US 200802991 61A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2008/0299161 A1 Sanderson (43) Pub. Date: Dec. 4,9 2008

(54) SOLID BIOCIDE COMPOSITION AND Related U.S. Application Data SEALED BOCDE ARTICLE (60) Provisional application No. 60/750,786, filed on Dec. (76) Inventor: William D. Sanderson, San 16, 2005, provisional application No. 60/812,632, Francisco, CA (US) filed on Jun. 12, 2006. Correspondence Address: Publication Classification MANELLIDENISON & SELTER 2000 MSTREET NW SUITE 700 (51) Int. Cl. WASHINGTON, DC 20036-3307 (US) AOIN 25/34 (2006.01) AOIN 59/08 (2006.01) (21) Appl. No.: 12/091,785 AOIP 5/00 (2006.01) (22) PCT Filed: Dec. 15, 2006 (52) U.S. Cl...... 424/408; 424/661 (86). PCT No.: PCT/US2006/047729 (57) ABSTRACT S371 (c)(1), A solid composition for forming dioxide on demand (2), (4) Date: Apr. 28, 2008 and a sealed biocide article.

Patent Application Publication Dec. 4, 2008 US 2008/0299161A1

US 2008/02991 6 1 A1 Dec. 4, 2008

SOLD BOCDE COMPOSITION AND 0009. Published US 2005/0249658 B2 describes a solid SEALED BOCDE ARTICLE chlorine dioxide releasing composition having increased temperature stability. The increased temperature stability is provided by using a combination of two chlorine-releasing 0001. This application claims priority to U.S. Provisional agents: Sodium dichloroisocyanurate and a hypochlorite salt. Patent Application Ser. Nos. 60/812,632, filed Jun. 12, 2006 The application also teaches that using an acidulant with a and 60/750,786, filed Dec. 16, 2005, the complete disclosures pKa of 2.8-6.0 further enhances temperature stability. of which are incorporated herein by reference. 0010. A -enhanced oxidizing composition and a solvent activated reactor are described in published applica FIELD OF THE INVENTION tions US 2005/O155936A1 and US 2006/0013751 A1. Solid 0002 The invention relates to a solid biocide composition. oxidizing compositions including chlorine dioxide are The composition rapidly releases chlorine dioxide when con described. The application describes the use of a metal chlo tacted with water or moisture. The invention also relates to a rite, oxidizing agent, and chloride Salt to produce chlorine sealed biocide article. dioxide. (0011 US 2006/0016765 A1 describes a composition for BACKGROUND OF THE INVENTION producing chlorine dioxide comprising an active oxygen compound and a chlorine dioxide-generating compound. See 0003 Chlorine dioxide is a highly reactive yellowish paragraph 23. Preferred active oxygen compounds are Sulfur green gas that produces useful aqueous solutions in a number containing oxy-acid compounds. See paragraph 26. Suitable of applications such as disinfection, Sterilization, and odor precursors for producing chlorine dioxide include chlorite control. It is a potent antimicrobial agent, bleaching agent, salt, alkali metal salt or alkaline earth halide salt. See para and as a germicide has found increasing receptivity of its use graph 26. The preferred composition is sodium chlorite, in municipal and drinking water treatment, cooling towers, potassium monoperSulfate, and magnesium chloride. This and food processing. publication discloses a large list of metal halides, which can 0004 Recent regulatory approvals have led to growing be added as a “catalyst to speed up generation of chlorine acceptance of its use in reducing pathogens in food process dioxide of which zinc bromide is listed. See paragraphs 42. ing applications such as poultry chill water tanks, beef and However, the Zinc bromide was used at a pH of 4.1. SeeTable pork carcasses washes, and raw agricultural commodities. 1. Furthermore, the publication teaches that calcium bromide 0005 Chlorine dioxide has many advantages over tradi at a pH of 3.7 is a "comparative example C, i.e. does not tional chlorine-based biocides due to its greater selectivity work, and it gives an orange color which may interfere with towards bacterial cell membranes. However, several draw results, thus, teaching away from using calcium bromide. See backs have limited the implementation of chlorine dioxide Table 1. Furthermore, this publication does not teach forming where its superior safety and environmental profile would at a pH of 5-9 or the many advantages benefit a wide variety of industries. thereof. 0012. There is a need for a solid biocide composition that PRIOR ART OF SOLID COMPOSITIONS rapidly produces chlorine dioxide in the presence of water or 0006. The prior art describes methods to produce chlorine moisture on demand, without producing Substantial amounts dioxide from dry compositions such as tablets, powders, and of chlorine gas or other undesired compounds. briquettes. The prior art has been extensively covered in pub lished U.S. patent applin ser. No. 2004/0135116, which is OBJECTS OF THE INVENTION incorporated herein by reference. 0013 The generation of chlorine dioxide from a chlorite 0007 U.S. Pat. No. 6,602,442 describes a “dry composi salt using a weak hypohalous acid with a pKa value of about tion' comprising lithium hypochlorite, sodium chlorite, and 8.6 as the oxidizing species. Sodium Sulfate. Although this mixture was found to 0014. The generation of chlorine dioxide from a chlorite very soluble and rapidly yield chlorine dioxide upon addition salt using a weak hypohalous acid with an acidity constant of to water, a Substantial amount of chlorine gas is undesirably 2.3x10. released since chlorine is produced above its solubility in water. See column 2, line 55-56 of this patent. Furthermore, (0015 Generating the ionic species OCl and/or OBr. the stability of the dry mixture is limited, especially in high when the present invention is contacted with water or mois humidity environments. These limitations preclude the addi ture. tion of large amounts to water since the excess chlorine pro 0016 Generating the ionic species HOCl and/or HOBr duction would cause the mixture to “flash'. when the present invention is contacted with water or mois 0008 Published U.S. patent applin ser. No 2004/0135116 ture. and U.S. Pat. No. 6,699,404 describe solid chlorine dioxide 0017. The generation of chlorine dioxide from a chlorite releasing “massive bodies, which comprise a mixture of salt using a weak hypohalous acid with an oxidation capacity granular particulate ingredients where the size of the particles of 1.33 electron volts as the oxidizing species. is substantially smaller than the size of the massive body. The 0018. The generation of hypohalous acid to form chlorine massive body is formed from the mixture of particulate ingre dioxide from a chlorite salt using a monopersulfate oxidizing dients by compression and is essentially a large tablet. The agent with an oxidation capacity of 1.44 electron Volts. tablets release chlorine dioxide and free chlorine when added 0019. The generation of chlorine dioxide at a reaction pH to liquid water. The patent claims a composition of a chlorite from 5.0-9.0 using an oxidizing agent, a chlorite salt, and a salt, an acid source, and free halogen source, with the pre bromide salt. ferred composition being sodium chlorite, sodium bisulfate, 0020. The generation of chlorine dioxide where a liquid and the Sodium salt of dichloroisocyanuric acid. halogen with a deep reddish brown color is formed as an US 2008/02991 6 1 A1 Dec. 4, 2008

intermediate step to formation of chlorine dioxide. The liquid (preferably about 6.5 to about 7.5) compared when using halogen is heavier than water and is found at the bottom of the . A rapid and high yield of chlorine dioxide reaction vessel. is released when hypobromous acid is produced in the pres 0021. The generation of chlorine dioxide where a liquid ence of chlorite ions. halogen is formed and has an atomic number of 35. 0039. The unique reaction is clearly visible as a brown 0022. The generation of chlorine dioxide where a bro liquid heavier than water and is formed immediately upon the mine-like odor is formed prior to the characteristic chlorine addition of the composition to water. The brown liquid col dioxide odor. lects on the bottom of the reaction vessel forming a thin layer 0023 The generation of chlorine dioxide where acidulant over the solid composition. The brown liquid is believed to be materials are not required to maintain a pH less than 5.0. the halogen, . As the reaction continues, the charac 0024. A solid biocide composition that does not possess a teristic yellow color of chlorine dioxide is quickly visible and chlorine-like odor. increases until the brown color completely disappears. In less 0025. A solid biocide composition that does not contain a than 5 minutes, the chlorine dioxide solution is a bright yel free halogen releasing compound in the composition. A free low color and has reached its maximum concentration. halogen releasing compound is defined where if added to 0040. This surprisingly enhanced chlorine dioxide releas water it will generate measurable free halogen. ing effect is believed to occur because of the different pKa 0026. A solid biocide composition consisting of only inor values of the two weak acids. Hypobromous acid has a pKa of ganic chemicals or where the carbonatom is not present in the 8.6 compared to a pKa of 7.5 for hypochlorous acid. At a pH formula. of 7.5, less than 50% of the active oxidizing agent HOCl is 0027. The generation of chlorine dioxide using any com present, compared to 94% for HOBr. The hypochlorous acid pound that produces hypobromous acid upon contact with pathway reactions utilized in the prior art require the use of Water Or SeaWater. additional acidulant materials to ensure rapid conversion of 0028. To produce a solid biocide article that is not subject the chlorite ion to chlorine dioxide. The hypochlorous acid to degradation by moisture, oxygen, and temperature. releasing formulations also generate free chlorine in the solu 0029. To produce a solid biocide article that is not subject tion that is not converted to chlorine dioxide. This is a disad to premature release of chlorine dioxide and active oxygen by Vantage is applications that require the reaction to be entirely moisture and temperature. chlorine-free. 0030. A structure that preserves the active oxygen content 0041. The oxidizing effect of the two hypohalous acids of the composition. can be easily demonstrated by comparing chlorine dioxide 0031. To produce a biocide article that is not subject to generation using a bromide Salt and a chloride salt. The reac premature release of chlorine dioxide by accidental spillage tion when Sodium bromide is oxidized to hypobromous acid, or leakage of moisture, water, or other aqueous fluids. in the presence of sodium chlorite, occurs very rapidly and 0032 To produce a solid biocide article that is not subject generates a 2-3 fold greater yield of chlorine dioxide, com to premature yellowing of the composition or packaging pared when oxidizing Sodium chloride under the same con material. ditions. The Surprising result is an increased yield and a 0033. To produce a solid biocide article that is safe to shorter reaction time required to attain maximum chlorine handle and does not require direct exposure to skin. dioxide release. 0042. The greater yield of chlorine dioxide is also believed SUMMARY OF THE INVENTION to occur because the reaction intermediate, bromine and 0034. An embodiment of the present invention relates to a hypobromous acid, are heavier than water and collect at the Solid biocide composition that rapidly generates chlorine bottom of the reaction vessel near the reaction site of the solid dioxide upon addition to water or moisture. composition. A thin layer of bromine was observed to cover 0035 Another embodiment of the invention relates to a the solid reactants on the bottom of the flask. It is believed that sealed biocide article comprising the biocide composition these phenomena contributed to the conversion speed and rate sealed between two layers of a high-barrier material. The of the chlorite ions to chlorine dioxide. Therefore it is composition of the sealed biocide article is detailed below. believed that the slower diffusion rate of bromine compared 0036. The current invention relates to a novel chemical to that of chlorine used in prior art compositions contributed pathway to generate chlorine dioxide from Solid ingredients. to the observed higher yield of chlorine dioxide. It utilizes an oxidation pathway employing a bromide Salt or 0043. To illustrate this point, consider the prior art of U.S. bromine-releasing agent and its corresponding hypohalous Pat. No. 6,699.404. It is stated that the high conversion rate acid product, hypobromous acid. The formed hypobromous results from the use of tablets because a pore structure devel acid then provides the oxidative potential to generate chlorine ops and produces a Substantially Saturated acidic solution of dioxide from its chlorite salt. chlorite anion. It also states that once the reactants have 0037. Chlorine dioxide generation in the prior art com dissolved into solution, further conversion of chlorite anion to monly utilizes the intermediate reactant species hypochlor chlorine dioxide is very small. ous acid as the oxidizing species to convert chlorite salt to 0044) Therefore without being bound by any theory, it is chlorine dioxide. Hypochlorous acid can be formed from a believed in the current invention that the slow diffusion rate of number of Solid ingredients, usually chlorinated isocyanu the intermediate bromine and the lack of need for an acidic rates, chlorinated hydantoins, alkali or alkali earth metal solution, since hypobromous acid (HOBr) operates effec hypochlorites, or metal chloride salts reacted with active oxy tively at neutral pH, contribute to the greater yield and gen compounds, such as potassium monoperSulfate. increased rate of chlorine dioxide conversion. 0038. In the present invention, when hypobromous acid is 0045. The current invention also pertains to packaging of instead utilized as the oxidizing species, the conversion of the the solid biocide composition. It was found that stability chlorite salt to chlorine dioxide occurs rapidly at a neutral pH problems existed in many of the Solid prior art compositions US 2008/02991 6 1 A1 Dec. 4, 2008

referenced above. The “massive body’ mentioned in U.S. Pat. releasing compound then the amount is based on the total No. 6,699.404 was found to undergo extensive yellowing weight of the chlorite and the compound. effect in humid conditions (moisture >40%). The composi 0055 Suitable examples of oxidizing agents include alkali tion of U.S. Application No. 2006/0016765A1 was found to and alkali earth metal persulfates, monopersulfates, and be even more reactive in humid conditions and Substantial ammonium persulfate; alkali and alkali earth peroxides Such release of chlorine dioxide was observed. The mixture as lithium, Sodium, potassium, calcium, Zinc, or magnesium described in U.S. Pat. No. 6,602,442 also exhibited premature peroxide, urea peroxide, percarbonates, persilicates, per release of chlorine dioxide gas. The current invention phosphates and their metal salts, and hydrogen peroxide. The addresses stability concerns and describes a method of preferred oxidizing agent is potassium monopersulfate. extending the useful shelf-life of solid mixtures and com 0056. Other example of peroxides other than hydrogen pressed solid mixtures of chlorine dioxide precursor materi peroxide include dialkylperoxides, diacylperoxide, per als. formed percarboxylic acids, organic and inorganic peroxides, and/or hydroperoxides. Suitable organic peroxides/hydroper BRIEF DESCRIPTION OF THE DRAWINGS oxides include diacyl and dialkylperoxides Such as dibenzoyl 0046 FIG. 1 illustrates a top view of a blister pack accord peroxide, t-butyl hydroperoxide, dilauroyl peroxide, dicumyl ing to the present invention; peroxide, and mixtures thereof. Suitable peroxy-acids for use 0047 FIG. 2 illustrates a side view of a blister pack in the compositions include diperoxydodecandioic acid (DP according to the present invention; and DDA), magnesium perphthalic acid, perlauric acid, perben 0048 FIG. 3 illustrates a side view of a strip pack accord Zoic acid, diperoxyaZelaic acid and mixtures thereof. ing to the present invention. 0057 Suitable examples of bromide salts include alkali and alkali earth metal bromides such as Sodium bromide, DETAILED DESCRIPTION OF INVENTION lithium bromide, potassium bromide, magnesium bromide, ammonium bromide, Zinc bromide, calcium bromide, and A. Composition of the Invention aluminum bromide. 0049. The composition comprises a solid source of source 0.058 Other examples of bromide salts include mixtures of of hypobromous acid and a solid source of chlorite. The active bromine-rich salts commonly found in nature Such as the ingredients of the composition are selected and present in Dead Sea salts and brines. These contain bromide salt in amounts such that the pH of a solution formed from dissolv combination with other common salts such as Sodium chlo ing the composition in water is from about 5 to about 9. ride, potassium chloride, magnesium chloride, zinc chloride, preferably from about 5.5 to about 8.5, and more preferably Sodium Sulfate, potassium sulfate, magnesium sulfate, about 6 to about 8, and most preferably about 6.5 to 7.5, Sodium iodide, potassium iodide, and the like. Any combina measured at 25°C. at a concentration of 1 g of active ingre tion of salts can be used as the bromide source. dients of the composition per 100 ml of water. The active 0059) Other exemplary combinations include: a bromide ingredients being the solid source of hypobromous acid and salt combined with a chloride or iodide salt. For example: the solid source of chlorite. bromide Salt+Sodium, potassium, lithium, magnesium, cal 0050. The solid source of chlorite comprises an alkali or cium, zinc, ammonium, or aluminum chloride. Or for alkali earth metal chlorite. The solid source of hypobromous example an iodide Salt of sodium, potassium, lithium, cal acid comprises an oxidizing agent and a solid bromide releas cium, magnesium, zinc, ammonium, or aluminum can also be ing compound. used. All can be used individually or in combination in the 0051. The alkalioralkali earth metal chlorite can be any as current invention. desired. Such as Sodium, potassium, lithium, calcium, Zinc, or 0060. The source of the halide salts required to produce magnesium chlorite, which are commercially available. the hypohalous acid can also be present in the water which is 0052. The composition typically contains from about 10 to to be treated. For example, seawater which consists of about about 90% of solid source of hypobromous acid and about 10 3.5% salt can be used as the sole source of the halide salt. The to about 90% of solid source of chlorite. All percentages are chlorine dioxide releasing composition then can be reduced weight percentage based on the total weight of the composi to two parts: chlorite source and the oxidizing agent. This tion unless otherwise stated. unexpected result was found when adding sodium chlorite 0053 A preferred composition comprises from about 10 and potassium monoperSulfate to seawater (See Experimen to about 90% of sodium chlorite, about 5 to about 90% of tal Example 6). sodium bromide, and about 5 to about 60% of potassium 0061 Also suitable are bromide-releasing compound in monopersulfate. More preferably, the composition comprises which the bromide ion is a salt of a suitable organic cation, about 20 to about 60% sodium chlorite, about 10 to about Such as for example, but not limited to ammonium bromide, 40% of sodium bromide, and about 10 to about 50% of alkylammonium bromide, dialkylammonium bromide, tri potassium monopersulfate. All percentages are weight per alkylammonium bromide, wherein said alkyl radicals are centage based on the total weight of the composition unless independently selected from Straight chain or branched ali otherwise stated. phatic, aromatic, or arylhydrocarbon radicals of between 1 to 0054 Oxidizing agents are typically acidic in nature. about 24 carbon atoms. Thus, preferably the amount of oxidizing agent is from about 0062 Also suitable as a bromide-releasing compound are 5 to about 50%, more preferably from about 10 to about 40%, bromide ion exchange materials. That is materials able to and most preferably from about 10 to about 30% of the exchange a bromide ion in the presence of the more common composition, based on the total weight of the oxidizing agent, chloride ion in aqueous solution, and which are typically chlorite and bromide-releasing compound. In the case of a water insoluble polymeric and mineral matrixes preloaded compound that is both an oxidizing agent and a bromide with high bromine ion content. US 2008/02991 6 1 A1 Dec. 4, 2008

0063 Ideally the salt should form hypobromous acid dur one, 1-bromo-3-chloro-, potassium salt (potassium ing oxidation with potassium monoperSulfate. Some salts or bromochloroisocyanurate CASH 29545-74-2). mixtures of salts will form a combination of hypobromous, (0072 Also 1,3,5-Triazine-2,4,6(1H.3H,5H)-trione, 1,3- hypochlorous, and/or . Hypochlorous acid is dibromo-5-chloro-(bromochlorisocyanuric acid CAS also a powerful oxidizing agent and will convert additional #666714-66-5); and 1,3,5-Triazine-2,4,6(1H,3H,5H)-trione, bromide salt to hypobromous acid. 1,3-dibromo-(dibromocyanuric acid CAS #151 14-43-9); 0064. Other forms of bromine-releasing compounds may and sodium monobromo-monochloro-isocyanurate (bromo also be used. The below compounds provide free bromine and chloroisocyanuric acid monosodium salt hydrate CAS the corresponding hypobromous acid when added to liquid #164918-61-0) are suitable. water. They can also serve as oxidizing agents to convert 0073. Additional suitable hypobromite-generating bromide salts to free bromine. Also suitable to provide free organic compounds include N-bromophthalamide, N,N-di bromine is liquid bromine in elemental form. This is a dark bromodimethylhydantoin, N,N-dibromodiethylhydantion, liquid at room temperature and standard pressure. N,N-dibromodimethylglycoluracil, dibromotriethylene-di amine dihydrogenchloride, and mixtures thereof. Hypohalite-Generating Compound 0074 Suitable hypochlorite-generating compounds include: Trichlorocyanuric acid, dichlorocyanuric acid, 0065. A hypohalite-generating compound can provide the mono-chlorocyanuric acid, sodium dichloroisocyanurate (di oxidation potential to oxidize sodium chlorite to chlorine hydrate and anhydrous), and potassium dichloroisocyanu dioxide. A hypohalite-generating compound can also pro rate. duce free bromine from bromide ions in aqueous solution. 0075 Also suitable hypochlorite-generating compounds Suitable compounds for providing the free available halogen including but not limited to N,N-dichloro-s-trizinetrione, concentration are hypochlorite-generating or hypobromite N-chlorophtalamide, N-dichloro-p-toluene sulfonamide, generating compounds. These compounds must be at least 2.5-N,N-dichloroazodicarbonamidine hydrochloride, partially or fully water soluble and generate an active halogen NNNN-tetrachloroglycoluracil, N,N-dichloroyl.N.N.N- ion (ie. HOCl, HOBr, OCl, OBr.) upon dissolving in water. trichloromelamine. N-chlorosuccinimide, methylene-bis(1- Thus, the hypohalite-generating compound can be consid chloro-5,5-dimethyethylhydantoin), 1,3-dichloro-5-methyl ered as both the oxidizing agent and the bromide-releasing 5-isobutylhydantoin, 1.3,dichloro-5-n-amylhydantoin, 1.3- agent. dichloro-5,5-dimethylhydantoin, 1,4-dichloro-5,5- 0066. Any of the following representative sources or mix diethylhydantoin, 1-1 monochlor-5,5-dimethylhydantoin, tures thereof include alkali and alkali earth metal hypobro Sodium-para-toluenesulfochloramine, dichlorosuccinamide, mite salts such as: lithium hypobromite, Sodium hypobro 1.3.4.6-tetrachlorogylcouracil, potassium and Sodium salts of mite, potassium hypobromite, calcium hypobromite, chloroisocyanuric acid, dichloroisocyanuric acid, potassium magnesium hypobromite, and Zinc hypobromite. and sodium salts of N-brominated and N-chlorinated succin 0067. Also suitable hypochlorite-generators are chlori imide, malonimide, phthalimide and naphthalimide, and mix nated trisodium phosphate, chlorinated trisodium polyphos tures thereof. phate, and chlorinated trisodium phosphate dodecahydrate, 0076 Halohydantoins, such as 1-bromo-3-chloro-5,5- and mixtures thereof. dimethylhydantion (BCDMH), 1-bromo-3-chloro-5-methyl 0068 Any of the following representative sources or mix 5-ethyl-hydantoin (BCEMH), 1,3-dibromo-5,5-dimethylhy tures thereof including alkali and alkali earth metal hypochlo dantoin (DBDMH), 1,3-dibromo-5-methyl-5-ethyl rite salts such as lithium hypochlorite, sodium hypochlorite, hydantoin (DBEMH) are suitable. potassium hypochlorite, calcium hypochlorite, magnesium 0077. Other suitable N-haloamines are trichlo hypochlorite, and Zinc hypochlorite are also Suitable. romelamine, tribromomelamine, dibromo- and dichloro dimethylhydantoin, chlorobromo-dimethylhydantoin, Halocyanurates N-chlorosulfamide (haloamide), chloramines (haloamine), 0069. Any of the following representative sources of halo and mixtures thereof. cyanurates or mixtures thereof including but not limited to 0078. Also suitable are partially chlorinated and bromi their lithium, sodium, potassium, calcium, magnesium, or nated compounds, including N-bromo-N-chlorodimethylhy Zinc salts may be used in the current invention. Tribromoiso dantion, N-bromo-N-chlorodiethylhydantoin, N-bromo-N- cyanuric acid, dibromoisocyanuric acid, monobromoisocya chlorodiphenylhydantoin, N-bromo-N,N-dichloro nuric acid, monobromo-dichlorisocyanuric acid, dibromo dimethylglycouracil, N-bromo-N-chlorosodium cyanurate, monochloroisocyanuric acid, and monobromo-monochloro bromochlorotriethylenediamine dihydrogenchloride and isocyanuric acid may be used to produce a free bromine and mixtures thereof. its corresponding hypobromous acid when added or con 007.9 The composition can contain other ingredients as tacted with water. desired. For example, if the composition is formed into a 0070 Also suitable hypobromite-generating compounds tablet, common ingredients such as binders, mold release include: 1,3,5-Triazine-2,4,6(1H.3H,5H)-trione, 1,3-di agents, compression aids, tablet lubricants, Swelling agents, bromo-, sodium salt (sodium dibromoisocyanurate—CAS carrier materials, fillers, and Surfactants can optionally be #151 14-34-8); and 1,3,5-Triazine-2,4,6(1H.3H,5H)-trione, added to the composition. 1,3-dibromo-, potassium salt (potassium dibromoisocyanu rate CAS #151 14-46-2). B. Structure 0071 Also suitable hypobromite-generating compounds 0080. The composition can be produced by any method include: 1,3,5-Triazine-2,4,6(1H.3H,5H)-trione, 1-bromo-3- known to one skilled in the art such as mixing, blending, chloro-, sodium salt (sodium bromochloroisocyanuric acid— granulating, pelleting, tableting, or extruding. The preferred CAS #20367-88-8); and 1,3,5-Triazine-2,4,6(1H,3H,5H)-tri method is tableting, which is carried out by methods familiar US 2008/02991 6 1 A1 Dec. 4, 2008

to one skilled in the art. Tablets provide a convenient form of foil layer 3 can be left unbound as shown at 5 and the area 6 example to demonstrate the second embodiment of the inven to provide a flap for opening the blister pack. The blister pack tion, which comprises a sealed biocide article comprising the can have perforations shown at 7 to allow separation of the claimed composition sealed in a high-barrier package. individual blisters. 0081. The invention will be further described with refer 0089. It was also found that the environmental conditions ence to a tablet, without being limited thereto. The stability of in the manufacturing and packaging operation can affect the the composition in tablet form is a function of two factors: 1) stability of the sealed composition. The ambient temperature Keeping moisture away from the tablet to prevent premature and moisture are the most important factors. The relative release of chlorine dioxide. 2) Prevention of release of active humidity is preferably kept below about 15% RH and the oxygen from the oxidant (ie. potassium monoperSulfate). temperature preferably below about 80° F. Most preferably, 0082 It has been found that stability problems arise in the relative humidity should be under about 10% and tem mixtures and compressed mixtures of chlorite+oxidant--ha perature under 70° F. lide salt (can be any two or three of the ingredients). These problems include premature release of chlorine dioxide gas, 0090. For example, the packaging operation can be per yellowing of packaging materials, yellowing of powder or formed on an automatic double-aluminum packing machine. tablets, build-up of chlorine dioxide gas in enclosed contain The two rolls of aluminum flexible laminate films can be fed ers, and undesired bleaching of Surrounding objects. The into the machine and temperature sealed around the tablet at stability concerns proved unacceptable in attempting to pro 150-200 F. Double sealed aluminum laminate film strips duce a product with adequate shelf-life (ie. >1 year). with the tablet enclosed can be cut into 4"x3" strips. The strips 0083 Various low-barrier packaging materials that were can then placed inside a labeled paper box. used to enclose the produced tablet have been found to be inadequate. In particular, low-barrier polymer films, such as EXPERIMENTAL SECTION PE, PET, and PVETOH (polyvinyl ethanol), were found to be ineffective to varying degrees. The thickness and porosity of 0091 All concentration readings were performed on a the films were thought to be important factors in failure to Hach DR 2500 Spectrometer. prevent decomposition of the tablet. 0084. A significant improvement to the stability of the Example 1 tablet was found when a high-barrier packaging material was used. Aluminum is the ultimate high-barrier material, since it 0092 is impervious to moisture and gas, and is, thus, materials containing an aluminum layer are preferred. However, other high-barrier packaging materials can be used. Aluminum polymer films from Alcan Corporation are examples of pre Sodium chlorite 1.0 gram Potassium monopersulfate (KMPS) 1.5 grams ferred materials. Sodium bromide 0.9 grams 0085 High-barrier polymer films are usually comprised of several layers of materials compressed into a composite, and usually include an aluminum layer. Some of the following are (0093. Add to 300 ml of water. The result was 1400 mg/Li examples of materials that are layered into the film: print, ter (1400 ppm) chlorine dioxide after 5 minutes at pH 6.5. paper, lacquer, aluminum, PVC, PE, PET, Sealant (coextru sion of PE and Surlyn), CERAMIS (aluminum-free lami Example 2 nate), adhesive, heat-seal coating. I0086 Preferably, two aluminum flexible laminate films 0094) are heat-sealed around a tablet of the present composition to form the sealed biocide article. This type of packing is referred to as Al-Alpacking. It is an unexpected result com Sodium chlorite 1.0 gram pared to prior art tablets for forming chlorine dioxide, since KMPS 1.2 grams previous enclosure methods did not yield suitable stability. Sodium bromide 0.9 grams The films are of various types and functions and are known as “Flexible Laminates” or “Blister Lidding”. 0087. A preferred sealed enclosure used to house the tab (0095 Add to 300 ml of water. The result was 1050 ppm lets is known as Strip packing, as shown in FIG. 3, which after 5 minutes at pH 7.0. comprises two sheets offilm 10 and 11 heat-sealed together at 12. The inside space between the two sheets offilm 10 and 11 Comparative Example A contains the tablet composition 2a of the present invention. The sealed enclosure provides the environment around the composition that prevents the entry of moisture and oxygen. 0.096 0088. The tablet composition 2a can also be sealed into a larger enclosure known as ablister pack, as shown in FIGS. 1 and 2. These are often used in child-resistant packaging. Sodium chlorite 1.0 gram Larger tablet sizes such as greater than 20 grams are more KMPS 1.2 grams conveniently packaged into blisters. The blister pack in FIGS. Sodium chloride 0.7 grams 1 and 2 comprises a foil layer 3 bound to a sheet offilm 1 using the adhesive 8. A space 2 between the foil layer 3 and the sheet (0097. Add to 300 ml of water. The result was 420 ppm of film 1 contains the tablet composition 2a. A portion of the after 5 minutes at pH 7.0. To get a higher yield using sodium US 2008/02991 6 1 A1 Dec. 4, 2008

chloride, the pH would have to be reduced to 4 or lower to the pH was too low, due to the large amount of potassium achieve an equivalent yield compared to Sodium bromide. monopersulfate, thus driving the reaction to form bromine. Example 3 Comparative Example B 0098 0108. This Comparative Example B is taken from Example 4 of published U.S. patent application No. 2006/ 0016765. In that Example 4, zinc bromide was used in a Sodium chlorite 1.0 gram composition at a pH of 4.1, when measured at less than 0.07 Sodium bromochloroisocyanurate 0.5 grams g per 100 ml of water. The pH was low because of the amount of OXONE (potassium monopersulfate) present in the com position at a high percentage, 72.6%. A 2.6 g tablet was 0099. Add to 300 ml of water. The result was 350 ppm dissolved in 3.785 liters of water, which translates to about after 15 minutes at pH 7.0 0.07g per 100 ml of water. Since the tablet contained inactive ingredients, the active ingredients were actually present in an Example 4 amountless than 0.07g per 100 ml water. If the concentration 01.00 of the active ingredients was increased to 19 per 100 ml, the pH would have been even lower than 4.1. 0109. In contrast, the Examples according to the present invention provided a pH in the range of 6 to 7, when 1 g of Sodium chlorite 1.0 gram Sodium bromochloroisocyanurate 0.5 grams active ingredient was dissolved in 100 ml water. Sodium bromide 0.5 grams Example 8 0101 Add to 300 ml of water. The result was 400 ppm 0110 Tablets were prepared as described above having the after 15 minutes at pH 7.0 formulation below: Sodium chlorite 31% Example 5 Sodium bromide 28% 01.02 Potassium monopersulfate 16% Sodium sulfate 8% Magnesium sulfate 10% Sodium chlorite 1.0 gram Magnesium stearate 7% Potassium monoperSulfate 1.2 grams 0111. An experiment was performed to determine biocide efficacy on three microorganisms: Saccharomyces, Zygosac (0103) Add to 300 ml of fresh seawater. The result was 600 charomyces, Brettanomyces. The results demonstrate potent ppm after 20 minutes at pH 6.0. biocide action on the three microorganisms. 0112 A solution was prepared by dissolving one tablet in Example 6 1 liter of deionized water and tested for microbial efficacy. 0113. The biocide test was performed by G3 Enterprises 0104 of Modesto, Calif. The results are shown in Tables 1-3.

TABLE 1 Sodium chlorite 1.0 gram Time Saccharomyces (cfil Ammonium bromide 0.5 gram Potassium monoperSulfate 1.2 gram (Sec) Concentration 10 1 0 1 0 1 0 10° 10' 109 -control O 0105. Add to 300 ml of water. The result was 900 ppm +control 102 x 107 after 5 minutes at pH 6.5 60 1.00 60 O.SO ------Example 7 60 O.25 -- -- 01.06 TABLE 2 Time Zygosaccharomyces (cful Sodium chlorite 1.0 gram Potassium monoperSulfate 2.0 grams (Sec) Concentration 10 1 0 1 0 1 0 10° 10' 109 Sodium bromide 0.9 grams -control O +control 9 x 107 60 1.00 0107 Add to 300 ml of water. A dark red color was formed 60 O.SO -- -- immediately that remained for over 2 hours. The characteris 60 O.25 -- -- tic odor of bromine was detected. The solution did not yield any visible or measurable chlorine dioxide. It is believed that US 2008/02991 6 1 A1 Dec. 4, 2008

4. A Solid composition according to claim 2, wherein the TABLE 3 bromide salt comprises at least one bromide salt selected from the group consisting of alkali and alkali earth metal Time As retariomyces (cful bromides. (Sec) Concentration 10° 10° 10' 10 102 10 109 5. A Solid composition according to claim 2, wherein the bromide salt comprises at least one selected from the group -control O +control 57x 107 consisting of Sodium bromide, lithium bromide, potassium 60 1.00 bromide, calcium bromide, magnesium bromide, ammonium 60 O.SO bromide, and aluminum bromide. 60 O.25 -- 6. A Solid composition for forming chlorine dioxide on demand according to claim 1, wherein the Solid source of chlorite comprises an alkali or alkali earth metal chlorite and ADVANTAGES OF THE PRESENT INVENTION the Solidinorganic Source of hypobromous acid comprises an oxidizing agent and a solid bromide-releasing compound. 0114 Generation of chlorine dioxide occurs rapidly at 7. A Solid composition according to claim 6, wherein the neutral pH. Solid bromide-releasing compound comprises at least one 0115 The present invention avoids the use of dangerous selected from the group consisting of brominated hydantoins, chlorine-releasing compounds such as hypochlorites and bromochlorohydantion. BCDMH, dibromodimethylhydan chlorinated isocyanurates and thus no free chlorine is gener toin, brominated isocyanurates and bromochloroisocyanuric ated in the solution. acid. 0116. The present invention avoids adding acidulant mate 8. A Solid composition according to claim 2, wherein the rials to the composition thereby increasing stability and oxidizing agent comprises at least one selected from the decreasing corrosive properties. group consisting of dialkylperoxides, diacylperoxide, per 0117 Generation of chlorine dioxide occurs rapidly at formed percarboxylic acids, organic and inorganic peroxides, high yield with no residue. hydroperoxides, organic peroxides, hydroperoxides, diacyl 0118. The present composition has a greater safety profile and dialkyl peroxides, dibenzoyl peroxide, t-butyl hydroper than previously described compositions. Sodium dichlor oxide, dilauroyl peroxide, dicumyl peroxide, and mixtures oisocyanurate has a NFPA rating of (3-1-2) and is classified thereof. by DOT as an oxidizer. Potassium monopersulfate has a 9. A solid composition according to claim 2, further com NFPA rating of (3-0-1) and is classified by DOT as a corrosive prising at least one peroxy-acid selected from the group con solid. sisting of diperoxydodecandioic acid (DPDDA), magnesium 0119 The present composition does not possess a chlo perphthalic acid, perlauric acid, perbenzoic acid, diperoxya rine-like odor as do previously described compositions. Zelaic acid and mixtures thereof. 0120 Chlorine dioxide release at high yield can be 10. A solid composition according to claim 2, wherein the achieved using only two precursors, unlike most formulations bromide salt comprises a bromine-rich sea salt or brine. that require three or more precursor compounds to be present. 11. A solid composition according to claim 6, wherein the 0121 While the claimed invention has been described in bromide-releasing compound comprises at least one selected detail and with reference to specific embodiments thereof, it from the group consisting of ammonium bromide, alkylam will be apparent to one of ordinary skill in the art that various monium bromide, dialkylammonium bromide, trialkylam changes and modifications can be made to the claimed inven monium bromide, wherein said alkyl radicals are indepen tion without departing from the spirit and scope thereof. dently selected from straight chain or branched aliphatic, 1. A Solid composition for forming chlorine dioxide on aromatic, or aryl hydrocarbon radicals of between 1 to about demand comprising: 24 carbon atoms. 12. A solid composition according to claim 6, wherein the a solid inorganic source of hypobromous acid; and bromide-releasing compound comprises a bromide ion a solid source of chlorite, wherein the Solid inorganic Source of hypobromous acid and solid source of chlorite exchange material. are present in an amount Such that the pH of a solution 13. A solid composition according to claim 1, further com formed from dissolving the composition in water is from prising a solid inorganic source of hypochlorous acid wherein 5 to 9, measured at 25° C. at a concentration of 1 g of one of the Sources is a salt. active ingredients of the composition per 100 ml of 14. A solid composition according to claim 1, further com water, the active ingredients being the total weight of the prising a source of hypoiodous acid. Solid inorganic source of hypobromous acid and the 15. A solid composition according to claim 1, wherein the solid source of chlorite. Source of hypobromous acid comprises a hypobromite com 2. A Solid composition according to claim 1, wherein the pound. solid source of chlorite comprises a metal chlorite and the 16. A solid composition according to claim 15, wherein the Solid inorganic source of hypobromous acid comprises an hypobromite compound comprises at least one selected from oxidizing agent and a bromide salt. the group consisting of alkali and alkali earth metal hypobro 3. A Solid composition according to claim 2, wherein the mite salts such as: lithium hypobromite, Sodium hypobro oxidizing agent is at least one oxidizing agent selected from mite, potassium hypobromite, calcium hypobromite, magne the group consisting of alkali and alkali earth persulfates, sium hypobromite, Zinc hypobromite, and mixtures thereof. monopersulfates, alkali and alkali earth peroxides, urea per 17. A solid composition according to claim 1, further com oxide, percarbonates, persilicates, perphosphates, and hydro prising at least one hypochlorite-generators selected from the gen peroxide. group consisting of chlorinated trisodium phosphate, chlori US 2008/02991 6 1 A1 Dec. 4, 2008

nated trisodium polyphosphate, and chlorinated trisodium 25. A Solid composition according to claim 1, comprising phosphate dodecahydrate, and mixtures thereof. at least one N-haloamines selected from the group consisting 18. A solid composition according to claim 1, wherein the of trichloromelamine, tribromomelamine, dibromo- and Source of hypobromous acid comprises a bromocyanurate or dichloro-dimethylhydantoin, chlorobromo-dimethylhydan salt of a bromocyanurate. toin, N-chlorosulfamide(haloamide), chloramines(haloam 19. A solid composition according to claim 18, wherein the ine), and mixtures thereof. bromocyanurate or salt of the bromocyanurate comprises at 26. A Solid composition according to claim 1, comprising least one selected from the group consisting of tribromoiso at lest one partially chlorinated and brominated compound cyanuric acid, dibromoisocyanuric acid, monobromoisocya selected from the group consisting of including N-bromo-N- nuric acid, monobromo-dichlorisocyanuric acid, dibromo chlorodiethylhydantoin, N-bromo-N-chlorodiphenylhydan monochloroisocyanuric acid, and monobromo-monochloro toin, N-bromo-N,N-dichloro-dimethylglycouracil, isocyanuric acid. N-bromo-N-chlorosodium cyanurate, bromochlorotriethyl 20. A solid composition according to claim 1, wherein the enediamine dihydrogenchloride, and mixtures thereof. Source of hypobromous acid comprises at least one selected 27. A solid composition according to claim 1, comprising a from the group consisting of hypobromite-generating com bromide salt combined with a chloride or iodide salt. pounds include: 1,3,5-Triazine-2,4,6(1H.3H,5H)-trione, 1,3- 28. A solid composition according to claim 27, wherein the dibromo-, sodium salt (sodium dibromoisocyanurate— chloride or iodide salt comprises sodium, potassium, lithium, CASH 15114-34-8); 1,3,5-Triazine-2,4,6(1H.3H,5H)-trione, magnesium, calcium, Zinc, ammonium, aluminum chloride, 1,3-dibromo-, potassium salt (potassium dibromoisocyanu and mixtures thereof. rate CASH 15114-46-2): 1,3,5-Triazine-2,4,6(1H,3H,5H)- 29. A Solid composition comprising: trione, 1-bromo-3-chloro-, sodium salt (sodium bromochlor oisocyanuric acid CAS #20367-88-8); 1,3,5-Triazine-2,4,6 about 10 to about 90% by weight of sodium chlorite: (1H.3H,5H)-trione, 1-bromo-3-chloro-, potassium salt about 10 to about 90% by weight of sodium bromide; and (potassium bromochloroisocyanurate CASH 29545-74-2); about 5 to about 90% by weight of potassium monoper 1,3,5-Triazine-2,4,6(1H.3H,5H)-trione, 1,3-dibromo-5- Sulfate, the weight percent being based on the total chloro-(bromochlorisocyanuric acid CAS 666714-66-5); weight of the composition, wherein the Sodium chlorite, 1,3,5-Triazine-2,4,6(1H.3H,5H)-trione, 1,3-dibromo-(dibro Sodium bromide and potassium monopersulfate are mocyanuric acid CAS #151 14-43-9); and sodium mono present in an amount Such that the pH of a solution bromo-monochloro-isocyanurate (bromochloroisocyanuric formed from dissolving the composition in wateris from acid monosodium salt hydrate CASH 164918-61-0). 5 to 9, measured at 25° C. at a concentration of 1 g of 21. A solid composition according to claim 1, wherein the active ingredients of the composition per 100 ml of Source of hypobromous acid comprises at least one hypobro water, the active ingredients being the total weight of the mite-generating organic compound selected from the group Sodium chlorite, sodium bromide and potassium consisting of N-bromophthalamide, N,N-dibromodiethylhy monopersulfate. dantion, N,N-dibromodimethylglycoluracil, dibromotrieth 30. A solid composition according to claim 2, comprising: ylene-diamine dihydrogenchloride, and mixtures thereof. about 20 to about 60% by weight sodium chlorite: 22. A Solid composition according to claim 1, further com about 10 to about 60% by weight potassium monopersul prising at least one hypochlorite-generating compound fate; and about 10 to about 40% by weight of at least one selected from the group consisting of trichlorocyanuric acid, of sodium bromide or ammonium bromide. dichlorocyanuric acid, mono-chlorocyanuric acid, sodium 31. A solid composition according to claim 2, wherein the dichloroisocyanurate (dihydrate and anhydrous), potassium bromide salt is other than calcium bromide and Zinc bromide. dichloroisocyanurate, N,N-dichloro-s-trizinetrione, N-chlo 32. A solid composition according to claim 1, wherein the rophtalamide, N-dichloro-p-toluene sulfonamide, 2.5-N,N- Solid inorganic source of hypobromous acid and Solid source dichloroazodicarbonamidine hydrochloride, NNNN-tetra of chlorite are present in an amount such that the pH of a chloroglycoluracil, N,N-dichloroyl.N.N.N- Solution formed from dissolving the composition in water is trichloromelamine, N-chlorosuccinimide, methylene-bis(1- chloro-5,5-dimethyethylhydantoin), 1,3-dichloro-5-methyl from 6 to 8, measured at 25° C. at a concentration of 1 g of 5-isobutylhydantoin, 1.3.dichloro-5-n-amylhydantoin, 1.3- active ingredients of the composition per 100 ml of water. dichloro-5,5-dimethylhydantoin, 1,4-dichloro-5,5- 33. A solid composition according to claim 1, wherein the diethylhydantoin, 1-1 monochlor-5,5-dimethylhydantoin, Solid inorganic source of hypobromous acid and Solid source Sodium-para-toluenesulfochloramine, dichlorosuccinamide, of chlorite are present in an amount such that the pH of a 1.3.4.6-tetrachlorogylcouracil, potassium and Sodium salts of Solution formed from dissolving the composition in water is chloroisocyanuric acid, dichlorocyanuric acid, and trichloro from 6.5 to 7.5, measured at 25°C. at a concentration of 1 g cyanuric acid, potassium and Sodium salts of N-brominated of active ingredients of the composition per 100 ml of water. and N-chlorinated Succinimide, malonimide, phthalimide 34. A solid composition according to claim 1, wherein the and naphthalimide, and mixtures thereof. solid source of chlorite comprises sodium chlorite and the 23. A solid composition according to claim 1, comprising Solid inorganic Source of hypobromous acid comprises a bro at least one halohydantoin. mocyanurate 24. A solid composition according to claim 1, comprising 35. A solid composition according to claim 34, wherein the at least one halohydantoins selected from the group consist bromocyanurate is bromochlorocyanurate. ing of 1-bromo-3-chloro-5-methyl-5-ethyl-hydantoin 36. A solid composition according to claim 1, wherein the (BCEMH), 1,3-dibromo-5,5-dimethylhydantoin (DBDMH), composition comprises from about 10 to about 90% of the 1,3-dibromo-5-methyl-5-ethyl-hydantoin (DBEMH), and Solid inorganic source of hypobromous acid and about 10 to mixtures thereof. about 90% of the solid source of chlorite. US 2008/02991 6 1 A1 Dec. 4, 2008

37. A sealed biocide article comprising a tablet having a Source of hypobromous acid and the solid source of chlorite, composition according to claim 2 sealed in a high-barrier to water such that hypobromous acid is produced from the package. Solid inorganic source of hypbromous acid and the hypobro mous acid is reacted with chlorite produced from the solid 38. A sealed biocide article according to claim 37, wherein source of chlorite to form chlorine dioxide. the tablet is sealed in a blister pack. 41. A method according to claim 40, wherein the solid 39. A sealed biocide article according to claim 37, wherein source of chlorite comprises sodium chlorite and the solid the tablet is sealed in a strip pack. inorganic source of hypbromous acid comprises Sodium bro 40. A method of producing chlorine dioxide comprising: mide and potassium monoperSulfate. adding a composition comprising a solid inorganic source of 42. A method according to claim 40, further comprising the hypobromous acid and a solid source of chlorite, wherein the step of using hypochlorous acid to convert a bromide Salt to Solid inorganic source of hypobromous acid and Solid source hypobromous acid. of chlorite are present in an amount such that the pH of a 43. A method according to claim 40, further comprising the Solution formed from dissolving the composition in water is steps of adding sodium chlorite and potassium monopersul from 5 to 9, measured at 25° C. at a concentration of 1 g of fate to seawater. active ingredients of the composition per 100 ml of water, the active ingredients being the total weight of the Solid inorganic