US 2010O239679A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2010/0239679 A1 Greene et al. (43) Pub. Date: Sep. 23, 2010

(54) ENHANCEDRETENTION CAPABILITIES Publication Classification THROUGH METHODS COMPRISING SURFACE TREATMENT OF FUNCTIONAL (51) Int. Cl. PARTICULATE CARRIER MATERIALS, AND AOIN 25/2 (2006.01) FUNCTIONAL PARTICULATE CARRIER AOIN 65/00 (2009.01) MATERALS MADE THEREFROM AOIN 59/6 (2006.01) AOIN 59/20 (2006.01) (75) Inventors: Michael Greene, Goleta, CA (US); AOIN 37/44 (2006.01) Jie Lu, Lompoc, CA (US) AOIN 43/74 (2006.01) AOIP I/00 (2006.01) Correspondence Address: AOIP3/00 (2006.01) FINNEGAN, HENDERSON, FARABOW, GAR AOIP 7/04 (2006.01) RETT & DUNNER LLP (52) U.S. Cl...... 424/490; 424/489: 424/770; 424/618: 901 NEW YORKAVENUE, NW 424/630; 424/635; 424/641; 514/561; 514/359 WASHINGTON, DC 20001-4413 (US) (57) ABSTRACT (73) Assignee: World Minerals, Inc., Santa Barbara, CA (US) Functional particulate carrier materials with enhanced reten tion capabilities are described. The materials comprise at (21) Appl. No.: 12/681,285 least one functional particulate carrier material Subjected to at least one surface treatment, and at least one active ingredient. (22) PCT Fled: Sep. 29, 2008 The at least one surface treatment may be at least one physical Surface treatment and/or at least one chemical Surface treat (86) PCT NO.: PCT/US08/78075 ment with at least one Surface treating agent. The at least one active ingredient may be a biocide, a fungicide, a mildewcide, S371 (c)(1), an antibiotic, an insecticide, a preservative, or an antimicro (2), (4) Date: Apr. 1, 2010 bial agent. Methods for enhancing the performance of plastics and liquid-based media, for example, coatings and paints, are Related U.S. Application Data also described by increasing the retention factors of active (60) Provisional application No. 60/976,950, filed on Oct. ingredients in those plastics and media through Surface treat 2, 2007. ment of functional particulate carrier materials. US 2010/0239.679 A1 Sep. 23, 2010

ENHANCEDRETENTION CAPABILITIES increase the retention of active ingredients as a method to THROUGH METHODS COMPRISING enhance the antimicrobial capabilities of the functional par SURFACE TREATMENT OF FUNCTIONAL ticulate carriers. PARTICULATE CARRIER MATERIALS, AND FUNCTIONAL PARTICULATE CARRIER SUMMARY OF THE INVENTION MATERALS MADE THEREFROM 0005 Disclosed herein are functional particulate carrier materials with enhanced retention capabilities and methods CLAIM OF PRIORITY for enhancing the performance of plastics and liquid-based media, for example, in coatings and paints, by increasing the 0001. This PCT International Application claims the right retention factor of at least one active ingredient through at of priority to, and hereby incorporates by reference herein in least one Surface treatment of at least one functional particu its entirety, U.S. Provisional Patent Application No. 60/976, late carrier material. Methods for using the functional par ticulate carrier materials with enhanced antimicrobial capa 950 filed Oct. 2, 2007. bilities are also disclosed.

FIELD OF THE INVENTION DETAILED DESCRIPTION OF THE INVENTION 0006. At least one functional particulate carrier material is 0002 This application and the inventions described herein Surface treated to chemically modify its Surface prior to expo discuss functional particulate carrier materials with enhanced Sure to at least one active ingredient with antimicrobial capa retention capabilities. bility. The at least one surface treatment may allow for higher retention of the at least one active ingredient, thereby enhanc BACKGROUND OF THE INVENTION ing the antimicrobial capability of the at least one functional particulate carrier material. 0003 Preventing microbial contamination is an essential concern in daily life, in everywhere from Surface areas in Functional Particulate Carrier Material bathrooms, to Surgical instruments, to wall paints. U.S. Pat. 0007. At least one functional particulate carrier material is No. 6,905,698 B1, which is incorporated by reference herein used as the material Subjected to at least one surface treat in its entirety, generally discusses certain methods by which ment, prior to exposure to an at least one active ingredient. biocides can be used. Furthermore, incorporating active Combinations of functional particulate carrier materials may ingredients, such as biocides, into plastics and liquid-based be used. The skilled artisan will readily understand appropri media by way of particulate carrier materials can prevent ate functional particulate carrier materials appropriate for use microbial contamination in a variety of applications, and the in the inventions described herein. In one embodiment, the functional particulate carrier materials can ideally incorpo functional particulate carrier material is any inorganic Sub rate the active ingredients into the finished products by addi strate whose Surface is capable of being modified through an tionally fulfilling, and without compromising, other filler at least one Surface treatment to allow chemical bonding with functions. However, the effectiveness of the antimicrobial at least one active ingredient. capabilities may decrease over time as the biocides diffuse 0008. In another embodiment, the functional particulate out of the embedded particulate carrier materials. carrier material is diatomaceous earth. Diatomaceous earth is 0004 Introducing active ingredients such as biocides into a sedimentary silica deposit comprising the fossilized skel or with carrier materials has apparently been disclosed for at etons of diatoms, which are one-celled algae-like plants that least some variety of applications, such as in U.S. Pat. Nos. accumulate in marine or fresh water environments. Honey 4,505,889,4,552.591, and 5,648,086, in U.S. Patent Applica comb silica structures generally give diatomaceous earth use tion Publication Nos. 2006/0035097 and 2006/0180552, and ful characteristics Such as absorptive capacity and Surface in the use of celite as a biocide carrier. Historically, however, area, chemical stability, and low bulk density. In one embodi functional particulate carrier materials have failed to retain ment, diatomaceous earth comprises about 90% SiO, mixed large amounts of the active ingredients (e.g., biocides), lim with other Substances. In another embodiment, diatomaceous iting the antimicrobial capabilities of the products, both in earth comprises about 90% SiO, plus various metal oxides, their initial antimicrobial capability and their continued anti such as but not limited to Al, Fe, Ca, and Mg oxides. In one microbial capability as the active ingredient may diffuse from embodiment, the diatomaceous earth is natural, i.e., unproc the carrier materials. Current practices attempt to prolong the essed. In another embodiment, the diatomaceous earth is antimicrobial capabilities of different materials by slowing calcined. In yet another embodiment, the diatomaceous earth the diffusivity of the active ingredients in various ways. U.S. is flux calcined. In a further embodiment, diatomaceous earth Patent Application No. 2006/0246.149 A1 discusses a protec is a commercially available Super-fine diatomaceous earth tive surface coating; U.S. Pat. No. 6,905,698 B1 also dis product, such as but not limited to SuperflossTM available cusses a protective Surface coating or Surface cleaning com from Celite Corporation. In yet another embodiment, the positions; U.S. Pat. No. 4,656,057 attempts to solve the diatomaceous earth is CelTiXTM, available from World Min problem through use of porous or perforated membranes. The erals Inc. impregnation of mineral particles with biocides is also 0009. In a further embodiment, the functional particulate known; for example, U.S. Pat. No. 4,552.591 describes a carrier material is perlite. Perlite, as used herein, identifies composition intended to protect polymer dispersions used in any naturally occurring siliceous Volcanic rock that can be oil field water treatment. However, none of those references expanded with heat treatment. In one embodiment, perlite appear to contemplate a Surface treatment that modifies the comprises between about 70% and about 74% silica, about Surface of the functional particulate carrier materials to 14% alumina, between about 2% and 6% water, and trace US 2010/0239.679 A1 Sep. 23, 2010

impurities. In one embodiment, the perlite is ore. In another not limited to, silica gels, silica colloids, synthetic fused embodiment, the perlite is expanded. In yet another embodi silica, and doped synthetic fused silica. In yet another ment, the perlite is fine. In still another embodiment, the embodiment, the functional particulate carrier material is an perlite is Harborlite 635, a very fine grade of perlite available aluminosilicate, with the basic structural composition from Harborlite Corp., a subsidiary of World Minerals Inc. AlSiO Exemplary aluminosilicates include, but are not lim 0010. In yet another embodiment, the functional particu ited to, calcium aluminosilicate, sodium aluminosilicate, late carrier material is kaolin clay, which may also be referred potassium aluminosilicate, Zeolite, and kyanite. to as china clay or hydrous kaolin. In one embodiment, kaolin clay comprises predominantly mineral kaolinite (AlSiOs Surface Treatment (OH)4), anhydrous aluminum silicate, and amounts of vari 0016. At least one surface treatment is used to modify the ous impurities. Exemplary kaolin clays include, but are not Surface of the at least one functional particulate carrier mate limited to, airfloat kaolin clay, water-washed kaolin clay, rial. In one embodiment, the at least one surface treatment at delaminated kaolin clay, and calcined kaolin clay. least partially chemically modifies the surface of the at least 0011. In yet a further embodiment, the functional particu one functional particulate carrier material by way of at least late carrier material is glass. In still another embodiment, the one Surface treating agent. Chemical modification includes, carrier material is a mineral filler for plastics. In still a further but is not limited to, covalent bonding, ionic bonding, and embodiment, the material is a metallic oxide. In another “weak' intermolecular bonding such as van der Waals inter embodiment, the functional particulate carrier material is a actions. In another embodiment, the at least one Surface treat synthetic calcium silicate hydrate (CaSiO). An exemplary ment at least partially physically modifies the surface of the at synthetic CaSiO is Micro-Cel E, available from Advanced least one functional particulate carrier material. Physical Minerals Corp., a subsidiary of World Minerals Inc. In yet modification includes, but is not limited to, roughening of the another embodiment, the functional particulate carrier mate material Surface, pitting the material Surface, or increasing the rial is vermiculite. In yet a further embodiment, the functional surface area of the material surface. In a further embodiment, particulate carrier material is a phyllosilicate. the at least one surface treatment at least partially chemically 0012. In one embodiment, the functional particulate car modifies and at least partially physically modifies the Surface rier material is talc. In another embodiment, the functional of the at least one functional particulate carrier material. In particulate carrier material is talc comprising greater than yet another embodiment, the at least one Surface treatment is about 90% MgSiOo(OH)· (magnesium silicate hydroxide) any chemical or physical modification to the Surface of the at and accessory minerals in varying amounts, including, but not least one functional particulate carrier material that results in limited to, chlorite, serpentine, quartz, tremolite, anthophyl increased retention of at least one active ingredient. lite, and carbonates Such as magnesite, dolomite, and calcite. 0017. In one embodiment the at least one surface treat In a further embodiment, the functional particulate carrier ment silanizes the at least one functional particulate carrier material is platy talc. In yet another embodiment, the func material, wherein the at least one surface treating agent is at tional particulate carrier material is industrial talc. In yet a least one siloxane. In general, siloxanes are any of a class of further embodiment, the functional particulate carrier mate organic or inorganic chemical compounds comprising sili rial is tremolitic talc. con, oxygen, and often carbon and hydrogen, based on the 0013. In one embodiment, the functional particulate car general empirical formula of RSiO, where R may be an alkyl rier material is mica. In another embodiment, the functional group. Exemplary siloxanes include, but are not limited to, particulate carrier material is mica with the general formula dimethylsiloxane, methylphenylsiloxane, methylhydrogen XYZOo(OH,F), in which: X may be, but is not limited siloxane, methyltrimethoxysilane, octamethylcyclotetrasi to, K, Na, Ca, Ba, Rb, or Cs;Y may be, but is not limited to, loxane, hexamethyldisiloxane, diphenylsiloxane, and Al, Mg, Fe, Mn, Cr, Ti, and Li; and, Z may be, but is not copolymers or blends of copolymers of any combination of limited to, Si,Al, Fe, and Ti. monophenylsiloxane units, diphenylsiloxane units, phenylm 0014. In another embodiment, the functional particulate ethylsiloxane units, dimethylsiloxane units, monomethylsi carrier material is selected from the group consisting of, but loxane units, vinylsiloxane units, phenylvinylsiloxane units, not limited to, activated carbon, powders of polyethylene, methylvinylsiloxane units, ethylsiloxane units, phenylethyl fibers of polyethylene, fibers of polypropylene, high aspect siloxane units, ethylmethylsiloxane units, ethylvinylsiloxane ratio Wollastonite, low aspect ratio Wollastonite, amorphous units, or diethylsiloxane units. silicas, amorphous aluminas, alumina trihydrate, barite 0018. In one embodiment, the at least one surface treat (Barium Sulfate), ground calcium carbonate, precipitated cal ment silanizes the at least one functional particulate carrier cium carbonate, calcium Sulfate, gypsum, carbon black, clay, material, wherein the at least one surface treating agent is at chlorite, dolomite, feldspar, graphite, huntite, hydromagnes least one silane. In general, silanes and other monomeric ite, hydrotacite, magnesia, magnesite (magnesium carbon silicon compounds have the ability to bond inorganic mate ate), magnesium hydroxide, magnetite (Fe-O), nepheline rials, such as at least one functional particulate carrier mate syenite, olivine, pseudoboehmites (forms of microcrystalline rial, to organic resins and materials. Such as at least one active aluminum hydroxide), pyrophyllite, resins, titania, titanium ingredient. The bonding mechanism may be due largely to dioxide (e.g., rutile), waxes, Zeolites (e.g., Y-Zeolites and two groups in the silane structure: the Si(OR) portion inter dealuminated Y-Zeolites), and Zinc oxide. acts with the at least one inorganic functional particulate 0015. In another embodiment, the functional particulate carrier material, while the organofunctional (vinyl-, amino-, carrier material is silica. Examples of silica include, but are epoxy-, etc.) group interact with the at least one active ingre not limited to, ground silica, novoculite silica, precipitated dient. silica, fumed silica, and fumed amorphous silica. In a further 0019. In one embodiment, at least one functional particu embodiment, the functional particulate carrier material is late carrier material is subjected to at least one surface treat synthetic silica. Examples of synthetic silicas include, but are ment Surface treated with at least one ionic silane. Exemplary US 2010/0239.679 A1 Sep. 23, 2010 ionic silanes include, but are not limited to, 3-(trimethoxysi 0023 Exemplary silanes having a quaternary ammonium lyl)propyl-ethylenediamine triacetic acid trisodium salt and moiety include, but are not limited to, quaternary ammonium 3-(trihydroxysilyl)propylmethylposphonate salt. In another salts of a Substituted silanes, 3-(trimethoxysilyl) propylocta embodiment, the carrier material is subjected to at least one decyldimethylammonium chloride, poly-(diallyldimethy Surface treatment with at least one nonionic silane. In a fur lammonium chloride), N-trimethoxysilylpropyl-N,N.N-tri ther embodiment, the carrier material is subjected to at least methylammonium chloride, octadecylaminodimethyl one surface treatment with at least one silane of Formula (I): trimethoxysilylpropyl ammonium chloride, and 3-(N-styryl (R'), Si(R)-R (I) methyl-2-aminoethylamino)-propyltrimethoxysilane hydro chloride. wherein: R is any hydrolysable moiety that may chemically 0024 Exemplary silanes having an aryl moiety include, react with any active group on the Surface of the at least one but are not limited to, 3-(trimethoxysilyl)-2-(p.m-chlorom functional particulate carrier material. Such as but not limited ethyl)-phenylethane, 2-hydroxy-4-(3-triethoxysilylpro to alkoxy, halogen, hydroxy, aryloxy, amino, amide, meth poxy)-diphenyl ketone, ((chloromethyl)phenylethyl)tri acrylate, mercapto, carbonyl, urethane, pyrrole, carboxy, methoxysilane and phenyldimethylethoxysilane. cyano, aminoacyl, or acylamino, alkyl ester, and aryl ester, X 0025 Exemplary silanes having an epoxy moiety include, has a value between 1 and 3. Such that more than one siloxane but are not limited to, 3-glycidoxypropyltrimethoxysilane bond may be formed between the at least one functional and 2-(3.4-epoxycyclohexyl)ethyltrimethoxysilane. particulate carrier material and the at least one silane; R is 0026 Exemplary silanes having an amino moiety include, any carbon-bearing moiety that does not substantially reactor but are not limited to, 3-aminopropyltrimethoxysilane, N-(2- interact with the at least one functional particulate carrier aminoethyl)-3-aminopropyltrimethoxysilane, trimethoxysi material during the treatment process, such as but not limited lylpropyldiethylenetriamine, 2-(trimethoxysilylethyl)pyri to Substituted or unsubstituted alkyl, alkenyl, alkaryl, alkcy dine, N-(3-trimethoxysilylpropyl)pyrrole, cloalkyl, aryl, cycloalkyl, cycloalkenyl, heteroaryl, heterocy trimethoxysilylpropyl polyethyleneimine, bis-(2-hydroxy clic, cycloalkaryl, cycloalkenylaryl, alkcycloalkaryl, alkcy ethyl)-3-aminopropyltriethoxysilane, and bis(2-hydroxy cloalkenyaryl, and arylalkaryl; R is any organic containing ethyl)-3-amino propyltriethoxysilane. moiety that remains Substantially chemically attached to the 0027 Exemplary silanes having aurea moiety include, but silicon atom of Formula (I) once the at least one Surface are not limited to, N-(triethoxysilylpropyl)urea and N-1-phe treatment is completed and that is capable or reacting or nylethyl-N'-triethoxysilylpropylurea. interacting with the at least one active ingredient, such as but not limited to hydrogen, alkyl, alkenyl, alkaryl, alkcycloalkyl, 0028. A nonlimiting example of a silane having a meth aryl, cycloalkyl, cycloalkenyl, heteroaryl, heterocyclic, acrylate moiety is 3-(trimethoxysilyl)propyl methacrylate. cycloalkaryl, cycloalkenylaryl, alkcycloalkaryl, alkcycloalk 0029. Exemplary silanes having an imidazole moiety enyaryl, arylalkaryl, alkoxy, halogen, hydroxy, aryloxy, include, but are not limited to, N-3-(triethoxysilyl)propyl amino, amide, methacrylate, mercapto, carbonyl, urethane, imidazole and N-(3-triethoxysilylpropyl)-4,5-dihydroimida pyrrole, alkyl ester, aryl ester, carboxy, Sulphonate, cyano, Zole. aminoacyl, acylamino, epoxy, phosphonate, isothiouronium, 0030. A nonlimiting example of a silane having a carbonyl thiouronium, alkylamino, quaternary ammonium, trialky moiety is 3-(triethoxysilyl)propylsuccinate. lammonium, alkyl epoxy, alkyl urea, alkyl imidazole, or alky 0031 Exemplary silanes with an isocyano moiety include, lisothiouronium; wherein the hydrogen of said alkyl, alkenyl, but are not limited to, tris(3-trimethoxysilylpropyl)isocyanu aryl, cycloalkyl, cycloalkenyl, heteroaryl, and heterocyclic is rate and 3-isocyanatopropyltriethoxysilane. optionally Substituted by, for example, halogen, hydroxy, 0032. A nonlimiting example of a silane having an amino, carboxy, or cyano. isothiourium moiety is the salt of trimethoxysilylpropyl 0020. In another embodiment, at least one functional par isothiouronium, Such as the chloride salt. ticulate carrier material with a hydroxyl-bearing porous Sur 0033 Exemplary silanes having an ether moiety include, face is Subjected to at least one surface treatment with at least but are not limited to, bis(3-methyldimethoxysilyl)propyl one silane. Such that the material Surface is covalently bonded polypropylene oxide and N-(triethoxysilylpropyl)-O-poly to the at least one silane. In Such an embodiment, the Surface ethylene oxide urethane. area of the at least one functional particulate carrier material 0034. A nonlimiting example of a silane having a Sul may limit the amount of the bound silane and, as a result, it fonate moiety is 2-(4-chlorosulfonylphenyl)-ethyltrichlo may be preferable to subject the carrier material to at least one rosilane. physical Surface treatment that increases the Surface area of 0035 Exemplary silanes having a urethane moiety the carrier material prior to treatment with the at least one include, but are not limited to, N-(triethoxysilylpropyl)-O- silane. polyethylene oxide urethane and O-(propargyloxy)-N-(tri 0021. In a further embodiment, the at least one functional ethoxysilylpropyl) urethane. particulate carrier material is subjected to at least one Surface 0036) A nonlimiting example of a silane having a sulfhy treatment with at least one silane having one or more moieties dryl moiety is 3-mercaptopropyltriethoxysilane. selected from the group consisting of alkoxy, quaternary 0037 Exemplary silanes having an amide moiety include, ammonium, aryl, epoxy, amino, urea, methacrylate, imida but are not limited to, triethoxysilylpropylethyl-carbamate, Zole, carboxy, carbonyl, isocyano, isothiorium, ether, phos N-(3-triethoxysilylpropyl)-gluconamide, N-(triethoxysilyl phonate, Sulfonate, urethane, ureido, Sulfhydryl, carboxylate, propyl)-4-hydroxybutyramide. amide, pyrrole, and ionic. 0038. In yet another embodiment, the at least one func 0022 Exemplary silanes having analkoxy moiety include, tional particulate carrier material is subjected to Surface treat but are not limited to, are mono-, di-, or trialkoxysilanes. Such ment with a combination of silanes, such as but not limited to: as n-octadecyltriethoxysilane, n-octytriethoxysilane, and N-trimethoxysilylpropyl-N,N.N-trimethylammonium chlo phenyltriethoxysilane. ride and bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane; US 2010/0239.679 A1 Sep. 23, 2010

3-aminopropyltrimethoxysilane and N-(triethoxysilylpro in a vapor phase, which causes the vapor of the at least one pyl)-O polyethylene oxide urethane: 3-trihydrosilylpropy silane to contact and react with the at least one functional lmethylphosphonate, sodium salt, and N-(triethoxysilylpro particulate carrier material. pyl)-O-polyethylene oxide urethane; 0042. In another embodiment, the at least one functional N-trimethoxysilylpropyl-N,N.N. Cl, trimethylammonium particulate carrier material is placed in a vacuum reactor and chloride and (3-glycidoxypropyl) trimethoxysilane: 3-trihy dried under vacuum. At least one silane may then be added to drosilylpropylmethylphosphonate, sodium salt and bis-(2- the vacuum chamber as a vapor and contact the at least one hydroxyethyl)-3-aminopropyltriethoxysilane; 3-(N-styrylm functional particulate carrier material. After a certain contact ethyl-2-aminoethylamino)-propyltrimethoxysilane time, byproducts of the reaction may be removed under hydrochloride and N-(triethoxysilylpropyl)-O-polyethylene reduced pressure. When the vacuum is released, the surface urethane: 2-(trimethoxysilylethyl)pyridine and N-(3-tri treated carrier material may be removed from the chamber. ethoxysilylpropyl)-gluconamide; trimethoxysilylpropyl-N, The actual treatment process may be carried out in a period N.N. Cl, trimethylammonium chloride and N-(3-triethox from about 1 minute to about 24 hours. The treatments can be ysilylpropyl)-gluconamide: N-trimethoxysilylpropyl-N,N. carried out attemperatures ranging from about 0°C. to about N—Cl, trimethylammonium chloride and 2-hydroxy-4-(3- 400° C. triethoxysilylpropoxy)-diphenylketone; 0043. The amount of at least one silane used in the at least mercaptopropyltriethoxysilane and N-(triethoxysilylpropyl)- one surface treatment may depend on various factors, includ O-polyethylene oxide urethane: 3-(triethoxysilyl)propylsuc ing but not limited to the amount of the at least one carrier cinic and N-(triethoxysilylpropyl)-O-polyethylene urethane, material to be surface treated, the number of hydroxyl groups trimethoxysilylpropyl-ethylenediamine, triacetic acid, triso on the surface of the at least one carrier material to be reacted, dium salt and N-(triethoxysilylpropyl)-O-polyethylene oxide and the molecular weight of the at least one silane. In one urethane: 2-(4-chlorosulfonylphenyl)-ethyltrichlorosilane embodiment, a stoichiometric amount equivalent to the avail and N-(triethoxysilylpropyl)-O-polyethylene oxide ure able surface hydroxyls plus some excess amount of the at thane; and 2-(4-chlorosulfonylphenyl)-ethyltrichlorosilane least one silane is used for the at least one surface treatment, and bis-(2-hydroxyethyl)-3-aminopropyltriethoxysilane. in an effort to reduce the number of potential side reactions. In 0039. In some embodiments, silanization may proceed another embodiment, greater than a stoichiometric amount of according to “wet' or “dry” processes well-known to the at least one silane is used to create a thicker or more dense skilled artisan. For example, a “wet process generally com surface treatment. In one embodiment, about 0 to about 500 prises reacting the at least one silane onto the at least one times Stoichiometric excess is used. In another embodiment, functional particulate carrier material in at least one solvent about 5 to about 100 times stoichiometric excess is used. In a (e.g., organic solvent or water). In one embodiment, heat is further embodiment, about 10 to about 50 times stoichiomet used in place of or in addition to the at least one solvent. Heat ric excess is used. In yet another embodiment, about 10 to or solvent is not required for the “wet process, but it may about 20 times Stoichiometric excess is used. improve the reaction rate and the uniform Surface coverage. 0044. In some embodiments, at least one silane with at In another embodiment, a “wet process includes in-line mix least one hydrolysable group may condense with at least one ing of slurries or liquids during typical silanization process hydroxyl group on the Surface of the at least one functional ing steps, including but not limited to filtration and drying. particulate carrier material and provide covalent coupling of 0040. In one embodiment, a “dry” process generally com organic groups to those Substrates. In one embodiment, at prises reacting the at least one silane with the at least one least one alkoxy group of the at least one silane chemically functional particulate carrier material in a vapor phase by reacts with at least one hydroxyl group on the Surface of the at mixing the at least one silane with the at least one functional least one functional particulate carrier material. In another particulate carrier material and then heating the mixture. In embodiment, at least one silane having at least one quaternary another embodiment, a “dry” process comprises reacting the ammonium moiety is used and the protonated, positive charge at least one silane with the at least one functional particulate of those silanes electrostatically attract to at least one depro carrier material in a stirred liquid phase by mixing the at least tonated group of the at least one functional particulate carrier one silane with the at least one functional particulate carrier material to facilitate fast and efficient reaction. material and then heating the mixture. In one embodiment, a “dry” process comprises mixing at least one silane with at Surface Treated Functional Particulate Carrier Materials least one functional particulate carrier material and incubat 0045. Further disclosed herein is at least one surface ing in a sealed container at elevated temperatures to speed up treated functional particulate carrier material, which is pro the Surface treatment process. In yet another embodiment, the duced from at least one surface treatment of at least one “dry” process includes mixing of dry powdered functional functional particulate carrier material. In one embodiment, particulate carrier materials and a liquid silane additive, the silanized functional particulate carrier materials have the where the amount of silane added is Small enough that the general formula selected from the group consisting of For reaction mass remains solid-like and can continue to be pro mulas (II) to (IV): cessed like a dry powder. Particle-O-Si(R').(R)-R (II) 0041. In one embodiment, the at least one functional par ticulate carrier material is Subjected to at least one Surface Particle-O-Si(R'),(R') RNR CH, C(-OR) treatment with at least one silane by adding the at least one R6 R'N' (R)Cl. (III) silane gradually to a rapidly stirred solvent, which is in direct contact with the at least one functional particulate carrier Particle-O-Si(R').(R), RORC(-OH)R material. In another embodiment, the at least one functional CHSO. Na' (IV) particulate carrier material is Subject to at least one Surface wherein R. R. R. and X may be the same as described above treatment with at least one silane by carrying out the treatment for Formula (I), so long as no more than four groups directly US 2010/0239.679 A1 Sep. 23, 2010 attach to the silicon atom; R. R. R may be independently carrier materials made according to the present invention. In hydrogen, Substituted or unsubstituted alkyl, alkenyl, alkaryl, one embodiment, the Surface treated functional particulate alkcycloalkyl, aryl, cycloalkyl, cycloalkenyl, heteroaryl, het carrier material absorbs the at least one active ingredient. In erocyclic, cycloalkaryl, cycloalkenylaryl, alkcycloalkaryl, another embodiment, the Surface treated functional particu alkcycloalkenyaryl, ether, esteriorarylalkaryl; and, R. R. R. late carrier material bonds to the at least one active ingredient. may be substituted or unsubstituted alkyl, alkenyl, alkaryl, alkcycloalkyl, aryl, cycloalkyl, cycloalkenyl, heteroaryl, het 0051. The at least one active ingredient may take any of erocyclic, cycloalkaryl, cycloalkenylaryl, alkcycloalkaryl, various forms and fulfill any of various functions. In one alkcycloalkenyaryl, or arylalkaryl radicals capable of form embodiment, the at least one active ingredient is any Sub ing two covalent attachments. stance that will bind to or otherwise interact with at least one 0046. In some embodiments, the product of at least one functional particulate carrier material that has been Subjected functional particulate carrier material Subjected to at least one to at least one surface treatment. In another embodiment, the Surface treatment with at least one silane may have at least one at least one active ingredient is any Substance that will bind to functional moiety. Exemplary functional moieties include, or otherwise interact with at least one functional particulate but are not limited to, a selection from the group consisting of carrier material that has been Subjected to at least one Surface quaternary ammonium, epoxy, amino, urea, methacrylate, treatment, the activated product of which is useful as an imidazole, Sulphonate, and other organic moieties known to additive to Substances such paints, resins, and plastics. In a react with biological molecules. In one embodiment, the further embodiment, the at least one active ingredient is cho functionally moiety is further reacted, using well-known Sen from the group consisting of biocides, insecticides, and methods to create further new functionalities for other inter fungicides. actions. 0052. In one embodiment, the at least one active ingredi 0047 Surface treated functional particulate carrier mate ent is at least one biocide. Exemplary classes of biocides rials made according to the present invention may be charac include, but are not limited to, germicides, bactericides, fun terized, for instance, by measuring Surface area, pore Volume, gicides, algaeicides, rodenticides, avicides, molluscicides, and pore size using methods known to the art, Such as a piscicides, insecticides, acaricides and products to control Micrometrics analyzer. For example, Surface area can be other arthropods, disinfectants, human hygiene biocidal characterized by BET technique. Pore volume and pore diam products, private area and public health disinfectants, veteri eter can be calculated by Barrett-Joyner-Halenda analysis. nary hygiene biocidal products, food and feed area disinfec Specific functional groups and molecular structure can be tants, drinking water disinfectants, pest repellants, pest attrac determined by NMR and IR spectroscopy. Carbon-hydrogen tants, antifouling products, embalming fluids, taxidermist nitrogen content can be determined by combustion tech fluids, and vertebrate control biocides. niques; from that analysis information, the treatment level on 0053 Exemplary biocides includes, but are not limited to, the particle surface can be calculated. The skilled artisan neem oil, isothiazolinones, silver oxides, silver salts (e.g., readily understands that the embodiments disclosed herein silverhalogenide, silver nitrate, silver sulfate, silver carboxy may utilize any method of characterizing the functional par lates (e.g., silver acetate, silver benzoate, silver carbonate, ticulate carrier materials. silver citrate, silver lactate, silver salicylate)), copper oxides, Uses for Surface Treated Functional Particulate Carrier Mate copper salts (e.g., copper Sulfide, copper nitrate, copper car rials bonate, copper Sulfate, copper halogenides, copper carboxy 0048. The surface treated functional particulate carrier lates), Zinc oxides, Zinc salts (e.g., Zinc sulfide, Zinc silicate, materials produced according to the present invention may be Zinc acetate, Zinc chloride, Zinc nitrate, Zinc sulfate, Zinc used in a variety of applications. In one embodiment, methods gulconate, Zinc lactate, Zinc oxalate, Zinc iodate, Zinc iodide), to use the Surface treated functional particulate carrier mate iodopopargyl butyl carbamate, aldehydes, formaldehyde rials to bind at least one active ingredient are disclosed. In condensates, triazines (e.g., 1,3,5-tris-(2-hydroxyethyl-1,3, another embodiment, Surface treated functional particulate 5-hexahydrotriazine)), dazomet (e.g., 3,5-dimethyl-2H-1,3, carrier materials are used to enhance the antimicrobial activ 5-thiadiaZinane-2-thione), glutaraldehyde (e.g., 1.5 Pen ity by capturing soluble active ingredients through electro tanedial), phenolics, carbonic acid esters, Surfactant for static, hydrophobic, and/or hydrophilic interaction mecha hypochlorite (commercially available as Accepta 8001 from nisms. AcceptaTM Advanced Chemical Technologies), bronopol 0049. In another embodiment, specific charged groups (10%) (such as Accepta 8004 available from AcceptaTM have been attached covalently to the surface of the functional Advanced Chemical Technologies), chlorine release tablets, particulate carrier materials so they can be used to capture at TriChloroisocyanurate (such as Accepta 8005 available from least one active ingredient electrostatically. The oppositely AcceptaTM Advanced Chemical Technologies), DiChloroiso charged materials may, therefore, be bound to the porous cyanurate Granules (such as Accepta 8007 available from treated surface. In a further embodiment, in addition to the AcceptaTM Advanced Chemical Technologies), Air Hygiene electrostatic attraction, hydrophobic or hydrophilic ligands Biocide (such as Accepta 8008 available from AcceptaTM are used to improve the binding and/or release characteristics Advanced Chemical Technologies), Multifunctional Chlo of the functional particulate carrier materials by hydrophobic rine Tablets, DiChloroisocyanurate (such as Accepta 8009 or hydrophilic interaction. The skilled artisan readily under available from AcceptaTM Advanced Chemical Technolo stands that the embodiments disclosed herein may utilize any gies), Bio-Dispersant (Oil Fouling) for Cooling Water Sys method to use the Surface treated functional particulate car tems (such as Accepta 8010 available from AcceptaTM rier materials to bind to active ingredients. Advanced Chemical Technologies), Eco-Friendly Biocide based on Hydrogen Peroxide & Silver (such as Accepta 8101 Active Ingredient available from AcceptaTM Advanced Chemical Technolo 0050. At least one active ingredient may bind to or other gies), Hard Surface Cleaner and Surfactant, Hydrogen Per wise interact with the surface treated functional particulate oxide/Silver (such as Accepta 8102 available from AcceptaTM US 2010/0239.679 A1 Sep. 23, 2010

Advanced Chemical Technologies), Tablets for Air Condi thyl-4-isothiazolin-3-one), N-haloalkylthio compounds (e.g., tioning Systems (such as Accepta 8205 available from N-dichlorofluoromethylthiophthalimide), a blend of 2-Me AcceptaTM Advanced Chemical Technologies), Chlorine thyl-4-isothiazolin-3-one (MIT) and 5-Chloro-2-methyl-4- Dioxide Tablets (such as Accepta 8502. Accepta 8505, and isothiazolin-3-one (CIT) known as CIT/MIT, a combination Accepta 8510, each available from AcceptaTM Advanced of CIT/MIT and hydroxymethyl ureide derivatives (such as Chemical Technologies Stabilised Chlorine Dioxide in Solu Acticide(R) FI(N) and Acticide(R) FS(N)), a combination of tion (1000 ppm) (such as Accepta 8520 available from CIT/MIT and formaldehyde (such as Acticide RHF), a com AcceptaTM Advanced Chemical Technologies), 2 Part Chlo bination of CIT/MIT and bronopol monovalent stabilized rine Dioxide Powder-0.3% solution in 25 L (such as Accepta (such as Acticide(R) LA), aqueous formulations of MIT, BIT, 8551 available from AcceptaTM Advanced Chemical Tech and hydroxymethyl ureide derivatives (such as Acticide(R) nologies), 2 Part Chlorine Dioxide Powder-0.3% solution in MBF), aqueous formulations of MIT/BITNovel CIT (such as 100 L (such as Accepta 8552 available from AcceptaTM Acticide(R) MBS), sodium nitrate stabilized bivalent metal Advanced Chemical Technologies), 2 Part Chlorine Dioxide free aqueous CIT/MIT formulation (such as Acticide(RMV), Powder-0.3% solution in 1000 L (such as Accepta 8553 avail magnesium and copper stabilized aqueous CIT/MIT formu able from AcceptaTM Advanced Chemical Technologies), lation (such as Acticide(R) RS), magnesium nitrate stabilized THPS (such as Accepta 2102 available from AcceptaTM aqueous CIT/MIT formulation (such as Acticide(R) SPX), and Advanced Chemical Technologies), Glutaraldehyde (such as a combination of bacticides and fungicides in aqueous sol Accepta 2103 available from AcceptaTM Advanced Chemical vent based and powder form (such as Acticide(RTBW. Acti Technologies), Sodium Bromide Solution (40%) (such as cide(RTBS, and Acticide(RTBP). In one embodiment, the at Accepta 2104 available from AcceptaTM Advanced Chemical least one active ingredient is Neem oil. In another embodi Technologies), Isothiazoline (such as Accepta 2113 available ment, the at least one active ingredient is an isothiazolinone. from AcceptaTM Advanced Chemical Technologies), Biocide Exemplary isothiazolin-3-ones include, but are not limited to, for Cooling Water Systems (such as Accepta 2301 available 2-methyl-4-isothiazolin-3-one, 2-ethyl 4-isothiazolin-3-one, from AcceptaTM Advanced Chemical Technologies), Biode 2-propyl-4-isothiazolin-3-on, 2-butyl-4-isothiazolin-3-one, gradable Biocide for Cooling Water Systems (such as 2-amyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothia Accepta 2302 available from AcceptaTM Advanced Chemical Zolin-3-one, 5-bromo-2-methyl-4-isothiazolin-3-one, Technologies), Bio-dispersant for Cooling Water Systems 5-iodo-2-methyl-4-isothiazolin-3-one, 5-chloro-2-butyl-4- (such as Accepta 2306 available from AcceptaTM Advanced isothiazolin-3-one, 5-bromo-2-ethyl-isothiazoline-3-one, Chemical Technologies), 1.5% Isothiazoline, (such as 5-iodo-2-amyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3- Accepta 2027 available from AcceptaTM Advanced Chemical one, 2-n-octyl-4-isothiazolin-3-one, 4.5-dichloro-2-n-octyl Technologies), DBNPA, 2.2-DiBromo 3-Nitrilo Propriona 4-isothiazolin-3-one and other similar analogues and homo mide (such as Accepta 2028 available from AcceptaTM logues within the genus. Other exemplary biocides are listed Advanced Chemical Technologies), Hypochlorite plus Sur in Commission Regulation (EC) No. 1048/2005 of 13 Jun. factant to Penetrate Biofilms (such as Accepta 2029 available 2005 from the Official Journal of the European Union, which from AcceptaTM Advanced Chemical Technologies), 5% is incorporated by reference herein in its entirety. Chlorite for Chlorine Dioxide Generators (such as Accepta 0054. In another embodiment, the at least one active ingre 2055 available from AcceptaTM Advanced Chemical Tech dient is at least one pesticide. Exemplary pesticides include, nologies), 8% Chlorite for Chlorine Dioxide Generators but are not limited to, (((2-dihydro-5-methyl-3(2H)-ox (such as Accepta 2056 available from AcceptaTM Advanced azolyl)-1-methylethoxy)methoxy)methanol, (((2-dihydro Chemical Technologies), 25% Chlorite for Chlorine Dioxide 5-methyl-3(2H)-oxazolyl)-1-methylethoxymethoxy)meth Generators (such as Accepta 2057 available from AcceptaTM oxymethanol, 1,1,2,3-tetramethyl butylamine dodecyl Advanced Chemical Technologies), Bromine Tablets benzene sulphonate, 1,12-Di(3-decyl-2-methylimidazolium) (BCDMH) (such as Accepta 2073 available from AcceptaTM dodecane dibromide, 1,2-benzisothiazolin-3-one, 1,2-Ben Advanced Chemical Technologies), Biodispersant (such as Zisothiazolin-3-one, 2-butyl-1,2-dibromo-2,4-dicyanobu Accepta 2075 available from AcceptaTM Advanced Chemical tane, 1,3-Bis(2-hydroxyethyl)-2-heptadecenyl Technologies), Stabilised Bromine (Activated) (such as imidazolinium chloride, 1,3-dibromo-5,5-dimethylhydan Accepta 2078 available from AcceptaTM Advanced Chemical toin, 1,3-dichloro-5,5-dimethylhydantoin, 1,3-Dichloro-5- Technologies), 3% isothiazolin (such as Accepta 2086 avail ethyl-5-methylhydantoin, 1,3-propane diamine dodecylben able from AcceptaTM Advanced Chemical Technologies), Zene Sulphonate, 1.3-Propanediamine, N-(3-aminopropyl)- Quaternary Biocide, Ammonium based plus Antifoam (Such N-dodecyl-1,4-bis(bromoacetoxy)-2-butene, 1-(2- as Accepta 2087 available from AcceptaTM Advanced Chemi hydroxyethyl)-2-alkyl-2-imidazoline, alkyl derived from tall cal Technologies), 0.5% Isothaizoline (such as Accepta 2093 oil fatty acids, 1-(2-Hydroxyethyl)-2-heptadecenyl-2-imida available from AcceptaTM Advanced Chemical Technolo Zoline, 1-(2-Hydroxyethyl)-2-n-alkyl (C18)-2-imidazoline gies), Bacteria Anti-foulant for Marine Cooling Water Sys 1-(3-chloroallyl)-3,5,7-triaza-1-azonia adamantane chloride, tems (such as Accepta 3553 available from AcceptaTM 1-(Alkylamino)-3-aminopropane(as in fatty acids of coco Advanced Chemical Technologies), Rapid Dissolving Micro nut oil), 1-(Alkylamino)-3-aminopropane diacetate (37% Chlorine Tablets (such as Accepta 9010 available from C18, 29% C16, 23% C18.3% C16', 3% C14, 1.5% C18", 1% AcceptaTM Advanced Chemical Technologies), Multifunc C14, 1% C12, 0.5% C15), 1-(Alkylamino)-3-aminopro tional Chlorine Tablets (200 g) (such as Accepta 9011 avail pane (47% C12, 18% C14, 10% C18, 9% C10, 8% C16, 8% able from AcceptaTM Advanced Chemical Technologies), C8), 1-(Alkylamino)-3-aminopropane diacetate (as in fatty amides (e.g., N(3,4-dichlorophenyl)-N,N-dimethyl urea), acids of coconut oil), 1-(Alkylamino)-3-aminopropane carbamates (e.g., methyl-N-benzimidazol-2-methylcarbam monoacetate (47% C12, 18% C14, 10% C18, 9% C10, 8% ate), thiocarbamates, thiocyanates, dibenzamidines, pyridine C16, 8% C8), 1-(Alkyl amino)-3-aminopropane propionate derivatives, triazoles, thiazoles, isothiazolones, (e.g., 2-me copper acetate complex 1-(alkyl-amino)-3-aminopropane US 2010/0239.679 A1 Sep. 23, 2010 hydrochloride 1-(alkylamino)-3-aminopropane 1-(alky 2-Mercaptobenzothiazole, Zinc salt, 2-Methyl-3(2H)-isothia lamino)-3-carboxymethylaminopropane, 1-Alkyl (C6 to Zolone, calcium chloride complex, 2-methyl-4,5-trimethyl C18) amino-3-aminopropane acetate 1-alkylamino-2-amino ene-4-isothiazolin-3-one 2-methyl-4-isothiazolin-3-one propane monoacetate, alkyl derived from coconut oil fatty 2-Nitro-2-ethyl-1,3-propanediol, 2-Nitro-2-methyl-1,3-pro acids, 1-Alkylamino-3-aminopropane hydroxyacetate, alkyl panediol 2-tert-Amylphenol 3 (2H)-chloro-2-methyl-3(2H)- derived from coconut oil fatty acids 1-bromo-3-chloro-5,5- isothiazolone, calcium chloride complex 3.3,4,4-tetrachloro dimethyl hydantoin, 1-Heptadecenyl-2-(2-hydroxyethyl)-2- tetrahydro thiophene, 1,1-dioxide 3,3,4,4-tetrachlorotetrahy imidazolinium chloride 1-hydroxyethyl-1-benzyl-2-alkyl drothiophene, 1,1-dioxide, other related 3,3,4-Trimethylox imidazolinium chloride. 1-Hydroxymethyl-5,5-dimethyl azolidine mixt. with 4,4-dimethyloxazolidine 3,4,4-trimethyl hydantoin 1-Hydroxymethyl-5,7-dichloroindazole, 1-me oxazolidine 3,4,5-tribromo salicylanilide, other related 3,4- thyl-1-tallow-2-amido ethyl-2-heptadecyl imidazolinium Dichloro-5-isothiazolecarboxylic acid, 3.5-dibromosalicyla nonemethosulfate, 1-methyl-3,5,7-triaza-1-azonia tricyclo nilide, 3-(Hydroxymercuri)-4-nitro-o-phenol, Sodium salt, (3.3.1.1.3.7) decane 10,10'-Oxybisphenoxyarsine, 2,2'-(1- 3-(trimethoxysilyl) propyl dimethyl octadecyl ammonium methyltrimethylenedioxy)bis-(4-methyl-1,3,2-dioxabori chloride, 3-Bromo-1-chloro-5,5-dimethylhydantoin, nane), 2,2'-(coco alkyl imino) bis(ethanol) with bis(2-ethyl 3-chloro-2-biphenylol, sodium salt, 4 & 6-chloro-2-phe hexyl)phosphate (1:1), 2,2'-(coco alkyl imino) bis(ethanol) nylphenol, 4 & 6-chloro-2-phenylphenol, potassium salts, with mono (2-ethylhexyl)phosphate (1:1), 2,2'-Dithiobisben mixed 4 & 6-chloro-2-phenylphenol, Sodium salts, mixed 4 & Zothiazole, 2,2'-Methylenebis(4,6-dichlorophenol) 2,2'-oxy 6-chloro-2-phenylphenol, other related 4 or 6-chloro-2-phe bis (4,4,6-trimethyl-1,3,2-dioxaborinane), 2,2-dibromo-3- nylphenol 4 or 6-chloro-2-phenylphenol, diethanolamine nitrilopropionamide 2.2-methylene bis(4,6-dichlorophenol) salt, 4'-hydroxy-m-phenoxybenzoic acid 4.4-(2-ethyl-2-ni Sodium salt, 2.2-oxybis (4-dodecyl benzene Sulfonate), 2.3, trotrimethylene) dimorpholine, 4.4-dimethyl oxazolidine, 5,6-tetrachloro-4-(methylsulfonyl)pyridine, 2,3,5,6-tetra 4,4-dimethyl-2-oxazolidinone, 4.5-dibromosalicylanilide chloro-4-(methylsulfonyl)pyridine, other related 2,3,5- 4,5-dichloro-2-n-octyl-3(2H)-isothiazolone, 4,6-dichloro-2- trichloro-4-(propylsulfonyl)pyridine, 2,3,5-trichloro-4- phenylphenol. 4,6-dichloro-2-phenylphenol, potassium salt, (propylsulfonyl)pyridine, other related 2,4,5- 4-(2-nitrobutyl) morpholine 4-chloro-2-cyclopentyl phenol, trichlorophenol. 2,4,5-Trichlorophenol salt of 2,6-bis potassium salt 4-chloro-2-cyclopentylphenol, 4-chloro-2-n- ((dimethylamino)methyl)cyclohexanone 2,4,5- octyl-3(2H)-isothiazolone, 4-chloro-2-phenylphenol, trichlorophenol potassium salt, 2,4,5-trichlorophenol, 4-chloro-2-phenylphenol, potassium salt, 4-chloro-2-phe potassium salt, other related 2,4,5-Trichlorophenol sodium nylphenol, sodium salt, 4-chloro-cyclopentylphenol, sodium salt 2,4,5-trichlorophenol sodium salt, other related 2.4.6- salt, 5,4-dibromosalicylanilide, 5-Bromo-2-methyl-5-nitro trichlorophenol. 2.4.6-Trichlorophenol sodium salt, 2,4-Xy 1,3-dioxane 5-chloro-2-((4-chlorophenyl)methyl)-3(2H)- lenol 2,6-bis(1-methyl heptadecyl)-p-cresol, 2-((2-amino isothiazolone, compound with 2-((4-chlorophenyl)methyl)- ethyl)amino) ethanol dodecyl benzene Sulphonate, 2-((hy 3(2 h)-isothiazolone (1:1), 5-chloro-2-(4- droxymethyl)amino)ethanol. 2-((hydroxymethyl)amino)-2- chlorophenylmethyl)-3(2H)-isothiazolone, 5-Chloro-2- methyl-1-propanol. 2-(2-(p-(diisobutyl)phenoxy)ethoxy) mercaptobenzothiazole, lauryl pyridinium salt 5-Chloro-2- ethyl dimethyl ammonium chloride, 2-(4- mercaptobenzothiazole, Zinc salt, 5-chloro-2-methyl-4- chlorophenylmethyl)-3(2H)-isothiazolone, 2-(decylthio) isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one ethanamine, hydrochloride salt, 2-(p-Hydroxyphenyl) calcium chloride with 2-methyl-4-isothazolin-3-one calcium oxoacetohydroximic chloride, 2-(thiocyanomethylthio) chloride, 5-hydroxy methoxy methyl-1-aza-3,7-dioxabicyclo benzothiazole with 2'-hydroxyethyl-2,3-dibromopropionate, (3.3.0) octane 5-hydroxymethyl-1-aza-3,7-dioxabicyclo 2-Alkyl-1 (or 3)-benzyl-1-(2-hydroxethyl)-2-imidazo (3.3.0) octane 5-hydroxypoly(methyleneoxy) (74% C2, 21% linium chloride (as 1 n fatty acids of tall oil), 2-Alkyl-1-(2- C3, 4% C4, 1% C5) methyl-1-aza-3,7-dioxabicyclo (3.3.0), hydroxyethyl)-2-imidazoline phosphate(100% C13), octane 6-chloro-2-phenylphenol, 6-chloro-2-phenylphenol, 2-Alkyl-1-(4-chlorobutyl)-1-(2-hydroxyethyl)-2-imidazo potassium salt, 6-tert-Butyl-4-chloro-m-cresol, 8-Hydrox linium chloride'(100% C6-C17), 2-Alkyl-1-benzyl-1-(2- ycuinoline, 8-Hydroxyquinoline benzoate, 8-Hydroxyquino hydroxyethyl)-2-imidazolinium nitrate (100% C11-C17), line citrate, 8-Hydroxyquinoline Sulfate a-(p-nonylphenyl)- 2-Alkyl-2-imidazolinium hydroxide-1-carboxymethyl oxy omega-hydroxypoly (oxyethylene) with an average of 4.2 ethyl carboxymethyl, disodium salt of * (as in fatty acids of moles of ethylene oxide.the nonyl group is a propylene Abi coconut oil), 2-alkyl-1-benzyl-1-(2-hydroxyethyl)-2-imida etylamine Acetalized polyvinyl alcohol complexed with Zolinium chloride (alkyd 2-bromo-4-hydroxyacetophenone iodine Acetic acid Acetic acid, sodium salt, (2:1) Acylamido 2-butoxy ethanol phosphate 2-butoxyethanol 2-chloro-4- alkylbenzyl dimethyl ammonium chloride, Alcohols, phenylphenol 2-chloro-4-phenylphenol, potassium salt, C4-C12, normal Alcohols, C8-10 Alkenyl (75% C18, 25% 2-chloro-4-phenylphenol, Sodium salt, 2-Chlorophenol, C16) dimethylamine acetate, Alkenyl (90% C18, 10% C16) 2-ethoxyethanol, 2-Heptadecenyl-2-imidazoline, 2-heptade dimethyl ethyl ammonium bromide, Alkenylamine o-phe cyl-1-hydroxyethyl-imidazolinium hydrochloride, 2-hepta nylphenate (C8-C18), Alkenyl dimethyl ammonium chlo decyl-1-methyl-1-(2-stearoyl amide) ethyl) imidazolinium ride'(75% C18, 25% C16"), Alkenyl-dimethyl ethyl ammo methyl sulfate, 2-heptyl-2-imidazolinium hydroxide-1- nium bromide:*(90% C18, 10% C16), Alkenyldimethyl carboxy methyloxy ethyl-1-carboxy methyl, disodium salt, ethyl ammonium chloride'(75% C18, 25% C16'), 2-Lauryl isoquinolinium bromide, 2-Mercaptobenzothiaz Alkenyl dimethyl ethyl ammonium chloride'(90% C18', ole, 2-Mercaptobenzothiazole, 1-(hydroxyethyl)pyridinium 10% C16") Alkyl (29% C14, 29% C13, 21% C12, 21% C15) salt, 2-Mercaptobenzothiazole, ferric salt, 2-Mercaptoben poly(oxypropylene) poly (oxyethylene)-iodine complex, Zothiazole, manganese salt, 2-Mercaptobenzothiazole, Alkyl (46% C12, 24% C14, 10% C16, 8% C10, 7% C8, 5% monoethanolammonium salt, 2-Mercaptobenzothiazole, C18) aminobetaine, Alkyl (47% C12, 18% C14, 10% C18, potassium salt, 2-Mercaptobenzothiazole, sodium salt, 10% C16, 15% C8-C10) dimethylbenzyl ammonium chlo US 2010/0239.679 A1 Sep. 23, 2010

ride, Alkyl (50% C12,30% C14, 17% C16.3% C18) dimethyl C16, 2% C18), Alkyl dimethyl 3,4-dichlorobenzyl ammo dichlorobenzyl ammonium chloride, Alkyl (50% C12, 30% nium chloride (65% C12, 22% C14, 10% C16, 3% C18), C14, 17% C16, 3% C18) dimethylbenzyl ammonium chlo Alkyl dimethyl 3,4-dichlorobenzyl ammonium chloride ride, Alkyl (50% C12, 30% C14, 17% C16.3% C18) dimeth (50% C14, 40% C12, 10% C16), Alkyl dimethyl 3,4-dichlo ylethylbenzyl ammonium chloride, Alkyl (50% C14, 40% robenzyl ammonium chloride (63% C12, 23% C14, 14% C12, 10% C16) dimethylbenzyl ammonium saccharinate, C16), Alkyl dimethyl 3,4-dichlorobenzyl ammonium chlo Alkyl (50% C14, 40% C12, 10% C16) dimethylbenzyl ride (68% C12, 27% C14, 5% C16), Alkyl*dimethyl 3,4- ammonium chloride, Alkyl (53% C12, 19% C14, 8.5% C16, dichlorobenzyl ammonium chloride'(C12 65%, C14 25%, 7% C8, 6.5% C10, 6% C18)-1,3-propane diamine, Alkyl C16 10%), Alkyl dimethyl 3,4-dichlorobenzyl ammonium (58% C14, 28% C16, 14% C12) dimethylbenzyl ammonium chloride'(75% C12, 25% C14), Alkyl dimethyl 3,4-dichlo chloride, Alkyl (58% C18, 40% C16, 1% C14, 1% C12) robenzyl ammonium chloride (60% C14, 30% C16, 10% trimethyl ammonium chloride, Alkyl (60% C14, 25% C12, C12), Alkyl dimethyl 3,4-dichlorobenzyl ammonium chlo 15% C16) dimethylbenzyl ammonium chloride, Alkyl (60% ride (42% C12, 27% C14, 13% C16, 18% C8-C18), C14, 30% C16, 5% C12, 5% C18) dimethylbenzyl ammo Alkyl dimethyl 3,4-dichlorobenzyl ammonium chloride nium chloride, Alkyl (61% C12, 23% C14, 11% C16, 3% polyethoxypolypropoxypolyethoxyethanol-iodine complex C10, 2% C8) dimethylbenzyl ammonium chloride, Alkyl (50% C12, 30% C14, 1 Alkyl dimethyl ammonium bro (61% C12, 23% C14, 11% C16, 5% C18) dimethylbenzyl mide:*(50% C12, 30% C14, 17% C16, 3% C18), ammonium chloride, Alkyl (61% C12, 23% C14, 11% C16, Alkyl dimethyl ammonium bromide:*(67% C16, 30% C14, 5% C8, C10, C18) dimethylbenzyl ammonium chloride, 3% C12-C18), Alkyl dimethylbenzyl ammonium chloride Alkyl (61% C12, 23% C14, 11% C16, 2.5% C8& C10, 2.5% (60% C14, 30% C16, 5% C18, 5% C12), Alkyl dimethyl C18) dimethylbenzyl ammonium chloride, Alkyl (65% C12, benzyl ammonium chloride' (50% C12, 30% C14, 17% C16, 25% C14, 10% C16) dimethylbenzyl ammonium chloride, 3% C18), Alkyl dimethyl benzyl ammonium chloride Alkyl (67% C12, 25% C14, 7% C16, 1% C8, C10, C18) (100% C16), Alkyl dimethyl benzyl ammonium chloride dimethylbenzyl ammonium chloride Alkyl (68% C12, 32% (55% C16, 20% C14, 20% C12, 5% C18), Alkyl dimethyl C14) dimethyl dimethylbenzyl ammonium chloride, Alkyl benzyl ammonium chloride (67% C12, 25% C14, 7% C16, (68% C12, 32% C14) dimethylethylbenzyl ammonium chlo 1% C18), Alkyl dimethylbenzyl ammonium chloride'(61% ride, Alkyl (70% C18, 27% C16, 3% C14) trimethyl ammo C12, 23% C14, 11% C16, 5% C18), Alkyl dimethylbenzyl nium chloride, Alkyl (90% C14, 5% C12, 5% C16) dimethyl ammonium chloride (41% C14, 28% C12, 19% C18, 12% dichlorobenzyl ammonium chloride, Alkyl (90% C14, 5% C16), Alkyl dimethyl benzyl ammonium bentonite (as in C12, 5% C16) dimethylbenzyl ammonium chloride, Alkyl fatty acids of tallow), Alkyl dimethyl benzyl ammonium (90% C14, 5% C12, 5% C16) dimethyl ethyl ammonium chloride (55% C16, 27% C12, 16% C14, 2% C18), bromide, Alkyl (93% C14.4% C12.3% C16) dimethylbenzyl Alkyl dimethylbenzyl ammonium chloride'(95% C16, 5% ammonium chloride, Alkyl (95% C14, 3% C12, 2% C16) C18), Alkyl dimethyl benzyl ammonium chloride'(100% dimethylbenzyl ammonium chloride dehydrate, Alkyl (95% C18), Alkyl dimethylbenzyl ammonium ion alkylamine C14.3% C12, 2% C16) dimethylbenzyl ammonium chloride (C12, C14, C16)*(C10, C12, C14, C16), Alkyl dimethyl monohydrate, Alkyl (95% C14, 3% C12, 2% C16) dimethyl benzyl ammonium chloride'(65% C12, 25% C14, 10% C16), benzyl ammonium chloride, Alkyl (98% C12, 2% C14) dim Alkyl dimethylbenzyl ammonium chloride'(93% C14, 4% ethyl 1-naphthylmethyl ammonium chloride, Alkyl (C10-16) C12.3% C16), Alkyl dimethylbenzyl ammonium chloride dimethyl amine oxide, Alkyl (C10-C14) benzene sulfonic (47% C12, 18% C14, 15% (C5-C15), 10% C18, 10% C16), acid, calcium salt, Alkyl (C12-C15)-poly(oxypropylene) Alkyl dimethylbenzyl ammonium chloride (58% C14, 28% poly(oxyethylene)-iodine complex, Alkyl (C14, C12, C16) C16, 14% C12), Alkyl dimethyl benzyl ammonium chlo dimethylbenzyl ammonium chloride, Alkyl (C8-C18) bis(2- ride (60% C14, 25% C12, 15% C16), Alkyl dimethylbenzyl hydroxyethyl)benzyl ammonium chloride, Alkyl benzene ammonium chloride'(60% C14, 30% C16, 10% C12), sulfonic acid, Alkyl dimethylamine, Alkyl dimethyl cumenyl Alkyl dimethylbenzyl ammonium chloride (65% C12, 23% ammonium chloride, Alkyl dimethyl ethylbenzyl ammonium C14, 12% C16), Alkyl dimethyl benzyl ammonium chlo cyclohexyl sulphonate, Alkyl dimethyl ethylbenzyl ammo ride (67% C12, 25% C14, 7% C16, 1% C8, C10, and C18), nium cyclohexyl sulfamate, Alkyl dimethyl isopropylbenzyl Alkyl dimethylbenzyl ammonium chloride (67% C12, 27% ammonium chloride, Alkyl imidazoline monocarboxylate, C14, 6% C16), Alkyl dimethylbenzyl ammonium chloride monosodium salt, Alkyl methyl isoquinolinium chloride, (68% C12, 25% C14, 7% C16), Alkyl dimethyl benzyl Alkyl monoethyoxyethanol, diethoxyethyl benzyl ammo ammonium chloride'(90% C14, 5% C12, 5% C16), nium chloride, Alkyl trimethyl ammonium bromides, Alkyl Alkyl dimethyl benzyl ammonium chloride (as in fatty (ethyl cycloimidinium) 3-hydroxy-3-ethyl sodium alcohol acids of coconut oil), Alkyl dimethyl benzyl ammonium ate, 2-methyl sodium carboxylate-tridecyl polyoxyethylene chloride (C8-18), Alkyl dimethylbenzyl ammonium chlo ethanol, Alkylbenzyl trimethyl ammonium chloride (56% ride (61% C12, 23% C14, 11% C16, 3% C10, 2% C18), C12, 27% C11, 9% C13', 4% C10', 3% C14, 1% C15'), Alkyl dimethylbenzyl ammonium chloride (40% C12, 40% Alkylbenzyl trimethyl ammonium chloride' (50% C12, C14, 20% C16), Alkyl dimethylbenzyl ammonium dichlor 20% C13, 10% C14, 10% C11, 10% C10), Alkyl-bis(2-hy oisocyanurate (60% C14, 30% C16, 6% C12, 4% C18), droxyethyl)amine acetate (65% C18, 30% C16, 5% C14), Alkyl dimethyl betaines (46% C12, 24% C14, 10% C16, Alkyldihydroxyethyl amine oxide:* (50% C12, 27% C14, 8% C10, 7% C8, 5% C18), Alkyl dimethyl ethyl ammonium 10% C16, 8% C10, 5% C8), Alkyl dimethyl 3,4-dichlo bromide:*(85% C16, 15% C18), Alkyl dimethylethylammo robenzyl ammonium chloride'(90% C14, 5% C16, 5% C12), nium bromide (mixed alkyl and alkenyl groups as in fatty Alkyl dimethyl 3,4-dichlorobenzyl ammonium chloride acids of soybean oil), Alkyl dimethyl ethylbenzyl ammo (60% C12, 25% C14, 15% C16), Alkyl dimethyl 3,4-dichlo nium chloride (60% C14, 30% C16, 5% C12, 5% C18), robenzyl ammonium chloride' (55% C14, 23% C12, 20% Alkyl dimethyl furfuryl ammonium chloride (65% C18, US 2010/0239.679 A1 Sep. 23, 2010

30% C16, 5% C14), Alkyl dimethyl isopropylbenzyl ammo Calcium, Carbonate, treated, Calcium, Chlorate, Calcium, nium chloride (60% C14, 30% C16, 5% C12, 5% C18), Chloride, Calcium ethylenebis(dithiocarbamate), Calcium Alkyl dimethyl trichlorobenzyl, Ammonium chloride (50% hydroxide, Calcium hypochlorite-dodecylbenzene sulfonate, C14, 40% C12, 10% C16), Alkyl dodecylbenzyl dimethyl, Complex, Calcium nitrite, Calcium oxytetracycline, Calcium Ammonium chloride (67% C18, 33% C16), phosphate, tribasic, Calcium silicate, Camphor, Camphor oil, Alkyl monoethoxyethanol diethoxyethanol benzyl, Ammo Capric acid, Caprylic acid, Cetyl dimethyl ethyl ammonium nium chloride (48% C12, 17% C14, 11% C18, 9% C16, 8% bromide, Cetyl pyridinium, Chloride, Cetyl pyridium bro C8, 7% C10), Alkyl N,N-bis(2-hydroxyethyl)amine (100% mide, Cetyl trimethyl ammonium bromide, Cetyl trimethyl C8-C18), Alkylpoly(oxypropylene)poly(oxyethylene)-io ammonium, Chloride, Chloramine B, Chloramine T. Chlor dine complex*(43% C10, 30% C14, 12% C12, 10% C16.5% bisan, Chlorhexidine, Chlorhexidine diacetate, Chlorhexi C18), Alkylsodium benzene sulfonate (56% C11, 33% dine digluconate, Chlorhexidine dihydrochloride, Chlorhexi C12, 7% C10, 4% C13), Alkyltolyl methyl trimethyl, dine gluconate, Chlorine, Chlorine dioxide, Chlorite, Clay, Ammonium chloride (100% C9-C15), Alkyltributyl phos Chloroethylene bisthiocyanate, Chlorophyllin, Chloroxyle phonium chloride'(95% C12, 3% C14, 2% C10), nol, Chromated zinc, Chloride, Citric acid, Citric acid ammo Alkyltrimethyl, Ammonium bromide:*(95% C14, 5% C16), nium salt, Coal tar phenols, Coconut imidazoline, Sodium, Alkyltrimethyl, Ammonium chloride derived from cotton Carboxylate, Condensation product of mixed, Cresols, form seed oil, Alkyltrimethyl, Ammonium chloride'(90% C18, aldehyde and Sulfanilic acid, Copper 2-pyridinethio-1-oxide, 10% C16), Alkyltrimethyl, Ammonium chloride'(70% Copper 8-quinolinoleate, Copper ammonium, Complex (ac C18, 27% C16.3% C14), Alkyltrimethyl, Ammonium chlo etate/carbonate), Copper hydroxide, Copper pentachlo ride (as in fatty, Acids of coconut oil), Alkyltrimethyl, rophenate, Copper Zeolite, Cuprous thiocyanate, Cyanuric Ammonium chloride (70% C12, 30% C14), acid, Cyanuric acid, Chloride, Cyanuric acid monosodium Alkyltrimethyl, Ammonium chloride (alkyl. As in fatty, salt, Decyl phenoxybenzene disulfonic acid disodium salt, Acids of soybean oil), Alkyltrimethyl, Ammonium chlo Decyl phenoxybenzene disulfonic acid, Decyl-N-methyl-N- ride (58% C18, 40% C16, 1% C14, 1% C12), (3-trimethoxysilyl)propyl)-1-decanaminium chloride, Dehy Alkyltriphenyl phosphonium cloride'(95% C12, 3% C14, droabietylamine, Dehydroabietylamine acetate, Dehydroabi 2% C10), Alkyl-1-(2-aminoethyl)-2-imidazoline, Acetate etylamine pentachlorophenate, Device (Swimming pool nickel sulfate complex, Alkyl-5-hydroxy-4-oxo-2(4H)- algaecide, bacteriacide, molluscicide) no guarantee required pyranylmethyl dimethyl, Ammonium chloride (49% C12, Di(alkyloxypropyl)dimethyl ammonium chloride (60% 17% C14, 17% C10, 10% C18, 9% C16, 8% C8), Alkyl-8- C8, 40% C10), Di(phenylmercuric) dodecenyl succinate diamine monobenzoate (as in fatty, Acids of coconut oil), Dialkyl (85% C18, 15% C16), dimethylammonium chloride, Alkyl-N,N-bis(2-hydroxyethyl)methyl, Ammonium chlo Dialkyl dimethyl ammonium polynaphthyl amine, ride (53% C12, 19% C14, 8.5% C16, 7.0% C8, 6.5% C10, Dialkyl dimethyl ammonium bromide:* (50% C12, 30% 6.0% C18), Alkyl-N,N-di(hydroxyethyl)amine (as in fatty, C14, 17% C16.3% C18), Dialkyl dimethylammonium chlo Acids of soybean oil), Alkyl-1,3-propylene diamine, Acetate, ride (70% C18, 26% C16, 4% C14), Dialkyl dimethyl Alkyl derived from coconut oil fatty, Acids, Alkyl-1,3-propy ammonium chloride(47% C12, 18% C14, 10% C18, 9% lene diamine, Adipate, Alkyl derived from coconut oil fatty, C10, 8% C16, 8% C8), Dialkyl dimethyl ammonium chlo Acids, Alkyl-1,3-propylene diamine, Alkyl derived from ride (50% C12, 30% C14, 20% C16), Dialkyl dimethyl coconut oil fatty, Acids, Alkylamine, Acetate, Alkylamine ammonium chloride' (50% C12, 20% C14, 15% C10, 10% hydrochloride, Alkyl derived from coconut oil fatty, Acids, C16, 5% C18), Dialkyl dimethyl ammonium chloride (48% Alkylaryl Sulfonates, Alkylaryl Sulfonates, Amine salts, C12, 17% C14, 10% C18, 9% C16, 8% C8, 7% C10, 1% C6), Alkyldimethylbenzyl, Ammonium chloride, Alkyldimethyl Dialkyl dimethyl ammonium chloride (74% C18, 26% ethylbenzylammonium chloride, Alkyltrimethyl, Ammo C16), Dialkylmethyl benzyl ammonium chloride (60% nium chloride, Alpha-alkyl (43% C10, 30% C14, 12% C12, C14, 30% C16, 5% C18, 5% C12), Diammonium ethylenebis 10% C16, 5% C18) poly (oxyethylene) poly (oxypropylene)- (dithiocarbamate), Diammonium phosphate, Dibenzyldim 12 complex, Alpha-Alkyl-omega-hydroxypoly(oxyethyl ethylammonium chloride, Dichloro-1,2-dithiol-3-one ene)ethanol-iodine complex*(100% C12-C15), Alpha-terpi Dichloro-s-triazinetrione, Dichloroisocyanuric acid potas neol, Amines, C10-16-alkyldimethyl, N-oxides, Ammonium, sium salt, Dichlorophene Dicoco dimonium chloride, Acetate, Ammonium carbonate, Ammonium hydroxide, Dicyandiamide, Didecyl dimethyl ammonium bromide, Ammonium hydroxide-C8 fatty acid silver complex, Ammo Didecyl dimethylammonium carbonate and didecyl dimethyl nium lauryl Sulfate, Ammonium nitrate Ammonium nitrite, ammonium bicarbonate, Didecyl dimethyl ammonium chlo Ammonium oxalate, Ammonium propionate, Arquad DMCB ride, Didecyl methylbenzyl ammonium chloride, Diethano (16908+047501), Benax 2-A-1 (079002+079003) Benzene, lamine dodecylbenzenesulfonate, Diethanolamine myristate 1.1'-oxybis-tetrapropylene derivatives, Sulfonated, sodium, iodine complex, Dihydro abietylamine acetate, Diiodomethyl Benzyl((dodecylcarbamoyl)methyl)dimethyl ammonium p-chlorophenyl sulfone, Diiodomethyl p-tolyl sulfone, chloride, Benzyl-C12-14-alkyldimethyl quaternary ammo Diisobutyl cresoxyethoxyethyl dimethylbenzyl ammonium nium compounds, Beta-bromo-beta-nitrostyrene, Bioban chloride-ortho-phenylphenol ethoxy nonyl phenol complex, p-1487, Biobor JF, Biphenyl, Bis (tributyltin) adipate, Bis Diisobutyl cresoxyethoxyethyl dimethylbenzyl ammonium (tributyltin) sulfone, Bis(trichloromethyl) sulfone, Bis(tribu chloride, Diisopropylcresol, Diisopropylamine dodecylben tyltin) dodecenylsuccinate, Bis(tributyltin) salicylate, Bis Zene Sulphonate, Dilauryl dimethyl ammonium bromide, (tributyltin) succinate, Bis(tributyltin) sulfosalicylate, Bis Dimethoxane, Dimethyl alkyl tertiary amines, Dimethyl (tripropyltin) oxide, Bromine, Bromine chloride, Bronopol, dicoco ammonium chloride, Dimethyl-1-(hydroxymethyl) BTC 2125-m, Butoxy polypropoxy polyethoxy ethanol-io pyrazole Dimethylalmine propylamine tridecyl benzene Sul dine complex, Butyl paraben, Butylamine dodecyl, Benzene fonate Dimethylamine dodecyl benzene sulfonate Dimethy sulfonate C12-16-alkyldimethylamines Calcium, Carbonate, lol dimethyl hydantoin Dimethyltetradecyl 3 US 2010/0239.679 A1 Sep. 23, 2010

(trimethoxysilyl)propylammonium chloride, Dinitro cresol, Methyl paraben calcium salt, Methyl paraben sodium salt, Dioctyl dimethyl ammonium chloride, Diphenylstibene Methylene bis(thiocyanate), Methylenebis(thiocyanate) with 2-ethylhexanoate, Dipropylene glycol, Dipyrithione, Diso TBTO, Metronidazole Mixed fatty alkyldiamines (42% dium 2,2'-methylenebis(3,4,6-trichlorophenate) Disodium C12, 26% C18, 15% C14, 8% C16, 5% C10, 4% C8), Mono 2,2'-methylenebis(4-chlorophenate), Disodium 2,2'-oxybis (trichloro) tetra (monopotassium dichloro) penta-s-triazine, (4-dodecylbenzene)sulphonate, Disodium 4-dodecyl-2,4'- Mono- and di-potassium salts of phosphorous acid, Monoet oxydibenzene sulfonate Disodium cyanodithioimido carbon hanolamine dodecylbenzenesulfonate, Monoethanolamine ate, Disodium mono ethanolamine phosphate DNOC sodium laurate, myristate, and related compounds, Monotributyltin salt, Dodecyl di(2-hydroxyethyl)benzyl ammonium chloride, salicylate, Morpholine, Morpholine dodecylbenzene sulpho Dodecyl dihydroxyethylbenzyl ammonium chloride, Dode nate, Morpholine ester of abeitic and oleic acids, Morpholine cyl dimethyl 2,4,5-trimethylbenzyl ammonium chloride, poly ethoxy ethanol, Morpholinomethyl dimethyldithiocar Dodecyl dimethyl ammonium chloride, Dodecyl dimethyl bamate, N.N"-1,6-Hexanediylbisguanidine, homopolymer, benzyl ammonium chloride, Dodecyl dimethyl benzyl hydrochloride N,N-bis(2-hydroxy ethyl) octanamide N.N- ammonium bromide, Dodecyl dimethylbenzyl ammonium bis-(2-(omega-hydroxypoly(oxyethylene) ethyl)alkylamine, cyclopentanecarboxylate, Dodecyl dimethyl trichlorobenzyl alkyl derived from coconut oil fatty acids N,N-bis-(2-hy ammonium chloride, Dodecyl guanidine hydrochloride, droxy ethyl)-cis-9-octadecenamide N,N-bis-(2-hydroxy Dodecylamine salicylate, Dodecylbenzene sulfonic acid, ethyl) alkylamine N.N-dimethyl-1,3-propane diamine dode Dodecylbenzene sulfonic acid amine salt, Dodecylbenzene cyl benzene Sulfonate N-(1-Alkyl ethyl)-1,3- Sulfonic acid calcium salt, Dodecylbenzenesulfonic acid-io propanediamine)*(as in fatty acids of cottonseed oil), N-(1- dine complex, Dodecylbenzyl alkyl (70% C12, 30% C14) Methylalkyl) dimethylamine (66% C12, 34% C14) N-(2- dimethyl ammonium chloride, Dodecylbenzyl octadecyl Ethylalkyl) dimethylamine (62.6% C14, 35.8% C16, 1.6% dimethyl ammonium chloride, Dodecylbenzyl trimethyl C12), N-(2-hydroxy propyl) octanamide N-(2-hydroxyethyl) ammonium chloride, Dodine, Epichlorohydrin, Erythromy ethylene diamine triacetic acid, trisodium salt, N-(3,4-dichlo cin phosphate, Ethanolamine, Ethyl alcohol, Ethyl dimethyl robenzyl)-N-dodecyl-N,N-dimethyl ammonium chloride, stearyl ammonium bromide, Ethyl paraben, Ethyl-2-heptade N-alkyl (soza)-N-methyl morpholinium sulfate cenyl-1-(2-hydroxyethyl)-2-imidazolinium bromide, Ethyl N-Alkyl dimethyl benzyl ammonium chloride' (57% C12, ene diamine dodecyl benzene Sulphonate, Ethylene oxide 18% C14, 8% C16, 6% C10-C18, 5% C8), alkylated cresol condensate, Ethylhexanoate, Ethylmercury N-Alkyl dimethylamine (76% C16, 12% C14, 10.5% C18, pentachlorophenate Fatty acid-silver complex*(100% C8), 1.5% C8-C12), N-Alkyl dimethylamine (90% C18, 8.5% Fenaminosulf, Fenticlor, Ferric nitroso dimethyl dithiocar C16, 1.5% C17), N-Alkyl-1,3-propylene diamine monoben bamate, Flumequine, Formaldehyde, Gentian violet, Glut Zoate, alkyl derived from coconut oil fatty acids, N-Cetyl-N- araldehyde, Glycolic acid, Grotan (Hexahydro-1,3,5-tris ethyl morpholinium ethylsulfate, N-Dialkyl (60% C14, 30% (2-hydroxyethyl)-s-triazine), Gurjun balsam oil, Heptadece C16, 5% C12, 5% C18) methylbenzyl ammonium chloride, nylimidazolinium chloride, Heptadecyl hydroxyethylimida N-Dodecylguanidine terephthalate N-isononyl-N,N-dim Zoline phosphate, Heptadecyl hydroxyethyl imidazoline, ethyl decanaminium chloride, N-methyl-N-oleoyltaurine Hexachlorobenzene, Hexachlorophene, Hexachlorophene Sodium salt, N-octadecenyl-1,3-propane diamine monoglu sodium salt, Hexahydro-1,3,5-tris(2-hydroxypropyl)-s-triaz conate, N-Polyethoxylated oleylamine, N-Polyoxyethylated ine, Hexamethylenetetramine cis-chloroallyl chloride, Hexy Stearylamine, Naphthalene Sulfonic acid/parametaldehyde lene glycol, Homosalate Hydrogen peroxide, Hydroxymer condensateammonium salt, Naphthalene-formaldehyde con curi-o-nitrophenol Hydroxymercuri-o-nitrophenol sodium densate, Sulfonic acid, metallic salts, Neomycin Sulfate, salt, Hydroxymercurichlorophenols, Hydroxymercuriphenyl Nitrapyrin, Nitrapyrin other related Nonyl phenoxy poly ammonium triethanolamine, Hydroxymercury cresol, (oxyethylene) amine Sulfonate ethanol, iodine, Nonyl phe Hypochlorite salts, Hypochlorous acid, Imidazoline acetate, noxy polyoxyethylene ethanol-iodine complex Nuosept 95 Inorganic phosphate, Iodine, Isopropyl 8-((((hydroxymethyl) (Use code nos., 107001, 107002 and 107003), o-(Chloromer amino)-2-napthalenyl)sulfonyl)salicylate hydrogen chloride, curi)phenol, o-(Hydroxymercuri)benzoic acid, cyclic anhy Isopropyl alcohol, Isopropylcresol, Isopropyl phenol Isopro dride o-cresol O-Phenylphenol, alkylamine-copper salt of pylamine dodecylbenzene Sulphonate, Isopropylamine *(100% C8-C18) o-Phenylphenol, alkylamine-zinc salt of methyl naphthalene Sulphonate, Isothan Q, Kaolin, Kasuga *(100% C18), o-Phenylphenol, tetradecylamine salt, Octade mycin, Kathon 886 (kathon biocide), Lactoxymercuriphenyl cyldimethyl trihydroxysilyl propyl ammonium chloride, ammonium lactate, Lauryl polyoxyethylene Sulfate, Lauryl Octhillinone, Octyl decyl dimethyl ammonium chloride, Sulfate salts, Lime, Lithium carbonate, Lithium hydroxide, Octyl dodecyl dimethyl ammonium chloride, Octylphenoxy Lithium hypochlorite, Magnesium carbonate, Magnesium polyethoxy ethanol-iodine complex, Octylphenoxyethoxy chlorate, Magnesium chloride, Magnesium chloride hexahy ethyl dimethyl 4-chlorobenzyl ammonium chloride, Oil of drate, Magnesium lauryl Sulfate, Magnesium nitrate, Magne hardwood, Oil of pine tar, Oleic acid triethanolamine salt, sium oxide, Magnesium pyrithione, Magnesium silicate, Oleyl dimethyl ethyl ammonium bromide, Omadine, TBAO, Malic acid, Mercuric dimethyldithiocarbamate, Mercury and Ortho-benzyl-para-chlorophenol, Ortho-benzyl-para-chlo inorganic mercury compounds, Meta-cresol, Metallic silver, rophenol potassium salt, Ortho-benzyl-para-chlorophenol Metam potassium, Metam-sodium, Methanol, Methyl sodium salt, Ortho-phenylphenol Ortho-phenylphenol alkylbenzyl trimethyl ammonium chloride'(C9H19 ammonium salt, Ortho-phenylphenol potassium salt, Ortho C15H31), Methyl benzethonium chloride, Methyl dodecyl phenylphenol sodium salt, Other chlorinated pyridines of benzyl trimethyl ammonium chloride, Methyl dodecyl ben Dowacil A-40 Oxalic acid Oxazolidine EOxolinic acid Oxy Zyl trimethyl ammonium chloride 80% and methyl, Methyl diethylene bis(alkyl dimethyl ammonium chloride) alkyl dodecyl trimethyl ammonium chloride Methyl dodecyl derived from coconut oilfatty acids, Oxytetracycline, Oxytet xylene bis(trimethyl ammonium chloride), Methyl paraben, racycline hydrochloride, OZone p-cresol p-Cresyl acetate US 2010/0239.679 A1 Sep. 23, 2010

p-tert-Octylphenoxyethoxyethyl dimethyl benzyl ammo related Potassium nitrate Potassium nitrite, Potassium para nium mercuric chloride, Para-chloro-meta-cresol, para tert-butylphenate, Potassium permanganate, Potassium per Chloro-ortho-cresol, Para-tert-amylphenol, Para-tert oXydisulfate, Potassium peroxymonosulfate, Potassium per amylphenol potassium salt, Para-tert-butylphenol, oxymonosulfate sulfate, (2 KHSO5.KHSO4.K2SO4), Paraformaldehyde PCP, PCP, other related PCP potassium Potassium phosphate, dibasic Potassium pyrophosphate, salt PCP, sodium salt PCP, sodium salt, other related Pen Potassium silicate, Potassium toluene Sulphonate, Potassium tachlorophenol, zinc salt Pentachlorophenol, zinc salt of triiodide, Potassium Xylenesulfonate, Probenazole, Propineb, alkyl-N-propanediamine (100% C16-C18), Pentachlo Propionic acid, Propyl paraben Propyl paraben calcium salt, rophenyl laurate, Peroxyacetic acid, Phenol, Phenols, Phenyl Propyl paraben Sodium salt, Propylene glycol, Quinoline 2-trimethylammonium ethanesulfonate methyl sulfate, Phe derivatives S-(2-hydroxypropyl)thiomethanesulfonate, Sali nyl mercury lauryl mercaptide, Phenylmercuric 2-ethylhex cylanilide, Salicylic acid, Silica gel, Silver acetate, Silver anoate, Phenylmercuric borate, Phenylmercuric carbonate, carbonate, Silver chloride, Silver copper Zeolite, Silver fluo Phenylmercuric chloride, Phenylmercuric dimethyldithio ride, Silver iodide, colloidal Silver nitrate, Silver orthophos carbamate, Phenylmercuric formamide, Phenylmercuric phate (Ag3PO4), Silver oxide (Ag4O4), Silver salt of par hydroxide, Phenylmercuric lactate, Phenylmercuric monoet tially polymerized mannuronic acid, Silver Sodium hydrogen hanolammonium acetate, Phenylmercuric monoethanolam zirconium phosphate (Ag0.18Na0.57H0.25Zr2(PO4)3), Sil monium lactate, Phenylmercuric nitrate, Phenylmercuric ver thiocyanate, Silver thiuronium acrylate co-polymer, Sil octanoate, Phenylmercuric oleate, Phenylmercuric propi ver Zeolite, Silver zinc zeolite, Silver, ionic Soap, Sodium onate, Phenylmercuric salicylate, Phenylmercuric thiocyan 1-naphthalenesulfonate, Sodium 2,2'-methylenebis(4-chlo ate, Phenylmercuritriethanolammonium lactate, Phenylmer rophenate), Sodium 2-ethylhexanoate, Sodium 2-naphthale cury 8-hydroxyquinolinolate, Phenylmercury benzoate, nesulfonate, Sodium acetate, Sodium acid phosphate, Phosphoric acid, Phosphoric acid, disodium salt, dihydrate Sodium alkyl naphthalene sulphonate, Sodium Phosphoric acid monopotassium salt, Phosphorous acid, alkylbenzene sulfonate (100% C9), Sodium alkylaryl sul Phthalaldehyde, Pine soap, Pine tar, Pine tar oil PMA, PMA, phonate, Sodium benzene Sulphonate, Sodium binoxalate, other related PMAA Poly(methylmethacrylate-co-tributyltin Sodium bisulfate, Sodium bromide, Sodium butyl naphtha methacrylate), Poly oxyethylene ethanol monoesters of lene Sulphonate, Sodium carbonate, Sodium chlorate, 5-(and 6-) carboxy-4-hexyl-2-cyclohexene-1-octanoic acid, Sodium chloride, Sodium chlorite, Sodium cresolate, Sodium complex with iodine, Poly propoxy polyethoxy ethanol, 12 decyl benzene sulphonate, Sodium dibutyl naphthalene sul complex Poly(oxyethylene) (dimethylimino)ethylene (dim phonate, Sodium dichloro-s-triazinetrione, Sodium dichloro ethylimino)ethylene dichloride, Poly(vinyl/divinylbenzyltri S-triazinetrione dehydrate, Sodium dichlorophenate, Sodium methylammoniumdiiodochloride/bromide/iodide), Poly dihydroxyethylglycine, Sodium diisobutyl naphthalene sul acrylonitrile-copper ion-quarternary ammonium compound phonate, Sodium diisopropyl naphthalene Sulphonate, Polybromide form of trimethylbenzyl ammonium resin, Sodium dimethyl naphthalene sulphonate, Sodium dodecyl Polychlorophenols and their sodium salts, Polyethoxy benzene Sulphonate, Sodium dodecylbenzene Sulfonate-io polypropoxy polyethoxy ethanol-iodine complex, Poly dine complex, Sodium formaldehyde sulfoxylate, Sodium ethoxypolypropoxypolyethoxyethanol-n-alkyl (54% C12, glycolate, Sodium hydroxide, Sodium hydroxymethylamino 18% C14, 9% C16, 9% C18, 5% C10, 5% C8), di(beta acetate, Sodium hypobromite, Sodium hypochlorite, Sodium hydroxyethyl)benzyl am, Polyethylene glycol ether of linear isopropyl naphthalene Sulphonate, Sodium laurate, Sodium secondary alcohol-iodine complex Polyhexamethylene bigu lauryl Sulfate, Sodium metasilicate, Sodium metasilicate, anidine Polymeric quaternary ammonium chloride, Polyoxy anhydrous Sodium methyl naphthalene Sulphonate, Sodium ethylene (10 moles), nonyl phenol-formaldehyde resin, Poly methyl nonyl naphthalene Sulphonate, Sodium methylunde oxyethylene (12 moles) methylene bis octophenol cylbenzenesulfonate, Sodium mono and dimethyl naphtha Polyoxyethylene (15) coconut amine, Polyoxyethylene (16 lene sulphonate, Sodium N-alkyl-N-palmitoyl taurate-iodine moles) hydroabietyl alcohol, Polyoxyethylene (18 moles) complex, Sodium N-cyclohexyl-N-palmitoyl taurate-iodine methylene bis(diamyl phenol), Polyoxyethylene (7-7.5 complex, Sodium N-methyl-N-oleyl laurate, Sodium naph moles) isopropylidene diphenol, Polyoxyethylene amylphe thalene sulphonate, Sodium nitrate, Sodium nitrite, Sodium nol-formaldehyde resin (10 moles), Polyoxyethylene con nonanoyloxybenzene Sulphonate, Sodium octylbenzene Sul densate with abietylamine, Polyoxyethylene dinonyl phenol, phonate, Sodium oxalate, Sodium p-chloro-m-cresolate, Polyoxyethylene dodecylphenol (6-12 moles), Polyoxyeth Sodium p-toluene sulfonyl chloramide, Sodium para-tert ylene octadecyl phenol, Polyoxyethylene p-tert-butyl phe amylphenate, Sodium para-tert-butylphenate, Sodium peroX nol-formaldehyde resin, Polyvinyl pyrrolidone, Polyvinyl ide (Na2(O2)), Sodium phenate, Sodium phosphate, Sodium pyrrolidone-iodine complex, Polyvinylpyrrolidone-formal polyethoxyethyl dodecylsulfate, Sodium propionate, Sodium dehyde complex, Polyvinylpyrrolidone-orthophenylphenol pyrithione, Sodium sesquicarbonate, Sodium silicate, complex, Polyhydroxyethylene(dimethyliminio)ethylene Sodium toluene sulphonate, Sodium tridecylbenzene sulpho (dimethyliminio)methylene dichloride. Potassium 2,2'-me nate, Sodium triisopropyl naphthalene Sulphonate, Sodium thylenebis(3,4,6-trichlorophenate), Potassium 2,4,6-trichlo triphenyl benzene sulphonate, Stearyl imidazoline, Sterilix, rophenate, Potassium 3,4-dichloroisothiazole-5-carboxylate, Streptomycin, Strontium dodecyl benzene sulphonate, Sul Potassium acetate, Potassium ammonium ethylenebis(dithio famic acid, Sulfuric acid, Tall oil fatty acid soap of N-alkyl carbamate), Potassium bisulfate, Potassium bromide, Potas (C16-C18) propyl diamine TCMTB Temasept-R, other sium carbonate, Potassium chlorate, Potassium dimethyl related Terbuthylazine, Terpineols, Tert-butylphenol oxy dithio carbamate, Potassium dodecylbenzene Sulphonate, ethylated adduct, Tetradecyl dimethyl benzyl ammonium Potassium glycolate, Potassium hydroxide, Potassium chloride, Tetradecyl dimethyl benzyl ammonium chloride hypochlorite, Potassium iodide, Potassium laurate, Potas dehydrate, Tetraglycine hydroperiodide, Tetrahydro abiety sium laurate and myristate Soaps, Potassium laurate, other lamine acetate, Tetrakis (hydroxymethyl) phosphonium Sul US 2010/0239.679 A1 Sep. 23, 2010 fate, Tetrasodium pyrophosphate, Toluene Sulfonic acid, isothiazolin-3-one and 2-methyl-4-isothiazolin-3-in-one Trans-1,2-bis(n-propylsulfonyl)ethane, Tri-n-butyl tetrade (CIT/MIT), 4.5 dichloro-2-n-octyl-4-isothiazolin-3-one cyl phosphonium chloride, Tribromsalan, Tributyltinacetate, (DCOIT), 2-n-octyl-4-isothiozolin-3-one (OIT), N-butyl-1, Tributyltin acrylate, Tributyltin benzoate, Tributyltin chlo 2-benzisothiazolin-3-one (BBIT), zinc-2-pyridinethiol-2-ox ride, Tributyltin chloride complex of ethylene oxide conden ide (ZPT), methylenebis (tiocyanate) (MBT), 2-(thiocya sate of abietylamine, Tributyltin chloride myristylamine salt nomethylthio)benzothiazole (TCMTB), tetrahydro-3,5- Tributyltin fluoride, Tributyltin isopropyl succinate, Tributyl dimethyl-2H-1,3,5-thiadiazine-2-thione (thione), (5-chloro tin linoleate, Tributyltin maleate, Tributyltin methacrylate, 2,4-dichlorophenoxyl)phenol (triclosan), o-Phenylphenol Tributyltin monopropylene glycol maleate, Tributyltin neo (OPP), glutaraldehyde, and peracetic acid. decanoate, Tributyltin oxide, Tributyltin resinate, Tributyltin 0060. In yet another embodiment, the at least one active sulfide, Trichloro melamine, Trichloro-s-triazinetrione, ingredient is chosen from a group consisting of phenolic Trichlorophenol sodium salt, other related Triclosan, Tricop biocides. Exemplary phenolic biocides include, but are not per dichloride dimethyldithiocarbamate, Tridecylpoly(ethyl limited to, (5-chloro-2,4-dichlorophenoxyl)phenol (tri eneoxy)ethanol-iodine complex, Triethanoalmine nonylphe closan), 3,4,4-trichlorocarbanilide (triclocarban), o-Benzo nyl poly oxyethylene Sulfuric acid, Triethanolamine, p-chlorophenol (OBCP), o-phenylphenol (OPP), pentachlo Triethanolamine borate, Triethanolamine complex (see DPR rophenol (PCP), phenoxyethanol, and p-hydroxybenzoates chem code 1615), Triethanolamine dodecylbenzene sulpho (parabens). nate, Triethanolamine ester of fish oil acids, Triethanolamine laurate, Triethanolamine laurate-myristate, Triethanolamine 0061. In another embodiment, the at least one active ingre lauryl sulfate, Triethanolamine myristate, Triethanolamine dient is chosen from the group consisting of antimicrobial octylsulfate-iodine complex, Triethanolamine phosphate, agents and preservatives. Exemplary antimicrobial agents Triethanolamine Sulphonate, Triethanolamine Sulfonate and preservatives include, but are not limited to, in-can pre tridecylpolyoxyethyleneethanol-bromine complex, Trietha servatives, film preservatives, wood preservatives, fibre pre nolamine thiocyanate, Triethylene glycol, Trioxymethylene, servatives, leather preservatives, rubber preservatives, poly Tripotassium phosphate, Tris (hydroxymethyl) nitromethane, merized materials preservatives, masonry preservatives, Trisodium phosphate, Turkey red oil, Turkey red oil sodium liquid cooling system preservatives, processing system pre salt, Undecyl benzene Sulfonic acid triethanolammonium servatives, slimicides, metalworking-fluid preservatives, salt, Urea, Vancide 30-R, Xylene, Zinc 2-pyridinethiol-1- food preservatives, feedstock preservatives, phenoxyethanol, oxide, Zinc 8-quinolinolate, Zinc bacitracin, Zinc chloride, triclosan, 7-ethylbicyclooxazolidine, benzoic acid, bronopol Zinc dehydroabietylammonium 2-ethylhexanoate, Zinc (e.g., 2-bromo-2-nitropropane-13-diol), butylparaben, chlo dodecyl benzene Sulphonate, Zinc silicate, Zinc sulfate hep rite, chlorphenesin, diazolidinyl urea, dichlorobenzyl alco tahydrate, Zinc sulfate, and anhydrous Zinc trichlorophenate hol, dimethyl oxazolidine, DMDM hydantoin, ethylparaben, hexamidine disethionate, imidiazolidinyl urea, imidiazolidi Ziram. nyl urea NF, iodopropynylbutylcarbamate, isobutylparaben, 0055. In one embodiment, the at least one active ingredi methylparaben, potassium sorbate NF FCC, propylparaben, ent is chosen from a group consisting of halogenated bio quaternium-15, sodium benzoate NFFCC, sodium caprylate, cides. Exemplary halogenated biocides include, but are not sodium dehydroacetate, sodium dehydroacetate FCC, limited to, 2,2-Dibromo-3-nitrilopropionamide (DBNPA), Sodium hydroymethylglycinate, sodium hydroxymethylgly 2-Bromo-2-nitropropene-1,3-diol (BNPD), 3-iodo-2-propy cinate, Sodium methylparaben, sodium propylparaben, Sorbic nylbutyl carbemate (IPBC), Chlorohexidine gluconate, acid NF FCC, anisic acid, benzethonium chloride, caprylic/ chloroisocyanurates, chlorothalonil, halogenated hydanto capric glycerides, caprylyl glycol, di-alpha-tocopherol, eth ins, and iodophors. ylhexylglycerin, glyceryl caprate, methyl isothiazolinone, 0056. In another embodiment, the at least one active ingre polymethoxy bicyclic oxazolidine, Tocopheryl acetate, alco dient is chosen from a group consisting of inorganic biocides. hol, benzalkonium chloride, benzethonium chloride, camel Exemplary inorganic biocides include, but are not limited to, lia sinensis leaf extract, candida bombicola?glucose/methyl cuprous oxide and inorgano-silver. rapeseedate, hydrogen peroxide, methylbenzethonium chlo 0057. In yet another embodiment, the at least one active ride phenol, pinus pinaster bark extract, Poloxamer 188, ingredient is chosen from a group consisting of nitrogen PVP-Iodine, Rosmarinus officinalis Leaf extract, Vitis vin based biocides. Exemplary nitrogen-based biocides includes, ifera seed extract, ammomium benzoate, ammonium propio but are not limited to, N-(3,4-dichlorophenyl)-N',N'-dim ante, 5-Bromo-5-nitro-1,3-dioxane, Chloroxylenol, Ethyl ethylurea (diuron), methyene-bis-morpholine (MBM), qua alcohol, Glutaral, Iodopropynyl butylcarabamate, Isothiaz ternary ammonium compounds (quats), Salicylamide, and olinone, Parabens, Pircotone olamine, Selenium disulphine, triazines. Sorbic acid (mold), Zinc pyrithione, Benzalkonium chloride, 0.058. In still another embodiment, the at least one active Benzethonium chloride, Benzoic acid, Dehydroacetic acid, ingredient is chosen from a group consisting of organometal Dimethyl hydroxmethylpyrazole, Formaldehyde, Hexeti lics. Exemplary organometallics include, but are not limited dine, Methyldibromo glutaronitrile, Salicylic acid, Sodium to, 10,10'-ozybisphenoxerside (OBPA), bis(tributyltin) oxide hydroxymethylglycinate, Sodium iodate, Zinc oxide, Benzyl (TBTO), tributyltin-chloride (TBTC), and triphenyltin chlo alcohol (mould), Boric acid (yeast), Chloroacetamide, Phe ride (TPTC). noxythanol, Orthophenylphenol, Benzalkonium chloride, 0059. In another embodiment, the at least one active ingre Benzethonium chloride, 5-Bromo-5-nitro-1,3-dioxane, Bro dient is chosen from a group consisting of organometallic nopol, Diazolidinyl urea, Dimethyl hydroximethylpyrazole, biocides. Exemplary organometallic biocides include, but are Dimethyl oxazolidine, DMDM hydantoin, Ethyl alcohol, not limited to, disodium ethylenebis, dithiocarbemate, potas 7-Ethyl bicycloxazolidine, Glutaral, Imidazolidinyl urea, sium dimethyldithiocarbamate, sodium dimethyldithiocar Isothiazolinone, Methenammonium chloride, Methylbromo bamate, 1,2-benzisothiaxolin-3-one, 5-chloro-2-methyl-4- glutaronitrile, Polymethoxy bicylooxazolidine, Quaternium US 2010/0239.679 A1 Sep. 23, 2010

15, Sodium hydroxymethylglycinate. Thimersal, Benzoic dopropynylbutylcarbamate, Diazolidinyl urea/methyl para acid, Benzyl alcohol, Chlorhexidine, Hexetidine, Phenethyl ben/ethyl paraben/butyl paraben/propyl paraben/isobutyl alcohol, Polyaminopropyl biguanide, Polyguarternium-42, parabe-n/2-phenoxyethanol, DMDM hydantoin/iodopropy nyl butylcarbamate, Glycerin/water/ethoxdiglycol/caprylyl Salicylic acid, Sodium iodate, Triclocarban, Zinc phenolsul glycol/sodium polyacrylate, Glyceryl laurate/caprylyl/phe phonate, Chloroacetamide, Chlorobutanol, Dehydroacetic nylpropanol/dipropylene glycol, imidazole, Isopropylpara acid, Neem seed oil, Phenoxyethanol, Tee trea oil, USnic acid, ben/isobutylparaben/butylparaben, Methyl chloroisothiaz Ammonim Benzoate, Ammonium Propionate, BenZiosthiaz olinone/methyl isothiazolinone, Methyldibromo olinone, Benzoic Acid, Benzotriazole, Benzyl Alcohol, Ben glutaronitrile/methylchloroisothiazolinone/methylisothiaz Zylhemiformal, Benzylparaben, 5-Bromo-5-Nitro-1,3-Diox olinone/phenoxyethanol, Methyldibromo glutaronitrile/phe ane, 2-Bromo-2-Notropropane-1,3-Diol, Butyl Benzoate, noxyethanol, Methylchloroisothiazolinone/methylisothiaz Butylparaben, Calcium Benzoate, Calcium Paraben, Calcium olinone, Methylparaben/ethylparaben/butylparaben/ Propionate, Calcium Salicylate, Calcium Sorbate, Captan, propylparaben/butylenes glycol, Methyl paraben/ethyl paraben/butyl paraben/propyl paraben/isobutyl paraben, Chloramine T. Chlorhexidine Diacetate, Chlorhexidine Methyl paraben/ethyl paraben/butyl paraben/propyl paraben/ Digluconate, Chlorhexidine Dithydrochloride, Chloroac isobutylparaben/2-p-henoxy-ethanol/bronopol, Methylpara etamine, Chlorobutanol, p-Chloro-m-Cresol, Chlorophene, ben/ethylparaben/butylparaben/propylparaben/1,3-butylene p-Chlorophenol, Chlorothymol, Chloroxylenol, Citrus Gran glycol isomer, Methylparaben/propylparaben, Methylpara dis (Grapefruit) Fruit Extract, Citrus Grandis (Grapefruit) ben/propylparaben/benzyl alcohol, Methylparaben/propy Seed Extract, Copper Usinate, m-Cresol, o-Cresol, p-Cresol, lparaben/bronopol/phenoxyethanol, Methylparaben/propy DEDM Hydantoin, DEDM Hydantoin Dilaurate, Dehy lparaben/bronopol/propylene glycol, Methylparaben/ droacetic Acid, Diazolidinyl Urea, Dibromopropamidine propylparaben/ethylparaben, Methylparaben/propylparaben/ Diisethionate, Dimethyl Hydroxymethyl Pyrazole, Dimethy propylene glycol/diazolidinyl urea, Oxazolidines, lol Ethylene Thiourea, Dimethyl Oxazolidine, Dithiomethyl 2-phenylphenol. 2,4,4-trichloro-2'-hydroxy diphenol ether, benzamide, DMDM Hydantoin, DMHF, Domiphen Bro diiodomethyl-p-tolylsulfone, N-alkyl-N,N-dimethyl-N-ben mide, Ethyl Ferulate, Ethylparaben, Ferulic Acid, Glutaral, Zylammonium chloride, Zinc 2-mercaptopyridine-N-oxide, Glycerol Formal, Glyoxal, Hexamidine, Hexamidine Dipa Phenoxyethanol/benzoic acid/dehydroacetic acid, Phenoxy raben, Hexamidine Paraben, 4-Hydroxybenzoic Acid, ethanol/benzyl alcohol/potassium sorbate/tocopherol, Phe Hydroxymethyl Dioxazabicyclooctane, Imidazolidinyl Urea, noXylethanol/chlorphenesin/glycerin/methylparaben/ben Iodopropynyl Butylcarbamate, Isobutylparaben, Isodecylpa Zoic acid, Phenoxyethanol/DMDM hydantoin/Iodopropynyl raben, Isopropyl Cresols, Isopropylparaben, Isopropyl Sor butyl carbamate, Phenoxyethanol/DMDM hydantoin/meth bate, Magnesium Benzoate, Magnesium Propionate, Magne ylparaben/propylparaben, Phenoxyethanol/isopropylpara sium Salicylate, MDM Hydantoin, MEA-Benzoate, MEA ben/isobutylparaben/butylparaben, Phenoxyethanol/meth o-Phenylphenate, MEA-Salicylate, Methylchloroisthiazoli yldibromo glutaronitrile/idopropynyl butylcarbamate, Phenoxyethanol/methyl paraben/butyl paraben/ethyl para none, Methyldibromo Glutaronitrile, Methylisothazolinone, ben/propyl paraben, Phenoxyethanol/methyl paraben/butyl Methylparaben, Mixed Cresols, Nisin, PEG-5 DEDM paraben/ethyl paraben/propyl paraben/isob-utyl-paraben, Hydantoin, PEG-15 DEDM Hydantoin, PEG-5 Hydantoin Phenoxyethanol/methylparaben/isobutylparaben/butylpara Oleate, PEG-15 DEDM Hydantoin Stearate, Phenethyl Alco ben, Phenoxythanol/triethylene glycol/dichlorobenzyl alco hol, Phenol, Phenoxyethanol, Phenoxyethylparaben, Phe hol, Polyaminopropyl biguanide?parabenS/phenoxyethanol, noxyisopropanol, Phenyl Benzoate, Phenyl Mercuric PPG-2 methyl ether/sodium benzoate/potassium sorbate/io Acetate, Phenyl Mercuric Benzoate, Phenyl Mercuric Borate, dopropynyl butylcarbamate, Propylene glycol/benzyl alco Phenyl Mercuric Bromide, Phenyl Mercuric Chloride, Phe hol/methylchloroisothiazolinone/methylisothaizolinone, nylparaben, Polyaminopropyl Biguanide, Polyaminopropyl Propylene glycol/diazolidinyl urea?iodopropynyl butylcar Biguanide Stearate, Polymethoxy Bicyclic Oxazolidine, bamate, Propylene glycol/diazolidinyl urea/methylparaben/ Polyduaternium-42, Potassium Benzoate, Potassium Eth propylparaben, Propylene glycol/MDMD hydantoin/meth ylparaben, Potassium Methylparaben, Potassium Paraben, ylparaben, Propylene glycol/MDMD hydantoin/ Potassium Phenoxide, Potassium o-Phenylphenate, Potas methylparaben/propylparaben, Propylene glycol/lichen sium Propionate, Potassium Propylparaben, Potassium Sali extract, Propylene glycol/phenoxyethanol/chlorphenesin/ cylate, Potassium Sorbate, Propionic Acid, Propyl Benzoate, methylparaben, and Sodium levulinate/phenylpropanol com Propylparaben, Quaternium-8, Quatemium-14. Quatemium binations. 15, Silver Borosilicate, Silver Magnesium Aluminium Phos 0062. In another embodiment, the active ingredient is an phate, Sodium Benzoate, Sodium Butylparaben, Sodium antibiotic. Exemplary antibiotics include, but are not limited p-Chloro-m-Cresol, Sodium Dehydroacetate, Sodium Eth to. Beta-lactam, Vancomycin, Macrollides, Tetracyclines, ylparaben, Sodium Formate, Sodium Hydroxymethane Sul Quinolones, Fluoroquinolones, Nitrated compounds, Ami noglycosides, Phenicols, Lincosamids, Synergistins, Fosfo fonate, Sodium Hydroxymethylglycinate, Sodium Isobu mycin, Fusidic acid, oxazolidinones, Rifamycins, Polymix tylparaben, Sodium Methylparaben, Sodium Paraben, ynes, Gramicidins, Tyrocydine, Glycopeptides, Sodium Phenolsulfonate, Sodium Phenoxide, Sodium o-Phe Sulfonamides and Trimethoprims. In a further embodiment, nylphenate, Sodium Propionate, Sodium Propylparaben, the active ingredient comprises at least one antibiotic and at Sodium Pyrithione, Sodium Salicylate, Sodium Sorbate, Sor least one antimicrobial agent. In yet another embodiment, the bic Acid, TEA-Sorbate. Thimerosal, Triclocarban, Triclosan, active ingredient is a fungicide. In yet a further embodiment, Undecylenoyl PEG-5 Paraben, Zinc Pyrithione or combina the active ingredient is a mildewcide. tions thereof, such as for example Benzyl Alcohol/methyl chloroisothiazolinone/methylisothiazolinone, Benzyl alco Methods of Adding Active Ingredients to Surface Treated hol/PPG-2 methyl ether/bronopol/deceth-8/iodopropynyl/ Functional Particulate Carrier Materials butylcarbamate, Chloroacetamide Sodium benzoate, 0063. At least one active ingredient may be added to, and Dehydroacetic acid/benzyl alcohol, Diazolidinyl urea/io caused to bind to or otherwise interact with, at least one US 2010/0239.679 A1 Sep. 23, 2010

functional particulate carrier material that has been subjected but are not limited to, Staphylococci, Micrococci, Escheri to at least one surface treatment through various methods now chia, Pseudomonas, Bacilli, Salmonella, Shigella, Porphy known to the skilled artisan or hereafter discovered. In one romonas, Prevotella, Wolinella, Campylabacter, Propioni embodiment, a powdered sample of at least one Surface bacterium, Streptococci. Cprunebacterium, Treponema, treated functional particulate carrier material is Surface-satu Fusobacterium, Bifidobacterium, Lactobacillus, Actinomy rated with at least one active ingredient and Subjected to ces, Candida, Malazessia, and Aspergillus. The skilled arti vacuum to drive off air from the pores of the particulate san readily understands that the embodiments disclosed functional carrier material, thus allowing the at least one herein may effectively inhibit the growth of any microorgan active ingredient to interact with the surface of the at least one ism, depending upon the at least one active ingredient added Surface treated functional particulate carrier material. In to the Surface treated functional particulate carrier material. another embodiment, a powdered sample of at least one Sur Uses for Surface Treated Carrier Materials with Active Ingre face treated functional particulate carrier material is surface dient saturated with at least one active ingredient and at least one 0066. The surface treated functional particulate carrier fluid (e.g., deionized water), which is then shaken overnight materials with at least one active ingredient may be used in at a temperature of about 50° C. The recovered samples may any application now known to the skilled artisan or hereafter then be centrifuged to further separate the attached active discovered, in which enhanced performance of the applica ingredients from the unreacted powder, and the mixing and tion is desired though increased retention of the at least one centrifugation steps may be repeated multiple times. In a active ingredient. In one embodiment, the Surface treated further embodiment, a powdered sample of at least one Sur functional particulate carrier materials with at least one active face treated functional particulate carrier material is surface ingredient are used informulations or applications, including, saturated with at least one active ingredient and Subjected to but not limited to, animal feed, cosmetic formulations, paints, vacuum to drive off air from the pores of the particulate inks, home care products, animal care products, building functional carrier material, and the sample is then dried at materials, paper products, fabric products (e.g., textiles), about 105° C. overnight. In yet another embodiment, the at products for personal and work hygiene, contact lenses, chro least one active ingredient is added the at least one particulate matography materials, medical equipment, protective topi functional carrier material that has been subjected to at least cals, pharmaceutical and especially dermatological formula one Surface treatment such that a series of covalent bonds tions, lacquers, coatings, polymers, and plastics. links the at least one active ingredient, the at least one Surface treating agent, and the at least one particulate functional 0067 Exemplary formulations and applications include, carrier material. In yet a further embodiment, the at least one but are not limited to, adhesives, sealants, antimicrobial surface treated particulate functional carrier material absorbs cleansers, Soaps, disinfectants, anti-fouling and antimicrobial the at least one active ingredient. In still another embodiment, paints for inside and outside use, anti-foulant marine coat the at least one active ingredient adsorbs onto the Surface of ings, animal husbandry products, antimicrobial wallpapers, the at least one Surface treated particulate functional carrier antimicrobial dressings and plasters, prostheses and bone material. In another embodiment, the at least one Surface cement with antimicrobial activity, dental fillings, dental treated particulate functional carrier material interacts with prostheses, formulations against gastrointestinal infections, the at least one active ingredient Such that a timed and/or active coal, antimicrobial cat litter, air conditioning (filters extended-release surface treated functional particulate carrier and ducts), air inflated construction (air halls), agricultural material is formed. and mulch films, all purpose adhesives, appliances and equip 0064. The at least one active ingredient may be added to ment, appliance adhesives and Sealants, aprons, artificial the at least one particulate functional carrier material in any leather, artificial plants, artificial wood, and plastic lumber, amount now known or hereafter discovered by the skilled Astroturf, automobile parts, automotive and truck upholstery, artisan. In one embodiment, the at least one active ingredient awnings, bags, bandages, barrier fabrics, bathroom accesso is added in an amount that will achieve the results intended or ries, bathtubs, bathtub cement, bedding, beverage dispensers, bibs, boats, boat covers, book covers, bottles, brush bristles, desired by the presence of the at least one active ingredient. In brush handles, brooms, building components (walls, wall another embodiment, the at least one active ingredient is board, floors, concrete, siding, roofing, shingles, hardware, added in an amount ranging from about 0.1% to about 2.0% carpet cleaner, ceilings and commercial and industrial appli by weight of the at least one particulate functional carrier cations), cable sheathing, caps (hats), cardboard, carpet and material. In a further embodiment, the at least one active carpet underlay, caster wheels, cat litter, clinical thermom ingredient is added in an amount less than about 2.0% by eters, coats, compact discs, convertible tops, cookware, cool weight. In yet another embodiment, the at least one active ers, cooling towers, cooling water, counter and table tops, ingredient is added in an amount of about 0.5% by weight. In conveyor belts, countertops, credit cards, crates (food and yet a further embodiment, the at least one active ingredient is non-food), cups, currency, curtains, cushion pads, cutting added in an amount of about 1.0% by weight. boards, decking, dishes, dish cloths, dishwasher components, Microorganisms diving equipment or Snorkels, drainage sewer pipe, draperies, dry-film paints, exercise equipment, equipment for slaughter 0065 Surface treated functional particulate carrier mate houses or creameries or diaries, equipment for gyms, saunas rials with at least one active ingredient may exhibit increased or massages, fan blades, fiberfill, filters, fittings, fences, floor antimicrobial activity according to the present invention and, coverings, floor and carpet baking, flooring, foam (cushion, therefore, can be used for the inhibition of the growth and mattress), food preparation appliances, food and beverage progeny of at least one microorganism. Microorganisms processing equipment, food and drink containers, storage and include, but are not limited to, bacteria (gram positive and bags, food handling equipment, food packaging, food and gram negative bacteria), yeasts, fungi, mildew, viruses, and meat crates, food trays and covers, food wrap, footwear (in combinations thereof. Exemplary microorganisms include, cluding boots, sports equipment, and tools), fruit and Veg US 2010/0239.679 A1 Sep. 23, 2010 etable brushes, fruit crates, furniture, garbage bags, garbage natural, and semisynthetic organic polymers. Examples of cans, garment bags, gaskets, general purpose containers, polymers include, but are not limited to: aliphatic and aro gloves, gowns (medical and consumers), grease traps, rigid matic polyesters, including polyethylene terephthalate, poly greenhouses, greenhouse films, grout and joint compound, butylene terephthalate, polyethylene isophthalate, polyhex heating, ventilation and air conditioning, hospital Surface and amethylene terephthalate, polylactic acid, polyglycolic acid, medical instrument disinfection, hoses, ice-making equip and liquid crystalline polymers for high performance resins ment and trays, in-can paints, incontinence care products, and fibers; polyester block copolymers; aliphatic and aro indoor and outdoor furniture, industrial equipment, inflatable matic polyamides including nylon 6, nylon 66, nylon 610, bed, insulation for wire and cable, insulators, intimate nylon 11, nylon 12, nylon 1212, poly-p-phenylene tereph apparel, jacket liners, janitorial equipment, kitchen and bath thalamide, poly-m-phenylene isophthalamide; copolymer room hardware, kitchen sinks and fixtures, kitchen towels, ised polyamides; polyolefins including polyethylene, laminate and tile adhesives, laying batteries, life Vests, liners, polypropylene, and copolymers thereof, vinyl polymers, mats, mattress cover pads and filing, mattress adhesives, including polystyrene, polyacrylonitrile, polyvinylalcohol, medical and dental apparel, metal working fluids, mineral polyvinyl acetate, polyvinylchloride, polyvinyl idene chlo slurries, mobile homes, mobile toilets, mops, money, natural ride, ABS resins and acrylic resins; copolymers of ethylene and synthetic fibers and fabrics, non-woven fabrics, oilfield, and vinyl acetate; fluorocarbon polymers, including polytet outerwear, packaging, pallets, paper products (wipes, tissues, rafluoroethylene. polyvinylidene fluoride and polyvinyl fluo wall coverings, towels, book covers, mulch), pillow covers, ride; polyurethanes; segmented polyurethane elastomers, pipes, pipe sealant and insulating materials, plaster, plastics, spandex or elastane elastomers; polyethers, including poly plastic films, plates and utensils, playground equipment, acetals; polyketones, polyetherether ketone (PEEK), poly plumbing Supplies and fixtures (including toilet bowl seats), ether ketoneketone (PEKK); polyether and polyester block plumbing adhesives and sealants, pool liners, process vessels, polymers; polysulfides; polysulfones: polysiloxanes such as protective covers, recreational water, resins, refrigerator polydimethyl siloxane; polycarbonates; thermosetting Syn components, roofing sheets, membranes, shingles and flash thetic polymers such as phenol-formaldehyde copolymer, ing, ropes, rugs, sales counter, sails, Sanitary pipes, sealers, polyurethane, polyesterurethane, polyetherurethane, poly sealing compounds for bathrooms, kitchens or glass, sheets etherurethaneurea, polyesterurethaneurea; natural polymers and blankets, shoes, shoe insoles, shower curtains, shower Such as cellulosics, cotton and wool; and regenerated or semi tubs, siding for housing, silage wrap, silos, sinks, siphons, synthetic polymers such as rayon, cuprammonium rayon, skylights, sleeping bags, sleepwear, socks and hosiery, acetate rayon, triacetate rayon, reconstituted silk and polysac sponges, sprinkler, sportswear and sports equipment, storage charides. Copolymers, terpolymers, and blends of species containers, stucco, Sun roof. Sun shades, synthetic latex poly listed are also contemplated. mers, napkins, tanks, tape, tarps, telephone boxes or public 0070. In a further embodiment, waterborne paints and lac phones, tents and other outdoor equipment, ticking (mattress quers may comprise Surface treated functional particulate pillow), tiles, tile grout, toothbrush handle and bristles, toilet carrier materials with at least one active ingredient. In yet paper and handkerchiefs, toilet blocks and cleaners, towels, another embodiment, Solvent-based paints and lacquers may toothbrush tumbler, toys, trim for Outerwear and garments, comprise the Surface treated functional particulate carrier trunk liners, tubing, umbrellas, undergarments, uniforms, materials with at least one active ingredient. upholstery, vacuum cleaner bags, wall and floor covering, wallpaper, waste bags, water tanks, waste containers, water Enhanced Antimicrobial Activity treatment, water and ice handling equipment and filters, wet 0071. The surface treated functional particulate carrier Suits, wipes, wire and cable, wood, wood filled plastics. materials of the present invention may retain larger quantities 0068. In several application areas, enhanced biocidal or of the at least one active ingredient, which may in turn antimicrobial activity may be useful in several stages of the enhance the antimicrobial and/or biocidal activity of the processing. In one embodiment, plastics and/or polymers materials. In one embodiment, improved antimicrobial activ comprising Surface treated functional particulate carrier ity is measured by the retention factors (R) of the functional materials with at least one active ingredient and exhibiting particulate carrier materials by testing with methods known in enhanced antimicrobial or biocidal capabilities according to the art, such as thin layer chromatography, which may mea the present invention can be stored in the form of Master Sure the concentration of the released active ingredient, by batches for a long period of time, without risking the con which the difference of the added and measured R, may then tamination of the Masterbatch with microorganisms. The be taken. In another embodiment, improved antimicrobial skilled artisan recognizes that the Masterbatch can be pro activity is measured by the retention factors of the functional cessed in the same way as known Masterbatches, or in pro particulate carrier materials by adding about 0.75 g of the at cessing methods hereafter discovered. The treated Master least one active ingredient dropwise to about 2.5 g of the batches may be useful in, for example, building and functional particulate carrier material, mixing for about 8 construction, household, items and furnishing, electrical and hours, charging with about 1000 mL of water, and stirring electronics parts, apparel, textiles and fabrics, coatings and continuously for about 90 minutes until the elution curve laminates, transportation and recreation, adhesives, Sealants plateaus. The suspension is then filtered and the water is and grouts, food contact items and water contact items (such analyzed for released biocide by any appropriate detection as plastic bottles and bottle caps), films, coextrusion films, technique, such as 2nd derivative UV-Vis spectroscopy or and exterior and interior automotive parts. Gas Chromatography Mass Spectrometry. Such an embodi 0069. In another embodiment, suitable plastics and poly ment may yield R, values from about 5% to about 250% for mers from which the articles may be fabricated comprising in siliceous materials, and may yield R-values of about 0% for part the Surface treated functional particulate carrier material diatomaceous earth not treated according to the present with at least one active ingredient may include synthetic, invention. US 2010/0239.679 A1 Sep. 23, 2010

I0072. In the inventions disclosed herein, a larger Regen 0080. The functional particulate carrier material of erally shows that the surface treated functional particulate Sample 3 was SuperflossTM, a super-fine diatomaceous earth carrier materials retain larger quantities of the at least one product sold by Celite Corp., a subsidiary of World Minerals, active ingredient compared to functional particulate carrier Inc. Sample 3 was not subjected to vacuum pressure and was materials that were not surface treated. The higher retention not surface treated before Neem oil was added by the process rate reveals increased antimicrobial activity in these Surface described below. Sample 3 had a retention factor of 0. treated functional particulate carrier materials. I0081. The functional particulate carrier material of 0073. Unless otherwise indicated to the contrary, all num Sample 4 was Micro-Cel E, a synthetic calcium silicate bers expressing quantities of ingredients, reaction conditions, hydrate (CaSiO) available from Advanced Minerals Corp., a and so forth used in the specification, including claims, are to subsidiary of World Minerals Inc. Sample 4 was not subjected be understood as being modified in all instances by the term to vacuum pressure and was not surface treated before Neem "about.” Accordingly, unless indicated to the contrary, the oil was added by the process described below. Sample 4 had numerical parameters set forth in the specification and a retention factor of 78. attached claims are approximations that may vary depending I0082. The functional particulate carrier material of upon the desired properties sought to be obtained by the Sample 5 was Harborlite 635, a very fine grade of perlite present disclosure. At the very least, and not as an attempt to available from Harborlite Corp., a subsidiary of World Min limit the application of the doctrine of equivalents to the scope erals Inc. Sample 5 was not subjected to vacuum pressure and of the claims, each numerical parameter should be construed was not surface treated before Neem oil was added by the in light of the number of significant digits and ordinary round process described below. Sample 1 had a retention factor of ing approaches. 154. 0074. Notwithstanding that the numerical ranges and I0083. The functional particulate carrier material of parameters setting forth the broad scope of the invention are Sample 6 was CelTiXTM. Sample 6 was subjected to surface approximations, unless otherwise indicated the numerical treatment by silanization as described below with a 1% solu values set forth in the specific examples are reported as pre tion of vinyltriethoxysilane, available from GE Silicone cisely as possible. Any numerical value, however, inherently under the designation “Silguest(R) A-151 Silane, before contain certain errors necessarily resulting from the standard Neem oil was added by the process described below. Sample deviation found in their respective testing measurements. The 6 had a retention factor of 330. section headings used in this disclosure are provided merely I0084. In the retention experiments, a powdered sample for the convenience of the reader and are not intended to limit was first surface-saturated with Neem oil by mixing 2 gram of the scope of the inventions described herein. a sample with 10 grams of Neem oil, vacuum was also used to 0075 Other embodiments of the invention will be appar drive offair from the pores so that the oil can get into them. ent to those skilled in the art from consideration of the speci After the treatment, 200 ml of DI water was than added into fication and practice of the invention disclosed herein. It is the flask, and shaken well to mix the contents, the sample was intended that the specification and examples be considered as then placed in a shaker set at 50° C. for overnight. The exemplary only, with a true scope and spirit of the invention recovered samples were then centrifuged to further separate being indicated by the following claims. the attached oil from the carrier powders. The mixing and 0076. By way of non-limiting illustration, examples of centrifugation were repeated for three times. The samples certain embodiments of the present disclosure are given were then dried at 105°C. for overnight, followed by ignition below. at 800° C., to burn off any retained Neem oil. After these treatments, the original untreated DE samples failed to retain EXAMPLES the oil, most of the oil were separated from the powders. The Surface-treated Samples, however, showed much higher Example 1 retentions. I0085. The functional particulate carrier material of 0077. Five control samples of powdered, non-surface Sample 7 was CelTiXTM. Sample 7 was subjected to vacuum treated functional particulate carrier materials were tested pressure and was subjected to Surface treatment by silaniza against two powdered functional particulate carrier material tion as described below with a 1% solution of 3-aminopropyl samples that had been subjected to surface treatment by triethoxysilane, available from GE Silicones under the des silanization. Then, the two non-control samples were then ignation “Silduest A-1 100 Silane.” before Neem oil was surface-saturated with the active ingredient biocide, Neem added by the process described below. Sample 7 had a reten oil. After various drying and separation techniques were per tion factor of 317. formed, as described below, the retention factors of the seven I0086 For the surface treatment by silanization, an appro samples were measured. priate amount of silane was added dropwise to the dry inor 0078. The functional particulate carrier material of ganic carrier. For these examples, approximately 10 g of Sample 1 was CelTiXTM, a diatomaceous earth product avail silane was charged to 1000 g of carrier and the mixture was able from World Minerals, Inc. Sample 1 was not subjected to blended in a V-shaped Rota-Vee Tumble powder blender for vacuum pressure and was not surface treated before Neem oil at least 60 minutes. was added by the process described below. Sample 1 had a I0087. For the addition of Neem oil, in a flask, two grams of retention factor of 0. each sample were surface-saturated with 10 grams of Neem 007.9 The functional particulate carrier material of oil. Samples 2, 6, and 7 were subjected to vacuum pressure of Sample 2 was CelTiXTM, as in Sample 1. Sample 2 was 20 mm Hg to drive off air from the pores of the particulate Subjected to vacuum pressure but was not surface treated functional carrier to allow the oil to better penetrate the before Neem oil was added by the process described below. sample. Then, 200 milliliters of deionized water was added Sample 2 had a retention factor of 0. into the flask and shaken well to mix the contents. The US 2010/0239.679 A1 Sep. 23, 2010 samples were placed in a shaker set at 50° C. overnight. The recovered samples were centrifuged using a Beckman Jó-MI TABLE 2 Centrifuge at 3000 RPM for 20 minutes to further separate the Surface %. Mildewcide attached oil from the powder. The mixing and centrifugation DE Treatment Mildewcide Retained steps were repeated three times. The samples were dried at Superfloss TM None None O.OO 105° C. overnight to drive off moisture, followed by ignition None Skane TMM-8 14.89 at 800° C. to burn off the retained Neem oil. The percentage O.6% A-1101 Skane TMM-8 22.26 O.6% A-151 Skane TMM-8 26.15 weight loss after the ignition was taken as the weight percent 196 PDMS Skane TMM-8 29.49 age of retained Neem oil, as follows: CelTXTM None None O.OO None Skane TMM-8 1.78 1% A-1101 Skane TMM-8 14.54 1% A-151 Skane TMM-8 36.74 where W was the sample weight after drying at 105° C. W. 190 PMDS Skane TMM-8 17.97 was the sample weight after ignition. 0088. The five control samples of different functional par 0094 Surprisingly and unexpectedly, surface treatment in ticulate carriers were tested against the two silanized samples. accordance with the present inventions resulted in greatly After the treatments, the un-silanized samples failed to retain improved mildewcide retention, as shown in Table 2. the oil and most of the oil separated from the powders, regard 1-51. (canceled) less of the presence or absence of vacuum pressure. The 52. A surface treated functional particulate carrier material, Surface treated samples, however, showed much higher reten comprising: tion. Table 1 shows these results. at least one functional particulate carrier material Subjected to at least one Surface treatment; and, TABLE 1. at least one active ingredient, wherein that the at least one functional particulate carrier Surface Retention material is chosen from the group consisting of diato Vacuum Treatment Factor (%) maceous earth, kaolin clay, mica, talc, Vermiculite, Syn Sample 1 NO NO O thetic calcium silicate hydrate, natural silicates, Syn Sample 2 YES NO O thetic silicates, alumino silicates, and salts thereof. Sample 3 NO NO O 53. The material of claim 52, wherein that the at least one Sample 4 NO NO 78 Sample 5 NO NO 154 functional particulate carrier material is diatomaceous earth. Sample 6 YES YES 330 54. The material of claim 52, wherein the at least one Sample 7 YES YES 317 Surface treatment is a chemical Surface modification with at least one surface treating agent chosen from the group con sisting of at least one silane and at least one siloxane. 0089 Surprisingly and unexpectedly, surface treatment in 55. The material of claim 54, wherein the at least one silane accordance with the present inventions resulted in greatly is chosen from silanes of Formula (I): improved neem oil retention, as shown in Table 1. (R'), Si(R)-R (I) wherein R' is alkoxy, halogen, hydroxy, aryloxy, amino, Example 2 amide, methacrylate, mercapto, carbonyl, urethane, pyrrole, carboxy, cyano, aminoacyl, acylamino, alkyl ester, or aryl 0090. In this example, DE materials that were subjected to ester; X has a value of 1, 2, or 3; R is substituted or unsub a surface treatment in accordance with the present inventions stituted alkyl, alkenyl, alkaryl, alkcycloalkyl, aryl, were used, as well as non-surface treated DE for comparison. cycloalkyl, cycloalkenyl, heteroaryl, heterocyclic, As noted in Table 2, 1.5 g samples of DE were mixed with 2 cycloalkaryl, cycloalkenylaryl, alkcycloalkaryl, alkcycloalk mL SkaneTM M-8 (mildewcide available from Rohm and enyaryl, or arylalkaryl; R is hydrogen, alkyl, alkenyl, Haas Company), and then placed into a vacuum oven set at alkaryl, alkcycloalkyl, aryl, cycloalkyl, cycloalkenyl, het 50° C. for 10 minutes. The samples were then vigorously eroaryl, heterocyclic, cycloalkaryl, cycloalkenylaryl, alkcy washed with water to wash off unretained biocide, by mixing cloalkaryl, alkcycloalkenyaryl, arylalkaryl, alkoxy, halogen, the samples with 50 mL of deionized water and shaking at 50° hydroxy, aryloxy, amino, amide, methacrylate, mercapto, C. and 200 RPM for two hours, followed by filtering. The carbonyl, urethane, pyrrole, alkyl ester, aryl ester, carboxy, filtered DE cake was then subjected to the same washing Sulphonate, cyano, aminoacyl, acylamino, epoxy, phospho process twice more. After the third washing, the DE cake was nate, isothiouronium, thiouronium, alkylamino, quaternary dried and ignited at 700° C. to burn off organics. The ignition ammonium, trialkylammonium, alkyl epoxy, alkyl urea, alkyl loss is compared with a blank DE sample and taken as the imidazole, or alkylisothiouronium; wherein the hydrogen of said alkyl, alkenyl, aryl, cycloalkyl, cycloalkenyl, heteroaryl, percent retention of biocide in Table 2. and heterocyclic of R is optionally substituted by halogen, 0091 A-1 101 is a gamma-aminopropyltriethoxysilane hydroxy, amino, carboxy, or cyano. sold by GE Silicones under the name Silduest(R) A-1 101, and 56. The material of claim 55, wherein the at least one silane is a technical grade of Silquest(R) A-1 100. is vinyltriethoxysilane. 0092 “A-151 is a vinyltriethoxysilane sold by GE Sili 57. The material of claim 55, wherein the at least one silane cones under the name Silduest(R) A-151 Silane. is 3-aminopropyl triethoxysilane. 0093. “PMDS” is a polydimethylsiloxane sold by Wacker 58. The material of claim 52, wherein at least one active Chemical Corporation under the name AK1000. ingredient is chosen from the group consisting of biocides, US 2010/0239.679 A1 Sep. 23, 2010

antibiotics, fungicides, mildewcides, insecticides, preserva 67. The material of claim 65, wherein the at least one tives, and antimicrobial agents. Surface treating agent is chosen from the group consisting of 59. The material of claim 58, wherein the biocide is chosen at least one silane and at least one siloxane. from the group consisting of Neem oil, isothiazolinones, sil 68. The material of claim 65, wherein at least one active Ver oxides, silver salts, copper oxides, copper salts, Zinc ingredient is chosen from the group consisting of biocides, oxide, Zinc salts, and iodopopargylbutyl carbamate. antibiotics, fungicides, mildewcides, insecticides, preserva 60. The material of claim 55, wherein the at least one tives, and antimicrobial agents. functional particulate carrier material is diatomaceous earth, 69. The material of claim 68, wherein the biocide is chosen the at least one silane is vinyltriethoxysilane, and the at least from the group consisting of Neem oil, isothiazolinones, sil one active ingredient is Neem oil. Ver oxides, silver salts, copper oxides, copper salts, Zinc 61. The material of claim 55, wherein the at least one oxide, Zinc salts, and iodopopargylbutyl carbamate. functional particulate carrier material is diatomaceous earth, 70. A surface treated functional particulate carrier material, the at least one silane is 3-aminopropyl triethoxysilane, and comprising: the at least one active ingredient is Neem oil. at least one functional particulate carrier material Subjected 62. The material of claim 52, wherein the material has a to at least one chemical Surface treatment with at least retention factor of at least about 100. one surface treating agent chosen from the group con 63. The material of claim 52, wherein the material has a sisting of at least one silane and at least one siloxane: retention factor of at least about 200. and, 64. The material of claim 52, wherein the material has a at least one active ingredient chosen from at least one retention factor of at least about 300. biocide, 65. A surface treated functional particulate carrier material, wherein the material has a retention factor of at least about comprising: 1OO. at least one functional particulate carrier material Subjected 71. The material of claim 70, wherein that the at least one to at least one chemical Surface treatment with at least functional particulate carrier material is chosen from the one surface treating agent, and, group consisting of diatomaceous earth, perlite, kaolin clay, at least one active ingredient, mica, talc, Vermiculite, and synthetic calcium silicate wherein the material has a retention factor of at least about hydrate. 100. 72. The material of claim 70, wherein the at least one 66. The material of claim 65, wherein that the at least one biocide is chosen from the group consisting of Neem oil, functional particulate carrier material is chosen from the isothiazolinones, silver oxides, silver salts, copper oxides, group consisting of diatomaceous earth, perlite, kaolin clay, copper salts, Zinc oxide, Zinc salts, and iodopopargylbutyl mica, talc, Vermiculite, synthetic calcium silicate hydrate, carbamate. natural silicates, synthetic silicates, alumino silicates, and salts thereof.