MX2015005340A

MX2015005340A - Anionic micelles with cationic polymeric counterions compositions, methods and systems thereof.

Info

Publication number: MX2015005340A
Application number: MX2015005340A
Authority: MX
Inventors: David R Scheuing; Rui Zhang; William L Smith; Travers Anderson; Erika Szekeres
Original assignee: Clorox Co
Priority date: 2012-10-30
Filing date: 2012-11-02
Publication date: 2015-07-14
Also published as: CA2889140C; AU2012393509B2; CA3041550A1; EP2914544A4; AU2012393509A1; CA2889140A1; CA3041550C; WO2014070202A1; CL2015001110A1; AR088975A1; EP2914544A1

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 MICELLAS WITH CATIÓNIC POLYMERIC CONTRAIONS, COMPOSITIONS, METHODS AND SYSTEMS OF THESE BACKGROUND OF THE INVENTION 1. Field of the invention The present invention relates to polymer-micelle complexes. 2. Description of the related technique Cleaning product formulations are based on surfactants and surfactant mixtures to provide cleaning (detergency), surface wetting, fabric stain removal, bleaching of stains, fungal and mildew discoloration and in some cases antimicrobial efficacy. A key aspect of these processes is the interaction of surfactants, oxidants and antimicrobial agents with the solid surfaces of the materials being cleaned, as well as the surfaces of the microorganisms, together with the effects of the formulations on the air interface. -water (surface tension). The reduction of the surface tension of the aqueous formulations, which is directly related to the effectiveness of the wetting of the solid surfaces and therefore the antimicrobial and detergency processes, can be manipulated by the use of mixtures of surfactants, as is known in the technique.

At the molecular level, surfactants and mixtures of surfactants in aqueous media exhibit the ability to adsorb to the air-water, solid-water and oil-water interfaces and this adsorption is, therefore, responsible for a wide range of phenomena, These include the solubilization of oils in the detergency process, changes in the properties of solids and dispersions of solids and the decrease in surface tension of water. It is generally known that the adsorption of surfactants to the interfaces increases with the concentration of the surfactant to a concentration of total surfactant known as the critical micelle concentration (CMC). In the CMC, the surfactants begin to form aggregates in the volume of the solution known as micelles, in equilibrium with the monomeric species of surfactants that are adsorbed to the interfaces.

The details of the structures and sizes of the micelles, as well as the properties of the adsorbed layers of surfactants or mixtures of surfactants, depend on the details of the shape and molecular charges, if any, of the hydrophilic "heads" of the surfactants The heads of surfactants with a strong charge tend to repel each other at interfaces, which precludes efficient packing of surfactants at the interface and also favors micellar structures that are relatively small and spherical. The loaded heads of many Surfactants, such as sulfates and sulfonates, will also introduce a counterion of opposite charge, eg, a sodium or potassium ion, into the formulations.

It is known that the nature of the counter-ion can affect the repulsion between charged surfactants in nuclles and adsorbed layers by partial shielding of the head charges from each other in aggregates of surfactants such as micelles. It is also well known that the addition of simple electrolytes, such as sodium chloride, to aqueous solutions can also be used to increase the shielding of similar head loads and, therefore, is a common parameter used to adjust the properties of surfactant micelles, such as size and shape, and to adjust the adsorption of surfactants on surfaces.

The addition of significant amounts of simple electrolytes to many formulations, such as spray cleaners of hard surfaces or non-woven cleaning cloths to which a cleansing lotion has been applied, is undesirable due to the residues left by the formulations when drying. An alternative method to adjust the properties of such formulations, including wetting of solid surfaces and stains on them, or wetting and interactions with microbes, is to include significant amounts of volatile organic solvents such as lower alcohols or glycol ethers. Volatile organic solvents, however, are increasingly subject to regulations because of their potential health effects, and the significant fraction of consumers who want effective disinfectant and cleanser products with a minimum amount of active chemical compounds, including compounds volatile, they do not prefer them. In the healthcare industry, there is evidence of effective formulations comprising lower alcohols, but they are considered to be deficient in their potential to irritate confined patients. These types of products present similar risks for clinical and cleaning personnel who must be exposed to such products on a daily basis.

There is a growing interest on the part of consumers, and a known need in the domestic and healthcare industries, to reduce the number of microorganisms in fabrics while using a family equipment such as washing machines. Concentrated products are required for an application of this type, due to the high level of dilution of the product in the rinse water, usually by a factor corresponding to a dilution of approximately 600 times. In the case of formulations comprising quaternary ammonium compounds, high concentrations of quaternary ammonium compounds are required in the concentrate in order to ensure that a degree occurs. of adequate adsorption to the microbes in a kinetically relevant time under the conditions of use of the dilution. As detailed above, it is desirable, and yet very difficult, to manipulate (ie, reduce) the CMC of a quaternary ammonium compound in such an application. Therefore, very high concentrations of quaternary ammonium compounds are used, which tend to be harmful to the skin and eyes, in concentrates, combined with elevated temperatures and prolonged exposure periods.

Therefore, methods and compositions that allow fine control of the properties of the surfactant aggregates are still needed in order to reduce or eliminate the volatile organic solvents. It also remains necessary to provide antimicrobial activity and / or stain removal due to the action of oxidants such as sodium hypochlorite on surfaces that are relatively difficult to wet with lower overall surfactant concentrations.

BRIEF COMPENDIUM OF THE INVENTION One aspect of the invention relates to a composition comprising an oxidant and a polymer-micelle complex comprising a negatively charged micelle that electrostatically binds to a water-soluble polymer that carries a positive charge. The water-soluble polymer that carries a charge positive does not comprise a block copolymer, latex particles, polymeric nanoparticles, cross-linked polymers, silicone copolymer, fluorosurfactant or an amphoteric copolymer. The complex does not conveniently form a coacervado.

Another aspect of the invention relates to a composition comprising an oxidant and a polymer-micelle complex comprising a negatively charged micelle that electrostatically binds to a water-soluble polymer carrying a positive charge. The water-soluble polymer carrying a positive charge does not comprise a block copolymer, latex particles, polymeric nanoparticles, crosslinked polymers, silicone copolymer, fluorosurfactant, amphoteric copolymer or a polymer or copolymer carrying anionic charges. The composition does not form a coacervate.

Another aspect of the invention relates to a composition comprising an oxidant and a polymer-micelle complex comprising a negatively charged micelle that electrostatically binds to a water-soluble polymer carrying a positive charge. The negatively charged micelle comprises a mixed micelle, which includes an anionic surfactant and a nonionic surfactant. The water-soluble polymer does not comprise a block copolymer, latex particles, polymeric nanoparticles, cross-linked polymers, silicone copolymer, fluorosurfactant or an amphoteric copolymer. The composition does not it forms a coacervate and does not form a film on a surface and is free of glycol ethers and alcohols.

Another aspect of the invention relates to a method for cleaning a surface. The method comprises contacting a surface with a composition comprising a polymer-micelle complex. The polymer-micelle complex includes a negatively charged micelle electrostatically bound to a water-soluble polymer that carries a positive charge. The water-soluble polymer carrying a positive charge does not comprise a block copolymer, latex particles, polymeric nanoparticles, cross-linked polymers, silicone copolymer, fluorosurfactant or an amphoteric copolymer. The composition conveniently does not form a coacervate and is not applied to trap organic contaminants in a location below the surface.

Another aspect of the invention relates to a method for treating a surface. The method comprises mixing a first composition comprising a water-soluble polymer having a positive charge with a second composition comprising a negatively charged micelle. The water-soluble polymer carrying a positive charge does not comprise a block copolymer, latex particles, polymeric nanoparticles, cross-linked polymers, silicone copolymer, fluorosurfactant or an amphoteric copolymer. The composition resulting from mixing the first and second compositions does not form a coacervate. He The method further comprises contacting the resulting composition with a surface so that the surface is treated.

Another aspect of the invention relates to a method for cleaning a surface. The method comprises contacting a surface with a composition comprising a polymer-mace complex. The polymer-micelle complex includes a negatively charged micelle electrostatically bound to a water-soluble polymer that carries a positive charge. The water-soluble polymer carrying a positive charge does not comprise a block copolymer, latex particles, polymeric nanoparticles, cross-linked polymers, silicone copolymer, fluorosurfactant or an amphoteric copolymer. The composition conveniently does not form a coacervate and is not applied to trap organic contaminants in a location below the surface. The composition does not comprise alcohols or glycol ethers.

Another aspect of the invention relates to a system for preparing a mixed composition for the treatment of a surface where the mixed composition is formed from two initially separated parts of the composition, wherein the system comprises: a first chamber containing a first oxidizing part comprising hypohalose acid or a hypohalite; and a second chamber containing a second reducing part comprising a nitrite, wherein the first and second chambers they are initially separated from one another to avoid premature mixing of the first and second parts; where, after mixing the first and second parts, the resulting mixed composition provides the oxidizing benefits provided by the oxidant for a limited period, where the oxidant reacts with the reductant so that the concentration of oxidant is reduced, so that they are avoided or minimize negative side effects that would otherwise be associated with prolonged oxidant exposure longer than the limited period.

In another aspect of the system, there is a system for preparing a mixed composition for the treatment of a surface where the mixed composition is formed from two initially separated parts of the composition, wherein the system comprises: a first chamber containing a first part oxidant comprising hypochlorite; wherein the hypochlorite comprises up to about 15% by weight of the two-part composition; and a second chamber containing a second reducing part comprising a nitrite, wherein the nitrite comprises from 0.01% to about 15% by weight of the two-part composition; wherein the first and second chambers are initially separated from one another to prevent premature mixing of the first and second portions; where, after mixing the first and second parts, the resulting mixed composition provides the oxidizing benefits that provides the oxidant for a limited period, where the oxidant reacts with the reductant to reduce the concentration of oxidant, so as to avoid or minimize the negative side effects that would otherwise be associated with longer exposure to the oxidant than the period limited.

In yet another aspect of the system, there is a system for preparing a mixed composition for the treatment of a surface where the mixed composition is formed from two initially separated parts of the composition, wherein the system comprises: a first chamber containing a first oxidizing part comprising hypohalite; where the hypochlorite is constituted by sodium hypochlorite; and a second chamber containing a second reducing part comprising a nitrite, wherein the nitrite is constituted by sodium nitrite, where the first and second chambers are initially separated from one another to prevent premature mixing of the first and second parts.; where, after mixing the first and second parts, the resulting mixed composition provides the oxidizing benefits provided by the oxidant for a limited period, where the oxidant reacts with the reductant to reduce the concentration of oxidant, so that they are avoided or minimized the negative side effects that would be associated in another way with prolonged oxidant exposure longer than the limited period.

In another aspect of the system, the first or second compositions comprise an oxidant. Optionally, the oxidant is selected from the group consisting of: hypohalous acid, hypohalite or sources thereof, hydrogen peroxide or sources thereof, peracids, peroxyacids, peroxoacids or sources thereof, organic peroxides or hydroperoxides, inorganic peroxygen compounds, chlorine solubilized, solubilized chlorine dioxide, a source of free chlorine, acid sodium chlorite, a compound that generates active chlorine, or a compound that generates chlorine dioxide, a compound that generates active oxygen, solubilized ozone, N-halo compounds and combinations of these.

In another aspect of the system, the oxidant is included within the second composition comprising the negatively charged micelle, and the first composition comprises the water-soluble polymer carrying a positive charge also comprising a non-ionic surfactant. Optionally, the non-ionic surfactant comprises an amine oxide.

In another aspect of the system, the nonionic surfactant comprises an amine oxide.

In another aspect of the system, the oxidant is included within the first composition comprising the water-soluble polymer that carries a positive charge and where the second The composition comprising the negatively charged micelle further comprises a non-ionic surfactant. Optionally, the non-ionic surfactant comprises an amine oxide.

In another aspect of the system, at least one of the first or second compositions further comprises a quaternary ammonium compound.

In another aspect of the system, the negatively charged micelle comprises an anionic surfactant selected from the group consisting of alkyl sulfates, alkylsulfonates, alkyl ethoxy sulfates, fatty acids, fatty acid salts, alkylamino acid derivatives, glycolipid derivatives including anionic groups, rhamnolipids, derivatives of rhamnolipids including anionic groups, sulfated derivatives of alkylethoxylatepropoxylates, alkylethoxylate sulphates and combinations thereof.

In another aspect of the system, the water-soluble polymer carrying a positive charge comprises a monomer selected from the group of diallyldimethylammonium chloride, quaternary ammonium salts of substituted acrylamide, methylacrylamide, acrylate and methacrylate, acrylate esters and amides with quaternized alkylamino, MAPTAC. { methacrylamidopropyltrimethylammonium chlorides), trimethylammoniomethyl methacrylate, trimethylammoniopropyl methacrylamide, salts of 2-vinyl W-alkyl pyridinium quaternary, salts of 4-vinyl AJ-alkyl pyridinium quaternary, salts of 4- vinylbenzyltrialkylammonium, salts of 2-vinyl piperidinium, salts of 4-vinyl piperidinium, salts of 3-alkyl-1-vinyl imidazolium or ethyleneimine and mixtures thereof or is a water-soluble polymer selected from the g of chitosan, chitosan derivatives carrying gs cationic, guar gum derivatives bearing cationic gs or a polysaccharide carrying cationic gs and combinations thereof.

In another aspect of the system, at least one of the first or second compositions further comprises a PH buffer.

After reading the preferred embodiments of the following detailed description other features and advantages of the present invention will be apparent to those skilled in the art.

BRIEF DESCRIPTION OF THE DRAWINGS To further clarify the foregoing and other advantages and features of the present invention, a more particular description of the invention will be provided with reference to specific embodiments thereof that are illustrated in the drawings located in the specification. It will be understood that these drawings represent only typical embodiments of the invention and, therefore, are not considered to limit their scope. The invention will be described and explained with additional detail and specificity by use of the accompanying drawings, in which: Figure 1 graphically depicts formulations of Example 2 regarding the boundary of the coacervate phase.

DESCRIPTION OF PREFERRED EMBODIMENTS I. Definitions Before describing in detail the present invention, it is to be understood that this invention is not limited to the systems or parameters of the process exemplified in particular that, obviously, may vary. It is also to be understood that the terminology used herein is intended only to describe particular embodiments of the invention and is not intended to limit the scope of the invention in any way.

All publications, patents and patent applications cited herein, whether earlier or subsequently, are hereby incorporated by reference in their entirety to the same extent as if it were indicated that each individual patent, publication or patent application is incorporated. specifically and individually by reference.

The term "comprising" which is synonymous with "including", "containing" or "characterized by" is inclusive or open and does not exclude steps from the method or elements that are not further mentioned.

The expression "essentially constituted by" limits the scope of a claim to the specified materials or steps "and those that do not materially affect the characteristic or the basic and novel features "of the claimed invention.

The term "constituted by", as used herein, excludes any element, step or ingredient not specified in the claim.

It should be noted that, as used in this specification and the appended claims, the singular forms "a," "an" and "the" include plural referents unless the content clearly dictates otherwise. Therefore, for example, the reference to a "surfactant" includes one, two or more surfactants of that type.

The term "water-soluble polymer" as used herein refers to a polymer that provides an optically clear solution free of precipitates at a concentration of 0.001 grams per 100 grams of water, preferably 0.01 grams / 100 grams of water, more preferably of 0.1 grams / 100 grams of water and even more preferably of 1 gram or more per 100 grams of water, at 25 ° C.

As used herein, the term "substrate" is intended to include any material that is used to clean an article or a surface. Examples of cleaning substrates include, but are not limited to, nonwovens, sponges, films and similar materials that can be incorporated into a cleaning accessory such as a mop. for the floor, a handle or a hand-operated cleaning tool such as a toilet cleaning device.

As used herein, the terms "nonwoven" or "non-woven network" refer to a network having a structure of individual fibers or threads that are interlocked but not in an identifiable manner as in a braided network.

As used herein, the term "polymer" used with reference to a substrate (eg, a nonwoven substrate) generally includes, but is not limited to, homopolymers, copolymers such as, for example, block copolymers , grafting, random and alternating, terpolymers, etc., and mixtures and modifications of these. In addition, unless specifically limited otherwise, the term "polymer" will include all possible geometric configurations of the molecule. These configurations include, without limitation, the isotactic, syndiotactic and random symmetries.

Unless defined otherwise, all scientific and technical terms and expressions used herein will have the same meaning as those customarily assigned to those skilled in the art to which the invention pertains. Although various methods and materials similar or equivalent to those described herein can be used by bringing the In the practice of the present invention, preferred materials and methods are described herein.

In the application, the effective amounts are generally those amounts listed as the ranges or levels of ingredients in the descriptions, which follow below. Unless stated otherwise, the amounts listed in percentages ("% by weight") are in% by weight (based on 100% by weight of the active compound) of the particular material present in the composition to which it is made reference, where any remaining percentage is water or a sufficient aqueous carrier that represents the rest up to 100% of the composition, unless stated otherwise. For very low weight percentages, the term "ppm" may be used, which corresponds to parts per million as a function of weight / weight, indicating that 1.0% by weight corresponds to 10,000 ppm.

II. Introduction The present inventors have determined herein that the use of water-soluble polymers comprising groups carrying or capable of carrying an electrostatic charge such as counterions (polymeric counterions) for micelles comprising at least one ionic surfactant selected so that the electrostatic charge net of the micelle is opposite to that of the polymeric counterion, it can provide, simultaneously, a very fine control of the interactions between the heads of the ionic surfactants as well as the adsorption of the ionic surfactant at the air-liquid and solid-liquid interface when the compositions are adjusted so that the precipitates or coacervates are completely absent from at least some embodiments of the compositions.

Surprisingly, this type of compositions in which the micelles with polymeric counterions exist as thermodynamically stable soluble aggregates exhibit a very high adsorption activity at the air-liquid and solid-liquid interfaces. Such characteristics completely eliminate the need to adjust the formulations so as to change their solubility, forming coacervates or precipitates, in order to provide adsorption of useful amounts of the ionic polymer and surfactant at these interfaces. Normally, it is observed that the micellar-polymer complexes formed when a water-soluble polymer comprising groups carrying or capable of carrying an electrostatic charge opposite to that of a micelle are somewhat larger than the micelles alone. The addition of a water-soluble polymer that carries electrostatic charges opposite to that of at least one surfactant in aqueous solutions can often reduce the CMC of a particular surfactant by a significant fraction, which can also have the effect of reducing the cost of certain formulations It has also been observed that fine control of the interactions within the micelles by the addition of oppositely charged polymers according to the invention increases the solubilization capacity of oils of the micelles to an unexpected degree. Without wishing to be bound by any theory, it is believed that this effect is due to the especially high charge density of the charged counterion which carries the charged polymer, which is clearly different from the effect of the normal counterions provided by the usual salt displacement electrolytes. It is thought that this increases the degree of association of the counterion of the charged polymers compared to normal electrolytes, even with very low polymer concentrations, which in turn favors increases in the micellar size and an increase in the efficiency of oil solubilization. . The inventors have found that the effect of enhancing the solubilization of oils develops only if the interactions are finely tailored so that the system is completely free of coacervates and, even so, is close to the boundary of the coacervates / water solubility phase.

Formulations comprising mixed micelles of an anionic surfactant, optionally a second surfactant such as an amine oxide, and a water-soluble polymer carrying a cationic charge with size control and net electrostatic charge can be produced. It is believed, unintentionally stick to no theory, that cationic polymers act as polymeric counterions for anionically charged micelles, either by increasing the size of those micelles or by collecting groups of those micelles in thermodynamically stable soluble aggregates that have a reinforced activity at the interfaces solid surface-solution aqueous, including hard surfaces such as floors, countertops, etc., as well as also soft surfaces such as fabrics, nonwovens and other surfaces such as the surfaces of microorganisms such as bacteria, viruses, fungi and bacterial spores. Depending on the use of the application, the surface may be hard, soft, live (eg, skin), non-living or otherwise.

In one embodiment, the compositions may comprise alcohol. In another embodiment, the compositions can be completely free of lower alcohols miscible with water. Similarly, the compositions may comprise glycol ethers miscible in water or be completely free of materials, sometimes referred to as "co-solvents" or "cosurfactants". Free compositions of lower alcohols or glycol ethers can not only provide acceptable antimicrobial behavior at a low cost, but also reduce irritation in patients and healthcare professionals, while providing formulations that can be considered more ecological or more sustainable due to total levels of reduced active compounds and the absence of volatile organic compounds. Those embodiments that are free of alcohols or cosolvents may be especially suitable as sanitizing cleansers, disinfectant cleaners or pet treatments in veterinary or domestic applications.

The compositions may be useful as immediate use cleaners and may be applied by spraying or pouring, but may also be supplied by application on non-woven substrates to produce pre-moistened cleaning cloths. The compositions may also be provided as concentrates that are diluted by the consumer (eg, with tap water). Such concentrates may comprise a part of a kit for filling a container (also optionally included within such a kit), such as an empty gun-type sprayer. The compositions may also be provided as concentrates for single-use products (unit dose) to clean floors, windows, counters, etc. Concentrated dishwashing liquids can be formulated that provide antibacterial behavior after very high dilutions, as well as concentrates that can provide sanitization of the laundry to be washed by adding it to the clothes to be washed ordinarily. This type of compositions and results can be achieved even without triclosan. This type of products Concentrates can also provide protection against the growth of biofilms and the associated consequence of mold in the drainage pipes associated with automatic dishwashers, washing machines and the like, and reduce unwanted odors that are sometimes detected by consumers.

Concentrated forms of the formulations may also be provided, which may be diluted by the consumer to provide solutions that will be used next. Concentrated forms suitable for dilution by automatic systems are also possible, in which the concentrate is diluted with water, or in which two solutions are combined in a particular proportion to provide the formulation for final use.

The formulations may be in the form of gels that are supplied to a reservoir or surface with a dispensing device. They may optionally be supplied in single-use sachets comprising a soluble film.

The cleaning, wetting and top extension behavior of the systems makes them especially suitable for delivery from aerosol packages comprising single or dual chambers.

In one embodiment, the compositions do not involve the formation of a durable film on a surface after application. A simple rinsing is sufficient to eliminate any residue, and even without this rinsing, those Embodiments of the invention that form a residue do not form durable macroscopic films. Therefore, any remaining waste does not constitute a film, but is easily destroyed, altered or eliminated in another way.

The compositions of the present invention will not be used or applied to trap organic contaminants at a location below the surface.

III. Definition of Dneta and P / Dneta parameters As will be shown later in the examples, a very fine control of the interactions between the micelles comprising an ionic surfactant and the water-soluble polymers that carry electrostatic charges opposite to those of the micelles and which, therefore, act as polymeric counterions of the micelles, can be achieved by manipulating the relative number of charges due to the ionic surfactants in the system and to those charges due to the water-soluble polymer.

Mixtures of surfactants, including mixtures of ionic and non-ionic surfactants, may be used. A convenient way to describe the net charge of the micelles present in the formulations of the present invention is to calculate the total number of head equivalents of the charged surfactants, both anionic and cationic, and then to determine which type of charged head is in excess in the formulation.

Surfactants that carry two opposing electrostatic charges in the formulations, such as the carboxibatinins and the sulfobetaines, act as "pseudo-nonionic" surfactants in the compositions of the present invention, since their net charge will be zero. Therefore, the concentration of such pseudo-non-ionic surfactants will not intervene in the calculation of Dneta. Similarly, phosphatidylcholine, an edible material that is a major component of the surfactant commonly called lecithin, contains both an anionically charged phosphate group and a cationically charged choline group in the head region and, therefore, could be treated as pseudo-nonionic in the compositions of the invention. On the other hand, a material such as phosphatidic acid, which contains only an anionically charged phosphate group in its head, would contribute to the calculation of Dneta, as described below.

Some surfactants, such as amine oxides, may be uncharged (non-ionic) over a wide range of pH values, but may acquire charge (eg, cationically in the case of amine oxides) with pH values acids, especially below a pH of about 5. Although this type of components may not contain two opposite and permanent electrostatic charges, applicants have observed that they can be treated explicitly as non-ionic surfactants in the formulations of the invention. As shown herein, compositions of the invention that are free of coacervates and precipitates comprising mixed micelles of an amine oxide and an anionic micellar component and a water-soluble polymer that carries cationic charges can be easily formed by adjusting of the P / Dneta parameter, the Dneta parameter and / or the presence of adjuvants such as electrolytes, without taking into account the precise value of any cationic charge present in the amine oxide.

Two parameters can be defined for any mixture of surfactants comprising heads bearing, or being capable of carrying, anionic or cationic charges or mixtures of both, said parameters being anionic D and cationic D.

The anionic D will be defined as - anionic D = (-1) x (anionic Eq) The cationic D will be defined as - Cationic D = (+1) x (Cationic Eq) A final parameter that expresses the net charge of the micelles is the Dneta, which is simply the sum of the parameters anionic D and cationic D, that is, Dneta = cationic D + anionic D In the above expressions, the anionic Eqs are the sum of the total number of equivalents or charges due to the heads of all the anionic surfactants present. For a formulation comprising a single surfactant with a head that bears or is capable of carrying an anionic charge: Eq anionic = (C anionic i x anionic i) / M anionic i where C anionic is the concentration of a surfactant with anionic heads in grams / per 100 grams of the formulation or composition of use, Q anionic is a number representing the number of charges Anionic substances present in the surfactant, which may be considered to have the equivalent units per mole, and M anionic is the molecular weight of the surfactant in grams / mole.

For a formulation comprising two different surfactants with anionic heads, the anionic Eq parameter would be calculated as the sum: Eq anionics = Eq anionicsi + Eq anionics2 = (C anionic x Anionic Q) / M anionic i + (C anionic2x Q anionic2) / M anionic2 Commercially available surfactants are often mixtures of materials due to the presence of a distribution in the number of, for example, methylene groups in the hydrophobic "tails" of the surfactant. It is also possible that there may be a distribution in the number of "heads" charged per molecule. In practical work with commercial materials, it may also be acceptable to use an "average" molecular weight or an "average" number of anionic (or cationic) charges per molecule mentioned by the manufacturer of the surfactant In the calculation of anionic D (or cationic D), it may also be acceptable to use values of the anionic Eq (or cationic Eq) derived from a direct analysis of a surfactant raw material.

In the above expressions, cationic Eqs are the sum of the total number of equivalents or charges due to the heads of all cationic surfactants present. For a formulation comprising a single surfactant with a head that carries or is capable of carrying a cationic charge: Cationic Ei = (C cationicai x Q cationicoi) / M cationicoi where C cationicai is the concentration of a surfactant with cationic heads in grams / per 100 grams of the formulation or composition of use, Q cationicoi is a number representing the number of charges cationic substances present in the surfactant, which may be considered to have equivalent units per mole, and M cationicoi is the molecular weight of the surfactant in grams / mole. In cases where the formulation comprises more than one surfactant with cationic heads, the sum of the equivalents of cationic heads will be carried out as in the case of the anionic surfactants described above.

By way of example, consider a formulation comprising a mixture of a single anionic surfactant and a single nonionic surfactant, but lacking a cationic surfactant. Also, consider that the anionic surfactant is present with a concentration of 2% by weight or 2 grams / 100 grams of the formulation, it has a group capable of developing an anionic charge per molecule and has a molecular weight of 200 grams / mol.

Then Eq anionic = (2 x l) / 200 = 0.01 equivalents / 100 g in the formulation.

Then, anionic D = (-1) x (0.01) = -0.01.

And cationic D = 0.

Therefore, Dneta = (0 - 0.01) = -0.01.

By way of a second example, consider a formulation comprising a mixture of a single anionic surfactant, a unique nonionic surfactant and a single cationic surfactant which is a germicidal quaternary ammonium compound. Also, consider that the anionic surfactant is present at a concentration of 2% by weight or 2 grams / 100 grams of the formulation, has a group capable of developing an anionic charge per molecule and has a molecular weight of 200 grams / mol . Also, consider that the cationic surfactant is present in the formulation with a concentration of 0.1% by weight or 0.1 grams / 100 grams of the formulation, has a group capable of developing a cationic charge per molecule and has a molecular weight of 300 grams / mol.

Then Eq anionic = (2 x l) / 200 = 0.01 equivalents / 100 g in the formulation.

And Eq cationic = (0.1 x 1) / 300 = 0.00033 equivalents / 100 g in the formulation.

Then, anionic D = (-1) x (0.01) = -0.01.

And cationic D = (1) x (0.00033) = +0.00033.

Therefore, Dneta = +0.00033 + (-0.01) = -0.00967. This negative value clearly indicates that the number of anionically charged heads in the mixed micelles comprising the anionic, nonionic and cationic surfactants present in the formulation exceeds that of the cationically charged heads.

A second parameter that can be used to describe the present invention and the interactions between a polymeric counterion and micelles of surfactants bearing a net charge is the P / Dneta ratio.

P is the number of charges (in equivalents) due to the polymeric counterion present per 100 grams of the formulation and can be calculated as follows: P = (Polymeric C polymeric x F polymeric x Z) / Polymeric M, where polymer C is the concentration of the polymer in the formulation in grams / 100 grams of formulation, polymeric F is the weight fraction of the monomeric unit carrying or it is capable of carrying a load with respect to the total polymer weight and, therefore, will be comprised between 0 and 1, polymeric Q is the number of charges that the monomeric unit capable of carrying a load is capable of developing and can be consider that it has the units of equivalents per mole, Z is an integer that indicates the type of load developed by the monomer unit and is equal to +1 when the monomer unit can develop a cationic charge or is equal to -1 when the unit monomeric can develop an anionic charge and polymeric M is the molecular weight of the monomeric unit capable of developing a charge, in grams / mol.

For example, consider a formulation comprising a homopolymer of polyacrylic acid (PAA) as a water-soluble polymeric counterion. PAA is capable of developing 1 anionic charge per monomeric unit of acrylic acid (which has a molecular weight of 72 grams / mol) and, therefore, polymeric Q = 1 and Z = -1. In addition, the polymer is a homopolymer, so that polymeric F = 1. If the PAA is present in the formulation with a concentration of 0.1 grams / 100 grams of the formulation, the value of P could be calculated as follows: P = (0.1 x 1 x 1 x -l) / 72 = -0.00139.

Using the net D-value of -0.00967 calculated in the example described above for a mixture of an anionic, cationic and non-ionic surfactant, the P / Dneta ratio would be calculated as: P / Dneta = (-0.00139) / (- 0.00967) = +0.144 This positive value of P / Dneta not only indicates the charge ratio due to the polymeric counterion and the load net of the mixed micelles, but also indicates, since it is a positive number, that the charge of the polymeric counterion and the net charge of the mixed micelles are identical, and that they are both anionic. In this case, there would not be the expected net electrostatic interaction between the polymeric counter ion and the mixed micelles and, therefore, the example would not be within the scope of the present invention, which requires that the polymeric counterion must have a charge opposite to that of the heads of the surfactant or mixture of surfactants comprising the micelle.

By way of another example, consider a formulation comprising a homopolymer of polydiallyldimethylammonium chloride (PDADMAC) or poly (DADMAC) as a water-soluble counterion. PDADMAC carries 1 cationic charge per monomeric unit of DADMAC (which has a molecular weight of 162 grams / mol) and, therefore, polymeric Q = 1 and Z = +1. In addition, the polymer is a homopolymer, so that polymeric F = 1. If the PDADMAC is present in the formulation with a concentration of 0.1 grams / 100 grams of the formulation, the value of P could be calculated as follows: P = (0.1 x 1 x 1 x 1) / 162 = +0.0006173 Using the Dneta value of -0.00967 calculated in the example described above for a mixture of one Anionic, cationic and non-ionic surfactant, the P / Dneta ratio would be calculated as: P / Dneta = (+0.0006173) / (- 0.00967) = - 0.06384.

This negative value of P / Dneta not only indicates the charge ratio due to the polymeric counterion and the net charge of the mixed micelles, but also indicates, since it is a negative number, that the charge of the polymeric counterion and the net charge of Mixed micelles are opposite. In this case, there may be an electrostatic interaction between the polymeric counter ion and the mixed micelles and, therefore, the formulation may be within the scope of the present invention.

Alternatively, if the manufacturer can provide the number of equivalents of the charged groups present per gram of polymer, or if it can be obtained from the synthetic route used to create the polymer, or if it can be obtained from the polymer analysis, then P also it can be calculated based on that information.

For example, P = (polymeric C x polymeric Eq x Z), where the polymer C and Z are as defined above, and polymer Eq is the number of equivalents of groups per gram of polymer with a charge consistent with the value of Z used.

For example, if a water-soluble copolymer is described as having 0.006173 equivalents per gram of polymer (active) of a cationically charged monomer, and it is used This polymer in a formulation with a concentration of 0.1 grams / 100 grams of the formulation, P is calculated as follows: P = (0.1 x 0.006173 x 1) = +0.0006173.

This value of P, with the same Dneta value used in the previous example, can then be used to calculate the P / Dneta relation.

P / Dneta = (+0.0006173) / (- 0.00967) = - 0.06384, which gives rise to the same result as described above.

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

Finally, in practical work, the absolute value of P / Dneta is an indicator of what loads are in excess and which are in deficit in the formulations of the present invention. When the absolute value of P / Dneta is greater than 0 but less than 1, the number of charges due to groups in the polymeric counterion is less than the net number of charges due to the heads of the surfactant or ionic surfactants comprising the micelles. say, the polymeric counterion is in deficit. When the absolute value of P / Dneta is greater than 1, the polymeric counterion is in excess and, obviously, when the absolute value of P / Dneta = 1, the number of charges due to the heads of the polymeric counterion is equal to the net number of charges of the surfactant or ionic surfactants comprising the micelles.

IV. Suitable polymers Many polymers are suitable for use as polymeric counterions in the present invention. In one embodiment, the polymers are water soluble, as defined herein. The polymers may be homopolymers or copolymers and may be linear or branched. Linear polymers may be preferred in at least some embodiments. The copolymers can be synthesized by processes that are supposed to give rise to copolymers of a statistically ra or so-called gradient type. In contrast, water-soluble block copolymers are not suitable since these types of polymers may form aggregates or micelles, in which the most hydrophobic block or blocks comprise the core of aggregates or micelles and the most hydrophilic block comprises a region of "crown" in contact with water. It is believed that these self-assembly processes compete with the electrostatic interactions required for a water-soluble polymer to act as a polymeric counter-ion with micelles of ordinary surfactants. Although mixtures of water-soluble polymers are suitable in at least some embodiments of the present invention, the mixtures selected should not comprise copolymers of block capable of forming the so-called "complex coacervate" micelles by self-assembly, since this micelle-forming process also competes with the interaction of the water-soluble polymer as a polymeric counter-ion of the micelles of ordinary surfactants. When the polymers are copolymers, the ratio of the two or more monomers may vary over a wide range, as long as the water-solubility of the polymer is maintained.

In one embodiment, the polymers should be water-soluble, as defined herein, and therefore should not be latex particles or microgels of any kind. In this type of embodiments, the polymers should not be crosslinked by the use of monomers capable of forming covalent bonds between independent polymer chains and the compositions and formulations should be free of crosslinking agents expressly added to this effect. It is believed that the polymeric aggregates that water can "swell" in the form of microgels or polymers that form crosslinked meshes will not have the proper full mobility of the polymer chains necessary to act as polymeric counterions with respect to the micelles of ordinary surfactants. Polymeric particles that can act as structurants for an aqueous composition by the formation of fibers or yarns are not suitable as water-soluble polymers for similar reasons. Similarly, it is believed that the latex particles are not suitable because many of the individual polymer chains in such particles are, in fact, confined to the interior of the particle and are not readily available for interaction with the aqueous phase. The latex particles may also lack the mobility of the chain necessary to act as counterions of micelles of ordinary surfactants.

The ra copolymers may comprise one or more monomers which carry the same charge or which are capable of developing the same charge and one or more monomers which are non-ionic, ie, are not capable of carrying a charge. The copolymers can be synthesized by grafting processes, which results in "comb-like" structures.

Water-soluble copolymers derived from a synthetic monomer or monomer which have undergone chain termination with a natural hydroxyl-containing material, such as a polysaccharide, which can be synthesized with ordinary radical initiators, are preferred. At least one of the synthetic monomers may carry or be capable of carrying a cationic charge. Methods for producing this type of copolymers are described in US Pat. UU No. 8,058,374, which is incorporated herein by reference in its entirety.

In one embodiment, the compositions are free of copolymers comprising at least one monomer that carries or is capable of developing an anionic charge and at least one monomer that carries or is capable of developing a cationic charge. It is believed that this type of copolymers, sometimes referred to as "amphoteric" copolymers, do not act as well or do not act at all as polymeric counterions of micelles carrying a net electrostatic charge for at least two reasons. The first, the proximity of both types (anionic and cationic) of charges along the polymer chains, if distributed randomly, interferes with the efficient pairing of a particular type of charge in the polymer chain with the head of a surfactant of opposite charge in a micelle. The second, this type of copolymers has the potential to establish electrostatic interactions between the anionic charges in a given polymer chain and the cationic charges of another polymer chain. This type of interaction could lead to the formation of complexes or polymeric aggregates in a process that is undesirably competitive with the interaction of the polymer with the micellar aggregates.

Suitable water-soluble polymers may include natural or sustainable materials that carry or are capable of developing cationic charges, such as chitosan and its derivatives. Chitosan is conveniently a natural or sustainable material. Water-soluble polymers may also include derivatives of natural polymers such as guar gum carrying added cationic groups, e.g. g. guar gums quaternized, such as Aquacat, marketed by Hereules / Aqualon.

Water-soluble polymers that carry or are capable of carrying a cationic charge can be obtained from synthetic monomers. Non-limiting examples of monomers bearing or capable of carrying a cationic charge include diallyldimethylammonium chloride, quaternary ammonium salts of substituted acrylamide, methylacrylamide, acrylate and methacrylate, acrylate esters and amides with quaternized alkylamino, MAPTAC (methacrylamidopropyltrimethylammonium chlorides) , trimethylammoniomethyl methacrylate, trimethylammoniopropyl methacrylamide, salts of 2-vinyl W-alkyl pyridinium quaternary, salts of 4-vinyl N-alkyl pyridinium quaternary, salts of 4-vinylbenzyltrialkylammonium, salts of 2-vinyl piperidinium, salts of 4-vinyl piperidinium , salts of 3-alkyl-1-vinyl imidazolium and mixtures of these. Ethyleneimine is an example of a monomer capable of developing a charge when the pH is conveniently reduced. Other suitable cationic monomers include the yonene class of cationic monomers.

Some non-limiting examples of monomers that are non-ionic, that do not carry or that are not capable of carrying an electrostatic charge include the alkyl esters of acrylic acid, methacrylic acid, vinyl alcohol, methyl vinyl ether, ethyl vinyl ether, ethylene oxide, oxide of propylene and mixtures of these. Other examples include acrylamide, dimethylacrylamide and other alkyl acrylamide derivatives and mixtures thereof. Other suitable monomers may include ethoxylated esters of acrylic acid or methacrylic acid, the related ethoxylated esters of tristyrylphenol of acrylic acid or methacrylic acid and mixtures of these. Other examples of nonionic monomers include saccharides such as hexoses and pentoses, ethylene glycol, alkylene glycols, branched polyols and mixtures thereof.

In some embodiments, water-soluble polymers comprising monomers carrying W-halo groups, eg, N-Cl groups, are not present. It is believed that interactions between polymers comprising groups of this type as polymeric counterions for micelles result in the degradation of the surfactants themselves and / or the degradation of the polymers by increased local concentration of the polymers on the surfaces of the micelles.

When the compositions comprise micelles of surfactants with, for example, a net anionic charge and a polymer or mixture of water-soluble polymers that carry or are capable of carrying cationic charges, then the compositions may be free of any additional polymers carrying an anionic charge , that is, a load opposite to that of the first water-soluble polymer that carries or is capable of carrying cationic charges. It is believed that the presence of a first water-soluble polymer carrying a cationic charge and a second water-soluble polymer carrying an anionic charge in the same formulation promotes the formation of complexes between the two polymers, ie the so-called polyelectrolyte complexes, which could compete undesirably with the formation of complexes between the micelles that carry the anionic charge and the polymer that carries the cationic charge.

However, compositions comprising micelles of surfactants carrying a net electrostatic charge and a water-soluble polymer that carries or is capable of carrying an electrostatic charge opposite to that of the micelles of surfactants may comprise additional polymers that do not carry charges, i.e. nonionic polymers. Such nonionic polymers may be useful as adjuvants for thickening, gelling or adjusting the rheological properties of the compositions or for adjusting the aesthetic appearance of the formulations by the addition of pigments or other suspended particulates. However, it should be noted that in many cases, the polymer-micelle complexes of the present invention, when adjusted to certain concentrations of total active compounds, may exhibit "self-thickened" properties and do not explicitly require an additional polymeric thickener, which is desirable. from the point of view of cost.

V. Suitable surfactants In one embodiment, the compositions are free of nonionic surfactants comprising blocks of hydrophobic and hydrophilic groups, such as Pluronic®. It is believed that micellar structures formed with large surfactants of this type, in which the hydrophobic blocks are assembled in the nuclear regions of the micelles and the hydrophilic blocks are present on the micellar surface would interfere with the interactions of the polymeric counterion with a charged surfactant. Additional incorporated into a mixed micelle, and / or also represent a competitive micelle assembly mechanism, similar to the use of block copolymers used as polymeric counterions, which are also preferably not present.

A wide range of surfactants and mixtures of surfactants, including anionic, nonionic and cationic surfactants and mixtures thereof, may be used. As mentioned previously in the description of Dneta and P / Dneta, it will be evident that mixtures of surfactants charged differently may be employed. For example, mixtures of cationic and anionic surfactants, cationic and nonionic mixtures, anionic and nonionic mixtures, and cationic, nonionic and anionic mixtures may be suitable for use.

Examples of cationic surfactants include, but are not limited to, quaternary ammonium compounds monomeric, monomeric biguanide compounds and combinations thereof. Illustrative quaternary ammonium compounds are available from Stepan Co under the tradename BTC® (eg, BTC® 1010, BTC® 1210, BTC® 818, BTC® 8358). Any other suitable monomeric quaternary ammonium compound may also be used. BTC® 1010 and BTC® 1210 are described as didecyldimethylammonium chloride and a mixture of didecyldimethylammonium chloride and n-alkyldimethylbenzylammonium chloride, respectively. Examples of monomeric biguanide compounds include, without limitation, chlorhexidine, alexidine and salts thereof.

Examples of anionic surfactants include, but are not limited to, alkyl sulphates, alkyl sulfonates, alkyl ethoxy sulfates, fatty acids and salts of fatty acids, linear alkyl benzene sulphonates (LAS and HLAS), secondary alkane sulphonates (for example, Hostapur® SAS-30), sulfonates of a methyl ester (such as Stepan® Mild PCL from Stepan Corp), alkylsulfosuccinates and alkylamino acid derivatives. Rhamnolipids bearing anionic charges may also be used, for example, in formulations that emphasize greater sustainability, because they are not obtained from petroleum-based materials. An example of a rhamnolipid of this type is JBR 425, which is supplied as an aqueous solution with 25% of active compounds, from Jenil Biosurfactant Co., LLC (Saukville, WI, USA).

In some formulations so-called "extended chain surfactants" are preferred. Some examples of these anionic surfactants are described in US Pat. Uü with No. of pub.2006 / 0211593. Non-limiting examples of nonionic surfactants include alkylamine oxides (eg, Ammonyx® LO from Stepan Corp.), alkylamidoamine oxides (eg, Ammonyx L DO from Stepan Corp.), alkylphosphine oxides, alkyl polyglycosides and alkylpolypeptides, alkyl poly (glycerol esters) and alkyl poly (glycerol ethers) and alkyl ethoxylates and alkylphenol of all types. Sorbitan esters and ethoxylated sorbitan esters are also useful as non-ionic surfactants. Other useful nonionic surfactants include fatty acid amides, fatty acid monoethanolamides, fatty acid diethanolamides and fatty acid isopropanolamides.

In one embodiment, a surfactant with phospholipids may be included. Lecithin is an example of a phospholipid.

In one embodiment, zwitterionic surfactants may be present. Non-limiting examples include N-alkylbetaines (for example, Amphosol® LB from Stepan Corp.), alkylsulfobetaines and mixtures thereof.

In one embodiment, at least some of the surfactants may be edible, as long as they exhibit water solubility or can form mixed micelles with edible nonionic surfactants. Examples of such edible surfactants include casein and lecithin.

In one embodiment, the surfactants may be selected according to a natural or ecological criterion. For example, there is a growing desire to use components that are not simply considered safe but are obtained naturally, processed naturally and are biodegradable. For example, processes such as ethoxylation can be undesirable when what is desired is to provide an ecological or natural product, since this type of processes can leave impurities or residual compounds. The "natural surfactants" of this type may be produced using processes that are perceived as more natural or ecological such as distillation, condensation, extraction, steam distillation, pressure cooking and hydrolysis to maximize the purity of the natural ingredients. Some examples of "natural surfactants" of this type that may be suitable for use are described in US Pat. UU Nos. 7608573, 7 618 931, 7629 305, 7939 486, 7939 488, all of which are hereby incorporated by reference.

SAW. Suitable adjuvants A wide range of optional adjuvants or mixtures of optional adjuvants may be present. For example, additives and chelating agents may be included, including, but not limited to, salts of EDTA, GLDA, MSG, gluconates, 2-hydroxy acids and derivatives, glutamic acid and derivatives, trimethylglycine, etc.

Amino acids and mixtures of amino acids may be present, either as racemic mixtures or as individual components of a single chirality.

Vitamins or vitamin precursors, for example, retinal may be present.

Sources of soluble zinc, copper or silver ions, such as simple inorganic salts or salts of chelating agents including, but not limited to, EDTA, GLDA, MGDA, citric acid, etc., may be present.

Dyes and colorants may be present. Polymeric thickeners may be present when used as set forth above.

Buffers may be present including, without limitation, carbonate, phosphate, silicates, borates, and combinations thereof. Electrolytes such as alkali metal salts including, for example, without limitation, chloride salts (e.g. sodium chloride, potassium chloride), bromide salts, iodide salts or combinations of these.

In some embodiments solvents miscible with water may be present. In some embodiments lower alcohols (eg, ethanol), ethylene glycol, propylene glycol, glycol ethers and mixtures of these miscible with water at 25 ° C may be present. Other embodiments will not include solvents of the glycol ether or lower alcohol type. When such solvents are present, some embodiments may include them only in small amounts, for example, of not more than 5% by weight, not more than 3% by weight or not more than 2% by weight.

Immiscible oils with water, which solubilize in micelles, may be present. Among these oils are those added as fragrances. Preferred oils are those that come from naturally occurring sources that include the wide variety of so-called essential oils that are obtained from various botanical sources. Formulations which are intended to provide antimicrobial benefits, together with improved overall sustainability, may conveniently comprise quaternary ammonium compounds and / or monomeric biguanides such as water-soluble salts of chlorhexidine or alexidine combined with essential oils. such as thymol and the like, preferably in the absence of alcohols miscible with water.

In one embodiment, the composition may further include one or more oxidants. Examples of oxidants include, but are not limited to, hypohalous acid, hypohalite, and sources thereof (eg, alkali metal salts and / or alkaline earth metal salts of hypochlorous or hypobromous acid), hydrogen peroxide, and sources thereof. eg, aqueous hydrogen peroxide, perborate and its salts, percarbonate and its salts, carbamide peroxide, metal peroxides or combinations thereof), peracids, peroxyacids, peroxoacids (eg, peracetic acid, percyclic acid, acid) diperoxydodecanoic, peroxyamidophthalimide, peroxomonosulfonic acid or peroxodisulfamic acid) and sources thereof (eg, salts (eg, alkali metal salts) of peracids or salts of peroxyacids such as peracetic acid, percitric acid, diperoxydodecanoic acid, peroxysulfate sodium and potassium or combinations thereof), organic peroxides and hydroxyperoxides (eg, benzoyl peroxide), inorganic peroxygen compounds (eg, perclo) and its salts, permanganate and its salts and periodic acid and its salts), solubilized chlorine, solubilized chlorine dioxide, a source of free chlorine, acid sodium chlorite, a compound that generates active chlorine or a compound that generates chlorine dioxide , a compound that generates active oxygen, solubilized ozone, halo-type compounds or combinations of any oxidants of this type. Additional examples of this type of oxidants are disclosed in U.S. Pat. UU No. 7517 568 and in the US publication. UU No. 2011/0236582, each of which is incorporated herein by reference in its entirety.

Hydrosoluble hydrotropes, sometimes called monomeric organic electrolytes, may also be present. Examples include xylene sulfonate salts, naphthalenesulfonate salts and cumene sulphonate salts.

Enzymes may be present, particularly when the formulations are adapted for use as laundry detergents or as cleaners for the kitchen and restaurant surfaces or as drain drainage or drainage maintenance products.

Applicants have observed that a wide range of surfactant mixtures can be used which result in a wide range of Dneta values. In many cases, the selected surfactants may be optimized to solubilize various immiscible materials with water, such as oils that are fragrances, solvents or even oily dirt to be removed from a surface in a cleaning operation. In cases of designing products that provide an antimicrobial benefit in the absence of a strong oxidant such as hypochlorite, a compound of quaternary ammonium or a salt of a monomeric biguanide such as germicidal chlorhexidine or alexidine and may be incorporated into micelles with polymeric counterions. Fine control over the spacing between the cationic heads of the quaternary ammonium compound or the germicidal biguanide that is achieved by the incorporation of a polymeric counter ion can result in a significant reduction in the amount of surfactant that is needed to solubilize an oil. which results in cost reductions and an improvement in the overall sustainability of the formulations.

In contrast to what has been described in the art, applicants have also observed that the precise magnitude and value of P / Dneta necessary to ensure the absence of coacervate and / or precipitate phases can vary widely, depending on the nature of the counter ion. polymer and the selected surfactants to form the mixed micelles. Therefore, since there is great flexibility in the selection of the polymeric counterion for a particular surfactant mixture to achieve a particular objective, applicants have adopted a systematic but simple strategy to quickly "scan" P / D intervals, with the To identify and compare formulations comprising polymeric counterions.

Formulations comprising mixed micelles with a net charge and a water-soluble polymer that carries charges opposite those of the micelles are useful as surface cleaners for immediate use which are supplied by prewetted nonwoven substrates (eg, cleaning cloths). ) or as powdered in various containers familiar to consumers.

Concentrated forms of the formulations can also be developed, which can be diluted by the consumer to provide solutions that will be used next. Concentrated forms suitable for dilution by automatic systems are also possible, in which the concentrate is diluted with water, or in which two solutions are combined in a particular proportion to provide the formulation for final use.

When the compositions comprise salts of chlorhexidine or alexidine as a cationically charged surfactant, the compositions may be free of iodine or iodo-polymer complexes, silver, copper or zinc nanoparticles, triclosan, p-chloromethylxyleneol, monomeric pentose alcohols, D-xylitol and its isomers, D-arabitol and its isomers, aryl alcohols, benzyl alcohol and phenoxyethanol.

SAW. Suitable non-woven substrates Many of the compositions are useful as liquids or lotions that may be used in combination with nonwoven substrates to produce pre-moistened cleaning cloths. Such cleaning cloths may be used as disinfectant cleaning cloths or for cleaning floors combined with various tools configured to incorporate the cleaning cloth.

In one embodiment, the cleaning pad of the present invention comprises a network or non-woven substrate. The substrate may be composed of non-woven fibers or paper.

VII. Examples How Zeta potentials and particle size were measured The diameters of the aggregates with the polymeric counterions (in nanometers) and their zeta potentials were measured with a Zetasizer ZS (Malvern Instruments). This instrument uses dynamic light scattering (DLS), also known as correlation spectroscopy. photons) to determine the diameters of the colloidal particles in the range of 0.1 to 10000 nm.

The Zetasizer ZS instrument offers a range of predetermined parameters that can be used in the calculation of the diameters of the particles from the untreated data (known as the correlation function or autocorrelation function). The diameters of the aggregates published herein used a simple calculation model, in which it was assumed that the optical properties of the aggregates were similar to the spherical particles of polystyrene latex particles, a standard calibration standard used for experiments of More complex DLS. In addition, the software package supplied with the Zetasizer provider provides an automatic analysis of the quality of the measurements taken, in the form of "Expert Advice". The diameters described here (specifically what is known as the average particle diameter "Z") were calculated from the untreated data that met the standards required by the "Expert Councils" consistent with acceptable results, to unless otherwise indicated. In other words, the simplest set of measurement conditions and predetermined calculation parameters were used to calculate the diameters of all the aggregates described herein, in order to facilitate direct comparison of aggregates with various polymeric and surfactant counterions, and avoiding the use of complex dispersion models that could complicate or avoid comparisons of the diameters of the particles of different chemical composition. Those skilled in the art will appreciate the particularly simple strategy adopted herein and will realize that it is useful for comparing and characterizing complexes of micelles and water-soluble polymers, regardless of the details of the types of polymers and surfactants used to form the complexes.

The instrument calculates the zeta potential of the colloidal particles from electrophoretic mobility measurements, determined by means of a Doppler laser velocity measurement. There is a relationship between electrophoretic mobility (a measurement of the velocity of a charged colloidal particle that moves in an electric field) and the zeta potential (electric charge, expressed in units of millivolts). As in particle size measurements, to facilitate the direct comparison of the aggregates with various polymeric counterions and surfactants, the simplest set of predetermined measurement conditions was used, that is, it was assumed that the aggregates behaved as particles of polystyrene latex, and the Smoluchowski model that refers to electrophoretic mobility and zeta potential was used in all calculations. Unless indicated otherwise, the average zeta potentials described herein were calculated from the data without treating that they fulfilled the norms demanded by the "Councils of the Expert" coherent with acceptable results. Aggregates carrying a net cationic (positive) charge will exhibit positive values of the zeta potential (in mV), while those carrying a net anionic (negative) charge will exhibit negative values of the zeta potential (in mV).

Example 1 Cleaner for immediate use with sodium hypochlorite A series of formulations with various P / Dneta values were prepared for the visual evaluation of the stability of the phase, followed by the measurement of the average Z diameters of the aggregates formed by dynamic light scattering. . The formulations are useful as hard surface cleaners, for example, for bathroom surfaces or kitchen counters, which are stained by fungi or mold or with very adherent food residues which require the action of cleaning the surfactants combined with the Stain removal benefits provided by bleaching sodium hypochlorite. A control formulation comprising mixed micelles of net anionic charge without the presence of poly (DADMAC) as the polymeric counter ion was also produced. The formulations were produced by simple mixing of the appropriate volumes of aqueous stock solutions of the surfactants, polymer, sodium carbonate (which provides significant buffering capacity). and which maintains the pH of the final formulations within a desired range) and a source of an aqueous solution of sodium hypochlorite. The compositions are summarized in the Table 1. 1.

Table 1.1 Ammonyx® LO (amine oxide, Stepan Co.) supplied as an active solution in water.

Dowfax ™ 2A1 (Dow Corp), supplied as a 45% active solution in water, with an average of 2 sulfonate groups per molecule (Q anionic = 2).

PDADMAC = poly (diallyldimethylammonium chloride), Floquat FL4245 (SNF Corp.), supplied as a 40% active solution in water, polymeric Z = 1, polymeric Q = 1, polymeric M = 162, polymeric F = 1 (homopolymer) .

Source of NaOCl = Clorox germicidal bleach, titrated immediately before use to determine the activity of sodium hypochlorite.

Table 1.2 Average Z diameters of micelles with polymeric counterions (polymer-micelle complexes) and control micelles determined by dynamic light scattering at 25 ° C The results of Table 1.2 indicate that the addition of poly (DADMAC) as polymeric counter ion for the mixed micelles comprising the amine oxide and the sulfonate results in the formation of complexes (formulations from Al to A4) having average Z diameters. larger than the mixed micelles themselves (formulation A5). The results also indicate that the predetermined parameters selected for the calculation of the diameters from the DLS measurements, as described above, provide highly reproducible results. For the triplicate analyzes of the formulations, the variation between the individual Z-average diameters was usually less than a relative 2%. Therefore, the calculated diameters for the formulations from Al to A4 can be considered different from each other and different from that of the control formulation A5. In another experiment demonstrating the reproducibility of the average Z diameters calculated from the dynamic light scattering data, a sample of the A5 formulation was placed in a sealed disposable cuvette and analyzed every 30 minutes after storage in the instrument (with temperature controlled at 25 ° C) throughout the night. The average Z diameter of 27 independent analyzes was 35.96 nm, with a standard deviation of 0.1907, or a percentage of relative standard deviation of 0.53%. Hereinafter, the Z-average diameters mentioned will be the result of at least 3 analysis of a sample. The relative differences of at least 2% relative in the average Z diameters measured for different formulations will be considered significant, unless the conditions of the measurement dictate otherwise.

It is believed, without wishing to be bound by any theory, that the average diameter Z of the mixed micelles in formulation A5 is at least 35.8 nm, which indicates the formation of rod-type micelles, due to the relatively high concentration of electrolyte ( carbonate buffer, sodium hypochlorite and sodium chlorite present in the sodium hypochlorite stock solution).

In some embodiments, the formulations of the present invention are free of coacervate and precipitated phases. As shown above, the adjustment of the P / Dneta parameter can be made by changing the concentration of the polymeric counter ion or changing the composition of the mixed micelles by changing the relative amounts of the anionically charged surfactant and any uncharged surfactant present or even changing the amounts relative to an anionically charged surfactant and a cationically charged surfactant present in the formulation. The visual examination of the formulations to determine their transparency is generally sufficient to identify samples that are transparent and free of coacervates and precipitates. However, the analysis of samples by dispersion of Dynamic light can also be very useful to confirm the thermodynamic stability of the soluble polymer-micelle complexes formed by the interaction of micelles carrying an electrostatic charge and a water-soluble polymer that carries an electrostatic charge opposite to that of micelles. In one embodiment, the polymer-micelle complexes should exhibit average Z diameters of less than about 500 nm, to exhibit colloidal stability.

Example 2 Formulations with sodium hypochlorite Adjustment of compositions of mixed micelles In this example, formulations comprising mixed micelles of a non-ionic amine oxide surfactant and an anionically charged surfactant and poly (DADMAC) such as cationic polymeric counter ion are provided, combined with the sodium hypochlorite oxidant which exhibits an elimination behavior of excellent stains and moisturizer.

The formulations in this example have a polymer concentration + total surfactant, carbonate buffer and a fixed bleach concentration and span a wide range of the absolute value of P / Dneta. As described above, the formulations of the present invention are free of coacervates and precipitates. That said, you may prefer formulations that are relatively closer to the boundary of the coacervate phase because of their speeds of extension on relatively faster polar and non-polar surfaces, which also results in faster stain removal by the oxidant.

Aqueous formulations were prepared by mixing appropriate amounts of stock solutions prepared with the individual ingredients, surfactant with sulfonate Dowfax ™ 2A1 (supplied as an aqueous solution, Dow Chemical), ammonium oxide Ammonyx® LO, sodium carbonate (supplied by Fluka), hypochlorite bleach, Floquat LF 4245 (cationic polymer, a homopolymer of diallyldimethylammonium chloride or poly (DADMAC) supplied as an aqueous solution, SNF International) and water to form the final formulations. The compositions were systematically varied by increasing the values of the load dilution parameter (CD) of the global surfactant with certain fixed polymer concentrations until solutions were obtained that were transparent and free of coacervates.

The load dilution parameter of the global surfactant, CD, is defined as: CD = Cno loaded / (Cno loaded + Ccargada) where the loaded Cno is the molar concentration of the non-charged surfactant and the charged C is the molar concentration of the charged surfactant.

Sample B1 represents the optimized formulation with 0.01% polymer and 1% polymer + total surfactant. Sample B2 represents another optimized formulation again to be free of coacervates while maintaining polymer + total surfactant again by 1%. Sample B3 represents an alternative formulation that is also transparent and free of coacervates.

Sample B4 represents a formulation that was found to be cloudy at about 25 ° C, but which was transparent at lower temperatures and, therefore, may not be sufficiently robust. However, an alternative formulation (sample B5) with better stability can be easily provided by a slight change in the CD parameter. Note also that the parameters of P / Dneta for all formulations are negative, which indicates that the polymeric counterion and the mixed micelles have an opposite charge and, therefore, fall within the scope of the present invention.

After mixing the stock solutions, the solutions were stirred for a few hours and visually inspected for the presence or absence of coacervate phases. With values of the load dilution parameter (CD) of the global surfactant, the interaction between the positively charged polymer and the anionic surfactant is strong, which leads to coacervation. With CD values higher, interactions weaken enough to avoid coacervation and precipitation. Optimized examples are selected so that they are transparent and do not have coacervates or precipitates.

Table 2.1 describes the visibly transparent optimized formulations compositions. Figure 1 also describes part of the formulations optimized in a phase map showing the limit of coacervation.

Table 2.1 Example 3 Concentrates suitable for dilution The present invention can also provide products that are prepared as concentrates that are diluted when they are to be used. Since the formation of a coacervate phase is not desired for the reasons mentioned above, the optimization of the formulations so that the coacervates are neither present in the concentrate nor at the desired dilution level may be an important feature to be provided. The optimization is achieved by creating a series of samples, varying the absolute value of P / Dneta by varying the concentration of the polymeric counter ion with a fixed mixed micelle composition, carbonate buffer and a bleach concentration until a formulation that is free of coacervates with the desired dilution. As will be readily apparent, the absolute value of parameter P / Dneta does not directly indicate which compositions are exempt from coacervates. This parameter may be modulated as described herein and although a specific threshold value may not correspond to a division of compositions that are free of coacervates and those that are not, this parameter still represents a useful tool.

Formulations of C1 to C4, although transparent and free of coacervates when concentrated, will have a cloudy appearance when diluted by a factor of 5 with deionized water and, therefore, are not suitable for this particular dilution. The absolute value of P / Dneta for these formulations is between 0.0077 and 0.0308. In formulations from C5 to C8, the absolute value of the P / Dneta parameter is reduced slightly, from a higher value of 0.0058 to a lower value of 0.0012, to generate concentrates that can be diluted by a factor of 5 without forming coacervates. C9 represents the control, without any Floquat 4540, the poly cationic polymer (DADMAC).

Table 3.1 Example 4 Compositions of two parts Polymer-micelle complexes, which exhibit superior spread and wetness on a wide variety of surfaces, may be prepared from precursor solutions that are mixed just before use. This type of two-part formulations may be desirable to enhance the stability of an oxidant such as sodium hypochlorite over long term storage, or may be desirable for use with automatic dilution systems for commercial or industrial use in restaurants, hospitals, etc.

The DI formulation is an example in which the mixed micelles comprising the amine oxide and the anionic surfactant and the optional buffer comprise the first part of the two-part system, while the water-soluble polymer (here poly (DADMAC), the Floquat 4540) and sodium hypochlorite comprise the second part of the two-part system. Both part A and part B are transparent solutions, free of coacervates and precipitates. When mixed in the volumes indicated in Table 4.1, the polymer-micelle complexes are formed without the appearance of coacervates or precipitates.

Formulation D2 is an alternative two-part system. Part A comprises micelles of the anionic surfactant in a solution with sodium carbonate buffer and sodium hypochlorite. Part B comprises micelles of the non-ionic amine oxide and the water-soluble polymer. Both part A and part B are transparent solutions. When they are mixed in the volumes indicated in Table 4.1, the surfactants are rebalanced to form micelles in the diluted solution. These mixed micelles, of course, will have a net negative charge due to the presence of the anionic surfactant (which is in excess of any cationic surfactant such as a quaternary ammonium compound) and, therefore, will interact with the water-soluble cationic polymer for produce the desired polymer-micelle complexes. Note that the P / Dneta parameter of the final solutions produced from the formulations DI and D2 are identical and are within the scope of the present invention (ie both are negative). The appearance of the diluted solutions produced from both formulations was checked immediately after the preparation and after 8 hours. There were no variations in the appearance immediately after the preparation or after 8 hours, as expected, since it is believed that the polymer-micelle complexes are thermodynamically favored structures and, therefore, stable.

Table 4.1 Example 5 Mixed masses comprising anionic, cationic and nonionic surfactant with a polymeric counterion The mixed macels of the present invention may comprise mixtures of anionic, cationic and nonionic surfactants. As discussed herein, the net charge of the mixed micelles should be anionic, in order to guarantee electrostatic interactions with a water-soluble polymer carrying cationic charges. The formulation El is an example in which the mixed micelles comprise a cationic surfactant which is a germicidal quaternary ammonium compound (Sanisol 08), an anionic surfactant (sodium octanoate, a soap) and a non-ionic amine oxide surfactant ( Ammonyx® MO). The formulation El is also an example of a formulation containing optional adjuvants including a buffer (sodium carbonate) and a hydrotrope, sodium xylenesulfonate, in an immediate use formulation that is transparent and free of coacervates and precipitates.

Sanisol has a molecular weight of 284 g / mol. Sodium octanoate has a molecular weight of 166.2 g / mol. poly (DADMAC) = poly (diallyldimethylammonium) chloride, Floquat FL4245 (SNF Corp.), supplied as a solution active at 40% in water, polymeric Z = 1, polymeric Q = 1, polymeric M = 162, polymeric F = 1 (homopolymer).

Source of sodium hypochlorite = Clorox germicidal bleach, titrated immediately before use to determine the activity of sodium hypochlorite.

The calculation of Dneta was made in the following way: Cationic Eq = 0.1x1 / 284 = 0.00035 equivalents / 100 g of formulation.

And cationic D = (+1) x (0.00035) = +0.00035.

Eq antionics = 0.08 x 1 / 166.2 = 4.813 x 10 ~ 4 equivalents / 100 g of formulation.

And anionic D = (-1) x 4.813 x 10-4 = -4.813 x 10-4.

Therefore, Dneta = +0.00035 + (-4.813 x 104) = - 1.3134 x 10-4 The negative value of Dneta indicates that the mixed micelles will carry a net anionic charge suitable for interaction with a water-soluble polymer carrying a cationic charge as polymeric counterion to form the polymer-micelle complexes of the present invention.

Poly (DADMAC) is a homopolymer with a molecular weight of 161.7 grams / mol in the repeating unit, which has a unique cationic charge. The polymer is present with a concentration of 0.05% in the El formulation. Therefore, P can be calculated as follows: P = 0.05 xlxlx (+1) /161.7 = +0.0003092 And P / Dneta, therefore, is calculated as: P / Dneta = + 0.0003092 / -0.00013134 = - 2.354.

The negative value of P / Dneta indicates that the mixed micelles and the water-soluble polymer carry opposite charges and, therefore, will have electrostatic interactions that will entail the assembly of the polymer-micelle complexes of the present invention. Since the absolute value of the P / Dneta parameter is greater than 1, the number of cationic charges due to the water-soluble polymer exceeds the number of anionic charges of the mixed micelles.

Table 5.1 Without departing from the nature and scope of this invention, the person skilled in the art can make various changes and modifications to the invention to adapt it to various uses and conditions. As such, these changes and modifications are adequately and equitably understood, and are intended to be understood, within the full set of equivalences of the following claims.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims

1. A composition comprising: an oxidant; Y a polymer-micelle complex, wherein the complex comprises: a negatively charged micelle, wherein said negatively charged micelle is electrostatically bound to a water-soluble polymer carrying a positive charge; wherein said water-soluble polymer carrying a positive charge does not comprise a block copolymer, latex particles, polymeric nanoparticles, cross-linked polymers, silicone copolymer, fluorosurfactant or an amphoteric copolymer; where said composition does not form a coacervate.

2. The composition of claim 1, wherein the oxidant is selected from the group consisting of: a. hypohalose acid, hypohalite or sources of these; b. hydrogen peroxide or sources of this; c. peracids, peroxyacids peroxoacids or sources thereof; d. organic peroxides or hydroperoxides; and. inorganic peroxygen compounds; F. solubilized chlorine, solubilized chlorine dioxide, a source of free chlorine, sodium chlorite acid, a compound that generates active chlorine or a compound that generates chlorine dioxide; g. a compound that generates active oxygen; h. solubilized ozone; i. compounds -halo; Y j. combinations of these.

3. The composition of claim 1, wherein the negatively charged micelle comprises an anionic surfactant selected from the group consisting of alkyl sulfates, alkyl sulfonates, alkyl ethoxy sulfates, fatty acids, fatty acid salts, alkylamino acid derivatives, glycolipid derivatives including anionic groups, rhamnolipids. , rhamnolipid derivatives including anionic groups, sulfated derivatives of alkylethoxylatepropoxylates, alkylethoxylate sulphates and combinations thereof.

4. The composition of claim 1, wherein the negatively charged micelle further comprises a nonionic surfactant and optionally the nonionic surfactant comprises an amine oxide.

5. The composition of claim 1, wherein the composition further comprises a cationic surfactant and, optionally, the cationic surfactant comprises a quaternary ammonium compound.

6. The composition of claim 1, wherein the water-soluble polymer carrying a positive charge comprises a monomer that is selected from the group consisting of: diallyldimethylammonium chloride, ammonium salts quaternary of substituted acrylamide, methylacrylamide, acrylate and methacrylate, acrylate esters and amides with quaternized alkylamino, MAPTAC (methacrylamidopropyltrimethylammonium chlorides), trimethylammoniomethyl methacrylate, trimethylammoniopropyl methacrylamide, salts of 2-vinyl h? -alkyl pyridinium quaternary, -vinyl 27-quaternary alkyl pyridinium, 4-vinylbenzyltrialkylammonium salts, 2-vinyl piperidinium salts, 4-vinyl piperidinium salts, 3-alkyl-1-vinyl imidazolium or ethylene imine salts and mixtures thereof or is a water-soluble polymer selected from from the group of chitosan, chitosan derivatives carrying cationic groups, guar gum derivatives bearing cationic groups or a polysaccharide carrying cationic groups and combinations thereof.

7. The composition of claim 1, wherein the water-soluble polymer carrying a positive charge comprises a hybrid copolymer derived from a synthetic monomer or monomers with a chain that has undergone termination with a natural material containing hydroxyl synthesized with a free radical initiator.

8. The composition of claim 1, further comprising a pH buffer, wherein optionally the pH buffer is selected from the group consisting of carbonates, phosphates, silicates, borates and combinations thereof.

9. A method to clean a surface, where the method comprises: contacting said surface with a composition comprising a polymer-micelle complex comprising: a negatively charged micelle electrostatically attached to a water-soluble polymer carrying a positive charge; Y wherein said polymer does not comprise a block copolymer, latex particles, polymeric nanoparticles, crosslinked polymers, silicone copolymer, fluorosurfactant or an amphoteric copolymer; wherein said composition does not form a coacervate; and wherein said composition is not applied to trap organic contaminants at a location below the surface.

10. The method of claim 9, wherein the composition comprising a polymer-micelle complex is a concentrate, wherein the method further comprises diluting the concentrate with water to form a dilute composition comprising the polymer-micelle complex, before contacting the surface with the diluted composition and where the diluted composition does not form a coacervate either.

11. The method of claim 9, wherein the composition further comprises an oxidant and optionally the oxidant is selected from the group consisting of: to. hypohalose acid, hypohalite or sources of these; b. hydrogen peroxide or sources of this; c. peracids, peroxyacids peroxoacids or sources thereof; d. organic peroxides or hydroperoxides; and. inorganic peroxygen compounds; F. solubilized chlorine, solubilized chlorine dioxide, a source of free chlorine, sodium chlorite acid, a compound that generates active chlorine or a compound that generates chlorine dioxide; g. a compound that generates active oxygen; h. solubilized ozone; i. N-halo compounds; Y j. combinations of these.

12. The method of claim 9, wherein the negatively charged micelle comprises an anionic surfactant selected from the group consisting of alkyl sulfates, alkylsulfonates, alkyl ethoxy sulfates, fatty acids, fatty acid salts, alkylamino acid derivatives, glycolipid derivatives including anionic groups, derivatives of rhamnolipids including anionic groups, sulfated derivatives of alkylethoxylatepropoxylates, alkylethoxylate sulphates and combinations thereof, optionally the negatively charged micelle further comprises a nonionic surfactant and optionally the nonionic surfactant comprises an amine oxide.

13. The method of claim 9, wherein the composition further comprises a cationic surfactant and, optionally, the cationic surfactant comprises a quaternary ammonium compound.

14. The method of claim 9, wherein the water-soluble polymer carrying a positive charge comprises a monomer selected from the group of diallyldimethylammonium chloride, quaternary ammonium salts of substituted acrylamide, methylacrylamide, acrylate and methacrylate, esters and amides of acrylate with alkylamino quaternized, MAPTAC (methacrylamidopropyltrimethylammonium chlorides), trimethylammoniomethyl methacrylate, trimethylammoniopropyl methacrylamide, 2-vinyl N-alkyl pyridinium quaternary salts, 4-vinyl W-alkyl pyridinium quaternary salts, 4-vinylbenzyltrialkylammonium salts, 2-vinyl salts piperidinium, 4-vinyl piperidinium salts, 3-alkyl-1-vinyl imidazolium salts or ethylene imine and mixtures thereof or is a water-soluble polymer selected from the group of chitosan, chitosan derivatives bearing cationic groups, guar gum derivatives which they carry cationic groups or a polysaccharide that carries cationic groups and combinations of these.

15. The method of claim 9, further comprising a pH buffer, wherein optionally the pH buffer is selected from the group consisting of carbonates, phosphates, silicates, borates and combinations thereof.

16. A system comprising: a) a dual camera device comprising a first camera and a second camera; b) a first composition comprising a water-soluble polymer carrying a positive charge disposed in the first chamber wherein said polymer does not comprise a block copolymer, latex particles, polymeric nanoparticles, cross-linked polymers, silicone copolymer, fluorosurfactant or an amphoteric copolymer; c) a second composition comprising a negatively charged micelle disposed in the second chamber; d) where the first composition of the first chamber is mixed with the second composition of the second chamber to form a resulting composition in which: i) the micelle is electrostatically bound to the polymer to form a polymer-micelle complex; ii) the resulting composition does not form a coacervate; Y iii) the resulting composition does not form a film on a surface.

17. The system of claim 16, wherein at least one of the first or second compositions further comprises an oxidant and optionally the oxidant is selected from the group consisting of: to. hypohalose acid, hypohalite or sources of these; b. hydrogen peroxide or sources of this; c. peracids, peroxyacids peroxoacids or sources thereof; d. organic peroxides or hydroperoxides; and. inorganic peroxygen compounds; F. solubilized chlorine, solubilized chlorine dioxide, a source of free chlorine, sodium chlorite acid, a compound that generates active chlorine or a compound that generates chlorine dioxide; g. a compound that generates active oxygen; h. solubilized ozone; i. N-halo compounds; Y j. combinations of these.

18. The system of claim 17, wherein the oxidant is included within the second composition comprising the negatively charged micelle, and wherein the first composition comprising the water-soluble polymer carrying a positive charge further comprises a non-ionic surfactant, where optionally the surfactant nonionic comprises an amine oxide.

19. The system of claim 17, wherein the oxidant is included within the first composition comprising the water-soluble polymer carrying a positive charge and wherein the second composition comprising the negatively charged micelle further comprises a non-ionic surfactant and, optionally, the surfactant nonionic comprises an amine oxide.

20. The system of claim 17, wherein at least one of the first or second compositions further comprises a quaternary ammonium compound.