CA2888961A1 - 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

CATIONIC MICELLES WITH ANIONIC P(.)1_,YMERIC COUNTERIONS
COMPOSITIONS, MF,THODS AND SYSTEMS 1TIEREOF
BACKSIWLIND OF 'TUE INVENTION
The Field of the Invention twesent invtntion relates to pOlymer-mitelle complexes,

2. Description of Relatml Art [OM) Cleaniakt product formulations, including those =4..vhich contain common antimicrobial agents such as quaternary ammonium compounds and higuanides such as chlorhexidine and alexidine, rely on surfactants and mixtures of surfactants to deliver cleaning (detergency) and antimicrobial efficacy, A key aspect of these processes s the interaction of the surfactants an antimicrobial agents with- the solid surfaces c.if the, materials Eseing cleaned, as well as the surfaces of microorganisms, together with the effects of the formulations on the aater interface (surface tension), Reducdon of the surface tension of aqueous formulations, whieft is directly related to the effectiveness of the wetting of solid surfaco and hencrthp detergency an .antimicrobial processes, can he manipulated through the 1.tse of inixture,s-of surfactants, s is known in the art.
10003i At a. -molecular level, surfactants and -surfactant mixtures .in aqueous. media -exhibit the ability to adsorb at the air-water, -solid-svater, and oil-water interfaces, and this adsorption is hence responsible for a wide. range Of phenomena, including the Solubilization of oils. ih the. detergency process, the changps in the properties of solids and dispemions- of solidsõ and the i0Weriog of the surface tension of water, Adsen-Ptiort of surtactantS at interfaces is generally known to increase with stirfactint concentintion up to a total surfactant concentration- known as the critical micelle concentration (CMC). M the CMC, surfactarits begin to fo.rrn aggregates in the bulk solution known as micelles, in equilibrium with the monomeric species of surfactants which adsorb onto the interfaces.
[0004I The details of the s.tructures and sizes of the inicelles, as well as the properties of the adsorbed layers of surfactants or surfactant mixtures, depend on the details of the .molectilar shape and charges, if any, on the hydroPhilic "headgroups" of the surfactants.
Strongly charge adgroups of surfactants tend to repel each other at interfaces, opposing the efficient packinps of the surfactants at the interface, and also favoring micelle structures that are .relatively small and spherical. The charged headgioups of many surfactants, such as the quaternary ammonium compounds, will also intrmluce a counterion of oppsite charge, for example: a chloride or bromide or into formulations.
[00051 It is known that the nature of the counterion can affect the repulsion between c.harged surfactants in rnicelles and adsorbed layers th.rough a partial screwing of ti.te headgroup charges _from one another in surfactant aggrtgates like micelles. It is alS0 well known that addition of simple electrolytes,. such as sodium chloride, into aqueous solutions can also be used to increase the screening of li.ke headgroup chargtes Brom each other, and thus is a common parametered to adjust the properties of stsrfaetant such as size and shape, and to adjust the adsorption of surfactants onto surfaces.
[0006j Addition of significant anlounts of simple electrolytes into iTiany formulations, such as hard surface spray cleaners or nonwoven wiNs loaded with .a cleanina on, is etridesirahle due to residues left behind on .drying of the formulations, An alternative .tnethod to adjusting the properties of such fortriulations, including the wetting of solid .sztrfaces and the antimicrohial.activity, is to inelude significant.amettrus of volatile organic.
-solvents such as lower alcohols or glycol ethers.. Volatile organic Solvents, hoWever, are coming under increasing regulation due tr...t their potential health effeets, and are not preferred by the significant .fraction of consumers who desire efficacious cleaning and disinfecting products with a mmum of chemical actives, including vOlatileS. la the he.althcare ind.ustry, efficacious fonnuiations comprising quaternary ammonim compounds .and lower alcohols are knownõ but are viewed as having shortgornings -in terms of-the potential for irritation of confined patients. Sitch products.
pose similar risks to cleaning and clinical personnel SWIM May be exposed to such produets opa .daily. basis.
[00071 There is an increasing intere.st from consumers, and .a kriovn need in the healthcare and housekeeping industries, to reduce the number of microorganisms on fabrics while tising familieir equipment such as washing machines.
Cone.entrated products are required for suth an application, due to the high dilution level of the product in the rinsewater,. typically by a factor of about 600 times dilution. In the case of formulations comprising quaternary ammonium compounds,. WO concenn-ations of the quaternary ammonium compounds in the concentrate are needed in order to ensure an adequate amount of adsorption mours in a kinetically relevant tittle onto the microbes under dilution tisc conditions. As detailed above, it is desirable, yet %,cry diffieult, to manipulate (i.e., reduce) the CMC of the quaternary anunoniutn compound in .%ich an application.
'I'hus very high concentrations of quaternary ammonium compounds, which tend to be

3 hazardous to the skin and eyes, are u9ed in the concentrates, in combination with high temperatures and 'long exposure tittles.
[00081 Thus, there is on ongoing nced for methods and compositions offering fine control o.f the properties of surfaciant aggregates comprising cationic species, esixtcially antimicrobial spmies such as-quaternary ammonium compounds and higuanides.
BRIEF SUMMARY OF THE INVENTION
it10091 One aspect of the invention is directed to a composition comprising a polymer-micelle complex comprising a positiveiy charged micelle comprisina a water-soluble catiortic materiai selected from the group consisting of a monomeric quaternary ammoniwn compound, a monomeric biguanide compound, and mixtures thereof The micelle is electrostatically bound to a water-solubk polymer bearing a negativ.e charge.
The: water-sOluble polymer rìn a negative charge comprises a hybrid copolymer derived from a synthetic monomer or monomers chain terminated with a hydroxyl -containing natural material synthesized with a free radical inator. The .polyrner does not comprise block eopolymer, latex -particles, polymer nanoparticies, cross-link-.ed polymers, silicOne copolymer, fluorosurfactant, or a hoterì copoiyner. The contplex advantageously does not form a coacervate,. and clees riOt fonn a film on a surface- (e.g., durable film remainingaller application of the composition to the. surface)..
!DOH)] Another embodiment of the. invention is directed to a composition comprising a polymer-micelle complex comprising. a positively charged trticelle. comprising a water-soluble cationic material selected. from the group consisting of a monomeric qaaternaty ammonium compound, a Monomeric biguartide compound, and mixtures thereof: The micelle is OTtrostatically hound to a wate.r-soluble polymer hearing a .negative charge.
The water-soluble pob/mer bearing a negative chargt., comprises a hybrid copolymer derived front a synthetic monomer or mr.tnoincrs chain tertninated with a hydroxyl-containing natural material synthesized with a free radical initiator. The polymer does tiot comprise block eopolymer, latex particles, polymer nanoparticlesõ cross-linked polymers, silicone copolymer, fluorosurfactant, or amphoteric copolymer. The composition advantageously does not form a coacervateõ and does not iticlude alcohols pgtrticularly lower alcohols) or glycol ethers.
l0011:1 Another embodiment of the invention is directed to a composition comprising a polymer-micelle complex comprising a positively charged micelle that is electrostatically bourtd to a water-soluble polymer hearing a negative charge: The i-vater-soluble r.)olyrrter does .not comprise block copolymer, latex particles, polymer nartoparticles, cross-linked

4 polymem, silicone copolymer, fluorosurfaetant, ampherterie coixdymer. The composition advantageouslyde.es not Nen a coacervate aM does not fo.mt a film on a surtke. additim to the polymer-micelie comp/ex, the composition ftirther comprises an oxidart, (.00121 In another embodiment, the composition inchtdes an oxidant, which may be selecteal from the group consisting t-tf: hypohalous acid, hypohalite or souroes thereot,hydmgen peroxide or eources thereof, peracids, peroxyacids peroxoacids, or sores thettotorganie- peroxides or hydroperoxides, peroxygenated inorganic compotmds;solubilized chlorine, solubilized chlorine dioxide, a source of free chlorine, acidic sodium chlorite, art active chlorine generating compound, or a=
chlorine-dioxide generating compound, an active oxygen generating compound, solubilized ozone, N-halo compounds, and combinations thereof, /00=13) in atlother emboditneet, the. positively charged nîceecomprises monotneric:
quaternary A3.11.01011i1AM COMpOltrid. .in falOther eMbt)olitnent, the positively charged micelle further cornprises a nonionic surfactant In another .embodiment, th.e rioniOnie surfactant comprises- an amine -oxide. In another embodiment, the positively charged micelle conprises a tnonomeric bigeanide compoued. = another embodiment, the IMMOIneric =
biguanide eompound is sehtted from the group consisting of chlorbexidhte, alexidine, and combinutions thereof.
100141in .another embodiment, the composition is free of io.dine, iodine-polymer complexes, nanopartieles of silver, nanoparticles of copper,. nanoptuticies of zinc, triclosan, p,chloro.methyl xylenol, M0110MtriC pent ose alcohols. D.-xylitol and its isomers, 114trabital .and its isomers, aryl alcohols, henzyl -alcohol, and phenoxyethanol.
[00151 In another embodiment, the composition further comprises a evater-immiseible oil that is solubilized into the positively charged micelle, in another embodiment, the.
composition is free of water-m i so ibl e alCohols and glycol ethers.
[90I6) in another embodiment:. the water-soluble polymer bearing a. negative charge is selected from the group consisting of' a copolymer of a polymccharide and a synthetic monomer, copolymers comprising maleic acid, a c.op yncr of dimethylacrylarnide and acrylic acid, a copolymer of acrylic acid and styrene, a copolymer of sulfonateet styrene and makic anhydride, and combinations thereof, ittflI71 In another embodiment, the invention is directed to a method for cleaning a surfaee. The method cotnprises contacting a surface with a composition comprng a polymer-mice/le complex,. The polymer-micelle. complex includes a positively charged ee eleetrostatkally bound to a svater-soluble polymer bearing a negaiive chaige. The positively ha/Ted micelle comprises a Water-soluble cationic material selected from the group consisting of a monomeric quaternary alliTri011it11)1 compound, a .monontcric biguattide conipound, and mixtures thereof, The water-soluble polymer bearing a negative charge does not comprise block copolymer, latex particles, poly.rmer nanorarticles, cross-linked polymers, silicone copolYmer, fluorosurfactantõ or amphoteric copolymer. The-composon advantageously does not tbrin a coacervate, and does not. .11-uln a film on a.
surface, [001.8I Anothr erbodiment of the invention is directed to a method for treating a surfam. The mettux/ comprises mixing a first composition comprising a water-soltible polymer having A negative charge with a second COMpOsition comprising a Ositively charged -micelle. he water-soluble 1.:*lyt-ner -hearing a negative charge dOeS
'not Cor.nprise block copolymer; latex partides, polymer nanoparticles, crosnked polymers, scone copolyiner, fltwosurfactant, or arnphoterie copolymer. The positively chargedeee -compiises a water-soluble -cationic material selected from the group consisting of a monomeric quaternary ammonium compound, a monomeric higuanide cornNund, and miturea thereof. 'The methol. further comprises contacting the composition resulting front mixing of he two partS with a surface -So as to treat the surface.
10019-1 ,Another cinbodiment of the invention .is directed to a method for treating bacteria ospores, fungal spores. or viruses, -Ihe method comprises contacting the endogwes, spores, or viruses with an aqueous- composifion that comprises a polymer-eomplex comprising eposithely charged micelle that is eleetrostatically bound to a water-soluble. polymer b.earing enegae charge. The posit/vely .charged micelle comprises a water-soluble cationic material .selected from the group consisting of a monomeric quaternary ammonium compourid, a monomeric biguanide COinpowd, and mixtures 'thereof. The water-soluble polymer bearing a negative charge does not corn/wise mock copolymer, latex partick?s, polymer nanoparticles, cross-linked polymem, silicone copolymer, fluorostitfactant, or amphoteric copolymer. The composition does not loon a coacervate.
(0020] Anotherembodirnent of the. invention is directed. to a method for killing bacteria arising to germination of bacterial endospores or fungi arising from germination .of fungal spores. The melhod comprises contacting the endospores with an aquwus composition that. comprises a polymer-micelle complex COmprising a positively charged micelle that is electrostatically bound to a water-sohlble polymer bearing a .negative charge., The .povely charged micelle comprises a Water-soluble cationic nutterial selected frOirk the group cortsisting of a monomeric quaternary ammonium compound, a monorne.ric biguanide compound, and mixtures thereof. The water-sOluble polymer bearing a negative charge does not coinprise block copolymer, latex particles, polymer nanoparricles, cross-linked polymers, sone copolymer, fluorosurfactant, or amphoterie =
copolymer._ The composition does not form a coacervate..
Wall Another aspect of the invergion is directed to a system comprising a dual chambered device comprising a first chamber, a SCCOlid chamber, a first composition in the first chamber, aral a second composition in the second chamber. The first composition comprises a water-soluble polymer bearing a negative charge that does .not comprise block copolyirter, latex particles, polymer nanoparticles, cross-linked polymers, silicone copolymer, fluorosurfactant, or anwhoteric copolymer-. The second compositio.n cornprisesa. poSitively charged micelle cOrtprising a water-soluble cationic material seleimxi from the group consisting of a monomeric- quaternary ammonium co/11pound, a monomeric biguanide compound, and mixtures thereof_ The system provides the ability to redx the first and second conipositions (e.g., prior to application) to result in a mixed composition for application in which the mieelle is eleetrostatically bound to the watxr-soluble polymer to form a polymer-micelle complex. The resulting: mixed composition advantageously .does. not form a coacervate, and does .not flum a film on a surface.
[00221 .Another embodiment title invention is directed to 4 system emnprising a. dual chambered deVice comprisinga firstchantlx.,r, a second chamber, &first composition in the first chamber; 'and a seoond -composition in the second chamber. The first composition comprises.a -water-soluble polymer bearing: a negative charge that does not comprise block copolymer, latex particleS, polymer nanoparticies, cross-linked polymers, silicone copolymer, fluorosurfactant, or amphoteric copolymer.. The. second composition comprises a positively charged micelle comprising a water-soluble cationio material selected front the group consisting of a monomeric quaternary ammonium coinpound, a monomeric biguartide compound, and mixtures thereof, The system provides the ability to mix the first and second compositions tr.3 result in a mixed composition for application in which the micelle is electrostatically botmd to the water-soluble polymer to .fonn a polymer-micelle complex. 'The resulting mixed composition advantageously does not form a coacervate, and -does not form a film otit a surface. The resulting composition does not imiude aieohols. or glycol ethers.

100231 Another aspect. of the invention is directed to a system comprising a dual chambered device comptising 1.k first chamber,. a second chamber, a first compoSition in tiw first chamber, arid a second composition in the second chamber. The first cormxisition comprises a water-soluble polymer bearing a negative charge that does not comprise block copolymer, latex particles, polymer nanoparticles, cross-linked polymers, silicone copolymer, fluorosurfactant,<r amphoteric copolymer. The st..kcond composition comprises a positively charged micelle comprising a water-soluble cationic material selecW from the group consisting of a monorne.ric quaternary ammonium compound, a monomeiic biguanide compound, and mixtures thereof At least one of the first or second compositions thither comprises an oxidant. Ihe system provides the abty to mix the first and .smorid compositions (e.g., prior to app ti) tra result in a mixed composition for application in which the micelle is electrostatically bound to the water-solikle polymer to form- a polymer-micelle c.omplex.. The resulting mixed composition advantageously does-not for a rwervate, anddoes. not for a. film on a surface.
[00241 Further features -and advantages. of the present inventioi. will tie.come apparent to those of ordinary skill in the tut in view of the detailed description of preferred ernbrxiimeras below.

DETAILED DESCRIPTION OF PREFERRED .EMBODIMENTS
I. Definitions [0025] Before describing the present invention irk detail, it is to be understood that this inventiork is not limited to particularly exemplified systenis or process-parameters that may, of cAmrse, vars.,. It is also to be understood that the terminology used 'hentin is for the purpoSe of describing particular embodiments of the inveMion only, and is not inten.ded to thrift the scope of the invention in any manner.
{00261 All publicatioris, patents and patent applications cited e.rein, whether supra or infra, are hereby incorporated by reference in their entirety to the same extent as if each individual publication, patent or patent application was specifically and individually indicated to he incorporated by reference.
I0027j The tern), -"comprising" which is synonymous with "including,"
"containing," or "characterized by," is inclusive or open-ended and does not .exclude additiorial, unreciteal elements or method steps.
100281 The tem "consisting essentially- of" lin:tits the scope of a claim- to the specified materials or Step "and those that- do not Materially aft the basic and novel characteristic(s)" of the claimed invention..
MO291 The term "consisting of" as used herein, excludes -any element, step, or ingredient -not specified. in the claim.
[0301 It Mag. be noted that, as kise4-1 in this specification and .the appended clairrks, the singular thrills "a," "an" and "the" include plural referents unless the content clearly dictates otherwise. Thus, for example, reference to a "surfactant" includes one, two. or iriore such surfactants.
[0031.1 The term -water-soluble polymer as used herein means a polymer which gives an optically clear solution free of precipitates at a concentration of 0.001 grans per 100 grains of water, preferably 0A)1 grans/1.00 Vann of water, more preferably 0.1 grams/100 puns of water, and even more pleferably 1 grain or more per 100 grams of water, at 25 *c.
[00321 .As used herein, the tern "substrate" is intended to include any material that is used to clean an article or a surface. Examples of cleaning substrates include, but are .not limited to nonwovens, sponges, films and similar materials which can be attached to a cleaning implement, such as a flioor mop, handle, or a hand held cleaning tool, such as a toilet cleaning device.

=

[04331 As used herein, Ole terms "nonwoven" or "nonwoven web" means a. svell baying a structure of individual fibers or threads which are interlaid, but not in an identifiable manner as in a knitted web.
100341 As used herein., the term "polyirrier" asUsed in reference to a substrate (e.g., a non-woyen substrate) genanily includes, but is not limited to, horoopeAymers, copolymers, such as fix. example, block, graft, ratidom and alternating copolymers, terpolymers, etc. and blends ard. modifications thereof. Furthermore, unless othervse specifically limited, die term "polymer" shall include al/ possible geometrical coofigurations of the molecule. These configurations include, but am not limited to isotactic, syndiotactic and random symmetries.
/00351 Unless defined otherwise, all technical and scientific; terms used herein have the Mina- meaning t4s commonly understwd by one of ordinary skill in the art to Which the Mention pertains, Although .a number of methods and Materials shrtilar or Nuivalent to those described herein can beused in the practice- of the ptesent invention, the preferred materials and methods are described herein.
MON In the application, effective amounts are generally those a/Mounts listed as the .ranges or levels of ingredients in the descriptions, Which follow hereto, Unless -otherwise stated, amounts listed in percentage ("wtWs"). are in wt% (baftd on 100 weight% aceoi,'e) of the particular material present ir. the referenced composition, any remaining percentage being water or an aqueous carrier sufficient to se:count tbr 100% of the composition, unless otherwise noted. For very low weight percentags, the term -"ppm"
corresponding to parts per million on a weight/weight basis may be used, noting that 1..0 vvt%
corresponds to 10,000 ppm.
futroduction [0037/ The present inventors have now determined that the use of water-soluble polymers comprising groups which bear or are capable. of bearing .an electrostatic charge as counterions (Nlymeric eounterions) for micelles comprising at least one ionic surfactant selected such that the net electrostatic charge on .the micelle is opposite to that of the polymeric. counterion can yield, simultaneously, very fine control of the interactions between the headgrOups of. the ionic sorfactant as well as the adsorption of' the ionic surfactant at the air-liquid and solid-liquid interface 'when compositions are adjusted such.
that precipitates or coacervaWs are completely absent from at least some embodiments of the compositions.

Et10381 Surprisingly, such corm)ositions in which micelles with polymeric couriterions exist as soluble, thermodynamically stable aggregates exhibit very high adsorption activity at both the air-liquid and. solid-liquid interfaces. Such characteristics completely eliminate the need to adjust formulations such that they change their solubility, ibrming coacervates or precipitates, in order to deliver adsorption of useful amounts of ionic surfactant and polymer to these interfaces. The micelle-polymer complexes fornied when a water-soluble pObTlier coinprising groups which bear or are capable of bearing an electrostatic charge opposite to that of a micelle are usually found to he sornewlun larger than the micelles alone. The addition of a wate.r-soluble polymer bearing electrostatic Charges opposite to that of at least one sur.factant in aqueous solutions often can.
reduce the CC
of the given surfactant by a significant fraction, which can also have the effect of reducing thecost of certain formulations-[
00391 Fine control of surfactant interactions within -micelles via additiors of oppositely charged pOiymers according to the invention has. also been found to increase the oil solubilizatiOn ability of the micellea to. an unexpected degree. Without being bound by theory,. it it believed that -this effect is due to the uniquely high counter io.rt charge density carried by the charged polyme,r, -which is distinctly different from regular counter ion effect provided by typical. salting out electrolytes. This is thought to increase the .degree of counter on association of charged polymers compared to regular electrolytes, even at very low polymer concentrations, which in turn promotes inmates iri rnieellar size and an increase in oil solubilization efficiency. The inventors have discovered that the oil solubilization boosting effect develops mil)/ if the interactions are fine-tuned such that the system is fully free of coacervate yet. is near the- water solubleicoacervate phase boundary, [00401 Folmulations Cf3Mprising mixed rrsicelles of a cationic, germicide (quaternary ammonium compound or a water-soluble salt of a biguanide such as chlothexidine or alexidine), optimaliy a second surfactant such as an airline oxide, and a water-soluble polymer bearing an anionic charge can be made with control of the size and net electrostatic charge. It is believed, without being. bouod by theory, that the anionic polymers act as polymeric counterions to the cationically charged micelles., either increasing the -size of those miceiles or collecting groups of these micelles into soluble, thermodynamically stable aggregates which have enhanced activity at solid surface-a.queous solution interfaces, including the surfaces of microorganisms such as bacteria, viruses, fi.ingi, and bacterial spores. This reduces or even eliminates the need tbr the presence of an alcohol to enhance or "potentiate"' the antimiembial performance of the cationic biocide.
ft10411 In one einbodiment, the coinpositions can comprise alcolloi. In another embodiment, the COMpOSitiOnS can be completely free of water-rriiscible lower alcohols.
Similarly, the compoons can comprise Water-miscible glycol ethers or be completely free of the materials, sometimes ieferred to as "co-solvents" or "co-surfactants".
Compositions fret of the lower alcohols or glycol ethers not only. can pnwide acceptable antimicrobial performance at lower cost, but also reduce irritation to patients and hea/tbcare worker's, while providing formulations which can be considered mote environmentally friendly or sustainable due to lowered ma/ actives levels and lack of volatile organic compounds. Those embodiments that are free of alcohols or co:solvents are especially suited as sanitizing deariers, disinfecting cleaners or treatments tbr1..-iets in borne or veterinary applications.
[0:142) Surprisingly, die compositions, even without. alcohol, show inactivation: of non-enveloped vinises -such as rhinoviruS, even though cationic biocides are typically not considered as i:Active against. such micrwrganisms. tit believed, without being bound .by theory, that the interfaciai activity of the micelles with polymeric counterims is so significant that the -viral proteins are. dis.rupted, denatured or otherwise damaged such that.
the viral particles are rendered non-infective, eVen when they are. exposed to significant-.dilutions such as those. during the microbiological test -protocols.
Surprisingly, the corripositions, even without alcohol, exhibit aCtivity -against mycobacteria, (bacteria responsible fin- tuberculosis), which are here.tofore known to be relativeb,,,-resistant to the actio.ns of cationie. germicides in aqueous formulations lackiDg a co-solvent or alcohol.
Stich resistance is thouaht to be dtw to the thick, waxy outer membranes characteristic of this type of bacteria.
[00431 The compositions may be used as ready to use cleaners, and may be applied via spraying or pouring, but may also be delivered by loading onto nonwoven substrates to produced pre-inoistenW wipes. The compositions may also be provided as concmtrates that are diluted by the consumer (e.gõ with tap water). Such concentrates may comprise a part of a kit for refilling a 'container (also opfionally included within such a kit), such as an empty trigger sprayer. The eotilpositions may sho be provide.d as Concentrates for single -use (ìt dose) p=roducts for cleaning floors, windows, counters, etc.
CAmcentrated dishwashing liquids that provide antibacterial performance on very high dilutions may be tbrmulatedõ as may concentrates which can deliver sanitization of laundry via addition to ordinary washloads. compositions: and results inay be achieved without inclusion of triclosan.. Such concentrated products also cm provide prok.q.s.tion against Me growth of biofihns and associated outgtowth a molds in drain lilies associated with autorriatic dishwashers; laundry washing machines, and the like, reducing undesirable odors which are sometimes encountered by consumers, 100-441 Concentrated fOrtlIS of the formulations may also be provided which may he diluted by the consumer to provide solutions that are the used, Concentrated forms suitable for dilution via automated systems, in- which the concentrate is diluted with water, or in which two solutions are combined in. a given ratio to provide the final use formulation are possible.
1:00451 1.µh formulations may be in the .form of gels delivered to a reservoir or surface With A dispensing. device. They may optionally be delivered. in Single-use poaches comprising a soluble film, [00461 The superior wetting, spreading, and. cleaning performance of the systems make them especially Suitable for delivery tiom ne.rosol packages comprising either -single or dual chambers.
[00.17) 'The compositions are useful in providing a reversal in the -native surface charge zeta .potential) of bacterial endospores and other microorganisms frs.im anionic (negative) to eatiotic (positive), or at. least. to less anionic as a result of contact with the compositions. Such a change in charge increases the elmnostatic binding of the Microorganisms to cleaning implements. web aspre-ruoistened nonwoven wipes, which typically have A native- anionic (negative) charge, hertce Unmoving thc re in ova:1 of the :microorganisms from surfaces being -cleaned. Because the eompositions pro:vide robust adsorbed layers of germicidal materials such as quaternary ammonium co.mpunds and 'biguartides, they are able to .kill bacteria which arise from the gemination of endospores under favorable environmental COncliti owL Such compositions may thus find utility in various applications inchsding combating weaponized spores such as Bacitha Anthracit:
'Low residue treatment solutions for surfaces which .may be infrequently cleaned whiCh may be subjett to outgrowth of bacteria or molds from contamination by air-borne spores can be pnxiticed with the eotripositions. in other words, the compositions do not result in the formation of a durable film on a surface Mier application.
Simple rinsing is sufficient to remove any residue, and eVCTA WittPlit rinsing, those embodiments of the invention that do exhibit a residue do not form macroscopic durable films.
Thus, any remaining residue does not constitute a film, but is easily disturbed, destroyed, or othemise removed.
100418j The invention also contemplates use of the polymer-micelle corriplexes for .delivering improved sanitization of surfaces and protection of treated surftwes through the same mechanism of enhanced adsorption of cationic biocides such RS qaatemary ammonium salts and biguanides onto living bacteria, bacterial endospores, tlingal spores, arid viruses, Examples of antimienabial actty atxhihited. by the inventive cotripsitions include, tan are not limited to killing of living bacteria, killing of bacteria anon gemination from bacterial endospores, .killing of living tiarigi, killing of ferigi upon germination from sporeii, damage to the proteins or lipids of viral capsids resulting in decreased or inhibited infectivity to a target hostõ adsorption onto the protein.s of viral capsids resulting in blockage of the p ro tein from a target. site irt a host, or increased binding of a bacterial entioarxife,. a fungal a.pore, or a virus to a non-animate sor.face resulting in a decrease in. physieal trans:mission to a host which in turn decreases the transini.s.sion of diseasc of the host or addition -contamination of other aurfitcea. /It/sending m application use, the surface may be hard, soft, animate., (e.g., skin), non -animate, or othertype surface.
ILL Defion of D net and Pinnet Parameters.
10049j As will.be shown in the exampleslx.x.low, very fine control of the intemetions between micelles comprising an ionic surfaztant. arid water-soh:61e pol3aners bearing electrostatic charges opposite tc.$ that ofthenticelles, and hence functiotfmg..as -polymeric counterions to he nicelles, can be achieved through inanipulation of the relative number of charges due to ionia surfactants in the system and those charges due to the water-soluble polymer.
[00501 Mixtures of surfactants, including mixtares .of ionic and nonionic surfactants, may be employed. A convenient way 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 headgroups of the surfactants, both anionic and cationic, followed by a detemination of which type of charged headgmup is in excess in the.
formulation.
[00511 Surfactants bearing two opposite electrostatic charges in the .formulations, such as carboxy-betaines and sulfo-hetainea, act as "pseudo-nonionic" suriktants in the -compositions of the instant invention, since the net ehatge on them will be zero. Thus, di.e calculation of Dnet will not involve the concentration latch psendo-nonionic surfactants.
Similarly, phosphatidyl choline, an edible material Avbich is a major component of the surfactant commonly referred to as lecithin,. contains both an anionically charged phosphate group and a cationicaily cliarged choline group in its .headgroup region, and thus would he treated as pseudo-nonionic in the inventive compositions. On the other hand, a material such as phosphatirlic acid, which contains only an.
anionically charged phosphate group as its headgroup, would coritribute to the calculation of .Dnet, as described below, [00521 Some surfactants, such as amine OXideS. Illay be uncharged (nonionic) over a wide rarige .of pH values, but ntay become charged (e.gõ cationically in .the case of amine oxides) at acidic pH values, especially below ilthout pH 5. Although such components ITtay not. contain two permanent and opposite electrostatic cllages, applicants have found that they may be treated explicitly as nonionic., surfactants in the inventive formulations. As taught herein, inventive compositions which are free of commutes and precipitates that -coniprisomixed -micelles of an antine oxide and a Qationic germicide:. such as a quaternary aonincom.pound and a water-soluble polymer bearing Mimic charges may be readily farmed through adjustment of the P/Driet parameter, the Drket parameter; and/or the presence of adjuvants MAI as elecrolytes, without regard to the precise value of any cationic charge. present on-the amine. oxide.
[N531 Two parameters can. he defined fOr any mixture a surfactants prising headgroups hearing, or catuthie .or bearing, anionic- or cationic charges ormixtu.res of both, said parameters being D. anipriic and D. eatiOnic.
D anionic.will be defined as anionie (-I) x(Eq anioriic) D cationic will be defined as¨

D cationic = (+I) x (Eq cationic) [0054j A final parameter expressing the net charge on the micelles is Dnet, which is simply the sum of the parameters D anionic and D cationic, Le., [)net D cationic D ardonic 10055/ In the expressions above. Eq anionic- is the sum of the total number of equivalents or Charges due to the hea4roups of ail anionic surfactants present. for a fonnulation comprising a single surfactant with a headgroup bearing or capable of hearirtg an anionic charge:
Eq anionic -- (C anionic l x Q anionici)/1\4 anionic wherein C anionic is the concentration of a surfactant with anionic headgroups in -grans/per 100 grants of the formulation or use composhion, Q anionic; is a number representing the numhe.r of anionic charges p.resent on the surfactant, which may be viewed as having the units equivalents per inole, and M anionic! is the molecuiar N,veight of the surfactant in gramsimole..
100S61 For a formulation comprising two different surfactams with anionic headgroups, the parameter Eq anionic would be calcuiated as the sum:
Eki anionic = Eq &1)101 + .Eq a1ion1c2=
(C.!nie X Q anionici)/M anionic!. (C anionic2x. Q aninniciyM anion1c2 [0057] Commercially available surfactants ate often MIXtUreS of materials due to the presence of a distribution in the number of, for example, Inethylem groups in the hydrophobic "taits" of the surtlictant. it is also possible that a distribution in the number of charged "headgroups" per molecule could exist. In practical work with commercial materials, it may al50 be acceptable to tale an "average' molecular-weight or-an "average"
munber of anionic. (or cationic) Charges per molecule quoted by the motufacturer of the surfactant. In the calculation of D anionic or .D cationic), it .may also be acceptable to use values of the Eq anionic. (or Fq cationic) derived froo. direct analysis -of a surfactant raw material, [0058) In the expr.essions above, Eq cation1/4 is the sum of the total number of equivalents or charges due to the headgroups of a cationic surfactants present. For- a formulation -comprising .a Single surfactant with a headgroup bearing or capable of bearing a cationic charge:
F.44 cationic! = (C cationic! x. Q cationicl)A4 cationic wherein C cationic is the concentration of a surfactant-with cationic headgrotTs gratnsiper 100 grants of the tbrmulation or use coMposition, Q cationic is a number representing; the number of cationic charges patsent on the surfactant, which may be viewed as having the units equivalents per 111010,, and cationic is the irioleculat weight of the surfactant M. gramslmole.. in cases where the thrmulation comprises mom than one surfactant with cationic headgmaps, the summation of the equivalents of cationic heatigroups vould.be performed as in the.case of the anionic surfactants described above.
100591 As an ex.ample, consider a formulation cornprising a mixture of a single anionic surfactant and a single nonionic surfactant, but lacking a cationic surfactant... Furthermore, consider the anionic surfactant is present at a concentration of 2 wt143 or 2.
gramsj-100 gams of the formulation, has one group capable of developing an anionic charge per tnolecule, and has a molecular weight of 200 grarrisimole.
Then. Eq anionic x. 1)/200 ¨ 0.01 equivalents/100g in the formulation.

Then, D 8.11jOrtie (-1) X. (0,0i) -0.01.
And I) cationic 0.
Thus, Dnet (0 - 0.01) =
inthitlf As a second example, consider a formulation comprising a r.nixture of a single anionic surfactant, a single nonionic surfactant, and a single cationic surfactant svhich is a gemicid.al quaternary ammonium compound.. Furthermore, consider the anionic surfactant is present at aconc'entration of 2 wflio or 2 grams/ 100 grams of the formulation, has one group capable of desteloping an anionic charge per molecule, and has a molmular weight of 200 gramsimole, Futtheimore, consider -the cationic surfactant is present in the formulation at a concentration 0.1 svt% or Ü. grams/ 100 grams of the fonnulation, has -one group capable of developing a cationic charge per molecule, and has a molecular weight of 300 grams/1=1p.
Then Eq anionic (2.x 1)/200 = 0.01 equiva1ents/100 g in the formulation.
And .Bq cationic 0.1 x 1)/300 = 0,00033 equivalents/ 100 g in the font ulation.
Then,. anionic = (-1) x 0.01.) ¨
And D. cationic- = (1)x (0,00033) = +0.00033, Thus; Dnet = +0.00033 + (-0.01) -0,00967, This negative -value clearly Mdicates that the nuMber of anionically charged headgroups the mixed micelles comprising the anionic, nonionic, ..and cationic surfactants present. in the formulation exceed that of the cationically charged headgroupS, [00611 A second parameter which can he used to describe the instant invention and the interactions behveen a polymeric counterion and surfactant micelles bearing a net charge is the ratio .P/Dnet. P is the number of charges (in equivalents) due to the polymeric counterion present per 100 grams of the formulation and can he calculated as follows:
P = polymer x F polymer x Q polymer x 7.)11v1 polymer, where C polymer is the concentration of the polymer in the .fonriulation in grams/ 1100 grams of formulation, F polymer is the weight fractia-m of the monomer unit bearing or capable of bearing a Charge uith respect to the total polymer weight and thus ranges from 0 to 1, Q polymer is the number of charges capable of being developed by the monomer unit capable of bearing a dharge and can be viewed as having the units equivalents per mole, Z is an integer indicating the type of charge develope-d by the monomer unit, and is equal to +I when the monomer unit can develop a cationic charge or is equal to -1 when the monomer tmit can develop an anionic charge, and. Tvi polymer is the molecular weight of the inonomer unit capable of developing a charge, in grams/mole.
[0062) For example, consider a formulation comprising poiyacrylic acid hotraopolymer (FAA) as a water-soluble polyinetic counterion. PAA is capable of developing 1 anionic charge pa acr.ylic acid monomer unit (which has a molecular weight. of '72 grams/mole), and hence poly.mer = 1 and Z = -1. In addition, the .po.lyrner is a homopolymer,so F
.polyrner = 1. If the ?AA is present itt the formulation at a .concentration of 0,1 grams/ 100 grams of the formulation, the value of P would he calculated as follows:
P xixix -1)/72=-0.00139.
1.0&531 Usiag the Dnet value of -0.00967 calculated in the example desctibed above for a mixture of an. anionic, cationic, and nonionic surfactant, the ratio P/Dnet w'ould 'be calculated as:
PiDnet = (-0.00139A-0.0096:D== +0,144 [00641 This positive- value of IliDnet not onlY indicates the ratio of the charges due. to the polymeric courtterion and the net charge on the tnixed micelles, but also indicates, . since it is a positive number, that the charge on the polymeric: counterion and the net charge on the mixed micelles are the sae, both being anionic. ht this ease, there- would he no net electrostatic interaction between the polymeric. counterion -ani.
the mixed micelles expected, and .hence the example viouid not be within the scope of the instant inVention, which requires that the ilolymeric cotalterion nulst be of opptsite .charge. to that of the heacigroups of the surfatnant. or Mixture-of surfactants comprising.the NO65). Now consider another example whichthe tbrmulation conaprises. a mixture of a single .trtionic surfactant, a single nonionic- surfactant, and a single cationic surfactant and a single cationic surfactant which is a germicidal quaternary ammonitun compound.
Ftatfierinore, c.onsider the anionic sur&ctatit is present at a co.ncentration of(. sv-t% or 0.2 grams/100 grams of the formulation, has one group capable of developing an anionic charge per molecule, and has a MOleculat weight of 200 grams/mole.
Furthemtore, consider the cationic surfactant is :present in the firmulatiOn at a conceatration 1.0 wt or 1.0 gram.sli 00 grams of the forinulation, has one group capable of developing a cationic charge per molecule, and has a molecular weight of 300 grams/moIe.
'Then Eq anionic = 0.2 x 1)/200 OAXII equivalents/ 100 g in the thrmalation.
And Eq cationic = (.1.0 x 1)/300 0.00333 equiValents/ .100 gín the formulation.
Thenõ D anionic = (-1)-x (0.001) = -0.001.

And D cationic = (I) x (0,00'333) 4Ø00333, [00661 Thus, Dnet = 4-0.00'333 -I- (-0.00.1) = 40.00233, This posve value clearly indicates that the number of canonically cinarg.ed headgroaps in the mixed micelles comprising the anionic, nonionic, and cationic surfactants present in the formulation exceed that of the anionically charged heatigroups, Such mixed micelles would be suitable for interaction with a polymeric counterion bearing anioniç charges.
ittt1671 Confirming this exarriple, now consider that the formulation also comprises a polyacrylic acid homopolyrner (PAA) as a water-soluble polymeric eounterien.
MA is capable of developing 1 anionic charge per acxylic acid monomer unit (which has a molecular weight of n gramerriole), and hence Q polymer 1 and Z In addition, the polymer is a hoinopolymer, so F polymer = I. If the PAA is present in the tbrmulation at a concentration of 0.1 grams/100 grarns of the tbrmulation,. the value of P
would be calculated as .follows;
P=(0.1 xlxlx Thus, for this formulation, .P/Drutt would be calculated as:
P/Dnet (-0,0013.9y(40.00233) - 0.5966, [0068.1 This negative value of PIDnet indicates that thc. charges on the polymeric Counterion .(AA ) and the mix.ed micelles are opposite to one another, indicating that there may be an electrostatic interaction between the PAA and. the micelles, and hence the composition may be within the scope- of the in5.4tati1. invention. Of -course, the value- t:$f RDnet also indicates the ratio of the Charges due to the .polymerie counterion and the net charge on the mixed micelles.
[0069I Alternatively, if the amber of Nitivaleats of charged groups present per gram of polymer is available from the manufacturer, or call be derived for the synthetic route used to create the polymer, or can be fierivtd froin analysis of the polymer, the P .may also be calculated based on that kformation.
[Om) For emimpie, P (C polymer x Eq polymer x Z.), where Cpolymer and Z are defined as aboveõ and Eq polymer is the number of equivalents of groups per gram of polymer with a Charge consistent with the value of Z used. For example, if a water-s:Ail:4e polymer that. is described as having 0.0139 equivalents per gram of polymf.s.r (actives) of an anionically charged monomer, and this polymer is ivied in a tbrmulation at coneentration of 0.I. grams/1N grams of the .formulation, P is calculated as follows:
P (0,1 x 0.0139 x -1)¨ - 0.00139, [0071/ This vaitie of P, with the Sa111C Dnet value used in the example above in which the micelles comprising an anionic surfactant, a nonionic surfactant and a cationic surfactant which is a quaternary ammonium compound, niay then be Itsed to calculate the ratio Pinnet:
PiDnet (-0.00139)/00.00233) - 0.5966, which yields the sae resuh as described above..
[eon] In the case of copolymers comprising more than one monomer of like charge or capable of developing a like charge, then the P he calculated for the formulation would be the sum of the 1> values calculated Rir each of the appropriate o& ors comprisina the polymer used.
[0073) Finally, in practical work, the absolute value of PfDrtet is an indicator of =vitich charges are in flxcess and whiCh ate in deficiency in. forrnulatiOTIS ofthe -instant invention.
When the absolute value of PiDnet is greater than. 0 Inn. less them I, the number of charges &le to groups ort the polymeric counterion is less than the- net number of charges due- to the headgroups- of the ionic surfactant or surfactants. comprising the micelles, i.e. the polymeric-cowrie/ion is in deficiency. When the absolute value of P/et is greater than I. the polymeric counterion is ittexcess, an. of course,. when the absolute value of P/Dnet I, the number of charges. due to the headgroups of the -polymeric. (=merlon equals the net number of charges of the ionic start:octant or surfactants eomprising the micelles.
W.Suitable Polymers 100741 iy[any polymers are suitable for use as poIymteric counterions in the instant invention. In one embodiment, the polymers are wate.r.-soltible asdefineni herein. The polymers may be hornopolymers or copolymers, and they may he linear- or branch-mi.
Linear pOlyMerS ma.y be pre.ferred in at least some embodiments..Col.lolymers may be synthesized by processes expected to lead to statistically random. or so-calied gradient type copolymers. In contrast, water-soluble 'block copolymers are not suitable, since these types of polymers ntay form %%regales or mit.)elks, in w.bich the more hydrophobic block or blocks comprise the eore .of the aggregates or micelles and the MOM
hydrOpilifiC biOCk comprises a "coma" regior in contact with water. lt is thought that these self-assembly processes compete with the electmstatic interactions required for a water-soluble pOlyMer to serve as a polymeric counterion with ordinary surfactant rceIIes. Although mixtures of water-soluble polymers are suitable in at least some embodiments of the present invention, the mixtures selected should not comprise block copolymers capable of forming so-called "complex coacervate" micelles through self-assenibly, since this micelle formation p.rocess also competes With the interaction of the water-soluble polymer as a polymeric counterion to ordinary surfactant micelks. When the polymers are copolymers, the ratio of the two or ntore monomers may vary over a wide range, as long as water solubility of the polymer is maintained (0075) in an eratxxliment, the polymers should tx.,;_water soluble, as defined herein, and therefore, should not be latex particles or tnicrogels of any type. In such embcaliments the rx)iymers should not be cross-linked through the use of monomers capable of forming covalent bonds been independent polymer chains, and the compositions and formulations should be free of cross-linking agents added expressly for this purpose. It .is believed that polymer aggregates that may be "swollen" by water in the form of rnicrogels or polymers that form cross -linked networks will not have the appropriate full mobility atilt polymer chains needed for thern to function as polymeric counterions with respect to ordinary surfactant micelles.
Polymerparticles µvhich can serve as structurants for an aqueous composhion through the formation of fibers or threads .are not suitable = as the w.ater-soluble polymers Mr similar reasons.
Similarly, latex particles are believed to not be suitable because many of the individual polymer chains: in such particles are, in fact, confined to the particle-interior and are not readily Vailahle for interaction with the aqueous phase. Latex- particles also lack the chain mobility required to limetion as counterions to ordinary surfactant micelles.
1007.61 The random copolymers may comprise one or more monomers bearing the same charge or capable of developing the: same charge and one or more monomers which are nonionic, i.e, .not capable of bearing a charge_ Copolymers may be synthesized by graft processes, resulting in "comb-like" stractures.
porn preferred copolynters include so-called "hybrid" materials front Akzo Nobel such as AlcoguardSìl5240. These materials are described as comprising polysaccharides and synthetic monomers which can function in the sarne manner as actylatelmaleate copolymers (i.e., a water-soluble polymer with anionically charged .groups) in cleaning formulations. Hybrid polymers such as those described in US Pat, N. 8,058,837 are pre.ferred in formulations where the overall sustainability of the forrnulation is of conaan to the end user. Such hybrid polymers are derived from synthetic monomers chain terminated with a hydroxyl-containing natural material, such as a polysaccharide, using free radical initiators, 1:0078.1 Various anionic polymers available from Akzo Nobel under the tradenames Alcoguard*, Alcospersek and AquatreatV are suitable for use. For example, Alcosperse 747, a .randorn copolymer,. Aquatreavt AR-4, an acrylic acid hoinopolyiner, and AleoguardttO 5240, a random graft copolymer, all of >yvhich contain calrbOXyie, acid groups, are additional exatnples of anionic polymers that may be employed.
.Alcoguarde 2300 is a random colx)iymer of the nonionic monomer dimethylacrylatnide and the anionic monomer acrylic acid. Alcospema, 465 is a poly(acrylic acid) homopolymer.
Versa-TIA 4 (Akzo Nobel) is another example a a suitable anionic polyiner, This material is described as a random copolymer of sulfonated styrene and maleic anhydride.
Another exainple of a suitable anionic polymer is poly(2-acrylamido-2-methyl-1-pmpanesulfonie acid), fikf> known aspolyAlvIPS.
[04791 In one embodiment, dm compositions are free of copolymers coinprising at least one monomer bearing or capable (-)f. developing an anionic charge and at least one -monomer hearing. or capable of developing a catio.nic charge. Such copolymers,.
-somethnes referred to as "arnphoterk" Wpolyram, are believed to not fanction is well or at all as polymeric counterions to micelles bearing a net electrostatic charge for at least to reasons. First the proximity of both types (mimic: and cationic) of clutrge.s alone the.
polymer chains, if randomly distributed, interferes with the e.fficient.
pairing of a given type of chargean the polymer chain with the headgroup of a surfactant of opposite charge in a micelle. Second, such copolymers have the potential for electrostatie interactions of thc anionic charges on a. given polymer chain with the cationic charges on another polynter chain. Such imeractions: could. lead. to the. formation of polymer aggregates or complexes in a process that is undesirably CCiMpetitive with the interaction-of the .polymer with micejlar aggregates..
[00801 The water-soluble .polynters may include natural or- sustainable materials bearing anionic groups, including inulin derivatives (extunple Carboxyline CM
or Dequest PB), anionically modified starshes with the proviso that they exhibit water solubility without cooking to achieve water solubility, vynter-soluble salts of alginic acids, anionically modified cellulosic materials such as carboxymetbyl cellulose, modified proteins, and the likeNon-limiting examples of monomers I.Nez.-iring or capable of E)earing an anionic charge are acrylic acid, tneAhacrylic acid, vinyl sulfbnate, acrylamido ptopyl tnethane sulfonic acid (AMPS), itaconic acid. naleic acid, &merle acid, *Italic acid, iso-phthalic acid, pyrornellitic acid, methallyi sul.fonate, sulfonated styrene., croto.nic acid, aconitie acid, cyanoacrylic acid, methylene malonic acid, vinyl acetic acid, ally1 acetic acid, .ethylidineacetic acid, propylidineacetic acid, angelic acid,. cinnamic.
acid, styrylac.rylic acid, citraconic acid, glutaconic acid, phertylacrylic acid, acryloxyptoprionic acid, vinyl benzoic acid, N-vinylsuccinamide acid, mcsaconie acid, rfletbacroyi alartine, acrylohydroxyglycine, sultbethyl aeryiate, styrene sulfonic acid, 3-(vinyloxy)propane-1-.
sulfonic acid, ethyelenesulforde acid, vinyl sulfuric acid, 4-vinylpherry1 sulfinic acid, vinyl phosphonic acid, =We anhydride, and mixtures thereof. Suitable monomers nlay include acid-litnctional ethylenically unsaturated monomers capable of polymerization or copoiyinerization via processes including free radical, polymerization, .AIRP
atni AT
polymerization conditions that are expected to -produce statistically random or g,radient copolymers vvith ethylenically unsaturated monomers which are incapable of developing a charge, the so-called nonionic monomers, [0081j Non-limiting examples of monomers which are nonionic, not betirig, or not capable of bearing an electrostatic Charge inctude the alkyl esters of acrylic acid or :methacrylic acid, vinyl alcohol, vinyl methyl ether, vitwl ethYI ether,-ethylene oxide, propylene .okide, and. mixtures thereof. Other examples inelude acrylainicle, dimethylacrylamide, mid other alkyl acrylarnide Kle.rivatives Other- suitable monotners rriay include ethoxylated esters of acrylic .acid.- or metlaticrylic acid, the related tristyryi phenol ethoxylated esters of acrylic acid, methacrylic acid or mixtures thereof Other examples of nonionic, monomers include saccharides such as hexoses and.
pentoses, ethylene glyeol, alkylene glycols, branched polyols, and mixturesthereof.
1:082/ In some eintxxliments Wate.r-Soluble polymers wmprising monomers which bear 14-halo- groups, for example, N-C1. groups, are not present. is believed- that interactions between polymexs coinprising -such groups. as i'..zlynterie counterirms to micelles leads to either a degradation of the surfactantsthseves andior a degradation of the polyinets through the enhanced local concentration of the polymers at the micelle surfaces.
f0083] When the compositions colnprise sur.factant rnicelles with, for example, a net cationic charge and a water-soluble polymer or mixture of rsolygners bearing or capable of hearing anionic charges, titer) the compositions tray be free of any additional polymers hearing a cationic charge, i.e., a charge opposite to that of the first water-toluble polymer bearing or capabk of bearing anionic charges. 'The presence of a first water-soluble polymer bearing an anionic charge and a second water-soluble polymer bearing a cationic charge in the same. forniulation is believed to give rise to the formation of complex.es between the two polymers, i.e.,. so-called polyelectrolyte complexesõ which would undesirably compete with the "'mutation of complexes between the micelles .i.naririg the catiords-, charge and the polymer bearing the anionic. charge.

[00841 However, compositions comprising surthetant micelles bearing a net electt=ostatic charge and a water-soluble polymer bearing or capable of bearing an electrostatic -thaw opposite to that of the surfactant micelles may cornprise additional polymers which do not hear charges, that is, nonionic polymers. Swell nonionic. polyniets ntay be usetbl as adjuvants for thickening, gelling, or Rejtming the theological properties of the coirpositions or tbr adjusting the aesthetic appearanef of the formulations through the addition of pigments or aim' suspended particulate,s. It should be noted, however, that in many cases, the pair/ter-micelle comple.xes of the instant invention, when &basted to certain to actives coricerArations, may exhibit "self-Thickening" properties and not explicitly require an additional polymeric thickener, which is desirable from a cost standpoint.
V. Suitabk Surfactants 100851 In one ernivaitnent, the compositions are -free of nonionic surfactants which -comprise bktics of hydrophobic, and hydrophilic groups, such as. the Pluronic.O. It is believed that the struetures formed with such large surfacbants, in which the hydraphobiC blocks assemble into the core Tegions of the micelles and the hydrophilic blocks are present at the. micellar surface would interfere with the polymeric eounterion interactions with an additional charged surfactant. incorporated intoa mixed and/or also represent a reure competitive micelle: assembly mechanism, in a manner .siinilat to that of the Use of block copolymers -used as polymeric counterions, which are also preferably not present.
[0086) A very wide range of surfactants and mixt wet of sitrfactants may be used, including anionic, nonionic .an catitmic surfactants and mixtures -thereof. As alluded to above in the description of Oriel and PfDriet, it will beapparent that -mixtures of-differently charged stufactants may be employed. For CXeMple, mixtures of cationic and anionic surfactants, mixtures of cationic and nonionic, mixtums of a/11'0111C and nonionic, and inixtutes of cationic, nonionic and anionic may be suitable for use.
(00871 Examples of cationic surtiun.ants include, hut are not limited to monomeric quaternary aitallOrgiUM compounds, monomeric. biguanide COMpounds, and combinations thereof. Suitable exemplary quaternary ammonium comrxxands are available from Stepan Co under the tradcoarne B-11711) (eg., EtTce two, EVIte 1210, BICID 818, BCV
83.54 Any other suiblble monomeric quatemary amtn011ii.lin compound may also be employed: WM* IWO and 131-01) 12l0 are described as didecyl dimethyl ammonium chimide and a mixture didevyl &methyl ammonium chloride and ri-alkyl dimethyl benzyl ammonium chloride, respectively. Examples of monomeric biguanidecram...tot/rids include, but are not limited to ehlorhexidine, alexidine and salts thereof.
I;0088l Examples of anionic surfactants include,. bta are riot limited to alkyl sulfates, alkyl sulfcmates, alkyl etboxysulfates, fatty acids and fittty acid salts, linear alkylbenzene sulfonates (LAS and HAS), secondary alkane sulfonates (for example Hostapurli0 SAS
3), methyl ester sulfonates (such as Stepan-Mildit PCI.. from Stepan Corp)õ
alkyl sultbsuccinates, and alkyl ainino acid derivatives. Rhamnolipids bearing an charges may also be used, for example, in formulations emphasizing gmter sustainability, since they are not derived from petroleurn-based materials. An example of such a tharnnolipid is Mg 425, which is supplied as an aqueous. solution with 25,10 actives, fraill Jenil Biosurfactant Co., LLC (Saukville, W.
[00891 So-!called "exte.ndtxl chain surfactants", are preferred in Some .formulations:
Examples of the.se anionic: surfactants are described in US Pats Pub. o. 2l3.
[0090) exam.ples of nonionic surfactants includealkyl arnMe oxides (for example AtranonyxV 1,0 from Stepan .Corp.) alkyl amidoamine oxides (for example Antimony/a 1.,MDO from Stepan Co, alkyl ptiosphine oxides, alkyl poyg osìe.s and alkYl PolYpentosides, alkyl rx)iy(slyercA ester)- and alkyl poly(glyeerol ethers), and alkyl and alkyl -phenol ethoxylates of all types anti mixtures thereof. Sorhitan esters and etboxylated sorbitan esters are also- useful nonionic surfactants.. Other usefill nonionk surfictants include,. but are not lifnited to, fatty acid amides, fatty 404 monoethanolamidea fatty acid diethanolamides, and fatty acid isopropanolamides..
[009lij In one erribodiment, a phospholipid surfactant may he included.
leeithin is an example of a phosphod, E00921 in one embtxtiment, synthetic zwitterionie surfactants may be present.
'Non-limiting examples include N-alkyl betaittes (for example Aniphosoll) LB from Stepan Corp.), alkyl sulfo-betaines and. mixtures thereof.
[011143) In one embodiment, at least some or the surfactants may be edible, so long as they exhibit -water solubility or can fOrm mixed micelles with edible rtonionic surfactants.
Non-limiting examples of such edible surfactants include casein or leeithin or mixtures thereof.
1.0094I In one embodiment, the surfactants may be selected based on green or n.atural criteria. For example, there is arz increasing desire to employ conn)onotts that are naturally-detived, naturally-prmessed, and bitidegiadable, rather than simply being recognized as safe. Jr example; processes such as etboxylation may be undesirable is desired to provide. a given or natural pmduct, as such processes can. leave residual compounds or impurities behind. Such "natural surfactants" nuay beprtxtuced ng processes perceived to be more. natural or ecological, such as distiliatiOtl, condensation, extraction, steam distillation, pressure cooking and lt,rnolysis to maximize the purit!,,, of natural inaralients, Examples of such "rtatur:al surfactants"
that may be suitable for use a.p;- (k.scribed in. U.S, Patent Nos, 7,608,573, 7,618,931, 7,629,305, 7,939,486, 7,959,488, all of which arc herein incorrated by retbrence, VI, Suitable Ad j trv ats 1.00951 .A Nviik range of optional adjuvant or mixtures of optional adjuvants nuty be present., For example, builders and cheating Agents, including but not limited to BMA
salts, GLDA, MSG, glucorattesõ 2-hydroxyacids and derivatives, zhitainic acid and derivatives, trimethylglycine., etc. may be included.
/00961 Amino acids and mixtures of amino acids may be present, as tidier manic inixttires or as individual components ofa single chirality.
[0097] Vitamins or vitamin precursors, for exampleretinal, rrtay be present, 10098) Sources of soluble ínc, copper, or silver ions may be present, as the simple inorganic- salts or salts of chelating agentS, including, but not limited to, EDTA, QLDA, NIG-DA, citric acid, etc.
10t$91 Dyes- and colorants may be peseta. Polymeric thickeners, when ttsed as tau&
above, may be present, fli81001 Buffers, including but not litnited to, carbonate, phosphate,-silicates, borates, and combinations thereof ay be present. Elmtrolytes such as alkali metal salts, for example including, but not limited to, chloride salts (e.g., sodium chloride, potaSsiuna chloride), bromide salts, iodide salts, or combinations thereof may be present:
[00101) Water-miscible solvents may be present in some emboditnents. Lower alcohols (e.g., ethanol), ethylene glycol, propylene glycol, glycol ethers, and mixtures thereof with water miscibility at 25GC may be present in some fallbodimerns, Other embodiments will include no lower alcohol or glycol ether solvents. Where such solvents are present, some etribt.xtiments may include them in only small amounts, for example, of not more than 5% by weight, not more titan 3% by weight,. or not more than 2%
by weight. .
f00/02) Water-immiscible solvents may be present, being solubilized into the [001031 Water-immiscible oils may be present, being solubilized into the micelles.
Among ttmse oils are those added as fragrances. Ptxtfened oils are those that are from naturally derived souteesõ including .the wide variety ()Is so-called essential oils derived trout a variety a botanical sources. Formulations intended to provide antimicrobial benefits, coupled .with improved overall sustainability may advantageously comprise quitternary ammonium compounds or water wluble salts a chlorhexidine or alexioline in combination with essential oils such as thyrnol and the like, preferably in the absence of water-miscible alcohols.
[00104I in on embodiment the composition IT/ay Rather include one or more oxidants. Exampks of oxidants include, but are not lted to hypohaious acid, bypoltalite and sources thereof (e.gõ alkaline mend salt andfor alkalirie earth metal salt of hypochlorous or hytx)hromous. acid), hydrogen peroxide and sources thereof (e.g., aqueous hydrogen pet-oxide, perrate and its salts, percarbonate and its salts, carbamide peroxide, nietal t)eroxides, or combinations thereof), peracids, peroxyaolds, peroxoacids (e.g.
peracetic acid, percittìc. acid, diperoxydodecanoic acid, peroxy amido phthalamide, peroxomonosuffonic acid, or peromlistilfzunic acid) and sores thereof (e.gõ
salts -alkali metal salts). of peracids or salts of peroxyacids such as peracefic acid, poreitric acid, diperoxydodecanoic acid sodium potassium peroxystiltitte, or combinations thereof), organic peroxides and hydroperoxides (e.g. benzoyI peroxide) poroxygenated inorganic .compormds (e.g. per chlorate and its salts, permanganate and its salts and periodic acid tird its salts), soiubilized chlorine, solubilized chlorine dioxide, a Source of free chlorine, acidic sodium chlorite, an active chli-aine generating compound, or a chlorine-dioxide generating compound an aCtive oxygen generating compound, solubilized ozone, .I-halo compounds, or combinations of any soh oxidants. Additional examples of such oxidants are disclosed in Q.S. Patent No. 7,517,568 and U.S. Publication No. 201 I/0236582 each of which is herein incorporated by reference in its entirety.
[001051 Water-soluble hydrotropes, sometimes referred. to as monomeric organic electrolytes, may also be present. Examples include xylene sulfonate salts, naphthalene sulfonate salts, and cumene sultbnate salts.
[001061 Enzymes may be presem, particularly when the. formulations are tuned for use as laundry detergents or as cleaners for kitchen and restaurant surfaces, or as drain openers or drain maintenance product.
1001.07) Applicants have found that a wide .range surfactant mixtures resulting in a wide range of Dnet values may be used. in many cases, the surfactants selected may be optimind for the solubilization of various water-immiscible materials such as fragrance OHS, sOlvents, or even the oily soil to be removed from a surface with a cleaning operation.

tlw cAses of the design of products which deliver ari antimicrobial benefit in the absence of a strong oxidant such as hypochlorite, a. germicidal quaternary ammonium compound or a salt of a monomeric biguanide such .as chlorhexidine or alexidine are often incorporated, and hence are Mcorporated intornieelles with polymeric- counterions. efine control (Wel-the SpaCing, between the cationic headgroups of the germicidal quaternary ammonium compound or biguanide which is achieved via the incorporation of a polymeric counterion can rest in a significant reduction in the amount of surfactant needed to solubilize an oil, resulting in cost redttetions and improvement in the overall sustainability of the .formulations, [00:1108) "In contrast to what is described in tile art, applicants have also found that the magnitude and precise value of P/Oriet needed to ensure the absence of rawipitates and/or coacervate phases can var3,-,- widely,. depending on the nature of the polyine.ric counterion and the .surfactaint seiwted to font the-mixed mieelles, 'Thus,.
since them is great flexibility in the selection of the polymeric counterion .for a given surfactant mixture to achieve a particular goal, applicant have adopted .a systematic, but.simple approach for quickly "scanning through" ranges of P/Dnet,. in order to identify, and to compare, formulations comprising. polymeric coons..
100109) The fonntilations comprising the mixed micelles of a .net charge and .a water,-&aluble polymer bearing charges opposite to that of the micelles. are taiefid as ready to use surface cleaners delivered via, pre -moistened nonwoven substrates (e.g., wipeS),. or as sprays in a variety of packages familiar to consumers.
10011Thl COncentrAted forms of the formulations may. also be develomi which may be dilutcµi by the. consumer. to -provide solutions that are then USed Conce.ntrated forms that snitable for dilution via automated systems, in which the cencentrate is diluted with water, or in .which two solutions are combined in a given ratio to provide the final use formulation are possible.
[001111 The formulations n11.1/.4., be in the form of gels delivered to a reservoir or surface with a dispensing device'. They may optionally be delivered in single-use pouches comprising a soluble film.
p801121 The superior wetting, spreading, and cleaning performance of the systems triake therri especially suiteble for delivery from aerosol packages comprising either single or dual chambers..
f00113] Vilhen .the compositions comprise chlorhexidine or rikxne salts as a cationically -charged surfacUtnt, the compositions may be free of iodine or iodine-polymer complexes, nanoparticles el silver, copper or zinc:, triclosan, p-chloromethyl xylem!, monomeric pentose alcohols. D-xylitol and its isonters, D-arabitol and. its isorners, aryl alcohols, henzyl alcohol, and phenoxyethanol.
WI. Suitable Nonwoven Substrates ille1141 Nlay of the COMpositions are useful. as liquids or lotions that may be used in combination with nonwoven substrates- to produce pre-moistened. wipes. Such wipes may be enaptoyed as disinfecting wipes or .for floor cleaning in combination with various tools configured to attach -to th=e 1001151 In one embodiment, the clear15'y.,: pad of the present invention comprises a nonwoven substrate or web. Ilte cleaning substrates can. be provided dry, pre-moistened, or impregnated with darting compsition, hut dry-to-the-touch. in OrIC aspect, dry cleaning substrates can be provided with dry -or -substantially dry cleaning or disinfecting agents. coated on.or in the multicomponent inuhilobal fiber layer. In addition, the cleaning substrates eau be: provided. in a pre-moistened aridtor saturated condhion..
The wet cleaning substrates can be mairnained over in a sealable container such as, for exar.nple, within a bucket with an attachable lid,.sealable plastic .pouches or bags, cõ.anisters jars, tubs and so forth..
ExamPles How Particle Size and Zeta Potentials 'Were Measortd 1001161 The diameters a the aggregates with the polymeric counterions (in nanometers) arid their zeta potentials were measured with a Zetasizer ZS
(Malvern Instruments). This instrument utilizes dynattlic light watering (DLS, also known as Photon CerrelatiOn spectroscopy) to determine the diatneters of colloidal particles in the ranp from 0.1 to I 0000 mil.
1:0011.7 The Zetasizu ZS instrument offers a range of default parameters which can be used in the calculation of 1.1artiele diameters from the raw data (1mc.5wn as the correlation function or autocorrelation function). 'The diameters of the aggre.gates reported herein used a simple calculation model, in which the optical proNrties of the aggregates ,ifere assumed to be slar to spherical particles of polystyrene latex particles, a cornmon -calibration standard used .for MOM complex .DLS experiments. In addition, the software paekne supplied with the. Zetasizer provides automated analysis of the quality of the measurements 'made, in the form. of "Exrert Advice". The diameters described herein (specally what is known as the "Z" average particle diameter) were calculated from raw data that met "Expert Advice" standards consistent with acceptable results, unless othenvise noted. In other words, the simplest set of default measurement conditions and calculation pantmeierS were used to calculate the diameters of all of the auregates described herein, in orcle,r to facilitate direct comparison of aggregates based on a variety of polyinerie counterions and surfactants, and avoiding the. use of complex Models of the scattering which ebedd cotriplicate or prevent comparisons. of the diameters of particles of differing chemicai composition. ose skilled in the art will appreciate the particularly sitnple aprroach taken here, and realize that it is useful in cotnparing and characterizing complexes of micelles and vatee-soluble polymers, independent of the detaiis of the types of polymers and safactants utilized to form the c-omplexes.
1001181 This instrument calculates the zeta potential of .colloidal particles from measurements of the eleetrophoretic mobility, determined .Via a. Doppler laser velocity measuretne.nt. 'There exists a relationship between the electrophoretic mobty (a measurement of the velocity .fa charged colloidal particle moyine::. in tin electric .field) and the zeta potential (electric charge., expreased in units ormillivolts)õ As in the particle size measurements, to facilitate direct comparison of Aggregatts based on a variety of polymeric counterions and surta.ctants, the -simplest sot of default measueement conditions Were Used, ìe.., the. aggregates were itg:StInied: to behave as polystyrene latex particles., and the Smoluchowski tnodel relating the electrophoretic mobility and the zeta potential svas usedin all calculations. Unless. otherwise noted, the mean zeta potentials de-scrilxxl herein were calculated -from raw data that met "Expert .Ativice" standards eonsistent with acceptable results. Aggregates bearing a. net cationic (positive) charge- will exhibit.
positive values of the zeta potential (in mV), while those beating a, net anionic (negative) Charge will exhibit negative values.of the zeta wtential. ìnmV), Example I
Ready to Use Disinfecting Spray Cleaner Formulation Mean Diameter and 7..eta Potential of Surfaetarit Tvlicelles With and 'Without Polymeric Counterion 100119) The interaction between mixed micelles comprising an amine oxide and two different germicidal. quaternary ammonium compounds and an anionic polymeric eounterion can be may illustrated by comparing the diameters of the mixed celks as measured by DLS) in the absence and presence of the .polymerie counterion. The aqueous control formulatiorta were prepared by mixing the gegnicklal quaternary ammonium raw material (supplied as aqueous solutions, Stepan Corp.) with the amine oxide .raw 'material (supplied as an Aqueous solution, Stepan Corp.) to form a mixed sur.factant stock solution.

.Appropriate amounts of the surfactant stock solution, ntonoeihanoiarnine (to adjust pH
above 9,0) and water were mixed to fonn the ftnat control formulatio.n containing the mixed micelles. in the case of the formulations comprising the .polymeric counterion, the same mixed surfactaa iztock soltaion, rnonoethanolarnine, .Alcosperset 747 (supplied as an aqueous solution, .Akzo Nobel), and water were, mixed in apropriate amounts to yield the .fmal formulations with different .PIDnet values, ha with the same mixed micelk cc.,..mpositions. The formulations., all of which were clear so/utions free of ctlacervate or precipitates., are summarized in Table 1,1: The measured values of the Z-average diameters and the zeta pk-nentials of die aggregates are -stiMtlifirizo.d in Table 1,2.
Table 1,1 Form-I Pdytnet. At 1 Gmxtieicial -homicidal Motiooth PrDne 1 Ettlet i ttitttion s Alcosixost Oxide, Qua:. Qt, tinplarnin t Name i a; 747 Ammonyg 111, incit = c, wt%
Hno, woi, 1210, svt:%-i 4. 2 I
Al 0.1- 0,36 I 0.1. 1 0 0,00099 I ................................................ i 4 ...... .,....- ,,,. ....
A2 0.23 1 õ 0.36 0,1 1 0 0.0010 I
.... _ ..,_...., ......................... i ..... ... _ A3: 0.02 (23I 036.
1 - . 0.1 - 0.1 0.00099 _________________________ ....õ ........... - ¨
A4 I 0,05 0.23- 0.36 . 0,1 - 0.00099 1 i 1 0,25. 4 ........................ ..
A5 I 0.02 023 - 0..36 I 0,1 1 -01 10.001 i e I
........................ -3---= ........ t .... i ...
A6 0..05 0.23 .., 036 _________________________ _.,4i i . __________________________________ 100120) Alcosperse31. 747 (Akzo Nobel) acrylic acid:styrene random copolymer supplied as aqueous solution (40 % actives) with Z -,. -1 and Eq polymer -0.005054 equivalents/gram of mlymer actives, 100.1.21 j BRA) 1010 quaternary ammonium germicide (Stepan Co.) supplied its aqueous solution (80 % actives) described as didecyl dimetby1 ammonium chloride, average molecular weight 362 grams/mole, Q - 1, [001221 BTCO 1210 quaternary ammonium germicide (Stepan Co.) .supplied as aqueous solirtion (80 A- actives) described as a Mixtvre of didmyi diethyl arnmorinim chloride and n-alkyl (50% C14, 40% C12, 1014C16) &methyl beazyl ammonium chloride, average molecular weight 360.5 grams/mole, Q=1, Table 1.2 FOralulation PiDnet Z average diametrA Mean zeta Com:meats Name rap ......... petemialt ..
I Al 0 1.032 +36,6 Mieeilar aggregate control I
A2 0 1.006 7+32,6 LMicellar agivegate control I A3 - 0.1 76.08 +56.8 With poiymeric counterion A4 - 0.25 83.13 1 +51:8 With polymeric counterion A5 0.1 79.14 1+50.0 = With polymeric counterion A6 0.25 92.57 +50,5 With poiymeric counterion [001231 The results in Table 12 -indicate that the .micellar aggregate controls at were around 1 11M in diameter, which is an expected size range for mieellar :aggregates r_ns ionic surfactants in aqueous solutions. 'These results suggest that the default panuneters selected for calculation a the diameters .from the 1X.õS
measurtments,õ as described tame, were reasonable, and. thus could. be used for comparing Changes in -diameter due to. the interactions Ivtweert the micellar aggregates -and .the polymeric counterions, 100124i Since- these aggregates calliprised mixed micelles of art amine 0.:ide sUrfactant, which is bxpected to. be uncharged at the high pH of the formulation and a, cationic, germididal quat,. a positive mean zeta potential- is expected and is obserml for the two control systems coMprising the -two distinct germicidal quaternary,' arrunortitun compounds.
[001251 The addition of the water-soluble anionic. polymer Alcosperse 747 to the formulations at ','net values of 0.1 and - 0.25 yielded clear solution.s that were free of coacervate. me strong electrostatic interactions between the polymer and the mixed micelles result in the fonnation of stable aggregates that are muCh larger in average diameter than the micellar controls, but which are still small enough to exhibit colloidal stability and a clear appearance. Increasing the absolute value of.ì>/ì.net from 0.1 to 0.25 correspo.nds to moving closer to the lower boundaiy of the coacervate region for mixed micelles of this composition and at this total surfactant concenn-ation, and hence the average diameters measured increase somewhat.

[00126] In order to test whether these larger aggregates comprising mixed micelles and the polymeric counterion were stable structures, repeated measurements of the aggregate diameters were made on undisturbed samples held in cuvettes in the instrument, every 5 minutes over the course a about one hour. Thin, any growth in the aggreeates, which might lv a precursor to rxmcervate or precipitate tb3ination and which would be less obvious than the haziness of samples detected visually: would be detectable frnm a trend in the Z-average diameters over time. No such trends were detected for samples A.
through A. All of these samples exhibited. relative standard devons of the Z-average diameters of less than 1% from the 11 sequential measurements rnade. The erage diameters for these samples, based on I measurements each, are those reported in Table 1.2, [00127) Since the aggregates. with-the polymeric counterions v,,ere formulated- at:ari absolute vahie of}VD:net < 1,0, the number of cationic charges provided 1:ry the germicidal quaternary ammonium compound in the :mixed micelle.s exceeds that of the anionic charges provided by the anionic polymer, and the stable colloidal aggregates formed would be expected to. her a.Piet CWiMIC Charge and hence a positive zeta potential. Table 12 shows that the aggregates klarmed with. the -polymeric counteriort have mean zeta potential values that are positive, even somewhat greater than the micelles alone, consistent with the -formation of distinct,= tunable ag.gregates. which cannot he formed without the use of a polyrivric counterlon, that is, that cannot be formed at the same total surfactant concentration and the sarne mixed micelle compositiona when the native counterions of thecationic: surfactant the gertnicidal quaternary ammonium compoUnd), 'here Chloride ions, are the. only ones present. A conservative estimate of the preon of all of the 7.,eta potential measurements referenced herein is about 0% of the reported mean value<
Example 2 Ready to Use Disinfecting Cleaner Lotion Suitable for 'Delivery from a Nonwoven Wipe Mean Diameter and Zeta Potential- of Surfactant Micelles Without and With Polymeric -Counterion A.t iow Y values [00128) A -series of formulations were prepared in the same manner as in Example 1: at a lower relative concentration of the germicidal quaternary mmonium comrxmndìn the mixed surfactant aggregates. Formulations irsin g these mixed Micelle compositions are suitable for =use as lotions which can he loaded onto nonwoven wipes and provide =

conve.nient disinfection of hard surfaces combined with gowl cleaning of greasy soils, all without the requirement tbr the addition of volatile organic solvents such as lower alcohols or glycol ethers. The formulations comprising the polymeric counterion were clew and I'm -of coacervate when the absolute value of ND/nu WM leSs than 0.30, according to an inspection of a series of samples covering a range of this parameter between 0 and 0.5 at this total surfactant concentration arxt micelle composition.
Table 2,1 I FiXTti- i Polymer Amine i Ciermieicial 1 Germieitial Mottoet P/Dnet D net ¨I
ullaion I A lonsperse Oxide, Quat, at. ha3101a111 paratneter Narne ' * 747 Ammonyx BTCO Bite inewt%
A7õ 2.03 0.36 0.1 0 +0.00099 i ........................ I---,- _____________________ , ..
A8 ... i 2.05 - Ø1 0 ........................ 4 .... .¨J, .....
A9 0.002 2.05- 0,36 .. 0.1 -0.01 +0.00099 1 .
, 4 ................... 1 .
A 1 0 0.02 i 2.05 0.36 s, OA +0.00099 i ...................................................... 1' I
i , . ..
All 0.02 2,05: ., 0.36 1 0.1 -0.1 1 +0,001 .............. . , Al2 0.05 2.05. -I0.36 -I 0.1 -0.25 +0.001 I .....................................
'Fable 2.2 IForm- I PiDfie. 7, average diameter, Mean zeta potential, ' Comments i Illation I 11111 #TIV
i Name . __ ' A7 0 2,505 (n=5, 2 +6.91 Mieellar aggregate control.
I
!preps) ¨4 ..---4 A8 0 2.417 or---6, 2 'Net measured Mieellar aggn,'.'gate control preps') ............................. , A9 -0.01 3.266 (n..3) +9.31 With polymeric counterion Al 0 -0.1 3,298 (n-3) +7,99 With polymeric counterion . =---1 All -0.1 I 3.114 (rt:::3) +4,18 With polymeric counterion ............ ! ..
Al2-8.25 1 3.680 (11=3) 44.69 With polymeric counterion , f001291 The results in Table 2.2 shovv that, rri this total surfactant concentration and mixed mioelie COMpOSitiOTI, the mixed micelles ttre somewhat larger than those formulated with the same quaternary ammonium compound and amine oxide as shown in Table 1, Without being bound by theory, it is believed that as the relative amount of quaternaty arrimonium compound in the mixed micelles decreases, an effet,-tive dilution of the charged quaternary Compouni headgroups in the micelles occurs due to the additional numbers of amine oxide molecuies, svhich allows greater averag.e spacing between the charged quaternary ammonium compound headgroups and a growth M the average micelle diameter. Also, due to the lower average number of qurnernary arrimmiunt cornpound molecules present- in the mixed aggregates, the measured mean ztta potential is reduced, but is confirmed to be poshive, i.e., cationic, as expected.
[00:130j The results in Table 2,2 also indicate that the addition of an anionic polymeric counterion a PiDnet values that do not cause formation of coacervates results in aggregates -whit* are. sigcantly larger than the micellar controls, but still small enough to exhibit colloidal stabilhy. The relative standard deviations of the measured Z-a.verage diameters of each of the fOrmulations viereagairt found to be less than 1.0%,-even 'When multiple preparations of the same compositions were ptepared on diffetent days, .and hence the differences in diameter be.tween the control tbrmulations arid those comprising the polymeric counterions may be considered detectable and significant [801311 The remits in 'fable 2.2 also indicate that the aggregates formed with the addition of the anionic polymeriC counterion,. at absolute -values of P/Dnet less than 1.0, exhibit a >otzitive(eationie) zeta potential,. as expected.
[001.321 Thus-, the addition of a polymeric counterion 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 eisewhere herein, such aggregates -exhibit sinprisirigly good antimicrobial performance, across a range of microorganisms, without requiring volatile organic materials such as alcohols or glycol.
ethers to boost or "potentiate" the -action of the quaternary ammonium compouhtl. It is believed, without beirtg bound by theoty, that the aggregates comprising polymeric counterims ear more readily act at the solid -liquid interface, including that of microbes..
enhancing the delivery of the germicidal quaternary ammonium compound and thus enhancing antirriicrobial efficacy.
Example 3 Ready to Use Disinfecting Cleaner .Lotion Suitable tbr Delivery .frorn a Nonwoven VVipe Mean Diameter and Zeta Potential of Sur.factant Micelles Without and With Polymeric Counterion At absolute values of PiDne >

100133] A series of formulations were prepa.red in the gime manner as in Example 1, at a constant mixed micelle mnpositiort and Drtet value which are suitable for use. as lotions which can be loaded onto nonwoven wipk..-'s or used as a ready to use spray cleaner with excellent hard surface %vetting propertie.s in the absence cgs volatile organic solvents such as alcohols or glywl ethers. The formulations comprising die polymeric counterion . were clear and free of coacervate at absolute values of PIDnet greater than 1.3, determined by an inspt..ction of a SefiCS of sairtples coverina a wide rag: of the absolute value of Moe between 0 and 2.0 at the total sur.factant concentration, 1.'he addition of the anion.ic polymeric counterions to the mixed micelles containing a quaternaty ammonium compound provides a mechanism to tune the. solubilization efficiency of µvater-inuniscible oils, through adjustment of both Dnet and the absolute vaitie of .P/Dnet.
l'able 3.1 riFortn- 1 :Pelyrner 1 A/1*W Oen/1101:M 1 Lireortm. Moneeth i PM D
.net Illation Ako.speme i Oxide, Qaet, I e.. wt% ai30111311in. 1 :1'W
Name * 747 I
Ainme. nyx11 BT('', ' 1..0, t vit'34 MO, kke% l I 4.., iki%
:
........................................................ .....1..... .
A 1 3 - 0.785 0.122 1 0.1. 0 I
+0.00033 i 7 ...................... t .......
A14 01. i 0..785 0.122 0,2 0:1 -1.50 +0.00033 __________________________________________ .4..
A150.1 0.122 ,. 0.1 -1.50 +0.00033 I LØ785 ,-/
....................................................................... i /
..................... ¨ J. ____________________ ¨, ..
Table 31 For- PAD net Z average diameter, Mean ma. Cogurkent$
ulatien nr.$ potential, trii/
Name Al 3 0 2,221 +7. 34 Micellar aggreaate control ' Al 4 -1,50 9.1.02 (n=5) - 2.31 With polymeric counterion Al5 1 -1.50 9,732 (n=4, 2 i -11.1 'With polymeric counterian 1 1 .1)1vPs) 100134] The results shown in 'fable 3.2 show that, at absolute values of 'Mite ereater than 1.0 and outside the region in which coacervates are .formed for this system, stable SOitIble aggregates are formed with the addition of the anionic polymeric counterion. 'The aggregates have somewhat larger Z-average diameters relative to micellar aggregate controls formed in the absence of the polymeric counterion. Addition of a significant amount a lirrionene, which is both a model fragrance oil comporierit as well as a model hydrocarbcn. solvent, to the aggregates eomprising the polymeric counterions readily achieved at the same PiDnet value as in the absence of the lirrionene.
Thus, the aggregates comprising the mixed surfactant and the polymeric cotinterion are capable of solubilizing svater-irisoluble materials such as liniment. It is believed, without being bound by theory, that the solubilization of limonene in the aggregates with the polymeric, counterions is possible Imause the aggregate structures inaintain a ploperty of ordinary tnixed micelles, i.e., a non-polar interior in which water-insoluble materials may he solubilized, even in the gaesence of the polymeric counterions, Example 4 Nintable Disfecting Foimulations 7:-.Average Diameter with and without Poirrieric Counterions of Diluted Forintilations IN 1 351 The addition a polymeric courderions to formulations eon/prising inixW
micelles of a.gertnioidal quateniary ammonium compound. and another surfactant provides cOncentrates 'which can. be. diluted either manuelly-or via the use of mt automated dilation -appannus to provide economical disinfecting solution& The enhanced wetting properties of the .formulatioris comprising the polymeric counterions, in the absence of volatile.
organic materials such as lower alcohols or glycol ethers,. provide excellent performance with a minimurn of .residues, which is of concern, fOr example, in floor.cleaning -of health care .facilities and the like..
too1361 In the. first step,. the appropriate PIDnet range for the concentrated formulations was determined, with different gennicidal quaternary -ammenirn eompound at an amine oxide surfactant mixture. The concentmtes also comprised tetrapotassium ethylenediamine tetraacetate a COMM011 chelant and buffer useful in controlling the effects of common tap vvater used as a diluent, arid Naa as an elamtilyte. Multiple concentrated tbrmulations which wem clear and free of eoacervate ate identified through the adjustment =
of P/net and Naa level.. Formulations suitable for dilution at a rate of 1:250 by volume are then idented through visual inspevtion. Formulations which appeamd to yield clear, soluble solutio.ns free of coacervate phase when diluted were then analyzed via ì).S to elmifirm that the aggregates comprising polymeric counterions fonned by a simple dilution process had diameters in the range expected to provide colloidal -stability, i.e., Z-average diameters los than 500 tun., as measured as described herein. The anionic polymeric counterion in these exaMples is Versa-110 4 (Altzo Nobel), described by the supplier as a=
random copolymer of sulfonated styrene and maleic anhydride, which is supplied as an aqueous solution at 25% activeS at pH 7.0, vyttich means the anionic sulfonate groups are .present in the salt form,. and that the maleic anhydride has been hydrolyzed to m.aleic acid via MtK:tiori With Water, and the acid groups are present in the ionized (salt) form. l'he nominal molecular weight of the potymer is described m. 20,000 daltos. The total number of anionically charged groups on this -polymer yields' 0.006427 -moles of anionic groups/gram of polymer solids, and this was used in the ealctilation of the PIDnet values listed below.
Table 4.1 - Concentrate Formulations. at Constant Y .:0.5 Farm- Polytne Mane. i Gamic Gamic- 1(.; NaCt Pintlet I Clear, (lair -1,ft:ion r Oxide,: 1 idal itial Farr , 1 61.iblt diluted Name Vema- Ainny Q. Ql.lat, A. iAit% z ConCe13 whition?
11A 4 xtV1.0, EVIX.A.: IfIrit wt% trale? YIN or - i AA% wt% 815.8 1210, YIN not lt,steõki Al6 - 4.08 I 6.4 . 1 1..0 5,0 0 Y . Y
................................. ti ..
i _____________________ -A17 - 4 .07 -i l&4 ' Y Y
..t ....................... 4 ..............
1 A1S 0.137 4.08 1 6.4 1 - 1,0 t 5.0 - 0.05 Y N
A.19 0.275 1 4.08 1 C4 11 1.0 5.0 - 0.10 Y N
_____________ -4 .. i-A20 0.4/ 2 4.08 i 6.4 I - 1.0 5,0 --OAS Y N
i 1 --1- ............................ . ..
A2.1 0.550 1 4.08 1 6.,4 1. Y N
............. t .... 4. ________ , ...
A22 0.688 4.08 6.4 i - .1 :.0 5.0 -&)25 Y N
__________________________ --t ................................ i A23 1.375 4.08 6..4 - 1.0 1-5.0 . - 0.5 Y ., ................................. 1 A24 2,75 4,08 6.4 .. r1.0 5.0 =[-: 1.0 N.' ., : ______________________________________________________ - .....
A25 344 4.08 + 6.4 . - 1 25 = i -- " :
............................................ 4 ...........
.A26 0.137 4,08 6,4 .. - 1 5.0 = -O.0 IN .
................... -+ .......................... 4 ...........
A27 0.275 4.08 6.4 . - 1 50 - 0.10 . N
- ..................................... i ..
A28 0.412 4,08 C4 - 1- 1 5.0 - 0.15 N ...

4- ................................................ 4 ........
A29 0,550 4.08 6.4 .05.0i= - .20 N .
__ ...............L. ............................. 1 . .................. 1 0,068 4.07 .. ,. 6.4 1.0 t 5.0 i - Y
Y

1 0.025 i A31 0.117 4.07 i -.................... 1 .... 6,4 1.0 5.0 t - 0.05- ' Y Y
_____________________________________________________ --t--:.
A32 0.275 4.07 1 - 6.4 1.0 5.0 -0õ10 i Y N
1 I i A33 íSAIJb 5.0 1- 0.15.
{N
A34 0.550 4,07 6.4 1..0 5,0 I -8.:0 Y
A35 0.068 4.07 6.4 5.0 -0,025 A36 0.137 4.07 6:4 3.0 -85 N
A37 0.275 4.07 6.4 5.0 *70.10 N
A38 1 0.412 4.07 6A 58 A39 110.550 4,07 - 6.4 - 0.20 N
_________________________________________________ -L-100137] The results ì able 4.1 illustrate thut multiple concentrate formulations which are -dear and free of eoacervate (A18 through A24) comprising the anionic polymeric counterion are .possible, even. up to absolute- values of PIDitet I.0, w.hen .sullicient total electrolyte (NaCI and KtEDTA)-is present. Form.ulations A16 and. A.17, in %vhich PiDnet 0 acted as Micelle controls, It iS believed, without being bound by -theory, that the interactions lletween the polymerie µsounterion and the MiXed micelles comprising quaternary ammonium compound and amine oxide can be adjusted thrOugh the .addition orditrary electrolytes like NaCI and K4FDTA, which partially -screen the charges on the soluble polymetic cotmteriorts from the opposite eharkges art the Mixed micelles, andior conmete With-the polymeric counteriorts for the oppositely charged quaternaryamatonium compound molecules in the -mixed Micelles. When the absolute value of the PiDnet parameter is at or near 1.0, the number of anionic: charges present are exactly or nearly sufficient to completely neutralize the cationic charges due. to the .gerrnicidal quaternary ammonium compound, which would he expected to lead to the lbrmation of coacervates or precates. SurpriSingly, however, the absolute liable of PiDnet alone is not a reliable nuide fku. avoiding coacervates or precipitates in tile formulations. Instead;
for a given desired PsDnet value, a given mixture of germicidal quaternary ammonium compound and another, uncharged surfactant such as an Artlint (vide, the cementation of electrolyte or mixture of electrolytes needed to prevent the formation of coac-ervates or precipitates; can be readily, and systematically determined.
[00138) Formulations A26 through 29, for example, can be compared with- A8 through A21, all of which cover a range of the absolute value of P/Dnet values less than M. which is of interest for lower total actives and hence lower cast.
Pcirmulartons A26 through A29õ have ail inStIffitiellt total electrolyte level due to the elimination of K-sEDTA
without an increase the. NaC1 concentratiom and hence are riot clear solutions which would not be suitable candidates for a concentrated formulation.
/00139) Sa.rly, Fonnulations A$0 through AM, in which a different germicidal quaternary amin011lUM compound is used, are acceptable concentrate candidates.
By comparison, formulations AS through A39, in which the to electrolyte conmtration AILS again reduced via elimination of K4 31A. ale not accer3table concentrate candidates, since none of tiltin were clear solutions, but in fact exhibited cloudiness due to the presence of coacervates /or precipitates.
(001401 in a second step, the behavior tpon dilution in vrater of the stable concentrates was evaluated. A sample of the concentrate (40 riliCMliteTS) Was added to 9.96 ml of v?ater coritro1kx1 hardness (representing the 1:250 fold dilution .rate of interest for this application) in a .capped vial aM mixed via ?llama!.
agitation for a few seconds-. The diluted samples Welt -Visually evaluated for cloudiness, haziness, or the presenee of precipitates immediately. Formulations .A30 and A31 are e.xamples of co:ncentrates which, upori dilution, form clear solutions that are free of coacervates or precipitates. MS was then tisedtoconfinn the presence of stable aggre.gates cmnprising the mixed micelles and the polymeric counterion, in comparison to m: ixed micelles comprising the sanle quate.rnary ammonium -.compound and amine oxide:
.surfaetant without the inAymeric counterion.
Table 4.2 --- Characterization of Diluted Formulations Prepared from Concentrates.
Form-'IEn Tz. average I Mean 2gia et3mments ulatiort diarnetty, potential, =
Name mV
A1.7 = 0 5.141+12.5 Control no polymeric counterion -- diluted in hard water (I:25 dilution) A31 - 0.05 167.7 (n=5) +44.5''it h polymeric. counterion diluted. 1:25) in hard water --....................................... freSh sample 4 ...... ".^^1^- __ A31 - 0.05. 1.78.7 (n=5) With polymeric counterion ....................................... diluted 1:250 in deionized water A30 - 0.025 136.8 (n.:5) With polymeric counterio.n ¨
diluted 1:250 in .hard INater fresh sample A30 - 0.025 140.0 (n..5) With polymeric counterion ¨
dilated 1:250 in hard .$vater aged 6 hours .......................... _J
*Synthetic hard water used for dilution.-...ontairied calcium and magnesium i.01/S-a a 3:1 mole ratio at a total concentration of 150 ppm.
[001411 'The results in Table 4.2 indicate that the Z-average diameter oldie micelles in the contro/ sample is significantly less than that a the formulations comprising the SEIM µ..ationie micelles and tie. anionic polymeric counterion. It should be note.c1 that successful DLS analysis of the micelle control fomtulation required that it be diluted only 'by a factor of 25,, in order to ensure an adequate and teproducible level of scattering. The amount of scattering from colloidal particles in tile DLS experiment is a fitnction of the average diameter of the particles to the sixth power, or proportional to (diameter)6. Thus, small increases in the average diameter result in very large inermses in the amount of scattered light, which in turn allows the detection -arid analysis of larger particles at much lower concentrations than smaller particles.. That ex;)ected trend is consistent with the measured diameters of the aggregates formed.upon dilution of t'orroulations A30 and .A31.
The results .also indicate that the quality Of the water did not have a large effect on the average diameter of the aggregates of fommlation 31 formed -upon dilution, R01.42 j In Table 4.2,'.fresh sample means that the first DLS analySis of the diluted sample was conducted within 10 minutes of the initial dilution step. Multiple .replicate measurements of the same sample (typically 4 or 5, as indicated:)- were usually mtkde.
Replicates could typically be hulloed. within 2,3 minutes of each other. The stability of th.e aggregates formed upon .dilutior./ of Formulation A30 was also checked.
by analyzing the same sample that Was allowed to age ..6 hours. in the instrument. The results indicate that no significant change in the X average diameter of the aggregates in the diluted stun* was observed, indicating that stable structures ar.e formed. immediately t4XIII
dilution of the concentrates, without need of any special pnvessing other than simple mixing.
[001431 The results in Table 4.2 also indicate that the zeta potential of the diluted sail:tole of the control micelles is positive (cationic.), as expected.. Since the absolute value of PlOnet for Formulation A31 is 0.05, i.e., significantly less than 1.0, the zeta. potential of the stable, soluble aggregates formed upon dihation is expected to be tmitive (cationic), and the measured result confirms this, at +44.5 mV.
fil01441 The tx.,sults in Table 4.1 and 4.2 also indicate that systematic adjustment of the PiDnet parameter and the electrolyte level (and, if desireti, the mixed micelle =
composition) may be used, with initial visual inspection, to identify concentrates whia, upon significant dilution., deliver stable, soluble aggregates comprising mixed micelles of a germicidal quaternary ammonium Millp01.111d and a second surfactant and an anionic polymeric counterion, in a solution free of coacervates tr precipitates.
Example 5 Formulations Suitable for Deliveiy from Nonsvovens Control a Micelle Interactions with Polymeric Counterions Over Wide .Ranze (AP/Dile The pH of the aqueous formulations comprising mixed micelles with a cationic charge and an anionic polymer nut), be adjusted over a wide range, providing tile polymeric counterion nu:din:aim its solubility in wate.r at the pH. of interest.
1001451 Thus, a series of aqueous fortrailationg in which the pH wits adjusted to about pH 7,6 were made in order to corrfimi the absence c3f.coacervate font:Ado/1 across the Plato: range of interest.
[00146j Sainples were prepared by making the follosving stock -solutions;
(1) 0,33 wt% MEA and 0.52 weii, glycolic acid at. a pH of 6,9, -(2) .1.2 wt 4 BT.V*
1010. and 6,8 .
wte/oAnntionyx0 1..0 at nan ital pH, and (3) 1,5 wt% Alcospersee 747 .adjuSted to pH 62 with glycolic ar..:id. The MEAlglycolie acid stool,: was the.n diluted in the proper amount of water followed by addition of the BIC* 1010/Arnmonyx* 1,0- stock and finally the.
Alcosperst-0 747 stock.. Final pH was measured and found to be between 7.6 and 7,3 f:*
these. formulas.
Table 5õ1 - Compositions suitable for delivery from nonwovens Fprtnulatioti 111101t). ' AmmonyØ0 .AkospetWgi I M8A
Cilys.I.lic pH
Name i IOW IA) wit% 747 I vet% acid, wi% I
................... 4, y=a%
B11 0.36 1 2 05 0.005 0-.1 0.1.6 4 7,6 .
........... 1 . .
B2 I 0.36 2.05OA
0.01 t ___ 0.16 1 7:6 i 1 ..
-17=B3 I 0.36 i 2.05 0õ02 0.1. 0,16 7.6 ! .............................
B4 ......... t i 0,36 F25.0 -,, 0.1 0.16 i t.6 B5 i 0,36 2.05 0.03 0.1. 0,16 1 7.6 1 ............................................................... i B6 0.36 2.05 0.05 0.1 0.16 7,5 !.Lii_ 0.:46 .1.05 0,1 0.1 --. .
B8 0.36 85 0,2 0.1 0,16 7.5 1--- ,-, i B9 0.36 2,05 0.25 0,1 0.16 7.5 1 ,...
B10 0.36 2.05 0.3 0..1 0,16 7.4 1.... õ...._,1 .......................................... -- 05 2.
811 0.36 0.32 I 0.1 0.16 7.4 B12 0,36 2.05 0,34 18I 0.16 7.4 i B13 0,36 2,05 0.35 = 0.16 7õ11. ' 814 0.36 2.05 0.37 T0,1 0.16 7.4 .......................................... -1 ................. -"B15 0.36 2.05 0.39 1 OA 0.16 7,3 i.........._ ,.... ______ i 1 B16 0.36 2.05 L0.49i 0.1 1 i .
Table 5.2 --- Characterization of Cationic 'Micelles with .Anionic Polymedc Counterions a ptl 7,3 to pH 7.6 1 Fonnulation WD net I Z average diameter, i Name .......................... nm t...!_.=
Bl -0.(n5 2.998 L_ .................
112 -0,05 3.197 113 -0,1 3.613 .... ............
134 -0.125 3,836 B5 -0.15 4.009 B7 -0.5 7.8,5 .118 -1,0 12.76 . ...................................................
89 -1:25 23.96 B10- 1 -1,5 26,62 Bil - ........ ,1.6 . 29.47 20.84 B1 a =.I.8 36.15 Bi4 -1.9 23.97 B15 -2M 725,66 ............................... t .............
B16 --2.5 i 36.62 ,.. .................... ., ....................... .
1001471 The visual inspeetion of the formulations in Table 51, comprising cationic .mixed micelles and an ani0J1k polymeric counterion indivne that clear, stable solutions were produoed across a range of the absolute value of PiDnet from less titan to significantly greater than A. In order to confirm the absence of small amounts of coacervate phase, the Z-average diameters of the series of samples Wi.lf.:
also measured.
The msults in Table 5.2 indicate that-the binding a the anionic poiymeric Cfnmterion to the cationic mixed micelles results in aggregates that ate all larger than mixed micelles of the same composition without the polymeric countcrion. The Z-average diameters of the micelles with polymeric counterions were striall enough to exhibit excellent colloidal stability. Leõ the diameters found %van < 500 run, and more preferably <100 tun.
Example 6 Stability of SiZe of Catimic Micelles with Anionic Polynnerk. Counterions at ./net >I
1001481 The absence of coacervate or precipitate phases from formulations prising micelles with polymeric counterions 'nay, in general, be readily determined by visual munination of samples made em the scale as small as abotit 10 to 15 1 in capped test tubes. As taught herein, cationic mixed micelles with an anionic polymeric counterion also exhibit the important property of solubilization of water-insoluble oils wh.en :coacervate or precipitate phases are absent, and this sOlubilization may also be evaluated through visual inspection of sari:toles. The absolute valueof the PlDnet parametet cannot be used alone to determine tbrmulations %hid) are free of coacervates or precipitates, but instead must be cortsidered together with the mixed Micelle composition and the type of water-soluble polymer selectg...d for use as a polymeric counterion. In order to avoid coacervate and precipitate phases, the polymeric eounterion must be soluble in aqueous compositions at the .p1-1 of the desired final. formulation. The solubility of polymeric counterions in aqueous compositions may also be readily evaluated through visual inspection .techniques. Thus, for example, the .solubility in water of Alcosperset 747,. a random copolymer, AquatreatV. AR-4, an acrylic acid honopolymer, and AlcoguardW
5240, a random graft eopolymerõ all of which contain carboxylic acid grotys,.
ma3.., compared over a range of pH values and .any polymer whichdoes not exhibit the neces9ary solubility at the pH of interest may be avoided, 1001491 Formulations comprising cationic tnicelles and anionic polymeric counterions tilat are free of coacervate and precipitates with the. absolute value- of the PIDnet parameter >I. can also be readily identified, for example, fortnulation BIO iri Ex.atriple 5. In addition to the visual inspection of this sample, which indicated it to be free of coacervates or precipitates, DIõS as used to monitor the Z-average diameter of these aggregates upon overnight aging to confirm their stability. Leõ as an alternative method of ensuring that the aggregates remained fine of coacervateaõ
1001501 'Thus, .formulation B10 was placed in a sealed euvette and a measurement of the Z-average diameter was taken every 38 minutes over a 1.15 hour .ileriod, with the ternptiatint emit:tolled 2,5`1;..Such a :pracf",(tWe 1My be. readily accornplishp4 with the Mal,sern Zetit SLter .tise& .and thoge skated in the at will realize that egaiyalent ni:easilrknAtn0 ht dittcle: :with dther instinments, Thei rewit$ tbi,s experiment p.re Wicrwri In Table 6, Table:6 Z avetagedlatnetoí Aggsgoo:COMptiktgr4.1tienie MiCtlIQS and Anionic Polyinetle oinitdriPri RA11)410 11 B10 StOradrgk Age pc:Sample, 7,-,4yetage dometer, hours .....
0.5 2196 23.61 Z!3.77 2 2343.
2.5 23;86 3 23,47 '3,5 4es 4 23,71 4.5 23.0i

5 24..04 5,5 24.44

6 24 2.2 6,5: 24,35

7:
7,5: 23:33 23.64

8 23.47.
8.5 24..37

9 23,19 9:5 24.33

10 23,67 24.19:
i 23,34 ............................ L__ r-- '11.$=
23.6 2 23:79 12,5 23.8' 13 23,97 3.5 25.01 Overall mean Z-average diameter:, nm 23.9 Relative Standard Deviation Of Diameter, %i. ............................... 1,73 ....
1001511 The results in Table 6 indicate thatthe Z-average. diameter a Formulation Ell 0 appears stable,. with a relativettandard deviation of less than 2% over a 13,5 hour period, confirming COTICitaions made with visual inspection of the salt*. The results also indicate that stable formulations free of coacervate and preCipitates with the absolute vable o /Dnet > I, comprising cationic micelles and anionic polymeric ttOtinterions nay be made, .Exa.mple 7 Formulations Suitable For Delivery from Nonwovens or as Disinfecting -Spray -Cleaners Acidic 10015.21 Forinulations comprising th.ixecl rriicelles of a germal quaternary ammonium compk-mrid- and. an amine oxide rimy also comprise adjuvants or butlers which can i)te used to adjust the pH. In these examples, monoethanolamine (MEA) was used to increase the Of of the tbrmulations. and glycolic ae..id was used to decrease the pH of the . fo:rmulations. Decreasing the pH of si.teh formulations may be .desirable for increasing certain aspects of cleaning performance, tbr example, the dissolution of hard water spots from sinks. tiles, dishes,. etc, The inactivation of certain viruses and bacteria is also known to improve when the pH is demasM below pH 7, to the acid pH range, (.7ertilin other aspects of cleaning pemance a 4111:ille oxides, such as residue deposition on hard surfaces which results in filming or streaking, and dmrea.sed ability to soiubilize greasy soils tend to be exacerbated as the pH of the firmulations is decreased, especially below pH 7. Surprisin.gly, the use of anionic polymeric counterions in formulations comprising f...,,enrticidal quaternary ammonium compound and amine oxides improves the wetting propetties of the formidations on a range of surf-skit-es, while decreasing residue formation.
Thus, the addition of volatile cosolvetds to the acidic formulations to improve performance properties titay be avoided wbert rtolytneric counterions are utilized.
[00153) In this exam*, the water soluble polymer (Alcoguarde 2300 from Akzo Nobel) Ik'as a random copolymer of the noilionic monomer dimethylacrylarnide (5 mole%) and the anionic monomer acrylic acid (5 mole%), which thus provides moles of anionic grovps per gram of polymer actives. This polymer is soluble in water at both low pH, e.g., pH 2.0, and high. pH, e.g., pH 10, and can. thus be employed as the anionic poiymeric counterion to mixed micelles of the germiCidal quateniary ammonium compound BIC4D 1010 (MW -=. 362 femoo gind the arnitle oxide A.mmonyx101,0.
100154) Vistsal inspection and DI.S were Lind tO determine the .formation of stable aggregates, the compo.sitions of which are stIrignarized in Table 7.1. In Table 7.2, the Z.-average diameters. art StlitiMarized,, and -indicate. the aggregates- formed as much larger than mixed micelles of the germicidal qttaternary ammonium compound and arnirte oxide in the absence of the polymeric counterion. PIDnet was catculate.d based on characteristics of the polymer and BIC 1010 quaternary amn/onitun compound.
Table 7.1 - Compositions 'Formulation .-1-1TCZ .ArnmortyxV ' Aeoard T2A Glycolic i pki Name 1010 LO wt% 23130 Avt% acid, witY6 wt% 1 wt%
I-C.1 0,36 0.23- 1,17 0,1 I 0 9,4 I ..............................................................
C2 0.36 0.23 i 1.01 0.1.1 rI0 1 9.2 i .
.................................................. i .....
C3 I 0,36 0.23 I 1.01 0.012 I 0.01 4,74 : ................................... 1 ...
e4 ' 0.36 0.23 I 0.78 0.009 0,01 4,87 ___________________________________________ t I
C5 .().36 0.23 o.23 t I o.828 0,01 5.4 -1 ........... 1- ............................. I
C6 . 0.36 0.23 I. .01 3,56 0.1 9.35 t C7 0.36 0.23 1 1.01 ()M2 0 1 i . - 4.73 C8 0,36 0,21 0.78 0,009 0.1 I 4.8 .......................................................... i ...
1C9 0.16 0.23 023 0.003 f(.

L ___ Table 7.2 - Characterization of Compositions Formulation T pale ] Z a yerage Comments 1 Name ' diameter, rim __ CI -1.5 26.33 "Iriaily clear ...................................... 4 ............. =.^..^.1 C2 -.1.3 25.98 i visually dear ...................................... I
C3 -1,3 3091 1-Vienally clear I
....................................................... t i C4 -1.0 24.88 Visua/ly clear ...................................... i __ 4- .................................................... 1 C5 -0.3 15.13 I Visually dear ;
....................................................... I
C6 -13 28.93 Visualiy clear ....................................................... 1 I 64.1. Visually clear 1 i.
CI 8 -1.0 I 31,11 ....... a Visually dear , l i 1.-F--- ............... 4 ...
I C9 I.-0.3 1 16.51. Msuaily clear i ...................................... .. ........
Example 8 Formulations Suitable For Deliver:,/ from Nonwovens or ss Disinfecting Spray Cleaners Acidic pH
(081551 Thi& example shows some addonal aeidic fonnulations.uskg mixtures of arginine, an ami.no acid, at d. glycolic acid to adjust the pH.
100156.1 Visual. inspection a to were used to determine the tbrination of: stable aggregates, the convositions of which are summarized in Table 8.1. In 'Fable 8.2, theZ,-average diameters are summarized, aM indicate the a.ggregates famed as much larger than mixed micelles of die germicidal quaternary ap111104111;1111 compound and amine nide in the abserice of the polymeric cow/tenon. P/Dnet was calculated based on characteristics of the polymer an1li3TOV 1010 quaternary ammonium compound, Table 8.1 - Compositions irTi-Trmulatkin IBM& Arnmonyxe AloogmardOD 1 Arginine Glycolic 1A-1 i -i Name i 1010 1,0 'ît% 2300 I wt.% acid, wt% ................................................... vvIii ........ _i___ r _ - .. i 1 CIO i 0.37 0. 523 0,088 I 0,174 0.08 .................. a ......... -4 ..
I Cli 0.35 I 0.21 0.22 ...... -.i. 0.174 1 0.097 5...¨

i ;. i .....
i C12 OA
i 0,24 0,45 0.174 .. 1 0.105 5 .
.................. i -I C13 0.34 1 0.21 0.67 0.174 0.112 5 ................................................................ , IC14 I 0.34 0.21 0.92 0..173 o.127 C15 1-6..34 0.21 1.43 0.174- 0,08 15 __________________________ .., .........
C16 10..35 0,22 1.37 0.1.74 i 0.08 5 .................................................... + ...
CI7 0.34 022 1,55 0.174 1 0,08 5 Table 8.2 ¨Characterization of Compositions I Formulation P/Dnet Z average TComments [ Name diameter, nth ..................
' C10 -0.1 13.5 / Visually dear¨I
rei 1l -0.25 17,15 ¨Visually dear C12 -0.5 17.56 Visually dear C13 -0.75 22.91 Visks.ily ewer C14 -1.0 3039 Visually dear F. ..................................... .1 ......
C15 - .. 11.95 25.78 %/way deer CIS -1.8 39.4/ Visually clear C.17 -2.12 2931 IVIisually dear i [001571 Sports (or more-properly, endosporeS) are .4 type of dormant eell produced by nlay types of bacteria, such .as .Bacillus anti Clo.sirdium, in response to. stressful enviro.nmental conditions. The exteriot coats of spores, -which are responsible for the resistance to extreme conditions, .f.tte multi-layer structures composed primarily of cross-linked potypeptides: When a spore encounters .an env.innurient favorable for growth of s=egetative cells, the spore (:oat also allows access to nutrients and water to the spore. and the production of a vegetative cell, in a germination process.
[00158) The connmitions of the polypeptides., proteins, and other mittor materials that make- up the coat of Bacillus Subtilis spores, for example, resuit in the spom exhibiting a net anionic charge (negative .zeta potential) A'hiil. the sports are dispased in water at neutral pH, i.e., pH 7. Poiypeptides in aqueous solutions will exhibit a net charge as a flinction of pH of the solution that is determined by the relative numbers of anionically and cationicaily charged amino acids in the polypeptide Chain. At El pli corresponding to the iscfrelectric point of a polypeptide, the net charge on the polypeptide is .zero, due to the presence of equal numbers of cationically charged and anionieally charged amino acids. The net charge on the polypeptideatpH values greater than the isoeleetric point will thus he negative (anionie), and will he positive (cationic) at pH
values below the isoelectric point. The isoelectric points (or point of zero charge) of various Bacillus spoms have been fotmd to lie between about pH 3 and pH 4. Thus, the zeta potential of the spores used herein was found to be cationic (positive) svhen the spores wem dispetsed water adjustW to around 012, i.e., well below the known isoelectricpoit [00 B91 Bacillus spates exhibit average diameters of around 1000 nrn (I
micrometer), and can thus act. as Charged scattering particles when dispersed in. aqueous Media. Mea.surements of the zeta pOtential of spores are thus readily accomplished using the aonn..mob of laser Doppler velocity determination that is implemented in rmiem ingruments, such as the ivialvem Zeta Sizer. 7.1143w skilled in the art will realize that an appropriate concentration of spores for such measurements of the zeta potential of the spores cart readily be determined, using dilutkals of standard dispersions of spores which arc commercially available: Typically, the spore concentrations in -these standard dispersions are expressed. as Spores/MI or colony forming units/nil of the dispersions.
Applicants have found that reproducible measurements of the zeta potential of Bacillus spores can easily be made at -spore concentrations of around 1 to 3.3 x 10' spoinslml.
Such concentrations are readily made by diltnion of cOmmercially available stocks with concentrations of 1 x sporestrrilõ
[001601 Spores contaminating surfaces such as towels; other laundty, or hard surfaces, such as floors, svalls., medical equipment, food prepatation. or service Counters, etc. will germinate and grow, prmiacing increasing numbers of organisms on the surf.ace, when the environment becOITICS favorable,. for example, when the surface becomes soiled or contaminated with materials that. are suitable nutrients for the microorganisms.
Germicidal quat.ernary ammonium compounds or biguanides have littic effect on dormant spores, but if they are present on the surface-of the spores in sufficient concentration, they may kill the organism at the initial stage- of gennination when the environmental conditions otherwise become favorable.
11001611 Exposure of spores to notations comprising trticelles with a net cationic charge dile to a gerinicklat quaternary arnMonium compound or a monomeric higuanide can /emit in the adsorption of some quaternary ammonium compound or bigtianide onto the spore surface, ik$St as would be the case with any other solid surface, as dewribed above. 1.1)e amount of adsorption of the quaternary ammonium compound or biguanide will increase as the total concentration of the quaternary ammonium compound or biguanide in solution increases, up to about the critical micelle concentration, at which it will become constant and maximum. The presence of cationic sites (due to catcally charged amino acids and other materials comprising the spore coat) on the spore surface will be expected to oppose and limit the adsorption. of cationic quaternary ammonium comivundorbiguanide.
001.621 Adsorption of the quaternary ammonium compound or biguanide i1 be =
favored at the anionic sites on the spore surface. If the medium surrounding the spore is sudderily changd, .for example by the additioi of lin organic soil load which could serve as a nutrient source to the spores and thus favor ination, then the adsorbed quaternary ammonium compound or biguanide, like any other surtirCtant, will re-equilibrate with the surrounding intAium, resulting in desorption oft least some of the quaternary arnmonium compound or biguatilde from the .spore surface,. tlits decreasing its antimicrobial efficacy during the subsequent getrrlinatiou of the spore, E00163) As is shown below, the composition& of the instant invention,. in which micellea -with a net cationic Charge are paired with- a =water-soluble polymer of anionic charge, While rennaining soluble and free of coacervates or precipitates, have the advanttige of tine control of the adsorption and desorption of cationic.
surfactants, including the germicidal quaternary ammonium compound and biguanides, which can he.
exploited to provide better antimicrobial efficacy against the proliferation of bacteria on surfaces due to the germination of spores, =
EXIMple 9 r.)emoristration of the Adsorption ofrie.micidal Quaternary Ammonium Compounds onto Spore 'Surfaces fmm Mixed Micelles and Mixed Micelles with Polymeric Counterions (Micelle-Polymer Complexes) The zeta potentials of Bacillus Subtilis spores suspended in water at ì7, the mixed -micelles without the polymeric counte.rion (P/Driet =- 0), or mixed micelles interacting with an anionic polymeric counterion were mea.sared using the NUN=

Zetasizer,. The presence of monoedranolamine 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.
1.001651 A cornm.ercially available stocl . suspension of Bacillus Subtitis spores was used to make all sat vies on a given day. Samples were analyzed within four hours (.)f preparation. Thirty microliters of the stock spol.a- suspension (I s.i cfulml) were mixed with 870 microliters of water (p1-1 7) to give a control sane contang about 3.3 'he entire saniple was loaded into a disposable capillary cell for measurement of the zeta potentiai a the spores, as described generally above. In the case of the formulations, thitty microliters of the stock spore suspension was mixed with 270 pi of the formulation, allowed to equilibnue 10 ininute.s, and then SO O ul of deionized water was added to again yield a spore suspension of about 3.3 x 106 clithni. This sample preparation Method as also followed in the cominrison of the gerdal activity via the spiral plating method usedinthe next example below.
Table 9.1 --Compositions For1IT olymer Arnim Germicidal Monoethano 1 PiDnet n Name Alcosperse Oxide, uat, amine wt%
747 Ammonyx BIOS}
LO, 1010, wt%
........................ wt%
DI. 0 1.8 02 0 .D2 0.0025.5 1,8 î 0.2 E3 I 0,102 _______________________ 1-1.S I 02 (.1 -2 =
Table 9.2 Zeta -potential of live-111as ,.5Ø4/1ìs spores 0.3 X 10^6 cfulml) in -water ad in Formulations of various Mild Spore treatment Absolute value, Mean Zeta PiD.net +potential, nW
Contol --spores N/A T
only in deionized water -Spores in Di 0 1 Spores itt D2 005 +12A
Spores in .D3 [001661 The results in Table 9.2 indicate that the zeta potential of the /web of spores used on this day exhibited an anionic (nevative) zeta potential, as expected.
Exposure of the spores to. formulation Di, the mixed micelles eomprising the.
germicidal quaternary ammonium compound .and amine oxide in the a:bsence of a poirrieric counterion, eases a large Shift in the=zeta potential of the spores in the cationic dimetion, and in fac.1 completely reverses the zeta potential of the spores to -I-20.5 mV.

[00167j This chartge ean be explained by the adsorption of the germicidal quaternary ammonium compound onto the spore surface, causirtg a COrflperWeioa of the negatively- charged surface sites, which would leave only cationically charged surface sites available to contribute to the zeta potential, It also possible that overcompensation of the negative sites on the spores could be achieved through the adsorption of multiple layers of quaternary ammonium compound molecules, causing art additional Shit.
in the zeta. potential of the spore in the same cationic direction. The results -also show that exposure of the spores to formulation D2 results in a shift of the zeta potential M. the cationic direction. Since the absolute value of PIDnet is less than 1.0, the aggregates (complexes) formed by the interaction of the- polymeric counterion and the mixed micelles have the cationic charges due to the quatemuy ammonium compound in excess, and thus have a catiortic charge, as shown above. The -shift in the zeta Weptial of the spores caused by eXposure to formulation D2. clearly indicates. adsorption of the germieidin quaternary ammonium compound, i.e., the presenc.e of the. polymeric -oeunterion does not interfere with the adsorption process: Since the magnitude of the Wit of the zeta potential is somewhat splinter fa exposure to formulation D2 compared to D.I, it is believed, without being bound by theory, that the adso.rption of some of the anionic polynteric counterion onto the spores also OCCU1rS, changing the. overall chemistry of the adsorbed layer.
[00168i Sutprisjneys exposure of the spores to formulation D3 also causes A
significant shift of the ze.ta potential ín the" cationic direction, to A
value Only -slightly lielow O. Tbus. even when the absolute value of P/Dnet is TrOiCh greater than indicating an excess of the aniot)ic charges. due to the polymeric counterion over that of the cationic charges due to the germicidal quaternary ammonium compound irt theak,wegates formed, significant adsorption of the germicide onto the spore surfaces still occurs.
Thusõ delivery of an adsorbent layer of germicidal quaternary ammonium compound onto the spores, which will be available to kill the bacteria- upon germination, can be accompiithed across a broad range of the absolute value of PIDnet,. which in turn allows adjustment of the formulations for other propertiesõ such as oil solubilization, greasy soil removal during a cleaning process, and .aesthetic properties such as lack of filming .or streaking on solid surfaces.
Example 1.0 Antimicrobial A,cly of Mixed Micelles Commed to Mixed Micelles with Polymeric Counterions (Mk:elle-Polymer Complexes) Against kacillreeSabriiis spores A simple method was developed to demonstrate the utility of fbrmulations comprising, mixed micelles of a germicidal quaternary ammonium compound with a water-soluble anionic polymeric counterion (micelle- polymer complexes) M
killing bacterial spores placed in an enviromnent favorable for gemination.
[001701 Serial dilution of concentrated cell suspensions followed by plating on a solid growth medium is a common way to determine the viable cells, or colony forming units (CRJ), in a the suspension. 'Me CFIJ multiplied by the relevant dilution factor relates back to the viable mietobes in the original saspension. Those skilled in the art recognize that the automated spreading of a spore suspension in a spiral 'formation from near the center- to the.' t;triphery of a circular plate containing solid microbial .wowth medium (agar medium described in detail here) simultaneously accomplishes dihnion and waY to determine the of the inicrobial suspension through deposition over an ever lengthening. area of the. solid medium. Standard ft...cognition software can visualize colonies on the .solid -medium and calculate the CIFt.1/m/ of the origin.al suspension based on the distance and matiber of colonies relative -to the center- of.the 1ate..
Such an approach is impleinented with commercially availableequipment,. SII.Ch as the Autoplater Model A1-11000 (-Advanced Instruments) used in the following ex.amples, 1.001711 -Spores.
'which have been treated with the inventive Impositions will 1.3e killed UpOit genninatien When they are deposited onto the growth medium due to a combination of the presence of some residual. amount of the aqueous formulation and the quaternary ammonium molecules which are !strongly adsorbed onto the surface of the spore. e spiral plating of the spore suspension accomplishes an exponentially increasing amount of dilution of the spores in a spiral pattern on the growth medium.
Thus, the concennation of the aqueous formulation deposited with the spores is exponentially decreased by dilution with the growth medium. hi addition, the chemistry of the aqueous environment surrounding the sponts changes dramatically towards one rich in nutrients such as proteins. Thus, the quaternary ammonium molecuks and any other surfactants adsorbed on the Surface of the spore will re-equilibrate ...with the surrounding growth medium through descAption (partial or complete) from the spore surfaee, and/or a displacement from the spore surface through the adsorption of other materials present in the growth inexlitim. In other words, the spind plating method expleses the spores suspended in the inventive eompositions to an exponentiaily increaeing "organic load"õ

whia is well-known in tile art to interfere with and or pievent the antimicrobial action of common germicides such as quaternary ammonium Of.3Inp011ildS.or biguanides.
[t10.1721 When suspensions of spores in the inventive compositions are deposited on growth medium via the spiral plating.technique, the. spores..neareSt the center of the spiral pattern will be niore likely to be. killed upon germination by the adsorbed f?prinicitial quaternary ammonium compound or biguanide, and thus them will he no colonies observed atter incubation in this, region. 'Thus, instead of the exitlected.
vim], pattern in Which there are. large numbers of comes cn-rwded together nearest the center of the plate, there *ill he a circular "hole" in the ;xittern due to the 'killing of the spores upon germination.. Farther away fmm the central starting point of the spiral, where the huge dilution has decreased the ability of the adsorbed biocidal species to kill the spore tii>on gerMination as described above, viable- colonies will appearand continue in a spiral to the ()yaw edge of the plate: Muss. the -diameter of the circular hole in the spiral pattern is larger for formulations which provide. more killing of spores upon gemiination under favorable conditions, [001-73i The equipment used for the spiral plating of the suspensions of the treated spores yields a pattern in which the central bole has a diatneter of about 2 cm when a. high concentration of spores that are v.jahle (in a control experiment, for example) are present at the start of the spiral. pattern. if the treatment of the spores results in killing upon germination of all of the spores, then the m_aximum diamete.r of the hole is about 8 cat, MOS, -values of the diameter of the central hole- between about 2 cm and 8 cm, .herein called the germicidal..-4one diameter, represent varying degr.ees of effectivene.ss or the treatment of the spores kr prevention fthe contarnination.of surface; by the germination of spores under extremely favt)rable conditions, with larger values of the diameter cating better effectiveness. Such testing methods are thus a. good Mdication of the efficacy 'of the inventive compositions under various teal life use conditions where s=arions organic loads may be present Or applied.
1001741 The treatment fbrinulations, and dilutions of their>, were placed in the wells of a 96 well plate, 0 microliters of the standard spore suspension were added and alknved to age for 10 MillUtOS, followed by the addition of 200 pi of sterile water and then 20 ul of the spore suspensions were then .spiral plated rmto the piats containing growth media.
The spore concentrations treated were all the same, about 1 x105, which is similar to the number of spores treated with the compositions in the determination of the changes in the zeta potential of the-spores described above, The plates we.re incubated overnight at 37 C, followed by a measur.ement of the diameter of the germicidal zone diamete.r.
t0017$1 Formulations comprising mixed micelles of the eertnicidal quaterna:ry arn.monium compound MT%) 1010 and ai amine oxide were made as described above, over a. range of P/et values., using the anionic Water-soluble polymer Alcosperse 747 as the polymeric counterion, Fo.rmulations El through F.,5 contained the same quaternary annrionium compound concentration, while formtilatic.m E.6 contained a significantly o'er quaternary ammonium compound concentration. The mlative arr,ouints of quaternary ammonium. compound and amine oxide in the mixed micelles, however, was ifui same, The compositions are shown in I'able Table 10, 1- -COmpositions for Testing Effects of Treatment of Bacillus Stibtilis spores IFormulation 1 Polymer Amine Ge.rmic ida I IvIonoethan PA) net Name i Alcosperse ()xide, Quat. olarnine a 747 A mmonyx lace wt%
L. wt 1 ol 8,. wt%
El 0 1,8 0.2 0.1 0 .................................. -.. ..
E2 .0,00255 1.8 0-.2 0.1 -0.05 E3 0.0255 1.8 ............................................. . ....... ¨......._ .E4 0.051 1.8 0.2 0:1 -1,0 ESI 0..10 l= .1.8 0.2 0.1 -2.0 f L E6 .. . ____ 0 i 0,225 0.025 .. I. (LI 0 f 001761 1-o cover a large -range of concentrations of the .germieidal -quaternary.
ammonium coMpound in the treatment of the spores, formulations El through E6 were used mat (dilution factor :--1), a.n.d at various dilutions (dilution factors-0.5 to 0,03125, or 2x to 32x times dilution of the original formulation). The results obtained with the spiral plati.n.g test are summarized. in Table 10.2 Table 10.2 - Spiral plate results -Effects of Fofillulations on Viability of .Bacillus zihibtilis pores ....., Dilution FaCtOf Prior to Spore Exposure Formulation 1 0,5 I 0.25 0.1.25 0,0625 - 0.03125 Absolute Value, __________________ ...._.,i Name i ............................... P/Driet ., I Spiral Plate Germicidal Zonediaineter, cm . .

=El 8 7.5 I 5.7 4.8 3.7 2 0 E2 I 7.9 7.4 1 5.6 5 4 0.05 E3 7 I 7 6,4 4.7 4 2 0.5 E4 1 __ / - 5 3.7 1.0 8 7.5 5.8 5 3.5 ... -t 2 2.0 E6 I 4.6 2.5 2 ....................... tt 2 100177] The results in Table 10.2 -show that Formulations E2 through E5 (all of which contain the same qutuernary ammonium compound concentration) all -exhibit exmllent pertbrmance in killing the spores upon germination,. as does the control fornutiation El., when tise d neat (dihnion factor 1),..yieltling germicidal 2.one diameters of 7 to 8 cm. Dilution of fommlations El through E5 by 32x (factor 0.03125) results in zone diameters of 2 CM, indicating no significant effect. ort-the growth of the spores when they art placed on the growth media. :Surprisingly. formulations in which.-the absolute value c4 /net are 1, (indicating an equal number of anionic .charges due to the polymeric counterion and the cationic charges due to the germicidal quaternary Ammonium compound) or even 2 (indicating. an excess itt the number .of anionic Charges.
due to the.
polymeric counterion over the cationic charges he to the- gennicidal quaternary ammonium compound) exhibit killing perfOrmanee corriparable to that of the -control fornmlation. across a. range of dilutions in this test,. confirmina the robustness of the adsorption of the germicidal quaternary ammonium compound onto the spore 'surfaces, and in line with the effects of the. fOrfriyhatiOTIS as measured by the changes in the zeta potential of the spores, as described above.
[001781 Control Formulation E6 included no polymeric counterion.
Fotmulation E6, when diluted 2x (factor 0.5) contains 0.0125 % quaternary amift0fillitll compound, and shows only a small amount of germicidal activity, as shown by a. germicidal zone diameter of 2.5 cm, Formulations E2 through E5, when diluted Lx (factor 0.0625), also contain 0.0125'Ite. quaternary ammonium compound. liowever, due to the presence of the polymeric counterion in these inventive compositions, the germicidal activity is sig,nificantly better than in the case of formulation E6. The germicidal zone diameters tneasured for treatment of spores with E2 through E5, at the dilutic.m factor of 0.0625, are all significantly greater than that of formulation ES at the dilution. factor of 0.5, indicating the significant -benefit of the presenee of the anionic polymeric Counterion in ensuring the kill of spore s during gemination wider favorable conditions. Applicants speculate, without being bound. tiy theory, that the presence of the anionic polymeric counterion along with the germicidal quaternary ammoilium compound in the adsorbt...4 iayers formed on the spore sur.faces decreases the tencle.ncy of the germicidal quaternary atrimonium, compound to desorb hrom th.e spore surface upon dilution of the spores in the gmwth medium an/or decreases the tendency of other siirface-ace molmiles in the growth medium from competitively displacing the germicidal quaternary -ammonium compound from the surface of the spores, thus prOViding thiprove d germicidal perforrnanee of the inventive formulations compared to the control .formulation containing mixed micelles without a polymeric couriterion.
Example:11 Antimicrobial Activity of Mixed Micelles Co par -to -Mixed Micelles with Polymeric.:
Counttrions I olymer .Corliplexes) .Against Bacifix SubtilL5 spores [001791 Some ad(titional inventive fonnulations were developed covering a range of P/Dnet values and tested for acty against the growth of spores in the same mariner as described in Ekample 10. A comparison with the actty of the control formulation E6 was also. made, for the reasons described .in.Example 10.
Table 11.1. - cornpOsitions for 'Testing Effects of Treatment of Bacillus Subillix spores r "F onnui atio '-Polymer 1 Amineoe Geranicidal MOTIOOthall PIO net n Naine Alcosperse Oxide, Quat, BID:10 olarriine 747 Arnmonyk. 1010, wt% wt,16 wt%
Fl 0.00255 1,8 0.1 -0,05 F2 0,0051 -02 1.8 0.1 -0.1 _______________________________________________________ 4.====
F3 0.0102 0.2 0.1 F4 0.0153 1F5 f_ 0.0204 0.2 1..8 F6 0.0459 0.2 1.8 ___________ L
E6 0 0:).15 0.025 0.1 0 Table 11.2 Spiral plate results- .Efferes of Formiations on Viability-of Bacillus Subii11.5 spores Dilution Factor Nor to Spore fix.posure bFormulation I 1 0.5 [0.25 I 0.125 1 0.0625 0.03125 A solute value, =
Na P/Driet me _____________________________ =
Spiral Plate Gernal Zone diameter, cm Fl 8 6.8 53 ¨ 5,3 4 23 0,05 F2 7,8 7,5 63 5.1 4 2.3 0.1 F3 8 6,8 6.3. 5 4.2 2.3 0.2 F4 8 7.5 6 5,2 8 73 5..8 5 4 2.2 0.4 F6 ........... 4 8 7.3 6.2 5.5 4 2.3 0.9 .E6 4,612.5 2 2 The results in Table 11,2 again indicate that formulations a the instant iri=ition exhibit. CNC:Client germicidal performance, killing spores placed in tin extremely favorable environment,: In addition, the formulationS show betterporformante at dilutions a 16x. (*Am 0.0625) than the control, which delivers the same total quaternary ammonium-compound -concentration of control. formulation E6 at a 2x dilution (factor 0;5). The similarity in killing p.erformance of the inventive compositions aCtOSS -a range a the absohne. value of PiDuet allows that optimization of other parameters of the-formulations, such as cost,. cleaning performance or kinetics, or surfatee -residue aesthetics can be adjusted -via .P/Dnet while. .maintaining the antiinicrobial properties of the formulations, due to the fine control of the interactions of the surfactants in the mixe:d micelles that can be .achieved with the use of a water-soluble. polymeric counterion of charge opposite- to that of the net .charge of the mixed micelles, Example 12 Antimicrobial Mixed Micelles with Pobrineric Counterions (Micelle-Polyiner Complexes) Delivered from a Nonwoven [00181.1 Formulations corriprising polymer mieelle complexes comprised of mixed micelles of a. germicidal quaternary aM11101/WITI compound and an arnine oxide and anionic water soluble polymers increase the antimicrobial efficacy of a formula delivered by a nonwoven wipe. .in this example polymer micelle complexes formulated over a range of PiDnet values are shown to outperfoim mixed micelles in the ASTM
International, Standard Practice for Evaluation of Pre-Saturated or Impregnated Towelettes for Hard Surface Disinfection, Test Methcid E 2362 (henceforth referred to as the towelette test) anainst Pseudomonas. 'This example also demonstrates -flexibility in choice of -polymer chemistry and the compatibty of micelle-polymer complexes with solvents and silver ions.
001821 Composhions and PM/let vahies a the formulations are shown in Table 12.1. Fomnulations we prepared 'by first mixing EITC.10 1010 (Stepan Co.) and Ammonyx LO (Stepan Co.) in the specified amounts with water, thus forming the mixed micelles. The pH was the adjusted using MEA and glycolic acid in the slmified amounts. lbe specified amount of anionic. polymer (Alcospersa 747õAlcoguard H5240 or Aicoguarn, 230(, all -from A.kzo Nobel) wen, then added to for the micelle-lxymer complexes. Nopylene glycol n-hutyl ether (Dowanolms PnB, Dow Chemical Co.) was added to. formulation 03 to demonstrate comptibility with solvents.
Silver dihydrogen citrate (1.sinosan SIX, Ciba) was added to thrmulation G6 at a raw material concentration of 0.125 vt.,4 (equal to 3 ppm silver ions) to dernoristrate compatibility with silver ions. The -formulations form. stable. aggregates, characterized by DI,S
analysis as ilescribed in exa.mples 1-6-and vvere visually clear%
1001831 Moist - towelettes were prepared for ASTM Test Method E 2362 by applying the- appropriate fotmulation to a mll of the towelettes. The mass- of the liquid formulation-added-to the rolls- of towelettes was 4.5 times the mass_ a the.
dry toweIettes.
ToweletteS used in this example were- nonwoven, 40. pro material purchased from N.R.
Spuntech InduStries Ltd. The MOiSt towelettes were allowed to equbrate- at room temperature for at.least 24 hours, Table 12,1 -Compositions suitable for delivery &Om nonwovens -- 1' t i ......... . ¨,--- .. --r ..

-4.
'5 0 ====== e:
e 'V 11 , :-.:-&.µ5 R
01 0.36 0,227 0 ----I 0 0, I 0 0 0 0 02 036 0.227 0.0099 5 i 0 0 0.1 0 0 0 -0:0 _______________________________________ .......
03 0.36 0.227 0.0099 0 0 0./ 0 04 0.36 0.227 0 1.014 4 0 0 0.066I 0 1 0- -1.3 ............................................................. _a , 05 0.36 0.227 0 0 0.0042 0.05 0..1 0 1 0-0.025 i I. ..................... i ........................... . ....
1 06 0.5 0.32 0,002 1 0 0 10 I 0.125 I -0.007 ....................... _1 1 -Table 12.2 - Antimicrobial activity of fo.mullations delivered from nonwovens.

Formulatien Name i Towelette 60 cattier test against Pseudomonas 3 ________________________________ minute contact time GI
G2 Pass (.33 Pass 04. Pass G5 Pass i1-06 Pass 1.00184.1 Comparing formulations GI and G2 show that addition of a SiTiall amount of anionic polymer to .fomi micelle-polymer COOrIplexes characterized by PiDnet increases the antimicrobial efficacy against. Pseudo/n(1nm enough to gtnterate. a -passing result. Formulation G3 shows thg the IlliCfOtffitACy fforrnplatioti G2 is preserved when 2 t3 of PiiB
is -added to the .formultaion, which fluty be desirable. for robustness of the formula as well as a variety of:aesthetic benefits. Fommlations G4 and .G5.
demonstrate that a wide range of Water soluble polyrilCrs .art suitable for forming the mieellespolyiner complexes. Fortnutation 04 also shows that illiceite-polymer complexes formulated at an absolute value of P/Dnet greater than 1.0 are capable of boosting antirnierobial activity relative to- that of-Mixed micelles without the polymeric counterions as well.
This result is particularly sininising considering that the cationic charge on the germicidal micenes is witiety accepted to be the driving force for adsotption of the :active ingredients onto microbes. Finally, lommlation G6 demonstrated the C;0Mpatibility of the Micelle-polymer complexes with silver ions.
Example .13 Kinetic Benefits of-Autimicrobial Mixed Micelles with Polymeric Co tens (Micelle.
Polymer Complexes) Delivered from a Nonwoven 1001851 Two of the fOrMulations described in Example 12 were tested at i minute eontact times against StapkilloCOCCUS MiretIS`. and PsetifkMOMIS Wing the.
ASTIVi International, Standard Practice for Evaluation of Pre-Saturated or Impregnated TOwelettes for Iliad Surface Disinfection, Test Method E 2362. l'hese=
formulas -demonstrate passing antirnicrobial efficacy at contact times considered to be extremely short for quaternary ammonium cointlound-haseci .formulas.. Formula GI, a Mixed micelle control which delivers the same concentration of germicidal spat without the polymeric counterion, is not capable of passing the towelette test at 3 minute contact times (see example /2).
[001861 'fable 13.1 Antimicrobial actty of fonnulations delivered from nonwovcris.
Formulation Name TmArelette 60 carrier Towelette 0 carrier test against test against Stapigylaeoccus Pseudomonas ====
.efureus minute minute contact time contact time G2 Pass Pass G6 Pass Pass Example 14 Dilutable for ton of Antimir,:robial Mixed Micelles with Polymeric Counterions (Micelle-Polymer Complexes) on Laundry [001871 Dilutable formulatiorts which nray aìn saz.ation a laundry are .governed hy the document EPA DIS1TSS-13 'Laundry Additives - Disinfmtion and Senitization", Such -fo.troulations =tat be. denionstrated to reduce the levels of bacteria (both Gram + and Gram -) by at lent 99,9% a specific test protocol known as the "Petrocei and Ciark.Laundry Addifives Method (sanitizing level)", [0111.881 This example demon:Mites the. delivery of antimic.robial efficacy benefits using dilutabIe formulations. comprising polymer-rnicelle complexes comprising: mixed micelles of a. gertnieidal quaternary ammonium compo.und and an amine oxide and anionic water soluble polymers, In. this formulation BTCO. 818 and Antrnony4 Mate mixed M
-water at the given concentrations, and then Alcoguard 5240 is added and mixed well.
formulation is visibly clear in the concentrated. form and when diluted in hard water as per the laundry sanitizer test protocol.
Table 14.1 composition of formulations .for a dilutable laundry sanitizer Fortnulation Polymer Germkidal I P.1) net Latmdr Name Alcoauard Oxide, QUA, 13.10V
5240 Ammonyx 818, wevil Sanitiza tion Test ¨
115g4 dilution H 0.146 3.02 11.7 I Pass H2o 0 1.1.7 1 0 Fail [00.1891 Formulation HI is capable of passing the laundry sanitization test .
mentioned above against Staphyioeoccus iturvuv and Klesiella Pneumonia at a 4 minute contact time when diluted I patt to 584 parts in hard water. The extreme dilution ratio and high bacterial loads make thi.s test method excetxlingly difficult to pass with quaternary amimmium chestries such fis formulation HI.
Example 15 Solubilization. "Enhancement with Polymer-Micelle Complexes Formal with an anionic polymeric counterion and inixed micelles.
[001901 Consigners. of aqueous based liquid cleaners frequently prefer fingranced fotmulatio.ns with excellent oily Soil rentoval,. while still demanding low residue on cleaned surfaces, The key to suceessfull,, satisfyin.g this consumer demand is that the total concentration- of sclubiiizer compounds be stitriciently Wait to fully incorporate the oily fragrance and any nonaqueous solvent compounds used to ensure excellent oily soil cleaning according to cmumer preferer3ces, he minimizing the unal concentration to lessen the visual residue left on the caned surfaces, especially in thertbserree Of a rinsing step. Applicants discovered thin the interaction betwcen mixed micelles comprising an amine oxide and germicidal quaternary ammonium compound and .an -anionic polymeric Cotmterion according to one embodiment of the invention enables a. tmique and surprising oil solubilization boosting effect. to tiatisf-y these consumer preferencts.
In other words, similar results can be achieved with significantly less solubilizer when employing the inventive complexes, [00.191) Tisheo solubzation bi-sosting effect of the polymer on the-rnixeti micelles is readily illustrated by comparing the lowest' total solubilizer concentration meded to solubilize 8.3% limonene used as a model oily compound, such that the compositions are visibly clear, free of excess oil, precipitate. and coacervate,. in the absence and presence of the polymeric counterions. In. this example, the total solubzer concentration is the sum of the concentrations of the polymer, the germicidal quaternary ammonium compound I3TCOD 1010, and the nonionic surfactant Anurtortyx10 W. The composons alt shown in-Table 15.1, Table 15.1 amplef3iiBTC:01010wt% Aramony,X0 1 Aieosjws-A, Limonette MEA Minimum 1.0 wt% = 465 ut% vt;t% total solubilizer ........................................................... need wt%

11 0 OAS 20 03 0.1 .3-

12 0 0.1 i 1.275 0.3 0,1 1,375 1 0 0.15 ...... 4 1,35 0 03 0.1 1..5 14 1 -Oki 0.05 1 0,596 0,96 0.3 0,1 = 0.646 J5 -0.0 i 0.1 0.754 Ã.93 0.3 0.1 0.854 Ã5 1 0,981 2,89 I 0.311 0 ' 31 ="`
1001921 In thís. exaznple, the 1)/Dnet parameter was fixed at a relatively low absolute value, in order to Minimize the cost of the polymer added to the formulntion:
Three-different concentrations of BTCO. 101.0 were. irivestigated. The lowest total solubilizer rt.,-qUired in-the absence of polymer as determined ,ta various concentrations by making. a series of fonandationsnwhiCh the concentration of the Ammonyx.I.) 1,0 was:
increased until the .formulation was completely clearõ corresponding: to full sOhibilization of the limonene oil. Solubilization of the limonene '&as not achieved in the series of samples made that ended with the control formulation J1, which was a -cloudy dispersion, Solubilization of the limonene could be achie.ved when the concentration of-the BTC
1010 cationic gennicidal surfactant:was increased somewhat, and if enough Ammonyx 1,0 was added, to-give the final total aolubilizer levels shown for formulations i2 and 13.
[001931 The same procedure was used to dete:mtine the minimum total soiubilizer requirement -in the pmence of polyineric counteriona at a fixed P/[.net -0,01. .ratio.
A.ppropriate amounts of the surfactant stock solution,- monoethanolarnine to adjust pI-1 above 9.0), limonene, and water were 3tixed to .form the final control formulation containing the .mixed miteiles. in the case of formulations comprising the polymeric counterion, the same mixed surf.actant stock- solution, monoethanolamine, limonerie, and Alcosperset 465 (a poly (acrylic acid) homopolymer supplied as an aqueous solution, Akzo Nobel), and water were mixed in appropriate amounts to yield the final formulations with the fixed P/[net values, and increasing levels of Arnmonyx 1,0 were added, thus varying the mixed micelle compositions, until a clear solution, indicating complete solubilization of the. limoriene, was OW i 101941 Comparing the optimized compositions in l'able 15.1, it is apparent that the formulations with polymeric count.erions 04, 15 and JO requite lower total solubilizer concentrations, demonstrating a significant oil soltibilization boosting effect resulting from thet.kolymer-mixed micelle interaction. For example, formulation 15 requires only 0.854%
total solubilizer to fully solubilize the limonene into a clear solution .free of coacervates or precipitates, he formulation S. which has the same concentration of the germicidal quatentary arnmoninin compound,. A.-quires a much higher total soiuber level, 1.315%, to fully solubilize the same c,oncentration of limoriene.
[00195) Another uniqtte aspect of the effect of the presence of the polymeric.
counterion .is the remattably AlcosperSee 465 rxtatier concentration, in the ppm range, that is needed kir the solubilintion boosting. This, in formulations such as hard stuface cleaners that n%y no; be rirtsed atter USe, very low levels of the polymeric counterion can dramatically also lower the total levels of surfactant needed to deliVer a wateroluble oil such as limonene, contributing to significant cost savings as well as a reduction or elimination of consurner-pmeptible residues ott surfaces cleaned with the formulations.
Example 16 Oil Solubilization Enhancement 10019(4 The enhancement or boosting of the solubilization of water-insoluble oils may be obtained with a wide .variety of water-soluble polymers, over a wide .range of P/Dnet values, offering considerable flexibility in meeting different antimicrobial performanceõ aesthetic or cog targets.
1.001971 Oil solubiliz.aticm optimization is eared out in the presence of 0.3 wt%
limonene model oil by, in a series of samples, simultaneously increasing the absolute value of .l.tDriet and the concentnition a the nonionic amine oxide surfactant at a fixed cationic sutfactant concentration until solutions which are clear, free of pA-teipitateõ
coacervate and excess oil are obtained. Optimized compositions are thus the ones that turn clear at the lowest added amine oxide surfactant concentration. The minimum total solubilizer values are this the sum of the BTOlb 1010, Ammonyi& 1.0, and polymer (if present) in the final formulations that yield cotnplete oil solubilizatim 101.98.1 Appropriate amounts of 13TC 101 0õAmmorlyx*
rno.noethanolamine to adjust pH above 9.0), limornme, and water were mixed to .form two series of samples .in which the A.mmonyxt LO level w&i increased at fixed MT.* 1010 concentrations until final control formulations Kl. and K5, contng the .mixed micelles and the solubzed limonene were obtained, [90:1991 In the case of formulations comprising the polymeric counterion, the 5f11110 surfactants, monoethanolamine, limonene, and Aosperset 747 (supplied as All aqueous solution, Akzo Nobel), and water were mixed in appropriate amounts to yield series of samples iti which the mixed micelle compositions were changed by increasing.
amounts of Amatorty.x0 1,0, at several different, fixed P/Dnet values. The optimized compositions, all (4 which are clear and I'm of coacervate, preCipitate and excess oil, are-sintunatiml in Table 16.1.
'fable 16.1 'Example Pir)õ.õ, Mince i Arriritettyxt 1 Aleosperse* r Litnonetle MEA I
Minim=
1010 i 1,0 wt% 1 st1.% 747 pprn wt% vet% Kai solubilizer need i II
Wt) i ................................................. 1 __ K1 0 0.1 1.275 0 0,3 i 0.1 , control ..... ¨ ___________ K2 41,1 : 0.1 1-.09 510 1 0.3 /
4 .............................................. i . ......
K3 11 i 0.1 0.91 510 1 0.3 ...................................................... , ................. it Al -0.91 510 l()'3 I 0.1 .1.061.
................................................. i ¨1¨ ' 0.2 ................ t K5 i 1.275 0 j() I 0.1 .1.577 -control ....... I /
-1, 0.2 1..091 1 1.02o K7 q -. 02 0.545 [1020 0,3 0,1 1 0.847 ____________________ . ................. I. .......... I .....
..._õõ __ =
100200l The results in Table 16.1 show that inventive formulations K2, K3, and K4 achieve complete limonene olubilization at lower total solubilizer levels than formulation Kl, indicating an enhancement or "boosting" of the -solubilization of the watesoluble oil when the water-soluble anionie copolymfdr is used as the polymeric counterion for the mixed micelles bearing a /let cationic charge. Surprisingly, the oil solubilization boosting can be achieved over a wide range of the absolute value of PiDnet, i.e., oil solubilization enhancement can he achieved with a wide range of compositions of mixed micelles title to the fine contml over the interactiOns between the cationic and noniimic -surfactants :in the mixed micelles that is possible through the use of the fltdiet* polymeric eounteriori.
...

Snìhry.formulations K6 and K7 exhibit lower minimal) total solubilizer concentnations than formulation S.
Example 17 Antimicrobial Compositions Containing a Monomeric Biguanide, Chlorhexidine Glucoriate [00201 The cationic germicide present in the mixed micelles rimy be a monomeric higtamide salt, such as chlothexidine gluconate (CHG). CHO was supplied as 20%

solution in water, from Sigma-Aldrich. CG has two catio.nic charges per ITIOlecule and a melecular weight of 897.8 girnole, The mixed. micelles may also cOmprise nonionic surfactants. The compositions summarized in Table 17.1 comprise two nonionic surfactants. Surfeniett 1õ.12-8 an alcohoi ethoxylate, fmm Huntsman Corp), and Olucopon0 325N can alkyl glucoside, from BASF Corporation) in. the mixed nlices with the CHG. Since the CIRI concentration is the same f91711Ulations LI, 1,2 -and L3, the ValtieaEticationic will aiso be the same and is calculated as follows:
Eq cationic = 2 x 0.015 x 1/897,8,-. 3.34 xìI equivalents/100g of formulation, And, since there is tIo anionic surfactant pitmen' in the fonnulation, then Dnet D cationic = +1 x 0:0000334= + 3.34 x [00202] The. water-soluble polymer tise d in this example as the polymeric counterion is poly(2-acrylamido-2-thyl-1-propanesulfonic acid), or polyAMPS.
It has 1 anionic charge per monomer talit, WhiCil has a molecular weight of 207.25 gimole. is formulation , lxliy.AMPS is present at a. concentration of 0.0035 wt% or 0.0035 gramil 00 grams of the formulation.
P is thus calculated as P = 0,0035 x 1 xlx(-1 )1207.25 -0.0000168878.
'thus, PiDnet := -0.0000168878/ + 3.34 x 10-5 = - o.sosa [00283] The values of P and P/Dnet for the other formalations are- summarized in Table 17.1 'fable 17.1 composition, wt % ..............................................
higrfAierit LI 1,2 I L3 CHG 0.015 0.015 0.015-i Surtbniee L12-8 035 0.016 0.016 Glacorsonit 325N 0.8 0.037 z 0.037 I

Ipoly(2-acrylarn ido-2-methyl-1- 0.0035 . 0.014 0,03c ' ipmpatussul Ionic itiz id) Dm-venal", DB .3.2 1 ' = ........-k Dowanorrn Pn13 0,7 1,,.. õ ..............
I Monoethanolf.,911 int 0.5 ................... ......õ,¨
NaCI
¨ ..............................................................
Fragrance_ oil 0.2 11 i , 7 D net 3.3415 x 104 3,3415 x 10"s I> : -1.68878 x 10'5 -6.75513 x ir ................ -0,000'1689 -0.50539606 -2.0215842311 -5,0539606 f00204) The negative values ()f PIDnet for the formulations in Table 17.1 indicates that the polymer and mixed micelles are of opposite charge, and hence within the op of the. instant invention. The. formulations also. illtistrate that fragrance o#
nuty be solubilized in the mixed TriiceNs, that the. fonnulationa rr.tay .comprise watemoluble glycol -ethers or not, mul that -the pH arid electrolyte levels of the formulations nuty be varied with appropriate adjuvants such as .raonoethan.ol.amine arid sociium chloride, Formulation Li is useful as .a. ready to use hard surface citaner, while formulations 12 and .1.3 are useful as lotions for pre,moistetted wipes or As hand sanitizers. Dowanolrm DB. and Dowanarm PnB are glycol ether s.olvents from DO* Corporation 'Fragrance oil svas a lemon fragrance from Firrnenich.
100205] Without departing from the spirit and -scope of this invention, one of ordina.ry skill ctut make Various changes and modifications to the invention to adapt it to varitius umges and conditions, .As such, these changes and modifications are prOperly,.
equitably, and Mtended to be, within thc. tail range of minis:Mel-ice of the tbllowing claims.

Claims (20)

1. A composition comprising:
a polymer-micelle complex, the complex comprising:
a positively charged micelle, wherein said positively charged micelle comprising a water-soluble cationic material selected from the group consisting of a monomeric quaternary ammonium compound, a monomeric biguanide compound, and mixtures thereof, said micelle being electrostatically bound to a water-soluble polymer bearing a negative charge;
wherein said water-soluble polymer bearing a negative charge comprises a hybrid copolymer derived from a synthetic monomer or monomers chain terminated with a hydroxyl-containing natural material synthesized with a free radical initiator;
wherein said polymer does not comprise block copolymer, latex particles, polymer nanoparticles, cross-linked polymers, silicone copolymer, fluorosurfactant; or amphoteric copolymer;
wherein said composition does not form a coacervate, and wherein said composition does not form a film on a surface.

2. The composition of claim 1, further comprises an oxidant, optionally the oxidant is selected from the group consisting of:
a. hypohalous acid, hypohalite or sources thereof;
b. hydrogen peroxide or sources thereof;
c. peracids, peroxyacids peroxoacids, or sources thereof;
d. organic peroxides or hydroperoxides;
e. peroxygenated inorganic compounds;
f. solubilized chlorine, solubilized chlorine dioxide, a some of free chlorine, acidic sodium chlorite, an active chlorine generating compound, or a chlorine-dioxide generating compound;
g. an active oxygen generating compound;
h. solubilized ozone;
i. N-halo compounds; and j. combinations thereof.

3. The composition of claim 1, wherein the positively charged micelle comprises a monomeric quaternary ammonium compound.

4. The composition of claim 3, wherein the positively charged micelle further comprises a nonionic surfactant.

5. The composition of claim 4, wherein the ionionic surfactant comprises an amine oxide.

6. The composition of claim 1, wherein the positively charged micelle comprises a monomeric biguanide compound, optionally the biguanide is selected from the group consisting of chlorhexidine, alexidine, and combinations thereof.

7. The composition of claim 6, wherein the composition is free of iodine, iodine-polymer complexes, nanoparticles of silver, nanoparticles of copper, nanoparticles of zinc, triclosan, p-chloromethyl xylenol, monomeric pentose alcohols, D-xylitol and its isomers, D-arabitol and its isomers, aryl alcohols, benzyl alcohol, and phenoxyethanol.

8. A method for cleaning a surface, the method comprising:
contacting said surface with a composition comprising a polymer-micelle complex comprising:
a positively charged micelle electrostatically bound to a water-soluble polymer bearing a negative charge, said positively charged micelle comprising a water-soluble cationic material selected from the group consisting of a monomeric quaternary ammonium compound, a monomeric biguanide compound, and mixtures thereof; and wherein said polymer does not comprise block copolymer, latex particles, polymer nanparticles, cross-linked polymers, silicone copolymer, fluorosurfactant, or amphoteric copolymer;
wherein said composition does not form a coacervate; and wherein said composition does not form a film on a surface.

9. The method of claim 8, wherein the composition comprising a polymer-micelle complex is a concentrate, the method further comprising diluting the concentrate with water to form a dilute composition comprising the polymer-micelle complex, prior to contacting the surface with the dilute composition.

10. The method of claim 8, wherein the concentrate is diluted at a dilution ratio of as high as about 1 to 600, and wherein the resulting dilute composition is capable of achieving sanitization of the contacted surface at a dilution ratio of about 1 to 600 within about 4 minutes.

11. Me method of claim 8, wherein the composition further comprises an oxidant.

12. The method of claim 8, wherein the positively charged micelle further comprises a nonionic surfactant.

13. The method of claim 8, the composition further comprising a water-immiscible oil that is solubilized into the positively charged micelle, optionally the composition is free of water-miscible alcohols and glycol ethers.

14. A system comprising:
a) a dual chambered device comprising a first chamber and a second chamber;
b) a first composition comprising a water-soluble polymer bearing a negative charge disposed in the first chamber wherein said polymer does not comprise block copolymer, latex particles, polymer nanoparticles, cross-linked polymers, silicone copolymer, fluorosurfactant, or amphoteric copolymer;
c) a second composition comprising a positively charged micelle disposed in the second chamber wherein said positively charged micelle comprises a water-soluble cationic material selected from the group consisting of a monomeric quaternary ammonium compound, a monomeric biguanide compound, and mixtures thereof;
d) wherein the first composition of the first chamber is mixed with the second composition of the second chamber to form a resulting composition in which:
i) the micelle is electrostatically bound to the polymer to form a polymer-micelle complex;
ii) the resulting composition does not form a coacervate; and iii) the resulting composition does not form a film on a surface.

15. The system of claim 14, wherein at least one a the first or second compositions further comprises an oxidant, optionally the oxidant is selected from the group consisting of:
a. hypohalous acid, hypohalite or sources thereof;
b. hydrogen peroxide or sources thereof;
c. peracids, peroxyacids peroxoacids, or sources thereof;
d. organic peroxides or hydroperoxides;
e. peroxygenated inorganic compounds;

f. solubilized chlorine, solubilized chlorine dioxide, a source of free chlorine, acidic sodium chlorite, an active chlorine generating compound, or a chlorine-dioxide generating compound;
g. an active oxygen generating compound;
h. solubilized ozone;
i. N-halo compounds; and j. combinations thereof.

16. The system of claim 14, wherein the positively charged micelle comprises a monomeric quaternary ammonium compound.

17. The system of claim 14, wherein the positively charged micelle further comprises a nonionic surfactant, optionally the nonionic surfactant comprises an amine oxide.

18. The system of claim 14, wherein the positively charged micelle comprises a monomeric biguanide compound.

19. The system of claim 14, wherein the composition is free of iodine, iodine-polymer complexes, nanoparticles of silver, nanoparticles of copper, nanoparticles of zinc, triclosan, p-chloromethyl xylenol, monomeric pentose-alcohols,D-xylitol and its isomers, D-arabitol and its isomers, aryl alcohols, benzyl alcohol, and phenoxyethanol.

20. The system of claim 14, further comprising a water-immiscible oil that is solubilized into the positively charged micelle, optionally the composition is free of water-miscible alcohols and glycol ethers.