EP2914235A1 - Micelles cationiques avec des compositions de contre-ions polymères anioniques, procédés et systèmes de ceux-ci - Google Patents

Micelles cationiques avec des compositions de contre-ions polymères anioniques, procédés et systèmes de ceux-ci

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Publication number
EP2914235A1
EP2914235A1 EP12887665.3A EP12887665A EP2914235A1 EP 2914235 A1 EP2914235 A1 EP 2914235A1 EP 12887665 A EP12887665 A EP 12887665A EP 2914235 A1 EP2914235 A1 EP 2914235A1
Authority
EP
European Patent Office
Prior art keywords
polymer
composition
micelle
polymeric
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP12887665.3A
Other languages
German (de)
English (en)
Other versions
EP2914235A4 (fr
Inventor
David R. Scheuing
Travers ANDERSON
Thomas F. FAHLEN
William L. Smith
Erika Szekeres
Rui Zhang
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clorox Co
Original Assignee
Clorox Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US13/663,862 external-priority patent/US8883705B2/en
Priority claimed from US13/663,830 external-priority patent/US20140121281A1/en
Priority claimed from US13/663,792 external-priority patent/US8728454B1/en
Application filed by Clorox Co filed Critical Clorox Co
Publication of EP2914235A1 publication Critical patent/EP2914235A1/fr
Publication of EP2914235A4 publication Critical patent/EP2914235A4/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395—Bleaching agents
    • C11D3/3956—Liquid compositions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0291—Micelles
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41—Amines
    • A61K8/416—Quaternary ammonium compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8147—Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8158—Homopolymers or copolymers of amides or imides, e.g. (meth) acrylamide; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8164—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers, e.g. poly (methyl vinyl ether-co-maleic anhydride)
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/005—Antimicrobial preparations
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/32—Amides; Substituted amides
    • C11D3/323—Amides; Substituted amides urea or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/80—Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
    • A61K2800/88—Two- or multipart kits
    • A61K2800/882—Mixing prior to application

Definitions

  • [0002J Cleaning product formulations including loose which contain common antimicrobial gge s such as y&teraary anrmonmm compounds and biguanides such as c orhextdhie and alexidine, rely on surfac an and mixtures of sor&eiaets to deliver eleanirsg (deisrgency) end aetlnderobial efficacy,
  • a key aspect of these processes is the Interaction of the serihetants and tmtlrmeroblal agents with the solid snrfaees of the materials being clearred, as weli ss the surfaces of microorganisms, together wit the effects of the fo mulatio s on the alo-waier interface (surface tension).
  • urfactants begin to term aggregates in the bulk solution known as micelles, in equilibrium with the monoroeric species of surfactants which adsorb onto die interfaces. i ⁇
  • One aspect of he invention is directed so a composition
  • a composition comprising a polymer- micelle complex comprising s positively charged mkelte comprising a water-soluble estiomc material selected from the group consisting of a monomerie quaternary amm ni m compound, a nton m dc biguanide compou d, and mixtures thereof.
  • the micelle is electrostatically bound to a water-soluble polymer bearing a negativ.e charge.
  • the -water-sokble polymer bearing a negative charge comprises a hybrid copolymer derived f om a synthetic monomer o monomers chain terminated vyitb. a hydroxy I- containing natural material synthesized with a free radios! initiator.
  • the polymer does uo comprise block copolymer, hue--: particles, pol mer nanopartides, cross-linked l e s, silicone copolymer, fluo sm&oiant, or amphoteric copolymer.
  • the complex advantageously does not form a eoacervate, and does not form a film on a surface (e. g., a durable film remaining after application of the composition to the surface),
  • Anorher embodiment of the invention is directed to a composition
  • a composition comprisin a polymer-micelle complex comprising a positively charged micell comprising a water- soluble eatlouie material selected from the group coexisting of a monomerie quaternary ammoniu c m und, a monomeric biguamd ⁇ compound, and mixtures thereof.
  • the micelle is eiectrmstat.isa bound to a water-soluble polymer bearing a .negative charge.
  • Use water-soluble polymer hearing a negative charge comprises a hybrid copolymer derived from a symbolic monomer or monomers chain terminated with a hydroxy!- eoptainiog natural material symth smad with a free radical initiator.
  • the polymer does not comprise block copolymer, latex particles, polymer nanopartides., eross «l ked polymers, silicone copolymer, fhtorosurfeetaot, or amphoteric copolymer.
  • the composition advantageously does not form a coaeervate, a d does not inemde alcohols (e.g., particularly l we alcohols) or glycol ethers,
  • compositions comprising a olyme ies I is complex comprising a positively charged micelle that is electrostatically • fco nd to a water-soluble polymer bearing a negative charge.
  • the waler-solubie polymer does not comprise block copolymer, latex particles, polymer oanopartloles, cross-linked polymers, silicone copolymer, fiuorosur&c ant, or amphoteric copolymer.
  • the composition advantageously does not form a csoaoervate and does not form a fifes oo a. surface, in addition to the po!ymer--mk;etle complex, die c m osi i n further com rises s oxidant
  • t e composition includes m oxidant, h ch may be selected from the group consisting of: hypobalous seid, hypohaiite or sor.sroes the?eof;hydrogen peroxide or sources thereof, petaeids, peroxyacids peroxoaeids, or sources thereoi;orgamc peroxides or hydroperoxides, psro ygenated inorganic componnds;solubiozed chlorine, soiubUized chlorine dioxide, a source of free chlorine, acidic sodkm chlorite, m active chlorine generating compound, or ch rine-riioxide generating compound, an ac ive oxygen generating compound, solubliked ozone, N « h3 ⁇ 4.lo compounds, sod combinations- ther of,
  • the positively charged micelle comprises a tnonotneric : quaternary ffisimoni m compound.
  • the ' positively charged micelle iurther comprises a ooniooie surfactant
  • the oooi.on.ic xur&el&n comprises an si oxide.
  • the positively char ed .micelle comprises 8 O'ionorneric biguanlde ooinpoHttd
  • the onomerie bigaaoide compound is selected from the group consisting of ch!orhexidhre, alexkhne, sod combinations thereof.
  • the composition is tree of iodine, iodine-polymer complexes, tranonarticles of silver., stsnopartieles of copper, oa opsstides of 5- inc. o/ieiosan, p ⁇ cMoro eihy! xylenoh monomeric pentose alcohols. D-3 ⁇ 4yh ' tol and its isomers, D-atabitol and Its is mer, my I alcohols, berszyl alcohol, and phenoxyethauol,
  • the composition further comprises a water-immiscible oil that is soiubilms ioto the positively charged rnkelle, in another embodiment, th composition is free of ster-toiscible alcohols and glycol ethers,
  • the water-soluble polymer bearing a negative charge is selected from the group consisting of a co lyme of a polysaccharide and a. synthetic monomer, copolymers comprising rna!eic sold, a. copolymer of dhrsethykcrylatnlde and acrylic acid, a copolymer of acrylic acid and s-rytene, a copolymer of sulfona ed styrene and rn&leie arshydrlde, md combinations thereof.
  • the invention is directed to a method for cleaning a surface.
  • the method comprises contacting a surface with a composition comprising a polymer-micelle complex.
  • the po!ymer-raicell complex ioclrtdes a positively charged micelle electrostatically bourn! to a water-soluble polymer bear- as a negative charge.
  • the positively charged micelle comprises a water-soluble estionio material selected from, the group consisting of a mooomerie quaternary ammonium compound, a mononierie biguam ' de compound, a no mixtures thereof.
  • the water-soluble pol ymer bearing a negative charge does not comprise block copolymer, ex particles, lymer nanopaslieks, crass- linked polymers, silicone copolymer, fl orosuffecu3 ⁇ 4t. or amphoteric copolymer.
  • The- composition advantageously does not form a coaeervate, and does not tbrm a b t ; on surface.
  • Another etnbodlmem of the invention i directed to a method for treating a surface.
  • the method comprises mixing a first composition comprising a water-soluble polymer having & negative charge with a second composition c mp s ng a positively charged micelle.
  • the water-solnhle polymer bearing a negative charge does not comprise block copolymer, iaiex particles, polymer nanopardoks, cross-linked polymers, ah k one copolymer, loorosurtactant, or amphoterio copolymer.
  • the positively charged mk.dk > comprises a water-Soluble cation Is material selected from the group consisting of a monomelic quaternary ammonium compound, a monomeric biguanide compound, and mixtures thereof.
  • the method further comprises contacting the composition respiting from, nrixing of the two parts with surface so as to beat the surface..
  • Another embodiment of the invention Is directed to a method for treating bacterial endospores, fungal spores, or viruses-.
  • the method comprises contacting the endos-pores, spores, or viruses with an aqueou composition that comprises a poiymer- mieehe complex comprising a positively charged micelle thai is electrostatically bound to a waiemsoiubk polymer bearing a negative charge.
  • the positively charged miee!k comprises a water-soluble eationk material selected from the group consisting of a mouomeric quaternary ammonium compound, a monomer! ⁇ biguanide compound, and mixtures thereof.
  • the water-soluble polymer bearing a negative charge does not comprise block copolymer, latex particles, polymer nanopanieies, cross-linked polymers, silicone copolymer,. fleorosoriactant, or amphoteric copolymer.
  • T ' he composition does net form a coacervate.
  • Another embodiment of the kvemloo is directed to a method for killing bacteria arising from germination of bacterial endospores or fungi arising from germination of fungal spores.
  • the method comprises contacting the endospores with an aqueous composition that comprises a polymer- micelle complex comprising a positively charged tnicells that is eiecti statlcaily bound to a water-soluble polymer hearing a negative har e, '
  • the positively charged micede com rises a water-sokhle cationic material selected from the group consisting of a oaomerie quaternar ammonium compound, a mo om n biguanlde compound, and m x u es thereof
  • the ater-sokbk polymer bearing a ne a ive charge does not comprise biock copolymer, latex particles, polymer rranopsrtkles, cross-linked polymers, silicone cop
  • Another aspect of the invention- is d e ted to a. system comprising a dual chambered device comprising a first chamber, a second chamber, a first composition In the first chamber, arid a second composit n in the second chamber.
  • the first composition comprises a water-soluble polymer bearing a negative cbargo that does not comprise biock copolymer, ktex particles, polymer nanopartlcles, cross-linked polymers, silicone copolymer, iiuorosariaetaat, or amphoteric copolymer
  • the second composition comprises a osi ive charged micelle comprising a ateosolabk catiook materkl selected from the gronp consisting of a monomer!c quaternary ammooiam compound, a monomark igusnide compound, sod mix ai es thereof.
  • the system provides the ability to mix the first and second compositions (e.g., prior to application ⁇ to result Its a mixed composition for application m whkh.
  • the micelle is electrostatically bound to the water-- soluble polymer to form a polymer-rnkclie com lex.
  • the resulting: mixed composition advantageously does not form a coaoervate, and does not k3 ⁇ 4 a film on a surface.
  • Another embodiment of the invention is directed to a system, comprising a d i chambered device comprising a first chamber, a second chamber, 3 ⁇ 4.
  • first cam-position m the first chamber, and second composition In the second chamber.
  • the first composition comprises. s water-sokibis polymer bearing a negative charge that does not comprise block copolymer, latex, particles, polymer nanopartleles, cross-linked polymers, silicone copolymer, iuorosariactant, or amphoteric copolymer.
  • the second c m os tion comprises a positively charged micelle comprising a water-soluble cadonlc material selected from the group consisting of a monomerie quaternary mnmonlurn com ound, a rnooomerie bigo&nids compoand, and ndxiures thereof
  • the system provides the ability to mix the first and second compositions to result in a mixed composition for application in which the micelle Is electrostatically bound to the water-soluble polymer to form a polymer-mieelk com lex.
  • the resulting mixed composition advantageously does not form a coacer vste 3 and does not form a film on a surface.
  • the resulting composition does not include alcohols or glycol ethers.
  • ⁇ Wt ⁇ nodser aspect of ihe invention is directed to a system comprising a dual chambered device comprising s first chamber, a second chamber, a first composition in the first chamber, and a se ond composition in the second chamber.
  • the first composition comprises a water-soluble polymer bearing a egative charge that does not comprise block copolymer, latex par e -.;, polymer nanopardcies, cross-linked polymers, silicone copolymer, iksorosrsrtaetaot, or amphoteric copolymer.
  • the second composition comprises a positively charged micelle comprising a wster-solnble catioolc m&tsrlsl selected from the group consisting of a monomelic qu ternary ammonkmi compound, a mooomerie bsgyarnde com ound s and m xtures thereof At least one of the first or second compositions further consprlses an oxidant.
  • the system provides the ability to mix the first and second compositions (e.g., prior to apphcaiiors) to res id ⁇ in a mixed composition for application in which the micelle is electrostatically bound to the water-soluble polymer to form s poiymerookeb ' e complex.
  • the rssohing mixed composition advantageously does not form a cn cer ate and d:oes not form film on a surface.
  • flMBlf l3 ⁇ 4e tes n water-soluble polymer as used herein means a. poly user which gives an optically clear solution ee of precipitates at a concentration of 0.001 grams per 100 grams of water, preferably 0.0 grams/100 grams of water, more preferably 0, 1 grams/1 0 grams of water, and even more preferably 1 gram or more per 100 grams of water, at 25
  • cleaning sobslrales include, bat are not limited to nonwovsns, sponges, films and similar materials which can be attached to a cleaning implement, such as a floor mop, handle, or a hand held cleaning tool, such as. a toilet cleaning device.
  • t e terms "nomvoveo" or no « oven web” means a web having a str c ure of kdivkfeal fibers or threads which are kterl&! , but not in art identifiable manne as m & knitted web.
  • ol mer * as used In reference to a substrate (e.g., a non-woven substrate) generally Inclu e , hut is not limited to, homopolymers, copolymers, such as for example, block, graft, random sod alternating copolymers, terpolyrners, etc. md blends and modifications thereof
  • polymer shall include all possible geometrical eonf!gurstioiis of die molecule. These configurations include, but are limited io isotaetle, syitdloisctic and random symmetries,
  • Such characteristics completely eliminate the need to adjust formulations such that they change their solubility, forming eoaoervaies or precipitates, in order to deliver adsorption of useful amounts of ionic surfactant and pol r to these huerfaces.
  • the r lcelle-polyurc complexes formed when a water- sokble polymer comprising groups which bear or are capable of bearing an electrostatic charge opposite to that of a mieeik are usually fbasd to he somewhat larger than, the micelles alone.
  • the addition of a water-solu k polymer bearing electrostatic charges opposite to that of at least one surfactant in aqueous solutions often can reduce the CMC of he given surfactant by a significant fraction, which can also have the effect of reducing the cost of certain formulations.
  • Fine control of surfactant interactions within micelles via addition of oppositely charged polymers according to the inven o has also been found to increase the oil solubilization ability of the micelles to an unexpected degree. Without be ng bound b theory, it is believed that this effect is doe to the uoiqnely high counter Ion charge density carried by the charged polymer, which is distinctly different from regular counter ion effect provided by typical salting out electrolytes. This is thought to increase the degree of counter Ion association of charged polymers com ared to regular electrolytes, e en at very low polymer concentrations, which in turn promotes Increases in nneellar size and an increase in oil socializ tion efficiency.
  • the anionic polymers act as polymeric eonoterions to the cationka!y charged micelles, either increasing the size of these micelles or collecting groups of these micelles into soinb!e, thermodynsmic&ily stable aggregates which have enhanced activity at solid surfaceTM aqueous solution interfaces.
  • the e-omposhio ⁇ s can comprise alcohol
  • the compositions can be completely fee of watermksclb!e lower alcohols.
  • the compositions can comprise waten-nvlseible glycol ethers or be completely free of the r-mn-nak.
  • soerethnes referred to as 'ko-solvents" or 'ko-surfactantsk €ompo$ k ⁇ s free of the lower alcohols or glycol ethers not only cars provide acceptable antimicrobial performance at lower cost bat also reduce Irritation to patients nd healthcare workers, while providing forrmbations which can be considered more environmentally ifkndly or sustainable due to lowered total actives levels and lack of volatile organic compounds.
  • Those embodiments that are tree of alcohols or cosolverris are especially suited as sanitizing cleaners, disinfecting d alers of treatments for pets in borne or veterinary applications.
  • the interfaeial activity of the micelles with polymeric countenons Is so signifkapt that the viral proteins are disrupted, denatured or otherwise damaged sack that the viral particles are rendered on-infective, even when they are exposed to significant dilutions such as those during the microbiological test protocols.
  • mycobacteria (bacteria responsible for takn alosis), which are heretofore known to be relatively resistant to the actions of eationk germicides m aqueous formulations lacking a co-solvent or aleohok Seek resistance is thooght to be dee to the thick, waxy outer mem brakes characteristic of this type of bacteria.
  • compositions may be sef l as ready to use cleaners, and may be applied via spraying or peering, but .may also be delivered by loading onto nonwoven substrates to produced pre-m olstened wipes.
  • the compositions may also be provided as concentrates that are diluted by the consumer (e.g., with tap water). Such concentrates may comprise a part of a kit tor refilling a container (also optionally included wit in such a kit), such as so. empty trigger sprayer.
  • the compositions may also be provided as concentrates for single-- use (unit diose) products for cleaning floors, windows, counters, etc.
  • Corseentraied dishwashing liq ids that provide antibacterial perionnapce upon very high dilations may be tornTu!ated, as may concentrates which can deliver sanitkation of laundry vis addition io ordinary washloads.
  • Saeh co ce rated products also can provide protection against the growth of biofilms ami associated out row h of molds in drain line associated with automatic dishwashers, laundry washing machines, a id the like, reducing undesirable odors which are sometimes encountered by consumers.
  • f3 ⁇ 4M4f Co c ntrated fbyms of the formulations may also be provided which may be diluted by me consumer to provide solutions thai are then used, Coneentraied forms suitable for dilation via amo aicd systems, io which the concentrate ?s diluted with water, or in which two solutions are combined In a givers ratio to provide the final use formulation are possible,
  • the formulations may be in tire form of gels delivered to a reservoir or surf ce with a dispensing device. They may optionally be delivered Irs siugk-use pouches com risin a soluble film..
  • compositions are useful in providing a reversal its the native surface charge (i.e.., se a potential) of bacterial enriospores and other microorganisms from anionic (negative) to eationk (positive ⁇ , or a least to less anionic as a result of contact with the compositions.
  • Saeh a change in charge Increases the electrostatic binding of the microorganism s to cleaning Implements such as pre-moistened ooowoven wipes, which typically have a native anionic (negative) charge, hence improving the removal of the microorganisms from surfaces being cleaned.
  • compositions provide robust adsorbed layers of germicidal materials such as quaternary ammon um compo nds and biguanides, they are able to kill bacteri which arise f om tne germination of endospore under favorable environmental conditions. Such compositions may thus find utility In various applications including combating weaponteed spores such as BacUI Amkracis. Low residue treatment solutions for surfaces which may be infrequently cleaned and which may be subject to outgrowth of bacteria or molds from contamination by air-borne spores can be oduced with the compositions. In other words, the compositions do not result in the formation of a dura le film, on a surface after application.
  • the invention also contemplates use of the poiynsewmkelle complexes for deli er g improved felixaikm of surfaces mid protection of treated surfaces through the same mec an sm of enhanced adsorption of caiionic bioei es such as quaternary ammonium salts and biguanides onto living bacteria, bacterial eodospores, fongul spores, and viruses, Examples of antimicrobial activity exhibited by the Inventive compositions kcla e, but are not limited to killing of hving bacteria, killing of bacteria upon germination fr m bacteria!
  • the surface may be hard, soft, animate (e.g., skin), non-animate, or other type smiace.
  • inventive compositions which are free of eoaeervates and precipitates thai comprise mixed .micelles of an amine oxide and a cationic germicide such as a qu ternar ammonium com .
  • pou3 ⁇ 4d and a water-soluble polyme bearing anionic charges may be readily formed through djnsP'ne ii of the P/Dnet parameter, the Drier parameter, and/or the presence of adjnvaats such as electrolytes, without regard to the precise value of any cationic charge present on the amine oxide,
  • Two parameters cars be defined for any mixture of surfactants comprising headgroups bearing, or capable . or bearing, anionic or cationic charges or mixtures of both, said parameters being D anionic and D cationic.
  • D anionic will be defined as - anionic :;: (-1 ) x (Eq anionic)
  • D cationic will be defined as -
  • a fiuai a am te expressing the net charge on the micelles is Dnet, which is simpl the sum of the parameters D anionic and D cation! e s i.e.,
  • Eq anionic- is the sum of the total number of equivalents or charges due to the beadgroaps of all anionic sarfaeinnts present.
  • C anmnic is the concentration of a surfactant with anionic headgronps in grams/per 100 grams of the formulation or use composition
  • Q anionics is a numbe represe t the number of anionic charges present an the surfactant, which rosy be viewed as having the units, eq alen s per mole, aad M anionic; is the molecular weight of the surfa an in grams/mole.
  • Eq cationk is the sum of the total number of equivalents or charges dee to e headgronps of ail cationk surfactants present.
  • C catiooici is the concentration of a surfactant with cationk headgroups In grams/per 100 g ams of the formulation or ase composition, Q eationic; is a number representing the number of ea ionic charges present on the surfactant which may be viewed as having the units equivalents per mole, and M cationk; is the molecular weight of the surfactant in grams/mole, I s cases where the fbnrtnlation comprises more than one surfa ant with eationic headgroaps, the summation of the equivalents of eationic hea.dgro ps would be performed as in the ease of the anionic surfact nts described above.
  • soasidet a formulation comprising a mi ture of a single anionic surfactant, a single acnio c surfactant, and a single catiook surfactant which is a germicidal quaternary ammonium c m ound.
  • the anionic surfactant is present at a concentration of 2 t% or 2 grs s/100 grams of the fonnaladon, has one group e table of developing an anionic charge per molecule, and as a molecular weight of 200 grams/mole.
  • cationk surfactant is present In die formulation at a concentration 0.1 wt% or 0.1 grams/100 grams of the formulation, has one group capable of developing & cationic charge per molecule, and has a .molecular Wei ht of 300 grains/mole.
  • a second parameter which can fee used to describe the instant invention and the interactions between polymeric oouu erion and surfactant micelles bearing a net charge is the ratio P/Onet, P is the number of charges (in equi valents) due to the polymeric connter n present per 100 grams of the formulation and can be calcokied as follows;
  • C polymer is the concentration of the polymer in the formulation in grams/100 grams of formulation
  • F polymer Is the weight fraction of the monomer unit bearing or capable of bearing a charge with respect to the total polymer weight and i m ranges from 0 to 1
  • Q polymer is the number of charges capable of being developed by the monomer unit capable of bearing a charge and can be viewed as having d e unds equivalents per mole
  • Z is an integer indicating the type of charge developed by the monomer unit
  • nd is equal to 4-1 when the monome unit can develop a cationic charge or is equal to ⁇ l when the mo ome m%it can develop an anionic charge and.
  • M polymer b the molecular weight of the monomer unit capable of developing a charge, k grams/moie.
  • FA A polyacrvl acid homopofymesr
  • the formulation comprises, a. mixture of a single aiuooic surfactant, a single nokonic surfactant, aod a single eationlc surfactant and a single eationk surfactant which Is a germicidal uaterna ammonium compound.
  • the anionic sarfeetam is present at a concentration of 0.2 wi% or 0.2 grams/100 grams of the formulation* has one group capable of developing an anionic charge per molecule, and has a molecular weight of 200 grams/mole.
  • cariomc surfactant Is present ia the formulation at a concentration L0 wi% or 1.0 grams/100 grams of the formulation has ooe group capable of developing a cationic charge per molecule, and has a rnokeokr weight of 300 gmrns/mole.
  • the formulation also comprises a polyaerylle acid ho nopolyme (PAA) as a ster-soloble polymeric counterlors.
  • PAA is capable of developing 1 aa ion c charge per acrylic acid monomer unit (which has a molecular weight of 72 pms/wole), a&d hence Q polymer ::::: 1 md Z ⁇ - I .
  • fee polymer s a bomopoiymer, so F polymer ::: I .
  • the P value calculated for the fonnu ' lsiion would be the sum of the P values calculated for each of the appropriate monomer comprising the polymer used.
  • the polymeric coanterion When the absolute value of F/Dnet is greater than 1, the polymeric coanterion is in excess, sad of coarse, when the bs lute value of P/Duet - 1.
  • the number of charges due to the headgroops of the polymeric eounteriou equals the net number of cha ges of the io ho surfactant or surfactants comprising the mlcehes.
  • fW f Many polymers are suitable for use as polymeric eounierions in the instant Invention..
  • the polymers are water-soluble as defined herein.
  • the pol mers may be homopolymers or copolymers, and they ma be linear or branched. Linear polymers may be preferred in at least some embodiments.
  • Copolymers may be synthesized by processes expected to lead to statistically random or so-called gradient type copolymers.
  • water-soluble block copolymers are not suitable, since these types of polymers may form aggregates or micelles, in which the more hydrophobic block or blocks comprise the core of the aggregates or micelles and Che more hydrophihe block comprises "c ona" region in contact with water, it Is thought that these self-assembly processes compete with the electrostatic interactions required for a water-soluble polymer to serve as a polymeric co nterion with ordinary surfactant micelles.
  • mixtures of water-soluble polymers are suitable in at least some embodiments of the present invention, fee mixtures selected should not comprise block copolymers capable of forming so-ea!led ''c lex coaeervate'" micelles through self-assembly, since this micelle forma ion process also competes with hs Interaction of the water-soluble polymer as a polymeric counterion to ordinary surfactant micelles.
  • the polymers are copolymers, the ratio of the two or more monomers ma vary over a wide range, as long as water solubility of ths polymer is mainta ned
  • the ol me s should be water soluble, as defined hereby and therefore, shou d not be latex particles or tuierogels of any type.
  • the polymers should not he crossdlnked through the use of monomers capable of forming covalent bonds between independent polymer chains, and the compositions and formulations should be tree of cross-linking agents added expressly for this piapose.
  • Ths r ndom copolymers comprise one or more monomers bearing the same charge or capable of developing die same charge and one or more monomers which are noniouie, he,, not capable of bearing a charge. Copolymers may he synthesized by graft processes, resulting in "eomb-!ike" structures.
  • Preferred copolymers include so-called ⁇ hyb id' ' materials from Akm Nobel such as Alcoguard® H 5240, These materials are described as comprising polysaccharides and synthetic monomers which can function in the same manner as aerylgts/ sleate copolymers (i.e., s water-soluble polymer with anionieally charged groups) in cleaning formulations.
  • Hybrid ' polymers such as those described in US Pat, No, 8 s OSS.S37 are preferred in formulations where the overall susiaiuabihfy of ths formulation is of concern io the end user.
  • Such hybrid polymers are derived from synthetic monomers chain terminated with a hydroxyl-eontaining natural material, such as a polysaccharide, using tree radical Initiators.
  • anionic polymers available from Akzo Model under the tradenames Aicoguard®, Aieospecse3 ⁇ 4y and Aqua rear® am suitable for use.
  • A!coguatd® 2300 is a random co olymer of the nonionic monomer d3 ⁇ 4ttsihyl&crylaffiide and the anionic monomer acrylic- acid.
  • AkospfcrseS? 46S is a poly(acry!ic acid) honsopolymer.
  • Versa- L® 4 (Akzo Nobel) is another example of a suitable anionic polymer. This materia! is described as a random copolymer of sulfonated styrene and aiek anhydride.
  • Another example of a sui able anio ic ol mer is oiy(2-3 ⁇ 4oryiamido « -2 ⁇ me hy! ! » propanesulfonk sck1) s also known as poly AMPS.
  • the compositions are .ties of copolymers comprising at least one monomer hearing or capable of developing an anionic charge and at least one •monomer hearin or capable of developing a eationie charge.
  • Such copolymers sometimes referred to as "amphoteric" copolymers, arc believed to no function as wed or si all as polymeric eouoi ⁇ rioos to micelles bearing a n t electrostatic charge tor at least two reasons. First, the proximity of both types (anionic: and canonic) of charges along the polymer chains, if randomly disirihmed.
  • the water-soluble polymers may lochtde naiaral or sastthnabk materials heading anionic g oups, Including mulct derivatives (example Carboxyline CM! or Bequest FB), anionkally modified starches with the proviso that they exhibit waier solubility without cooking to achieve water solabiHty, a er-s luble salts of al inic acids, aniosical y modified eelkiosk materials suc as carboxy ethyl cellulose, modified proteins, and the Hke oiwhmking examples of monomers hearing or capable of bearing an anionic charge are acrylic acid, mediacrylic acid, vinyl sulfonate, acrviamkio propyl methane sulfonic acid (AMPS), itaoorae acid, ma!eic acid, fumarie acid, phihalk acid, iso- phthallc acid, pyro e!
  • acetic acid ethylidlneaeetic acid, propyl id ineaee k acid, angelic acid, c-innam - acid, styryl acrylic acid citracoolc a.cid, glu aconk acid, phenyiacrylk acid, scryioxypropriomc acid, virryi e zo acid, -vinyisuccmamide ac d, mes&come acid, methacroy! alanine, aeryloimdroxyglyeine, sulfoeihyl acryfate, siyrene ulfonic acid, 3* ⁇ viay foxy ⁇ propane ⁇ ⁇ .
  • Suitable monomers ma inelade acid ⁇ unetion et ylenicslly unsaturated T.oouomers capable of polyraeiixation or copoiymerization via processes i cluding free radical polymerization, ATRP and RAFT polymerization co ditions that are expected to produce statistically random or gradient copolymers with edvykmcally unsaturated monos&ers which are Incapable of developing a charge, the so-cal!ed nonionic monom rs,
  • Examples of monomers which are nonlonk, mi bearing, or not capable of bearing m electrostatic charge include the alky! esters of acrylic acid or meihaerylie acid, vinyl alcohol, vimy! methyl ether, vinyl ethyl ether, ethylene oxide, propylene oxide, and mixtures thereof.
  • Other exam les include acsykrcids, dimethyiseryiamide, and other alkyl serylamide derivatives.
  • Other ' suitable monomers ma include ethoxylated esters of acrylic acid or rnethseryl acid, the related tristyryl phenol ethoxyiaied esters of acrylic acid, methaeryllc acid or mixtures thereof.
  • Other examples of ' nonionic monomers nclude s ccha ides such as hexoses and pentoses, ethylene glycol alkylene glycols, branched polyols, and mkrarerlhereof.
  • water-soluble polymers comprising monomers which bear N ⁇ hal groups, for example, N ⁇ €S. groups, are not present. It is believed ihsfc interaetioos between polymers comprising sm groups as polymeric coanterions to micelles leads to either a degradation of the surfactants themsekes and/or a degradation of the polymers through the enhanced local concentration of the ol mers the micelle surfaces,
  • compositions comprise surfactant micelles with, for example., a net cationie charge and a water-soluble polymer or mixture of polymers hearing or capable of hearing anionic charges
  • the compositions may he ree of any additional polymers bearing a cationie charge, i.e. , a charge opposite to that of the first warer-solabk polymer bearing or capable of bearing anionic charges.
  • first aier-sohrb!c polymer bearing an anionic charge and a second water-soluble polymer bearing a cadonic charge in the same formulation is believed to give rise to the formation of complexes between the two polymers, i.e., so-called poly electrol te complexes, which wo ld undesirably compete with the formation of complexes between the micelles bearing die cationie charg and the polymer bearing the anionic charge.
  • compositions comprising surfactant micelles bea i a net electrostatic charge and a water-soluble polymer bearing or capable of bearing an electrostatic charge opposite to thai of the surfactant micelles may comprise additional polymers which do not bear charges, that s, noniooic polymers, Such nonionfc polymers may be useful m adjuvants for thickening, gelling, or adjus ing the theological properties of the compositions or for adjusting he aesthetic a ea nce of the formulations through the addition of pigments or other suspended particulates, it should be noted, however, that many cases, the polymer-micelle c m lexes of the instant invention, hen adjusted to certain total actives concentrations, may exhibit 'h dMhiokenin " properties arid not explicitly requir an additional polymeric thickener, which is desirable from a cost standpoint.
  • compositions are free of not onie surfactants winch comprise blocks of hydrophobic sod. hytirophllio groups, such as the Plumules®, It is believed that the mieeikr structures formed with such large surfactants, in which the hydrophobic blocks assemble into the core regions of the micelles and the hydrophillc blocks are present at the micellar surface would interfere with the polymeric eouaisrion Interactions with so additional charged ⁇ .surfactant, incorporated into a mixed micelle, and/or also represent a more competitive micelle assembly mee.bani.sm, in a mann r similar to that of dm axe of block copolymers used as polymeric eoontstions, which are also pxderably not present.
  • a very wide range of surfactants and mixtures of surfactants may be used * Inclu ing an ic, noolonie and eabonlc serfsci&nis and mixtures thereof As alluded to above In the description of Dnet and P/Dneh it will be apparent that ixtures of differently charged surfactants may be employed. For example, mi tur s of catlotuc and anionic surfactants, mixtures of ca.tio.nic and nonkmic, m x ur s of anionic and nooiotbc, and miliums of caiionky nouionic and anionic ay be suitable for use.
  • eationie surfactants include, bat are not limited to monomenc quaternary ammonium compounds, monomenc bigoanlde compounds, and combinations thereof Suitable exemplary quaternar anaooolum compounds are available from Siepsn Co under the tradename BTC® (e.g., ⁇ 1010, BTC® 1210, BTC® 8 I S, BTC® S3S8).
  • BTC® e.g., ⁇ 1010, BTC® 1210, BTC® 8 I S, BTC® S3S8.
  • BTC® 1010 and BTC® 1210 are described as didecyl dimethyl mmonium chloride and a mixture didecyl dimethyl ammo ium chloride and nmlkyi dimethyl benzyl ammonium chloride, respectively.
  • monomerie blgnanid compounds include, hut are not limited to ehlorhexidine, alexidlne and satis thereof.
  • anionic snriaeiaras include, but are not limited to alkyf sulfates, alkyi siilf riates, alkyl eiboxysalfates, fatty acids sad fatty acid salts, tinea? alkyibeoxerse sulfonates (LAS and Hi. AS.), secondary slksne sulfonates (for example Bes ow® SAS- 30), methyl ester sulfonates (such as Sie a -M t- PCL from Stepau Corp), alkyl suifosuccinates, and alkyl amino acid derivatives.
  • harnnollpids bearing anionic charges may also be used, for example, it; formulat ons emphasizing greater sustalnabiiity, since they are not derived from petroleum-based .materials.
  • An example of such a rhanmoHpi is JBR 425, which is supplied as an a ue us solut on with 25% actives, f m Jenil Biosurfa ani Co., LLC (Ssukvsiie, Wk USA).
  • Sorbltan esters and eihoxylsted se-rbi ' ten esters are also useful no ionk surfactants.
  • Other useful noniomc surfactants include, but ate not limited to, fatty acid amides, ferity acid monoethauolamides, fatby acid dlelhanoiamidex, and fatty acid Isopropa-ootaosides, j3 ⁇ 4H f Irs.
  • a phospholipid stn'&etant m y be mehaied. Lecithin is an example of a phospholipid,
  • syathetie xwittenonic surfactants may be present.
  • Non- limiting examples include N ⁇ alkyl beiaiaes ii r example Amphosoi® LB from Stepan Corp.), alkyl suffo-beiaioes and mixtures thereof.
  • the surfactants may be edible, so long as they exhibit water solubility or can fbrrn mixed micelles with edible nonloaic surfactants.
  • edible surfactants include casein or lecithin or mixtures thereof
  • the surfactants may be selected based on green or natural criteria.
  • green or natural criteria there is an increasing desire to employ components that arc naturally-derived, naPuaily-proeessed. and biodegradable, rather than simply being recognized as safe.
  • processes seek as el soxylation may be undesirable where 3 ⁇ 4 is desired to provide a green or natural product, as such rocesses can. leave residual com ound or impurities behind.
  • Such "natural surfactants ⁇ may be produced usin processes perceived to be more natural or ecological, uch as distillation, conde sation, extraction, steam distillation, pressure cooking a id hydrolysis o m& biize the purity of nateal ingredients, Examples of such "natural s rt1 ⁇ 4cte.ts' that may be suitable for use are described in U.S. Patent Nos, 7,608,5 /3, 7,618,93 h 7,6-29,305, 7,939,486, 7,939,488, all of which are herein, incorporated by reference,
  • optional adjuvant or mkmtes of optional adjuvants may be present,
  • builders and chelating agents including bat not limited to EDTA salts, GLDA, MSG, gluconates, 2-bydroxyaclds and derivatives, -glutamic- acid and derivatives, rimethy [glycine., stc. may be included.
  • Amino acids and mixtures of amino acids may be present, as either raeemie mixt res or as individual components ofa single chiraliiy,
  • Vitamins or vitam In precursors, for example retinal may be present, fdl)98f
  • Sources of soluble zinc, copper, or silver ions may be present, as the simple inorganic salts or salts of chelating agents, me fading, but not limited to, EDTA, GLDA,
  • ytC j Buffers including but not limited to, carbonate, phosphate, silicates, borates, and combinations thereof may he present.
  • Heettolytes such as alkali metal salts, for example including, but not limited to, chloride salts ⁇ e.g,, sodium chloride, potassium chloride), bromide sabs, Iodide salts, or combinations thereof may be present.
  • eiMJ Water-mi scibie solvents may be present in some embodiments.
  • Lower alcohols e.g., ethanol
  • ethylene glycol, propylene glycol, glycol ethers, and mixture thereof with water misclbility si 2S C C may be present In some embodiments.
  • Other embodiments will include no lower alcohol or glycol ether solvents, Where such solvents are present, some embodiments may include them in only small amounts, for example, of not more than S% by weight, not more th&n 3% by weight, or not more that; 2% by weight.
  • Wate -imm!selbb solvents may be present, being solubihzed into the m Scheme.
  • Waierdmmlselbie oils may be present, being solubillzed into the micelles.
  • these oils ape those added as fragrances.
  • Preferred oils are those that are f om naturally deri ed sources, including the wide variety of so-called essential oils derived from & variet of botanical sources.
  • Fonrmladoos teuded to provide antimicrobial benefits, coupled with Improved overall xustainabilky may advantageously comprise quaternary ammonium compounds or water soluble salts of ehiorhexldine or aiexidme in combination with essenlial oils such ax thymol anil the like, preferably In the absence of water-mi seiihie alcohols.
  • the ' composition may farther include one or more oxidants
  • oxidants nclu e* bet are not limited to bypoh&lous acid, hypofralite d sources thereof (e.g., alkal ne metal sab and/or alkaline earth metal salt of ypochlorous or hypohromons acid), !vydcogen peroxide and sources the eof (e.g., queous hydrogen peroxide, perborate and its sal s, percarbonate and Its salts, carbamide peroxide, metal peroxides, or combinations thereof), per&cids, peroxy acids, peroxoaeids (e.g.
  • Water-soluble rydrotropes sometimes referred to as monornerie orgastic electrolytes, may also be present. Examples include xylene salibnate salts, naphthalene sulfonate salts, and crmiene sulfonate salts.
  • Enayoms may be present, particularly when e- formulations ar « tuned for use as laundry detergents or as cleaners for kitchen and restaurant surfaces, or as drain openers or drain maintenance products.
  • the surfactants selected may be optimised for the solubilization of various waterdmmlseibie materials, such as fragrance oils, solvents, or even the oily soli to be removed from a surface with a cleaning operation.
  • the design of products which deliver m antimicrobial benefit is the absence of a stroE g oxidam ch as hypochlorite, a germicidal uaternary ammoni m compound or a salt of a monornerle bi .
  • si e tPete s great flexibility in the selection of the polymeric coanterion Ibr a given surfactant mixtu e to achieve a particular goaf applicants have adopted a syste na ie, bur slsisple approach for quickly "scanning through” .ranges of IkDnef in order to identify, a d to compare, formulations comprising: polymeric co n erions.
  • the formulations comprising the mixed micelles of a se charge and a waier-seiable polymer hearing charges opposite to that of the micelles are usefoi as ready io use surface cleaners delivered via pre-s-nqistensd noowoven substrates (e.g., wipes), or as sprays in a variety of packages familiar to consumers.
  • Concentrated forms of the formulations may also be de veloped which may be diluted by the consumer to provide solutions that are then used. Concentrated fonns that suitable for dilution vis automated s s ems, in -which the concentrate Is diluted with w fer, or in which two solutions are combined in a given ratio to provide the final use formulation are possible,
  • the fonmslations may be in the orm of gels delivered to a reservoir or surface with a dispensing device. They may optionall be delivered In single-use pouches comprising a soluble film.
  • the composltlosis may be free of iodine or iodine-polymer complexes sanopsrtk-tes of silver, copper or zmc, trkka&n, p-c loromsf yl xylenoL monomeric pentose alcohols, D-xyHrol and its isomers, D-arabitol and its isomers, aryl.
  • compositions are useful as liquids or lotions that may be used in combination; with norrwoven substrates to produce pre ⁇ ruol stoned wipes.
  • wipes may be employed as disinfecting wipes or for floor cleaning in combination with various tools configured to attach to he wipe.
  • the clea ing pad of the present invention comprises a nonwoven substrate or web.
  • the cleaning substrates can be provided dry, premiokiened, or impregnated with cleaning composition, but dry o-the-touch, in one aspect, dry cleaning substrates can be provided with dry or substantially dry cleaning or disinfecting agents coated on. or in the midticomponeni multiloba! tlber layer.
  • the cleaning substrates can be provided in a prc-moistened and/or saturated condition.
  • the wet cleaning substrates ca fee maintained over time in a sealabk container such as, for example, within a bucket with an attachable l d, scalable plastic pouches or bags, canisters, jars, tubs and so forth,
  • the Zstasker ZS instrument offers a range of default parameters which can he used in the calculation of particle diameters from the raw data (known as the correlation function or autocorrelation function).
  • the diameters of the aggregates reported herein used a simple calculation model 3 ⁇ 4 which the optical properties of the aggregates were assumed to be si ikr to spherical particles of polystyrene latex particles, a common calibration standard used for more complex DLS experiments.
  • the software package supplied with the Zetasker provides automated analysis of the quality of the meas ments made, in the form of "Expert Advice".
  • the diameters described herein (specifically what is known as the "Z" average particle diameter) were calculated .from raw data that met ' '" Expert Advice "1 standards consistent with acceptable results, unless otherwise noted, I other words, the s m lest set of default measurem nt conditions md calculation parameters were used to calculate die diameters of all of the aggregates described herein, m order to facilitate direct comparison, of aggregates based on a variety of polymeric connterions and surfactants, and avoiding the use of complex aiodeis of the scattering which could com lic e or prevent comparisons of the diameters of particles of differing chemical composition.
  • This instrument calculates the zsta. potential of colloidal particles from measurements of the sleetrophoretic mobility, determined via a Doppler laser velocity easu ement. There exists a relationship between the slecirophoretie mobility (a measurement of the velocity of s charged colloidal panicle m vi g In an electric Held) and the zeta potential (electric charge, expressed in units of millivolts). As in the particle size measurements, to facilitate direct comparison of aggregates based on a variety of polymeric coan3 ⁇ 43 ⁇ 4rIons and s rfactaBts, the simplest set of default aieasnremeni conditions were used, Le,, the.
  • the iateraodon between mixed micelles comprising an amine oxide and two different germicidal, quaternary ammonium compounds and aa anionic polymeric connteriors cm he readily illustrated by comparing the diameters of the mixed micelles (as measured by DLS) in the absence and presence of the polymeric countersom
  • the a ueous control formulations ' were repa ed by mixing the germicidal quaternary ammonium raw material (supplied as aqueous soluti ns; Stepan Corp.) with, the amine oxide raw material (supplied as an aqueous solution., Stepan Corp.) to form a mixed surfactant stock solution.
  • BTC® 1210 quaternary smmonium germicide (Stepan Co.) supplied as aqueous solution (10 % acti es) described as a mixture of didecyl dimethyl ammon m c3 ⁇ 4Io «de md n ⁇ alky! (50% C14 ; 40% CI 2, !0%C16) dimethyl ben yl ammonium chloride, average molecular weight 360.5 grams m le. ,
  • micellsr aggregate controls at Dne - were around 1.
  • nm In diameter which is m expected size mt%$& for mteeilar aggregates of i nic surfactants aqueous solutions.
  • Tr s any growth in the aggregates, whkh m ght he & precursor to coacervate or precipitate formation and whkh would he less obvious than the haziness of samples detected visually, would be detectable from, a trend in the -avemge diameters over time.
  • Mo such treads were detected for samples A3 through ⁇ 6. All of these samples exhibited relative standard deviations of the Z-average diameters of less than 1% from the 1 1 sequential meas ements maele, The Zmverage diameters for these sam les, based on 1 1 measurements each, are those reported m Table 1.2.
  • Table 1.2 shows that the aggregates formed with the olymeric eo nterioa have .mean seta potential valises that are positive, eveo somewhat greater time the micelles alone, consistent with the torraation of distinct, tunable aggregates which car ot be f med without the irss of a polymeric comttetiom that is, t at eaeeot be formed 3 ⁇ 4t the same total anrfaetani eoncentratloa and the same mixed micelle compositions when Ih rrative coo eriarss of the cationlc: surfactant (the germicidal quaternar amm nium com o nd.),- her chloride ions, are the only ones present, A conservative estimate of the precision of ml of the se potential measuremems referenced hereto is about 10% of the reported, mean value.
  • surfactant the germicidal quaternar amm nium
  • the forrmdsiions om rsing the polymeric cotmterion were clear md fee of coacervate whers the absolute val3 ⁇ 4s of F/ oes. was bss than 0.39, according to m Inspection of a serks of sam les covering a range of this parameter between 0 md 0,5 ai this total surfactant cot>cerstraion md micelle cons ostion.
  • the ddi ion of a polymeric countsrion yields stable, soluble aggregates with a tunable size and charge which can be adjusted through the mixed micelle composition and the P/Dnet value.
  • such aggregates exhibit surprisingly good antimicrobial performance, across a range of rnferoorga «ism3 ⁇ 4. without requiring volatile organic materials such as alcohols or glycol ethers to boost or "potsntiats" the action of the quaternary ammonium compound.
  • the aggregates comprising polymeric coemptio s can more readily act at the solid-liquid interlace, includiog that of microbes, enhancing the delivery of the germicidal quaternary ammonium compcamd and thus snhaucing amlmicrooiai efficacy.
  • anionic polymeric counterions to the mixed missiles coniammg a q aternary ammonium compound provides a msehsnssrn to tune the sobAi!iaatioo efficiency oi waer-immiscibk oils, through aojhisment of both Dnet and the absolute value of P/Dnet.
  • the aggregates comprising the mixed surfactant nd the polymeric coemsrion are capable of solabili3 ⁇ 4ing waier-1 ⁇ 2soksbte matesiafs mcb as Hmonene.
  • the appropriate P/Dnet range for the concentrated fornmiatlons was determined, with different germicidal quaternary ammonium compound and an amine oxide surfactant mixture.
  • the concentrates also comprised telrapotasslum eihy!enediarnlrse tetraacetate, a common ehe-!ant and buf er useful in controlling the effects of common tap water used as a diluent, and aCl as an electrolyte, Multiple concentrated formulations which were clear and free of coscervaie arc identified trou the adjustment of P/Dnet and Nad level.
  • Formulations suitable for dilution at a rate of 1 :250 by volume are then identified through visual Inspection. Formulations which appeared to yield cleat; soluble solutions free of eoaeervate phase when diluted were then analyzed via DLS to confirm thai the aggregates comprising polymeric counterions formed by a. simple dilution process had diameters in the range expected to provide colloidal stability, I.e., Z-average diameters less than 500 nan as measured as described herein.
  • anionic polymeric cotsnterkwi m these examples Is Vsrss-TL® 4 (Akzo obel), described by the su lier as random co ol me of sulfonated styrene md m&kk anh dride, which s supplied as an aqueous solution at 25% actives si pH 7,0, which means the anionic sulfonate groups are present in the salt form, and thai t e m&kk anhydride has ee; hydrol ed to m&l&k acid via reaction with water, a d the acid groups are sent in the soaked (salt) form, '
  • the nomina molecular weight of the polymer is described as 20,000 d&itons.
  • the total n mber of amonk&lly charged rou s oo this polymer yields 0.00642? moles of anionic groupsgram of polymer solids, and this a used in the calculation
  • Pormidalions A30 through A34 Irs which a different gs.mik.kkl quaternary ammonium compound s used, are acceptable concentrate candidates.
  • Formulations A30 artd A31 are examples of concentrates which, upon dilation, f m clear solutions that are free of coaeervates or preeipkates, DLS was then esed to confirm the presence of stable aggregates comprising the mixed micelles and the polymeric eounterloo. In comparison to mixed micelles comprising the same qua ernary ammonium compound and amine oxide samadant wi out the polymeric counterlon.
  • cationk mixed micelles with anionic polymeric eounterion also exhibit dte important property of solu il zation of waterAasoieble oils w en ooaeervate or precipitate phases are abserP, and tins solubilization may also he evaluated through visual Inspection of samples.
  • the absolute value of the P/Doet parameter cannot be used alone to determine formulations " which are free of eoaeervates or precipitates, but instead must be considered together with s e mixed micelle c mposition and the type of water-soluble polymer selected for use as a polymeric couetsr!oo.
  • the polymeric eounterion in order to avoid eoseervate and precipitate phases, the polymeric eounterion must be soluble aqueous compositions at the H of the desired final .formulation.
  • the solubility of polymeric countsrions in aqueous compositions may also be readily evaluated thoug visual inspection techniques.
  • the .solubility in water of Al.cosperse® 747, a random copolymer, Aeaatreat® a random copolymer
  • AR-4 an servile acid homopolymer
  • Akogaard® 5240 a random graft copolymer, all of which contain carhoxyiic acid groups, may be compared over a range of pH values and any polymer which does not exhibit the necessary solubility at the pH of interest may he avoided,
  • Formulations comprising mixed micelles of a germicidal u ernar mmoni m com ound and -an.
  • amine oxide rosy also comprise adjuvants or heifers w ich can be used to adjust the pH.
  • monoetbanolamioe MEAs was osed to increase the pH of t e fotmaiatious, and glycoik .acid was used to decrease the pi! of the formulations. Decreasing the pH of such formulations may he desirable for increasing cerhiio aspects of cleaning performance, for example, the dissolution of hard water spots torn sinks, hies, dishes., etc.
  • the inactivatioo of certain viruses ami bacteria is also known io improve when the pR is decreased below pH ?, to the acid pH rasuge. Certain other aspects of cleaning performance of am ne oxides, sack as residue deposition on hard surfaces which results in filming or streaking, and decreased ability to solabiltee greasy soils tend to he exacerbated as the pH of the formulations is decreased, especially below pH ?.
  • anionic polymeric counterioes in formulations co prisin germicidal quaternary smmoafem compound and amine oxides improves the ettin properties of the formulations on a range of surfaces, while decreasing residue formation.
  • the addition of volatile con ents to t e acidic fbrm latioas to improve performance properties may be avoided when polymeric coimierioo* are utilized.
  • the water soluble polymer f Aioogtrard® 2300 from Afczo Nobel was a andom copolymer of the no onk monomer dis ⁇ tbylacryiamide (95 moie%) and the anionic mosiomer acrylic acid (5 moie%), w ich thus provides 0,00600 moles of anionic grou s per grarn of polymer actives.
  • This polymer is soluble in water at both lo pfi, eg., pli 2- , d high. p!:L e.g.. pE 10, arsd can thus be employed as the anionic polymeric eountsrion.
  • Polypeptides in aqneous solutions will exhibit a e cha ge as a functiono of pH of the solution that is de ermin d by the relative num e s of amonioaily and cationically char ed Smin ⁇ acids in the polypeptide chain.
  • rise net charge on the polypeptide is ze o, due to the presence of equal numbers of cahonicahy charged and aniaiiicatly charged amino acids.
  • the net charge on rise polypeptide at pH values greater the isoelectric pai t will t m be negative (anionic-), sod will he positive (cationfc) at pH values below the isoelectric point.
  • the isoelectric points, (or point of zero charge) of various Baciiius spores have beers found to lie between about pE 3 and pH 4 .
  • B i!hs spores exhibit average diameters of mx d 1000 u (1 micrometer), and cars thus act. as charged scattering ar icles when dispersed In aqueous media. Measurements of the zeia potential of spores are thus readily accomplished using the approach of laser Doppler velocity determination ih&t is implemented in modem instruments, such as the Malvern Zeis S!zer.
  • compositions of tin; instant invention in which micelles wi h a net cs!ionfc charge are paired i h s - ater-sokhle polymer of anionic charge, white mma lsg sol able and free of eoacervates or precipitates, have the advantag of ine control of the adsorption and desorption of p ion ic surfactants,nc uding the germicidal quaternary ammonium compound and biguanides, whkh can he exploited to provide better antimicrobial efficacy against the proliferation of hastens on surfaces doc to the germination of snores.
  • a eommerelaiiy available stock suspension of Bttciiius Su&i! is spores w s used to make all samples on a given day. Samples were analyzed within four hours of preparation. Thirty microliters of the stock spore suspension (I x 10 " efu/ml) were mixed with 870 microliters of water (pH 7) to give a control sample con a n n about 3.3 X 10" cfu/mt. The entire sample as loaded into a disposable capillary cell for meas rement of the ze&s potenf of the spores, as described generally above.
  • Se l dilation of concentrated ceil sirspenslons followed by plating on a solid growth medium is a common way to determine the viable ceils, or colony forming units (CPU).
  • CPU colony forming units
  • the CPU multiplied by the relevant dilution factor relates baok i the viable microbes in the original suspension.
  • S and rd recognition software eats visualize colonies on the solid medium and calcula e the CfU/rai of the or ginal suspension based on the distance , and somber of colonies ela ive to the center of the plate,
  • Such an approach Is implemented with commercially available equipment; such as the Antoplater Model APSOOi) (Advanced instrumen s) nssd in the fxdlowdng examples,
  • the chemistry of the a ueous environment sonoanding the spores changes dramadcaby towards one rich in .nutrients such as proteins.
  • the quaternary amm nium molecules and any other suf&ctaotx adsorbed on the surface of the spore will re-equilibrate with the sumrnuding growth medium through desorptlon (partial or complete) from the spore surface, and/or a displacement from the spore surface through the adsorption of oilier materials present In the growth medium.
  • the spiral plating method exposes the spores suspended in the inventive compositions to as exponentially increasing "organic loadT wh ch Is well-kno n m she art to interfere t and or revent t e antimicrobial action of common getmkides suc as quaternary a m nium compounds or big eanides.
  • the equipment used for the spiral plating of the suspensions of the treated spores yields a pattern In which the central hole has a diameter of about 2 cm when a high concentration of spores that are viable (m a control exp riment, for example) are resent at the start of the spiral pattern. If the treatment of the spores results i killing, upon: germination: of all f t the spores, then the maximum diameter of the hole Is about 8 em, ' Tims, values of the diameter of the central hole be ween about 2 cm and S cm, herein called the germicidal diameter, represent varying degrees of effectiveness of the treatment of the spores for prevention of the con amination .
  • Formulations comprising mi ed micelles of the germicidal quaternary ammoniu compound BT €S> 101 md an am me oxide were made as described above, over a range of iP/Dnst values, using the a o ic waier-solab!e polymer Aicosperse® 74? as the polymeric com3 ⁇ 4ierioa.
  • Formulations El through E5 c-OBia ed the same quaternary ammon um compound concentration, while formula o E6 contained a significantly lower quaternary ammonium compound concentration.
  • the relative amounts of quaternary ammonium compound and amfe oxide in the mixed micelles was the same.
  • the compositions are shown in Table 10.1 .
  • formulations in which the absolute valise of P/I3net are E (mdksting an equal number of anio ic .charges due to the polymeric eoanis.rion and the cationie charges d e to die germicidal quaternary ammonium compound) or even 2 (indicating, an excess itx the .number .of anionic charges due to the polymeric ooant rion over the eat ionic charges d sc to the germicidal quaternary ammonium compound) exhibit kilting performance comparable to that of the control formulatio across a.
  • Control Formulation Eh included no polymeric eounteriom Formulation Eh, when diluted 2x (factor 0.5) contains 0,0125 % quaternary ammonium compound, and shows only a small amount of germicidal activity, as shown by a germicidal 3 ⁇ 4one diameter of 2.5 cm . ronrndatsoos E2 through b3 ⁇ 4 s wrseu diluted l.ox (.factor 0..OP2 ). also contain 0.0125% quaternary ammon m compound. However, due to the presence of the polymeric coonterson in these inventive compositions, the germicidal activity is significantly better than in rise ease of form elation E6.
  • Table 1 1 .1 - Compositions for Testing Effects of Treatment of BaciUtis Snlni!is spores
  • the similarity in killing erformance of the inventive compositions -across a range of the absolute, value of P/Drset shows that optimlzatioo of other parameters of the icrrmharions. such as cost, cleaning perfona ⁇ pe or kinetics, or sarisce residue aesthetics cm be adjusted -vis P/Dnsi. while maintaining the antimicrobial properties of the formulations, dm to the fine control of the Interactions of the surfactants in the mixed mkeiies that cm be achieved with the se of & water-soluble. r»ly erie eounterion. of charge opposite to that of the net charge of the m ed micelles.
  • Formulstiom comprising polymer micelle complexes c mprised of mixed micelles of a- ermicidal quaternary aramoniw com ound and an amiss oxide and anionic water soluble polymers increase the antimicrobial efficacy of a bnmda delivered by a soewoven wipe.
  • polymer micelle complexes formulated over a range of P D «et values arc shown to outperform mixed micelles in the AST Irstematiorsai, Standard Practice for Evaluation of Il-Ssierated or Impregnated To eiettes for Bard Surface Disinfection.
  • Test Method E 2362 (henceforth, referred to as the towelett® test) against Pseudcrmorm. ' This example also demonstrates flexibility in choice of polymer chemistry and the compatibility of rmcslfe-polysior complexes with solvents and silver ions,
  • compositions and F/ ' Dnet valises of the brrmdatioos g e shows* m Table 2, 1.
  • Formulations we prepared by first rak ng BTC® 1010 (Slepan Co,.) and Ammonyx® LO (Stepasi Co,) tho specified amounts with water, t as fomtmg the mixed mkelies. The pH was then adjusted using MEA aod glyoolic acid In the specified amounts.
  • the specified arrsorsfb of anionic polymer iAIcosperse® 747, Aicogaard® 145240 or Alcoguard® 2300, all from Afczo Nobel) were than added to form the micelle- polymer complexes.
  • ropykoe glycol n-b sty! ether (DO SB TM POB, DOW Chemical Co.) was added to formtdaiion 03 to demonst a e eon ⁇ mtibility with solvents.
  • Silver dihydrogen citrate (Tinosarr® S0C ⁇ Ciba) was added ⁇ tbraudaiion G6 at a raw mate i l concostratiors of 0.123 wt% ⁇ equal to 3; ppm silver loos) to de «loas3 ⁇ 4-&ts eorrjpatiblhty with silver ions.
  • the foraralations form stable aggregates, elmtactsr1 ⁇ 2ed by DLS analysis as described la examples 1-6 ' and were visually clear,
  • Moist towefeties were prepared for ASTM Test Method E 2362 by applying th appropriate formulation to a roil of the toweiettss.
  • the mass of the liquid formaiabon added to the rolls of towebites was 4.5 times the mass of the dry towdettes, Towelebe nssd in this example were rsoawoverp 40 gsm material purchased .from N.R, Spijatee ladastr s Ltd. '
  • the moist towebttes were allowed to equilibrate at room isaspsrabae for at least 24 hoars.
  • Fo mulat ons G4 and G5 demonstra that a wide range of water soluble polymers are suitable for forming dm micelle-polymer complexes.
  • Foomoiatkai 04 also shows thai mieeHe-polymer completes formulated at an absolute value of P/Dne greater than Li) are. capable of boosting amimiorobial activity relative ro that of mixed micelles wit ou the polymeric couuterions as well.
  • This result Is particularly surprising considering that the eatiordc charge on the germicidal micelles Is widely accepted to be the dri ing force for adsorption of the active Ingredients onto microbes.
  • formulation G6 demonstrated the compatibility of the micelle-polymer complexes with silver ions.
  • P3 ⁇ 4l ⁇ 81 This example demonstrates the delivery of antirnkrobkl efficacy enefits usin dilutable formulations comprising polymew ice le complexes comprising; mixed micelles of a germicidal quaternary snvmonhrm compound and an amine oxide a d anionic water soluble polymers.
  • this formulation ⁇ € 8 IS 6 Am onyx® DO are mixed in • water at the given concentrations, and then A ognard 5240 is added and mixed well.
  • the formulation is visibly clear In the concentrated form and when diluted in hard water as per the laundry sa3 ⁇ 4itl3 ⁇ 4sr test protocol.
  • Table 14.1 Composition of formulations tor a dilutable laundry saodker
  • Formnladon HI capable of passing the laundry ssniluatton test mentioned above against Siaphyfa xx - Aureus am! Klesiei Pneumonia a a 4 minute contact time hen diln ed ! part to 584 parts in hard water.
  • the ex.treme dilution ratio and high bacterial loads m ke t is test method exceedingl difficult to pass with quaternary ammonium chemistries such ss formulation H2.
  • the total solublMzer concentration is the sum of the eoneentrsdons of the polymer, the germicidal usternary ammonium compound BTC® 1010, and the nonlonic surfactant Ammonyx® CO,
  • the F/Dnet parameter was fixed ax a relatively low absolute value, m order to minimize ike cost of the polymer added to the formulation Throe dif&rent concentrations of Wt ' C®. 1010 wots investigated.
  • Solu il zation of the llmonene could be achieved when the concentration of the ETC® l OfO catlonlc germicidal surfactant was irai osaed sonnswh t, and if enough Aama ⁇ nyx® LO was added, to give the final total solubili sr levels shown lor fou d ti s J2 and . [ ⁇ 195] The same procedure was used to detetad.no the mittimusi? total solabiHser requirement tit the presence of polymeric coontetioas at a fixed P/Dnet ::; - 0.01 ratio.
  • formulation J5 re u es only 0.854% total sohmihzer to fully sorobilixe the limonene mto a clear solution tree of coaeervates of precipitates, w lfc formulation 12, which has the *>&m «s concentration of the germicidal quaternary ammonium com ound, re uires a much higher total solebiiizer level, 1 375%, to fully solubilize the same eoocem ation of limonene.
  • the enhancement or boosting of tire sohrbi!kation of water-insoluble oils may be obtained with a wide variety of water-soluble polymers,, over a wide range of F/Dnet values, offering considerable flexibility in meeting different arrtitnlerobial performance, aesthetic or cost targets.
  • Oil solubilization optimization is carried oat in the presence of 0.3 wt% Hmouene mode! oil by, in a series of samples, simultaneously Increasing the absolute value of F/Dnet and she concentration of the sronlonic amine oxide surfactant at a fixed catk k surfactant concentration until solutions which are clear, free of precipitate, eoacervate and excess o!i are obtained.
  • Optim zed compositions are thus the ones that turn clear at the lowest added amine oxide sar acteat concentration.
  • the minimum total solnbilizer values are thus the sum of the BTOS? 1010 . , ⁇ LO, and polymer (if present) in the final tbrrmdstions thai yield complete oil solubilization.
  • compositions of isked micelles dee to the fine control over i3 ⁇ 4 « interactions between the cationic and nonlonlc sarfaciaats in the mixed micelles that is possible through the use of the anionic polymeric counterion.
  • formulations K5 and 7 ex ibit lower minimum total soto lker sone &imlGns thm formulation 5.
  • Antimicrobial Compostions Coatammg a Mooonsenc Biguarhde, Chlorhexidine
  • the caliomc germicide present n the mixed i ce!les may be a mooomerio i uisiside salt, such as chlorhexidine gluconate (CHG).
  • CHG was supplied as 20% solution In water, from Sigrna-Aldrieh.
  • CHG has two oatiorac charges per moieeole md a moleeeiar weight of 7.S g/mole
  • the mixed micelles m y also comprise omomc s fectams.
  • compositions sirmmariiied m Table 17.1 comprise two ao kmie surfactants, SarfoBki3 ⁇ 4 L12-S (an alcohol etboxylste, from Hunsman Carp), ssd G1 ⁇ 4cofxm ⁇ D 32SN (as alky! gs coside, from BASF Corporation) k.
  • the mixed micelles with the CHG, Sioee the CHG cooceotrntion is tire same In orrautechnischs LL L2 arrd L3, the value of Eq catkkc will ls be the same md is c lculated as lo s
  • the water-sokh!e polymer osed s this example as the polymeric eountenon is p l ⁇ 2 ⁇ 3 ⁇ 4ci temldo-2-Tn®thyl-l- o a3 ⁇ 4es lo lc acid), or ' poly AMPS, it has I arriorne charge per morojsser unit, which has & molecula weight of 207,25 g/mole. in formulation LP poly AMPS is preseot at a eoocersteatlon of 0.0035 wt% or 0,0035 gras i/1 0 rams of the formulation.
  • L2 and L3 are useful as lotions for pre-moisiened wipes or as hmd sadtizers.
  • DowanolTM DB and D wanoP ⁇ PnB are glycol elisor solvents from Dow Corporation. Fragrance oil was a ierrson fragrance fro Fi oterbch,

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Abstract

L'invention concerne un complexe polymère-micelle. Les complexes polymère-micelle comprennent une micelle positivement chargée choisie dans le groupe constitué d'un composé d'ammonium quaternaire monomère, un composé de biguanide monomère, et des mélanges de ceux-ci. La micelle positivement chargée est électrostatiquement liée à un polymère hydrosoluble portant une charge négative. Le polymère ne comprend pas de copolymère séquencé, de particules de latex, de nanoparticules de polymère, de polymères réticulés, de copolymère de silicone, de tensioactif fluoré, ou de copolymère amphotère. Les compositions ne forment pas un coacervat, et ne forment pas un film lorsqu'elles sont appliquées sur une surface.
EP12887665.3A 2012-10-30 2012-11-02 Micelles cationiques avec des compositions de contre-ions polymères anioniques, procédés et systèmes de ceux-ci Withdrawn EP2914235A4 (fr)

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US13/663,862 US8883705B2 (en) 2012-10-30 2012-10-30 Cationic micelles with anionic polymeric counterions systems thereof
US13/663,830 US20140121281A1 (en) 2012-10-30 2012-10-30 Cationic micelles with anionic polymeric counterions methods thereof
US13/663,792 US8728454B1 (en) 2012-10-30 2012-10-30 Cationic micelles with anionic polymeric counterions compositions thereof
PCT/US2012/063433 WO2014070201A1 (fr) 2012-10-30 2012-11-02 Micelles cationiques avec des compositions de contre-ions polymères anioniques, procédés et systèmes de ceux-ci

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US20220117869A1 (en) * 2019-02-11 2022-04-21 Reckitt Benckiser Health Limited Topical sanitizing compositions
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US5360571A (en) * 1992-03-31 1994-11-01 Osi Specialties, Inc. Surfactant compositions
US5888957A (en) * 1997-05-09 1999-03-30 Colgate Palmolive Company Liquid cleaning compositions containing a negatively charged surfactant complex
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US20030073606A1 (en) * 2001-10-17 2003-04-17 Diversey Lever, Inc. Cleaning composition and method for using the same
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