WO2014070202A1 - Anionic micelles with cationic polymeric counterions compositions, methods and systems thereof - Google Patents

Abstract

The invention relates to a polymer-micelle complex. The polymer-micelle complexes include a negatively charged micelle that is electrostatically bound to a water-soluble polymer bearing a positive 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

ANIONIC MICELLES Wffll CAT!OMC POLYMERIC CO1J TE I0 S COMPOSITIONS, METHODS AND SYSTEMS THEREOF

BAC GROUND OF THE INVENTION

1. The Field of the fo eas.®®

[§§01] The reset mvortfott relates to polymer-mieeile com l es,

2. Dexriptfoft ofHebteil AH

Cleaning product formulations rely on surfactants md mixtures of surfactants to deliver cleaning (deteigeoey), wedlng of surfaces,, stain removal from fsbrics, bleaching of stains, decolorkatioxi of mold a d mildew, and ¾ some cases, ai imierobiaf efficacy, A key aspect of these p cesses is the Interaction of the soriactaiits, oxidants, and antimicrobial agents with he solid su faces of the mater als being cleans!, as well as the surfaces of ffiicroofgaaisms, together with, the effects of the formati ns on the alo-water mterfaee (surface tesion). Reducti n of the surface tension of aqueous foundations, which is directly relate to the effectiveness of the: wetting of solid .surfaces and hem® e detergersey rid antimicrobial processes, cars be mani ulate through the use of mixtures of x n detants, as Is known in the art.

H J At a rsoleeukr level .surfactants md ai&etant mixtures in ueous media exhibit the ability to adsorb at tie air-water, solid-water, arid oil-water interfaces, and this adsorption is fence res onsible for a wide range of phen mena, including the sol bi iza ion of oils in the detergersey process, the changes la the properties of solids sad dispersions of solids, and the lowering of the -surface ension of water. Adsorption of surfactants at interfaces is generally known to increase with surfactant concentration «p to ¾ total surfactant eoneeno;ailon known as the critical micelle concentration (CMC). At die CMC, surf&etots begin to form aggregates In the boik sedation known as micelles. In equilibrium with the monomerle species of surfactants which a sor onto the Interfaces.

ffl M] The details of the structures sad sixes of the rn elles, as wed as the properties of the adsorbed layers of surssctasta or surfactant omiures, depend on the details of die molecular shape and charges, If y, on the hydrophdic ⁴¾eadgroups^w of the surfactants. Strongly charged aesdgroups of surfactants iend to repel each other at interfaces, opposing the efficient packing of the surfactants at the interface, and also favoring micelle structures thai are relatively small, d spherical. The charged headgrou s of many su fac ants, such s sulfates and sulfates, will also Introduce a eountenoo -of opposite olmrgsf for example a sodium or potassium toe. Mo femirdations.

|# S) It is know that the nature of t e eouaterion cm affect the repulsion between charged surfactants micelles nd adsorbed layers through a partial serosa ing of the feadgroup charges f om one aooiher m surfaeiam aggregates like mkehes, It is also well known that addition of simple eleehtdytes, such as sodium chloride, into aqueous solutions can also be used to Increase the screening of like headgroap charges from each other, and th s is & common parameter used to adjust the properties of surfactant micelles, such as siz and shape, and to adjust the adsorption of surfactants onto surfaces.

|©0O Addition of significant am unts of simple electrolytes into many fomtulstions, such as hard surface spray c eaners or nonwoven wipes loaded with a cleaning lotion, is undesirable due to residues left behmd upon drying of the bno latious. An alternative method, to admsimg the properties oi such formulations,, including the wetting of solid surfaces and stm on em, or the xwt&ag sad interactions with microbes, is to include signirlesnt amounts of volatile organic- solvents such as lower alcohols or glycol ethers. Volatile or anic solvents, however, are gommg under increasing regulation due to their potential health effects, and are eo preferred by the significant traction of consumers o desire efficacious cleaning and disinfecting products with a .minimum, of chemical actives, Including vo!ailles, in th healthcare industry- efficacious immolations comprising lower alcohols ajs kno n, but ate viewed as having shortcomings in terms of the potential for Irritation of confined patients. Such products pose similar risks to cleaning and clinical persotmel may be exposed to such products on a daily basis.

|0 ?| There is increasing interest om consumers, and a known need in the healthcare and housekeeping industries, to reduce the number of microorganisms on fabrics while using familiar equipment such as w&s ing machines. Concentrated products are required for such an application, doe to the high dilution lev l of the product the rinse-water, typically by a factor of about 600 times dilution. In the ease of lobula ion comprising quaternary ammonium compounds, lege concentrations of the quaternary ammonium compounds m the concentrate are eaded in order to ensure an adequate amount of adsorption oocers in a kineficai.lv relevant rime onto the microbes under dilution use conditions. As detailed above, it is desirable, yet very difficult to manipulate (i.e., reduce} the CMC of the quaternary ammonium so pound in. syc¾-:sis application. Thus very high concentration of quaternary attunonlum com unds, which tend to be hazardous to the skin, and eyes, arc used in lbs concentrates, in comb nation with hign teamerahnes a d kmg exposure times.

Thus, there is an ongoi g need for methods &ηά compositions offering See control of the properties of surfactant aggregates, m order to reduce or elimin te volatile organic solvents. There is also m o going need to deliver mm removal and/or sohmisrobial activity due to the action of oxidants such as sodinrn hypochlorite on s rf ces which are relatively difficult to wet with lower overall surfactant concentrations,

BRIEF SUMMARY OF THE E EM^'TION

One aspect of the Invention is directed to & composition comprising oxidant and a polymer-micelle complex comprising a negatively charged micelle thai is electrostatically bonnd to a waier-solnble polymer hearing a positive charge., Tbe water-sokrble polymer bearing a positive charge does not comprise block copolymer, latex particles, polymer nsnopsrticles, cross-linked polymers, silicone copolymer, ficotosuriaoraat. or amphoteric ■copolymer. The complex advantageously docs not torn a ooacervate,

|P1 ) Another aspect of the Invention is directed to a -composition com is ng an oxidant and a polymer-micelle complex comprising a negatively charged micelle that Is electrostatically bound to a water-soluble polymer bearing a. positive charge. Tbe water- soluble polymer eariag a positive charge does not comprise block copolymer, brtex particles, polymer nanopartieles, cross4inked polymers, silicone copolymer, iiaorosaTracianl amphoteric copolymer, or a polymer or copolymer bearing anionic charges, ^'The composition does not form « eoaeerva e,

OUj Another aspect of the invention Is directed to a composition com is ng ars oxidant and a polymer-micelle compkx comprising a negatively charged nneeik that is electrostatically boand to a. wstsr-soishie polymer bearing a positive charge. ^'The negatively charged micelle comprises a mixed micelle, kelndmg an anio ic surfactant and a noniomc surfactant. The a er-soluble polymer does not comprise block copolymer, late particles, polymer nanopartieles, cross-linked polymers,, silicone copolymer, flaorosoffacianh or amphoteric copolymer, Tbe com osition does act te m a eoacervate and does not form a film on a surface and is free of alcohols and glycol ethers.

lll!21 One aspect of the invention is directed to a method for cleaning a surface. The method comprises contacting a surface with a composition comprising a polymer-mlcehe complex. The poiyinar-miceife complex deludes a negati ely charged micelle e troststttpaUy boun to a aier-so! b!e polymer bearing a- positive charge. The wate - soluble ol mer beanrig a positive charge does not comprise block copolymer, latex particles, polymer nsaopartieles, cross-ds&ked polymers, silicons copolymer, .tkmrosoTfeetant, or amphoteric copolymer. The com osition advantageously does mi form a eoacervste. and s not applied to trapping organic ©GntaraHjants in a subsurface location.

f¾013] Another aspect of the invearion Is directed to a method tor masting surface. The method comprises mixing a first composition com rising a water-soluble olyme having a positive charge with a second composition comprising a negatively charged m celle. The water-soluble polymer bearing a positive charge does not comprise bioek copolymer, latex particles, polymer nanopariieies, cross-lmked polymers, silicone copolymer, ikorosmftciani, or amphoteric copolymer. The composition resulting from mixing of die first and second compositions does n t form a eoaeervate. The e h d farther comprises contacting the resa! ing composition with a surface so as to treat the surface.

f®01 If Another aspect of the Irme ion is directed to a method for classing & surface. The method comprises eonasoting a surface with «. - x osition- comprismg a po!yeiem keile complex. The polymer-micelle complex inoTudes a negatively charged micelle dectros!atisslly bound to a water-soluble polymer bearing a positive charge, The water- soluble polymer bearing a positive charge does not comprise block copolymer, l tex pariieks, polyme nsnopanicles. cross-linked polymers, silicone copolymer, iiuorosiataeia , or amphoteric copolymer. The composition advantageously does not form a coacervate, ar?d is «©i applied to trapping organic contaminants a sabsnrfke location. Use-composition does not comprise alcohols or glycol ethers,

1 0.151 Another as ect of the invention is directed to a system for preparing a mixed composition for treatment of a surface where the mixed com osit n is formed from two initially sepa ate compoaiiloa parts, the system comprising; a first chamber eomaking an oxidant first part comprising hypohaious acid or a hypohalite; and a second chamber containing & redueiaai second part comprising a nhr!te, wherein the first ami second chambers -sre initially separated from one another o pre vent p ematura mixing of the tarsi and second parts; where upon mixing of the first and second parts, the resnldng mixed composition provides xidking benefits provided by the oxidant for a limited duration, dm oxidant reacting with the redactant to reduce the oxidant concentration so as to prevent or nbniraize ne ative side effects otherwise associated with prolonged oxidant ensure longer t an the limited duration.

\mi€f in anot er aspect of the system, her is a sys em for preparing a mixed com osition for treatment of a s face where the mixed composition is formed fran two initially separate composition ar s, the system comprising: a first c ambe containing m oxidant first part comprising hypochlorite; the hypochlorite comprising up to abou 15% by weight of the two-part composition ; and a second chamber containing s rednatant second part comprising a nitrite, the nitrite comprising from 0.01% to about 15% by weight of the two- part composition; wherein, the first and second chambers a e initially sepa ated from one another to prevent premature mixing of the first asd second parts; where upon mixing of the first TOd second pa ts, the resulting h&d composit on provides oxidis g benefits provided by the oxidant or a limited dura on, the oxidant reacting with the reduetsnt to reduce die oxidant soncentmtion so as to prevents or minimize negative side effects otherwise associated with prolonged oxida t exposure longe tlnm the limited d ration,

|0§i7] In yet another sspeci. of me system, there is a system for preparing a mixed composition o tea ment of & surf ce w sre the mixed composition is ibm;ed from, two initially se arate composition, parts, the system comprising: a first chamber containing m oxidant first part comprising, hypohaiife; the hypochlorite consisting of sodium hypochlorite; and a second chamber containing a_. ie ue &nS second part comprising a nitrite, the nbme consisting of sodium nitrite, wherein the first and second chambers are initially separated from one another to prevent remature mixin of the first and secon pans; where u on mixing of the first gad second parts, the resulting mixed com osition provides: oxidizing benefits provided by the oxidant fo a l mi e duration, the oxidant reacting with the mkc!an! to fstkee the oxidant concentration so to prevents or irnnbnfee negative side effects otherwise associated wish p ol n ed o dan ex osure longer ih s the limited duration,

fk1!S| in another aspect: of the system., the first or seeomi compositions comprise m. oxidant. Optionally the oxidant is selected from the groap consisting- of hy ohaious acid, hypbhalite or soorces thereof, hydrogen peroxide or sources thereof, peraeids, neroxyacids peroxoaeids, or sources thereof organic peroxides or hydroperoxides, peroxygen&ied inorganic cornponnds. soiubiilzed chlorine, soiubibxed c lorine dioxide, a source of free chlorine, acidic sodium chlorite, a active chlorine generating com ou , or a chlorine- dioxide gsaer ikg compound_s m act ve oxygen generating com ound, soiabl&ed ©zo¾ ₉ ho- h& . com o n s md combinations e eof.

S19| another as ect of .the system, the oxstet is indaded within the second composition comprising the oegat vdy charged micelle, and h« first composition c mprises the water-soluble polymer bearing & positive charge further comprises a nosiome surfactant. Optionally, the aonio k sirr&ctani comprises m amine oxide.

> 2§] In another aspect of the s stem, the oonionic sariscisni comprises &n ine oxide. [i >2i] in another aspect of the system, the oxidant is incladsd within he first composition comprising the water»so bk polymer bearing a positive charge, pd wherein the second composition comprising the negatively charged micelle further comprises a nonio.ok surfactant. Optionally, the oonionic suriaefe t comprises m amine oxide.

| M¾2| I® another aspect of the system, at least one of the first or second compositions further comprises & Quaternar anioioaiam compound.

¾3J fe another aspect of the syste , the negatively charged micelle comprises m an on c sarfectaot selected from the group c sisting of sikyi sulfates, alkyl sulfon es, alky eth ^ saifetss, My acids, fatty acid sa , aihyl amino acid derivatives, glyoolipid derivatives mc!irding anionic groups, rhamnollpids, rhaomslipid derivatives Ineladhig anionic groups, sulfate derivates of sikyi ethoryia e propoxyiafcs, aikyl stboxyiase srdiatas, md coPibi.aat.ioos thereof.

[WH\ another aspect of the y tem, the w&ter-solu k polymer bearin s positive charge comprises a monomer selected from the groap dlallyi dimethyi ammorrlum. chloride, quaternary ammonium salts of s bstituted aendamide, mefhylacry!armde, acrylate and me hacrylatfe, qoaleroked alky! amino aeryiate esrers and amides,. MA.PT.AC (methacfyla iilo propyl trimetbyi ammoninm chlorides), inmet yyl ammonium methyl melhacrylate_v irimothyl ammordom propyl metbacrykmide, 2-vis l M-sIkyi quaternary pyridinbrm salts, 4~v y! N-alky! quaternary pyridinkm salts,. » yinylbeffiyitriaikykmoionium salts, 2-vinyl piperldhhnm sabs, 4-vlnyi piperidinkm saltsc3~ alkyl 1 -vinyl i ida¾olia:m salts, or ef ylensimme and otktures thereof or is a ate-xol fefe polymer selected fpo the group ehbosao, chilossn derivatives bearing caiionie groups,, guar derivatives bear ng caiionie groups, or ¾ polysaccharide bearing caiionie groups, and combinations thereof [δ©25 Is ¾ftothe? ss eci of the s stem ,_· at least, one of. the first or second eomrx^moB fo ker comprises a pH u fer.

C ] Further restores and ad anages of the prese t mvzmkm il bec me ap arent to those of ordinary skill n the art so view of the detailed description of preferred m odiments below.

BMEF ISC F !ON ΟΨ THE DRA INGS

¾7J To further dta-ify he above md other adva ages- and feaures of the preset myentioft. a more particular de rs km of the ioverrtion. will e rendered by reference -to specific em odmens thereof which ¾re illustrated in the drawings located hi the specification. It is appreciated that these drawings depie only typical embodiments of th invention and are thefefors no to be considered limitn of Its scope. The invemioo will be described mi explained wih additional specificity and detail through the use of the ac mpa ying dawn s in ic :

fCRUff Figure 1 plots ibttnulatums of Example 2 relative to the eoaecrvate phase boundary,

ESCMFTI N OF THE PREMREB EMBODIMENTS

[O09J Before describing the present mv¾otlofi k deail, it is to be understood that this Invention is not limited to particularly exmplife systems or process parameters thai may, of course,, vary. It is also to be understood .that the iennirsology esed herein Is for the purpose of describing particular embodiments of the inventio only, and is not intended to limit the scope of the invention in .any manner.

tSii] AH^' ptrMieatiomo patents and patent applications cited heds, whether septa or kfra, are hereby incorporated by reference is their entiety to the same extent as if each individual ublication, patent or aent a plication was specifically and individually indicated to be incorporated by n;t¾rence.

1_.0311 The term ^com ising'' which is synonymous with ' nclu ing ' "containing," or "charaterized by," is inclusive or open-ended and does not exclu e additional unreclied elements or method steps.

IM3:!| The "costsisimg essentially of Ik is the scope of s claim to the specified materials or slo s ¾nd those that do not materially afTea the basic and n vel ehameterlstkis of the claimed invention.

0331 The term Con istin of as used hereio, ludes any element. Step, or ingredient not speeirled o the claim

[09341 It must be noted that, as osed In this specification and the appended claims, the singular forms "s," ¾^s d ¾s^,! include plural referents unless the cons nt clearly dictates otherwise. Thus, tor example, efe&ce- to a "sarfacta · mc des ooe_s <? or more such surfactants.

S 3S] The term water-soluble polymer a used herein mams a polymer which gives an optically ekar solution free of precipitates at a co eerdrsoors of 0.001 grams per 100 gratis of water, preferably 0.0! grams/100 grams of water, mo pefeabiy 0.1 grs s/100 grams of wate , an evett more preferably 1 gram or more per 100 grams of water, ®i 25 X.

003^1 As used herein, the term "sabstrate" is intended to imhi my material that is used to clean an article or a su face, Examples of e snlrsg sabstxates include, but are nor limited to non ovens, sponges, films m similar materials which can he attached to a cleaning implement, such as s floor mop, h dle, or a hmd h«ld cleaning tool s ch as a toilet cieamng device.

\W37] As used here n the terns ¾oo ovet or 'h oswovao web" meaos a eb hsvbg a struct re of individual fibers or thread which a e interlaid, but not m . identif a l manner as in a knitted web.

ffM S] .As used herein, the term " olymer^* as used in reference to a substrate (e.g._s a nosv- woven sabstrais) geoemlly includes, bi is oot limited to, hr> opolymers_:: copolymers, such as for example, block, graft, randora sod alte nating copolymers, terpoly ers, etc. and blend and o dif atioas thereof Furthermore, unless otherwise specifically limited, the term "pol me-*^1, shall include all possible geometrical co figurations of he moieeaie. These eoofsgoratioas include, but arc not limited to isotsetk, syad tactic aad rs d ui symoiet ies. f0§39] Uckss derived otherwise, all technics! and scientific terms used herein have the same meaning as comBiosly understood hy one of ordinary skill in the art to wbkb the invetstioa pertains, Although a number of mstiiods sod materials similar or eoaivaieri to those described herein can be used is the practise of the preserd invention, the preferred materials and methods arc described herein.

[8 t f| In th spplkadoo, efkcdve s cnta art^; generally those amounts listed as the ranges or levels of ingredients in the descriptions, which fellow hereto, Unless otherwise sta d, amounts listed in pereeotage are so wl% {based < 100 wetghtiii active) of the particular material present in the referenced composition, ao remaining percentage be n water or an a ue us carrier sufficient to account for 100% of the composition, unless otherwise noted. For very low weight percentages, the term "ppm" corresponding to parts per million on a. weight/weight basis -may be used, noting thai 13 t¾ correspond to 10,000

|# 1 J The present iaventors av« now determined that the use of w«ter^«s0l«bl« polymers comprising ro ps which tear or are cap ble of bearing m electrostatic charge as counterfoil ( olynisnc- eouoterioos) for micdles comprising at least o«« ionic surfactant selected such that t e net electrostatic charge on the rnieelk is opposite to that of the ol raedc eoenterlon can yield, simultaneously, very fme cm roi of the interactions betseeea the headgroups of the iome sarfactsst as well as the adsorption of the iardc sarfseiarsi at the ΐΑϊφύά an solid- liquid nterface whet* compositions are adjusted such that precipitates or eoaeervstes are completely sbseot from at least some embodiments of the compositions,

{ ill Surpds giy, saoh compositions b which micelles with olymeric counterkms exis as soluble, ^'i ermodysiamic&lly stable aggregates exhibit very high adsorption activity si both the air-li uid ark solid i aid interfaces, Saeh characteristics ooire ieteiy elim na e the need to adjust faraaktass syc that they change their solubilit ; iorrabg. coacervates or precipitates, in orcfef to deliver adso tion of seful amou& s of ioolc sar¾ctaoi and pdyn r to these kterhaoes. The mket - oh mer complexes formed when a atsr-sokbk polymer com r s ng g s which beer or arc capable of bearing en electrostatic charge -opposite to that of » micelle^' are usually foarsd to be somewhat larger thm the micelles alone, The addbioo of a wster-sokrbie polymer bearing electrostatic charges opposite to thai of ai least mi mi h a ueous solutions often can reduce the CMC of the given surfactant by a significant traction, which can also have the effec of reducing the cost of certain formulations,

fl a-j Fine control of surfactant irdsractio s within micelles: via addition of oppositely charged polymers according to the invention have also beea fooad to increase the oil solcbihzatioo ability of the missiles to an n^ex ee ed degree. Without being boand by theory, is believed that this effect is due to the vmicfas!y high counkr im charge density carried by the charged polymer, which is distinctly dlffereoi Iron? regular cosnier ion effect provided by typical salting oat electrolytes. ^'This i th ught to increase the degree of coun e im association of charged polymers compared lo regalar electrolytes, «v.ets at very low polymer concentrations, which in tarn promotes increases mieeliar size and an increase in oil soksbiiksho efficiency. The inventors have discovered t at the oil solubilization boosting effect develops only if the b ieose us are . fme-i sed such thM the system is M\y free oicoacervate yei is ssear the water sokifek/eossces-vatc ase boaodary,

| I44| Fo m rss compriiing mixed mkeiies. of m anionic sisrr ciimi, optkstt&Oy a seeoad surfsctant mc an &mm^' z ox de, mi a wsreo-sol ble polymer bearing eationic charge ca» be made with control o e s e attd net electrostatic charge. It s believed, without being bound by t eo y, that he c&doslc polymers act as polymeric eoiaiterioos to the aniorikaUy charged micelles, either incre&siftg the size of these micelles or collecting grou s of these .micelles into soluble, Iherrnod narrhcally stable aggregates which have enhanced activity at solid sorisse-a eoes: sdatiors interfaces, iticiadlag hard surfaces such as floors, eo ateri ps, eic, ss web as soft surfaces such as fabrics,. rrorewoven materials, and other surfaces such ss the surfaces of microorganisms such as bacteria,, viruses, ItMgi, and bacterial ^•spores. Depending on application use, the ssrfsce m&y be ha d, soft, animate (e.g., skis), TOR- animate, o.r othe type surface,

S! in one em odiments tie composition o&a comprise alcohol to another en-tbodimerny the compositions can be completely fee of a er-misvibie lower alcohols, Similarly-, the com sitions esn comprise atewrdsci!ae glycol ethers or be completely free of the materials, somefe.es referred to as "co-sol veots^''! or ''co-surfactants" Compositions free of the lower alcohols or glycol ether not only can provide, acceptable antimicrobial perfbrsTta ee at lower cost, hot also reduce irritation to patients and healthcare workers, -while providin iomiu!aisons which esc he eoosidered mor enviroaovenialiy friendly or sasta mble due to lowered total actives levels ami lack of volatile organic compounds. Those embodiments that are free of alcohols or cosoivems ma be especially suited as sarntkkg ^gleaners, disioieetmg cleaners or tre tment for pets la home or vetetinsfy applications;.

|0§ 1 The compositions s«ay be use!tfJ as ready to use cleaners, aed may be applied via spraying or pourlag, but ttsay also be delivered by loadin onto riou oven substrates to produced pre-moistened wipes. T¾s compositions may also be provided as concentrates that are dilated b the cossurrrgr (e.g., with tap w¾ter). Such concentrates may. omprise a past of a kit ^'lor^' refilling a container (also optionally incl ded w t k each a kill such as an empty trigger sprayer. The core positions may also be provided concentrates for single-use ( ah dose) products ior cleaning floors,^•windows, cen e s, etc. Corscee rated dishwashing liquids that provide anubac erial performance upon very ig dilutions may be formulated as may concentrates which can deliver saaitixstiori of laundry via addition to ordinary washioads. Such compositions ami resul s may be achieved it out inclusion of triclosan. S ch eonoenh rted products also > provide protection against the growth of hiofiims atsd associated outgrowth of molds, in 4mn tines associated with automatic- dlshwsshers₅ laundry ash ng machines, mi tfre like, re oelrsg undesirable odors which are sometimes encountered by consumers.

10 4^*?! Concentrated form of the formulations may also be provided which may be diluted by the consumer to provide solutions that are then used. Concentrated forms suitable for dilution via automated sys ems, which the concentrate is diluted with water; or in which two solutions arc combined in. a given ratio to provide the final ax formulation are possible.

§ 4§| The^' formulations may be the form of gels delivered to a reservoir or surface with a dispensing device. They ro¾y optionally be delivered in siag!e«use poaoh.es comprising a soluble film.

he; superior wetting, spreading, and cleaning performance of the s stems make ^•dsem especially suitable for delivery from aerosol acka es comprising either single or deal c ambers.

|@ 5 ) In am ensbodlnicffi, the compositions do rsot result in ths f rmation of a durable film on s surface after application, Simple rinsing Is sofiieierd to rem ve any residue, and even without rinsing, those embodiments of the invention that do brni a residue do not .fbm macroscopic durable films. Thus, any remsialng residue does not constitute a illnp but Is easily disturbed, destroyed, or otherwise removed.

The compositions of the present invention are not to be applied or used to trapping organic contaminants in a sobsurface location,

ΙΒ,Ι βίίίο» of Dsset m$ ^'PI mi Parameters

i rS¾ As will be shown In th e am les below, very fine control of the interactions between micelles comprisin an ionic surfactant and water-soluble polymers; bearing electrostatic charges opposite to that of the mise!les, and. hence fto-retionkg a polymeric eounterions to the mleedes, cs¾ be achieved through manipulation of the relative number of charges due to Ionic surfac a ts in the system and those charges -due to the water-soluble polymer.

[§953| Mixtures of s rfes ants, ioclnding mixtures of ionic and non ox c surfactants_*, my be employed. A convenient way to describe die net charge on the micelles r sent in the f rmu tioas of the imtot kvmtkn is io o&lcis¾t® the total number of eqaivafeak -of the- charpd hea groaps of k surfactants, both skomc and eatlon followed fey s detem_i»atfc>a of which type of charged hesdgroup k m excess h ids formulation.

|@0:S | S rfac ant's bearing two opposite electrostatic charges in the formuktioni, such as csrbexy-betakes ami sk o :s€aiaes_} act as " se -aonismk" surfactants in the com os ns of the kstam nven ion since the net charge OR them wilt be ero- Thus, the calculation of Dnet will not mvolve die concentration of such pseudo-nomonlc smi etaets. Similarly, phosphatidyl choline, a edible rnate iai which is & ns&fo? com onent of e surfactant commonly rsfered to as lecithin, eoeklm both as sniordeaily charged phosphate group ¾¾d a oatkalealty charged choline group its headgroap region and Idas would be treated as psendo-ftoaionte in the hvsntive compositions. Do the other hand., a mate ! such as phosphaddic acid, which eoekms only m aaknleshy charged phosphate group as its foeadg up, would condk¾te to the calculation of Brest as described below,

|0¾SS^'l Some surfac ants, such as amme ©xids-s, may be uncharged noaionie) ovsr a- wide ange of pH vskes, but may become charged (e.g., eailonieaify k the ease of amine oxides) at acidic pU V8iaes_> especially below about pH 5. Although suc com onen s may not contain t o penrisneat md opposite electrostatic charges, applicants ha iomd that they may be treated explicitly as oo oshc s«r¾etw s in. the hws.ati.ve tormukdoos. As taught hete inventi e compositions which are free of coaecrvates and precipitates that cotPptise mixed micelles of an amke oxide and a anionic mket e component and a wster-so ble polymer bearing cationic charges may be readily formed through adj estment of the P/Dnet pgrajneter, the Dnet pamreeisr, and/or the presence of adjnvsnts suc as ekeiroiy cs, without regard to the precise value of an earkaic charge present, on the amine oxide,

|0δ$6| Two parameters east he def ned for airy ix ure of surfactants comprising headgroups bear g, or capable or bea in , anionic or eationk c arges or mixtures of both, said patarnetets feeing aniool and 0 erdionic.

D anionic will be efined as - D anionic ^;;; h I ) x (Eg aeionic)

e&tkmie will be defined as -

D cationic™ (-H) x (Eo, cationic)

|S S? A final parameter expressing the n charge on the micelles is Dnet, which is simply the sum of the parameters 0 anionic and D caiioek, he., Duet D cattemc * D anionic

|S6S§1 In the ex ressions. akjw, E an onic is d>e sum of the tots! number of equi alents^' or charges doe o das hesdgro ps: of a|! anionic surf¾¾i3ats esse . For a fenmdation comprising a s ngle sarike ant with a beadgrou bearing or capable of bearing an s^'niome- charge:

Eq aniorbo; ^:;; {€ anionics x Q anionicj) aaionisj

wh rein C an on c; is the concenfratso of a s«.rt½tant with anionic esdgroitps m grams/per 100 grams of e formulation or use composition Q anionic; is a number e essing the number of anionic charges^' present on the surfactant, which may be viewed^' as having the units equivalents er mok, and M io ic* is the molecular weight of the sar&ci&at m grams/mole,

fSIK ] For a fbrrouiation co j n two different surfactants with anionic- headgroups, the parameter Eq anionic would be calculated u the sum:

Eq anionic ~ lq anionic; - Eq sn o^k^ ^::::

(C asvioniei x Q_.anio»iCj) &momz-_: * (C anion cs Q a:aloaio:?)/M arbonl¾ (§§6§ Commerciady available suriknants are ften mixtures of materials due to the presence of a distribution in the number of. for example, msileylene groups k the hydrophobic ^t l '^" of the sarisetanf It is also possible t ai a distribution in the number of charged 'lieadgroups⁵⁵ per mokcuk could exist in practical work with commercial materials., it may also be acceptable to use so "'a erage^'" molecular weight or an "average" number of anionic (o eaticmie) charges per molecule quoted by the manufactur r of the surfactant I» the calculation of an nic {or JD cat sicy it may also be^■ acceptable to use values of the Eq anionic (or Eq catlorhe) derived f born direct analysis o a surfactant raw material

1 in the ex ressions above, Eq eatiorbe is the sun? of the total sumber of equivalents o charges due to hs beadgrcops of all cstionic surfactants present.. For a fornu adon comprising a single s aolafii with a headgroup hearin or capable of bearing a. cationic charge:

Eq canonic;™ (C eatiomci x Q catlonie /M catio ic;

wherein C cloncs is the conees ration of a. surfactant with c& ioaic beadgroaps in grams/per 100 gratis of the formulation or use composition, Q cationic ds a number representing the number of ca onie charges p esent on the surfactant, which may he viewed as hav^'issg the amis equivalents par mok, c»ia¾kjis. he moecular sig¾ of he surfaetaM kgrnms/m le, Irs. c ses where the l^maioa comprises more iUm one mrf t with cailonlc headgroups, the summaton of the equivalents, of c&tio«ie. h&adgrosps would be performed ss in t e case .of the amome suri&ctassts described above.

fW&S] As an ex&mpk, consider a fonmskion comprising & rrsixture of & ng lmk surfactant and a smgle nonionic surfactant, but la king a c&tionie sar&ctssit, ^'Furt^'hermors, consider the anionic anr&ciam is resent at a concentration of 2 wt% or 2 grams/i O grams of the form¾ on, has one^' group capable of de*¾iopiag anionic charge per olecule, and has a mokctslar weight of 200 grams/mole.

Then Eq anionic™{2 x i)/200 - 0.0 i squivak s/tOOg m the jfortnufatian.

Then, I) anionic^{■■■■■} (4) x (0.01) - 4).01.

And ^'D eationie - 0.

Thus, Dnct - (0 - M) ~ -0,01.

|θθ¾¾3] As a seeaad exam le, consider a ibrmoiadoi> comprising a m¾u?s of a single anionic; surfactan,, sn le soniontc sarfgetet, and a s½gis ca¾onk s f&c st which, is. a gefobeidal ^' uaer ary nmo ium compound. Furthermore, consider the ¾nk>ms sudkstet is present at a oorffierrn-aboo of 2 t¾ or 2 grams/ 100 grams of the formulation, has one grou capable of develo ing m anionic charge per moieoiOe, and has a m leadar weight of 200 grams/mote. Fsnbermore. consider the eatlosie surfactant is present in the formulation at g concentration 0.1 wi% ot 0.1 grasps/I 00 grams of Ore formulation, has one group , capable of developing s-c toRic charge pe moleaile, and has & molecn rwelght of 30 gramsmo!e.

Then Eqsirh n ~·(2.χ 1 }/200 - 0.01 equivakms100 g m the tbrm latiom

And Eq cationic = {0.1 x 1 )/3 0 - 0.00033 equivalents/ LOO g the jbfmutati&i.

Then, D anionic - Γ-Ι) x (0.0 i) - -0,0b

And D eaboulc ^«* (1 ) x (0.00033) -rOJXM a.

Thus, Baet +0.90033 -$- (-0.01 ) - -0.00967.. This negative value clearly indicates that the numbe of atb nioally charged beadgronps k the mixed micelles caroprisisg th anionic, nonlonic grid cafiodc- surfciaiits res t In the-formu!stiosi exceed that of th catteically charged headgroups,

f0§6 j A second parameter which can be used to describe the instant n ntio d the interactions between a polymeric cousterion. and surfacant micelles bearing a ne c¼¾e is the ratio ?Dne WS] F h the mb of charges {½ equivalents) doe to the pdynwb coamerlors presnt er 100 grams of the ibrmubibn and esa be ealcabtedas .follows.:

F

x F polymer x Q polymer a Z) polymer, where C polymer tha concentration of fits olymer b the iomm!a!ios in grarrasAOO grams of Tomdadoa, F polymer the weight fraction of the monomer unit bearing or capable of bearkg a char e with respect to the total polymer weight nd hm ran es m 0 to 1, Q polymer is the number of charges capable of beiag developed by the monome end capable of hearing a charge aad can be viewed as having the unts equivalents per mole, Z b m integer indicating the type of charge developed by the moaomer aoip aad is equal t +{ whe the monomer uait esa develop a catkmic charge or is eqaa! to -1 when the monomer aak eaa. develop an. anionic charge, and M polymer is ths mofecu!sr weight of the mo omer unit capable of developing a charge, b grants/mole,

|%¾¾f For exam le, co sider a iArmubiron eom m g polyaerylle add homo olymer (FAA) as s sbr-so bie polymeric coantenom PAA is capable of developing 1 mimic charge per aery sic sold monomer msh (which has a. moleea r weight of 72 gr&mxAno ), and fcisace Q polymer™ 1 and Z - A., i additi n, the polymer is a homopolymsiyso F polymer i. If the PAA is present in the fombaiion at a eonaenirallori of 0.J gramsiCM) grams of the formaiadoa, ths value of P ould be calculated as follows::

F- (0.1 xl x l A)/72-"0i>0BA

|I) T| Using the Dnet va e of -0.0096? calculated in t e exam le described above t r a mixture of aa a onic, eatlorde, and aoa e sm ci b the ratio P/Dnei would be calculated as;

P/Onet - (AhOOI39 Ab00967) - +0Λ 4

fB Uj Tills positive vaioe of P/Dn«t ot ordy dbates the ratio of the charges dae to the polymeric coantetioo aad the oei charge on the mixed micelles, but also indicates, sbce a is a positive number, that the charge o¾ the polymeria eoaaterion arid the nst charge on the mixed micelles are the same, both being anionic. In this caas, there wobd be no net electrostatic Intef!ieii a between the polymeric coonterioa and the mixed micelles expected, aad heace the example wmacl nod he wlihin be scope of the sbnt ventlom which requires that the polymeric c at) tenors must be of opposlb charge to that of the hoadgroops of the surfactant or mix»K of siafbciains comprising ifse micelle. As another e m le, consider ¾ ibrmda&p corapri^'sfeg- po!yiyiiailyl dimethyfeminonmm chloride) homopolymer (PDADMAC) or poiy(DADMAC) as a water- soluble .coumenoii. PDADMAC bears 1 esiiorhc charge per DAO AC mo omer aisit (which as & molecular weight of 162 gmm¼ok),_. nd hence Q polymer =* 1 and Z^{' ;::} +L In addlt o, the polymer is a homopolymer, so F o mer =1. lithe PDADMAC is resent in the formulation st a cooceodstlon of OJ gra s/iOO grams of the f mas!atjon, the yalue of P would be calculated as follows:

P-tO.t x i x lxt)/162 - ·¾·Ο.ΟΟ06!?3

fCM>?®| Using the Drset vskse of -S.00%7 esleidsisd Is the example described above for a mktare of an srdook, satiomc. and ooreomc sorfactsot, the fatso WDnet would be ca!o kisd as;

P/Drse - (+0,OaO6173)/(^»O.O0 67) - - 0.06384,

Ths B a&vs vahte of P/Doei eo only i Icmes he ratio of She- charges due to the polymeric eor;aterion and the ne charge oo the mixed micelles, hut slso kidlea ., ssace it is a negative -num er, that the cha?g« m the polymeric eouoiedoo. ao the se charge os die x xsd mieeiks are opposite. In. this , there m&y he ao electrosta c ioieraetiors bet eeo the po!ymefie coooierion nd the mixed micelles, sad hence the formolaiioo .may be x^'th the scope of t he instant mw m.

072| Alternatively, if the n- moe? of equivalents of charged groups present per gmrrs of polymer is available om the maorriact rer, or can be derived fro the symihedo roots osed to crests the polymer; or csn be derived from anaysis of the polymer, then P^' may .also be calculated based oo that inferarstloir.

[88731 For exam le, F ~ (C polymer x Eq polymer x Z% where Cpolymcr and Z are defined as above, a d Eq olymer Is the membe of equivalents of groups per gram of polymer with a charge -consistent, with the value of Z used.

|θ©74) For exam le, if a water-soluble copolymer that is described as baviog 0.006173 equivalents per gram of polymer ^'{actives} of a eahomcaliy charged monome, aod this polymer is used in a formoladoo at a cooeeniratioti of iU grams/I 00 grams of the fomMkit n, P¾ calculated as follows:

P - (0.1 x 11006173 x !) = +0.0006173.

|@07S| This yalue of P, with the same Dnei value used itt the example above, may the be used to calculate the ratio P/Doet. P/Bnet - ( 0.0006 i?3yf0.&0¼7) - -€',06384, which yields to s&m& result as described abo e:.

f§§Hf IK the case of copolymers comprising more tte one mooomer of like charge or capable of developing & like charge, then the F value calculated for the iormalal oB would ^'be the sum of the F values calculated for each of the appropriate monomers comprising the polym r used,

[¾7?| Finally, ia practical work; the absolute value of P/Dnel_. Is m ndicator of which charges are k excess mi which are m deficiency in formulations of the msCsnt Invention.. Wh the absolote vakse of P/0oet Is greater than 0 but less than 1 , the sure her of charges doe to groups on the polymeric eoanteriori is less than the net number of charges due to the keadgroups of the ionic surfsctet or surfacteits comprising the micelles, be, the polymeric couatcrion Is k def ie&c . When the absolute value of P/Dtse Is greater than L the polymeric coemerion Is m excess, &ηά of course, when the absolute valu of F/Dnet ^:= k the number of charges diss to the headgroups of the ^'polymeric- counterion eqil ls the net number of charges oitihe ionic sca aet m or s rfactants comprising the micelles.

1 t7S| Mmy polymers are suitable for use as polymeric eouatsrlons Irs the insec invention. In one embodiment, the polymers are wster-soiub!e s defined herein. The polymers may be bomepolymers or copolymers, rid they may be !kear or branched. Linear polymers ma be preferred la at least seme embodiments. Copolymers may be synthesized by processes expected to lead to statistically random or so-called gradient type copolymers. In contrast, water-soluble block copolymers are not suitable, since these types of polymers may form aggregates or micelles, in which the more hydrophobic block or- blocks comprise the core of the aggregates or mfcsiles and the more nydrophi!!c block comprises 8 ^cor n " region k contact with water, ft Is thought that these self-assembly processes compete with the electrostatic interactions required for a watewsokfele polymer to serve as a polymeric soonterlsn with ordkary surfeclsnt micelles. Although .mixtures of water-soluble polymers are suitable Irs at least some embodiments of the present Inveofioo, the mixtures selected s ould not comprise block copolymers capable of farming so-called "complex eoacervate" micelles through self-assembly, skce this micelle formation process also com et s with the kter&ctioo of the water-soluble polymer as a polymeric eoosterloa to ordinary surfactant mtcslks. When the polymers are copolymers, the ratio- of the two or mo e monomers may vary over a wide range, ¾s long as water aofobOiby of the polyrnei is m intained.

[0H?9| m embod ment, the polymers s ould; he water soluble_; as denned her to sod therefore, should not be ex pariteies or mierogels of my type. In such embodiments the polymers should not be eross-l Inked through the use of moooniers capable of forming covalem bonds between independent polymer chaias, and the compositions and formulations should be fee of cross-linking ag eats added expressly for this pa^ppose, it believed that polymer aggregates that may he "swollen" by water m the form of microgeis or polymers that form cross-linked networks will not have the appropriate foil mobility of the polymer chains needed for them to function as polymeric coimterions- with respect to ordinary s t fociatn micelles. Polymer anicles which can serve as structurants for an s ueoas com sitio through she formation of fibers or threads ate not seliahte as the water-soluble polymers for similar reasons. Similarly, ktex particles a e believed to not. be suitable became many of the individual polymer efisks In saeh &rtleies a e, in fact confined to the particle interior and are not read available for interaction with the a ceous phase. Latex psntleles also lack the chairs mobility re uired to function, m m tzfmm to ordinary, surfactant micelles.

|S98§1 The ra dom .copolymers may comprise on or more monomers bearing the same charge or capable of develo ng the same charge, and one o more monomers which sre non onfc, i.e., so capable of bearing & charge. Copolymers ros be synthesized by graft processes, . resulting i "comWike" structures.

p Si^'j Wster-sol ble copo!yroers derived !rom a synthetic monomer or monomers chain terminated with a hydroxyimontainsng natural material such as a polysaccharide, which can be synthesized wi h ordinary free-mriieai initiators are preferred. At least one of the synthetic monomers may hea or he capable of bearing- a catiomc charge. Methods of producing such copolymers are described is U.S. Patent No. 8,05137 , herein incorporated by reference in Its entirety.

£00$2| In one embodiment, the compositions m free of copolymers comprising at least one monomer bearing or capable of developing so an onic charge and at kast one monom r bearing or capable of developing a catfonic charge. Snch copolymers, sometimes referred to as "amphoteric" copolymers, arc believed to not. function as well or at all as polymeric eonnterions to micelles bearing a net electrostatic charge for at least two reasons. First, the proximity of both types (anionic and eationk) of charges along the polymer chains, if randomly distr buted, interferes with the efficient pairing of a givers type of charge on the polymer chain with the headgroup of a .sur&ciant of opposite charge s a micelle. Second, saeh copolymers have the potential for electrostatic b teraedens of the anioaie charges or? a givers polymer chain with the cationie charges OB smother polymer c mn> Such interactions eould lead to ihe -formation of pol mer aggregates or com lexes m a process that is ndes ab competit ve with the interaction of the olyrner with m cella?- aggregates.

|H S The suitable water-sokb!e polymers may keiude naiatal or sustainable materials bearing or capable of developing c-atiorsfe charges, c . as cMtosan and its derivatives, Chitosan is advajitagsomiy a nst tsl or sasfennabie material. The water-soluble polymers ma also include deri at ves of Batumi po ymers such as guar bearing added callonie grou s_* e.g.. ustemteed guars, such as Aqeaeat, commercially available from Hercules/Aqualon. |#SS ] Suitable water-soluble polymers bearing or capable of bearing a cation ie charge may be derived from synthetic monomers.■ Nondinbtin examples of monomers bearing or capable of bearing a ea ionlc cbsrge include tikiiyl dimethyl, atiimoaium chloride, quaternary ammonium: salts of sisbstiuned ger iamide, ffiethylacry rrdde acry!ate and. methaerylate, quatemked a!ky.1 amino- acrylate esters m4 amides, MAFTAC (ffiethaorylamldo propyl ifi methyl ammomnm chlorides), trlmethyl ammonium methyl methacryiale, trimethyl. ammonkm propyl ethacrylamide, 2-vinyl -a!kyl q aternary pyridmlom salts, 4-vij_yl N- alkyl aternary pyridadnrn salts, 4"Vinyibcn¾:yltriaikylann'noniorn salts, 2-wmyl piperidkuum salts, 4-vinyl pipendkium s lts, 3-slkyi l-vk j. i id olkm salts and mixtures (hereof. ESryletseimioe la an example of a monomer capable of developing a charge when the pB is suitably redyeed. Other suitable caiioaic monomers inchsde the iooene class of Internal canonic monomers,.

j§0§5) Non-iimiikg examples of monomers which are nonio e, not bearing, or mi capable of hearing an electrostatic charge me!cde the alky! esters of acrylic acid methaeryHc acid, vinyl alcohol, vinyl methyl ethsr, vkyl ethyl ether, ethylene oxide, propylene oxide, and mixtures thereof. Other examples include aeryiamlde, dimetliy½cry!amick nd. other alky!^' acryiamide derivatives and m tures^' thereof <¾ er suitable mo omers may Includ ethoxylated esters of acrylic acid or met.hscry.Hc acid, the related tristyryl phenol ethoxy ated esters of acrylic acid or meihaerylie acid and mixtures thereof. Other examples of ootuonio monomers include saccharides snch as hexoses and pe toses, ethylene glycol, alkyiene glycols, branched polyols, and mixtures thereof hSbf l® some embodiments, water-soluble polymers compmibg mo»ofeers which bear N-halo. groups, for example, -Gi groups, are not present S is believed^' (feat interactions bet een: polyroers comprising such groups as polymeric eormtenons to micelles- leads to either & egr ation ef the sur ctaBis themselves and/or a degradation of the polymers th o gh the en anced local concentration of the polymers at the micelle surfaces.

!§W?! When the compositions comprise ssrfk-tet micelles with, lor exam le, a net anionic charge m& a water-soioble polymer or raktare of polymers bea ing or capable of bearing cahoaie charges, hen the compositions may be free of any additional polymers bearing m anionic charge, i.e., a charge opposite to that of the first water-soluble polymer bearing or capable of bearing cabooic charges, The presence of a first wateosolah polymer bearing an estiorde charge aod a second waierosolabie polymer bearing a anionic charge io the sam -fomisJa ioift h believed to give rise to the !brmadoo of complexes be ween the two polymers;, ie.„ so-called polyeleerro!yte complexes, which woaki undesirably compete with the formation of coroploses beiweeo the micelles bearing the anionic eiwge nd the polymer bearing tlhe catio e charge;

p S| However, compositions comprising sarf etarit micelles bearkg a net electrostatic charge and a water-soluble polymer bearing or capable of bearing m electrostatic charge opposite to that of the surfactant micelles ma comprise additional polymers which do oot bear charges, that is, noolonic polymers. Such nonionle polymers may be useful as adjuvants for thickening, gelling, or adjus ng the riieologieal properties of the compositions or tor adjusting d e aesthetic appearance of the formulations through the addition of pigment or other suspended particulates, it shoeld be noted, however, that -in many eases, the polymer- micelle complexes of the instant invention, h n adjusted to certain, total actives concentrations, may exhibit ¾If-ibickemn ^,÷ properties sod not explicitly re re an additional polymeric thfckeaer, which is desirable from a cost standpoint.

PI 89] Irs one embodiment the compositions are free of noniooie sariserants which comprise blocks of hydrophobic and hydrophihe groups, seed as the Pl onfc®, It is believed thai the miesllar structures formed with such large s iac-tams, in which d e hydrophob c blocks assemble ioto the core regions of the micelles .and the hydrophlllc blocks are present at Ite .mfcel - surface wo ld miertere with the polymerie eosnfenos ktferaettons with an add tions! c arged suifsatmi ^or orsted duo a mixed micelle, and/or ¾lso represent a mo e competitive t dcelfc assemb nmchatbsny m & mmsrn si ile to that of the us of block copolymers osed as polymerie co«nterion&, whish s e also pr i¾?& rso ^'present.

S9I| A very wide range of surfactants aad mlxleres of swfat^a s may be used, including anionic, ooolosbc md cariomc sisrfktass and mixtures thereof As alluded to above m die description of Dnet nd P/Dnel, It will be apparent that mixtures of differently charged surf ctant tmy be employed. For example, msx ares of cabonie d anionic surfactants, mixieres of estlonle md n hak, nnxioms of arskss ic and oomonie, md mixtures of eariooic, nomonie sod anionic msy be suitable for use.

] Examples of cat oic surfactants include, fed are not limited to monotnerie quaternary ammonium com ou ds, moimmerie bigoanide compounds, and combinations thereof Suitable exemplary quaternary aramomyro compounds am available from Stepan Co ¾R½ the Rename BTOt- (e.g., BtCsf 1010, W 1210, BTCD gi g, Τ€ 35«). Amy other suitable moi omeric quaternary ammorrhtm compound msy also be employed, BTOI> 1010 and BTC 1210 described dideoy! dimethyl ammonium ebloride and a mixta? didecyl dimethyl ammo um chloride mi toask l dlmsdryi benzyl, rnmmmm ehiobde, respectively. Examples of monomerle blgnsmde compounds nclude, bist a not limited to cMorhexidme, slexidine sod salts thereof

(00§2f Examples of anionic sorfae ams include, bet are not limited to alky! sulfates, o!leyl sulfonates, slkyl ethoxysulfktes, laity seids and istiy acid salts, linear aikyihenzsoe sidiboates (LAS snd KLAS)_S secondary alfcane- sulfonates (for example I!osrspuPi $A$-30>₅ methyl ester sulfonates (soch as Stepso® Mild FCL from Step&n Corp), alkyl. s itosoecinstes, aad alley! amino acid derivatives. amrm!lpids bearing solonie chsrges muy also be sed, tor example, in fo m a& empbaslslng greater sostamabllity, sloce they are sot derived from petroleo -hased materials, An example of such & rhsmnoilpid Is JBR 425, which is supplied as an aqueous solut on with 25% actives, from ie i Bioseriactant Co.,. LLC (Saekvllk, f, USA).

§ 3| SoeaRed ''extended chain s rfacteis'\ are preferred lo some formyd&tioos. Examples of these k serikdaols are described m US Pat. Pub. No.. 2006/0211593, Noa- limifeg examples of nonloolc surfactan s include aifc i amine oxides (for example Am nonyx© LO from Stepan Corp,) aikyl amldoamim; oxides (for example Ammonyx L IX) itoffi Slepan Corp,}, alky) phosphine oxides, all ys po!ygiuebsides i aikyl fxsfypentosides, alky! poly (glycerol esters) asd alky j»ly(gjtycefti et&rs), &ad allryl and alky] phenol et oxylates of ad ty es, Sorbhao s ers a d efhoxylated sorbitan esters are also usef l atmksik sorrkiards. Other useful rronfonio surfa tants include iy acid amides, M acid rnoBoe&anoiamides, M acid disihaookmldes a^d fatty acid isopropartolarrbdes. ¾| la one- embodiment, ¾ phospholipid suriktaffi ^'ma be included. Lecithk Is an ex m le of a phospholipid,

!§95f In one embodiment, synthetic ¾wit†erio?sie surfactants t y be presmi. Nou~ limiting examples Include bbatkyl beiarees (for exa ople Arophosol® LB from Stepan Corp.), and lk ? sidfo-betaines sad mixtures thereof.

[$®¾J In one embodiment, at least some of lbs suriktents may be edible, so long a they e i i wste? solubility or cm form mixed micelles, with edible nornonie sar&eiaois. Examples of such edible sarfesfaois Include cased wad lecithin,

Ψ Ί] rse embodiment, \ s sarfaetaatS: may be selected based on gree or^' nature! criteria. For example, here is an increasing desire to em loy com o ents that sr naturaMy- derived, n n aby processe , md biodegradable, rather than sim l being recognised as safe. For example, processes such as eihoxyktion, may rmdeslrabfe whsre It is desired to provide a green or natural product, as such processes coo leave resldoal -compounds or impurities ^'behind. Such "natural surfactants" may be produced using proce ses perceived to be more natural or ecological, such as dlstiikboo, condensation, extraction, steam distillation, essure cooking ^'and hydrolysis to maximize/the purity of natural ingredients. Exsropies of s h, Natural surfac ants that may be suitable tot use are described in LIS, Patent Mos. 7,608,573, 7,6 .8,93.1, 7,629,305, 7,939,486, 7,93*48$, ail of which are herein Incorporated by reference,

VI. Ssiti k Ad|¾^y»fs

[§0?ttj A wide range of optional adjuvan or mixtures of options! adjuvants may be preserst For example, builders aod vhekliog agents, including but not hoisted to EDTA salts, GLDA, MSG, l c ses, 2½dfoxyae;ds and derivatives, glutamic- acid and derivatives, trimethylgryeiee, etc. may be Included.

\W99] Amino acids and mixtures of areisio acids m&y be present, as either raeentie mixtures or as ind vidual components of a single ehiraliiy.

IhMHelll Vitamins or vluunin precursors, for example retinal, may be present. I Jj Soiace of soluble m, cop er, or silv r ioas fee present, is^' te si le laargastk salts or salts of chela in agents, including, bat not l mi ed: to, BD A, GLDA, MOD A, elh¼ acid, eta,

[00! Ii2] Dyes md w xmts may k resent Polymeric thickeners, when ss d as taught above, may be present.

{00163] Buffe s, mcluding but ssot limited to, carbonate, phosphate, silkat.es, borates, and combinations the eof may be resent Elsetmtytss such as alkali el&l sabs, for e am le including, but sot limbed to, chloride salts (e.g., sodiam shioride, otasskmt chloride), bromide salts, iodide salts, or combinations thereof may be presgnt

il04| Wster^rasdbie solvents smy be present io some. mbodiroenfe. Lower alcohols (e,g., ethsnol)_; ethylene glycol propylene glycol, glycol et e s, sad mixtures thereof with wate miscibilit at 2S . may be present ½ some ensbodiaseats. Other embodiments will nclud oo lows^'r alcohol or glyet)! ether solvents. here such solverds ate presets some mbofeertis may mdmk them h only small amouots, for example, of cot more thsa 5% by weight so more thao 3% by weight, or not msre ihm 2 % by weight.

Water-muniseibie oils may be present, bein sokbltkiid mto the micelles. Among these oils are those added as Ikgraoeea, P eferred oik are those tha are f om ostumily derived soorces, melading the wide variety of so-called essentia! oils derived from a variety of b tanical sources. Formulations ia saded to provide ao imkrohlal benefits, coupled with im roved overall sastamahiliiy .may a vatttageoosly comprise quafernary mmonium eorrrpoaads arsd/or monotrjerk biguarddes s ch as water soluble salts of e^'hforhexid e or alexidine io combination with essential oils susb as thymol and the like, preferably m the sence of water-raiiseibla akolwis.

1st one embodiment He composition, may further iac!u e one or more oxidants. Examples of oxidants mekde, but are not limited to hypohaloos add_s hypohahts a i sources thereof (e.g., alkaline mstai salt arid/or alkaline earth metal salt of hypoehjorous or hypob oraoas acid), hydrogen peroxide mi source thereof (e,g., aeneous, hydrogen peroxide, perborate d its salts, psrearboasie and its salts, carbamide peroxide, metal peroxides, or combinations t e eof), erasids, peroxyaeids, petoamcids (e.g. peraeelk acid, percitrie acid, dipemxydodecanoie acid, psroay amido phihakrnide_f peroxomonosulf nk acid, or peroxodisultanrio acid) and sources thereof (e.g., salts (e.g., alkali metal salts) of perscids or salts of peroxyaeids sach as peraeeiic acid, pe?x¾rsc acid, diperosydodecanoic acid sodinm otassium peroxyseiiate, or. -combinations hereof), organic peroxides and hydroperoxides (e.g. benzoyl peroxide) peroxygenated inorganic compounds (e.g. pes hbrale and its salts, ermanganate md i s.saits an e iodic acid and ks salts), so!uhliized chlorine, sohfollized chlorine dioxide, a source of free chlorine^ acidic sodium chlorite, as active chlorine generating compound, or a chlorine-dioxide generating com o nd, active oxygen generating compound, sofubilked 020150, -haio compounds, or cossfemations of any suck oxidants. Additions! examples of such oxidants are disclosed In U.S. Patent No. ?,S I7,56§ arid U.S. Publication No. 20 1/02365S2, eac¾ of which is herein incorporated by reference ia ts entirety.

|0Ο ΦΤ| Water-solohie hydrotropes, sometimes referred to as monomerie organic electrolytes, may also be present Exam les include xylene sulfonat salts, naphthalene sulfonate salts, and csmene sulfonate salts..

t! §] Enzymes tnay be prese partic kd wtem the form alsilons are tuned for use as laundry detergents or as cleaners tor kitchen sod restaurant surfaces, or as drsin openers or d m maintenance products..

Applicants a e found that & wide range surfactant m^'ktn s resulting in a

wide mng¾ of .Dnei alues tnay e \jse . in many Gases, the surihciaots selected may fee ptimised for the sokb?li¾¾tk>n of va io s watendinnnscible materials, such as fragrance oils, solvents, or even the oily soil to be removed Item a surface with a cleaning operation. In the oases of the design of products which deliver an antimicrobial benefit in the absence of a strong xidant such as hypochlorite, a germicidal quaternary aron murm compound or a salt of snonomerie biguanide such as cliiorhexldine or alexidins are often Incorporated, and may be insorporated Into micelles with polymeric, oounterions. The fine control over the spacing between the es ionic headgron s of the germicidal aternary ammorkium compound or biguanide which is achieved via the incorporation of a polymeric countetlon can result in a significant redaction in the amount of surfactant needed to solubihse an oil esumin in cost reductions and im oveme t in the overall snstasnabliity of the formulations.

flQUff In contrast to what is described in the art, applicants have also found that the magnitude and precise value of P/Dnei needed to ensu e the absence of precipitates and/or coacervate phases can vary widely, depending on the nature of the polymeric eounterion and foe surfactants selected to form the mixed micelles. Thus, since there Is great flexibility in the selection of the polymeric eounterion for a given surfactant mixture to achieve a particular goal, a plicants have -ado ted a systematic, but ui p approach for quickly ''sqgntib through"^' rang s of lVD.rse-i in order idcrmiy, mi to c m are, formula ions somprisbg polymoric conrstenons,

|00l 111 The forma rions eomprismg the mi ed micelles of a ret charge and a water- mfabk polymer e&rmg charges opposite to thai of die mieelfes §r§ aseibi as ready to use surface c!essws delivered via pre-s Kdstened nmwwm substrates (eg„ wipes), or as sprays in a variety of packages familiar to c mm.

[110112] Co/acentraied forms of he formu!atio S may also be developed which may he diluted by the consumer to provide solutions &at are then. osed. Concmt ed forms tha sidishie for dilution via automated systems, in which the concentrate is diluted with water, or m which two solutions are combi ed In a given ratio to provide the final use formulation are possible

f 00113! The formulations may he m the form of gels delivered to a reservoir or ^'surfa e with s ^'dispensin device. They m y optionally be delivered In single-use po ebes comp ising a soluble m,

|Stl!4] the- saperlor wetting, spreading, and elesmng performance of the systems ¾ke them especially suitable .for delivery f om aerosol packages comprising either s- gte or daaf chambers.

|.0 iI5) When the compositions comprise cklorhexidine or a!ex!dine salts as & csrionieslly charged surfactant, the compositions may he tree of iodine or iodine-polymer complexes, :n¾naparticles of silver,- copper or zinc, i ieiossm p-chloromedsyl xylenol monomeri peatoss alcohols, D-xylhoI and its isomers, -arabltol aad its Isomers, sryl alcohols, benzyl alcohol, and henox eihsB l.

VI S¾it¾* ow¾v®« Stfetratea

Many of the compositions are usef l as liquids or lotions that may be used its eombmaiioa with oonwoven substrates to produce re-molstened wipes. Such wipes- may be employed as disinfecting wipes, or for floor cfeairmg in combination with v ious tool configured to attach io the wipe,

|©01i?| fe ose embodiment the deanrng- pad of the present inveatiori comprises s oonwoven substrate or web. The substrate may be composed of norr oven fibers or paper. ¥11, Examples

How P rtlde Ske mi IM& fotot!A ere Measured

|.00^'i| i The- diameters of the aggregates: with the polymeric eoaraerions -(m. nanometers) and their ?,e†¾ potentials were measured -with a Zetasizer ZS (Malvern lastmmettts), This inst umen utilizes dynamic light seattermg (DLS, also keowa as Photon Correlation spectroscopy) to dstesme th¾ diameters of collo ds] particles k the nge from 0J to iOOOO rm

\mtW] The Zetasteer ZS ss rass offers a range of delimit parameter which can he used in the cak¾ktk>a of particle diameters f om the raw da a (known as the correlation function or autocorrelation function). The diameters of the aggregates reported herein used simple calculate model la which the optical properties of the aggregates were assumed to be similar to &ph¾dcai particles of polystyrene latex particles, ¾ common calibration standard used for ^'more complex DLS experiments. In addhioa, the sottware pa.ck.age supplied with the Zsiasizet provides automated analysis of the quali y of tire measarernents ma e, the form of ¾ srf Advieeff The diame e s described hereia (specifically what is known s the avemge particle diameter) were calculated torn raw data hst met ^:Έ^χρ¾η Advice" standards consistent wife acceptable results, unless otherwise noted. In other words, the simplest set of default e su ement conditions and c lculation paipmeters were used to calculate the diameters of all of the aggregates described herein, in order to f cilitate direct comparison of aggregates based on a variety of polymeric coonterions md smfaciams, and avoiding the use of complex models of -the scattering which could complicate or prevent comparisons of tire diameters of particles of differing chemical composition. Those skilled in the art will appreciate the particularly simple approach taken, here, t d realize that it is useful m com aring^' and character zin complexes of micelles a».d. wst r«sol¾ble polymers, ½«te ende of the: details, of the types of polymers md surfactants utilized to form the complexes.

[011128] Tills Instrument calculates the zeta potential of colloidal particles from, measureme ts of the ekctrophorstlc mohiiihv,, determined via a Doppfer laser velocity measurement. Them exists a relationship bet een the electrophoretic mobility (a messi ement of the velocity of a charged colloidal particle moving In an electric field) sad the ma potential (electric charge, -exp essed in un ts of millivolts). As In the particle sixe measurements, to facilitate direct comparison of aggregates based on a variety of polymeric oouDter oms mi s iaoiamA the Sim lest set of dsf¾eli me&¾iremem conditions were used, lc, the aggregates were assumed to behave as polystyrene latex paAldes, arid the Sffioloc owskl m del sskt the el¾c¾ >pfeoretk-.mo IiiCy m the xe-t potential as used hr all calculat ons. Unless otherwise n ed, the me zm potentials described her in wer¾ calculated torn raw data hai met "Expert Advlcs" standards consisten with acceptable results. Aggregates bearkg a i eatlorde (positive) ehargs will ex ibit positive values of the ¾:eta potential ( s.V), while Ihoss hmiag a net amo fc (negative) charge will exhibit negat ve valees of the eta potential ( mY).

Example 1

Ready to Use Cleaner With Sodiem Hypochlorite

Ϊ21} A series of formulations at w bus P/Doei values were prepared i¾r vmsl evakaiioo of phase slabs lity, followed by measuremen of the Z-averago diameters of the ag egates ormed via dyratmic light scattering, The form !atious are ese&l as ted s rf ce clean ^ ibf exam le for bathroom surfaces or U k col ers,, thai are stained by mold or mildew or with teo.ado8 food residues that require the cleardog aeikrn of s&rfkstas s combined with the s a& remo l^' .benefits provided by sodmm hypochlorite b!gadt. A soeiroi formulat on comprtskg mixed micelles of aei aaiordc charge without, the presence of polyiPADMAC) as the polymeric eoasterion was also made. The formulations wore made by simple mixing of apprOpriata volumes of aqe ous stock sohahorts of the surfactants,, polymer, the sodium carbonate (which provides sigaifioaet buf r capsoiiy and whieb keeps the pll of the final formrslatioos wixhirs a desirable rarsgeh ami a source of sodium hypochlorite a aeosis solution. The compositions. -gre summarize is 1 able 1.1.

Table 1 ,1

I'CSIR- ¾t% P/Dsret Appssnmce a ulatiaf! Am sosyx® Dowiax Ϊ¾Α¾ ^' aOC! fDADMAC

Name LO

A| -2 0,2652 2,5 0.025 «0.109 Clear

Ai 4 0.691$ 0.2584 2,5 0,9984 \ 0,05 -0,346 Clear-

A3-.-S 0.5824 - 0,2176 2.5 0.9984 0.2 •0.644 Clear

A4-5 1 0.1456 0.0544 2 5 0,9914 0,8 -26,300 Clear

AS- 12 0.721 0.272 2.5 0.9984 0 0 Clear

-0A.I ; Cloody

^M 0.6552 0.244$ 2.5 0-9984 0.1

(clear at 24 ; and

lowers

A O 0,1272 0.072S 2.5 0.9984 Cloudy

101221 AmaK>s x .LO (amne oxide, St safi Co.) supplied as active solution b water.

{98U3J .Oowfe™ 2A1 (Dow Corp), supplied as 45% active sdutioB in water, and with an average of 2 sulfonae groups per molecule <Q &m ~2),

[Οθί 24] PDA AC - pdy(d iyl dimethyl ammonhitt chloride), F!o ia FL424S (S^'MF Corp.), supplied as 40% active solution m water. Z polymer =1, Q lym r -1, M polymer -- 162, F ol mer = i (hontopoiynier).

f!HHSl aOCI source™ Clorox germicidal bleach, titrated immediately prior to se to detemhoe the sodium hypochlorite activity.

Table 1.2

22aver¾ge dbn¾eters oiMbbles with ¥ y mc Co mdoiS (PoIymer^ leelle Complexes) sib. Coatrol Micelles^' ifetenjtiaed by ^' ynamis Light Seader.b 25

Formi!at!OP Absolute: Value, | Z-svergge dbroeteo m® (% relative ujodsrd ame FDuet ! deyiatioo at r s

A I 0.1 $9 j 44.4} (IA1)

A2 0346 56.9 (0.75)

A3 1.644 71.92 (0.201)

Λ4 26,306 49,21 (l.OS)

A5 0 3S.S (0,396) I I The results m Table .1.2 ndicate that be addition of poiy(DAD AC) s a polymeric eouberioo for the rnbed micelles com risn the same oxide and sulfonate results b the formation of complexes (formulations Al through A4) ic have larger Z- averago diameters than die mixed micelles emsel es (fonrsuistion A5). The resibs also dkate that the defsm! parameters .selected for calculators of the diameters IVorn the BLS preasisresrsents, as described: ibove, gave very reproducible results. For the trip! bate anal ses of the formulations, th® vsri&ioa beweeo Irdivkb&l Z-everage diameters was typically less ban 2% relative. Hence, the diameters calculated tor loorjbatbns Al through A4 can be considered different from one a other a¾d difdereot from that of the eoohol formulation AS. In soot r

demonst a in the reproducibility of t e Z-average diaraeter* es!ealated fom he dynamic lig&t sca tering dafc¾ a sample of formulation AS was loaded into a sealed dis osable c ve te sod was an l sed every 3b utm apors storage as the instrutitest (with the tem erate cont olled to 23^C ) overnight ^"I¾ mean Z-average dkmeier lk>5« 2? separate analyses was 35,96 r*m, whh a standard dev at on of 0.1907, or a percent relative standard devia ion of 0.53%. Merels belo , Z~aves¾g di&meters quoted will fee the esul of at least 3 analyses of a sample. Relative differences of at least 2% relative in the ~average diamete s measu ed tor difletxmt formulations will be considered slgnifica , unless the measurement conditions dictate otherwise,

¾4 I2?1 it Is believed, without feeing bound by theory, t at the Z-avera diameter of the mixed micelles m. formukiioB AS Is, at 35..S rm_t ladicaiive of the !oft tioo of rod-dike micelles, due to the relatively high coacemration of electrolyte (carboaais bui&r, sodmm hypochlorite and the sodium chloride- present the sodium hypochlorite stock sohitiorr). OliS] 1ST some embodimem forinuktiom of the i stani iavetstion are free of precipitates ami eoacemte phases. As shown above, adjustment of the P/Daet arameter can fee oods, by e as glstg either the coBeearratioa of the polymeric cou ted®?, or by chsiigmg the composition of th mixed micelles- by- ehs¾giag the relative amounts of the aoiosioaily charged surfeetafit and my oeharged surfactant present, or even by changing the relative amounts of an sa ieadcaily charged surtectant.and a cstiomcaily charged sariktant resent in the ibormlstiom sua examination e>f the- formulations lor clarity is generally sufficient for idersiifying samples which are clear and tr e of coseervaies aad precipitates. However, analysis of samples via dynamic light scattering can also be very useful in .confir ing the thermodytratmc stability of the soluble polymer-micelle complexes formed, by the interaction of micelles bearing m electrostatic charge and a water-sokrh!e polymer bearing aa electrostatic charge opposit to that of the micelles, la m bodi t, the polymer-micelle complexes sh ld exhibit 2-average diameters of less thaa about 500 mrp in order to exhibit colloidal stability, mi iim with Sodium Bypoeblorite

Adjissirrserit of M ixed Micelle Compositiorrs fhfl!l^] In this example. forrmdaticms c mprising mixed micelles of a nomoolc amine oxide surfactant mi.m anlonicaily charged sarfaetaot and οίν{ί>ΑϋΜΑ£} as the cstionk polymeric eonnterion, in osshkarioo with the oxidant sod um hypochlorite, whloh sxh t- excellent wetting a d s ain ygmovsl perforrnaaee are provided.

[M130J ^'The tonmdatlons In this example have a feed: otal sur&elaot+polymer concentration, carbonate bidder, 4 bleach concentration, an cover a wide r¾8g« of the absolu e value of F/Dnet. As described abo e, the formulations of the simi invention are free of eoacervates and precipitates. Thai said, Ibrmukilons that are relatively earer to a eoacervate phase boundary am be preferred due to their relati vely faster rates of spreading s» both pola and aoa-po!ar surfaces, which also esells in more rapid slain removal by the oxidant,

M31J Aqueous i nmdations were re a ed by mixing appropriate amounts of stock solutions made with the Ind vidu ingredients, j jwfax^'m 2A1 saltbnatis surfactant (sapplled _:as aqueous solution, Dow Chemical), Ammonyxi^; 1,0 amine oxide, Sodium earbo Pe (scppiled by Plirka), hypochlorite, bleach, Floqnat PL. 4245 (Cationie polynief, a bomopolymer of dlailyl dimethyl ammoibnm chlnrlde or ..poly(0AD A.C) supplied as aqueous soiuboo, S F International) and water to form the final d irm latlons. The compositions were systematically varied by increasing the overall sarmetant charge dilution parameter (CD) values ai a given, fixed polymer concentrations pntil solutions which wer clear and free of eoacervate were obtained,

[08132^') The overall sarfaclant: charge dilotlon parameter, CO, is defined as:

is ik§ molar eooeentration of the uncharged surfactant and C_C|_i3:gfiii Is d e molar coacentrstion of the charged surfactant.

p1§133] Sam le Bl represents the formulation optimised at 0,01% polymer and 1% total saifsci&at + polymer. Sample B2 represetPs another formulation again optimised to be free of eoacervate while m&lm&imng the total siafaetan polymer again at 1 %. Sample B3 represents an alternative ihrmaiatkm which Is also clear and tree of eoacervate.

|8 134] Sample B4 represents a forrpillatlon winch was observed to b cloudy at aboot 2$%-_} hat which was clear at lowe ieeiperstures, and hence may not be sufficiently _.robust However, an alternative formulation (Sample 5) with, better stability eao be readil provided through a slight ohaage in the CD parameter. Note too that the !VDnel parameters for ali of the formulations are negative, indicating rbat ifee polymeric coanterlon and the mixed micelles are of opposite charges, and hence within the scope of the Instant laverition. After ns cifig ths st ck s lu o s h« am les were a la^d for s tew hours and were visis&lly inspected to dtec l&e presence or^' abso se of soaee st phases. At. lower overall surfectant charge dilution parameter (CD) vskes th«- meraei e between tbe positively charged pol mer and the tomc surfactant is strong, le&dlrsg to ooaeorvatiou, At higher CD values the interactions weaken eooogh to avoid eoscevatlos? d preeip kst Optimised examples are selected such that they re clear md have so oacer ate or •precipitate.

0!36] Table 2,1 describes die compositions of die visibly clear, optimized formulations, Figure I farther describes: ome of the opiiroked ibrnnilatiom ø« a phase map showin the eoacsrvabors boundary.

Table 2, i

Exam le 2^» Coace ratss. S«itabfe for Dilution

|S813?| The imi&nt iRventiba. $m- also r v de roducts, that. m& pre ared as concentrates which ar dtiutei upon e, Since the formation of a eoscervaie phase Is undesirable for the re sons cited above, optimization of the formuiatioas such t co80@rvates are not present in both the eor^erdraie- and at the love! of dilut on desired ma bs m important dmrni v c to provide, The optimization is aehiwd by creating a series of samples, varying the absolute value of ?/¾« via varying the coneentratio« of the polymeric eoanterion at a fixed mixed, mics!k composition, carbonate heifer, and. bleach. mce mooa. eot^'d a formulation which is free of coscervates a she desired dilmion is identl ied. As wit! he readily arent, eompositios s which are tree of eoacervate are no directly indicated by the absolute valus of the P/Dnet parameter. This parameter ma be modulated ¾$ described herein,; d while specific threshold value rosy not correspond to a division of com si ions that &i¾ fee of eoacervate aud.tbos¾ tha am no this parameter still ^ ese s a useful tool 1¾ 13S| Formulations CI through C4_> ^'although- dear asd Hoe of eoacervat M concentrates, appear cloudy when diluted by a factor of 5 with deionfeed water, ar d hence are sot suitable foe this, particular ^'dilation. Hie absolute, valise of P/Dnet for hese formulations ranges from 0,00?? to 0.0308. Is Formulations C5 tfeftftgh C8_S the absolute, value of the P/Dast parameter is reduced slightly, tk m a high of 0.0058 to a low of 0,0012, to yield concentrates that can be dilated by a factor of 5 without Id-rising coacsrvaies, CO represents the control without a&y Fioquat 4540, the. rx?iy(DADMA£:) oadonis polymer.

Table 3 d

ID Dowikx™ Ν¾>(Χ¼ bfeOCi Fioquat Appearance POF

1.0 2A1 t¾¾ wt¾ FL4S40 .after 5.x dilution

wt% wt% wt% with Dhwater

CI 0,885 0.205 2,215 0.821 0.Θ035 cloudy -0.0308

C2 0.885 0,205 2.215 0,828 0,0009 cloudy 41.0077

O o.sss 0 205 2,215 :0.82g 0.0818 cloud -0.0154

C 0JS5 0,205 2,215 0,§28 0,0027 cloudy 4X0231

C5 0.885 i),2Q5 2.215 0,828 0,0002 clear A1.0019

C6 0.885 0,205 2.215 0,828 0.0004 clear "0.0039

C7 oils 0.205 2.215 0.828 0.0007 clear "0.0058 C8 0.885 0.205 1 2,215 0,828 Ο.ΘΟΟ clear ~Oi>0!2

CO 0.885 0-205 | 2.215 .S28 0 polyme free 0

; control; clear txsnspk 4

Two Part Compositions

[001.39] The olymer-micelle complexes, which exhibit superior wetting snd spreadin on a wide variety of surf kes, .may be prepared from precursor solu ions which are mixed fast prior to use. Sueis two-part formulations may be desirable for enhancing h stability of mi oxidan such as sod um hypochlorite over longer-term storage, or may ho desirable for use with automated dilution s stems for commends! or industrial use In estaurants, hospitals, etc.

Fonrs latlots D i Is an exam le Its which the mixed nrieell.es comprising the amine oxide and- ani nic surfactant and the optional buffer comprise the firs pari of the two part sys em, while the water-soluble polymer (hes^'e oly(DA^;D AG}, oho f qmi 4540) and the -s dium hypoohlorlfe comprise the second, part of the two pari system. Both Pari A add Fast B are ele&r .solutions, free of cosoervsles and precipitates. Whets mixed m the volumes Indicated in table 4,1 , the poiymer-miedls complexes are fo ced without the appearance of eoaeemtes or precipitates,

f$814!| Formol tion B2 is so alternative two-part system. Fart A comprises micelles of the anionic surfactant in a solution with the sodium earboame buffer and sodium hypoehlorite. Part B comprises micelles of the nomonlc amine oxide and the water-soluble polymer. Both Part A ≠ Fail B sre clear solutions. When mixed in the volumes indicated la table 4.1, the surfactsots re-equilibrate to form mixed micelles its the diluted solution. These mixed micelles, of course, will have a net usgatlve charge dae to the presence of the ardonic surihctan (which is in excess of say egtlonie surfactant such as a qnamraary a moshnm compound), an will thus . i ternet with the ca.iio.ole-: wstc -so^'iubks polymer to produce the pQlymer-mlceils complexes desired. Mote t st the P/^'Dnet a a ete of the final, solutions produced thorn formulations Dl and 02 are the same, e d within the scope of the iostasP Invention (i.e., both negative). The appearance of fee diluted solutions produced f om both formulations was cheeked immediately upon preparation, ami alter 8 boats, . The appearance both immediately after preparation and after 8 hoars was unchanged, as expected. sfece: the >olymer~m elts com lex s ^thoeght to &g snaodymmiesO fm.omd md hence shsMe strueteres:,

Ta le 4.1.

ID Amt«x ;<® N¾€% aOCs parts' to

1,0 p:r.5.i0

wt½ %

1)1 Pari A 1.071 0.400 4.588 1.192

Fait B 2.189 0.438 1 clear

mix 9.582 0.218 2,49$ 0,998 0,200 clear -1.644 Λ Ϊ5

D2 Fart A 0.325 3.730 1,493 2,010 clear

PartB 1.758 0. Θ4 1 clear

mix 0,5S2 0.218 2.495 0.206 d sr -1,644

Exass k ¾

Mixed Micelles Comprising_. Anonc, Cai!oaio, srsd Noalorsio S«r£¾ean with Polymeric

C U terion

| 12] The mixed rslcdks of the kals kvs.at e may com rise rmxtares of aarome, caisenic, an nonioak surfactants-. As taught herein, he net charge on the mi ed micelles s ould be selome, order to easiae electrostatic mteractioos with s wster-soksble polymer bearin eaticaile charges, Formakrioa El. an exa ple ^"m which the mi ed mkel!es comprise a eaiiorc suractant which is a germicidal quaternay am onium com und (Sanisol OS), . ml k sariaei&at (sodium, . csisoat^ a. soap},, m & mnk k amms oxide sarikcisrsi (Ama¾otrxi⁾ MO). Porrrralatlou El s als example of a ibrmalaioa ^•sontam^'kg: optonal fw&its ibut molac!e a buffer {sodksM carbonate) aad a hydrolrop-e, sodium, xylene s&li oals, a ready to use focmiiiai!ors which is clear

free of eoacervst.es. sad precipitates.

il43] Sasisoi has a molecular wei ht of 284 gmok. Sodi : ootauoate has a molecular weight of 166,2 grooie. POI.44] p£>ty(DAD AC) ^::: poly asiyi dimethyl am oimsm ehlqridey F al FL4245 (SNF Cotp. sts Bed as 40% actree. m hn is water , Ί polym«r-l, Q polymer ^«1, M pofymer 162, F pcdymsr ^ I (homepoly er).

p.1 5f Sodium hypochlorite source ~ Ckrox gsrrmsidal bieaeh, titrated immediately prior to use to detrmine the sodium hypochlorite activity.

{68146 j ¾e c kdat n of On&t is dom as follows:

Eq cationie - 0.1x1/284 0.00035 equivatentsftOOg formulation.

And D cailorhe - (+1) χ (G.G0035) - 40.00035.

Eq anionc - 0,08 x 1/166,2 - 4.813 x 10^" equivalents/I 80g ionnuktkm.

And D atonic - (-1) x 4J x W⁴ - .S13 x.1ST

Thus, D t - 40.00035 ÷ (^«4.813 x 10 ) ···· 3134 x 10^"4

[ 014/] The eepiive value of ^'Dee bdefe thai the mixed mcelles will bear a nst anlorrie e rge sdtafelg fo Imerser e. with, s water-salable polymer hsarmg catiomc charge as a poiyroeric eo-einterion to form, the po!ytser-eiecllc cori lejies of the iestath ieveotion. ΛΙ4¾1 PolyiDADMAC) Is a hamopoiyraer wit a moleeo!sr weight, of Ibf? gmrsa/moleiis die repeat athf which has a single estiorrlo ehafgs.. The polymer is pesen at a concentration of 0,05% in ferrrmiatiors El. They P cm be calculated as below-:

P=0.05 x f iVfOU - 0,0003092

And P/Dnet is thus calculated as:

F/Dnct - -0,0030$2 0.0001 !34 - - 2.354,

|ih149f The negative value of F/Dsct indicate ai the mixed nacelles aed water- soluble polymer bear opposite charges m will thus- ¾ve electrostatic Interactions which drive the assembly of t e rxd mer-rnkeile com lexes of the ksiam irwetrhm S ies the absolute value of the P/Driei parameter is greater i L the num e &f cshorhe charges due to the water-soluble poiy&ar e ceeds the umbe of anionc charges on ilm mixed micelles,

Table 5.1

Ingredient Formiiklioo El.

isodiem hypochlorite

Sodium e rboeate 2.50% octyl dimethyl sszyl. ammonium

chloride (Sanlsol 08) 0.10%

M OJ Without departmg from the spirit and scope si this mventfoa, -orse of ordinary skll c&n make various ch&nges md modifications to the in s doo ¾o ada t it to various usages aaci m&mss.. As such, these ch¾mgss arid moditlca oas arc properly* equta ly, aitd intended to be, within the foil range of equivalence of the following claims.

Claims

CLAIM

! , A co position m pmmg:

an oxidant; mi

a olymer-m elk com lex, e complex com rsng

a negatively charged micelle, hersb s¾kl negatively staged la ds is •electrostatically hewxd to & aieM kibfe p lymer eain a positive charge;

eren said water-soluble polymer bearing a positive char e does sot comprise bbck copolymer, latex particles, polymer naaopartscfes, cross-lisked polymers, sllicose copolymer, ilaorosurfactot, or amphoteric copolymer;

wherein said o sition does not form s coacervate,

2. The c-omposhioa. of clam I , vvheebs the oxidaot is selected from the group eonsistkg of:

g. hypo alocs acid; hy ohslite or s .ree¾ thereof;

h, .hydrogen peroxide .or sources thereof;

c. perseids, peroxyaoids peroxo&eids, or so rces thereof;

d. organic peroxides or hydroperoxides;

e. peroxygsoafed inorga ic compounds;

f. solubilixed cMorae. solubi&ed chlorine dbxi.de,. a soorce of fee c onoe, acidic sodium chlorite. ar¾ acti ve ehjorine .generating eosnpma L or a chlorine-dioxide genera n cornpeond;

g. m active oxygen generating compound;

h. soiublked ossone;

i ri-hs!o compounds; a d

j. combinations thereof.

3. The cornpositioa of claim I, %¾«rehi the negatively charged micelle ooraprises an i tic -SUifactstit. selected irom the group consisting of alk l sulfates, a!kyl sulfon e , mlky eihoxystd!ktes, tatty acids, fatty acid salts, alky! aosko acid derivatives, glyeolipki derivatives Including anionic groups, rhemaoliplds. r arstiolipid derivatives Incudi g anionic groups, sulfate derivafes of a!kyl eroxyiate propo ylates, alky! ethoxykte sul tes, and combinations thereof. ^•4. T¾s com osition of claim h wherein the negatively c arged micelle further comprises u-wmmk surfac ant optionally the oonlonic sur&eiant comprises an amine oxide,

5. The composition of claim L her n the composition further comprises a eatsomc s rfac ant o io al ! die oaiiorac surfactant comprises g q¾at maiy ammoBiom composted.

6, ¾ composition of claim wherein the water-soluble polymer bearing a positive charge comprises & mono sr selected -from i t group consisting of: dlallyi dimethyl ammonium chloride. quaternary tarmtonkm salts of substituted acryk ids, meihviaorylamide, acr l&ts and meihacrykte, ua emized alley! amino acfylitte esters and amides, MAPTAC Cme acry mido propyl ttim thyl am omam ehiondesl trinsethy! amraoaiium methyl methscry aro, hi efbyl ammonium propyl methaarvlsmicfe, 2-vkyl - aikyl quaternary pyridlmum salts, 4-vmy! ^" -slkyi tnrtemary pyridmisro salts, 4- vinyibetrayltrislkyiatrsKsotsiuns salts, 2-vky! p!peridkhtm salts, 4^«vtnyi plpsriamln . salts, 3- alky! 1 -vinyl ims «oii s» salts, or sihyfeteimme and mixtares thereof or Is a ater-solnbk polymer selected from- the group ehiiosam ohhosan derivatives bearing estiomc groups, guar derivatives be ring eaiionie groups, or a polysaccharide earing catlonk groups, and combinations thereof

?, The composition of claim 1 , wherein the waier-sol bk polymer bearing a positive charge comprises a hybrid copolyme derived from a synthetic monomer or monomers chairs terminated with a hydroxybcorstaimng natural material synthesized with a f radical Initiator,

H The composition of claim I, further comprising a pH buffer, op iorsahy thepH buf!er is selected fro the group eomisimg of earboaates, phosphates, silicates, borates, and com inations^' thereof

9, A method for cleaning a sarkee, the method comprising:

contesting said surface with composition comprising a polymer-micelle complex comprising: a. jee threly charged mieette electrostatically homd to a witer-sokb!e polymer- bearing a osst s char ; d

wherein said olymer does i t comp ise block co olymer,, latex particles, posymer rmsoparticies, cross-linked polymers, silcone co lyme, feo surfseta , or amphoteric copolymer:

wherein said co ostion does ao form a coaeervate; aod

wherein said composition is not applied to trapping organic cooismioants a subsurface locate.

10. The mei¾od of skim 9₅ wherein the composition comprising a pol raeMttteelle complex is a c ncentrate, the method further comprising diimm the concentrae with wafer to form a dilute eoisiposstiofi comrisin the polymer-micelle com ex, prior to cootsdmg the mtf wit die dilute com osiion and w eein ie dlued OOTpositiori also does sot ΐοπή a eosoemte,

11·.. The me od of claim % w¾srei the. composi ioo further comprises m o idant optionally de oxidant is selected from the group consistin of:

a, hypohsloos acid_; . hyaohaJ lie or so rees thereof:

b, hyd.roge.¾ peroxide or sources thereof;

c. peracids. peroxyaekJ s peroxoacids, or sources thsreof;

d. organic peroxides or hydroperoxides;

& pefoxygenaCed i organle com.poy.ads;

f. sotubilked. chlorine, sok ilked chlorine dioxide, a. source of free c orme, acidic sodium ohldriie, active ch nrse geoemilrsg eompoimd_s of a chlorine-dioxide gerreraimg c und;

g. active oxygen generstmg eompouad;

h. soltd lked ozone;

i. N~hslo com ounds; and

j, corabloatiops thereof

12, The method of claim w cr is? the negatively charged micelle comprises an anionic surfactant selected ixom the group eonsisdog of alki sulfates, al!ad sulfonates, alfcyl ei oxy ifa&s, fetty acids, fatty acid salts, aikyi amino acid derivatives. grycoiipid deri atves mending anionic grou s, , rhamoobpic derivatives ii&iudmg anionc o s, suifsie derivaiss ofslkyi stb xykie propoxyiafcs, allcyi eihoxykte sid&tes, arid combinatons thereof,

optioMl!y the negstiveiy charged tmoeite further comprises a raamooie ^wfactaat, opiiorsaMy the nonionic sar&ctaat comprises m amine oxide.

13. The method of claim % whereis the com osti n further comprises a cstiome surfactant, optionally t e eabooie surfactant com rses s quaternar am ooiaio corapoe .

14. The method of clai^'at 9, wherein the ator-soksble olymer be&riag a posits v© charge com ris s a monomer selected from the group diallyi dboedryi gi moniarn chloride, quaternary anffimium sabs of subsituted acryfamide, meihyiaerykotide, acrylaie aad etha.cryiste, tomised aikyi amino Servi n stes d sondes, MAPTAC (mehasryfamido propyl irimethy! smmoaium chlorides)., tnnaethyi arm¾orbum roe thy i meth&cry!ate, riiraetbyl smnKmiura propyl .aactiiao koddg, 2-virryl N-alkyl uaternary pyridirbum salts, 4-vinyl -aikyl qu ernary pyridmUrm salts, 4- ¥mylbeB¾ foia!k !ammo«krp salts, 2~viay! olperidisiam salts., -vmyi piperidir rm sals, 3~ aikyi 1-yfeyl steolium salts, or ethyieodmioe &od .mixtures thereof or is a_: water-soluble poiyrer selected fr m the group chitosan, chitosso derivatives bearing eationic: groups, ga&r derivatives besr g caboose groups, or a ol sacc aide beari g eaiiorbe groups, sod combinations, thereof

15. The method of cki 9, further comprising ¾ pH bailer, o t nally the pH buffer is selected froot the group consisting of carbonates, phosphates, silicates, borates, md comfemati ns thereof.

16. A system^' comprising:

a) a dws! chaoaber d device comprsin a ilrslehsmber and a s cond chamber;

b) a first composition comprising a water-sokbfe polymer bearing a positive charge disposed k the first damber wherein said polyraer docs oot comprise block copoly er, ktex anicles, polymer nanopartiees, cross-lkksd polymers, silicone copolymer, ifeorosurfaaaiai, or amphoteric co lymer:

0} a second composite comprising a .negatively charged mice^'H dis osed m the second c am er;,

d) erein the first composites of the first chamber s .mixed with t e second co positon of the sec nd chamber to form s resetkig eoirmoshioo in which;

i) the mc lle Is electrostatically booed to the polymer to form a polymer- micelle complex;

is) ie resulting composition does n t form a oo&cervate; a&d

ill) the rssidt g composition does net form a Ska on a surface.

17, Use- system of claim 16, vy erek a least -one of the first or second compositions further com rses sr> xdant opoocahy the Oxid t Is selected from the group eoosl sting of:

a. , hypohsloos acid, I pohailto or sources thereof;

b, hydrogeo peroxide or sources thereof:

0. peraek¼ peroryacids peroxo&c s. or sources thereof;

it organic peroxides or hydroperoxides;

e. peroxygenated inorgams c mpounds;

f. soiuhlized chlorine, soiohdbed chlorine dioxide, g sorrrce of free vkloritie, acidic s dium chlorite, so active chlorice geoersiiog compound, or a. ch!orico-dloxidc generating compound ;

g. an. active oxy en generating com o nd;

h_< solubilked ozo e;

1. N- c- compounds; mi

j , com bosaiiocs thereof

IS, The system of claim 17, wherein the oxidant is Incicdsd within the second composltiort comprising the negatively charged micelle, acd >v heroic the first com osition comprising the water-soluble polymer bearing & positive charge further c mp ses a oomo le surfactant optionall the trordoitk surfectet comprises an amine oxide.

19. The syssem of cl&im 17, wtesk the mimi Is included vvk¾k-fee first com osition com risng he watesvso!uMe polymer earn a positive cha e, arid wherdrs. the second eomposidoa. comprising t s negaively charged mieefcfe further com rises a riositmic surfactant, optionally e isomeric surfi iant m ises mi oxide,

20, ^'The system of claim .17, wherein at least ne of the first or second compositions further comprises a quaternary animoftium compound.