MXPA97000958A - Biocidal compositions in po - Google Patents

Abstract

The present invention relates to a biocidal powder and deodorant for sustained release of chlorine dioxide, characterized in that it comprises: particles containing chlorite anions, and a hydrophobic core having said particles on a surface thereof, the hydrophobic core containing an agent acid liberator and said particles and said core being substantially free of water, said particles being capable of releasing chlorine dioxide by hydrolysis of the liberating agent of

Description

f 'BIOCIDAL COMPOSITIONS IN POWDER BACKGROUND OF THE INVENTION The present invention relates generally to a biocide composition < It releases chlorine dioxide. The invention relates to a mixed material formulated as a powder. ^ I "1 rORO dioxide (CIO2) is an oxidizing agent Lf) top widely used as a bleach, disinfectant, fumigator or deodorant. It can penetrate the cell wall or membrane, and asthma of spores of molds, bacteria, and other corymal bacteria, at concentrations below one part per million and destine them. 15 The incorporation of chlorine dioxide or clop + or sodium in the food packaging has induced studies to determine if the residual levels of these preservatives cause a significant genetic or carcinogenic risk to humans. Iier and others studied the effect of Acute and synchronous oral administration of chlorine, chlorine dioxide, sodium chlorite and sodium chlorate on the induction of cronosormous aberrations and spermatozoa head abnormalities is in Feviron mice. Mutagenesis, 7_, 201 (1185)]. Only the high hypochlorite in reactive + reactivated ~ > ? result a weak positive effect for potential, rnu + agen co .. The omitted o + ros, including chlorine dioxide and clop or they did not induce any crino- sinic aberration or increased number of chronuclei in the bone marrow of mice. I saw lagines and others attribute the relatively innocuous effect of chlorine dioxide to its inability to produce halogen et anos, unlike the hi-potion and chlorine rProc.

AUUfl Disinfect. Semm., 24 pp. (1977); Chern. Abs. 93, .I73513f] "Recently, Richardson and others reported that an extensive study of the reaction of chlorine dioxide with organic compounds from water by the environmental pro + ecc on agency confirmed this CEnviron observation. Sci. Technol., 28, 592 (L994)]. Japanese Koka Nos. 63/296, 758, 63 / 274,434 and 57 / 168,977 describe deodorants containing chlorine dioxide incorporated in a polymer, ceric spheres or calcium silicate wrapped in non-woven fabric, respectively.

The genes that generate chlorine dioxide to be used as topical applications for disinfection are described in Kenyon v ^ t o, 3rn. D. Vet. Res., XS45 (5), 1101 (1986). Chlorine dioxide generator gels are usually formed by mixing a gel containing suspended sodium clopto with a gel containing Lactjco acid immediately before use to prevent the release of premature chlorine dioxide, the dioxide-releasing gels of chlorine have been used to change in 1 to 1% by weight,. Encapsulation procedures have also been used in the preparation of chlorine dioxide sources. L Canadian Patent No. 959,238 describes the generation of chlorine dioxide by separate encapsulation of sodium chlorite and < lactic acid in polyvinyl alcohol and mixing the capsules with water to produce chlorine dioxide. Tice et al., Patent of E.U.A. No. 4,585 48? It describes the gradual hydrolysis of polyetheric acid, anhydride, anhydride, or polyacrylate, or alternatively co-glycol, to generate acid that can liberate chlorine dioxide from lop or sodium. A polyalcohol and water humectant is encapsulated with polyahlypide or polyacid in a nylon coating. After the ".odium clopto" is diffused in the capsule through a nylon pair, a layer of impermeable polymer is placed around the nylon capsule. The capsules can be coated on surfaces to release chlorine dioxide, although the capsules provide biocidal action for several days to months, the release of chlorine dioxide begins immediately after the capsules are prepared. The intermittent procedure used to prepare the capsules also involves numerous chemical reactions and physical procedures, some of which involve problems of environmental waste.There is a need for an intermediate body that can be easily activated to initiate release of chlorine dioxide during use A composition that is composed of and generated only substances approved by the FDA, or those jr ^ -u) reasonably recognized as safe, it is particularly necessary to pair food and other applications where substances can be ingested by or come in contact with human beings.

BRIEF DESCRIPTION OF THE INVENTION Among the objects of the invention, therefore, is / > You can notice the provision of a composition that releases a sufficient concentration of chlorine dioxide to eliminate bacteria, fungi, molds and viruses; the provision of a composition that releases chlorine dioxide concentrations after activation for a period of up to several months; the provision of a composition that is free flowing and that can be easily mixed with other ingredients before the application; the provision of a membrane that penetrates porous surfaces; the provision of a composition that increases the rate of release of chlorine dioxide in proportion to the increased temperature and humidity that promote the growth of fungi and bacteria; and the provision of a composition that only releases substances approved for human exposure or ingestion by humans and that is relatively expensive. The present invention is directed to a biocidal powder for sustained release of chlorine dioxide that includes particles containing chlorides + and a nucleus f ~ Irophobic that has the particles on a surface thereof, the hydrophobic core containing an acid-releasing agent. The particles and the hydrophobic core are substantially free of water, and the particles can liberate chlorine dioxide under hydrolysis of the acid release agent. Or r-a mode of the invention is a procedure to prepare a powder that? provides sustained release of chlorine dioxide which includes forming paiticles containing clopto anions, and spraying a hydrophobic material containing an acid releasing agent onto a fluidized bed of the particles to form a powder having a core containing the hydrophobic material and a layer of chlorite-containing particles on a surface of the core. Another embodiment of the invention is directed to a method of retarding bacterial, fungal, and mold contamination on a surface and / or deodorising the surface by treating the surface with a powder that does not release chlorine dioxide into the surface. absence of moisture, and exposing the treated surface to moisture to release chlorine dioxide from the dust into the surrounding atmosphere of the supi-flic. The powder has a hydrophobic core that contains an acid releasing agent and has chlorite anions on a surface of the same. Other objects and advantages of the invention «oran biden is from the following detailed description.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic list illustrating the conversion of an amine precursor to iminium clonium; Figure 2 illustrates hydrolysis of an acid anhydride in a hydrophobic phase and migration of the hydronium ion to the imino lorite to release chlorine dioxide gas; Figures 3a, 3b and 3c are schematic views of mixed multilayer bodies to provide sustained release of chlorine dioxide; Figure 4 is a graph of the chlorine dioxide liberation rates for various powder compositions; Figure 5 is a graph of chloro dioxide liberation rates for a mixed body formed in caps; Figure 6 is a graph of chlorine dioxide release rates in relation to atmospheric temperature and humidity; Figure 7 is a graph of chlorine dioxide release rates for a mixed body formed in layers; Figures 8 and 9 are graphs of chlorine dioxide release rates in relation to temperature and rKoedad atmosfep cas; Figure 10 is a maximum chlorine dioxide concentration, a non-volatile function of a container; and Figure 11 is a graph of concentration of chlorine dioxide as a function of time.

DETAILED DESCRIPTION OF THE PREFERRED MODALITIES In accordance with the present invention, it has been It has been discovered that the sustained release of chlorine dioxide can be generated from a mixed body containing clopto anions when the mixed body is exposed to moisture. The mixed body comprises a hydrophilic material and a hydrophobic material. The mixed body can be, for example, a dispersion composed of hydrophilic and hydrotobic phases, or a mechanical combination of hydrophilic and hydrophobic materials, such as powders and adjacent pellets. The powder has a nucleus embedded in it with cloned particles. Adjacent films comprise layers separate materials Hydrophilic and Hydrophilic. Preferably, the mixed layer comprises about 5.0% by weight and about 95% by weight of hydrophilic material and about 5.0% by weight and about 95% by weight of hydrophobic material, very : > preferably about 15% by weight and about 95% by weight of hydrophilic material and entr-e about 15% by weight and about 95% by weight of hydrotoxic material. If the mixed body is a dispersion, any material can form the continuous phase. The continuous phase constitutes between about 15% by weight and about 95% by weight of the dispersion and the dispersed phase consists between about 5% by weight and approximately 85% by weight of the dispersion, and preferably, the The continuous phase constitutes between about 50% by weight and about 95% by weight of the dispersion and the dispersed phase constitutes about 5% by weight of about 50% by weight of the dispersion. The hydrophobic material of the mixed material can be completely composed of an acid releasing agent or can comprise the acid releasing agent in combination with a diluent * and / or a plas etor. Any acid releasing agent that can be hydrolyzed by ambient humidity 1-acceptable for the purposes of the present invention. Preferably, the acid releasing agent does not react with the hydrophilic material and does not exude or is extracted into the environment. The hydrophobic material comprises between about 10% by weight and about 100% by weight of the acid releasing agent, up to about 80% by weight of the diluent, and up to about 60% by weight of the plastifier, and preferably between about 40% by weight. % by weight and approximately 100% by weight of the acid releasing agent, between about 20% by weight and about 30% by weight of ? ror, and up to approximately 20% by weight of plasti f. The hydrophilic material of the mixed material can be composed entirely of a source of clop anions and can comprise the chlorite anion source in combination with another hydrophilic material. The hydrophilic material preferably contains an amine, an amide or an alcohol, or a compound containing inoperated, arnide or hydroxyl portions and having a high hydrogen bond density. a source of clop anions or is incorporated in hydrophilic material and preferably constitutes between about 2% by weight and about 40% by weight of the hydrophilic material in the form of clopto anions and counterions, and very preforming between about 8% by weight and approximately 10% by weight of the hydrophilic material. When the chlorite source is a dopt salt, the salt is dissociated in the ludrotilic material so that the inert ion in the mixed body includes anions of clop and co-ori. However, if the hydrophilic material is an amine and the source of clopto is gaseous carbon dioxide, the chlorine dioxide reacts with the amine to form an in situ chloro- phope, if the oxidation potential of the amine is sufficiently low \ > for the amine to be oxidized. rj has found that the acid-releasing agent wi the hydrophobic material is hydrolyzed by absorbed moisture, releasing acid and diffusing ions that are diffused lü - * "From the hydrophobic material to the hydrophobic material that contains certain ions, the hydrophilic ions react with the chlorite anions in the hydrophilic material, releasing gaseous chlorine dioxide that diffuses out of the mixed material into the surrounding atmosphere during a period of approximately 6 months in order to prevent the growth of bacteria, molds, fungi and viruses on a surface that has been irritated. Hydrophobic and hydrophilic materials lack water subst ance 1 to prevent water loss. If the chlorine dioxide is used before using the mixed material, for the purposes of the present invention, a hydrophobic material, a hydrophobic material, or a dispersion thereof is substantially free of water if the amount of water is too low. The water in the raw material does not provide a path for the transmission of hydronium ions from the hydrophobic material to the hydrotoxic material. The hydrofobic and hydrophobic Lestes can include up to about U.1% by weight of water without providing such a trajectory for the fusion between the materials. Preferably, each material contains less than about 1.0 X 10-3% by weight, and preferably between about 10 X 2-2% by weight and about 1 x 100-3% by weight of water. Substantial amounts of water can hydrolyze a portion of the acid-releasing agent to produce acid and ions of hollow mud or mixed material. However, the ions of hydrome (** "diffuse into the hydrophilic material until it is present sufficient to transport the hydronium ions.) Clopto anions generally do not react with the hydrotilic material, but are surrounded by hydrogen bonds to which the nitrogen or hydrogen contributes. of the hydrophilic material Suitable sources of clopto that can be incorporated into the mixed body of the present invention include alkali metal clopto such as sodium clopto or potassium clopto, metal clones to the mote r reoal. Calcium chloride, or clopto salts of a metal ion of transmission or a primary, secondary, tertiary or protonated quaternary amine Many sources (Je elopto, such as sodium chlorite, are stable at processing temperatures in excess of about 100. ", allowing processing at relatively high temperatures, I <tfigure I illustrates the preparation of a mixed body that has an element of material. l hi drop 1 ico > There is still a hydrophobic acid releasing agent in contact with it (both P-0-S-hydrocarbon and maleic anhydride are shown in Figure 1). Chlorine dioxide (CIO2) is reduced by extracting an electron from the amine, forming an arnine radical cation (not shown) and a chlorine ion (CIO2). The arni cation is rapidly converted to a cation of iminium by the loss of one proton from an adjacent carbon atom of the oxidation by another molecule of chlorine dioxide. The mechanism for the previous reaction in a system »» '? It is described by Rosenbatt and others ,. ,3. Org. Chern. 28, 2790 (1963); J Ainer. Chem. Soc. 89 (b), 1158, 1163 (1967). <; Conversions of chlorine dioxide to clopto are obtained if the anion of clopto and / or ionium ion which is generated by the initial electron transfer of the amine are rapidly formed into complexes and stabilized by a hydrophilic molecule. In some formulations, the anion of clop or that is not forming complex can be depleted by subsequent reactions with minimal counter ion at temperatures above 60 ° C. Chlorites are also subject to disproportionation in chloride and chlorate. An amine with a high pKa is preferred because it reacts rapidly with chlorine dioxide and acts with a more effective proton dissipater, maintaining the pH required for chlorite ion stability. Figure 2 illustrates the mechanism for the release of chlorine dioxide from iminium clone when moisture contacts the incoming material. The hydrolysis of the acid-releasing agent provides hydroxide cations (I-I2O +) that react with methyl chloride to liberate chlorine gas dioxide, the decomposition products of the reaction being an ammonium cation (shown as Nv '\' H2 * in the figure?), a <; arhox? side (COO-, not shown in La 11 gui 2), and Cl- .. These products are retained within the mixed matepal. It has been found that in some cases, the nninium elopto can be decomposed if the mixed material is ap e to temperatures that exceed approximately 60 ° C, reducing the concentration of available chlorine for conversion to chlorine dioxide. In order to maximize the release of chlorine dioxide (chlorine material), it has been discovered that the clopto source can be omitted from the mixed material until the mixed material is applied to a surface when the hydrophilic material in the mixed material is an amine After the application, the mixed material is exposed to gaseous chlorine dioxide which reaction with the amine to form clop + or of irinium n 11 or dissolve in the same pair to provide clopt anions. Mixed material is then activated in the presence of moisture to release chlorine dioxide, This method allows the mixed material to be exposed to elevated temperatures during processing, storage and application as compared to temperatures at which the clopto It decomposes, because the material does not contain '.Ionio de iminio < J no clopto ani. The method also relies on the premature release of mixed material chlorine dioxide. Chlorine dioxide can be provided on the site by passing the mixed material through a chlorine dioxide generator. The conventional chlorine dioxide generators generate an atmosphere of chlorine dioxide that is saturated with water. The chlorine dioxide that comes in contact with the mixed material of the invention must first be dissolved in a material that does not absorb water such as a hydrocarbon wax or a f ^ of chlorohi dr-ocarbide of low melting point. Alt, the chlorine dioxide is dried with a desiccator. Chlorine dioxide is therefore left from a wet industrial process to the mixed material without exposing the body to water. In order for an amine to form a clone of the ion in a net form or in the presence of a plas ticator, the amine must be sufficiently rich in electrons and the nitrogen in the amine _webe to be locally mobile. The electron attraction groups must be separated from the amine center by at least two netylene groups so that the chlorine dioxide removes one electron from the amine. The movement of the bonds around the nitrogen center of the amine is required for the formation of scale. If the amine is frozen in a vitreous grnat, the amine nitrogen will not be mobile and the amine will not be converted to an iron moiety. A vitreous amine can be softened to increase mobility by adding about 10% by weight of a plastiflator, such as a low molecular weight amide, to the amine at a transition temperature of about 10% by weight. bottom glass below the reaction ur-a temperature. Other suitable plasmicators are well known in the polymer art. The rate of release of dioxide from the mixed material can be altered by changing the viscosity of the hydrophilic and hydrophobic materials, changing the dispersion capacity of the hydrophobic and hydrophobic materials, ^ "I adjust the temperature of the mixed body, changing the concentration of acid-releasing agent in the mixed body, adding a desiccant or humectant to the mixed body to control the release of chlorine dioxide from the body 5 once it is exposed. Moisture, or walking the volume fractions of hydrophobic and hydrophobic materials to produce continuous or discrete phases in a digestion, the maximum release of chlorine dioxide from a body The limit can also be achieved by stabilizing the cent anion. The clopto of i imo is unstable to attack nucleo fil Lco by the anion of clopto. It has been found that the life time at room temperature of the clopid anion is substi - mally extended when a strong base, like a Metallic alkoxide is present in the hydrophilic material containing the irninium clopto. The mechanism of stabilization of alkoxide of the counterion of clop + or is shown with inuación ,.

R'ONa 0 ER-2 = CR2_ + CIO2 > R-2N-CR2-0R "NaC102 wherein R'2 and R2 are groups corresponding to those of the selected amine and R- is an alkyl or hydrogen group. In the absence of water, the iminium ion is immediately "> 5 decomposed in an a-ammo ether and a more stable sodium chlorite salt, if the water is present during the oxidation of the tertiary amine, an alcohol a - unstable arrimo is formed that D attack the clone + amon or unless the clopto anion has been effectively complexed by the hydrophilic solvent. The addition of water after the resolution of the clopto ion is not so harmful. Acceptable strong bases for use in the stabilization of chlorite include metal alkoxides such as nitroxides, ethoxides, prophoxides or sodium, potassium or calcium oxides, metal oxides or aluminum oxide or sodium oxide, metal ions such as Na +, salts of tpalquilamomo of alkoxides, ammonium salts of alkoxides, acetates co or sodium acetate, substituted acetates or other materials that can generate a strong basic reaction to attack the nitrogen center of the ironium clopto. In a hydrophilic material that contains a tertiary amine (dimet and non-acrylated lame), N-methacetamide and urea, a ter-o-inode and a clonium sai are formed when the clopto is stable. plast tfi cant and inonomerKO or substituted oligomeric, orno succin na id, for aini or N-rnet 11 fopna i da, can be replaced by N-rnetiiacetainida to soften the amine.Form amide and N-methylformamide are They are not preferred in applications that include human contact.If the amine center is sufficient, it is not necessary to add a plasticizer.Uurea improves the assimilation of chlorine dioxide and the efficiency of release of the material hydrophilic because it has a high hydrogen bonding density and does not With the acid releasing agent, the compounds having a high concentration of amide can also be used to improve the efficiency of the hydrophilic material.Preferably, the bulk body consists of about 5% by weight and approx. 95% by weight of the hydrophilic material and between about 5% by weight and about 95% by weight of the hydrophobic material .. The hydrophilic material consists of between about 5 to about 30% by weight of a "mine" and from about 70 and about 95% by weight of a hydrophilic solvent including about 35 and about 55% by weight of urea, between about 35% by weight and about 55% by weight of plasticizer and about 10% by weight of base It has also been found that no more than 0.5 moles of chlorine dioxide per millimeter of amine should be added to the hydrophilic material or the stability of the material could be increased. The preferred amides for use as the hydrophilic material include forrnarnide, acrylamide-i sopropy lacrylamide, copolymers of formármela and acrilarnida-isopropilacrilarní da, oopolymers of acp lamí «la, isopropilacri lamí da or N, N ~ metíquina bisacr If a primary amine or a secondary amine is present, amides may be useful vehicles for the distribution of film before exposure to chlorine dioxide, which does not react with efficient electron alkylates such as chlorine dioxide. < cp 1 a ida.

Suitable amines for use as the hydrophilic material include primary amines, secondary amines and tertiary amines having pendant hydrogen bonding groups. An amine substituted with electron donating groups that donate electrons to convert chlorine dioxide to clopto is preferred. The electron withdrawing groups concentrate the electron density in groups such that it is difficult for the chlorine dioxide to extract an electron from the amine. Tertiary amines that have pendant groups that do not bind hydrogen that are dissolved in a hydrophilic solvent are also acceptable. Representative amines include: alkanolane i ña; copolymers of arninoalkanes and alkenobisacri. licked; alkylaininopy ridine; alkenodiamines; alqui lamí nocid oal canos; to the one who lied no-c boxiarnido l canos di suelos in a diluent; so that they have the formula R3-xNHx; Ri R 2 NCH 2 CH 2 C (0) NH 2; N (CH2CH20H) 3-x soluble Hx 1, R3 N (NOH2 CI-I2 C (0) NH3) 2, (CH3) 2 N (CI-I2) 2 N (0H3) 2, * 5R6N (ÜH2) H0 (0) NH2 - • CCH.3. H. • CH.CH-C- -NHCH-NHCC H-CH-- - NH NH Mr are, in alkyl, cycloalkyl, benzyl, acniarnine or pindyl; Ri, R2, Rs, and Re are alkyl, R3 is straight chain Ce to C12 alkyl; R 4 is cycloalkyl or benzyl; m is 1-100; n is 2 or 3; x is 0, 1 or 2; and it is 1 or 2 and z is 1-6. In general, the above compounds may be solids placed in formaldehyde, isopropylated lamellate or other conventional plasti fi ers. Preferred amines include ringtone, ringtone, ring, < anolanine, a 1-mer copolymer of 1,3-diarynopropane or 1,2-diaminoethane and N, N-meth and lenobisacplamide, 4-d? metlarinopyridine, tetraphenyl ether, N, N- dunet 1 l í nocí clohexane, 1 - (N-di? r-op? lamino) -2-carbox? ? n? solubilized dodene or 1- (Nd? methylamino) -2-car'box iarní doet ano, an amine pr-L ar a with the phoNuLa Ri NH2, a secondary amine with the formula R2R3NH, N (CH2 CH2 OH) 3 , N- CH-D to H.N-CH- 3 N-NH.

NRs e R7 so 1 ub i 1 ized, (CH3) 2 NOH2 H2 N (OH3) 2, ß R9 NCH2 CH2 CIO) MH2, Rl or N (NCH2 CH2 C (O) N fe) 2. Rl 1 l 2 N (CH 2) 3 NHC (O) NH 2, N (OH 2 OH 2 NHC (O) NH 2) 3, wherein: Ri is -CH2CH2OCH2CH2OH, -C (CH3) 2CH2? H, CH2CH2NHCH2CH2OH, -CH (CH3) 2, -CH2CH2OH, oCH or H, • CCH2D2-. p2 and R3 s n, independently, '-xyl, benzyl, n-propyium, isopropyl, cyclohexyl, acr'i lamide, or -CH2CH2OH; R is cyclohexyl or benzyl; R5 and Rβ are methyl; R7 is cyclohexyl or? -pyridyl; Rβ and are, i dependently, methyl, n-propyl or isopropyl; Rio is n-CßHi3 or n-Ci2H25, "R1 and VR12 are, independently, methyl, ethyl, n-propyl or isopropyl, rn is an integer from 1 to 100, and n is 2 or 3. Suitable diluents include forrnamide or The acrylarnide-isopropyl acrylarnide secondary amines or oligonuclear amines converted to tertiary amines acplainide substiuted by the reaction of riichael with acpramyms are also suitable because the amide group does not react with the acid-releasing agent. 1 icos, including ethylene glycol, glycerol, methanol, ethanol, ethoxyethyl, ethoxy ethanol or other alcohols, can be used as the hydrophobic material. However, the liberation of dioxide can be very quickly when a hydroxyl compound is incorporated into a mixed body and I can limit the applications of mixed bodies to dioxide do lort ation systems > r -a ask. Suitable acid-releasing agents include carboxylic acids, steres, anhydrides, acylha halides, phosphorus acid, phosphate esters, prnet lysilyl phosphate esters, dialkyl phosphates, acidic fonols, esters of a sulphonic acid, sulphonic acid chlorides and ers phosphosilanes based on glycerol. The examples of The acid liberation agents include an anhydride or phosphate ester mixed with or grafted to polypropylene, polyethylene, or ether, or esters of titanium 1 1 if li 1 phosphate. The formulas (OH3) 3S? OP (0) (0R) 2, wherein R is a non-hydrogen, alkyl or aryl linking group. The star or linear oligomers (eg, a molecule similar to a molecule with a lipid wall and a nucleus P ~ 0-S?), Such as a phospholsilane "le? N ester based on glycerol, / ,, are the pre-acidic acid release agents because they can be fused or processed with solvents with the option of being interlaced after processing to provide film stability. A phosphosilane of a preferred glycerol-based ester is known as LPOSI and has the formula where G is the formula An alkene in a polishable free form and a radiant or condensable group in the terminal end of a lipid is a representative oligomer. Acidic anhydrides are also preferred acid releasing agents and include organic acid anhydrides, mixed organic anhydrides mixed with an organic anhydride or a mixed inorganic acid anhydride and copolymers of an organic anhydride or an inorganic acid anhydride mixed with a monomer containing A double bond, the preferred mixed inorganic acid anhydrides contain a phosphorus-oxy-silicon bond. Preferred anhydrides include copolymers of maleic anhydride, methacrylic anhydride, acetic anhydride, ico-anhydride or succinic anhydride, and vimol, styrene or an alkene, ff Germanic anhydride polymers, or grafts of the same with olefins co or polypropylenes, polyethylenes or polystyrene. The copolymers of acid anhydrides and esters of lactic acids or glycolics can provide a rapid initial rate of release of chlorine dioxide, followed by a slow rate of release. The hydrophobic material may also include an atactic polypropylene dilute, Halocarbide wax, chlorinated cora, polymer wax, and light weight poly olefins.

Molecules, polyesters, polyolef copolymers to derivatives or mixtures thereof. Digests can be included in the hydrophilic material as well. The plastificant.es can also be incorporated in either the hydrophobic or hydrophilic materials as known in the art. Generally, the would be given and the propylcplarnide-acp licking are acceptable plasticants. A moisture scavenger, such as sodium sulfate, calcium acetate, silica gel, alumina, zeoiites, and calcium chloride can be added to the body. premature hydrolysis of the acid releasing agent. Conventional film-forming additives can be added to hydrophobic and hydrophilic materials as necessary. Such additives include agents in relacion, flame retardants, ernul si f i cadores v cornpat ib 1 izador es, '> The mixed bodies of the present invention can be formulated in vain ways to accommodate a large scale. f * end-use applications. The mixed body can be formulated as an extruded material, such as a film or pellets, or as a powder using conventional extrusion and spray drying methods, respectively. When the mixed body is formulated as a powder, the particles containing clopto are formed by dissolving a source of clopto in a hydrophilic solvent and extruding the solution through nozzles of a spray dryer .. Once the solution is converted into particles spray dried, the particles can be conducted to a cyclone separator to isolate small particles, preferably with a diameter of between about 5 and about 150 microns, the particles can then be stored in a dry atmosphere. Once the chlorite particles are formed, they are fed into a fluidized bed.The hydrophobic material containing the acid-releasing agent is formed into an aerosol by passing the material to small small-diameter nozzles inside the chamber. of the fluidized bed where they can collide-on the fluidized clopto containing particles Under contact with the fl ied particles, the chlorine dioxide releasing powder is formed when the hydrophobic material solidifies to form a hydrophobic core having a layer of the "clopto-crusta" particles on the outer surface of the same.The aggregation is minimized because the chlorite particles are hard inorganic materials.The particles can then be packed in a container 2 b f * ila dry. fll form the dioxide-liberating dust and chlorine, the anhydrous particles, such as anhydrous sodium sulfate, calcium sulfate, magnesium sulfate or a dissipated moisture silica gel can be included in the fluidized bed to form a mixture of clopto particles and anhydrous particles. Anhydrous particles delay the release of chlorine dioxide that is catalyzed by atmospheric moisture. The anhydrous particles can also be post-mixed with the chlorine dioxide-liberating powder to delay the release of chlorine dioxide. While the hydrophilic and hydrophobic materials can be formulated as described above for the instant body, it is preferred that the cloned powder contains a clone or alkaline or alkaline earth. The hydrophobic material preferably contains a bai fusion hydrocarbon wax, elorohi dicarbide wax, atactic polypropylene, full polyethylene film, a low molecular weight polyolefin, a derivatized polyolefin copolymer, or mixtures thereof .. An acid releasing wax, such as a hydrocarbon solution of a Lipoglycerol Costón Side reacted with silicon alkoxides to produce P-0-? mixed anhydrides, it is preferred as the hydrophobic material, Fl LPO T is an acid release wax particularly suitable for use in the preparation of the chlorine dioxide releasing powder. * ~ i the acid-releasing wax is extruded? < At a viscosity of between about 10 to approximately 1000 cP through nozzles of between about 1 and about 10 microns in diameter, a fine mist of melted wax from about 5 to about 400 microns in diameter is generated. In the case of the formation of mixed powder bodies, the mixed bodies of the present invention may be , "Formulas" in solvents to allow film casting or other application methods. The mixed body can be applied as a film using well known methods of hot melt, investment coating, spray coating, curtain coating, dry wax, waxing and hardening. The mixed bodies can also be provided as a layer 12 composed of a hydrophobic and hydrophobic material icrodi sperso as shown in Figure 3b or as a multilayer body 14 including a separate hydrophobic layer 16 and a separate hydrophilic layer 13 or is shown in figure 3a. The hydrophobic and hydrophilic layers can be applied by melting the hydrophilic layer on a substrate 20 and subsequently melting the hydrotoxic layer on the hydrophilic layer, as shown in Figure 3a. The multi-layer or single-layer composite body can be applied in conjunction with moisture regulating layers 22 to control the rate of moisture ingress into the hydrophilic material or into the hydrophilic material. 0 hydrophobic material to control the release of chlorine dioxide from the mixed body of multiple layers when activated by moisture. To generate chlorine dioxide in a controlled manner it is useful to limit the access of water to the hydrophobic layer containing the acid releasing agent and to control the contact surface area between the layer that releases the hydronium ion and the hydrophilic layer. which contains the clopto. Such Controlled can be obtained by melting the hydrophobic and hydrostatic materials 16, 18 as separate layers with an intermediate division layer 24 that regulates the hydro ion transport or between the materials as shown in Figure 3c. The layered mixed bodies of the present invention are designed to maintain a desired rate of release of chlorine dioxide olsols / sec / crn2 of film) < In the presence of atmospheric moisture at a supeificy for a length of time I traveled so that the chlorine dioxide would be absorbed on the surface and kill bacteria or other microbiological contaminants. However, leakage from a container or an exposed surface reduces the concentrations of chlorine dioxide on the surface, due to the diffusion of chlorine dioxide into the atmosphere. The concentration of chlorine dioxide released from the film for a chosen period of time can be calculated given the escape velocity and velocity. < Jad «Absorbency on a surface. In this way, 2 < í * - Therefore, to measure the escape velocity, the mixed body is formulated in such a way that it contains a sufficiently large reserve of the target reacting at a sufficient velocity to compensate the escape velocity for the desired period of time of sustained release. Therefore, the design of a mixed chlorine dioxide-releasing body suitable for biocidal action and controlled release within a container must take into account several aspects, to taste, the rate of production of chlorine dioxide from the controlled release film, the division of chlorine dioxide between the phases within the container (eg, gaseous, liquid and solid phases) in a reversible (absorbed) or irreversible (reacted) form, and the gas escape velocity from the container. The design of this modified body is described in Example 15. A preferred extended release system of the present invention retains the chlorite pool by issuing a series of periodic pulsed-time-controlled releases to coincide with the so-called bacterial contamination times. , viral or fungal, or the typical incubation time of the biological of interest. The system design can be optimized to maintain the desired elimination concentration for the time required at atmospheric lithium dioxide exhaust velocities compounded by the specific application. A mixed body «the last layers of liberation jr * > Typically, it includes water-soluble films fl and B of a thickness of about 5 microns with a hydrophobic layer fl and a hydrophilic layer B as described above for the body. The hydrophobic layer R contains an acid releasing agent such as anhydride and hydronium ions generated by anhydride hydrolysis. The hydrophilic layer B contains cloptoids such as those provided, for example, by dissolving a source of sodium odorant or other clone in a hydrophilic solvent. The hydrophobic and hydrophobic layers are separated by an intermediate layer of water C having a thickness of 1 (typically about 5 microns) and a diffusion constant D. Effective ion concentrations applied to the boundaries of the layer Intermediate C by layers R and B are a strong function of the water transport properties of layer 0. The intermediate layer 0 can be composed of an age and material age, since the carbon dioxide can be diffused equally well both in hydrophobic linked matrices > These materials include polymers such as oligo- or polyalkyl which are protonated and neutralized, sulphonated or phosphonated, such as polyethylene, polypropylene, alkylacrylates and copolymers thereof, and substituted polyhydroxy lipid phosphates and phosphosilicates. and their mixtures with alkene polymers and oligorneros are also preferred.The finely divided anhydride salts or desiccants can be added to any N Layers to delay The reaction of chlorine dioxide that you catalyzed by water. It has been discovered that the construction of a mixed multilayer body in which the arrangement of the layers in the reinforced body is defined by formula C (RCB) nC (where n represents the desired number of pulses) provides a Periodic pulsed release of high concentrations of chlorine dioxide during several weeks or months. Such pulsed release can be coordinated for the growth, incubation and contamination of viruses, molds, fungi and bacteria. Cycle time and peak concentrations of chlorine dioxide would be controlled by the thickness of the layer, chlorite and anhydride charge, and the characteristics of ionic permeate and water in layers fl, B and C. The release Pulsed occurs when each layer (flCB) is successively penetrated by water vapor and hydronium ions. Structures of the CDC type can also be made where T) a mixture or emulsion of fl and B of a phase size of between about 0.2 and about 100 microns. The construction materials for the mixed bodies CDC can be the same as those used in the manufacture of the mixed bodies C (RCB) nC. Finally, a mixed multilayer body C (DCD) can be made to provide a pulsed release as described above. pulsed releases of chlorine dioxide that vary from about one day to about 200 days, can be recorded for films 5, 5, and 5 "*" "» Thickness, separating the phobic hydro layer fl containing the acid releasing agent from the hydrophilic layer B containing clopto amons by means of an intermediate layer C capable of supporting varying transport speeds of the hydro ion. capabilities pulsed release of a multilayer film can be calculated as shown in ei l: Jem 16. lsa lica for bodies my cough are numerous mixed bodies can be sa < 1os almost any environment.? Where exposure to moisture occurs Mixed bodies can be used to prevent the growth of molds, fungi, viruses and bacteria on the surface of a material and / or to decontaminate a material by treating the surface with an It releases chloride dioxide in the absence of moisture, and exposes the treated surface to moisture to release chloride dioxide from the mixed body into the atmosphere that surrounds the material. It is usually a portion of a container or is part of a substrum placed inside the container. The biocidal atmosphere generated inside the container can be used in the storage of food products including blueberry varieties, raspberries, strawberries, and other fruits, ground beef steaks, chicken fillets, and oats, improved food products, animal feeds, dry foods, cereals, grains, or most J '^ any food product for bacterial contamination or mold growth. Bar soap, laundry detergent, stored paper document, clothing, paint and seeds can be protected by mold growth. Medical instruments, devices, and supplies, such as disposable or non-disposable personal care items, can be sterilized to prevent microbial contami- nation. Fi biological medical waste can also be sterilized to kill microbes within the waste. Odors from athletic shoes, disposable footwear, and jeans can also be reduced to a minimum when contained within a treated container. Conventional containers may be used such as cartons or cardboard containers, corrugated, non-spun, plastic or polyethylene containers, cellulosic, plastic or paper bags, packs or waste containers. The treated surface may be a removable or disposable mesh or sheet including a dental tray cover, a surgical tray cover, a bath mat, a non-spun bandage fabric, a meat cutting board, a coating to drawers or boxes, a thing inserted for gymnastic bags or lockers, a wrapper for food, a sheet of paper to separate hamburger meat steaks, a tray for packing meat, a bag such as used to pack bags This is a fresh fruit separator or box liner, an absorbent pad for birds, meat, seafood or fruits, or an absorbent liner for use in diapers. Said meshes or sheets are typically made from paper, cellulose, polyester, woven or non-woven fabric materials. A method as such can be used to reverse the surface of a seed to protect the seed from mold and fungi during storage and to protect against fungal growth when the seed is planted. When coated, when activated by moisture, it creates a chloride-rich micro-structure in the dirt in the vicinity of the seed and inhibits the growth of seeds that normally prevents seed germination. This coating has no effect on the "germination of the seeds. The seeds in storage do not have to be physically coated to be protected but they can be in a closed container containing the active material as a package, "bag" or "liner" in the container. The paper impregnated with the mixed body generates enough carbon dioxide to protect the seeds. Although any seed can be protected by the coating, edible seeds such as corn kernel, sunflower seeds, or soybeans, remain tight for human consumption once they are coated. In this way, coated seeds can be provided for planting or for human consumption after they have f ~ tJo coated. The surface can be treated with any of the mixed bodies of the present invention by means of conventional coating, extrusion, lamination and impregnation methods well known in the art. Another embodiment of the invention is a method to prevent the growth of fungi, bacteria or molds on a surface and / or to relax the surface by treating the surface with a mixed body that does not release chloride dioxide into the surface. the absence of moisture, and exposing the treated surface to moisture to release chloride dioxide from the body in the atmosphere surrounding the surface. A preferred application includes a foot powder to prevent athlete's foot and other fungi. The powder can be applied directly to the top of the foot or it can be incorporated into a shoe insert. The body can be applied to the clothing cover and foam pad dc-1 shoe insert, impregnated inside the foamed pad, or impregnated or reversed in a shoe counter or upper liner. The chloride dioxide generated from the moisture inside the shoe diffuses from the mixed body into the atmosphere to kill fungi and "jesodopza the shoe. The powder can be mixed with conventional ingredients such as talcum, corn syrup, fragrance, iconazole nitrate, tolnastate silica, rich acid, aluminum chlorohydrate, salicylic acid, and cellulose. The powder can also be mixed with P * • ros ingredients and used in bath products or powders used in the treatment of crural tub ,. Fl powder can also be applied on carpet to remove odor from carpet. Commonly incorporated ingredients in powdered carpet deodorizers or cleaners may be mixed with the powder of the present invention. The body can also be formulated in microcapsules that divide after being stuck and are deactivated by moisture. Said microcapsules can be impregnated in the floor, in the bath mats or they can be used in the deodorization of carpets. Another use for mixed bodies is the provision of self-sterilization packaging, which is particularly useful in the medical industry. The mixed body can be coated in tubing, connectors, fittings or other components as separate layers of hydrophobic or hydrophilic material in separate components that are activated when press-fitted together. Pipe fittings used with raincoat bags, for example, may be treated in a way that a surface of a tube fitting is coated with a hydrophobic film containing acid releasing agent, a surface of another tube fitting is coated with a hydrophilic film containing clone, and the treated surfaces of the fittings are connected in the presence of moisture to initiate the release of chloride dioxide from the treated surfaces in the atmosphere surrounding the material. the settings It includes permanent catheters, needles, peptoneal dialysis, percutaneous devices, percutaneous accesses, colostomy bags and other medical devices can also be treated in accordance with this method, in addition, the closures in a package can be treated. to provide self-sterilization packaging for devices, instruments and medical supplies, the mixed body of the present invention is expected to kill bacteria on the surface of meats, however, we do not expect to eat a ground beef steak. It has been discovered that chloride dioxide that arose from the paper treated with the mixed body can fec ively measure the total thickness of a bist cy mat -u- bacteria such as F. coli and Salrnonel that result from contamination. «During the processing of meat, F. col i 0157. H in rotten carcass has caused death and severe disease and seems to be specifically resistant to fermentation and drying. typical < It produces meat steaks for commercial consumption, the meat is ground, cured and formed into steaks that are separated by sheets of coated paper that prevent adhesion of the individual steaks. After packing, rnolKa meat can be exposed to chloride dioxide over a period of time when it is in refrigerated storage to kill and inhibit growth in the bacteria. The following examples are presented to describe the preferred modalities and utilities of the 3'rl The invention is not intended to limit the present invention unless otherwise specified in the claims appended thereto.

EXAMPLE 1 A hydrophilic material was made containing a solution of 7% by weight of sodium chloride in a mixture of amide composed of 33% by weight of forrnarnide, 33% of acyl and 33% by weight of isopropyl-lamide. A hydrophobic material consisting of a 40% solution of a compound copolymer of 33% molar anhydride and 66% molar styrene in an ethylbenzene classifier was then made. The hydrophobic material was mixed to form 1 L oar not with the hydrophilic material. The resulting white mixture of the two dispersed materials began a sustained release of chloride dioxide in the absence of added water during f > minutes at room temperature, the water interface diffusion den + ro do The dispersion initiated hydrolysis of the anhydrous .. The hydronium ions formed5"during the hydrolysis reacted with chloride ammonium to liberate chloride dioxide. be reduced by cooling the mixture to 0 ° C or by increasing the viscosity of the materials.

"EXAMPLE 2 1 - . 1- (Nd? Prop? Lamino) -carboxylamidoethane (DPflCflF) was made by reacting 0, .2 moles of d? (N-propy1) arn? Na with 0.1 mole of acri lick in the presence of a small amount of acetic acid as a 10% by weight solution in methane !.

The reaction was carried out for 3 hours at 70 ° C. After evaporation under vacuum of the excess amine and crystallization in the presence of the pentane, a solid of molten point under white was obtained (Tm ~ fi0oC), which tended to lose amine and was mar-acr Long time of heating over the melting point. 1- (M-dirnet il ami no) -2-carboxynaridoethane (DMflCRE) was made by reacting 0.2 moles of dimethylamine (as a 40% by weight solution in water) with 0.1 moles of acne lick as a solution of 10% by weight in methanol. The reaction was carried out for 1 hour at room temperature. After evaporating the excess amine, methanol and water in vacuo, the DMRCRE was absorbed in methylene chloride, dried with magnesium sulfate and isolated as a low melting point hydroscopic solid (Tm --- 45 ° 0). ). DPRCRE and DHACAE crystallized only slowly and thus could be studied in the liquid state at room temperature. No pure liquid formed irinium chloride. However, solutions of 10-30% by weight in formality or .- «in larn? Da-? soprofu lacn la í da formed clopto de nninio al r exposed to chloride dioxide.

EXAMPLE 3 The reaction of amine-chloride dioxide was studied by layering the required amount of b.OXlO-5 molar solution of chloride dioxide in pentane at approximately 3.0X10-4 molar of amine, in pure form or in free form. 10-30% by weight in formandide or isopropylane-acrylate. The chloride dioxide-pentane solution was prepared by reacting sodium clique stoichiome with potassium persulfate in a small amount of water in the presence of pentane with swirling in ice water, the pentane supernatant layer was after When it is removed and kept dry in a container-sealed over inorganic sulphate, the formation of dope was detected by acidifying the reaction product and observing the odor and color of chloride dioxide by UV / vis spectroscopy. after exposure to dilute-HCl. In some cases, the presence of the method was also seen by observing the IR spectrometer. The IR absorbance characteristic of clopto to R30 crn-i verified its presence. The following pure primary amines formed chlorite upon exposure to chloride dioxide: H2 NCH2 CH2 OCH2 CH2 OH, H NC (CH3) CH2 OH, H2 NCH2 CH2 NHCH2 CH2 H, "VlCI 1 (CH3) 2 H2 NCH2 CH2 OH H, N g__ CCHH, 2._ 52- N H2N CH232 NH - > H, N - C CH ,. , - 'N - CH ,} - f The fiber was also formed by secondary secondary imines having the formula R2R3NH wherein R2 and R3 are, independently, hexyl, benzyl, n-propyl, isopropyl, cyclohexyl, acp-lamide, or -CH2CH2OH. These amines also formed a clone when the amine was in forrnarnide solvent. The following secondary amines produced clopto L5 to serotypes with for arnida or sipro-acrylaridate: • CH2 - CH2 - C- • NH- -CH Fn where R¿, is cyclohexyl or -i 2 benzyl, and In «londe n is 2 or 3. l 1 nsopropilacp lamí a-acn lamida and amina also ; > Pi were pre-painted and were formed by heating the film to a "C" in the presence of "approximately" 0.01% of initiator.

'* "Obisisobutironitri, by providing chlorite as long as the film temperature exceeded the glass transition temperature A hydrogen bound amine having the formula Rβ R NCH 2 CH 2 C (0) NH 2 wherein Rβ is methyl and R9 is n-propyl being in formamide or? soprop? lacplam? da-acplarn? l solvent produced clopto.However, when R? and R9 were isopropyl groups, the pure amine did not produce clopto. the formula N (CH2Cl-l20H) 3 produced chlorite, which was also formed when the amine was in forrnarnide or isopropyl alcohol solvent, to determine whether the hydrogen lipoid was necessary, a process of addition of Michael was used to provide a reaction product of 2-propemtil and (1- C3H7) NHCH2C6H5 as the amine moiety of the pro-luc <or did not have any hydrogen bond and the portion of mtplo was ^ Very polar. The polarity was not sufficient to generate stable clopto when the pure amine or the soluble amine in the fonnaini was exposed to chloride dioxide. The nitrile group blocked formamide so that the cyproate again attacked the amine and decomposed the chlorite in a form that could not be converted back to chloride dioxide. In this way, it was discovered that the amines in support environments react with chloride dioxide but the clonium ion is unstable in such an environment. The tertiary amines bound to non-hydrogen of the «-number NR5 6R7 where R5 and R & they are methyl and R7 is cyclohexyl or 4-Δpd, or the sol-ub is located in fornarnide or opium-lactide-lactide-acne lick and formed a stable elopto. The amines wherein R5 is benzyl, R1 is cyclohexyl and R7 is lodedlo or wherein R5, Re and R7 are n-butyl or ethyl groups were insolubles in forrnarnide and could not form any clonium. (CH3) NCH2CH2N (CH3) 2 fv soluble in fopnarnide and produced clonium, but did not produce clop or in , -i or? orp? lacn larnuja-acplamida although it was solubilized by the solvent; the amine, being pure or in acetone, did not produce chlorite. In this way, it was discovered that an amine having a sufficiently high pKa nitrogen soluble by a hydrophilic material or substituted by l groups? < Hydrogenous substitutes, such as hydroxyl, amide, primary amine or secondary amine substitutes, form clopto by oxidation with chloride dioxide. The reaction of arnide dioxide to chloride as described above was repeated where the amine was released in vain solvents to determine the effect of the solvent on the reaction efficiency. All the chloride dioxide was released in water. More chloride dioxide was released into either 1-cerin or ethylene glycol than was released in 1-acetyl, acetyl, methoxyethanol, ethane L or ethoxyethanol. The eiopto suspended it or dissolved in a hydrophobic material, as a solution diluted in toluene or benzene, and In response to dioxide, the chloride reacted with chloride dioxide but only released a smaller amount of chloride dioxide when acidified. Many of these solvents, such as ethanoi, will not retain clopto counter-ion during long term storage unless the clopto de i imo is stabilized (on a strong base to retain the clone to counter ion.

EXAMPLE 4 The amines that are rnonos? Bstj tuidas with apolar cuts, such as (OH3) 2 CH2C (0 = NH2, (n-03 H7) 2 NCH2 OH2 C (0) NI I2, and (1 -3 H7) 2 NCH2 CH2 C (0) H2, formed a stable one-way in. The amines that were replaced with short apolar groups, mainly (CH3) 2NCH2CH2C (0) NH (? - C3H7), (n-C3H7) 2NCH20H C (0) NH (1 C3H7) v. 1 -C3H7N (CH2CH C (0) H2) 2, did not form stable cloptoe. However, those with linear alkane lengths greater than or equal to 6, such as n-CdHi3N (CH2CH C (0) NH) 2 and n-0i2H25 (CH2CH2C (0) H2) 2, did not form stable clopto in forrnarnide. It is possible that once the length of the apolar chain has attained a certain length, a separation of micro phase in nicelules with discrete hydrophobic regions r-Ofjeadas by continuous hydropic regions occurs. The apolar base of destabilization L ization of this way was removed from the reaction environment.

EXAMPLE 5 The following polymers were synthesized, characterized in using NMR techniques, and evaluated to determine the physical properties and the absorption capacity. (and liberation) of chloride dioxide: r-CH 2 CH 2 N (CH 2 CH 2 CH 3) - 3n C -OCH 2 CH (CH 2 N (CH 3) 2) -3n C-CH 2 CH 2 CH 2 CH 2 NICH 3 > 2) "L-CH2CH (C (0) N (H) CH2CH2CH2N (CH3) 2) ~ ln Of these polymers, the latter polymer has the flexible amine which contains side group and exhibited the most efficient absorption and release of chloride dioxide in forrnamide which is a substantial improvement over that demonstrated with chain amines. The polymer was also soluble in urea in molten form.

EXAMPLE 6 the following compounds containing a N-amido bond and a tertiary-nia center were synthesized in pure form from the corresponding primary or secondary a, sodium cyanate, and hydrochloric acid as described by J. March, " fldvances in Orgamc Chein istry: Reaction Mecha srns and Structure, to Fd., John Uiley, NY-, p " 903 (1992) ..

Me-, N (CH,) -, NHC (0) H2 HNMR: 1.5, 2.1, 2.2, 2.95, 5.5, 6 N (CH, CH2NHC (0) :: H2) 3 HNMR: 2.4, 3.S, 5.65 , 6.25 HNMR: 2.35, 3.2, 5.6, 6.05 ppm Each of these compounds reacted with chloride dioxide and then released at the time of acidification in forrnarnide, indicating that the tertiary amine compounds with N-arnide substitution of their primary and secondary amines can form a chloride dioxide complex, being dissolved in a suitable hydrophilic solvent. The addition of urea to the apuda clearly improves the absorption and release efficiency.

EXAMPLE 7 Up to 50% by weight of the dimethylated moacp tertiary amine lamellar (DMOfl) was added to a hydrophilic solvent containing 50% by weight of urea and 50% by weight of solvent of n-inet-ilacetarnide (NMfl) at 50 ° C and Quickly cooled to room temperature. The solution remained in the individual phase indefinitely at room temperature. The same behavior was noted for the addition of 20% by weight of DMflfl to a solvent , iß contains 30% by weight of urea, 30% by weight of NMfl and 33% by weight of sodium acetate, a solvent containing 35% by weight of urea, 55% by weight of NMfl and 10% by weight of methoxide of sodium, and a solvent that contains 70% of urea and 30% in po of sodium acetate. The above mixtures were exposed to a chloride solution of chloride in pentane and were observed to rapidly absorb chloride dioxide (one minute) for each two amine groups before the reaction substantially decreased. The final pH of the hydrophilic material remained on the basic side. A slight cloudiness was observed on the mixture of 50% by weight of urea / 50% by weight of NMfl-DMflfl and the mixture of 33% by weight of urea / 33% by weight of NMfl / 33% by weight sodium acetate- DMflfl while «the mixtures of DMflfl-35% by weight« the urea / 55% by weight of NMfl / 10% by weight of sodium methododene per anecioron clear. At the time of acidification by 0.1M HCl (? Ll < 5), the complete release of chloride dioxide from these three mixtures was observed up to 30 minutes after the formation of the chlorite salt. The release of chloride dioxide was calculated by referring to the color of the solutions containing can io "known" chloride dioxide. After this different time the behavior was observed. For example, after two hours, the mixture of 50% by weight of urea / 50% by weight of NMfl-DMflfl did not liberate chloride dioxide. The mixture of 33% by weight of urea / 33% by weight of 40 'dfl / 13% by weight of sodium acetate completely liberated chloride dioxide after two hours at room temperature. However, only one third of chloride dioxide was released after 24 hours at 5 ° C, without any chloride di xide being produced after an additional 24 hours at room temperature. The mixture of 35% by weight of urea / 55% of NMfl / 10% by weight of sodium methoxide exhibited the highest eloptate salt stability in that the complete release was observed after 3 days of storage at 5 ° C. C. The complete release was also noted after 24 hours at room temperature. The presence of a strong inorganic base greatly improves the stability of the clopto salt in urea based solvents. A mixture of 20% DMAA-35% by weight of urea / 55% by weight of NMR / 10% by weight of sodium rnetoxide was examined at ñ ° C for up to one hour in 300 MHz of NMR proton to see if any decomposition of DMDfl occurred. From the toxic point of view, any decomposition of the DMOfl into secondary amine and toxic acine would be highly invasive. No decomposition was observed during the heating period of 1 hour. Achenlamide alkene resonances were expected between f > - h pprn, however none was observed. Part of the polymerization of urea was revealed by the broad band under a band of sharp urea * ', "6-7 ppm. The NMR obtained after" heating to L20 ° C dur-ante 2 hours, above 50 ° C to which the DMflfl was mixed in the base or urea solvent, revealed extensive polymerization. of urea that was evident from the increase in line width in the complication in the urea resonance in re 0 and 6 [prn. However, no resonance of alkene acrylamide was observed. In this way, the 20% DMflfl-35% by weight rt® urea / 55% by weight NMA / 10% sodium methoxide system did not produce any toxic alkene product. To avoid the variability in the stability of clopto to paitir of incomplete drying Jel solvent, 40% by weight of carefully dried urea (vacuum dried: 80 ° C, LB hours, 0.1 torr) and b0% by weight of NMfl (Cao). overnight at reflux and distillate) were mixed and heated for 18 hours at 120e> C. The aicoxides were first isolated with dry powders by reacting the required amount of clean sodium metal with the alcohol and the Isolate the product by means of washing with ether, the whole mixture was carried out under a dry nitrogen atmosphere, the pre-drying of the urea / NMO mixture resulted in stability at room temperature. Minimum clopto for at least one week at room temperature The desired amount of alkoxide was then dissolved in the e? rea / NMA solvent using minimal heating followed by DMFlfI to form a clear viscous liquid at room temperature. ie the absor tion and The presence of chloride dioxide from mixed bodies of hydrotylic material of sodium alkoxide / urea / DMfl / DMflfl are presented in table 1. The release characteristics are based on a relative scale that vanes < 1e excellent (9) to def "i cient (1)" TABLE 1 cn a Methyl and t-butyl alkoxides are commercial products b Percentages are based on the material already present in the mixture at that stage and not the final body c Based on the amine d These experiments were done without prior drying of the Urea MIA GÍ'2 The presence of an alkoxide promotes the long-term stability of irninium chlorite. However, the addition of more than 0.5 moles of chlorine dioxide per mole of amine substantially decreased the stability of the imipene clopto. Excellent long-term stability at room temperature was found for the phases containing 23% sodium ethoxide, 31% sodium lsopropoxide or 30% sodium t-butoxide, in which at least 60% dioxide of chlorine was released with the aci diffi cation of the phase after three weeks of storage in dry and dark conditions.

Since no change was seen in the release of chlorine dioxide after one week, these phases were considered indefinitely stable after one week.

EXAMPLE 8 i) In order to make a hydrophobic acid releasing wax, first hydrocarbon wax (Tm = 60 ° C) or atactic polypropylene (PPfl) was melted at 70 ° C in nitrogen under stirring. Then an equivalent weight was dissolved in glycerol monostearate or distilled to gii cerol in wax or molten PPfl. I add only two equivalents (based on phosphorus) of phosphorous pentoxide "ulverize" or by 3 equivalents of hydroxyl functions composed of glycerol in the molten bath to avoid agglutination. After stirring the molten bath another 2 hours at 80 ° C, an equivalent of "c". orthosil icato of t bringfilo and dectecto the immediate evolution of ethanol. The agitation was continued for another 4 hours while the temperature was slowly raised to 100 ° C and the ethanol mixture purged with 1 Ocrn 3 / ml of nitrogen flow. Subsequently the reaction flask is evacuated to 100 ° C will separate any remaining ethanol or tet raetoxy silicate, fill with nitrogen and cool. The softening of the wax-acid releasing agent (LPOST) began at approximately 60-70 ° C. The viscosity of the wax was 100 cP at 100 ° C. The procedure for preparing the LOPST can be summarized as follows. When hydrolysed, silicon dioxide and a phospholipid are formed. 60-80C The clop + powder was prepared by first dissolving commercial sodium clopto in 3% dry methanol and filtering the resulting solution to remove the impurity from sodium carbonate. After the solution was extruded f > or , cori or in an anhydrous dry nitrogen atomizer at 100 ° C through an extruder head with automatic siphon drive and coaxial flow of fluid and nitrogen. After directing a cyclone separator to isolate small sodium clopto particles of about 5 microns in diameter, the powder was stored in a dry atmosphere. A pure powder of sodium rite or mixtures of sodium clopid powder and sulfa + or anhydrous sodium was fluidized in a ratio of 1: 1 to 1: 2 by weight in the bottom of a vessel filled with nitrogen. A stream of acid-releasing wax was then directed to the fluidized layer through a nozzle of 177.8 nm diameter with a nitrogen back pressure of 2.11-5.82 kg / cm2 to produce wax particles encapsulated with clopto particles and sulfate (indicated as 1: 1 pre and 2: 1 pr in Figure 4). The freely flowable powders were then stored in a dry atmosphere. In some cases anhydrous sodium sulfate was previously mixed < on the clone to-wax particles (ie, 1: 1 fiost and 2: 1 post in Figure 4). Figure 4 shows the release rate of chlorine dioxide of 200 g of mixed mixed powder slots placed in a < ~ j Petp of approximately 62 crn3 of volume with a leak of 2 x 10-9 moles / sec. The controlled release is carried out for a few days at approximately 23"B ° C and 40% relative humidity. r > 6 EXAMPLE 9 A hydrophobic acid releasing wax was made as described in Example 8. A controlled release layer was formulated for an immediate release system by melting about 127 u of acid-liberating wax in a low melting hydrocarbon wax. (f) 0 ° C = Tm) on both sides of a piece of cardboard. Then, approximately 127 u of thick 10% by weight caries, recrystallized rnetanol, sodium clopto in the low melting wax on the acid-releasing layer were covered. An approximately 127-fold acid-free layer was coated on the layer containing chlorite. The total volume of controlled release material was 0.25 cm3,. Two measuring sensors for chlorine dioxide (0-10 ppm and 0-100 ppm) are intercalated with a computer that can be used to measure chlorine dioxide. - .. record the concentration of chlorine dioxide as a function of the time during a period of two weeks automatically together with humidity and temperature. Both ends of the sensors were exposed under a chlorine dioxide atmosphere in a ca- Pet? closed through two small holes drilled in the upper cover «je the Petp. The humidity and temperature of the room were close to the measurement in the Petp box because the Petn boxes were of the "breathable" type in which the cover made contact with the base on a fluted edge and no effort was made to isolate the box Petri of your ? - ers. In this configuration, the acid-releasing layer was placed in direct contact with the phase containing chlorite and the immediate release of chlorine dioxide was observed as soon as the film was placed in the Petri dish. At the concentration of chlorine dioxide gas, it decreased from a maximum of 13 pprn to 1 ppm in 5-days exponentially as shown in Figure 5 (note that the error of , + 0.5-1.0 ppm resulted in less than 0 in concentration). However, the concentration maxima that were superimposed on this exponential behavior were surprisingly correlated with temperature and not with relative humidity as shown in figure 6. Three species were cultivated, ie molds, Chaetorni? Rn globosum (CC) , flspergill? s terreus (AT), and Aspergí! 1? S niger (AN), in oblique cultures of nutrient-free fiery minerals using cardboard or nutrient. All the culturing studies were carried out according to the normal method of TflPPI T 487? Rn-85 titled "Resistance to paper and cartilage fungi" Six samples were tested for fungal resistance for two weeks at room temperature by duplication. The photographic comparisons showed considerable development after two weeks on the control samples, while no development was observed on the controlled release films, The use of dioxy or chlorine to kill these three molds was evident in the two-week study.

EXAMPLE 10 h In a delayed release system, one side of a piece of cardboard was coated with an acid-releasing layer separated from a clopho layer by a medium layer of wax. The hydrophobic phase of thick of 12? pm in the layer The chlorite was a clear mixture containing 10% by weight of sodium clopto, 50% by weight of (H2C (0) CH2CH20CH2CH2.2O and 40% by weight of formates. clone of the acid-releasing I.POST wax of approximately 127 nm in thickness The total volume of the controlled release material was approximately 0.25 cm3. There was a delay in the release of dioxide from doro quartz, the acid liberating layer was separated from the layer "< It contained chlorine or an interposed layer of wax. In this case, a maximum was noted in the release after 1 day is noted in Figure 7. The individual concentration maxima superimposed on the common behavior were correlated again with the temperature and not with the humidity as shown in figure 3. The three species of mold subjected to '.JR signs in the example and in agar cultures loaded with ineral, but free of nutrients using carton as a nutrient and - according to the normal method of TAPPT T 487 prn ~ B5. Six samples were tested for fungal resistance during the two weeks at room temperature in duplicate. The results were presented in the Table 2. The photographic comparisons showed considerable development after two weeks on the control samples, while the majority of the controlled release films showed no development. In the few cases that mold grew on the release films, only one nucleus was responsible.

Invariably, this nucleus was a large mass of mold spores in which a certain self-protective effect and structure of the aggregate was generated. _ TABLE 2 i Agar covered with mold spores. 2 Paper soaked in mold spores.

EXAMPLE 11 The porous paper used in all these examples gives you end 'The untreated side and one side' was bright and shiny. The chlorine dioxide-releasing layers were applied to the untreated side of the paper with mixed chlorine dioxide-liberating sheets with the glossy side facing outward. Therefore, only the lustrous side of the paper is in contact with the flesh. Leaves of approximately 91.44 cm x 20.32 cm were cut to facilitate handling during the reverse procedure. The original weight of the paper was "Je 5 mg / c? N3. LPOST acid-releasing wax was applied to the paper «1e porous substrate in a dry box filled with nitrogen containing a large dish of phosphorous pentoxide ag «ta using a wax coating operating at approximately 87.7 ° C. If multiple coatings were used, the paper was allowed to cool before applying the subsequent coatings. Once the paper is coated, sealed in a suitable dry atmosphere for storage. The paper "containing a methanol solution" was applied using a coating that operated at room temperature. A typical solution of The coating was first dissolved 25 grams of poly-N-VI-Pyrrolidone (PVNP, 1.7x106 molecular weight) in 500 ml of methanol followed by 15 grams of sodium chlorite (technical grade). Immediately the homogeneous solution was used. If you wanted multiple coatings on a single subs, ')! • it was allowed to dry- the reverse between the applications .. Then the paper «jue conte a clorito en el aire fil eca for storage. Immediately before use, the film containing chlorite at room temperature was compression molded with the LPOSI-containing film to form a double layer mixed body that released chlorine dioxide.

Pressures less than 703 μg / ern2 were sufficient to induce cold flow and adhesion of the wax to the film containing clone t. Samples are randomly drawn from each individual sheet of double layer of substrate overlapped during the pressing operation in order to quantify the charges of dope and wax. These leaves were cut, measured, and weighed, 1 ueqo compared to the data obtained from the uncoated paper as shown in Table 3. Calculations of the theoretical production of acid based on the phosphorous pexide and the reaction: CIO2- * 4 H + > 4 C102 • 2 H20 • 01" they indicate a ratio of approximately 0.14 g of NaC102 / g of wax to an optimal use of CIO2. fi? CAAERO 3 The concentration of chlorine dioxide released from the films was inspected along with the humidity and temperature in a Petri dish under atmospheric conditions using the sensor system and the gas leak ratio previously described in Example 9. The samples were inspected during several days. The figure shows a typical graph generated by the data acquired from a sample composed of sheets with two layers of each phase (2 .2). The samples were inspected at various different levels (G load). All the samples showed an immediate maximum release of 10-20 ppm chlorine dioxide within the first 2-3 hours followed by a gradual reduction in water release. -for the next few days, ls The higher charges served to increase the initial initial concentration and prolong the release.

EXAMPLE 12 2: 2 papers were used as horn fi3 sideboards between ground beef patties packed at different densities that were loaded imitatively with high loads of units for the formation of colomas (CFU) of E. coli bacteria. Substantial reductions in bacterial development were noted as shown in Table 4. In the winter months, the chlorine dioxide gas had access to the inside of the empanada, resulting in a more complete annihilation throughout. .

TABLE 4 EXAMPLE 13 Cultivation of Eschepchia coli ATCC (Collection of American Type Cultivation) # 26 in Triptych Soy Broth (Difco 0370-17-31 until achieving a logarithmic phase activity with an optical density of 0.8 to 600 rnm that covers 1000,000 units for colony formation per culture rnl. The concentration was verified using plate counts in 3 separate layers. h The uniform dispersion of the bacteria in the densely packed car was ensured by the following method of inoculation. Loin was placed with ground chili purchased six hours before use and stored at 8 ° C in a saucepan and pressed to form a uniform sheet. 5 holes were drilled in the meat with a glass rod, and 0.1 rnl of bacterial culture was pipetted into each hole. The flesh was then kneaded to disperse the bacteria uniformly. This was repeated three more times, at least with a minute of vigorous kneading each time. When the 2 inoculum was added to the meat at a culture concentration of 109 .fu per ml, a concentration of 1,000,000 ctu per gram was introduced into the meat. Again the meat was ground to a fine texture in a sausage grinder mounted on a bench and with a hand-operated crank, and patties were formed by replacing the meat in the (-acerole and cutting the empanadas with a piece of tubepa would form a patty as a positive comparison pattern (ie, E. < ol added bacteria) .The back was ground as a negative comparison pattern (ie, no bacteria added) from the same source First in the non-contaminated grinder to avoid its own contamination, S prepared the empanadas in duplicate and it consisted of negative comparison patterns subjected to the 0 and (50 hor-as, positive comparison patterns tested at 0, 4, 24 and 60 hours, and test samples (it's fi5 ^ cir, em? ana "those exposed to a chlorine dioxide releasing film of the present invention) at 0,, 24 and 60 hours. The patties were placed between either the paper or the paper and the papers coated with a 2: 2 chlorine dioxide liquefying film (as described in Example 11) in plastic boxes. of LO cm of diameter with cover. Two Petp boxes containing duplicate samples were placed in plastic bags which could be reclosed and stored for the required time at 4 ° C in the main station. Two samples of each pie were rolled, one of the upper surface, T, was contacted either with the unmodified paper or with the test paper with the chlorine dioxide film, or from the middle one third of the empanada, M. Samples were obtained with forceps of inclined angle by means of either pinching at three points of the surface to obtain a small scraping of meat, or by means of digging and exposing the third intermediate region of thickness . The forceps were sterilized between the samples by immersing in isocopanol and flame. Pre-sterile water forms of 10 nrn in screw-capped test tubes were tared to 0 on a sensitive electronic scale, and samples of approximately 1 gram were added to the tubes and the weights were recorded. The tubes were then plugged and vigorously shaken to dispense the flesh and release the bacilli. 0.1 ml of floating material was smeared on agar from fifi and Triptych (Diufco 0369-17-6) in duplicate and scattered with a triangle "Je glass on a" rotating jisco. The glass spreader was sterilized between the laminations with isopropanol and subjected to flame. The viable bacterial content of the samples was visualized by reversing the plates after 24 hours of incubation at 37 ° C. The uninoculated negative comparison patterns showed the normal number of bacteria commonly seen in the ground or with a substantial development noted during bO. hours at 4 ° C. The inoculated positive comparison patches showed large amounts of bacterial development all the time with very slight differences in the upper and intermediate samples. If the unmodified paper had some anti-microbial effect, it was very slight. Ib When comparing the colony counts of the test samples exposed to chlorine dioxide, an annihilation of 100-100 was noted for the surface sample compared to the indoor test sample and the positive comparison pattern samples. , except for the 0 reduced annihilation on the surface on the sample put in contact with the weakly releasing film. As for the test samples exposed for 4 hours, the development of the colony to the surface was 50-1 OOX lower than the indoor test sample for positive comparison patterns. The surprising observation made in the sample "Je 60 horas was the high annihilation in both the interior section and the The fierce nature of the samples exposed to be purchased with the samples of the positive comparison path. Since positive comparison test plates were expected to be overloaded, a direct comparison for quantification purposes was not accurate, although an estimated count revealed a 50- to 200-fold reduction in the colony count at some time. . As an alternative, the plate counts were compared instead. 'test with the signed title of inoculo. I wanted to make a rough comparison between the Ccf? and the inoculum figure (corrected for sampling dilution). This is called the relation to the inoculum (RTI), which is intended to compare the roadway of the treated sample and the maximum possible count in cfu. The RTIs were calculated for the 60-hour plates based on the Ccfu count. The mean RTT for the upper samples of the, plates for the empanadas that were exposed for chlorine dioxide and "were tested for 60 hours was approximately 170," which would represent a decrease of 170 times in viability. The average RTI for the interior of these empanadas was approximately 50. At 60 hours, however, short reductions in bacterial viability were seen in the center of the empanada. Fl cooking empanadas that were exposed to chlorine dioxide and subjected to testing for 60 hours produced a normal-looking hamburger without it (strange smells would be noticed.

EXAMPLE 14 Hand-rolled loin patties 1.9 c thick were formed by hand loosely packed with approximately 25 cm2 of top surface area immediately after mixing and grinding in an E. coli ATCC # 26 broth (105-106 c / gram). The initial inoculum was cultured at a slightly lesser extent than the inoculum used in Example 13. The packed was used to aid in the penetration of the chlorine dioxide through the air passages that were connected. The empanadas between papers were then placed Chlorine dioxide liberators of 2: 4 or 3: 6 as described in Example 11, and covered with a Petp box cover and enclosed in a resealable plastic bag. The samples were then stored at 4 ° C for 3.5 days. After that exposure time the meat that is in contact with the 3: 6 paper did not show bacterial development either of the surface or interior sample when it was finished as described in Example 13. The inside of the pie exposed to the low concentration of chlorine dioxide (2: 4) showed no bacterial development either in the surface or intermediate samples when it was washed. When compared to the results of example 13, these results confirm the deep penetrating biocidal action of chlorine dioxide when released from controlled pie for 2.5-3 days at 4 ° C. Obviously, the biocidal action is Effective for a porous meat structure, an additional experiment was also carried out using chicken breasts, a chicken breast fillet was repeatedly immersed in undiluted E. coli ATCC # 6 broth (106-109 cfu). rnl), placed between 2: 2 chlorine dioxide release films and then enclosed inside a Petri dish that was placed in a resealable plastic bag and placed in a refrigerator at 4 ° C for 3.5 l. The < -car-ne was then cleaned and plated to obtain an indication of bacterial death, again no bacterial growth was observed after incubation.

EXAMPLE 15 Here, the "one" of a standard for the release of dioxide suitable for controlled release and the biocidal product of a container is discarded. The equation describing the concentration of the dioxide of chlorine in thickness coating-, l, (0 <x <l) that is coating the inside- of a permeable container of total thickness 1 + a, where "a" is the thickness- of the gas space (l < x < l a), per part of the coating. Chlorine dioxide is generated by means of a thin, completely permeable film of infinitesimal thickness that rests on the upper part of the coating at xd. or »Qan2e" DCcos (a "x) | eb ?? is? d? C (x, t) =? n = 0 [C (h-k'an?) - + (í + ') an- + h ] eos? arí) where, b = T) cc.n2, k '= 4l / P, h-D9 / (l_D The terms ofn, in the previous infinite series are the roots of the equation: an (d) --hk' «2 T) c - Chlorine dioxide diffusion constant (cp »2 / sec) in the coating. Da = Dioxide diffusion constant of chlor-o (crn2 / sec) e n fa s e g e s. 1 = Phenomenological length (crn) of the leakage pore. P = Crßc (Xd) / Caaß (xd) = Constant «je the law« Je Henry for the partition of chlorine dioxide between the coating and the gas phase. - Constant generation of chlorine dioxide «Je the release film controls« Ja (rnoies / cm2 / se < g2). k = a, the total thickness of the gas layer. s = inverse of the maximum release time of the chlorine dioxide from the controlled release film. C (x, t) is evaluated for a given group of diffusion constants, leak rate, h, phase and dimensional partition constant, chlorine dioxide liberation rate, 0, and reverse relaxation time for release, s, - yTaf? C (or) against a a t-s-1. As an example, C (l, t) is calculated for a Petp box with a cross section of 62 cm2 of a total thickness of 1 cm, which includes gas space of O.Ocm and 0.2crn of Agar. Since biological samples are introduced at x = l and grow on the agar, it is important to calcify this concentration. This calculation is needed because of the strong partition of chlorine dioxide in the liquid phase once it is generated by the controlled release film. At the velocities e release generated by a film «He test, the concentration in gas phase was so low (<; 0.1 pprn) which could not be measured by the detector. To finish the calculation, 0, s, P, Dß, Dc and L must be assigned or measured. "Since the Agar is 90% water, it is assumed that P = 40 TJ.J. Kaczur and D.ü. Ca lfield, Kirk-Othmer-Fncycl. Chem. Tech. (4th Ed.), 5, 971 01993) 1. D «= .5 x Id-5 un2 / sec and D9-0.12 crn2 / ° eg, are reported in Chern's Handbool. and Phys., 52nd ed., F47 (1971). In reality, Da appears in the model only in conjunction with the "position" for the purposes of the calculation, it is assumed that Cs is uni orme in l < x < the. The leakage flow constant, D9 / l, is evaluated by injecting a small amount (approximately 10 pprn) of dioxy or chlorine into the Pe p box that does not contain Agar and measuring the concentration of chlorine dioxide as a function of time. The Petn box used will escape relatively quickly due to the serrated edges of the bottom of the disc which is used to ensure good exchange.

Cesapo trusted biological growth.

When the supply function of the form Qte-bt is integrated from time 0 to infinity, Qte "btdt = Q / b2 = total moles" chlorine dioxide di spombles For calculation purposes, the controlled release film "Density 0.8 grams / cm3 and total volume 0.315 cm3 contains 15% by weight of sodium chloride" molecular weight 90.44 g per mole or 3.35 x 10 moles available chlorine dioxide (assuming complete reaction of 5 moles of C102-1 to 4 moles of chlorine dioxide) and shows a maximum release velocity in one day or ~ = 86,400 sec. This release maximum is typical of an acid-releasing film _ separated from the clopid. It contains film by a layer of intermediate wax. In this way 0 is calculated as 7.23 x 10-16? Noles / cm2 / sec2 for a base area of 62 cm2 of the Petn box where the velocity of release of the area is assumed not to have a later-on dependence on all the surface of the plate. Elista is a valid assumption since even though the trajectory of the controlled Release occupies a small area of the cross-sectional area of the plate, the velocities of diffusion of both the gas and the dioxide Agar , "" chlorine are large in comparison to the scale "Je time of the release rate. Then the concentration in the gel phase C (l, t) co or a time function is calculated for a fu- el velocity scale, h as shown in Figure 10. At fast leak rates (l0S < h < i0_1 cm_i), The release rate maximally increases to ts-1 and the maximum concentration is proportional to h. In essence, the concentration to any - time if nificati amente greater or the average time fiara The flight, is simply some constant factor multiplied by * the times of generation speed and supply. However, by decreasing the leak rate 10_? < h < 10-5, the maximum concentration is generated only at one time with significantly greater. Of course, at h-0, no leakage occurs, L a with < The maximum proportion is approximated as a result, and a total of 3.36 and 10-4 moL of chlorine dioxide (for example Qs ~ 2 x 62 crn2) are distributed between the 0.2 cm thick gel phase and the 0.8 cm thick gas phase. With the purpose of estimating how closely the concentration h = 0 approaches h = 8.31 x 1Q- * crn-1, the concentration in the gel phase is used at t-6.0 x 105 sec, x =? (2.4 x -5 moles / cm3) to calculate the total amount of chlorine dioxide in the Petri dish. r? 8crn (62 cm2) l / 40) + (0.2 c) (62 cn2) 1 (2.4 x 10-5 moles / crn3) = 3.27 x 10- * moles This value is very close to the expected «Jo for h-0. For the measured leak rate for the Petri dish, in which the biological growth experiments are carried out, a maximum concentration of 2.5 pprn is expected in the gel phase at xd with a concentration of 0.06 pprn in the phase of gas. Approximately 0.25 ppm is required to kill mold spores. A slightly more complicated medium sena a box of ~ the same dimension as the Petp box but with its gas space filled with absorption particles packed with a fraction «Je volume, _ = 0.5 crn3 / crn3. The "Jif? SLon of gas through such mixed body medium CR.M. Sweep and D.M. Grove, rans. Far. Soc, 4_7, 826, 837 (1951) R. Ash and D.M. Grove Trans. Far. Soc., 56., 1357 (1960) 1. The diffusion constant of a gas that flows to birds from a porous medium must be replaced by * * by: D9pd9 / [] 2Ke / | -. where Ks = Coefficient of the Law of Henry of surface in the relation Cß '-KßC9 where Cß' is the number of moles of absorbed gas / surface crn2 and C9 is the concentration in gas phase in moles / cr? - 3, r is the equivalent pore radius for a group of capilapities directed axially within a solid having porosity £ and internal surface, A (cm2 / cm3), r = 2e / A. Par-to the purposes of the calculation of the concentration The chlorine dioxide surface inside the porous medium, the particles are considered small enough so that the concentration of chlorine dioxide throughout the thickness of the particles is balanced with the concentration of gas. For the purposes of this calculation, the entire concentration of particles is concentrated on the particle surface. In this case, the coefficient of Henry's Law of - * - surface is related to the volume coefficient, V 0 / by CP (i -e) / Ac, '- [(? -e) /A.?PC9? ß = (i - e) Kp / A At a porosity of 0.5 and a partition coefficient of 40 in the particles, the diffusion constant for the flow through the porous medium of absorption would be reduced by a factor of 0.0244. This substantial reduction of the apparent phase phase diffusion constant proportionally reduces the leak rate, h, resulting in a proportional increase in the expected concentration at any time. The quantity, placement and controlled release characteristics required for a biocide film are estimated where the film is protecting a small box full of 62 c-3 particles that are supposed to escape at the same speed as the c , h = 8.3 x 103 crn- 1 (an assumption very good pair-to a typical box sealed loosely) ,. A 7 b The fact that boxes are well packed, folded (unpacked) would be an analogous case. Since the death of the mold spore is guaranteed in an exposure of 1 ppm of chlorine dioxide for a few minutes, any strategy must generate at least this concentration in a pulsed release in most regions of the box, preferably «After several days of delay. Mold growth destruction requires only 0.1-0.5 ppm for a few minutes. The destruction of cell growth mechanisms is so complete that strains with a natural immunity to chlorine dioxide can not develop. Conveniently, these concentrations are below the human olfactory detection limit of about 10 ppm. Practically, given that such a short exposure is required, the ideal system would be a cell that releases pulsed dioxide in a pulsed form, and, of course, depending on the storage medium, this behavior would ensure that the initial infection of the spores of mold (originating in and out of the box) and any subsequent infections (originating outside the box) were destined before any growth could occur.A continuous release of 1 ppm thus spent approximately 98% of the available clopto The preparation of such a film is deciphered in example 16. Figure 11 shows the expected release characteristics for a controlled release film.

A maximum of 10 days, 3.35 x 10 ~ 4 moles available chlorine dioxide (film of 0.33 cm3, sodium clopto 15% by weight), coLocada in a box of porosity 0.5 with a coefficient of Henry's law of volume of 40 contr-to the air leak with h = 202.76 c? n ~ i. A maximum concentration of 10.4 pprn is reached after 10 days and at least 1 pprn dur-ante 0.4 d? A < t < 46 days Approximately 0.31 crn3 of liberation material is needed for this purpose. At a materials cost of $ 2.20 / kg, the required cost of controlled release material to do the job would be approximately 0.056 cents. In this way, a box containing 1.1 liters of material could be protected by 1 cent with the parameters listed above.

EXAMPLE 16 The pulsed-release capabilities of a multiple stratified body can be calculated as follows, to determine whether the instant body will provide the sustained release rates desired for a particular application. The time required for complete cat- aly exchange can be predicted from the concentration of the mobile ion in ca, when i is A, B, or C. To determine such a period, considers "} that the transport of hydrogen through the intermediate layer C is the step that < , - speed control, and the diffusion constant and concentration of the mobile ion effective for the hydrogen ion are considered the same in layers A, B and C. The chlorite ion is considered to be relatively immobile, and it is considered that The reaction chlorite to chlorine dioxide occurs instantaneously once a hydrogen ion enters the hydrophilic layer B. The mobility of the hydrogen ion in the intermediate layer C can be estimated using experimental data reported by -d.L. Crowley et al., D. Poly. It, Poly. Phys. Ed., L4_, 1769 (1976). Crowley and others studied Ionic mobility in a copolymer "le graft" Je pol? Et? It has a density (79% by weight) and sulphonated poly (21% by weight) as a function of ion type, water content and temperature. Tones sodium, potassium and silver travel along sulfonate groups linked to the Lunero po by exchange with hydronium cations. A high water content of 3 to 6% by weight Probably the phase elimination of clusters of ions in a hi drotobic matrix. The mobility read silver reported and the concentration of the mobile ion is much higher under these conditions (u = 3.0X1Q-* cm2 / Stat.V-sec, C = 3.3X10-4 rnoles / cc). However, in "dry" films, both the mobility and the concentration of the mobile ion decrease substantially (μ - 1.4X10-4 cm2 / StatV-sec, 0 = 8.3X10- * moles / cc). The ion diffusion constant D can be calculated from the lomea mobility reported using the equation D = (kTμ) / g, where is the Boltzman constant, T is the absolute temperature, u is the IvilLity of the ion and q is the charge of the electron. The calculated ion diffusion constants are 1.21X10-8 crn2 / sec and 2.58X10-8 crn2 / sec for a counterion loaded film [dry and wet ilata (6% by weight in water), respectively. The morphology of such a copolymer would be similar to that of the two-material system of the present invention in which both include clusters of partially connected ions, located at spherulite boundaries within the foamed hydrophilic layer. 10 The total amount of hydro ion that has diffused through the AC limit (rnoles / crn2) at time t is represented by the function 0: 00 0 (t) / lCA - (Dt / 12) -? 6 - 2 (tr) -2 i (-l) nn-2 exp (-Dn2'rf21 / 12) lti n = l Breaking of the hydro ion in the hydrophilic layer B will occur at (Dt / 1) -0.1 (td ? .4 in, Id.27X10- 2cm) and diffusion of state ", ont? N? Oa (Dt / 12) - .45 (t = 46.9 min, Ld..27X1 O-2 crn) is reached. The first two terms in eL domain of the above equation are reached after the continuous state. In this way, under "wet" conditions (6% in water), Q (t) ~ 1CA IdDt / l2) - 1/61 = 5.72x10-5 inoies / di -crn2 to 1.27X10-2 ein « thickness. The hydro ion or a film with an area of 1 cm2 and a thickness of 1.27X10-2 cm (1.65X10-5 5 moles of hydro ion or i ni cient) must react almost completely in the clopto layer in 7 hours. Fn the "dry" eluate that is typical of polyethylene contaminated with ions, 0 f) = DtCA / 1 - 6.83X10-8 moles / day-c 2, at 1.27X1Q "2 cm" The thickness- Due to the concentration of the very lower mobile ion, 247 days are required for the hydronium ion to diffuse completely towards the hydrophilic layer B. In this way, a multiple layered mixed body can be formulated which provides from about one day to about 247 days of chlorine dioxide release, using the dual layer mixed bodies of the present invention. The rate of release of chlorine dioxide is generally fast when the release of chlorine dioxide is initiated in a mixed body that has an intermediate layer because the decomposition of chlorine is a function of pH. A minimum concentration of hydronium ion is transfered before the decomposition of chlorite into chlorine dioxide occurs due to the regory action of the hydrophilic layer containing the clopto. The effect of viscosity on the reaction rate, the speed of hydration of the film required to produce the minimum amount of free water necessary for the catalysis of the production of chlorine dioxide, and the changing concentration of the ion moved 1 and diffusion constant supported by layers A, B and C can affect the transport of hydro ion. There must be present water in the intermediate layer C to transport hydrogen ion. The water is transported to tr-birds from a hydrocarbon matrix as 01 decuLas simple, except for higher water activities where some tendency to form clusters is noted. The rate of penetration of water through a polyethylene film "Je high density of 1.27X10-2 cm" Je thickness of a front area of 1 c 2 would be 6.89X10-6 rnoles / d? A / cm2 / l. 27X10- 2 cm (90% RH, 38 ° C), as reported by lessling and others., Fncyel. Poly. Sci. Eng., 1_7, 510 (1989). This speed of penetration is significantly less than that observed for polyethylene ions that typically contain 3.35x10-4 rnoles / cc of ionic groups to a minimum (4.08X10-5 rnoles / d? A / cm2 / i .27X10-2 c [Zutty et al., Encycl., Poly. Sci. Tech., 6, 425 (1967) 3. The above ionic content is "Jected for layers A, B and C each of which have the potential to absorb 3.3X10- * inoles / cc x 10 molos of water (assuming 10 l-_0 /? on H3? +) or 4.2X10-5 mol of water / crn2 /! .27X10-2 crn (6% by weight Therefore, 1.27X10-2 cm of layers A and B would require approximately + 1 day to saturate < • «6% of water from an initial dry state, then an additional day would be required. To saturate the intermediate layer C. Although the invention is susceptible to different modifications and alternative forms, the specific embodiments thereof have been shown by way of example in the drawings and have been described in detail in FIG. It should be understood, however, that it is not intended to limit the invention to the particular form described, but rather to the The intention is to cover all the modifications, equivalents and alternatives that fall "within" the spirit and scope of the invention as defined by the appended claims.

Claims (1)

B3 NOVELTY OF Lñ INVENTION CLAIMS

1. - A biocidal powder and deodorant for sustained release of chlorine dioxide comprising, particles containing clopto amons; and a hydrophobic core having said particles on a surface on the same, the hydrophobic core contains an acid releasing agent, said particles and said hydrophobic core are substantially free of water, said particles are capable of liberating dioxide and chlorine by hydrolysis of the acid releasing agent. 2 - Fl powder according to claim 1, further characterized "? Which includes anhydrous particles on the surface of the nucleus huiro foi > i co. 3. The powder according to claim 2, characterized in that the anhydrous particles comprise sodium sulfate, calcium sulfate, magnesium sulfate, or silica gel depleted of moisture. 4. The powder according to claim 2, characterized in that the particles contain an alkali metal clopto, an alkaline earth metal chlorite, or a clopto-salt of a metal ion transition or a primary, secondary protonated amide. tertian or quaternary; The hydrophobic core also comprises atactic polypropylene, hydrocarbon wax, chlorinated wax, polyethylene wax, 04 , polyolefin, polyester, a polyolefin polyolefin, or mixtures thereof; and the acid releasing agent includes a carbohydrate acid, an ester, an anhydride, an acyl halide, phosphoric acid, a phosphate ester, a t-ester ester, a dialkyl phosphate. ilo, sulfuric acid, a suifromic acid ester, a sulfoic acid chloride, a phostosyl cato, or a phosphoresis of an ester based on glycerol. 5. The powder according to claim 1, characterized in that the hydrophobic core comprises a liquid acid brine. 6. A process for the preparation of a powder to provide sustained release of chlorine dioxide, the process comprises forming particles containing cytosite ammonium; and applying by spray a hydrophobic material containing an acid releasing agent on a fluidized bed of the particles so as to form a powder which has a core containing the hydrophobic material and a layer of the olopto-containing particles on a surface of the core. 7. The process according to claim 6, characterized in that the fluidized bed includes anhydrous particles of such that the layer of particles on the surface of the hydrophobic core includes the anhydrous particles. 8. The process according to claim 7, characterized in that the anhydrous particles they take up sodium sulfate, calcium sulfate, magnesium sulfate, or "depleted silica from hurne" gel. the «1. 9. The process according to claim 6, characterized in that the particles contain an alkali metal chlorite or an alkaline metal clopto; The hydrophobic phase further comprises atactic polypropylene, hydrocarbon wax, chlorinated wax, polyethylene wax, polyolefin, polyester, an iron copolymer, and mixtures thereof; and the acid releasing agent includes a carboxylic acid, an ester, an anhydride, an acyl halogenide, a phosphate ester, a phosphate ester, a prist ii siiylphosphate ester, a phosphate of d? It is a sulphonic acid, a sulphonic acid ester, a sulphonic acid chloride, a nitrosophilic acid, or a phosphorylane of an ester based on glycerol. 10.- A method to retard contamination by bacteria, fungi and viruses and growth of molds on a surface and / or deodorize the surface; The method comprises exposing the surface to a powder that does not release chlorine dioxide in the absence of moisture, the powder having a hydrophobic core containing an acid releasing agent and having clonal amons on a surface thereof; and exposing the surface to moisture to release chlorine dioxide from the dust into the atmosphere surrounding the surface.