WO2009137014A1

WO2009137014A1 - Cationic latex as a carrier for active ingredients and methods for making and using the same

Info

Publication number: WO2009137014A1
Application number: PCT/US2009/002744
Authority: WO
Inventors: Venkataram Krishnan
Original assignee: Mallar Creek Polymers, Inc.
Priority date: 2008-05-06
Filing date: 2009-05-04
Publication date: 2009-11-12
Also published as: KR20110004461A; US20080233062A1; CA2722974A1; BRPI0912581A2; RU2010149893A; EP2306966A1; WO2009137014A8; JP2011524337A; CN102159181A; EP2306966A4

Abstract

This invention relates to the field of polymeric materials that can be used in combination with a wide variety of substrates, such as textiles, metal, cellulosic materials, plastics, and the like, and to the field of active agents including, for example, antimicrobial, antibacterial, and antifungal materials. This invention further relates to latex polymer coatings that comprise at least one active component as well as methods for making and using such latex compositions.

Description

CATIONIC LATE=X AS ACARRIER FOR ACTIVE INGREDIENTS AND METHODS FOR

MAKING AND USING THE SAME

CROSS-REFERENCE TO RELATED APPLICATIONS This application is a continuation-in-part of U.S. Serial No. 11/895,541 filed on August 24, 2007, which claims priority to U.S. Provisional Application Serial No. 60/839,973 filed August 24, 2006, the contents of each are hereby incorporated by reference.

FIELD OF THE INVENTION

BACKGROUND OF THE INVENTION

The deposition of latex polymer coatings on solid substrates has long been utilized to impart certain end-use performance properties to those substrates, such as hydrophobiάty, strength, adhesive properties, compatibility, or other characteristic. Depending upon the selection of the starting monomers, surfactants, emulsion polymerization conditions, and other parameters, the deposited polymers can be designed to carry an anionic, a cationic, or an amphoteric charge, a feature which directly influences coating performance. Further, the resulting latex poiymer can be biended with a range of other functional materials to impart additional or enhanced features to the final coating material.

One particularly useful feature exhibited by cationic latex polymers disclosed in U.S. Patent Application Publication Number 2005/0003163 is their inherent antimicrobial characteristics. Cationic polymers can also be blended with compositions containing small molecule bioactive compounds, species more typically associated with antimicrobial activity, in order to enhance these properties. These antimicrobial components are usually employed in relatively small amounts as formulating ingredients that are added after the polymer has been made. While such blends are useful, many practical issues remain in attempts to enhance or control the extent of antimicrobial protection these compositions might afford. For example, such compositions and methods are often inadequate for providing long-term protection of materials, especially in their antifungal properties. Methods to augment or to more finely control the antimicrobial properties are also needed. Regulatory issues associated with introducing a new antimicrobial material, namely the polymer, may be significant. Moreover, approaches to prolong or extend the effectiveness of the antimicrobial properties remain elusive.

Therefore, what are needed are new methods and approaches to impart and to enhance antimicrobial activity of latex polymers, as well as the coatings and articles prepared therefrom. What are also needed are methods to more closely manage the antimicrobial activity of such materials, including approaches to extend the effectiveness of their bioactivity.

SUMMARY OF THE INVENTION

This invention encompasses new methods and approaches to incorporate active ingredients, including but not limited to bioactive components, such that the properties of the latex can be enhanced and controlled. As will be further discussed herein, the phrase "active ingredient" includes organic and inorganic components and should be construed in broad terms as an additive that provides a desired end benefit. As one example, an active ingredient of the present invention includes but is not limited to one or more bioactive components that impart antimicrobial, antibacterial, antifungal, antiviral, or antiparasitic activity. As another example, an active ingredient of the present invention includes but is not limited to one or more moisturizing, anti-aging, UV filters, tanning, or anti-dandruff agents.

More explicitly, this invention also encompasses new methods and approaches to incorporate a variety of active ingredients. The present invention also relates to new types of active cationic polymer latex materials. In one aspect, this disclosure provides a method for incorporating active ingredients such as, for example, antimicrobial ingredients, into a latex during the polymerization process.

In one aspect, this invention provides a polymer latex composition comprising: a) a latex polymer comprising the polymerization product of: i) at least one ethylenically unsaturated first monomer; and ii) at least one ethylenically unsaturated second monomer that is cationic or a precursor to a cation; b) at least one active component at least partially encapsulated within the latex polymer; and c) optionally, at least one stericaOy bulky component incorporated into the latex polymer; wherein the composition provides antimicrobial activity. In another aspect, this invention provides a method of deodorizing comprising controlling bacteria through the use of a personal care product having antimicrobial activity. The antimicrobial activity reduces odor and may be combined with an antiperspirant composition. The personal care product may comprise at least one cationic polymer latex composition capable of forming a film. The at least one cationic polymer latex composition may further comprise at least one active component at least partially encapsulated within the latex polymer or at least one post-process active component or a combination thereof. The at least one additional active component may exhibit antistatic, antidandruff, antiacne, preservative, color, chelating, antioxidant, fragrance, conditioning, styling, moisturizing, softening, hydrophobic/hydrophilb, hair depilatory, insect repellant, or sunscreen functionality. The personal care product may be applied to at least one animate surface, inanimate surface, or air and may be formulated as a sunscreen, body wash, shampoo, lotion, or deodorant The deodorant can be a roll-on, stick, or spray. In one embodiment, the personal care product exhibits a foam height of at least 700 ml, a pH of from 6 to about 7, and a foam density of from about 3 seconds to about 30 seconds.

Previously, antimicrobial agents have been added to a latex after the polymerization process and in relatively small amounts as preservatives for the latex product or for the end use application such as paints. The present invention allows the use of higher concentrations of a wide range of active ingredients, including highly hydrophobic ingredients, which can be readily incorporated into the latices, such that the resulting latex particles function as carriers for the active ingredients. The thorough incorporation of an active ingredient in this manner can afford a substantially homogeneous distribution of the additive and result in superior and sustained performance compared to pre-made dispersions.

In one aspect of this invention, an emulsion polymerization is carried out such that one or more active agents is incorporated into the polymer during emulsion polymerization, typically by dissolving the respective one or more active components in a monomer stream. In this manner, the active agents can be at least partially encapsulated within the latex polymer matrix. The one or more active ingredients may be added to the monomer stream at any time during the polymerization process, however, those skilled in the art will recognize that certain active ingredients would benefit from addition late in the polymerization process to maintain the integrity and function of the active ingredient One advantage provided by this process is the ability to incorporate or encapsulate large amounts of active ingredients, including hydrophobic components, without substantially degrading the respective active agent. In another aspect, this invention also provides a tunable system based on a cationic latex that has some inherent antimicrobial properties, which also functions as a carrier for at least one active ingredient and optionally further including one or more additives that can be blended with the latices disclosed herein. Thus, these latices can have a multifunctional purpose such as providing binding, strength, and dispersion properties in addition to being a carrier for an active functional ingredient, and optionally constituting one component of a blended composition.

In one aspect, because the active ingredients are typically incorporated into a latex during the emulsion polymerization process, these active components can be at least partially encapsulated within the latex polymer matrix. In another aspect, the active components can be substantially encapsulated within the latex polymer matrix. While not intending to be bound by one theory, it is believed that, by delivering the active ingredient to a desired end use application, the latex polymer with the encapsulated active ingredients can provide sustained and controlled exposure of the active ingredients to the environment in which they are deployed, thereby providing longer and more effective protection to the product or the application. Moreover, because both the active cationic latices described herein can be formed by existing emulsion polymerization processes, the polymerization methods advantageously allow for the preparation of high molecular weight polymers.

In a further aspect, the methods disclosed herein also provide the potential to adjust the behavior of the active agent using a combination of approaches to deploy the active agent. For example, highly tailored antimicrobial properties can be imparted to a product by both incorporating an antimicrobial ingredient into a latex during the emulsion polymerization process, and by combining the resulting latex product with the same or different antimicrobial component in a blend. This approach allows antimicrobial properties to be selected and adjusted using the polymer, the additive, or both, depending on the circumstances and the performance required. Similarly, other functionalities may be controlled as well.

In yet a further aspect, the techniques disclosed herein can provide the ability to encapsulate larger amounts of the active ingredient into a latex composition than are afforded by standard methods. For example, antimicrobial components are usually employed in relatively small amounts as formulating ingredients once the latex polymer has been prepared, and such antimicrobials typically are utilized at concentrations ranging up to about 1000-2000 ppm. In contrast, the antimicrobial component of the resulting latex compositions of the present invention can be utilized in concentrations as high as about 40 weight percent based on the total monomer weight. In this aspect, this invention can provide stable, concentrated dispersions that can be used as such, or as an additive, or concentrated dispersions that can be diluted and added to other systems which require antimicrobial protection. High antimicrobial component concentrations provide flexibility and ensure the utility of these latex compositions as concentrates as well as in non-concentrated form.

While the methods disclosed herein can be applied to any active ingredient, including but not limited to either organic or inorganic agents, the present invention should be interpreted to encompass methods for providing or enhancing the properties of a latex, substrate, or particular end product through the encapsulation of any beneficial material. As one example, the present invention includes a bioactive latex which can include antimicrobial activity, antibacterial activity, antifungal activity, antiviral activity, antiparasitic activity, or any combination thereof, depending upon the particular selection of bioactive agents.

As used herein, the term "active" component includes, but is not limited to, antimicrobials, antibacterials, antifungals, antivirals, antiparasitics, UV agents, pharmaceuticals, neutraceuticals, vitamins, cosmeceuticals, cosmetics, oxides, minerals, pigments, and the like. In other words, the term is used to include all ingredients capable of encapsulation that provide a benefit to the resulting latex composition. As one example, a moisturizing agent is considered an active component or ingredient of the present invention. Similarly, a UV agent is considered an active component or ingredient of the present invention. Thus, the present invention further includes a latex that incorporates both a moisturizer and a UV agent.

In another aspect, this invention provides an active cationic polymer latex comprising: a) a latex polymer comprising the polymerization product of: i) at least one ethylenically unsaturated first monomer; and ii) at least one ethylenically unsaturated second monomer that is cationic or a precursor to a cation; b) at least one active component at least partially encapsulated within the latex polymer; and c) optionally, at least one sterically bulky component incorporated into the latex polymer.

In another aspect, this invention provides a bioactive cationic polymer latex comprising: a) a latex polymer comprising the polymerization product of: i) at least one ethylenically unsaturated first monomer; and ii) at least one ethylenically unsaturated second monomer that is cationic or a precursor to a cation; b) at least one bioactive component at least partially encapsulated within the latex polymer; and c) optionally, at least one sterically bulky component incorporated into the latex polymer.

As such, the term active includes but is not limited to bioactive. In these aspects, a wide range of weight percentages of ethylenically unsaturated first monomer and ethylenically unsaturated second monomer that is cationic or a precursor to a cation, which can be referred to as the "cationic" monomer, can be used. For example, the latex can comprise from about 0.01 to about 75 weight percent of the cationic second monomer based on the total monomer weight.

Also, while the at least one sterically bulky component incorporated into the latex polymer is an optional component, this invention also provides for use of a wide range of amounts and concentrations of this component. Thus, as will be understood by the skilled artisan, in active cationic polymer latices that do not incorporate at least one sterically bulky component, latex stability can be enhanced by increasing the relative proportion of the cationic second monomer, by the addition of surfactants such as nonionic surfactants, and the like, including any combination of such methods. The relative proportion of the cationic second monomer can be reduced and/or surfactants can be eliminated in the presence of at least one sterically bulky component.

Further, the latices of this invention can also comprise a sterically bulky component which is incorporated into the cationic polymer latex to sterically stabilize the latex. These sterically bulky components can include, but are not limited to, monomers, polymers, and mixtures thereof as set forth below. Thus, a monomer can be incorporated as a co- monomer that can attach to, or constitute a portion of the backbone of the cationic polymer, examples of which include an alkoxylated ethylenically unsaturated third monomer. A polymer can be incorporated by adsorbing or being grafted onto the latex surface, an example of which includes polyvinyl alcohol.

In still another aspect, this invention provides a method of making an active cationic polymer latex comprising initiating an emulsion polymerization of an aqueous composition comprising, at any time during the emulsion polymerization: a) at least one ethylenically unsaturated first monomer; b) at least one ethylenically unsaturated second monomer that is cationic or a precursor to a cation; c) at least one active component; d) at least one free-radical initiator; e) optionally, at least one sterically bulky ethylenically unsaturated third monomer; f) optionally, at least one sterically bulky polymer; and g) optionally, at least one nonionic surfactant.

In yet another aspect, this invention provides a method of making a bioactive cationic polymer latex comprising initiating an emulsion polymerization of an aqueous composition comprising, at any time during the emulsion polymerization: a) at least one ethylenically unsaturated first monomer; b) at least one ethylenically unsaturated second monomer that is cationic or a precursor to a cation; c) at least one bioactive component; d) at least one free-radical initiator; e) optionally, at least one sterically bulky ethylenically unsaturated third monomer; f) optionally, at least one sterically bulky polymer; and g) optionally, at least one nonionic surfactant.

Thus, in one aspect, the at least one active component can be dissolved in the monomer feed at any time during the emulsion polymerization process. Further, in another aspect, the aqueous composition components and the at least one active component can be provided as a dispersion prior to initiating the emulsion polymerization. Thus, this invention provides for batch processes, in which the at least one active component is present in the seed stage. In this aspect, the emulsion polymerization is initiated when all the components of the composition, including the at least one active component, are present from the time of initiation. Further, this invention also provides for semi-continuous processes in which the emulsion polymerization is initiated at a time when all components of the composition are not present from the time of initiation, but some are added at various times after initiating the polymerization. In this aspect, for example, the at least one active component can be added at any time after the seed stage. In another aspect, for example, any other component or combination of components provided above can be added at any time after the seed stage, except for at least a portion of the total amount of any component that is required to initiate and propagate an emulsion polymerization. Thus, the active cationic latex provided herein can be made by any variety of batch or by a semi-continuous processes. For example, the at least one active component can be provided as a dispersion and can be added to the composition during the emulsion polymerization process. The present invention also relates to a disinfectant composition comprising an active cationic polymer latex comprising: a) a latex polymer comprising the polymerization product of: i) at least one ethylenically unsaturated first monomer; and ii) at least one ethylenically unsaturated second monomer that is cationic or a precursor to a cation; b) at least one active component at least partially encapsulated within the latex polymer; and c) optionally, at least one sterically bulky component incorporated into the latex polymer.

The disinfectant can further comprise at least one active component such as a natural plant-based wax, animal derived wax, natural mineral wax, synthetic mineral wax, synthetic wax, an alcohol comprising a carbon chain length of greater than one, an ester of an alcohol, metal stearate, carboxylic acid, fatty acid, oil, fatty amide, cosmeceutical or nutraceutical ingredients or the like.

In one aspect, an active latex of this invention can be provided or used as a coating, which can be applicable to medical implants, including artificial ball and socket joints, rods, stents, dental implants, pins, screws, catheters, and the like. Such coatings can also be provided on everyday surfaces, such as air-conditioning coils, air filters, pipes, roofing, bathroom items, kitchen items, and the like. Such a coating can prevent microbial infections, such as bacteria and mold, in vehicles as well as homes, hospitals, and other buildings. Further examples of uses of the resultant products are use as an aqueous solution or directly in powder form, for example, for sterilizing cooling-water circuits, or indirect use, for example by addition to paints or other surface coatings.

In another aspect, an active latex of this invention can be provided or used for personal care products, pharmaceutical, cosmeceutical, or nutraceutical applications. Non- limiting examples include odor control agents, moisturizing agents, anti-wrinkle and anti- aging agents, antiacne agents, anti-dandruff agents, anti-static agents, preservatives, conditioners, styling aids, chelating agents, antioxidants, ultraviolet blockers and absorbers, skin bronzing or tanning agents, vitamins and herbal supplements, botanical extracts, free radical scavengers, coloring agents, fragrances, and perfumes. Further, an active latex of the present invention may be used in the packaging of such applications.

These and other features, aspects, embodiments, and advantages of the present invention will become apparent after a review of the following detailed description of the invention. It should be understood, however, that these aspects, embodiments, and examples are provided for illustrative purposes only, and are not to be construed in any way as imposing limitations upon the scope thereof. Further, the present invention includes combinations of embodiments and aspects as herein provided.

BRIEF DESCRIPTION OF THE FIGURES

Figure 1 is a graph showing the evaluation of the antimicrobial properties of various antimicrobial latexes, coated on Kraft paper, using ASTM G21.

Figure 2 is a graph showing the results of a 30- 111 fungal test, based on making a 1"X1" chip of the dried latex, inoculating the fungal species directly on to the sample, and then observing its growth after 7 days.

Figure 3 is a graph showing the results of a second round of testing of coated paper samples, tested according to ASTM D-3273 over a period of 28 days. In this study, the fungal species were not directly inoculated on the surface, but rather, were maintained in the humidity chamber as spores that would then land on the surface of the coated paper.

Figure 4 is a graph showing the evaluation of the antimicrobial properties of paper in which an antimicrobial latex was incorporated into the paper in a wet end process, as compared to coated paper, using ASTM D-3273.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides new latex polymeric materials that can be used in a wide variety of end-uses, such as personal care products, including but not limited to skin and hair products, pharmaceuticals, cosmeceuticals, nutraceuticals, or as coatings on textiles, metal, cellulosic materials, plastics, and the like, in which the polymeric materials include active components incorporated into the latex polymer. This invention also provides new methods and processes that allow incorporating high concentrations of an active ingredient such as antifungal agents during the emulsion polymerization. In one aspect, for example, the disclosed process can be used to incorporate from about 0.01 percent to about 40 percent, based on the total monomer weight ("phm" or parts per hundred of monomer), of a substantially hydrophobic ingredient during the emulsion polymerization. While the active ingredient can be introduced at any stage during the polymerization process including very early during the seed formation stage, in one aspect, the active component or additive can be added during the later stages of polymerization process, for example, when from about 30 percent to about 90 percent of the monomer has been fed into the polymerization reactor.

Useful active additives can be solids, liquids, or combinations thereof. Many of the active additives that can be employed in this invention are substantially water insoluble or have limited solubility in water. In this aspect, the typical water insoluble, hydrophobic active agent can be soluble in at least one of the monomers employed in the emulsion polymerization. Thus, the typical hydrophobic active ingredient can be introduced into the polymerization reactor by substantially or partially dissolving it in a monomer feed at the appropriate time. Therefore, as one example, the typical ingredients chosen for imparting antimicrobial properties usually will be soluble in the monomers that are used to make the polymer latex. In another aspect, useful active additives in this invention can also be substantially water soluble, one example of which includes o-phenylphenate (deprotonated o-phenylphenol), and similar agents. In this aspect, it is not necessary that such a hydrophilic active additive be soluble in any monomer that is to be polymerized.

In another aspect, it is not required that active ingredients be soluble in at least one of the monomers used, as these ingredients can also be added as a pre-made dispersion in water. In this aspect, the dispersions can be made, among other ways, by using a relatively concentrated amount of the additive and dispersing by using surfactants, dispersants, and the like, and typically employing a mixing device such as a high speed mixer, a homogenizer, an Eppenbach mixer, or similar devices. In such a case, the dispersion can be fed into the reactor to deliver the appropriate amount of active ingredient into the latex.

In one aspect, this invention encompasses an active cationic polymer latex comprising: a) a latex polymer comprising the polymerization product of: i) at least one ethylenically unsaturated first monomer; and ii) at least one ethylenically unsaturated second monomer that is cationic or a precursor to a cation; b) at least one active component at least partially encapsulated within the latex polymer; and c) optionally, at least one sterically bulky component incorporated into the latex polymer.

As provided herein, the at least one sterically bulky component incorporated into the latex polymer can be selected independently from at least one sterically bulky ethylenically unsaturated third monomer, at least one sterically bulky polymer, or any combination thereof. Each of these components, as well as optional or additional components, is considered herein.

In one aspect of the present invention, a disinfectant composition can be prepared comprising a) a latex polymer comprising the polymerization product of: i) at least one ethylenically unsaturated first monomer; and ii) at least one ethylenically unsaturated second monomer that is cationic or a precursor to a cation; b) at least one active component at least partially encapsulated within the latex polymer; and c) optionally, at least one sterically bulky component incorporated into the latex polymer.

The disinfectant composition can further comprise a variety of common disinfecting compounds such as, for example, quaternary ammonium compounds, phenols and alcohols as well as any surfactants or solvents used for household cleaning including glycol ethers, alcohols, chlorinated solvents such as methylene chloride, and petroleum derivative solvents. Inorganic detergent builders such as phosphates, silicates, carbonates and zeolites may also be added. When combined, the disinfecting compounds may provide short-term disinfectant activity while the latex polymer having at least one active component at least partially encapsulated may provide long-term disinfectant activity. The pH of the disinfectant composition can be less than or equal to 4 or greater than or equal to 9.

In another aspect, this invention also encompasses a method of making an active cationic polymer latex comprising initiating an emulsion polymerization of an aqueous composition comprising, at any time during the emulsion polymerization: a) at least one ethylenically unsaturated first monomer; b) at least one ethylenically unsaturated second monomer that is cationic or a precursor to a cation; c) at least one bioactive component; d) at least one free-radical initiator; e) optionally, at least one sterically bulky ethylenically unsaturated third monomer; f) optionally, at least one sterically bulky polymer; and g) optionally, at least one non nonionic surfactant. In yet another aspect, this invention provides a method of making a bioactive cationic polymer latex comprising initiating an emulsion polymerization of an aqueous composition comprising, at any time during the emulsion polymerization: a) at least one ethylenically unsaturated first monomer; b) at least one ethylenically unsaturated second monomer that is cationic or a precursor to a cation; c) at least one bioactive component; d) at least one free-radical initiator; e) optionally, at least one sterically bulky ethylenically unsaturated third monomer; f) optionally, at least one sterically bulky polymer; and g) optionally, at least one nonionic surfactant.

In yet another aspect, this invention provides a method of making an active cationic polymer latex comprising: a) providing an aqueous composition comprising: i) at least one ethylenically unsaturated first monomer; ii) at least one ethylenically unsaturated second monomer that is cationic or a precursor to a cation; iii) optionally, at least one sterically bulky ethylenically unsaturated third monomer; iv) at least one free-radical initiator; and v) optionally, at least one non-ionic surfactant; b) initiating an emulsion polymerization of the composition; and c) adding at least one active component to the composition during the emulsion polymerization process.

In another aspect, this invention provides a method of making a bioactive cationic polymer latex comprising a) providing an aqueous composition comprising: i) at least one ethylenically unsaturated first monomer; ii) at least one ethylenically unsaturated second monomer that is cationic or a precursor to a cation; iii) optionally, at least one sterically bulky ethylenically unsaturated third monomer; iv) at least one free-radical initiator; and v) optionally, at least one non-ionic surfactant; b) initiating an emulsion polymerization of the composition; and c) adding at least one bioactive component to the composition during the emulsion polymerization process.

Many compounds and species that can be used as ethylenically unsaturated first monomers, ethylenically unsaturated second monomers, and sterically bulky components are disclosed in the European Patent Number EP 1109845 and the corresponding PCT Published Patent Application WO 00/8008077, each disclosure of which is incorporated herein by reference in its entirety.

Ethylenically Unsaturated First Monomers

Various ethylenically unsaturated first monomers can be used in the latex of the present invention. In one aspect, ethylenically unsaturated first monomers can be non- cationic. Examples of suitable monomers can be found at least in U.S. Patent Number 5,830,934, U.S. Patent Application Publication Numbers 2005/0065284 and 2005/0003163, and European Patent Number EP 1109845, all to Krishnan, each disclosure of which is incorporated herein by reference in its entirety. In this aspect, examples of such monomers include, but are not limited to, vinyl aromatic monomers, halogenated or non-halogenated olefin monomers, aliphatic conjugated diene monomers, non-aromatic unsaturated mono- or dicarboxylic ester monomers, monomers based on the half ester of an unsaturated dicarboxylic acid monomers, unsaturated mono- or dicarboxylic acid monomers, nitrogen- containing monomers, nitrile-containing monomers, cyclic or acyclic amine-containing monomer, branched or unbranched alkyl vinyl ester monomers, halogenated or non- halogenated alkyl acrylate monomers, halogenated or non-halogenated aryl acrylate monomers, carboxylic acid vinyl esters, acetic acid alkenyl esters, carboxylic acid alkenyl esters, a vinyl halide, a vinylidene halide, or any combination thereof, any of which having up to 20 carbon atoms.

In this aspect, it is the Applicant's intent to disclose acrylate and methacrylate moieties when either moiety is disclosed in a suitable monomer. Thus, the disclosure that an acrylate monomer is a suitable ethylenically unsaturated first monomer also encompasses the disclosure that the corresponding methacrylate monomer is also a suitable first monomer. The abbreviation (meth)acrylate can be used to represent such a disclosure.

Many different ethylenically unsaturated first monomers can be used in preparing the active latices of this invention. In one aspect, suitable examples of ethylenically unsaturated first monomers include, but are not limited to, styrene, para-methyl styrene, chloromethyl styrene, vinyl toluene, ethylene, butadiene, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, glycidyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, monomethyl maleate, itaconic acid, (meth)acrylonitrile, (meth)acrylamide, Λ/-methylol (meth)acrylamide, N- (isobutoxymethyl)(meth)acrylamide, vinyl neodecanoate, vinyl versatates, vinyl acetate, C₃- C₈ alkyl vinylethers, C₃-C₈ alkoxy vinyl ethers, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, perfluorobutyl ethylene, perfluorinated C₃-C₈ alpha-olefins, fluorinated C₃-C₈ alkyl vinylethers, perfluorinated C₃-C₈ alkyl vinylethers, perfluorinated C₃-C₈ alkoxy vinyl ethers, and the like, or any combination thereof. Thus, halogenated analogs of suitable ethylenically unsaturated first monomers are encompassed by this disclosure, and it is Applicant's intent to disclose any and all suitable halogen- substituted analogs or derivatives of these monomers, including fluorine-substituted analogs, chlorine-substituted analogs, bromine-substituted analogs, and iodine-substituted analogs. The term "halogen-substituted" is meant to include partially halogen substituted and pemalogen substituted, in which any halogen substituents can be the same or can be different. In this aspect as well, it is the Applicant's intent to disclose both acrylate and methacrylate moieties when either moiety is disclosed in a suitable monomer.

In another aspect, the ethylenically unsaturated first monomer can be halogenated or can be non-halogenated. Similarly, the ethylenically unsaturated first monomer can be fluorinated or can be non-fluorinated. For example, fluorinated analogs of alkyl acrylates or methacrylates can be used, as well as the non-fluorinated compounds. The ethylenically unsaturated first monomer can also be chlorinated or can be non-chlorinated. The ethylenically unsaturated first monomer can also be brominated or can be non-brominated. The ethylenically unsaturated first monomer can also be iodinated or can be non-iodinated. For example, fluorinated analogs of alkyl acrylates or methacrylates can be used, as well as the non-fluorinated compounds.

In yet another aspect of this invention, the latices provided herein can comprise from about 20 percent to about 99.5 percent by weight of the ethylenically unsaturated first monomer, based on the total monomer weight. In this aspect, the latex of this invention can also comprise from about 30 percent to about 99 percent, from about 40 percent to about 97 percent, from about 50 percent to about 95 percent, from about 60 percent to about 90 percent, or from about 70 percent to about 90 percent by weight of the ethylenically unsaturated first monomer, based on the total monomer weight. In this aspect, the Applicant's intent is to disclose individualy each possible number that such ranges could reasonably encompass, as well as any sub-ranges and combinations of sub-ranges encompassed therein. In this aspect, as understood by the skilled artisan, the particular chemical and physical properties of a specific monomer will have a bearing on the range of weight percentages most suitable for that monomer.

Ethylenically Unsaturated Cationic Second Monomers

In still another aspect, the latex polymer of the present invention also comprises the polymerization product of at least one ethylenically unsaturated second monomer that is cationic or a precursor to a cation. As provided herein, the at least one ethylenically unsaturated second monomer that is cationic or a precursor to a cation can be collectively referred to by the term "cationic monomer," that is, any monomer which possesses or can be made to posses a positive charge. In one aspect, this positive charge may be imparted by the presence of a heteroatom in the monomer, such as nitrogen, that can constitute the site of attachment of a proton or any other cationic Lewis Acid that would impart a positive charge to the monomer. For example, quaternary amine monomers can be used as a "cationic monomer" in the latex of the invention, which includes quaternary amine monomers obtained from any neutral amine monomer disclosed herein by, for example, protonation using an acid or by alkylation using an alkyl halide. Exemplary heteroatoms include, but are not limited to, nitrogen, sulfur, phosphorus, and the like. Thus, the cationic monomer is typically incorporated into the latex polymer by virtue of its ethylenic unsaturatjon.

Examples of suitable cationic monomers can be found at least in U.S. Patent Application Publication Numbers 2005/0065284 and 2005/0003163, to Khshnan. In this aspect, examples of cationic monomers include, but are not limited to, an amine monomer, an amide monomer, a quaternary amine monomer, a phosphonium monomer, a sulfonium monomer, or any combination thereof, any of which having up to 20 carbon atoms. Further, suitable examples of ethylenically unsaturated cationic monomers that can be used in the latex of the present invention include, but are not limited to, dimethylaminoethyl acrylate; diethylaminoethyl acrylate; dimethyl aminoethyl methacrylate; diethylaminoethyl methacrylate; tertiary butylaminoethyl methacrylate; Λ/,Λ/-di methyl acrylamide; N₁N- dimethylaminopropyl acrylamide; acryloyl morpholine; Λ/-isopropyl acrylamide; Λ/,Λ/-diethyl acrylamide; dimethyl aminoethyl vinyl ether; 2-methyl-1 -vinyl imidazole; Λ/,Λ/-dimethyl- aminopropyl methacrylamide; vinyl pyridine; vinyl benzyl amine; dimethylaminoethyl acrylate, methyl chloride quarternary; dimethylaminoethyl methacrylate, methyl chloride quarternary; diallyldimethylammonium chloride; N,N-dimethylaminopropyl acrylamide, methyl chloride quaternary; trimethyl-(vinyloxyethyl) ammonium chloride; 1-vinyl-2,3-dimethylimidazolinium chloride; vinyl benzyl amine hydrochloride; vinyl pyridinium hydrochloride; or any combination thereof. While these listed examples include both free base compounds, and various quarternary salts such as hydrochloride or methyl chloride quarternary salts, any suitable Lewis acid that imparts a positive charge to the monomer can be used to form the cationic monomers of this disclosure.

In a further aspect, other amines or amine salts can also be used as ethylenically unsaturated second monomers to prepare the latex polymer of the present invention. For example, various amine salts can be obtained, for example, by the reaction of an epoxy group with a secondary amine and the subsequent neutralization of the newly formed tertiary amine with an acid. For example, the reaction of glycidyl methacrylate with a secondary amine can be carried out and the product can be free radically polymerized. Quaternary amine functionality can also be generated as a "post-reaction" on a preformed polymer having, for example, an epoxy group. Examples of such reactions are described in the article, "Polymer Compositions for Cationic Electrodepositable Coatings," Journal of Coatings Technology, VoI 54, No 686, March 1982, which is incorporated herein by reference in its entirety. It should also be appreciated that cationic functionality can also be imparted using sulfonium or phosphonium chemistry, examples of which are described in the above-cited reference, and will be appreciated by one of ordinary skill in art.

In a further aspect, the latex polymer of this invention can comprise from about 0.01 to about 75 percent by weight of the ethylenically unsaturated second monomer that is cationic or a precursor to a cation, based on the total monomer weight. In this aspect, the latex of this invention can also comprise from about 0.025 to about 70 percent, from about 0.05 to about 60 percent, from about 0.1 to about 50 percent, from about 0.25 to about 40 percent, from about 0.5 to about 30 percent, from about 1 to about 20 percent, or from about 1.5 to about 15 percent, by weight of the cationic second monomer, based on the total monomer weight. In this aspect, the Applicant's intent is to disclose individually each possible number that such ranges could reasonably encompass, as well as any sub-ranges and combinations of sub-ranges encompassed therein.

Sterically Bulky Components

As disclosed herein, one aspect of this invention encompasses a cationic polymer latex comprising: a) a latex polymer as disclosed herein; b) at least one active component at least partially encapsulated within the latex polymer; and c) optionally, at least one sterically bulky component incorporated into the latex polymer. In another aspect, this invention encompasses a cationic polymer latex comprising: a) a latex polymer as disclosed herein; b) at least one active component at least partially encapsulated within the latex polymer; and c) optionally, at least one stericaOy bulky component incorporated into the latex polymer. In yet another aspect, this invention encompasses a cationic polymer latex comprising: a) a latex polymer as disclosed herein; b) at least one bioactive component at least partially encapsulated within the latex polymer; and c) optionally, at least one sterically bulky component incorporated into the latex polymer.

The at least one sterically bulky component incorporated into the latex polymer can be selected independently from at least one sterically bulky ethylenically unsaturated third monomer, at least one sterically bulky polymer, or any combination thereof. In this aspect, and while not intending to be bound by theory, this sterically bulky component is typically incorporated into the cationic polymer latex to sterically stabilize the latex.

As used herein, the term "incorporated" with respect to the use of the at least one sterically bulky ethylenically unsaturated third monomer includes, but is not limited to, the attachment of this third monomer to the cationic polymer, for example, by co-polymerization of the third monomer with the first monomer and second cationic monomer disclosed herein, to form the cationic polymer latex. Further, the term "incorporated" with respect to the at least one sterically bulky ethylenically unsaturated third monomer can also include the attachment of this third monomer to the cationic polymer in any other fashion, such as, for example, by grafting onto the polymer backbone. In another aspect, the term "incorporated" with respect to the use of the at least one sterically bulky polymer includes, but is not limited to, the attachment or association of this polymer into the latex for methods including, but not limited to, adsorbing or grafting the sterically bulky polymer onto the latex surface. For example, polyvinyl alcohol can be incorporated into the latex in this manner. This sterically stabilizing component can encompass a nonionic monomer or nonionic polymer which incorporates steric stabilization to the latex particle without affecting the deposition characteristics of the cationic polymer latex.

Exemplary monomers that can be used as sterically bulky ethylenically unsaturated third monomers include, but are not limited to, those ethylenically unsaturated monomers that contain alkoxylated (for example, ethoxylated or propoxylated) functionalities. In one aspect, examples of such monomers include, but are not limited to, at least one a sterically bulky ethylenically unsaturated compound selected independently from the following: a) CH₂=C(R^1A)COO(CH₂CHR^2AO)_mR^3A, wherein R^1A, R²*, and R^3A can be selected independently from H or an alkyl group having from 1 to 6 carbon atoms, inclusive, and m can be an integer from 1 to 30, inclusive. In this aspect, R^1A, R²*, and R^3A can also be selected independently from H or methyl, m can be an integer from 1 to 10, inclusive; b) CH₂=C(R^1B)COO(CH₂CH₂O)_n(CH₂CHR^2BO)pR^3B, wherein R^1B, R^2B, and R^3B can be selected independently from H or an alkyl group having from 1 to 6 carbon atoms, inclusive, and n and p can be integers selected independently from 1 to 15, inclusive. Also in this aspect, R^1B, R^2B, and R^3B can be selected independentlyfrom H or methyl, and n and p can be integers selected independenfly from 1 to 10, inclusive; c) CH₂=C(R^1c)COO(CH₂CHR^2CO)_q(CH₂CH₂O)_rR^3C, wherein R^1C, R^2C, and R^3C can be selected independently from H or an alkyl group having from 1 to 6 carbon atoms, inclusive, and q and r can be integers selected independently from 1 to 15, inclusive. Further to this aspect, R^1C, R^2C, and R^3C can be selected independently from H or methyl, and q and r can be integers selected independently from 1 to 10, inclusive; or d) any combination of any of these compounds.

In another aspect of this invention, a number of other types of unsaturated compounds can be used as sterically bulky ethylenically unsaturated third monomers including, but not limited to, polymerizable surfactants. Thus, further examples of suitable sterically bulky ethylenically unsaturated third monomers include, but are not limited to, alkoxylated monoesters of a dicarboxylic acid; alkoxylated diesters of a dicarboxylic acid; polyoxyethylene alkylphenyl ethers such as NOIGEN RN™; or any combination thereof. In this aspect, for example, ethoxylated mono- and diesters of diacids such as maleic and itaconic acids can also be used to achieve the desired stabilizing effect. Acrylate, methacrylate, vinyl and allyl analogs of surfactants, referred to as polymerizable surfactants, can also be used in this manner. Examples of such polymerizable surfactants include, but are not limited to, TREM LF-40™ sold by Cognis. In one aspect, these surfactants are typical in that they possess ethylenic unsaturation that allows the surfactants to be incorporated into the latex polymer itself, as well as possessing hydrophobic and hydrophilic functionality that varies. In another aspect, surfactants that are particularly applicable to the present invention include the nonionic surfactants, wherein the hydrophilic character is believed to be attributable to the presence of alkylene oxide groups. Examples of suitable nonionic surfactants include, but are not limited to moieties derived from, ethylene oxide, propylene oxide, butylene oxide, and the like. In such species, the degree of hydrophilicity can vary based on the selection of functionality.

The at least one sterically bulky component incorporated into the latex polymer can also constitute at least one polymer. Again, while not intending to be bound by theory, it is thought that such polymers provide steric stability to the resulting latex polymer. Such polymers are sometimes referred to in the art as protective colloids. Examples of sterically bulky polymers include, but are not limited to, polyvinyl alcohols, polyvinyl pyrollidone, hydroxyethyl cellulose, and the like, including any combination of these materials or a derivative thereof. Moreover, mixtures or combinations of any of the aforementioned sterically bulky monomers and any of these sterically bulky polymers can also be used as the at least one sterically bulky component that is incorporated into the latex polymer. A number of other monomers and polymers that can be used in the present invention that can impart stability are provided in U.S. Patent Number 5,830,934 to Krishnan et ai, the entirety of which is incorporated herein by reference.

The optional at least one sterically bulky component can be present in an amount ranging from 0 to about 25 percent by weight, based on the total weight of the monomers. In this aspect, the latex of this invention can also comprise from about 0.1 to about 20 percent, from about 0.2 to about 18 percent, from about 0.5 to about 15 percent, from about 0.7 to about 12 percent, or from about 1 to about 10 percent by weight of the sterically bulky component, based on the total monomer weight. In this aspect, the Applicant's intent is to disclose individually each possible number that such ranges could reasonably encompass, as well as any sub-ranges and combinations of sub-ranges encompassed therein.

Free Radical Initiators

In still a further aspect, the latex of the present invention can indude a free radical initiator, the selection of which is known to one of ordinary skill in the art. Thus, while any polymerization initiator whether it is cationic or anionic in nature can be used as a polymerization initiator, for example, persulfates, peroxides, and the like, typical initiators are azo-based compounds and compositions. Moreover, in this aspect, for producing a cationic latex, any free radical initiator which generates a cationic species upon decomposition and contributes to the cationic charge of the latex can be utilized. Examples of such an initiator include, but are not limited to, is 2,2'-azobis(2-amidinopropane)dihydrochloride), which is sold commercially as WAKO V-50™ by Wako Chemicals of Richmond, Virginia.

Active Agents and Their Incorporation

The cationic latex polymerization and encapsulation method disclosed herein can be utilized with a wide range of active agents, alone or in combination. Cationic latex has proved very useful due, in part, to the inherent antimicrobial attributes of the cationic polymer which can be supplemented with at least one antimicrobial agent.

In one aspect, this invention also provides methods to prepare an antifungal fortified cationic latex and to deposit such a latex through a wet end process onto pulp fibers, such that the resultant sheet of paper is substantially antifungal. This method, which includes deposition onto pulp fibers, highlights the utility of this process that incorporates an antimicrobial active ingredient into a resulting cationic latex for deposition, in part, because the process is facilitated by opposite charges on the pulp fibers and the cationic latex. This opposite charge features typically leads to substantial uniformity of deposition of the cationic latex on the fiber and a substantially homogeneous product. In this aspect, the typical initiators also include azo-based compounds and compositions. As provided herein, a wide range of polymerization conditions can be used. In one aspect, the active component or additive is typically soluble in at least one of the monomers employed, or soluble in a monomer mixture, or composition used. In another aspect, the active additive can be introduced at any stage during the polymerization process including very early during the seed formation stage, including initiating the emulsion polymerization when all the components of the composition, including the at least one active component, are present at the time of initiation. In another aspect, the additive can be added during a later stage of polymerization process. For example, the active ingredient can be introduced into the monomer feed when about 30 percent of the monomer has been fed into the polymerization reactor.

While not intending to be bound by theory, it is believed that introducing the active component into the monomer feed relatively late in the polymerization process could help minimize degradation of the active agent arising from the polymerization conditions. For example, it is possible that the active agent could be degraded at the temperature under which polymerization is conducted, or could react with certain monomers or other components. Accordingly, to minimize any such degradation process, the active agent can be added at such a time in the process, for example, when the process is more than about 50%, more than about 60%, more than about 70%, more than about 80%, or more than about 90% complete, thus minimizing the contact time between the active agent and other components underthe polymerization conditions. Another approach to minimize degradation of the active agent is to employ active agents that comprise "latent" active moieties that can be activated by thermal, chemical, photochemical, or similar means, at a suitable time after the emulsion polymerization.

In another aspect of this invention, the active additive can be introduced at any stage during an emulsion polymerization process, including, for example at such a time during the process at which the resulting latex exhibits an activity that is not substantially diminished relative to a standard activity exhibited by the same latex prepared by adding the active component when the emulsion polymerization is about 50% complete. Thus, this standard activity is the activity of the same latex synthesized from the same active component and the same latex at substantially the same concentrations, prepared by adding the active component when the emulsion polymerization is about 50% complete, as evaluated under similar conditions. The term "not substantially diminished" is used to refer to any difference in activity of the resulting active latex, relative to this standard activity, that meets any one, or more than one, of the following criteria: 1 ) the measured activity of the resulting active latex is less than or equal to about 15% lower than the measured activity of the standard; 2) the activity of the resulting active latex has a numerical activity rating based on an arbitrary activity scale that is less than or equal to about 35% lower than the numerical activity rating of the standard; or 3) the empirically-based descriptive rating of the activity level of the resulting active latex is no more than two descriptive rating levels lower than the activity rating level of the standard. As an example, the measurement of antimicrobial activity can be determined according to any one, or more than one, of the following test standards: ASTM E2180-01 ; ASTM E2149-01; ASTM E1882-05; ASTM D3273; AATCC Test Method 30, Part 3; AATCC Test Method 100; ASTM D5590. An example of criterion 1) of "not substantially diminished" is as follows: A bioactive additive can be introduced at a time, or introduction can be initiated at a time, during an emulsion polymerization process so as to provide a resulting antimicrobial latex having a minimum inhibitory concentration (MIC) of 0.009 mg/mL, which is less than 15% lower than a MIC of 0.010 mg/mL for the standard. An example of criterion 2) of "not substantially diminished" is as follows: The bioactive additive can be introduced at a time, or introduction can be initiated at a time, during an emulsion polymerization process so as to provide a resulting antimicrobial latex having numerical activity rating of bioactivity based on an arbitrary activity scale of 5, which is less than 35% lower than the numerical activity rating of bioactivity of 7 for the standard. An example of criterion 3) of "not substantially diminished" is as follows: In an empirically- based descriptive rating system that includes contiguous rating levels of "excellent activity," "very good activity," and "good activity," the bioactive additive can be introduced at a time, or introduction can be initiated at a time, during an emulsion polymerization process so as to provide a resulting antimicrobial latex having an activity rating of "good activity," as compared to an activity rating of "excellent activity" for the standard. In any of these measurements of bioactivity, the bioactive additive can be introduced at any time during the polymerization process that provides this result, or introduction can be initiated at a time during the polymerization process that provides the result, disclosed above.

In another aspect, it is not necessary to introduce the active component into the monomer feed relatively late in the polymerization process. For example, the additive agent can also be added when about 0 percent, about 10 percent, about 20 percent, about 30 percent, about 40 percent, about 50 percent, about 60 percent, about 70 percent, about 80 percent, about 90 percent, or about 100 percent of the monomer has been fed into the polymerization reactor. In this aspect, the emulsion polymerization is initiated at a time when all components of the composition are not present from the time of initiation, but some are added at various times after initiating the polymerization, including, but not limited to, the at least one active component. Also in this aspect, the Applicant's intent is to disclose any and all ranges between such numbers, and to claim individually each possible number that such ranges could reasonably encompass, as well as any sub-ranges and combinations of sub-ranges encompassed therein.

In another aspect, polymerization can be effected at a range of temperatures, typically selected between the lowest temperature that affords reasonable polymerization rates, and the highest temperature allowable fiat does not result in substantial degradation or decomposition of the antimicrobial active ingredient. In one aspect, the polymerization can be carried out at the lowest temperature possible such that polymerization proceeds. In this case, the polymerization temperature should be sufficiently low to not substantially degrade or decompose any active ingredient that is incorporated, yet high enough such that polymerization rates and times are adequate for useful production of the final latex polymer.

The active agent can also be fed as a pre-emulsion made by emulsifying a mixture of monomer, additive, surfactants, water, and the like, using methods and materials known to one of ordinary skill in the art. For example, in this aspect, the dispersions can be made, among other ways, by using a relatively concentrated amount of the additive and dispersing by using surfactants, dispersants, and the like, and typically employing a mixing device such as a high speed mixer, a homogenizer, an Eppenbach mixer, or similar devices. Moreover, any other conceivable process or process known to one of ordinary skill that provides emulsion polymers in which the additive is a dispersion, an emulsion, a suspension, or the like, or substantially dissolved in the monomer mixture prior to polymerization, can be utilized.

In one aspect, useful active agents that provide antifungal and antibacterial properties can be, in many cases, susceptible to oxidation or reduction, especially when exposed to higher temperatures. Therefore in addition to bioactive agent solubility, another aspect of selecting and incorporating bioactive agents is diminishing any oxidation or reduction reaction that would degrade such components. The processes of this invention can typically achieve this result by controlling the polymerization temperature, adjusting the time period that the active ingredient is added into the reaction to control exposure to the polymerization temperature, by adding an appropriate oxidant or reductant at some time during the polymerization to diminish or moderate any redox degradation, or any combination of these methods.

In one further aspect of the present invention, the at least one bioactive component can be selected independently from undecylenic acid; undecylenic alcohol; the reaction product of undecylenic acid with hydroxylethyl (meth)acrylate or polyethylene glycol (meth)acrylate; the reaction product of undecylenic alcohol with (meth)acrylic add, maleic anhydride, or itaconic acid; chitosan or modified chitosans; or any combination thereof. Additional active components that can be used in the present invention are provided in U.S. Patent Application Pubflcation Number 2005/0003163, to Krishnan, which is incorporated herein by reference in its entirety. Another aspect of this invention provides that the at least one active component can be selected independently from copper, copper salts, silver, silver salts, zinc, zinc salts, silver oxide, zinc oxide, chlorhexidine, chlorhexidine gluconate, glutaral, halazone, hexachlorophene, nitrofurazone, nitromersol, povidone-iodine, thimerosol, Ci- to C₅-parabens, hypochlorite salts, clofucarban, clorophene, poloxamer- iodine, phenolics, mafenide acetate, aminacrine hydrochloride, quaternary ammonium salts, oxychlorosene, metabromsalan, merbromin, dibromsalan, glyceryl laurate, pyrithione salts, sodium pyrithione, zinc pyrithione, (dodecyl) (diethylenediamine) glycine, (dodecyl) (aminopropyl) glycine, phenol, m-cresol, o-cresol, p-cresol, o-phenyl-phenol, resorcinol, vinyl phenol, polymeric guanidines, polymyxins, bacitracin, circulin, octapeptins, lysozmye, lysostaphin, cellulytic enzymes, vancomycin, ristocetin, actinoidins, avoparcins, tyrocidin A, gramicidin S, polyoxin D, tunicamycin, neomycin, streptomycin, or any combination thereof.

Yet another aspect of this invention provides that the at least one active component can exhibit fungicidal activity. In this aspect, suitable fungicides that are applicable to this disclosure include, but are not limited to, azoles, quaternary ammonium compounds, dithiocarbamates, dicarboximides, or any combination thereof. For example, in this aspect, an azole fungicide can be selected from propiconazole, tebuconazole, azaconazole, biternatol, bromuconazole, cyproconazole, diniconazole, fenbuconazole, flusilazole, flutnafol, imazalil, imibenconazole, metconazole, paclobutrazol, perfuazoate, penconazole, simeconazole, triadimefon, triadimenol, uniconazole, or any combination thereof. Also in this aspect, a dithiocarbamate fungicide can be selected from mancozeb, maneb, metiram, zineb, or any combination thereof.

In another aspect, suitable fungicides can include, but are not limited to, fludioxonil, fluquinconazole, difenoconazole, 4,5-dimethyl-Λ/-(2-propenyl)-2-(trimethylsilyl)-3- thiophenecarboxamide (sylthiopham), hexaconazole, etaconazole, triti con azole, flutriafol, epoxiconazole, bromuconazote, tetraconazole, myclobutanil, bitertanol, pyremethanil, cyprodinil, tridemorph, fenpropimorph, kresoxim-methyl, azoxystrobin, ZEN90160™, fenpiclonil, benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, orfurace, oxadixyl, carboxin, prochloraz, triflumizole, pyrifenox, acibenzolar-S-methyl, chlorothalonil, cymoxanil, dimethomorph, famoxadone, quinoxyfen, fenpropidine, spiroxamine, triazoxide, BAS50001 F™, hymexazole, pencycuron, fenamidone, guazatine, and the like, including any combination thereof. Still another aspect of this invention provides that suitable fungicides can include, but are not limited to, benomyl (also known as benlate), captan, carbendazim, capropamid, ethirimol, flutolanil, fosetyl-aluminum, fuberidazole, hymexanol, kasugamycin, iminoctadine-triacetate, ipconazole, iprodione, mepronil, metalaxyl-M (mefenoxam), nuarimol, oxine-copper, oxolinic acid, perfurazoate, propamocarb hydrochloride, pyroquilon, quintozene (also known as PCNB), silthiopham, MON™ 65500, tecnazene, thiabendazole, thifluzamide, thiophenate-methyl, thiram, tolclofos-methyl, triflumizole, and the like, including any combination thereof. Moreover any combination or mixture of any of these fungicides can be employed.

In a further aspect of the present invention, the at least one active component can be a hydrophobic component selected independently from natural plant-based waxes, animal derived waxes, natural and synthetic mineral waxes and synthetic waxes such as paraffin, carnauba, ozocertie, montan wax, polyolefin waxes, such as, for example, polybutylene, beeswax, or lanolin, candelilla and carnauba wax; alcohols comprising a carbon chain length of greater than two, preferably greater than four carbons, especially fatty alcohols such as cetyl alcohol, stearyl alcohol, cetostearyl alcohol, behenyl alcohol, propylene glycols, myristyl alcohols, arachidyl alcohol, lignoceryl alcohol; esters of the aforementioned alcohols such as stearates and myristates; metal stearates such as calcium stearate, zinc stearate, magnesium stearate or barium stearate; carboxylic acids such as caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, palmitic acid, behenic acid, terephthalic acid, phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, cyclohexanedicarboxylic acid, cyclohexanediacetic acid, succinic acid, adipic acid, and sebacic acid, especially carboxylic acids having a chain length greater than three carbons; fatty acids such as stearic acid, oleic acid, undecylenic acid and linoleicacid; oils such as perfume oils, essential oils, vegetable oil, fish oil, paraffin oil and mineral oil; fatty amides including primary amides such as stearamide, oleamide, erucamide, secondary amides such as stearyl stearamide, stearyl erucamide, bis amides such as ethylene bis stearamide, ethylene bis oleamide, alkanolamides such as coco mono ethanolamide, coco diethanolamide, oleic diethanolanide, lauric diethanolamide and stearic diethanolamide, as well as other various fatty amides such as caprylamide, pelargonamide, capramide, lauramide, myristamide, palmitamide, stearamide, arachidamide, behenamide, stearyl stearamide, palmitoleamide, oleamide, erucamide, linoleamide, linolenamide, oleyl palmitamide, stearyl erucamide, erucyl erucamide, oleyl oleamide, erucyl stearamide, and ricinoleamide; fatty bisamides such as ethylenebisstearamide, ethylenebisoleamide and ethylenebis 12-hydroxystearamide or any combination thereof.

In another aspect of the present invention, the at least one active component can be a cosmeceutical or nutraceutical ingredient. For example, the active component may be a moisturizing or anti-wrinkle/anti-aging agent ingredient such as glycerin, propylene glycol, polyethylene glycol, hyaluronic acid, chondroitin sulfate, elastin, collagen, polysaccharide, glycosaminoglycan, ascorbic acid, ascorbic acid derivatives, glucosamine ascorbate, arginine ascorbate, lysine or tyrosine ascorbate, gluthathione ascorbate, nicotinamide ascorbate, niacin ascorbate, allantoin ascorbate, creatine ascorbate, creatinine ascorbate, chondroitin ascorbate, chitosan ascorbate, DNA ascorbate, camosine ascorbate, tocotrienol, rutin, quercetin, hesperedin, diosmin, mangiferin, mangostin, cyanidin, astaxanthin, lutein, lycopene, resveratrol, tetrahydrocurcumin, rosmarinic acid, hypericin, ellagic acid, chlorogenic acid, oleuropein. alpha-lipoic acid, niacinamide lipoate, gluthathione, andrographolide, carnosine, niacinamide, polyphenols, pycnogenol and mixtures thereof; UV blocker and absorber ingredients such as benzophenones, benzotriazoles, homosalates, alkyl cinnamates, salicylates such as octyl salicylate, dibenzoylmethanes, anthranilates, methylbenzylidenes, octyl triazones, 2-phenylbenzimidazole-5-sulfonic acid, octocrylene, triazines, cinnamates, cyanoacrylates, dicyano ethylenes, etocrilene, drometrizole thsiloxane, bisethylhexyloxyphenol methoxyphenol triazine, drometrizole, dioctyl butamido triazone, terephthalylidene dicamphor sulfonic acid and para-aminobenzoates as well as ester derivatives thereof; antiacne agents such as salicylic acid; anti-dandruff agents such as zinc pyrithione; skin bronzing or tanning agent ingredients such as dihydroxyacetone, erytrulose, melanin; antioxidants such as vitamin C and derivatives thereof (e.g. ascorbyl acetate, ascorbyl phosphate and ascorbyl palmitate), vitamin A and derivatives thereof; folic acid and derivatives thereof; vitamin E and derivatives thereof such as tocopheryl acetate, flavons, or flavonoids, amino acids such as histidine, glycine, tyrosine, tryptophan, and derivatives thereof; carotenoids and carotenes; uric acid and derivatives thereof; citric acid, lactic acid, malic acid; stilbenes and derivatives thereof; and pomegranate extracts; vitamin K1 or K2, vitamin K1 oxide orvitamin K2 oxide, hormones, minerals, plant or botanical extracts, anti-inflammatory agents, concentrates of plant extracts, emollients, skin protectants, humectants, silicones, skin soothing ingredients, analgesics or anti-itch agents, skin penetration enhancers, solubilizers, alkaloids and processing aids; coloring agents including various dyes and pigments; and perfumes or fragrances for the body; or any combination thereof. In one embodiment of the active cationic polymer latex, a sunscreen may be formulated comprising at least one ultraviolet blocker synergistically used in combination with zinc oxide or titanium oxide to provide broader UV/Visible spectrum protection. The at least one ultraviolet blocker can be bound to the polymer or dispersed or encapsulated within the polymer.

The at least one active component can be a free radical scavenger such as cuprous halide, cupric halide, cupric acetate, cupric formate, cuprous acetate, cuprous formate, ferrous halide, ferric halide, ferrous sulfate, ferric sulfate, cysteine, glutathione, N- acetylcysteine, L-alpha-acetamido-beta mercaptopropionic acid, S-nitroso-glutathione, N- acetyl-3-mercapto-alanine, butylated hydroxyanisole, butylated hydroxytoluene, L-2- oxothiazolidrie-4-carboxylate, desferrioxamine, allopurinol, superoxide dismutase and salen- manganese complexes; and any combination thereof.

In yet another aspect of this invention, amounts of active component that can be added during the emulsion polymerization can range from about 0.01 percent to about 40 percent by weight active additive, based on the total monomer weight. In another aspect, amounts of active component that can be added during the emulsion polymerization can range from about 0.025 percent to about 35 percent, from about 0.05 percent to about 30 percent, from about 0.1 percent to about 25 percent, from about 0.25 percent to about 20 percent, or from about 0.5 percent to about 15 percent by weight active additive, based on the total monomer weight. In this aspect, the Applicant's intent is to disclose individually each possible number that such ranges could reasonably encompass, as well as any subranges and combinations of sub-ranges encompassed therein. As compared to the amount of active component added as a "post-add," these concentrations of active additive are typically much larger than the post-add amounts. Among other things, this feature provides stable, concentrated dispersions that can be used as concentrates, as additives, or as concentrated dispersions that can be diluted and added to other systems which require the desired functionality, for example antimicrobial protection, moisturizing, UV protection, or the like.

As disclosed herein, in one aspect, the active component is typically dissolved in the monomer feed during the emulsion polymerization process. Thus, the active additive is typically at least partially soluble in one or more of the monomers employed. Further, the active additive can be moderately soluble, substantially soluble, or highly soluble in one or more of the monomers employed. This feature can allow, among other things, the incorporation of hydrophobic active ingredients, the use of high amounts and concentrations of active ingredients, greater control over the properties of the active agent, including for bioactive materials by enhancing the effectiveness of the antimicrobial properties, the use of minimal amounts of surfactant, and at least partial encapsulation of the active ingredient. In some instances, the latex polymer can substantially encapsulate the added active component, thus the latex polymer can function as a type of carrier for the active ingredients. This process also allows for the incorporation of the active ingredients without substantially degrading the activity of these compounds.

The composition of the invention may also include at least one post-added additive inorganic component In one embodiment, the at least one post-added additive inorganic component is not encapsulated but may aid in film formation. Suitable post-added additive inorganic components include, but are not limited to inorganic pigments including, but not limited to, titanium oxide or zinc oxide; black pigments, such as iron oxide blad<; fancy or multi-colored pigments, such as ultramarine or iron oxide red; lustrous pigments, metal effect pigments, pearlescent pigments as well as fluorescene or phosphorescent pigments; metal oxides, metal hydroxides and metal oxide hydrates, mixed phase pigments, sulfur- containing silicates, metal sulfides, complex metallo-cyanides, metal sulfates, metal chromates, metal molybdates, yellow iron oxide, brown iron oxide, manganese violet, sodium aluminum sulfosilicate, chromium oxide hydrate, ferric ferrocyanide, and cochineal. The post-added inorganic component can also be at least one inorganic solids such as seed, broken seed nut shells, beads, luff a particles, polyethylene balls, clay, calcium bentonite, kaolin, china clay, talc, perlite, mica, vermiculite, silicas, quartz powder, montmorillonite, calcium carbonate, a talc or a member of the mica family or a chemical equivalent thereof. Still further, the at least one post-added inorganic component can be a nano-inorganic material such as nano clays, nano oxides, nanotubes, or the like. Although implied, the present invention includes any combination thereof. The aforementioned post- added additives may also be at least partially encapsulated in the active cation ic polymer latex.

In another aspect, useful active additives in this invention can also be water soluble to any extent, including substantially water soluble, examples of which include o- phenylphenate (deprotonated o-phenylphenol), glycerin, propylene glycol, and similar agents. Thus, it is not necessary that such a hydrophilic active additive be soluble in any monomer that is to be polymerized. In still another aspect, useful active additives in this invention can be substantially insoluble in the monomers being polymerized and substantially insoluble in water. In this aspect, a dispersion of the active component can be made by, among other ways, by dispersing a certain concentration of the additive with the use of surfactants and the like, typically with the use of high speed mixers or homogenizers.

Because the post-added additives are typically dispersions that are post-mixed into a formulation, it can be difficult to adequately disperse the active additive into the polymer film, binder, coating, or the like, in which they are used. Moreover, typical additive dispersions that are used today can cause or be associated with moisture sensitivity and leaching of the additive, and many post-adds do not persist within the product for a sufficient period of time to provide adequate antifungal protection. The approach provided inthis disclosure allows the use of minimal surfactants to incorporate the active additives into the latex, and because the additives are introduced during the polymerization, they are typically encapsulated and are not easily released from the resulting latex. As a result, there can be less leaching of the active component, and better overall distribution of the active ingredient throughout the polymer film, binder, coating, and the like. Accordingly, this method can provide a potentially safer and more environmentally friendly dispersion, while also offering sustained functionality, such as antifungal or antibacterial protection. The active agent may also be released in a modified or controlled manner, if that is so desired, by appropriate selection of the polymer carrier and the active additive.

The process disclosed herein also allows the latex to be used as a concentrate, in contrast to the typical concentrate dispersions that are not as stable as those provided herein. As a result, the typical concentrate dispersions are not as easily manipulated and therefore cannot be incorporated as easily into a finished product, and can have deleterious effects on performance, such as water sensitivity, if dosage is increased. A concentrate of the latex provided herein can be diluted and used with or without other materials if such materials are needed to provide an adequate level of additive. Intimate incorporation of an active ingredient in this manner can afford a homogeneous distribution of the additive and result in superior and sustained performance compared to a pre-made dispersions.

An additional benefit of this intimate incorporation of the active agent is apparent in films that are prepared using these latices, which are observed to be substantially transparent. This feature highlights the highly homogeneous assimilation of the active agent into the latex particles and how this uniform distribution can provide useful properties for applications such as transparent active films. In one embodiment, the active ingredient can be released from the formulation, such as film, over a period of time (namely, modified or controlled release) and the period of release may depend on the surrounding conditions such as the pH of the environment where the polymer latex composition is utilized or the properties of the particular active ingredient. The particle size of the resulting polymer latex may be from about 15 nm to about 5 microns. More preferably, the particle size is from about 20 nm to about 2 microns and, most preferably, from about 50 nm to about 1 micron.

Other Additives

In another aspect of this disclosure, the latex provided herein can also include other additives to improve the one or more physical or mechanical properties of the polymer, the selection of which are known to one skilled in the art. Such additives include, for example, processing aids and performance aids, including but are not limited to, cross-linking agents, natural or synthetic binders, plasticizers, softeners, foam-inhibiting agents, froth aids, flame retardants, dispersing agents, pH-adjusting components, sequestering or chelating agents, or other functional components, or any suitable combination thereof.

Polymer A As will be appreciated by those skilled in the art, any cationic polymer latex may be used in the present invention. As one example, Polymer A represents a cationic polymer latex of the present invention.

Components 1 and 2 were charged to a reactor. Components 3, 4, and 5 were charged to an aqueous monomer tank. Components 6 and 7 were charged to the monomer tank. The initial and feed catalyst were prepared. Approximately 10% of each monomer was charge fed to reaction. The reaction vessel was purged w/ N₂ and heated to approximately 155⁰F. While holding at temp, components 8 and 9 were charged. The reaction was held for 30 min. The feeds were initiated, with aqueous monomer over approximately 5 hours, monomer over approximately 5 hours, and cationic over approximately 5.5 hrs. (330 min.) Components 12, 13, 14, and 15 were charged and the reaction was held for 15 min. Components 16, 17, 18, and 19 were charged and the reaction was held for 15 min. The reaction was allowed to cool.

Polymer A has a actual solids content of 41.10% and -100% conversion. The particle size is 140.O nM. The viscosity is 117.00. The final pH is 3.1. Exemplary Substrates and Applications for Active Cationic Polymer Latices

The deposition of the latex polymer coatings of this disclosure on any number of different substrates, such as textiles, metal, cellulosic materials, plastics, and the like, can impart desired end-use performance properties to those materials, and therefore tailor the substrates for a range of applications. For example, in one aspect, the present disclosure provides a treated fibrous material which can comprise at least one fiber and at least one active cationic polymer latex as provided herein. In one aspect, the treated fibrous material can comprise at least one fiber and at least one active cationic polymer latex deposited on, or associated with, the at least one fiber. If desired, the active cationic polymer can be applied to the fiber in the form of a powder, or the polymer composition can be deposited on the fiber by any suitable method known to the skilled artisan.

As used herein, the term "fiber" is intended to be broadly construed and can include single or multiple filaments that can be present in a variety of ways. It should be appreciated that only a single fiber can be treated with the active cationic polymer latex of the invention if so desired. Fibers that can be used in conjunction with this invention can encompass natural fibers, synthetic fibers, or any combination or mixture thereof. Natural fibers include, but are not limited to, animal fibers (for example, silk and wool); mineral fibers (for example, asbestos); and vegetable-based fibers (for example, cotton, flax, jute, and ramie). Synthetic fibers include, but are not limited to, those made from polymers such as polyamides, polyesters, acrylics, and polyolefins. Other examples of fibers include, but are not limited to, rayon and inorganic substances extruded in fibrous form such as glass, boron, boron carbide, boron nitride, carbon, graphite, aluminum silicate, fused silica, and metals such as steel. In another aspect, cellulosic or wood fibers also can be treated with the bioactive cationic polymer latex of the invention if so desired. Recycled fibers using any suitable fiber such as the above materials may also be employed. Any mixture of fibers can be treated with the active cationic polymer latex of the invention if so desired.

The treated fibrous material can, in another aspect, have at least one other polymeric layer deposited on the fiber so as to form a composite fibrous structure, thus multiple polymeric layers of various types can be used if desired. For example, anionic polymer latices may be deposited on the treated fibrous material to enhance specific properties of the treated fibrous material. In another aspect, the fibrous material can be treated in a sequential fashion using, alternately, active cationic polymer latices and anionic polymer latices, to form multiple layered structure. While not intending to be bound by theory, it is thought that simple coulombic interactions between cationic and anionic polymers enhance the stability of such structures, leading to treated fibrous materials that are robust. Layers of various other polymers that do not contain any active agent can be employed similarly, for example, deposited on the cationic polymer latex which is present on the fibrous material to form a composite structure. In this fashion, unique layering architecture can be constructed with specially modified surfaces in accordance with this invention.

In a further aspect, the present invention also provides an article of manufacture comprising a substrate and an active cationic polymer latex deposited or positioned thereon, as provided herein. For the purposes of this disclosure, the term "substrate" is intended to be construed and interpreted broadly to include all those formed from inorganic materials, organic materials, composites thereof, mixtures thereof, or any type of combination thereof. For example, the substrate can encompass, but is not limited to, fibers, fillers, pigments, and the like, as well as other organic and inorganic materials.

In one aspect of this invention, as disclosed herein, a fibrous substrate can be employed. The term "fibrous substrate" is also intended to be construed and interpreted broadly to include at least all the fibers, woven textiles, and non-woven textiles disclosed herein. Thus, the fibrous substrate may be present, for example, in the form of a web, a yarn, a fabric, a textile substrate, and the like. Further examples of fibrous substrates include, but are not limited to, natural fibers such as cotton and wool to synthetic fibers such as nylon, acrylics, polyesters, urethanes, and the like. Known application processes can be used to apply the bioactive cationic polymer latex, such as rod/knife coating, impregnation, back coatings, printing, as pretreatments on individual fibers, or as a finished good. Also as used herein, the term "textile substrate" can be defined according to its use in U.S. Patent Number 5,403,640 to Krishnan et al., the disclosure of which is incorporated herein by reference in its entirety. In this aspect, for example, "textile substrate" can encompass a fiber, a web, a yarn, a thread, a sliver, a woven fabric, a knitted fabric, a non-woven fabric, an upholstery fabric, a tufted carpet, a pile carpet, and the like, including any combination thereof, formed from any of the fibers described herein.

The active cationic latex composition of this invention also can be applied to a wide variety of plastic or rubber substrates. Examples of such materials include, but are not limited to, commodity molded thermoplastics such as polyolefins; engineering thermoplastics such as polysulfones, acetals, polycarbonates, and the like; thermosets such as epoxies, urethanes, and related materials; and as extruded or blown films. The polymer could be applied as a coating on the surface by rod/knife coating, spray, dipping, as a laminate coating during the extrusion process, or as a coating applied in the mold during the molding process. Rubber products could include sheets, extruded/molded articles, composites, and the like. In another aspect, the active cationic latex compositions of this invention also can be deployed in solid form. In this aspect, for example, the inventive latices can be coagulated or spray-dried to provide the solid active cationic latex, which can be employed in solid form as an additive in plastic products, in processes such as extrusion or blow molding, as additives for various polyethylenes, polypropylenes, and the like, and in any number of other polymer and plastic applications.

The active cationic latex composition of this invention also can be applied to wood or metal substrates. In this aspect, suitable substrates would include all kinds of natural and engineered wood substrates. Suitable metal substrates would include both metals and metal alloys, such as carbon steel, stainless steel, and including solid steel bars, sheets, coils, ropes, and such, wherein the composition is applied as a coating by one of the numerous processes such as spraying dipping, brushing, roller coating, and related methods.

In this context, an article of manufacture comprising a substrate and an active cationic polymer latex deposited or positioned thereon can be made in accordance with standard procedures known to one of ordinary skill in the relevant art. The article of manufacture can have, in another aspect, at least one other polymeric layer deposited thereon so as to form a composite structure, thus multiple polymeric layers of various types can be used if desired. For example, other layers of various polymers can be deposited on the bioactive cationic polymer latex which is present in the article of manufacture to form a composite structure. In this aspect, deposition of a bioactive cationic latex can be followed by the deposition of an anionic latex or other polymers to enhance specific properties of the article of manufacture. Thus, uniquely tailored articles with specially modified surfaces can be made in accordance with the present invention.

In a broader aspect, the present invention also provides a coated material comprising any material and an active cationic polymer latex deposited or positioned thereon, wherein additional layers of other materials optionally can be used in combination with the active cationic polymer latex of this invention. As used herein, the term "material" is intended to be used broadly to include, but not be limited to, any inorganic material, any organic material, any composite thereof, or any combination thereof. Examples of suitable materials include, but are not limited to, a fiber, a filler, a particle, a pigment, composites thereof, combinations thereof, mixtures thereof, and the like.

A multiple deposition process can also be used to make composite films that have applications in areas other than textiles and fibrous materials. In one aspect, for example, an active cationic polymer latex of this invention can be used to fabricate multilayer elastomeric gloves. Cellulosic structures can also be made using the bioactive cationic polymer latex provided herein including, but not limited to, cellulosic composites and heavy duty cellulosic structures. Examples of cellulosic composites include, but are not limited to, those composites relating to filtration, shoe insoles, flooring felt, gasketing, and the like. Heavy duty cellulosic structures include, but are not limited to, dunnage bags, industrial wipes, and related structures. In a further aspect, the deposition process and active cationic polymer latex of this invention also can be used in other technology arts including, but not limited to, flocculants, wet and dry strength additives for papermaking, retention aids, cement modifications, dye fixation, redispersible powders, and the like.

The present invention can afford certain advantages as compared to previous methods used to fabricate active materials. In this aspect, for example, an active cationic latex can be substantially deposited on a substrate such that residual active latex does not remain in the processing fluid medium, providing a potential advantage from an environmental standpoint. Moreover, active cationic latices can be preferentially deposited on any substrate that carries a net negative charge, and deposition can ocσur in a uniform manner, thereby using less latex polymer. Further to this aspect, and while not intending to be bound by theory, the active cationic latex is thought to be capable of forming substantially uniform monolayers of polymer material on a negatively charged substrate, thereby allowing the use of less latex to provide the desired coverage. Because the active cationic latices can be formed by existing emulsion polymerization processes, the fabrication methods advantageously allow for the preparation of high molecular weight polymers.

The active cationic polymer latices disclosed herein can also obviate the need for cationic retention aids and cationic surfactants. In one aspect, for example, the active cationic polymer latices can be substantially devoid of cationic surfactants. This feature can be particularly desirable because cationic surfactants generally are not retained well and can cause foaming and other adverse effects in aquatic environments. However in another aspect, this disclosure also provides for the use of active agents that can exhibit cationic surfactant behavior and/or for the use of retention aids. Moreover, if desired, the polymer latices can be devoid of conventional surfactants including, for example, nonionic surfactants.

As provided herein, the latex composition of the present invention can be applied to a wide variety of substrates using various techniques that are well known to one of ordinary skill in the art. As a result, there are numerous applications for the present invention, many of which are provided in the following listing. In this aspect, while this listing is not comprehensive, specific applications include, but are not limited to: textiles such as residential and commercial carpets or tiles; liquid and air filters for HVAC or vacuum cleaners, or automotive uses; medical surgical gowns, drapes, dressings, covers, and the like; pretreatment for fibers, printed or dyed fabrics for apparel, furnishings, sheets, towels, and the like; diapers and incontinence articles; interior automotive applications such as trim, upholstery, mats, filters, and such; upholstery coatings; laminating and bonding adhesives; foams for sound absorbency; foamed articles such as pillows and mattresses; belting or other machinery parts for food handling and the like; tapes such as masking tapes, surgical tape, industrial tapes, and the like; electrical, industrial, and household cleaning wipes, cloths, and sponges; shoe products such as insoles, box toes, and such; plastic and/or rubber items such as tool handles, tool grips, toys, rubber gloves, sheets, or other articles; machinery housing such as for computers, display and diagnostic devices or instrumentation; medical devices such as catheters, balloons, tubing, syringes, diagnostic kits, and the like; packaging or product protection, as applied to perishables, computer peripherals, semiconductors, memory chips, CDs, DVDs, and the like; impact modifiers for acrylics, polycarbonates, and such; overdips or underdipsfor gloves such as gloves for clean rooms; breathable films; antipenetrant for fabric supported gloves; cutting boards; extruded and blown films for packaging; paper products such as vacuum bags, book covers, air filters, liquid filters, wallcoverings, wet and dry wipes, tissues, and such; felt for vinyl floor coverings; molded pulp applications; packaging such as boxes, cartons, molded articles, and related items; size press coatings for gift wraps, ink jet media, breathable coatings, and the like; wet end additives in paper, tapes, labels for use in masking, surgical applications, general purpose applications, and such; binders for use in paper; binders for use in wallboard such as gypsum wallboard and the like; adhesives for use in tapes, labels, decals, films, book bindings, pressure sensitive applications, flexible packaging and laminating adhesive (FPLA), and the like; inorganic and/or organic materials such as coating or encapsulation of fillers or pigments, construction sealers and grouts, gypsum wallboard coatings or binders, exterior or interior coatings, and the like; tile adhesives; floor coatings for use in hospitals, clean rooms, clinics, schools, and related environments; coatings for hospital and medical environments; ceiling tiles; glass fiber coatings such as glass mats, insulation, filter materials, reinforced composites, and such; coatings for air conditioning or refrigeration coils; other components for air conditioning systems, heat exchangers, ion exchangers, process water systems including cooling water treatment, solar-powered units, coated pipes, and the like; kitchen items; components of sanitary equipment; components of water systems; operator units of devices such as touch panels; materials used in bathrooms such as shower curtains, fixtures, toilet items, and even jointing or sealing compounds; medical devices such as use in coatings for stents, implants, prostheses, catheters, tubing, contact lenses, contact lens cleaners or storage solutions, protective or backing films, medical instruments, and other medical devices for providing the sustained action of bioactive agents; articles which are contacted by large numbers of people such as telephone handsets, stair rails, door handles, window catches, grab straps and grab handles in public conveyances, and the like; wound or surgical treatments; wound or surgical dressings, including any layers such as absorbent layers of wound or surgical dressings; medical or athletic tapes; surgical drapes; tapes or tabs used in adhering medical devices such as sensors, electrodes, osteomy appliances, or the like; liquid disinfectants and cleaners; personal care or hygiene products such as shampoos, lotions, creams, hair and skin care products, deodorant body wash, cosmetics, toilet items, and the like; hygiene coatings of surfaces other than floors, such as in hospitals, clinics, schools, homes, offices, and the like; hard and porous surface coatings as applicable to walls, ceilings, floors, counter tops, and the like; decorative concrete; wood such as oriented strand board (OSB) coatings; decking and construction materials for coating or impregnation; composite construction materials; furniture coatings; hygiene coatings such as used in table tops, counter tops, door knobs, door handles, fixtures, and the like; flooring applications such as in laminates, hardwood flooring, and other composite flooring materials; decorative laminates such as table tops, counter tops, furniture, and the like; other construction materials such as roofing material, wall material, facades, fencing, or for wood protection applications; marine applications such as in boat hulls, docks, buoys, drilling platforms, or ballast water tanks; metal such as cabinets, door knobs, handles, fixtures, and such; and furniture, coatings as applicable to appliances, original equipment manufacture (OEM), and the like.

In one aspect, the antimicrobial formulations of the invention can be useful as a biofouling inhibitor, in particular, in cooling circuits. To prevent damage to cooling circuits by infestation with algae or bacteria, the circuits typically have to be cleaned frequently or be appropriately oversized. In the open cooling systems usually found in power plants and in chemical plants, the addition of microbiocidal substances, such as formalin, is generally not possible. Other microbiocidal substances are frequently highly corrosive or form foams, preventing their use in systems of this type. Deposition of bacteria or algae on components of the system can thus be effectively inhibited. Therefore, the formulations and materials of this invention can be quite useful in such applications.

In another aspect, the present invention can also provide a process for sterilizing cooling-water streams or process water systems, by adding antimicrobial formulations in dispersed form to the cooling water. The dispersed form can be obtained in the preparation process itself, for example, by emulsion polymerization as detailed herein, but also by precipitation polymerization, or suspension polymerization, or subsequently by milling of the antimicrobial polymer obtained by any of these methods, for example, in a jet mill.

An antimicrobial latex polymer of the present invention can be applied or used as a coating composition, which can be used for a wide variety of purposes in connection with which antimicrobial action is desired. For example, in one aspect, the antimicrobial latex polymers disclosed herein can be used in connection with a wide range of insulating materials such as wrapping materials for pipes, which are a particular risk of bacterial attack. Thus, the materials of the invention are useful when used in connection with elastomeric insulating materials. Such coating compositions can also be used in connection with industrial insulation, such as is used for insulating pipelines, examples being heating pipes, and for insulating valves and ducts. Moreover, antimicrobial latices disclosed herein can be used in conjunction with all thermal and/or acoustic insulations and related insulating materials for numerous end applications. The latices provided herein can also be used in conjunction with industrial foams and foam materials as substrates for antimicrobial coatings. Such coatings comprising the antimicrobial latices disclosed herein also can be used as coatings for air-conditioning plants, condensers, refrigerators and other refrigeration units, and also parts thereof, and also for coating compositions as paints for marine craft and for wood preservation. Coatings comprising the antimicrobial latices of this disclosure can also be employed as the coating of substrates such as metal, plastic, or ceramic, in hygiene installations, hospitals, or in the food industry, or any articles involving frequent contact of any type which may easily transmit infection pathogens, such as door handles, sanitary fittings, switches, and grips. In the case of such coatings the use of a coating composition in the form of powder coatings can be advantageous.

In addition, the latex polymer coatings containing at least one active component can be deposited on any number of different substrates to impart desired end-use performance properties to any of the aforementioned materials or provide a wide range of cosmeceutical or nutraceutical benefits. For example, in one aspect, the present polymer latex comprising at least one active component can be utilized in or as part of various moisturizing agents, anti-wrinkle agents, anti-aging agents, ultraviolet blockers and absorbers, skin bronzing or tanning agents, vitamins and herbal supplements, botanical extracts, free radical scavengers, coloring agents, hair dyes, fragrances and perfumes.

Applications of Active Latices to Medical Devices

The term "medical device" as used herein refers to any material, natural or artificial, that is inserted into a mammal, or used in the process of inserting a material into a mammal. Particular medical devices suited for application of the antimicrobial latices and compositions of this invention include, but are not limited to, peripherally insertable central venous catheters, dialysis catheters, long term tunneled central venous catheters, long term non- tunneled central venous catheters, peripheral venous catheters, short-term central venous catheters, arterial catheters, pulmonary artery Swan-Ganz catheters, urinary catheters, artificial urinary sphincters, long term urinary devices, urinary dilators, urinary stents, other urinary devices, tissue bonding urinary devices, penile prostheses, vascular grafts, vascular catheter ports, vascular dilators, extravascular dilators, vascular stents, extravascular stents, wound drain tubes, hydrocephalus shunts, ventricular catheters, peritoneal catheters, pacemaker systems, small or temporary joint replacements, heart valves, cardiac assist devices and the like, prosthesis including bone prosthesis, joint prosthesis, dental prosthesis, and the like.

In one aspect, the medical devices that can be used in conjunction with the active cationic latices of this invention include, but are not limited to, non-metallic materials such as thermoplastic or polymeric materials. Examples of such materials include rubber, plastic, polyethylene, polyurethane, silicone, GORTEX™ (polytetrafluoroethylene), DACRON™ (polyethylene tetraphthalate), polyvinyl chloride, TEFLON™ (polytetrafluoroethylene), elastomers, nylon and DACRON™ sealed with gelatin, collagen or albumin. As one example, the amount of each bioactive cationic latex used to coat the medical device varies to some extent, but is at least a sufficient amount to form an effective concentration to inhibit the growth of bacterial and fungal organisms.

In one aspect, the active latices can be used alone or in combination of two or more of them. Each active latex can comprise one or more active components as provided herein. Any application or use disclosed herein can further encompass the use of at least one active latex in conjunction with at least one other active agent that can be dispersed throughout the application surface. The amount of each active latex and each active agent used to impregnate the surface varies to some extent, but is at least of an effective concentration.

In one aspect, the bioactive agent can be selected from any pharmaceutical, for example, an antibiotic, an antiseptic, a disinfectant, or any combination thereof. In another aspect, the antimicrobial agent can be an antibiotic including, but not limited to, penicillins, cephalosporins, carbepenems, other beta-lactam antibiotics, aminoglycosides, macrolides, lincosamides, glycopeptjdes, tetracylines, chloramphenicol, quinolones, fucidins, sulfonamides, trimethoprims, rifamycins, oxalines, streptogramins, lipopeptides, ketolides, polyenes, azoles, echinocandins, or any combination thereof.

In one aspect, at least one pharmaceutical or drug can be applied to a medical device using bioactive latices provided herein, and used in combinations with drugs that can adhere to, rather than be encapsulated by, the bioactive latices. For example, a cationic bioactive latex coating can be applied as a coating to a medical device that can have an ionic charge. Subsequently, drugs having a complimentary charge can be applied to, and can bind to, the charged coating applied to the surface of device when the charged coating and the drug are exposed to one another. The strength of bonding between the drug and the coating can be used to influence how readily the drug can be released from the surface of the device. In one aspect, this disclosure provides for delivering an implant or medical device having this drug delivery feature to a selected anatomical site. In this aspect, typically drugs that are useful include, but are not limited to, antimicrobials and antibiotics such as neomycin and sulfa drugs, anti-inflammatory agents such as steroidal or nonsteroidal anti-inflammatory agents, or combinations thereof.

Although any methods, devices, and materials similar or equivalent to those described herein can be used in the practice or testing of the invention, the typical methods, devices and materials are herein described. All publications and patents mentioned herein are incorporated herein by reference for the purpose of describing and disclosing, for example, the constructs and methodologies that are described in the publications, which might be used in connection with the presently described invention. The publications discussed herein are provided solely for their disclosure prior to the filing date of the present application. Nothing herein is to be construed as an admission that the inventors are not entitled to antedate such disclosure by virtue of prior invention.

As used herein, the disclosure or claim of a range of any type, for example a range of temperatures, a range of concentrations, a range of numbers of atoms, a weight percent, or the like, the intent is to disclose or claim individually each possible number that such a range could reasonably encompass, as well as any sub-ranges and combinations of subranges encompassed therein. Thus, a disclosure or claim of a chemical moiety having a certain number of carbon atoms, the intent is to disclose or claim individually every possible number, sub-range, and combination of sub-ranges that such a number range could encompass, consistent with the disclosure herein. For example, the disclosure that R is selected from an alkyl group having up to 12 carbon atoms, or in alternative language a C₁ to Ci₂ alkyl group, as used herein, refers to an R group that can be selected from an alkyl group having 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 , or 12 carbon atoms, as well as any range between these two numbers for example a C₃ to C₈ alkyl group, and also including any combination of ranges between these two numbers for example a C₃ to C₅ and C₇ to C₁₀ alkyl group. Thus, Applicants retain the right to replace the terminology such as "group having up to 12 carbon atoms" with any individual number that such a range could reasonably encompass, as well as any sub-ranges and combinations of sub-ranges encompassed therein. In another example, by the disclosure that the molar ratio typically spans the range from about 0.1 to about 1.0, Applicants intend to recite that the molar ratio can be selected from about 0.1 :1 , about 0.2:1 , about 0.3:1 , about 0.4:1 , about 0.5:1 , about 0.6:1 , about 0.7:1 , about 0.8:1 , about 0.9:1, or about 1.0:1 , as well as any sub-ranges and combinations of sub-ranges encompassed therein. Similarly, the disclosure that a particular weight percent can be from about 80 percent to about 90 percent by weight, Applicants' intend to recite that the weight percent can be about 80 percent, about 81 percent, about 82 percent, about 83 percent, about 84 percent, about 85 percent, about 86 percent, about 87 percent, about 88 percent, about 89 percent, or about 90 percent, by weight.

Applicants reserve the right to proviso out or exclude any individual members of any such group, including any sub-ranges or combinations of sub-ranges within the group, that may be claimed according to a range or in any similar manner, if for any reason Applicants choose to claim less than the full measure of the disclosure, for example, to account for a reference that Applicants may be unaware of at the time of the filing of the application. Further, Applicants reserve the right to proviso out or exclude any individual substituents, additives, compounds, monomers, surfactants, structures, and the like, or any groups thereof, or any individual members of a claimed group, if for any reason Applicants choose to claim less than the full measure of the disclosure, for example, to account for a reference that Applicants may be unaware of at the time of the filing of the application.

For any particular chemical compound disclosed herein, any general disclosure or structure presented also encompasses all isomers, such as conformational isomers, regioisomers, stereoisomers, and the like, that can arise from a particular set of substituents. The general structure also encompasses all enantiomers, diastereomers, and other optical isomers whether in enantiomeric or racemic forms, as well as mixtures of stereoisomers, as the context requires.

The present invention is further illustrated by the following examples, which are not to be construed in any way as imposing limitations upon the scope thereof. On the contrary, it is to be clearly understood that resort can be had to various other aspects, embodiments, modifications, and equivalents thereof which, after reading the description herein, may suggest themselves to one of ordinary skill in the art without departing from the spirit of the present invention or the scope of the appended claims.

In the following examples, unless otherwise specified, the reagents were obtained from commercial sources. Reference to reagents may include reference to a generic description, a brand or trade name, or both. General procedures, including general synthetic testing procedures for cationic polymer latices, are provided in U.S. Patent Application Pub.cation Numbers 2005/0065284 and 2005/0003163, to Krishnan, each disclosure of which is incorporated herein by reference in its entirety.

DEMONSTRATIVE EXAMPLE 1 As one of ordinary skill in the art appreciates, deodorant compositions may comprise a variety of chemical components in various amounts. Table 1 sets forth a demonstrative deodorant composition and the amounts of each component. This demonstrative deodorant composition may be prepared by first combining components 1 and 3. Next, the preparer may slowly add the resulting mixture into component 2 in the presence of agitation and heat (75°C) and then add component 4 to the resulting batch and mix the batch until component 4 dissolves. Next, the preparer slowly adds component 5 to the batch, mixes the batch until component 5 dissolves, and then cools the batch to a temperature of 45⁰C. The preparer then adds components 6-7 to the batch and mixes until a uniform batch results. Lastly, the preparer homogenizes the batch at 4500 rpm for 10 minutes resulting in an deodorant formulation. Such deodorant compositions may be formulated as a roll-on, stick or spray and may, optionally, be combined with an antiperspirant.

Table 1

DEMONSTRATIVE EXAMPLE 2

Body wash formulations may comprise a variety of chemical components in various amounts. Table 2 sets forth a demonstrative body wash formulation and the amounts of each component. This demonstrative body wash formulation may be prepared by dissolving component 2 in component 1. Next, the preparer adds component 3, mixes and heats (75°C) the resulting batch to form a first phase. The preparer then combines components 4 and 5, heats to 70⁰C and mixes until the batch fully melts to form a second phase. Next, the preparer adds the second phase into the first phase with agitation and mixes until a uniform batch results. The preparer may then add components 6-8 one by one into the batch with mild agitation and cool to 40⁰C. Next, the preparer adds components 9 to the batch, mixes the batch and adjusts the pH to 6.0-6.5 with component 10, as needed. Finally, the preparer adjusts the viscosity to 7,000-15,000 CPS with a 20% NaCI solution, as needed. Within 30 minutes of preparation, the viscosity of the formulation of the present example was determined using a Brookfield RVT#4 at 20 RPM, 30 sec. At 12 hours post-preparation, viscosity was again determined using a Brookfield RVT#5 at 20 RPM, 30 sec.

Table 2

DEMONSTRATIVE EXAMPLE 3

As one of ordinary skill in the art appreciates, shampoo formulations may comprise a variety of chemical components in various amounts. Table 3 sets forth a demonstrative shampoo formulation (control) and the amounts of each component. This demonstrative shampoo formulation may be prepared by first combining components 1-5 (first phase) and heating the resulting phase to a temperature of 75^CC with slow mixing. Next, the preparer may combine components 6-7 (second phase) and heat the resulting phase to a temperature of 75°C with slow mixing. The preparer then adds the second phase to the first phase and mixes the two phases until a uniform batch at room temperature results. Next, components 8-9 may be added to the batch one at a time. Finally, the pH of the resulting batch may be adjusted to 6.0-6.5 with component 10. Table 3

SYNTHETIC EXAMPLE 4

A deodorant composition comprising at least one antimicrobial polymer component was prepared according to the method of Demonstrative Example 1 comprising the components set forth in Table 4.

Table 4

SYNTHETIC EXAMPLE 5

In the present example, a base body wash formulation was prepared according to the method of Demonstrative Example 2 comprising the components set forth in Table 5. The preservative, Glydant^® (DMDM Hydantoin), was mixed with component 10 and added to the batch just before pH was measured. To determine foam height, 5 grams of product and 145 grams of water were weighed and added into a blender. The product and water was grated for 10 seconds and poured into a 1000 ml graduated cylinder. The foam level was read, followed by a 2 minutes waiting period, and then the liquid level was read. To determine foam density, 10 grams of product and 145 grams of water were weighed and added into a blender. The product and water was grated for 10 seconds and the resulting foam was poured into a 100 ml graduated cylinder. A rubber stopper was then dropped into the graduated cylinder at which time a timer was started when the stopper reached the 80 ml mark. The timer was stopped when the stopper reached the 30 ml mark. The time was then recorded. Foam drainage was determined based on the amount of liquid collected at the bottom of the graduated cylinder once the stopper reached the 30 ml mark.

Table 5

SYNTHETIC EXAMPLE 6

In the present example, a base body wash formulation was prepared containing 0.2% polyquarternium-10, such as that sold under the tradename Polymer JR 400, without glycol stearate. The polyquarternium-10 was dispersed in water and mixed until hydrated before adding components 1-3 set forth in Table 6. The body wash was then prepared according to the method set forth in Demonstrative Example 2. The viscosity, foam height, foam drainage, and foam density were measured according to the methods set forth in Synthetic Example 5.

Table 6

SYNTHETIC EXAMPLE 7

In the present example, a base body wash formulation was prepared containing 0.2% polyquarternium-10 according the method set forth in Demonstrative Example 2. Table 7 sets forth the body wash formulation of the present example and the amounts of each component. The viscosity, foam height, foam drainage and foam density were measured according to the methods set forth in Synthetic Example 5.

Table 7

SYNTHETIC EXAMPLE 8

In the present example, a body wash formulation was prepared containing a 1.0% polymeric material (without glycol stearate) according the method set forth in Demonstrative Example 2. Table 8 sets forth the body wash formulation of the present example and the amounts of each component. As described in more detail herein, the present example includes Polymer A. The viscosity, foam height, foam drainage, and foam density were measured according to the methods set forth in Synthetic Example 5.

Table 8

SYNTHETIC EXAMPLE 9

In the present example, yet another base body wash formulation was prepared containing a 1.0% poly meric material according the method set forth in Demonstrative Example 2. Table 9 sets forth the body wash formulation of the present example and the amounts of each component. The viscosity, foam height, foam drainage and foam density were measured according to the methods set forth in Synthetic Example 5.

Table 9

SYNTHETIC EXAMPLE 10

Shampoo formulations were prepared comprising at least one polymer for evaluation. In the present example, a shampoo formulation was prepared according the method set forth in Demonstrative Example 3 and contained an antimicrobial polymer. Table 11 sets forth the shampoo formulation and the amounts of each component. Viscosity was determined using a Brookfield RVT#5 at 20 RPM. To determine foam height, 5 grams of product and 145 grams of water were weighed and added into a blender. The product and water was grated for 10 seconds and poured into a 1000 ml graduated cylinder. The foam level was read, followed by a 2 minutes waiting period, and then the liquid level was read. To determine foam density, 10 grams of product and 145 grams of water were weighed and added into a blender. The product and water was grated for 10 seconds and the resulting foam was poured into a 100 ml graduated cylinder. A rubber stopper was then dropped into the graduated cylinder at which time a timer was started when the stopper reached the 80 ml mark. The timer was stopped when the stopper reached the 30 ml mark. The time was then recorded. Foam drainage was determined based on the amount of liquid collected at the bottom of the graduated cylinder once the stopper reached the 30 ml mark.

Table 11

SYNTHETIC EXAMPLE 11

In the present example, another shampoo formulation was prepared according to Demonstrative Example 3 and contained a fragrance but no antimicrobial polymeric material. Table 12 sets forth the shampoo formulation and the amounts of each component. The pH of the resulting batch was adjusted to 6.69 with component 10. The viscosity, foam height, foam drainage and foam density were measured according to the tests outlined in Synthetic Example 10.

Table 12

SYNTHETIC EXAMPLE 12

In the present example, another a shampoo formulation was prepared according to the method set forth in Demonstrative Example 3 that contained a fragrance as well as an antimicrobial polymeric material. Table 13 sets forth a shampoo formulation and the amounts of each component. The pH of the resulting batch was adjusted to 6.66 with component 11. The viscosity, foam height, foam drainage and foam density were measured according to the tests outlined in Synthetic Example 10. These physical properties for Demonstrative Example 3 and Synthetic Examples 10-12 are summarized in Table 14.

Table 13

Table 14

SYNTHETIC EXAMPLE 13 Active Cationic Latex Prepared by Early Introduction of a Bioactive Agent

A one-gallon reactor can be charged with the following ingredients: about 1142 g of water; about 5.95 g of the nonionic surfactant ABEX^® 2525 (Rhodia); about 11.90 g of methoxy polyethyleneglycolmethacrylate (MPEG 550 from Cognis); and about 31.7 g of dimethylaminoethyl methacrylate methyl chloride quaternary (AGEFLEX™ FM1Q75MC from Ciba Specialty Chemicals). The reactor contents then can be deoxygenated by subjecting the reactor to several vacuum / N₂ fill cycles, after which about 59.5 g of butyl acrylate and about 119 g of styrene can be added to the reactor. The reactor is again subjecting to several vacuum / N₂ fill cycles, after which the temperature of the reactor contents can be increased to about 165 ⁰F, at which time an initiator solution of about 23.80 g of water and about 2.38 g of WAKO V-50 (Wako Chemicals) is injected into the reaction mixture. This reaction mixture is maintained at about 165 ⁰F for approximately 30 minutes before starting the following feeds into the reactor.

After the 30 minute "hold period," the following components can be fed into the reactor:

1) A butadiene feed consisting of about 238 g of butadiene, fed over about 5 hours;

2) A mixed monomer feed of about 102 g of butyl acryiate, about 517 g of styrene, and about 119 g of any suitable bioactive agent such as those disclosed herein. The total feed time of the entire mix can be about 5 hours. The bioactive ingredient can be introduced into the mixed monomer feed after about 1 hour of the mixed monomer feed, which involves dissolving about 119 g of the bioactive agent in about 495 g of the styrene/butyl acrylate monomer mixture that is introduced into the reactor over the final 4- hour feed period of the mixed monomer feed;

3) An aqueous monomer feed consisting of about 152 g of water, about 47.60 g of MPEG 550 (Cognis), about 47.60 g of dimethyl aminoethylmethacrylate methyl chloride quaternary (AGEFLEX™ FM1Q75MC from Ciba Specialty Chemicals), and about 74.5 g of /V- methylol acrylamide. This aqueous monomer feed can be fed into the reactor over an approximately 3-hour period; and 4) An aqueous initiator feed consisting of about 202 g of water and about 4.8 g of WAKO™ V-50, which can be fed into the reactor over about 5.5 hours;

When addition of the feeds is completed, the reaction is continued until most (greater than about 98%) of the monomers have reacted. The reactor contents are then cooled down and the vacuum stripped to remove unreacted monomers and to raise the solids concentration to about 40 percent by weight. If necessary or desired, the pH of the latex can be adjusted as required before stripping the reaction volatiles.

SYNTHETIC EXAMPLE 14 Bioactive Active Cationic Latex Prepared by Late Introduction of a Bioactive Agent

An emulsion polymerization reaction can be conducted according to the details provided in Example 13, except that an approximately 49 g-sample of bioactive component can be introduced into the mixed monomer stream after about 4 hours of a 5 hour styrene/butyl acrylate feed. This process involves dissolving the bioactive agent in about 124 g of the styrene/butyl acrylate monomer mixture that is introduced into the reactor over the final 1-hour feed period of the mixed monomer feed.

SYNTHETIC EXAMPLE 15 Evaluation of Cationic Latex Incoφoraϋng Antifungal Agents

Antifungal wallboard was identified as a target for the evaluation of a cationic latex incorporating an antifungal agent. The goal of this example was to deliver the antifungal agent is through a cationic polymer incorporated into the paper facing of the gypsum wallboard in a conventional wet end process used for paper making.

Several cationic polymers were made, with a variety of antifungal additives incorporated into the polymers during the polymerization process, at various levels. The polymers were tested both as coatings on paper as well as by addition in a wet end process. The main antifungal evaluations were conducted based on ASTM G-21 and ASTM D-3273, which showed that the best antifungal results were obtained using a combination of two antifungal additives (propiconazole ("PZ') and tebuconazole ("TZ")).

The coating study indicated that a PZ/TZ level of 0.4% on a wet basis had a significant inhibitory effect, and that the PZ/TZ could be transported through the wet end and deposit cleanly on the paper. A series of cationic polymers (without any additive incorporated into the polymers) were evaluated for antibacterial properties (both low and high levels of cationic monomer) using AATCC-100 method. The polymers showed >99% kill, whereas a control polymer that was not cationic did not show any kill. Results and Discussions:

The antifungal additives used in this study are shown inTable-15

Table- 15 - List of additives used in polymerization

Ideally, the materials are substantially unreactive during the polymerization conditions, so they are not degraded during polymerization. In some embodiments, low levels of additive might be observed, whether due to degradation, or difficulty in extraction from the polymer latex. In any case, retention of the additive in the latex leads to retention of antifungal properties in the finished paper.

Initial polymerization work with Arnica! showed that the Amical was degraded when it was incorporated in relatively high amounts. The polymerization temperature was investigated as a potential contributor to degradation, and it was kept as low as was feasible (typically <70°C). The samples were stripped at the end of polymerization to the desired solids content.

Initial testing of the samples is shown in Table 16. This testing involved ASTM G-21 , in which fungi were inoculated directly on the coated paper samples and then maintained in a humidity chamber for 28 days. The latex coating was applied on the paper using a # 10 Meyer rod, and only a single coat was applied. However, it was determined that this was not an adequate coating thickness, considering that the paper may not have been fully covered, and this is reflected in the fungal growth data shown in Figure 1. The latex samples with the PTJlZ combination (MB-38 set forth in Synthetic Example 13; MB-39 set forth in Synthetic Example 14) exhibited potent fungal inhibition characteristics.

Additive levels recovered from the latex samples were determined and compared with the amounts of additives originally added. This data is summarized in Table 16.

Table-16- Analytical data on the additive levels in latex

In this example, Amical tended to be poorly incorporated into the latex even when significant amounts were added during polymerization. Significant amounts of the PZ/TZ combination, as well astriclosan, were recovered.

The results observed in the ASTM G-21 study were also duplicated in a shorter (7 day incubation) fungai study (referred to herein as 30-III). The results are shown in Figure 2. Microban Z01 , zinc pyrithione at 0.4% (wet basis), and PZ/TZ all performed well. The 30-III fungal test was based on making a 1"X1" chip of the dried latex and inoculating the fungal species directly on to the sample and then observing its growth after 7 days. This is not as rigorous a test as the G-21 test, but gave a quick indication of the efficacy of the additives. In this test, the Amical samples showed some fungal inhibition.

In this test, the cationic polymers by themselves, without any additive, did not exhibit significant fungal resistance qualities. Variation of the cationic charge did not seem to affect the antifungal performance. This is in contrast to a different antifungal test where a polymer film was inoculated with a fungal species and left in a humidity chamber for 6 months without any fungal growth. One reason for this result could be that the films tested were much thicker films (about 4 mils or 100 microns) than those tested here. A second round of testing was performed using an increased coating thickness to ensure full coverage of the paper surface. The second round of testing of the coated paper samples were tested according to ASTM D-3273. In this study, the duration remained the same (28 days), but the fungal species were not directly inoculated on the surface. Rather, they were maintained in the humidity chamber as spores that would then land on the surface of the coated paper as in a real world example. The results of this study are outlined in Figure 3.

In this study, Amical and PZfTZ were effective, but Z01 did not perform well. The cationic polymers without any additive also did not seem to show antifungal properties, and appeared to be similar to the uncoated paper samples. The analytical data shown in Figure 3 was based on measurements of the coated sample before the start of the fungal study. The recovery of the additive from the paper is not quantitative.

The next phase of the study was to demonstrate that the same performance could be obtained through the wet end process same as in coated paper. The deposition of latex on to paper involved depositing a fixed amount of latex (10% based on fiber) on to softwood fibers and sending these for antifungal evaluations The amount of additive in the latex was around 7.5% (in one sample, 2.5% PZ and 5% TZ by weight). This data is summarized in Figure 4. In this study, paper samples were made using the cationic latex with (MB-87) and without the PZ/TZ additive (MB-86). As mentioned earlier, the amount of PZ/TZ additive in the latex was -7.5% (dry basis). This would give about 6680 ppm of PZ/TZ in the finished paper and 10% polymer or latex on a fiber basis weight.

A dispersion of PZ/TZ (M-3078) was also provided, with an activity of 28%. This was used as a post add with the cationic latex MB-86 to give essentially the same amount of PZ/TZ. Hence, the post added sample with the dispersion had a PZ/TZ concentration of about 10%, much more than that of the polymerized latex sample, and would result in a PZfTZ concentration of around 9000 ppm in the finished paper. The antifungal results of the plain latex (MB-86), MB-86 with post added PZ/TZ, and the polymerized PZ/TZ sample MB- 87 is shown in Figure 4.

Just as in the coated sample study, the paper with just the cationic latex did not pass the fungal D-3273 test. Both the post added and the polymerized PZ/TZ samples passed the test. It should be noted that the polymerized additive sample (MB-87) had -3000 ppm less of the PZ/TZ, but still seemed to perform as well as or slightly better than the post added sample. No fungal growth was observed.

Experiments were conducted to demonstrate the incorporation of various active ingredients. The active ingredients are incorporated into the polymer during the emulsion polymerization process by dissolving the active components in the monomer stream. One of ordinary skill in the art will appreciate that one or more latex polymers may be utilized in the resulting composition.

SYNTHETIC EXAMPLE 16

An experiment was conducted to evaluate the incorporation of bound UV stabilizer, 2-(4-benzoyl-3-hydroxyphenoxy) ethyl acrylate, hereinafter referred to as BHPEA (available from Bimax^®, Incorporated), as an active ingredient such that the resulting latex particles function as carriers for the active ingredient. The resulting latex formulation can be used as a sunscreen. Alternatively, an acceptable amount of UV stabilizer can be post-added (unbound) and dispersed in the latex composition in addition to the bound UV stabilizer.

In the present example, the emulsion polymerization was carried out such that the active agents were incorporated into the polymer during the emulsion polymerization by dissolving the active component in a monomer stream. Table 17 sets forth a cationic latex formulation and the amounts of each component. First, components 1-4 were charged to the reactor. Next, components 5-9 were added to monomer tank. Components 10-12 were then added to the monomer tank. The initial catalyst (components 13-14) and feed catalyst (components 15-16) were then prepared. Next, 10% of a feed comprising components 10- 11 were fed to the reaction. The reaction vessel was then purged with an inert gas (nitrogen) and heated to a temperature of 14O⁰F. Once the target temperature was attained, the reaction was held for 30 minutes. Aqueous monomer (components 5-9) was then fed for 3 hours along with the monomer stream (components 10-12) for 5 hours. The catalyst feed was fed to the reaction for 5.5 hours. After two hours, the reaction temperature was elevated to 170⁰F. Next, components 17-20 were charged to the reaction and held for 15 minutes. Lastly, the reaction was cooled.

The components listed in the tables below are abbreviated using ordinary conventions. Definitions for some terms are provided. If a particular abbreviation is not specifically defined herein, the abbreviation should not be considered indefinite but rather used within the ordinary vernacular of those skilled in the art.

DW — deionized water; BA - butyl acrylate;

Abex^® 2525 -- nonionic surfactant; MMA - methyl methacrylate;

FMQ75MC - a cationic monomer, N₁N- Wako V50 - 2,2'-azo bis (2- dimethylaminoethyl methacrylate methyl methylpropionamidine)dihydrochloride chloride quaternary (where FMQ80MC, TBHP - tertiarybutylhdroperoxide; likewise, is chemically the same, with AWC - sodium formaldehyde differences in activity); sulfoxylate;

MPEG550MA - methoxypolyethyleneglycol SFS - sodium formaldehyde methacrylate; sulfoxylate;

Special NMA - proprietary blend of N- STY - styrene; methylol acrylamide and acrylamide; ST — styrene;

Table 17

The actual % solids of the resulting latex polymer formulation was determined via a microwave solids oven. Particle size of the resulting latex polymer formulation was determined by via a Coulter^® light scattering particle size analyzer. Viscosity was determined using a Brookfield DV-E viscometer #4 at 20 RPM. The test results are summarized in Table 18.

Table 18

SYNTHETIC EXAMPLE 17

Experiments were conducted to evaluate the incorporation of a different amount of BHPEA, as an active ingredient according to the method of preparation set forth in Synthetic Example 16. Table 19 sets forth a cationic latex polymeric formulation and the amounts of each component. The resulting physical properties are summarized in Table 20.

Table 19

Table 20

Final Physical Properties

SYNTHETIC EXAMPLE 18

In the present example, the active ingredient silicone polyether copolymer (available as Y-15790 from GE Silicones) was incorporated in the polymer latex formulation. Table 21 sets forth the cationic latex formulation and the varying amounts of each component. Components 1 and 2 were charged to the reactor. Next, components 2-4 were charged to the monomer tank followed by components 5-6. The initial catalyst (components 9-10) and feed catalyst (components 11-12) were prepared and 10% of each monomer (component 3-8) was charged and fed to the reaction. Next, the reaction vessel was purged with an inert gas (nitrogen) and heated to a temperature of 70⁰C . Once reaction attained 70⁰C, components 9-10 were charged. The reaction was then held for 30 minutes. Aqueous monomer (components 3-5) and monomer (components 6-8) was then fed for 5 hours along with the feed catalyst for 5.5 hours. At three hours, monomer (components 6-8) was added to the feed. The reaction was then held for 30 minutes. Next, components 13-16 were charged and held for 15 minutes. Lastly, components 17-20 were charged and held for 15 minutes.

The polymer was vacuum stripped and adjusted to a solids content of about 41- 42%.

Table 21

SYNTHETIC EXAMPLE 19

In the present example, the active ingredient poiysiloxane (avaiiabie as Coatosii 1211 from GE Silicones) was incorporated in the polymer latex formulation. Table 22 sets forth the cationic latex formulation and the varying amounts of each component. The polymer latex formulation was prepared according to the method set forth in Synthetic Example 18.

Table 22

SYNTHETIC EXAMPLE 20

In the present example, cetostearyl ether (available as Love A Canal wax from Warren Chemical) served as the active ingredient incorporated in the polymer latex formulation. Table 23 sets forth the cationic latex formulation and the varying amounts of each component. The polymer latex formulation was prepared according to the method set forth in Synthetic Example 18.

Table 23

SYNTHETIC EXAMPLE 21

In the present example, the active ingredient, polydimethyl siloxane (available as Dow Corning Silicone Fluid 200), was incorporated in the polymer latex formulation. Table 24 sets forth the cationic latex formulation and the varying amounts of each component. The polymer latex formulation was prepared according to the method set forth in Synthetic Example 18.

Table 24

SYNTHETIC EXAMPLE 22

In the present example, the active ingredient, polyethyleneglycol (available as PEG 600 from Dow Chemical), was incorporated in the polymer latex formulation. Table 25 sets forth the cationic latex formulation and the varying amounts of each component. The polymer latex formulation was prepared according to the method set forth in Synthetic Example 18.

Table 25

SYNTHETIC EXAMPLE 23

In the present example, the active ingredient, glycerine (available from JT Baker), was incorporated in the polymer latex formulation. Table 26 sets forth the cationic latex formulation and the varying amounts of each component. The polymer latex formulation was prepared according to the method set forth in Synthetic Example 18. Table 26

PROPHETIC EXAMPLE 24

A variety of active components can be encapsulated in the cationic latex polymers in any amount to produce the desired result. For example, the following active components can be encapsulated from about 1% to about 2%, or more based on parts per hundred monomer (phm): organic UV filters such as benzophenones, benzotriazoles, homosalates, alkyl cinnamates, for example, octylmethoxycinnamate, octyl salicylate; self-tanning active components such as dihydroxyacetone (DHEA); anti- dandruff agents such as zinc pyrithione; moisturizing agents such as aloe vera extracts; and free radical scavengers such as vitamin A, C, and E, and other antioxidants such as phenolic antioxidants, for example, BHT (butylated hydroxytoluene) and BHA (butylated hydroxy anisole).

PROPHETIC EXAMPLE 25

A variety of inorganic active components can be encapsulated in the cationic latex polymers in any amount to produce the desired result. For example, the following active components typically can be encapsulated from about 0.01 % to about 2% or more based on parts per hundred monomer (phm): pigments including, but not limited to, titanium oxide or zinc oxide; black pigments, such as iron oxide black; fancy or multicolored pigments, such as ultramarine or iron oxide red; lustrous pigments, metal effect pigments, pearlescent pigments as well as fluorescence or phosphorescent pigments; metal oxides, metal hydroxides and metal oxide hydrates, mixed phase pigments, sulfur- containing silicates, metal sulfides, complex metallo-cyanides, metal sulfates, metal chromates, metal molybdates, yellow iron oxide, brown iron oxide, manganese violet, sodium aluminum sulfosilicate, chromium oxide hydrate, ferric ferrocyanide, and cochineal. The inorganic component can also be at least one inorganic solid such as seed, broken seed nut shells, beads, luffa particles, polyethylene balls, clay, calcium bentonite, kaolin, china clay, talc, perlite, mica, vermiculite, silicas, quartz powder, montmorillonite, calcium carbonate, a talc or a member of the mica family or a chemical equivalent thereof. The at least one inorganic active component can be a nano- inorganic material such as nano clays, nano oxides, nanotubes, or the like. Although implied, the present example may include any combination thereof.

In the specification, typical embodiments have been disclosed and, although specific terms are employed, they are used in a generic and descriptive sense and not for purposes of limitation. It should be clearly understood that resort can be had to various other embodiments, aspects, modifications, and equivalents to those disclosed in the claims, which, after reading the description herein, may suggest themselves to one of ordinary skill in the art without departing from the spirit of the present disclosure or the scope of these claims. The specific test results observed may vary according to and depending on the particular composition, as well as the type of formulation, and mode of testing employed, and such expected variations or differences in the results are contemplated in accordance with practice of the present invention.

Although specific embodiments of the present invention are herein illustrated and described in detail, the invention is not limited thereto. The above detailed descriptions are provided as exemplary of the present invention and should not be construed as constituting any limitation of the invention. Modifications will be obvious to those skilled in the art, and all modifications that do not depart from the spirit of the invention are intended to be included with the scope of the appended claims.

Claims

CLAIMSI Claim:

1. An active cationic polymer latex comprising: a) a latex polymer comprising the polymerization product of: i) at least one ethylenically unsaturated first monomer; and ii) at least one ethylenically unsaturated second monomer that is cationic or a precursor to a cation; b) at least one active component at least partially encapsulated within the latex polymer; and c) optionally, at least one sterically bulky component incorporated into the latex polymer.

2. The active cationic polymer latex according to Claim 1 , wherein the at least one ethylenically unsaturated first monomer is a vinyl aromatic monomer, a halogenated or a non-halogenated olefin monomer, an aliphatic conjugated diene monomer, a non-aromatic unsaturated mono- or dicarboxylic ester monomer, a monomer based on the half ester of an unsaturated dicarboxylic acid monomer, an unsaturated mono- or dicarboxylic acid monomer, a nitrile-containing monomer, a cyclic or an acyclic amine-containing monomer, a branched or an unbranched alkyl vinyl ester monomer, a halogenated or non-halogenated alkyl acrylate monomer, a halogenated or non-halogenated aryl acrylate monomer, a carboxylic acid vinyl ester, an acetic acid alkenyl ester, a carboxylic acid alkenyl ester, a vinyl halide, a vinylidene halide, or a combination thereof, any of which having up to 20 carbon atoms.

3. The active cationic polymer latex according to Claim 1 , wherein the at least one ethylenically unsaturated first monomer is styrene, para-methyl styrene, chloromethyl styrene, vinyl toluene, ethylene, butadiene, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, glycidyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, monomethyl maleate, itaconicacid, (meth)acrylonitrile, acrylamide, (meth)acrylamide, Λ/-methylol (meth)acrylamide, N-

(isobutoxyrnethyl)(meth)acrylamide, vinyl neodecanoate, vinyl versatates, vinyl acetate, a C₃-C₈ alkyl vinylether, a C₃-C₈ alkoxy vinylether, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, chlorothfluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, perfluorobutyl ethylene, a perfluorinated C₃-C₈ alpha-olefin, a fluorinated C₃-C₈ alkyl vinylether, a perfluorinated C₃-C₈ alkyl vinylether, a perfluorinated C₃-C₈ alkoxy vinyl ether, or a combination thereof.

4. The active cationic polymer latex according to Claim 1 , wherein the at least one ethylenically unsaturated second monomer is an amine monomer, an amide monomer, a quaternary amine monomer, a phosphonium monomer, a sulfonium monomer, or a combination thereof, any of which having up to 20 carbon atoms.

5. The active cationic polymer latex according to Claim 1 , wherein the at least one ethylenically unsaturated second monomer is dimethylaminoethyl acrylate; diethylaminoethyl acrylate; dimethyl aminoethyl methacrylate; diethylaminoethyl methacrylate; tertiary butylaminoethyl methacrylate; Λ/,Λ/-di methyl acrylamide; N₁N- dimethylaminopropyl acrylamide; acryloyl morpholine; Λ/-isopropyl acrylamide; N₁N- diethyl acrylamide; dimethyl aminoethyl vinyl ether; 2-methyl-1 -vinyl imidazole; N₁N- dimethyl-aminopropyl methacrylamide; vinyl pyridine; vinyl benzyl amine; dimethylaminoethyl acrylate, methyl chloride quartemary; dimethylaminoethyl methacrylate, methyl chloride quartemary; diallyldimethylammonium chloride; N₁N- dimethylaminopropyl acrylamide, methyl chloride quaternary; trimethyl- (vinyloxyethyl) ammonium chloride; 1-vinyl-2,3-dimethylimidazolinium chloride; vinyl benzyl amine hydrochloride; vinyl pyridinium hydrochloride; or a combination thereof.

6. The active cationic polymer latex according to Claim 1 , wherein the at least one sterically bulky component is at least one sterically bulky ethylenically unsaturated third monomer, at least one sterically bulky polymer, or a combination thereof.

7. The active cationic polymer latex according to Claim 1 , wherein the at least one sterically bulky component is: a) CH₂=C(R^1A)COO(CH₂CHR^2AO)_mR^3A, wherein R^1A, R²*, and R^3A are selected independently from H or an alkyl group having from 1 to 6 carbon atoms, inclusive, and m is an integer from 1 to 30, inclusive; b) CH₂=C(R^1B)COO(CH₂CH₂O)_n(CH₂CHR^2BO)pR^3B, wherein R^1B, R^2B, and R^3B are selected independently from H or an alkyl group having from 1 to 6 carbon atoms, inclusive, and n and p are integers selected independently from 1 to 15, inclusive; c) CH₂=C(R^1c)COO(CH₂CHR^2CO)_q(CH₂CH₂O)_rR^3C, wherein R^1C, R^2C, and R^3C are selected independently from H or an alkyl group having from 1 to 6 carbon atoms, inclusive, and q and r are integers selected independently from 1 to 15, inclusive; or d) a combination thereof.

8. The active cationic polymer latex according to Claim 1 , wherein the at least one sterically bulky component is: a) CH₂=C(R^1A)COO(CH₂CHR^2AO)_mR^3A, wherein R^1A, R²*, and R^3A are selected independently from H or methyl, and m is an integer from 1 to 10, inclusive; b) CH₂=C(R^1B)COO(CH₂CH₂O)_n(CH₂CHR^2BO)pR^3B, wherein R^1B, R^2B, and R^3B are selected independently from H or methyl, and n and p are integers selected independently from 1 to 10, inclusive; c) CH₂=C(R^1c)COO(CH₂CHR^2CO)_q(CH₂CH₂O)_rR^3C, wherein R^1C, R^2C, and R^3C are selected independently from H or methyl, and q and r are integers selected independently from 1 to 10, inclusive; or d) a combination thereof.

9. The active cationic polymer latex according to Claim 1 , wherein the at least one sterically bulky component is an alkoxylated monoester of a dicarboxylic acid; an alkoxylated diester of a dicarboxylic acid; a polyoxyethylene alkylphenyl ether; a polymerizable surfactant; or a combination thereof.

10. The active cationic polymer latex according to Claim 1 , wherein the at least one sterically bulky component is a polyvinyl alcohols, polyvinyl pyrollidone, hydroxyethyl cellulose, or a combination or a derivative thereof.

11. The active cationic polymer latex according to Claim 1 , wherein the at least one active component is natural plant-based wax, animal wax, natural wax, synthetic mineral wax, synthetic wax, paraffin wax, carnauba wax, ozocertie wax, montan wax, polyolefin wax, candelilla wax, carnauba wax; alcohols comprising a carbon chain length of greater than two carbons, cetyl alcohol, stearyl alcohol, cetostearyl alcohol, behenyl alcohol, propylene glycol, myristyl alcohol, arachidyl alcohol, lignoceryl alcohol, stearates, myristates, calcium stearate, zinc stearate, magnesium stearate or barium stearate, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, palmitic acid, behenic acid, terephthalic acid, phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, cyclohexanedicarboxylic acid, cyclohexanediaoetic acid, succinic acid, adipic acid, sebacic acid, stearic acid, oleic acid, undecylenic acid, linoleic acid, perfume oil, essential oil, vegetable oil, fish oil, paraffin oil and mineral oil, stearamide, oleamide, erucamide, stearyl stearamide, stearyl erucamide, ethylene bis stearamide, ethylene bis oleamide, coco mono ethanolamide, coco diethanolamide, oleic diethanolarride, lauric diethanolamide, stearic diethanolarride, caprylamide, pelargonamide, capramide, lauramide, myristamide, palmitamide, stearamide, arachidamide, behenamide, stearyl stearamide, palmitoleamide, oleamide, erucamide, linoleamide, linolenamide, oleyl palmitamide, stearyl erucamide, erucyl erucamide, oleyl oleamide, erucyl stearamide, ricinoleamide, ethylenebisstearamide, ethylenebisoleamide, ethylenebis 12-hydroxystearamide, or a combination thereof.

12. The active cationic polymer latex according to Claim 1 , wherein the at least one active component is titanium oxide, zinc oxide, iron oxide black, ultramarine, iron oxide red, lustrous pigment, metal effect pigment, pearlescent pigment, fluorescene pigment, phosphorescent pigment, metal hydroxide, metal oxide hydrate, mixed phase pigment, sulfur-containing silicate, metal sulfide, complex metallo-cyanide, metal sulfate, metal chromate, metal molybdate, yellow iron oxide, brown iron oxide, manganese violet, sodium aluminum sulfosilicate, chromium oxide hydrate, ferric ferrocyanide, cochineal, seed, broken seed nut shell, bead, luffa particle, polyethylene ball, clay, calcium bentonite, kaolin, china clay, talc, perlite, mica, vermiculite, silica, quartz powder, montmorillonite, calcium carbonate, talc, or a combination thereof.

13. The active cationic polymer latex according to Claim 1 , wherein the at least one active component is hyaluronic acid, chondroitin sulfate, elastin, collagen, polysaccharide, glycosaminoglycan, ascorbic acid, ascorbic acid derivative, glucosamine ascorbate, arginine ascorbate, lysine ascorbate, tyrosine ascorbate, gluthathione ascorbate, nicotinamide ascorbate, niacin ascorbate, allantoin ascorbate, creatine ascorbate, creatinine ascorbate, chondroitin ascorbate, chitosan ascorbate, DNA ascorbate, carnosine ascorbate, tocotrienol, rutin, quercetin, hesperedin, diosmin, mangiferin, mangostin, cyanidin, astaxanthin, lutein, lycopene, resveratrol, tetrahydrocurcumin, rosmarinic acid, hypericin, ellagic acid, chlorogenic acid, oleuropein, alpha-lipoic acid, niacinamide lipoate, gluthathione, andrographolide, carnosine, niacinamide, polyphenols, pycnogenol, benzophenone, benzotriazole, salicylate, dibenzoyl methane, anthranilate, methylbenzylidene, octyl triazone, 2-phenylbenzimidazole-5-sulfonic acid, octocrylene, triazine, cinnamate, cyanoacrylate, dicyano ethylene, etocrilene, drometrizole trisiloxane, bisethylhexyloxyphenol methoxyphenol triazine, drometrizole, dioctyl butamido triazone, terephthalylidene dicamphor sulfonic acid, para-aminobenzoate, salicylic acid, zinc pyrithione, dihydroxyacetone, erytrulose, melanin, vitamin C or a derivative thereof, vitamin A or a derivative thereof, folic acid or a derivative thereof, vitamin E or a derivative thereof, tocopheryl acetate, flavons, flavonoids, histidine, glycine, tyrosine, tryptophan or a derivative thereof, carotenoid, carotene, uric acid or a derivative thereof, citric acid, lactic acid, malic acid, stilbene or a derivative thereof, pomegranate extract, vitamin K1 , vitamin K2, vitamin K1 oxide, vitamin K2 oxide, hormone, mineral, plant extract, botanical extract, anti-inflammatory agent, concentrates of plant extracts, emollient, skin protectant, humectant, silicone, skin soothing ingredient, analgesic, skin penetration enhancer, solubilizer, emollient alkaloid, dye, pigment, perfume, fragrance, cuprous halide, cupric halide, cupric acetate, cupric formate, cuprous acetate, cuprous formate, ferrous halide, ferric halide, ferrous sulfate, ferric sulfate, cysteine, glutathione, N-acetylcysteine, L- alpha-acetamido-beta mercaptopropionic acid, S-nitroso-glutathione, N-acetyl-3- mercapto-alanine, butylated hydroxyanisole, butylated hydroxytoluene, L-2- oxothiazolidine-4-carboxylate, desferrioxamine, allopurinol, superoxide dismutase, salen-manganese complex, or a combination thereof.

14. The active cationic polymer latex according to Claim 1 , comprising from about 20 percent to about 99.5 percent by weight of the ethylenically unsaturated first monomer, based on the total monomer weight.

15. The active cationic polymer latex according to Claim 1 , comprising from about 0.01 percent to about 75 percent by weight of the ethylenically unsaturated second monomer, based on the total monomer weight.

16. The active cationic polymer latex according to Claim 1 , comprising from about 0.01 percent to about 40 percent by weight active additive, based on the total monomer weight.

17. The active cationic polymer latex according to Claim 1 , comprising from 0 percent to about 25 percent by weight sterically bulky component, based on the total monomer weight.

18. The active cationic polymer latex according to Claim 1 , further comprising a nonionic surfactant.

19. The active cationic polymer latex according to Claim 1 , wherein the latex polymer is substantially devoid of cationic and anionic surfactants.

20. A coating comprising the active cationic polymer latex according to Claim 1.

21. An article comprising the active cationic polymer latex according to Claim 1.

22. A glove comprising the active cationic polymer latex according to Claim 1.

23. An underdip or overdip for a supported or unsupported glove comprising the active cationic polymer latex according to Claim 1.

24. A method of making an active cationic polymer latex comprising initiating an emulsion polymerization of an aqueous composition comprising, at any time during the emulsion polymerization: a) at least one ethylenically unsaturated first monomer; b) at least one ethylenically unsaturated second monomer that is cationic or a precursor to a cation; c) at least one active component; d) at least one free-radical initiator; e) optionally, at least one sterically bulky ethylenically unsaturated third monomer; f) optionally, at least one sterically bulky polymer; and g) optionally, at least one non nonionic surfactant.

25. The method of making an active cationic polymer latex according to Claim 24, wherein the method is a semi-continuous process, and wherein at least one active component is dissolved in the monomer feed at any time during the emulsion polymerization.

26. The method of making an active cationic polymer latex according to Claim 24, wherein the method is a batch process, and wherein the at least one active component is present in the seed stage of the emulsion polymerization.

27. The method of making an active cationic polymer latex according to Claim 24, wherein the aqueous composition components and the at least one active component are provided as a dispersion prior to initiating the emulsion polymerization.

28. The method of making an active cationic polymer latex according to Claim 24, wherein the at least one ethylenically unsaturated first monomer is a vinyl aromatic monomer, a halogenated or a non-halogenated olefin monomer, an aliphatic conjugated diene monomer, a non-aromatic unsaturated mono- or dicarboxylic ester monomer, a monomer based on the half ester of an unsaturated dicarboxylic acid monomer, an unsaturated mono- or dicarboxylic acid monomer, a nitrile-containing monomer, a cyclic or an acyclic amine-containing monomer, a branched or an unbranched alkyl vinyl ester monomer, a halogenated or non- halogenated alkyl acrylate monomer, a halogenated or non-halogenated aryl acrylate monomer, a carboxylic acid vinyl ester, an acetic acid alkenyl ester, a carboxylic acid alkenyl ester, a vinyl halide, a vinylidene halide, or a combination thereof, any of which having up to 20 carbon atoms.

29. The method of making an active cationic polymer latex according to Claim 24, wherein the at least one ethylenically unsaturated first monomer is styrene, para-methyl styrene, chloromethyl styrene, vinyl toluene, ethylene, butadiene, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, glycidyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, monomethyl maleate, itaconic acid, (meth)acrylonitrile, (meth)acrylamide, Λ/-methylol (meth)acrylamide, N- (isobutoxymethyl)(meth)acrylamide, vinyl neodecanoate, vinyl versatates, vinyl acetate, a C₃-C₈ alkyl vinylether, a C₃-C₈ alkoxy vinylether, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, perfluorobutyl ethylene, a perfluorinated C₃-C₈ alpha-olefin, a fluorinated C₃-C₈ alkyl vinylether, a perfluorinated C₃-C₈ alkyl vinylether, a perfluorinated C₃-C₈ alkoxy vinyl ether, or a combination thereof.

30. The method of making an active cationic polymer latex according to Claim 24, wherein the at least one ethylenically unsaturated second monomer is an amine monomer, an amide monomer, a quaternary amine monomer, a phosphonium monomer, a sulfonium monomer, or a combination thereof, any of which having up to 20 carbon atoms.

31. The method of making an active cationic polymer latex according to Claim 24, wherein the at least one ethylenically unsaturated second monomer is dimethylaminoethyl acrylate; diethylaminoethyl acrylate; dimethyl aminoethyl methacrylate; diethylaminoethyl methacrylate; tertiary butylaminoethyl methacrylate; Λ/,Λ/-di methyl acrylamide; Λ/,Λ/-dimethylaminopropyl acrylamide; acryloyl morpholine; Λ/-isopropyl acrylamide; Λ/,Λ/-diethyl acrylamide; dimethyl aminoethyl vinyl ether; 2- methyl-1-vinyl imidazole; Λ/,Λ/-dimethyl-aminopropyl methacrylamide; vinyl pyridine; vinyl benzyl amine; dimethylaminoethyl acrylate, methyl chloride quarternary; dimethylaminoethyl methacrylate, methyl chloride quarternary; diallyldimethylammonium chloride; N,N-dimethylaminopropyl acrylamide, methyl chloride quaternary; trimethyl-(vinyloxyethyl) ammonium chloride; 1-vinyl-2,3- dimethylimidazolinium chloride; vinyl benzyl amine hydrochloride; vinyl pyridinium hydrochloride; or a combination thereof.

32. The method of making an active cationic polymer latex according to Claim 24, wherein the at least one sterically bulky component is at least one sterically bulky ethylenically unsaturated third monomer, at least one sterically bulky polymer, or a combination thereof.

33. The method of making an active cationic polymer latex according to Claim 24, wherein the at least one sterically bulky component is: a) CH₂=C(R^1A)COO(CH₂CHR^2AO)_mR^3A, wherein R^1A, R²*, and R^3A are selected independently from H or an alkyl group having from 1 to 6 carbon atoms, inclusive, and m is an integer from 1 to 30, inclusive; b) CH₂=C(R^1B)COO(CH₂CH₂O)n(CH₂CHR^2BO)_pR^3B, wherein R^1B, R^2B, and R^3B are selected independently from H or an alkyl group having from 1 to 6 carbon atoms, inclusive, and n and p are integers selected independently from 1 to 15, inclusive; c) CH₂=C(R^1c)COO(CH₂CHR^2CO)_q(CH₂CH₂O)_rR^3C, wherein R^1C, R^2C, and R^3C are selected independently from H or an alkyl group having from 1 to 6 carbon atoms, inclusive, and q and r are integers selected independently from 1 to 15, inclusive; or d) a combination thereof.

34. The method of making an active cationic polymer latex according to Claim 24, wherein the at least one sterically bulky component is: a) CH₂=C(R^1A)COO(CH₂CHR^2AO)_mR^3A, wherein R^1A, R²*, and R^3A are selected independently from H or methyl, and m is an integer from 1 to 10, inclusive; b) CH₂=C(R^1B)C00(CH₂CH₂O)_n(CH₂CHR^2B0)_pR^3B, wherein R^1B, R^2B, and R^3B are selected independently from H or methyl, and n and p are integers selected independently from 1 to 10, inclusive; c) CH₂=C(R^1c)COO(CH₂CHR^2CO)_q(CH₂CH₂O)_rR^3C, wherein R^1C, R^2C, and R^3C are selected independently from H or methyl, and q and r are integers selected independently from 1 to 10, inclusive; or d) a combination thereof.

35. The method of making an active cationic polymer latex according to Claim 24, wherein the at least one sterically bulky component is an alkoxylated monoester of a dicarboxylic acid; an alkoxylated diester of a dicarboxylic acid; a polyoxyethylene alkylphenyl ether; a polymerizable surfactant; or a combination thereof.

36. The method of making an active cationic polymer latex according to Claim 24, wherein the at least one sterically bulky component is a polyvinyl alcohol, polyvinyl pyrollidone, hydroxyethyl cellulose, or a combination thereof or a derivative thereof.

37. The method of making an active cationic polymer latex according to Claim 24, wherein the at least one active component is natural plant-based wax, animal wax, natural wax, synthetic mineral wax, synthetic wax, paraffin wax, carnauba wax, ozocertie wax, montan wax, poly olefin wax, candelilla wax. camauba wax; alcohols comprising a carbon chain length of greater than two carbons, cetyl alcohol, stearyl alcohol, cetostearyl alcohol, behenyl alcohol, propylene glycol, myristyl alcohol, arachidyl alcohol, lignoceryl alcohol, stearates, myristates, calcium stearate, zinc stearate, magnesium stearate or barium stearate, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, palmitic acid, behenic acid, terephthalic acid, phthalic acid, isophthalicacid, naphthalene-2,6-dicarboxylic acid, cyclohexanedicarboxylic acid, cyclohexanediacetic acid, succinic acid, adipic acid, sebacic acid, stearic acid, oleic acid, undecylenic acid, linoleic acid, perfume oil, essential oil, vegetable oil, fish oil, paraffin oil and mineral oil, stearamide, oleamide, erucamide, stearyl stearamide, stearyl erucamide, ethylene bis stearamide, ethylene bis oleamide, coco mono ethanolamide, coco diethanolamide, oleic diethanolamide, lauric diethanolarride, stearic diethanolamide, caprylamide, pelargonamide, capramide, lauramide, myristamide, palmitamide, stearamide, arachidamide, behenamide, stearyl stearamide, palmitoleamide, oleamide, erucamide, linoleamide, linolenarride, oleyl palmitamide, stearyl erucamide, erucyl erucamide, oleyl oleamide, erucyl stearamide, ricinoleamide, ethylenebisstearamide, ethylenebisoleamide, ethylenebis 12-hydroxystearamide or a combination thereof.

38. The method of making an active cationic polymer latex according to Claim 24, wherein the at least one active component is titanium oxide, zinc oxide, iron oxide black, ultramarine, iron oxide red, lustrous pigment, metal effect pigment, pearlescent pigment, fluorescene pigment, phosphorescent pigment, metal hydroxide, metal oxide hydrate, mixed phase pigment, sulfur-containing silicate,_^ metal sulfide, complex metallo-cyanide, metal sulfate, metal chromate, metal molybdate, yellow iron oxide, brown iron oxide, manganese violet, sodium aluminum sulfosilicate, chromium oxide hydrate, ferric ferrocyanide, cochineal, seed, broken seed nut shell, bead, luff a particle, polyethylene ball, clay, calcium bentonite, kaolin, china clay, talc, perlite, mica, vermiculite, silica, quartz powder, montmorillonite, calcium carbonate, talc or a combination thereof.

39. The method of making an active cationic polymer latex according to Claim 24, wherein the at least one active component is hyaluronic acid, chondroitin sulfate, elastin, collagen, polysaccharide, glycosaminoglycan, ascorbic acid, ascorbic acid derivative, glucosamine ascorbate, arginine ascorbate, lysine ascorbate, tyrosine ascorbate, glutathione ascorbate, nicotinamide ascorbate, niacin ascorbate, allantoin ascorbate, creatine ascorbate, creatinine ascorbate, chondroitin ascorbate, chitosan ascorbate, DNA ascorbate, carnosine ascorbate, tocotrienol, rutin, quercetin, hesperedin, diosmin, mangiferin, mangostin, cyanidin, astaxanthin, lutein, lycopene, resveratrol, tetrahydrocurcumin, rosmarinic acid, hypericin, ellagic acid, chlorogenic acid, oleuropein, alpha-lipoic acid, niacinamide lipoate, glutathione, andrographolide, carnosine, niacinamide, polyphenols, pycnogenol, benzophenones, benzotriazoles, salicylates, dibenzoylmethanes, anthranilates, methylbenzylidenes, octyl triazones, 2-phenylbenzimidazole-5-sulfonic acid, octocrylene, triazines, cinnamates, cyanoacrylates, dicyano ethylenes, etocrilene, drometrizole trisiloxane, bisethylhexyloxyphenol methoxyphenol triazine, drometrizole, dioctyl butamido triazone, terephthalylidene dicamphor sulfonic acid, para-aminobenzoates, salicylic acid, zinc pyrithione, dihydroxyacetone, erytrulose, melanin, vitamin C and derivatives thereof, vitamin A and derivatives thereof, folic acid and derivatives thereof, vitamin E and derivatives thereof, tocopheryl acetate, flavons, flavonoids, histidine, glycine, tyrosine, tryptophan and derivatives thereof, carotenoids, carotenes, uric acid and derivatives thereof, citric acid, lactic acid, malic acid, stilbenes and derivatives thereof, pomegranate extracts, vitamin K1 , vitamin K2, vitamin K1 oxide, vitamin K2 oxide, hormones, minerals, plant/botanical extracts, anti-inflammatory agents, concentrates of plant extracts, emollients, skin protectants, humectants, silicones, skin soothing ingredients, analgesics, skin penetration enhancers, solubilizers, emollients, alkaloids and processing aids, dyes, pigments, perfumes or fragrances for the body, cuprous halide, cupric halide, cupric acetate, cupric formate, cuprous acetate, cuprous formate, ferrous halide, ferric halide, ferrous sulfate, ferric sulfate, cysteine, glutathione, N-acetylcysteine, L- alpha-acetamido-beta mercaptopropionic acid, S-nitroso-glutathione, N-acetyl-3- mercapto-alanine, butylated hydroxyanisole, butylated hydroxytoluene, L-2- oxothiazolidine-4-carboxylate, desferrioxamine, allopurinol, superoxide dismutase, salen-manganese complexes, or a combination thereof.

40. The method of making an active cationic polymer latex according to Claim 24, wherein the active cationic polymer latex comprises from about 20 percent to about 99.5 percent by weight of the ethylenically unsaturated first monomer, based on the total monomer weight.

41. The method of making an active cationic polymer latex according to Claim 24, wherein the active cationic polymer latex comprises from about 0.01 percent to about 75 percent by weight of the ethylenically unsaturated second monomer, based on the total monomer weight.

42. The method of making an active cationic polymer latex according to Claim 24, wherein the active cationic polymer latex comprises from about 0.01 percent to about 40 percent by weight active additive, based on the total monomer weight.

43. The method of making an active cationic polymer latex according to Claim 24, wherein the active cationic polymer latex comprises from 0 percent to about 25 percent by weight sterically bulky component, based on the total monomer weight.

44. The method of making an active cationic polymer latex according to Claim 24, wherein the active cationic polymer latex is substantially devoid of cationic and anionic surfactants.

45. A method of making an active cationic polymer latex comprising: a) providing an aqueous composition comprising: i) at least one ethylenically unsaturated first monomer; ii) at least one ethylenically unsaturated second monomer that is cationic or a precursor to a cation; iii) optionally, at least one sterically bulky ethylenically unsaturated third monomer; iv) at least one free-radical initiator; and v) optionally, at least one non-ionic surfactant; b) initiating an emulsion polymerization of the composition; and c) adding at least one active component to the composition during the emulsion polymerization process.

46. The method of making an active cationic polymer latex according to Claim 45, wherein the at least one active component is bioactive.

47. The method of making an active cationic polymer latex according to Claim 45, wherein the at least one active component is either organic or inorganic.

48. A polymer latex composition comprising: a) a latex polymer comprising the polymerization product of: i) at least one ethylenically unsaturated first monomer; and ii) at least one ethylenically unsaturated second monomer that is cationic or a precursor to a cation; b) at least one active component at least partially encapsulated within the latex polymer; and c) optionally, at least one stehcally bulky component incorporated into the latex polymer; wherein the composition provides antimicrobial activity.

49. The polymer latex composition of claim 48, wherein the antimicrobial activity reduces odor.

50. The polymer latex composition of claim 48, further comprising an antiperspirant composition or deodorant composition or a combination thereof.

51. The polymer latex composition of claim 48, wherein the composition is capable of forming a film.

52. The polymer latex composition of claim 51 , wherein the film controls the release of the at least one active component.

53. The polymer latex composition of claim 52, wherein the release of the at least one active component is dependent on pH.

54. The polymer latex composition of claim 48, wherein the latex polymer has a particle size of about 15 nm to about 5 microns.

55. The polymer latex composition of claim 48, wherein the at least one ethylenically unsaturated first monomer is styrene and butyl acrylate.

56. The polymer latex composition of claim 48, wherein the at least one ethylenically unsaturated second monomer is dimethylaminoethyl methacrylate methyl chloride quaternary, and optionally methoxypolyethyleneglycol methacrylate.

57. The polymer latex composition of claim 48, wherein the at least one active component is at least one odor control agent, moisturizing agent, anti-wrinkle or anti-aging agent, antiacne agent, anti-dandruff agent, anti-static agent, preservative, conditioner, styling aid, chelating agent, antioxidant, ultraviolet blocker, stabilizer or absorbers, skin bronzing or tanning agent, vitamins or herbal supplement, botanical extract, free radical scavenger, coloring agent, fragrance, or perfume.

58. The polymer latex composition of claim 57, wherein at least a portion of the at least one active component is post-added to the latex composition as a dispersion.

59. The polymer latex composition of claim 57, wherein the ultraviolet blocker is dispersed in the latex composition.

60. The polymer latex composition of claim 57, wherein the at least one active component is an ultraviolet blocker and further comprises zinc oxide or titanium oxide or a combination thereof.

61. A method of deodorizing comprising controlling bacteria through the use of a personal care product having antimicrobial activity, wherein the personal care product comprises at least one cationic polymer latex composition.

62. The method of claim 61, wherein the at least one cationic polymer latex composition comprises at least one active component at least partially encapsulated within the latex polymer.

63. The method of claim 61, wherein the personal care product further comprises at least one post-process active component

64. The method of claim 61, wherein the cationic polymer latex composition further comprises at least one additional encapsulated active component exhibiting antistatic, antidandruff, preservative, color, chelating, antioxidant fragrance, conditioning, styling, or sunscreen functionality.

65. The method of claim 61, further comprising applying the personal care product to at least one animate surface, inanimate surface, or air.

66. The method of claim 61 , wherein the personal care product is a sunscreen, body wash, shampoo, lotion or deodorant.

67. The method of claim 66, wherein the deodorant is a roll-on, stick, or spray.

68. The method of claim 61, wherein the cationic polymer latex composition is capable of forming a film.

69. The method of claim 61 , wherein the personal care product exhibits a foam height of at least 700 ml.

70. The method of claim 61 , wherein the personal care product exhibits a pH of from 6 to about 7.

71. The method of claim 59, wherein the personal care product exhibits a foam density of from about 3 seconds to about 30 seconds.

72. A disinfectant composition comprising an active cationic polymer latex comprising: a) a latex polymer comprising the polymerization product of: i) at least one ethylenically unsaturated first monomer; and ii) at least one ethylenically unsaturated second monomer that is cationic or a precursor to a cation; b) at least one active component at least partially encapsulated within the latex polymer; and c) optionally, at least one sterically bulky component incorporated into the latex polymer.

73. The disinfectant composition according to Claim 72, further comprising an alcohol.

74. The disinfectant composition according to Claim 72, further comprising at least one active component chosen from natural plant-based wax, animal derived wax, natural mineral wax, synthetic mineral wax, synthetic wax, an alcohol comprising a carbon chain length of greater than one, an ester of an alcohol, metal stearate, carboxylic acid, fatty acid, oil, fatty amide, cosmeceutical or nutraceutical.

75. The disinfectant according to Claim 72, wherein the pH of the disinfectant composition is less than or equal to 4.

76. The disinfectant according to Claim 72, wherein the pH of the disinfectant composition is greater than or equal to 9.