the B and electrolyte levels of the .formulations ma be varied with appropriate adjuvants

a d sodium chloride. Fonmsistion LI is usei as a . ready to use hard surface cleaner, while- fom i!atioiss. L2 and L3 are useful as lotions for pre-moisiened wipes or as hmd sadtizers. Dowanol™ DB and D wanoP^ PnB are glycol elisor solvents from Dow Corporation. Fragrance oil was a ierrson fragrance fro Fi oterbch,

| 20^§] Without departing from the spirit and scope of this invention, one of ordinary skill can make various changes and modifications to the in vention to adapt it to various usages and conditions. As such, these changes and modifications are properly, equitably, and intended to be_s within the fn!! range of equivalence of the follo in claims.

Claims

I . A composition comprismg:

¾. oi mer-3 5ieslls complex, the complex comprising:

a positively charged micelle, wte¾ i said positively charged micelle comprising a water-soiuble carionk material selected from the group eoissisdng of a raonomsrie quaterna y ammonium compound, & moooraeriv bigiranirle compound, md mixtures; thereof; said mfcslie being electrostatR&iiy bo d to a water-soluble polymer bea ing a negat e c ar ;

wherein said water-soluble polymer be in a ne ative charge comprises a hybrid copolymer derived (torn a synthetic maeomer or nomers chain terminated with a hydroxyl-eooi&imng at ral material synthesized with a free radical initiator;

wherein ssid polymer does not comprise block copolymer, latex particles, olymer neuopar iclea, smss-liaked polymers, silicone copolymer, fluorosyrfaetarrt, or amphoteric copolymer;

wherein said composition does not form a eoaoervsre, md wherein said composition does mi form a film on a srniaee.

2. The com osit on of daws 1 , further comprises an oxidant, optionally the oxidant is selected from the group consisting of;

a. hypohaioas acid,, hypobalite or sources thereof

b. hydrogen peroxide or .sources thereof;

c. peracids, peroxyscids paroxoseids, or sources thereof;

d. organic peroxides or hydroperoxides;

e. peroxygenated inorganic compounds;

f. solubs.li.ged chlorine, sol billzed chlorine dioxide, a ource of free chlorine, acidic sodium chlorite, an active chlorine generation com ou d, or a chlori»e» dioxide generating compound;

g. an sethve oxygen generating compound;

h. soln ilized osone;

i. N-halo cornpoonds; and

j. com inations thereof,

3. Ths composition of claim i_:> wherein the positively charged rnlcelk comprises a mosomenc quaternary ammonium c-ompouad.

4. The com osition of claim 3, whereio t e positive y c arged micelle further ompr ses a nonlonie s faetaut

5. The composition of claim 4, wherein the nooionic surfactant comprises a:a amine oxide,

6. The composition of claim ! , wherein the positively charged micelle comprises a monomerie bigusoide compound, optionally tire mgeanide is selected r the group consisting of chlorhexidine, dexidlns, and combinations thereof.

7. The composition of claim d, wherein the composition is free of iodine, iodine- polymer complexes., nsnopariieles of silver, nanopanieles of copper, nsnopartioies of :rine, rri.closan, p-chloirorpeih l xyleoo!₅ moriornerie pentose alcohols, D-xyidod and its isomers, D-arabMol d its isomers, ar l alcohols, benzyl alcohol, and phenoxyelhanob

8, A method for cleaning a sut&ce, the .meth d comprising:

contacting said surface with a composition comprising polymer-micelle complex comprising:

positively charged rajee!!e electmstaticaliy hoand to a w8i¾?^»sof.ubfe polyme hearing a negative charge, said positivel charged micelle comprising a water-sokble cslsonle material selected from the group consisting of a monorae.de quaternary smrnoniom compound, a monorneric bigaanide compound, and tpklores thereof; and wherein said polymer does not comprise block copolymer, late particles, polymer nanoparticlcs, etoss-hnked polymers, silicone copolymer, fiuorosnrfactant, or amphoteric copolymer;

wherein said composition does not form a eoaeervate; and

wherein said composition does not form a dim on. a surface,

9.. lire method of claim S_s wherein the composition comprising a. polymer-micelle complex is a concentrate, tire method further c mpris ng dilnting the concentrate with water to form a dilute composition comprising the poiymer-unioetie complex, prior to contacting the surface with the dilute composition,

10,. The method of claim 8, wherein the concentrate is dilated at a dilation ratio of as high as about 1 to 600, and wherein the resulting dilute composition Is capable of achieving saniii a!lon of the contacted surface at a dilation ratio of about 1 to 600 within about 4 minutes.

1 1. The method of claim 8, wherein the composition further comprises an oxidant. 12, The met od of .claim 8_S wherein e positively charged micelle further compr.is.es a noTi oaic surfactant

13. The method of claim 8, t e composition further comprising a wa r dmmiseible oil that is so!ubi&ed into the positively charged micelle, optionally the composition is free of wamr-rslseible alcohols md glycol ethers.

14. A system comprising;

a) a dual chambered device comprising a f rst chamber and .a second, chamber; b) a first composition comprising a water-sotuMs polymer be&tmg a negative charge disposed in the first chamber wherein said polymer does not comprise block copolymer, latex psrtkles, polymer nanoparticles, cross-linked polymers, silicone copolymer, tlimr surfaetant or amphoteric; copolymer;

e) second composition comprising a positively charged micelle disposed in the second chamber wherein said positively charged micelle, comprises a water-soluble eationk material selected from the group consisting of ¾ monomeric quaternary ammonium compound, a monomeric bigaanide compound, and mix res diereo y

d) wherein the first composition of the first chamber Is m xe with the second composition of the second chamber to form a rss^!ikg composition in which.:

I) the micelle is electrostatically bound to he polymer to form a poiymer- micelfe complex;

ii) the resulting composition does not form a eoaeervate; and hi) the resultin composition does not form s film on a surface.

.1 S. The system of claim 14, wherein at least one of the first or second compositions farther comprises an oxidant, optionally the oxi ant is selected from the group consisting or

a. hypohalous acid, Irypoh&lite or sources ereof;

h. hydrogen peroxide or sources thereof;

c. peraekhy psroxyacids peroxoaolds. or sources thereof;

<L organic peroxides or hydroperoxides;

e. peroxygensied inorganic compounds; f. solttb-iized chlorine, solubiiked chlorine dioxide, a source of free chlor e, acidic s dum chlorite, so sciivs chlorine g<meraimg compound, or a chlorine- dioxide generating com ou d;

g. an active oxygon generating compound;

h. soiubilizod mo ;

i. H-h&io compounds; sod

j, eombin nons thereof

16. Th® s stem of s!skn 14, wherein the positively charged micelle comprises a mo omene qu ternay ammomum corn onnd.

1?. The system of claim 14, wherein die positively c a ed rn!celk mPher comprises » s >nionie sirrfeetsmt optionally the ooo ionic sariaeisn comprises a amine oxide.

IS, The system of claim 14. wherein the positively charged micelle comprises a onornenc hi uanide: eomponnd.

1 . The sysksrn of oiaim 14, wherein the eomposirioo is tree of iodine, iodine-polymer complexes, naoopmiicles of silver, nsnop&rieies of copper, nanopartidss of zinc, irieiossrp p-chloro eoHy 1 yienof monomel c pento e alcohols, D-xyiito! and its isomers, D~arahiiol md its isomers, aryi sleoho , benzyl alcohol, and phenoxyetharmh

30. The system of claim 14. iln her comprising & ster«½«niss»bte oil that is solnbiiized into the posilivdy charged mcelle, o ionaly de composition is Ike of wamo mlscible alcohols d glycol ethers.