MXPA97001044A - Transparent biocidal compositions of release sustain - Google Patents

Abstract

The present invention relates to a composition for retarding contamination by bacteria, fungi and viruses and mold growth characterized in that it comprises an acid liberating polymer, a hydrophilic material, and chlorite anions, each component of the composition has a particle size of no more than of approximately 1,000 angstroms and the composition is substantially free of water and capable of liberating chlorine dioxide by hydrolysis of the liberating polymer.

Description

TRANSPARENT BIKE COMPOSITIONS OF SUSTAINED LIBERATION REFERENCE OR RELATED REQUESTS This application is a continuation request in part of E.U.A. provisional Series No. 60 / 000,144 filed on June 12, 1995.

BACKGROUND OF THE INVENTION The present invention generally relates to an optically transparent or translucent biocide composition that releases chlorine dioxide upon aciv elation, and methods for using the composition. Ib Chlorine dioxide (CIO2) is a widely used superior oxidizing agent with a bleach, disinfectant. an + e, fumigator or deodorant. It can penetrate the cell wall or membrane and cytoplasm of spores of molds, bacteria and other icrobiological contaminants at concentrations below 0 part per million and destroy them. Chlorine dioxide or sodium clopto + arnb? In have been incorporated into food packaging. Studies have shown that residual levels and said preservatives do not cause significant genetic or carcinogenic danger to human beings. Rieier et al. studied the effect of acute and synchronous oral administration of chlorine, chlorine dioxide, sodium clonium, and sodium chlorate on the induction of cryosomal aberrations and abnormalities of the spermatozoid head in mice CEviron. Mutagenesis, 7_, 201 (1985)]. Only the highly reactive hypochlo- ride resulted in a weak positive effect for mutant potential. The other compounds, including chlorine dioxide and sodium chlorite, did not induce any crornornic aberration or increased number of micronuclei in the bone marrow of mice. Vilagmes and others attribute the relatively innocuous effect of chlorine dioxide to its inability to produce halogenornetanes, unlike hypodorite and chlorine [Proc. AUIA Dismfect. Semin., 24 pp. (1977); Chem. Flbs. 93_, 173513 f]. Recently, Richardson and others reported that an extensive study of the reaction of chlorine dioxide with organic compounds from water by the environmental protection agency confirmed this CEnviron observation. Sci. Fechnol., 28, 592 (1994) 1. Japanese Kol-ai Nos. 63 / 296,758, 63 / 274,434 and 57 / 168,977 describe deodorants containing chlorine dioxide incorporated in a polymer, ceramic spheres or calcium silicate wrapped in non-woven fabric, respectively. Gels that generate chlorine dioxide for use as topical applications for disinfection are described in Kenyon et al., A. 3. Vet. Res., XS45 (5), 1101 (1986). Chlorine dioxide generating gels are usually formed by mixing a gel containing suspended sodium chlorite with a lactic acid-containing gel immediately before use to prevent release of premature chlorine dioxide. Chlorine dioxide-releasing gels have also been used in food preservation. Encapsulation procedures have also been used in the preparation of chlorine dioxide sources. Canadian Patent No. 959,238 describes the generation of chlorine dioxide by encapsulation separately from clop or sodium 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. 4,585,482 describes gradual hydrolysis of polyvinylmethyl-anhydride ether or polylactic-glycolic acid in alternating form to generate acid that can liberate chlorine dioxide from sodium chlorite. A polyalcohol and water humectant is encapsulated with polyanhydride or polyacid in a nylon coating. After the sodium chlorite is diffused into the capsule through the nylon wall, a layer of impermeable polyethylene is coaserved around the nylon capsule. Solvents are required for reaction and application of the capsules. The capsules can be coated on surfaces to liberate 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 imply problems of environmental waste. Uellinghoff and others have formulated mixed bodies that include a hydrophobic phase containing an acid releasing agent and a hydrophilic phase containing chlorite ammonium. The mixed body lacks substantially water until it is exposed to moisture, once exposed to moisture, acid and hydronium ions are generated in the hydrophobic phase. The hydronium ions cross the hydrophilic phase and react with clopto to liberate chlorine dioxide from the mixed material. These mixed bodies are composed of and generate only substances approved by the FDA or substances generally recognized as safe. Mixed bodies can be used for food packaging and other applications where substances can be ingested by or in contact with human beings. These mixed bodies are described <; = n the Patent of E.U.A. No. 5,360,609 and the U.S. Patent Application no. 08 / 465,358, 08 / 465,086, 08 / 462,164, 08 / 461,716, 08 / 464,304. Uellmghoff et al., U.S. Patent Application. Series No. 08 / 462,039 describes a mixed body formulated for maximum release of chlorine dioxide in which the hydrophilic material contains? N ether of-a? N? No and a clopt-o salt formed by the reaction of? N clopto of i minio and a base. The chlorite of i minium is unstable to the nucleophilic attack by the clopto anion. When the chloroimide is reacted with a base, however, the stable cf-arnino ether and the chloro salt are formed. Uellmghoff et al., U.S. Patent Application. Series No. 08 / 461,706 discloses a method for maximizing the release of chlorine dioxide from an amine-containing mixed body by omitting the clopto source until it is applied to the mixed body to a surface. After being applied, the mixed body is exposed to gaseous chlorine dioxide which reacts with the amine to form clocy of irni or m situ or dissolves in the amine to provide chlorite. The mixed body is then activated in the presence of moisture to liberate chlorine dioxide. The mixed body can be exposed to elevated temperatures during processing, storage and application because the hydrophilic material does not contain minimal clopto or any clopto anions that could decompose at such temperatures. The method also prevents the premature release of chlorine dioxide from the mixed body. Barenberg et al., US Patent Application No. 08 / 465,087 describes numerous methods for using mixed bodies such as those described by lellinghoff and others to retard contamination by bacteria, fungi and viruses and the growth of mold in food, agricultural products, meats and other materials and deodorize carpets and the like. Although the mixed bodies of Uellinghoff et al. Are effective biocides, there is a need for biocidal compositions in which the acid-releasing component and the chlorite-containing component form an optically transparent or translucent single-phase mixture.

BRIEF DESCRIPTION OF THE INVENTION Among the objects of the invention, therefore, it may be noted to provide an optically clear or translucent composition that releases a sufficient concentration of chlorine dioxide to remove bacteria, fungi, molds and viruses; provide a composition that releases said chlorine dioxide concentrations after activation for a period of up to several months; provide 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 provide a composition that only releases approved substances for human exposure or ingestion by human beings; and providing a composition that is low in cost that does not adversely affect the appearance or mechanical properties of a substrate to which it is applied. The present invention is directed to a composition for retarding contamination by bacteria, fungi and viruses and the growth of molds containing an acid releasing polymer, a hydrophilic material and clopto anions as components, each component of the composition has a particle size no greater than about 1,000 angstroms, and substantially lacks water and can release chlorine dioxide under hydrolysis of the acid release polymer. Another embodiment of the present invention is directed to a composition for retarding contamination by bacteria, fungi and viruses and the growth of molds comprising an amide, chlorite anions and an acid-releasing terpolymer formed from polyvinylpyrrolidone, lactic acid. and glycolic acid. Each component of the composition has a particle size no greater than about 1000 angstrorns, and substantially lacks water and can release chlorine dioxide under hydrolysis of the acid releasing polymer. Another embodiment of the invention is directed to a terpolymer having the formula where PVNP has the formula: and R is a lower alkyl group or a lower alkyl ester, n is from 5 to 500, x is from 1 to 5,000, and is from 0 to 5,000 and z is from 0 to 5,000, provided that yoz is at least 1. Other The embodiment of the invention is directed to a mixed multi-layer body to provide sustained release of chlorine dioxide. The mixed body contains a water-soluble layer comprising an acid-releasing polymer, a hydrophilic material and chlorite anions, a superior moisture-regulating layer in contact with an upper surface of the water-soluble layer, and a moisture-regulating layer. bottom in contact with a lower surface of the water soluble layer. The water soluble layer is substantially free of water and each component of the layer has a particle size no greater than about 1,000 angstrorns. The moisture regulating layers are insoluble in water, such that moisture penetrating the moisture regulating layers hydrolyzes the acid releasing polymer to initiate the release of chlorine dioxide from the mixed body in multiple layers. Another embodiment of the invention is directed to a process for preparing a composition by mixing a hydrophilic material, a chlorite salt, an acid-releasing polymer and an organic solvent to form a mixture in which each component has a non-particle size. greater than about 1,000 angstroms, the mixture substantially lacking water and being able to release chlorine dioxide under hydrolysis of the acid releasing polymer. Another embodiment of the invention is directed to a process for preparing an acid releasing polymer by mixing an oligomer of polyvinylpyrrolidone, lactic acid, glycolic acid and water, and heating the mixture in the presence of an esterification catalyst to form a terpolymer of polyvinylpyrrolidone, lactic acid, glycolic acid having acidic end groups. The terpolymer is dissolved in an organic solvent and neutralized to esterify extreme acid groups of the terpolymer to form the acid liberating polymer. Another embodiment of the invention is a method for retarding contamination by bacteria, fungi and viruses and the growth of molds on a surface and / or deodorize the surface by treating a surface of a substrate with a composition that does not release chlorine dioxide in the absence of moisture, and exposing the treated surface to moisture to release chlorine dioxide of the composition towards the atmosphere surrounding the surface. Each component of the composition has a particle size no greater than about 10,000 angetrorns. Yet another embodiment of the invention is a method for retarding contamination by bacteria, fungi and viruses and the growth of molds on a surface of a material and / or deodorizing the material by exposing a surface of a material with a composition that does not release dioxide. of chlorine in the absence of moisture, and exposing the composition to moisture to release chlorine dioxide from the composition into the atmosphere surrounding the material. Each component of the composition has a particle size no greater than about 1,000 angstroms. Yet another embodiment of the invention is a method for retarding contamination by bacteria, fungi and viruses and the growth of molds on a surface of a material and / or deeodorizing the material by incorporating a composition that does not release chlorine dioxide in the absence of moisture on the surface. a material and exposing the moisture material to release chlorine dioxide from the composition into the atmosphere surrounding the material. Each component of the composition has a particle size no greater than about 1,000 angstroms. Other objects and advantages of the invention will be apparent from the following detailed description.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic view of a multi-layer mixed body to provide sustained release of chlorine dioxide; DETAILED DESCRIPTION OF THE PREFERRED MODALITIES In accordance with the present invention, it has been found that sustained release of chlorine dioxide can be generated from a mixed body containing chlorite anions when the solution is exposed to moisture. Although the chlorine dioxide releasing compositions are known, this solution is unique in that it is optically transparent or translucent and essentially not noticeable when applied to a substrate. When the solution has been applied to a substrate, the substrate can clearly be seen through the film formed on the substrate. If the solution, for example, is coated on a cardboard box printed with graphics, the graphics remain clearly visible through the coating. Although the coating releases chlorine dioxide oxidant, the coating does not alter the graphics or affect the color of the graphics. The solution can also be coated on a surface of a transparent or translucent substrate to provide biocidal action while maintaining the quality of "transparencies" of the substrate. If the solution is coated on a transparent plastic container for food, for example, a consumer can see the food inside the container before buying the food. The biocide solution protects the food against contamination by microbes while allowing consumers to see the food without opening the container. Therefore, the solution allows the visual inspection of a material while releasing chlorine dioxide to sterilize, deodorize or protect the material against contamination or infestation. For the purposes of the present invention, a solution is a mixture of components each having a particle size no greater than about 1000 angstroms, preferably no greater than about 500 angstroms, and most preferably no greater than about 100 angstroms as measured by microscopy or light scattering methods that are well known in the polymer art. A solution of the present invention can also be a mixture comprising components each having a particle size no greater than 2000 angstroms when the refractive index of each component of the mixture is the same or substantially similar entity. A solution that includes components that have some of the above particle sizes is optically transparent or translucent in appearance and visually to be a single phase mixture because its phase structure is of a diameter well below the wavelength of visible light. A solution is optically transparent for purposes of the invention when at least about 80% of the light, preferably at least about 90%, is transmitted through the solution. The solution does not scatter light and is stable to crystallization that would produce particles larger than 1000 angstrorns. The particle size of the solution is preferably small enough so that the compounds are uniformly dispersed. The chlorine dioxide is released from the composition when an acid releasing polymer within the composition is hydrolyzed by absorbed moisture, and releases acid and hydrous ions. The hydro ions diffuse from the polymer to react with the clopto amons in the composition to liberate gaseous chlorine dioxide. The gaseous chlorine dioxide diffuses out of the composition into the surrounding atmosphere for up to about 6 months in order to prevent the growth of bacteria with molds, fungi and viruses on a material. The single-phase compositions provide a more complete conversion to chlorine dioxide than that provided by the two-phase compositions because the acid-releasing polymer and the chlorite anions are in closer proximity to one another than in a two-phase mixed material. . Compositions that release at least about .1.0 x 10-6 moles of chlorine dioxide / cm2 for a period of at least 1 week, 1 month or 6 months can be formulated by the methods of the present invention for a variety of end uses. Preferably, the composition comprises between about 0.1% by weight and about 20% by weight of chlorite and ion anions, between about 10% by weight and about 70% by weight of a hydrophilic material, and between about 1.0% by weight. weight and about 50% by weight of an acid-releasing polymer, most preferably between about 10% by weight and about 20% by weight of chlorite anions and counterions of between about 10% by weight and about 50% by weight of hydrophilic material and between about 10% by weight and about 30% by weight of acid releasing polymer.

Any acid releasing polymer that forms a solution with the chlorite anions and counterions and the hydrophilic material and which is capable of being hydrolyzed by ambient moisture is acceptable for purposes of the present invention. Preferably, the acid releasing polymer is not exuded or extracted into the environment. The acid releasing polymer preferably has a degree of polymerization in number of between about 10 and about 10,000, most preferably between about 50 and about 1000, and most preferably between about 100 and about 300. The acid releasing polymer it is preferably copolymerized with a hydrophilic oligomer to make the acid liberating polymer compatible with the chlorite anions and the hydrophilic material. A preferred acid-releasing polymer is a copolymer of a phase compatibilizing oligomer such as polyvinylpyrrolidone, polyvinyl alcohol, polyanhydride or polyacrylate, and an acid such as lactic acid, glycolic acid or other α-hydroxyl acids or mixtures of these acids. Preferred polyanhydrides have the formula: where R is: is 1 or 2, n is an integer from 4 to 12, and X is 0 or N-Ch3. A particularly preferred acid-releasing polymer is a terpolymer of polyvinylpyrrolidone, lactic acid and glycolic acid. Each of the portions lactic acid, glycolic acid and polyvinylpyrrolidone. The terpolymer preferably has a degree of polymerization in number between about 1 and about 5,000, preferably about 5 and about 50 and preferably even between about 10 and about 30. The most preferred acid-releasing polymer has the formula: where PVNP has the formula: and R is a lower alkyl group or a lower alkyl ester, n is from 5 to 500, x is from 1 to 5,000, and is from 0 to 5,000 and z is from 0 to 5,000, provided that it is already at least 1 R is preferably a methyl group, n is preferably from 5 to 100, and x, y and z are preferably 1 to 1,000. The optimum proportions of lactic acid, glycolic acid and polyvinylpyrrolidone in the terpolymer are selected based on the adhesiveness, stiffness or other properties required for a desired application of the composition. A person skilled in the polymer art would know how to optimize the proportions of lactic acid, glycolic acid and polyvinylpyrrole suitable in the copolymer to obtain the desired properties in the composition. Any hydrophilic material that forms a solution with the chlorite and counterions and the hydrophobic material is acceptable for purposes of the present invention. The hydrophilic material is preferably an amide, an amine or a polyhydric alcohol. When the source of clspto is a clopto salt, the salt dissociates into the hydrophilic material to form chlorite anions and counterions. However, if the hydrophilic material is an amine and the chlorite source is gaseous chlorine dioxide, the chlorine dioxide reacts with the amine to form imino chlorite in situ, if the oxidation potential of the amine is sufficiently low so that the amine is oxidized. The composition of the present invention preferably includes an amine as the hydrophilic material to provide adhesive properties to the composition. The amide is preferably selected from the group consisting of urea or oligomeric amines. Urea is most preferred because its high hydrogen bond density improves chlorine dioxide uptake and release efficiency of the composition, dissolves and plasticizes polyvinylpyrrolidone, does not react with the acid release polymer, and provides greater stickiness in the composition. The composition may include up to about 30% by weight of amides, preferably between about 5 and about 20% by weight of amide and preferably between about 10 and 15% by weight of amide. Chlorite anions generally do not react with the hydrophilic material or the acid-releasing polymer, but are surrounded by hydrogen bonds with which the nitrogen or hydroxide contributes inside the hydrophilic material or acid-releasing polymer. Suitable chlorite sources that can be incorporated into the composition of the present invention include alkali metal chlorites such as sodium chlorite or potassium chlorite, alkaline earth metal chlorite such as calcium chlorite, chlorite salts of a metal ion. of transition or a primary, secondary, tertiary or quaternary protonated amine or iminium chlorite salts. Many chlorite sources, such as sodium chlorite, are suitable at processing temperatures that exceed approximately 100 ° C, allowing processing at relatively high temperatures. The components of the composition lack substantially of water to avoid significant release of chlorine dioxide before using the composition. For purposes of the present invention, the composition substantially lacks water if the amount of water in the composition does not provide a path for the transmission of hydronium ions from the acid liberating polymer to the chlorite anions. Generally, the components of the composition can include up to a total of about 1.0% by weight of water without providing said path for hydronium ion transmission. Preferably, each component contains less than about 0.1% by weight of water, and most preferably between about 0.1% by weight and about 0.1% by weight of water. Substantial amounts of water can hydrolyze a portion of the acid releasing polymer to produce acid and hydronium ions within the composition. The hydronium ions, however, do not dissipate to the chlorite anions until sufficient water is present in free form to transport hydronium ions. A preferred composition of the present invention includes between about 10% by weight and about 30% by weight of a terpolymer of polyvinylpyrrolidone-lactic acid-glycolic acid, between about 10% by weight and about 30% by weight of urea, between about 10 % by weight and between about 20% by weight of chlorite anions, and between about 10% by weight and between about 30% by weight of a polyvinylpyrrolidone homopolymer. The composition may also include co-compatibilizer to compatibilize the acid-releasing polymer with the hydrophilic material and the clopto-amons in the composition. A compatibilizer is preferably added when the acid-releasing polymer does not include a significant portion of the hydrophilic oligomer that compatibilizes the polymer with the remainder of the composition. Preferred compounds include homopolymer of polyvinylpyrrolidone, or their copolymers with alkene oligomers. Polyvinylpyrrolidone is a preferred co-catalyst and also serves to increase the mechanical strength of the composition. The polyvinylpyrrole don preferably has a degree of average polymerization number of between about 1 and about 10,000, most preferably between about 100 and about 10,000, and preferably between about 300 and about 5,000. A plater can be added to the composition to soften the acid releasing polymer. The plasticizer is preferably any onomeric or oligomeric amide generally known in the polymer art as a plasticizer, such as succinamide, formamide or N-methylformamide, and N-methylacetamide and isopropylacrylamide-acrylate. Forrnarnide and N-methyl formamide are toxic and are not preferred in applications that include human contact. If the amine center of the polymer is sufficiently mobile, the addition of a plasticizer is not necessary. A vitreous polymer can be softened to increase mobility by adding at least about 10% by weight, preferably between about 10 and about 30% of a plasticizer to the polymer to lower the glass transition temperature below the reaction temperature. Other amides that can be used as plasticizers for the acid-releasing polymer of the invention include H2NC (0) (CH2CH2O) "CH2CH2C (0) H2 wherein n ee 1 to 10, H2NC (0) (CH2CH20) nCH ((OCH2CH2) mC (0) NH2 2 where n is 1 to 5 and n is 1 5, and N (CH2 CH20) n CH2 CH2 (0) NH2 >; 3 wherein n is 1 to 10. A moisture scavenger, such as sodium sulfate, calcium sulfate, silica gel, alumina, zeolites and calcium chloride can be added to the composition to prevent premature hydrolysis of the releasing polymer of acid. Moisturizers may be added to make the composition more hydrophilic and increase the rate of hydrolysis of the acid releasing polymer. Conventional film-forming additives can also be added to the composition as necessary. Such additives include entanglement agents, flame retardants, and ulsifiers and cornpatibilizers. These additives must be hydrophilic and soluble in the composition if the composition is to be optically transparent or translucent. Preferred amides for use as the hydrophilic material include urea, formanide, acrylonitrile-isopropylacrylamide, copolymers of forrnaride and acrylamide-isopropylacrylate, and copolymers of acrylamide, isopropyl acrylamide or N.N.-methylene biaacrylamide and a primary amine or a secondary amine. Such amides can be useful vehicles for the film distribution prior to exposure to chlorine dioxide, which does not react with efficient electron alkenes polirner.izabl.es such as acrylamide. Suitable amines for use with 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 chlorite 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. The tertiary amines that have groups that do not bind hydrogen that are dissolved in a hydrophilic solvent are also acceptable. Representative amines include: alkanolamines; copolymers of aminoalkanes and uenobieacrylate idae; alkyninopyridine; alq? enodiamines; alkylaminocycloanes; alkylamino-carboxyamidoalkanes dissolved in a diluent; amines having the formula R3-xNHx; R? R2NCH2CH2C (0) NH2; N (CH2CH20H) 3-? H? solubilized, R 3 N (NCH 2 CH 2 C (0) NH 3) 2, (CH 3) 2 N (CH 2) 2 N (CH 3> 2.

R 5 R 6 N (CH 2) 2 NHC (0) NH 2, N (CH 2 CH 2 HC (0) H 2) 3, or i »CCH23nNH- • CHjCH. -NHCH-.NHCCH-, C HN NH "^ H, N • CH233- N - HJJJ-NH. where: the R substituents are, independently, - (CH2CH2?) and H, -C (CH3> 2 (CH2) -. OH, (CH2)? NH (CH2CH2?)? H, -CH (CH3) 2. alkyl, cycloalkyl, benzyl, acrylamine or pyridyl; Ri, R2. R5 and e are alkyl; R3 is methyl or ethyl; rn is 1-100; n is 2 or 3; x is 0, 1 or 2; and is 1 or 2 and z is 1, 2 or 3. In general, the above compounds can be solubilized in formamide, isopropylacrylamide-acrylamide or other conventional plasticizers. Preferred amines include rnonoethanolarnin, diethanolamine, triethanolarnin, a copolymer of 1,3-diaminopropane or 1,2-diaminoethane and N, N-methylenebisacrylamide, 4-dimethylaminopyriridine, tetramethyleneethyldiaia, N, N-dimethylaminocyclohexane, 1- (N-) di-ropylamino) -2-carboxyamido-ethanol solubilized or l- (N-dimethylamino) -2-carboxyamidoethane, a primary amine with the formula R1NH2, a secondary amine with the formula R2R3 H, N (CH2CH2? H) 3, HN ~ NH H-N - CCHj. , - N N-CCH23j- H- Solubilized NR5R6R7, (CH3) 2NCH2CH2 (CH3) 2. Rs R 9 NCH 2 CH 2 C (0) NH 2, R 1 N (NCH 2 CH 2 C (0) NH 2) 2. Rl 1 Rl 2 N (CH 2) 3 NHC (0) NH, N (CH2 CH2 NHC (0) NH2) 3.

C H23nNH CH2CH2? - Í-N. • C? - NHCH2NH? C? H2C "^ -1- CCHH - CCHH - + r - C- • NH- • CH.CH-CHjN C H33 m wherein: Ri is -CH2CH2OCH2CH2OH, -C (CH3) 2CH20H, CH2CH2NHCH2CH2OH, -CH (CH3) 2, -CH2CH2OH, 3J¡N NH; R2 and R3 are, independently, n-propyl, isopropyl, acrylamide, or -CH2CH2OH; R5 and Re are methyl; R7 is 4-pyridyl; Re and R9 are, independently, methyl, n-propyl or isopropyl; n and R12 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 acrylamide-isopropyl formamide or acrylamide. The secondary oligomeric or polymeric amines converted to acrylamide tertiary amines substituted by the reaction of nichael with acrylamides are also suitable because the amide group does not react with the acid releasing agent. The polyhydric compounds, including glycerol, sorbitol, polyvinyl alcohol and polyhydric alcohols, can be used as the hydrophilic material. However, the release of chlorine dioxide can occur more rapidly when a hydroxyl compound is incorporated into the composition and can limit the applications of such compositions to chlorine dioxide rapid release systems. The compositions of the present invention are prepared by mixing the hydrophilic material, a chlorite salt, the acid releasing polymer and an organic solvent to form a mixture having a particle size no greater than about 1,000 angstroms. The mixture is substantially free of water and capable of liberating chlorine dioxide under the hydrolysis of the acid releasing polymer. The acid releasing polymer is prepared by mixing an oligomer, a carboxylic acid and water to form a mixture. The mixture is heated in the presence of an esterification catalyst to form a copolymer having acid end groups. The copolymer is dissolved in an organic solvent and neutralized to esterify the acid end groups to form the acid releasing polymer. A preferred acid-releasing terpolymer is formed by mixing oligomer of polyvinylpyrrolidone, lactic acid, glycolic acid and water to form a mixture, heating the mixture in the presence of an esterification catalyst to form a terpolymer of polyvinylpyrrolidone-lactic acid-glycolic acid have acidic end groups, dissolving the terpolymer in an organic solvent, and neutralizing the terpolymer to esterify acid end groups of the terpolymer to form the acid releasing polymer. The preparation of this terpolymer is described in example 2. The esterification catalyst is preferably selected from the group consisting of p-toluene sulphonic acid or other strong protic acids (i.e., acids that form an aqueous solution that has a pH no greater than 1). An organic solvent is suitable for preparing the compositions of the invention if the chlorite salt is substantially soluble in the organic solvent and the solvent is substantially free of water. The organic solvent is preferably methanol or ethanol, and is most preferably methanol. A preferred solution includes between about 10% by weight and about 30% by weight of a terpolymer of polyvinylpyrrolidone-lactic acid-glycolic acid, between about 10% by weight and about 30% by weight of urea, between about 10% by weight and between about 30% of chlorite anions, between about 10% by weight and about 30% by weight of polyvinylpyrrolidone polymer furnace, and between about 30% by weight and about 60% by weight of methanol. The methanol in the solution evaporates when the solution is melted as a film or formed into some other final product. Chlorine dioxide is released, for example, from this preferred composition by exposing the composition to moisture. The moisture hydrolyzes the acid releasing terpolyner, forming an oligomer of polivilpyrrolidone, lactic acid and glycolic acid within the composition. Lactic acid and glycolic acid react with water to form hydronium ions. The hydronium ions react with a chlorite salt to form chlorine dioxide and metal salts of lactic or glycolic acid. The hydrolysis is illustrated below: H20 ^ tfas - • > t ---- tBjat-bs CH. HO- PVNP - CH-.C0H HOCHjC - OH I J II • + Z HOCH C - OH wn * C c i 02-D ( o o CIO-, - M * 0-CCH20H + M'O'CCHOH CH3 The rate of release of chlorine dioxide from a composition can be controlled when the composition is prepared, by changing the viscosity of the composition, by changing the concentration of the acid-releasing polymer in the composition, changing the crystal content of the components in the composition. , and adding a desiccant or humectant to the composition to control the release of chlorine dioxide from the composition once it is exposed to moisture. The rate of release of chlorine dioxide can be controlled during the use, by changing the temperature or the moisture content of the composition. Compositions of the present invention containing an amine can form iminium chlorite in place of the dissolved chlorite anions. The iminium chlorite is formed when the hydrophilic amine material is in contact with the hydrophobic acid-releasing polymer. Chlorine dioxide (CIO2) is reduced by removing an electron from the amine, forming an amino radical cation (not shown) and a chlorine counterion (CIO2). The minium 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 above reaction in an aqueous system is described in Rosenbatt et al., 3. Org. Chem. 28, 2790 (1963); 3 Arner. Chem. Soc. 89 (5), 1158, 1163 (1967). Conversions of chlorine dioxide to chlorite are obtained if the chlorite anion and / or iminium cation which is generated by initial electron transfer of the amine are rapidly co-settled and stabilized by a hydrophilic molecule. In some formulations, the uncomplexed chlorite anion can be dissipated by sub-sequential reactions with the irionium counterion at temperatures above 60 ° C. Cloptos are also subjected to disproportionation in chloride and chlorate. An amine with a high pK is preferred, because it reacts more rapidly with chlorine dioxide and acts as a more effective proton dissipator, maintaining the pH required for clopto ion stability. Chlorine dioxide is released from imitium chlorite when moisture contacts the composition. Hydrolysis of the acid-releasing polymer provides hydromine (H3O +) cations that react with minimal clopto to liberate chlorine dioxide gas. The decomposition products of the reaction are salts of aminium chloride and organic carboxylates. These products are retained in the composition. It has been found that, in some cases, the minium clopto can decompose if the composition is exposed to temperatures exceeding approximately 60 ° C, reducing the available concentration of clopto for conversion to chlorine dioxide. To maximize the release of chlorine dioxide from the mixed body, it has been discovered that the source of ciorite can be omitted from the composition until the composition is applied to a surface when the hydrophilic material in the composition is an amine. After application, the composition is exposed to chlorine dioxide gas which either reacts with the amine to form in situ clopto, or dissolves in the amine to provide clopto amines. The composition is subsequently activated in the presence of moisture to liberate chlorine dioxide. The mixed body can be exposed to elevated temperatures during processing, storage and application because the hydrophilic material does not contain irinium chlorite or any chlorite anions that can decompose at such temperatures. The method also includes the premature release of chlorine dioxide from the mixed body. The chlorine dioxide can be provided in situ by passing the composition through a chlorine dioxide generator. For an amine to form iminium chlorite in clean form or in the presence of a plasticizer, the amine must be sufficiently rich in electrons and the nitrogen of the amine must be locally mobile. The electron attraction groups must be separated from the amine center by at least two methylene 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 aminium. If the amine is frozen in a vitreous matrix, the amine nitrogen will not be mobile and the amine will not be converted to iminium chlorite. A vitreous amine can be softened to increase mobility by adding at least about 10% by weight of a plasticizer, such as a low molecular weight amide, to the amine at a lower glass transition temperature below the reaction temperature. . Other suitable plasticizers are well known in the polymer art. The maximum release of chlorine dioxide from a composition can be achieved by stabilizing the chlorite anion. Imimium chlorite is unstable to the nucleophilic attack by the chlorite anion. It has been found that the life-time at room temperature of the clopid anion is substantially extended when a strong bath, such as metal alkoxide, is present in the hydrophilic material which contains the ammonium clopto. The alkoxide stabilization mechanism of the clopto counterion is shown below.

R "ONa CR-2N = CR2] + CIO2-> R-2N-CR2-0R" + NaC102 wherein R'2 and 2 are groups corresponding to those of the selected amine and R- is an alkyl or hydrogen group. In the absence of water, the imimo ion is immediately decomposed into an a-amino ether and a more stable sodium clopto salt. If water is present during the oxidation of the tertiary amine, an unstable or-amino alcohol is formed which can attack the clopto anion unless the clopto anion has been effectively supplemented 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 stabilizing the clopto include metal alkoxides such as sodium, potassium or calcium methoxides, ethoxides, prophoxide or butoxide, metal oxides such as aluminum oxide or sodium oxide, metal ions such as Na +, trialkylamino salts of alkoxides, ammonium salts of alkoxides, acetates such as sodium acetate, substituted acetates or other materials that can generate a strong basic reaction to attack the nitrogen center of the clopto of írnimo. The compositions of the present invention can be formulated in various ways to accommodate a wide range of end-use applications. The composition 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. The composition of the invention can be formulated as a powder. Although the powder is not optically transparent, it provides a low velocity release rate of chlorine dioxide compared to clopto particles coated with a hydrophobic material. To prepare the powder, the clopto particles are fed in a fluidized bed. A solution of the acid-releasing polymer, the hydrophilic material and the chlorite atoms in an organic solvent such as that described above is sprayed by passing the material through small diameter nozzles into the fluidized bed chamber where they can collide on the fluidized anhydrous particles. Under contact with the fluidized particles, the chlorine dioxide releasing powder is formed when the solution solidifies to form an acid releasing core having an anhydrous particle layer embedded in the outer surface thereof. The aggregation is minimized because the clopto particles are hard inorganic materials. The particles can then be packed in a dry sealed container. By forming the chlorine dioxide releasing powder, the anhydrous particles delay the release of chlorine dioxide that is catalyzed by atmospheric moisture. Suitable anhydrous materials include anhydrous sodium sulfate, calcium sulfate, magnesium sulfate and a silica gel of dissipated moisture. The additional anhydrous particles can also be post-mixed with the chlorine dioxide-liberating powder to delay the release of chlorine dioxide. In addition to the formation of mixed powder bodies, the composition of the present invention can be formulated in solvents to allow film casting or other application methods. The composition can be applied as a film using known methods of hot melt, ironsion coating, spray coating, curtain coating, dry wax, wet wax, coextrusion and lamination. The co-positions can also be used to form a multi-layered mixed body 10 which includes a translucent or transparent optically water-soluble layer 12 consisting of an acid-releasing polymer, clopto-ammoniums and a hydrophilic material with the shown in Figure 1. The water soluble layer 12 is placed on a moisture regulating layer 14 on a substrate 16, and a moisture regulating layer 18 is subsequently placed on the water soluble layer 12. The moisture regulating layers 14 and 18 are water-permeable and water-insoluble films that prevent the water-soluble layer 12 from degrading in the presence of moisture. This provision makes it possible for a chlorine dioxide atmosphere to be provided over a period of days, weeks or months. The moisture regulating layers also control the rate of moisture ingress into the water soluble layer to control the release of chlorine dioxide from the multi-layered mixed body when activated by moisture. Suitable water-insoluble and water-insoluble films can be composed of copolymers of poly (ethylenepropylene) or poly (acrylic ester acrylate) or ionomers of the miemoe as sulphonated polyethylene-propylene salts). Copolymers of hydroxyethylmethacrylate, methoxyethymethacrylate of at least one hydrophilic component and at least one hydrophobic component and other water insoluble and water permeable films well known in the art are also suitable. The layered mixed bodies of the present invention are designed to maintain a desired rate of release of chlorine dioxide (moles / sec / c 2 of film) in the presence of atmospheric moisture to a surface for a length of time required for the dioxide of chlorine is absorbed on the surface and eliminates 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 the absorbency velocity at a surface. In this way, after measuring the escape velocity, the mixed body is formulated such that it contains a sufficiently large reserve of clopto reacting at a sufficient rate to compensate for 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, namely, the rate of production of chlorine dioxide from the film of controlled release, 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 rate of gas escape from the container. The design of such a mixed body is described in example 15 of the co-pending patent application of E.U.A. No. of senes 08 / 461,304. A preferred extended release system of the present invention preserves the clopto reserve by issuing a series of periodic pulsed releases controlled in time to coincide with the presumed bacterial, viral or fungal contamination times, or the typical incubation time of the biological interest. The system design can be optimized to maintain the desired elimination concentration for the time required at the atmospheric chlorine dioxide exhaust rates imposed by the specific application. A typical multi-layer controlled release mixed body includes water soluble layers A which are each formed by a composition of the invention. The layers typically have a thickness of about 5 microns, and are separated from one another by a water-swellable intermediate layer C The intermediate layer C can be composed of a wide variety of materials, since the chlorine dioxide can be diffused equally well. both in hydrophobic and hydrogen linked matrices. Such optically transparent or translucent materials include copolymers of at least one monomer? Hydrophilic oligomer and at least one hydrophilic monomer or oligomer, polyionized as protonated and neutralized, sulphonated or buffered oligo- or polyalkylene, such as polyethylene, polypropylene, alkyl acrylates and copolymers thereof. The substituted polyhydroxy lipid alcohol phosphates and phosphosilicates and their mixtures with alkene polymers and oligomers can be used, but they do not form an optically transparent mixed body. The finely divided anhydride salts or desiccants can be added to any of the layers to delay the reaction to the chlorine dioxide that is catalyzed by the water. It has been found that the construction of a mixed multilayer body where the arrangement of the layers in the immediate body is defined by formula C (ACB) nC (where n represents the desired number of pulses) provides a periodic pulsed release of high concentrations of chlorine dioxide for several weeks or months. Such pulsed release can be coordinated for the growth, incubation and contamination of viruses, molds, fungi and bacteria. The cycle time and peak concentrations of chlorine dioxide would be controlled by the layer thickness, the chlorite and acid-releasing polymer charge, and the ionic and water permeate characteristics of layers A and C. The release Pulsed occurs when each layer (ACA)? it is successively penetrated by water vapor and hydronium ions. Pulsed releases of chlorine dioxide ranging from approximately one day to more than 200 days can be achieved for films 5 and 5 microns thick, separating layers A by an intermediate layer C capable of supporting varying speeds. of hydrometer ion transport. The pulsed-release capabilities of a multilayer film can be calculated as stipulated in Example 16 of copending US Patent Application Serial No. 08 / 461,304.

The applications for the compositions of the invention are numerous. The water soluble compositions can be used in most any medium where exposure to moisture occurs while the compositions are protected from degradation by a water insoluble material permeable to water or incorporated as a component of a material. The compositions can be used to prevent the growth of molds, fungi, viruses and bacteria on the surface of a material by deodorizing the material or inhibiting infestation by means of the. treating a surface of a substrate with a composition that does not release chlorine dioxide in the absence of moisture, and exposing the treated surface to moisture to release chlorine dioxide from the composition in the atmosphere surrounding the surface. The release of chlorine dioxide retards bacterial, fungal, and viral contamination and the growth of mold on the surface, deodorizes the surface and inhibits infestation. Each component of the composition has a particle size no greater than about 1,000 angstroms. The surface can be treated with a composition of the present invention by conventional coating, extrusion, lamination and impregnation methods well known in the art. The treated surface is generally a portion of a container, a part of a substrate placed inside a container, or a packaged film or other type of packaging. When an optically clear composition of the invention is applied to a substrate, the surface of the substrate can be clearly seen through the film formed on the surface. If the composition, for example, is covered in a cardboard box printed with graphics, the graphics will remain clearly visible. A container or substrate can be protected with a coating of the comp > biocidal oeición although the composition is transparent and virtually imperceptible to a consumer. The biocidal atmosphere generated within the container or other packaging can be used in storage of food products including the biocidal atmosphere generated within the container or other packaging can be used in storage of food products including blueberries, raspberries, fresae, and other products, meat cakes from ground beef, chicken fillets, and other meats, improved foods, pet foods, dry foods, cereals, grains, or almost any food subject to bacterial contamination or mold growth. They can also protect themselves from growth of mold, fungus and algae bar soap, laundry detergent, stored paper documents, clothing, paint, seeds, footwear and packaging thereof. Medical instruments, devices and supplies, disposable and non-disposable personal care products, and soil can be sterilized to prevent microbial contamination. Medical, biological or biohazardous wastes can also be sterilized in hospitals, laboratories, and clinics to kill microbes within the waste. The smells of athletes' shoes, disposable footwear, and waste, when contained within a treated container, can also be minimized at the same time. Composition or exposure to the composition can also be treated with elecal equipment or supplies or photographs, such as VCRs, videotapes, audio tapes, audio components, cameras, photographic film, camera lenses, lenses within medical equipment, and medical monitors and other medical equipment p-ara to prevent growth of mold, fungi and algae. The biocidal composition can be incorporated into a molten polymer used to make a portion of the equipment and supplies such as the video tape carge or equipment housing. The carge or housing may also include a film of the composition adhered to the interior thereof. The biocidal composition can replace the silica gel packs typically used in shipping and storing electronic and photographic equipment. The components of the invention are essentially suitable for application to, or incorporation in, transparent or translucent products. The compositions can also be applied to the surface of a transparent or translucent substrate to provide biocide action while maintaining the "see through" quality of the substrates. If the solution is covered in a clear plastic food container, for example, a consumer can see the food inside the container before buying the food. The biocidal solution protects the food from microbial contamination, allowing the same time consumers to inspect the food without opening the container. Therefore, the solution allows visual inspection of a material while releasing chlorine dioxide to sterilize, deodorize or protect the material from contamination or compromise. When the compositions are applied to clear surgical bandages, the wound is sterilized by means of chlorine dioxide and is visible through the bandage, allowing inspection of the wound without removing the bandage and exposing the wound to contamination. Transparent or translucent products that can be treated with the compositions of the invention include clear packages such as "clam shell" containers, clear packaging films such as plastic food sheath, disposable eating utensils, plates and cups, serving products food, food bags, food storage containers, and other food packaging, filters for portable water to treat water during camping, boating, trips or emergencies, waste containers or bags for medical or biohazardous waste. The packages can be treated with the composition to preserve food products that have a long-term shelf life, such as processed foods stored in "freecos" storage maintained at room temperature that includes soft tortillas, cakes or other baked goods, energy bars, sweet , snack food, and the like. Clear biodegradable and non-biodegradable sutures for use in humans and animals can be treated to avoid infection at the site of use, maintain sterility of sutures during storage, and sterilize sutures to be used as an alternative to steam, ethylene oxide, and gamma irradiation . They can also be treated with the multi-layered mixed bodies described above, clear bandages to "see through", bandages and surgical bandages to reduce microbial contamination and infection. The compositions of the invention are also especially suitable for providing a clear, invisible coating on products such as furniture and floors used in facilities prone to microbial contamination such as hospitals. The compositions can also be incorporated or coated in filters and ducts for heating, ventilation and air conditioning to avoid microbial contamination, align the "sick building syndrome", and prevent the outbreak of Legionnaires' disease resulting from the bacterium Legionella premophilia . Conventional containers such as cardboard or cardboard boxes, corrugated, non-woven, plastic, foamed or multi-laminated-polymeric containers, "clam shell" containers commonly used in the fast food industry, cellulose, plastic or paper bags can be used. , seed packaging, or waste containers. The treated surface may also be a reusable or disposable mat or sheet including a dental tray cover, a surgical tray cover, a shower mat, nonwoven bandage material, a meat cutting board, a drawer or shelf liner. , an insert for athletic bags or gym locker, a food bag, a sheet of paper to separate hamburger meat steaks, a tray to pack meat, a bag such as those used to pack bags intravenosae, a freeca fruit ejaculator or box liner, a buffing pad for avee, meat, seafood or fruit, or an absorbent layer for use in diapers. Said mats or sheets are typically made of paper, cellulose, polymeric, woven or non-woven fabric materials. Such a method can be used to coat the surface of a seed to protect the ovo and fungi seed during storage and to protect against fungal growth when the seed is planted. The coating, when activated by moisture, creates a microscopic atmosphere of chlorine dioxide in the dirt in the vicinity of the seed and inhibits fungal growth that normally prevents seed germination. This coating has no effect on the germination of the sernillae. 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, "tea bag" or liner in the container. Paper impregnated with the mixed body generates enough chlorine dioxide to protect the seeds. Although any seed can be protected by the coating, edible seeds such as corn grain, sunflower seeds, or soybeans, remain tight for human consumption once they are coated. In this way, coated seeds can be provided p >to plant or for human consumption after they have been coated. An optically transparent composition of the invention can be applied to the seeds to ensure that the appearance of the seeds will not be altered by the composition. Another embodiment of the invention is a method for preventing the growth of fungi, bacteria or molds on a surface and / or deodorizing the surface by treating the surface with a composition that does not release chlorine dioxide in the absence of moisture and exposing the surface treated to moisture to release chlorine dioxide from the composition into the atmosphere surrounding the surface. A preferred application includes foot powder to prevent athlete's foot and other fungi. The powder can be applied directly on the surface of the foot or it can be incorporated in a shoe insert. The powder can be applied between the fabric cover and the foam pad of the shoe insert, impregnated inside the foam pad, or impregnated or coated or a strong counter or shoe upper lining. The chlorine dioxide generated from the moisture inside the shoe diffuses from the mixed body into the atmosphere to kill fungi and deodorizes the shoe. The powder can be mixed with conventional ingredients such as talc, corn starch, fragrance, miconazole nitrate, tolnase acetate, boric acid, aluminum chlorohydrate, salicylic acid, and cellulose. The powder can also be mixed with other ingredients and used in bath powders or powders used in the treatment of crustaceans. The powder can also be applied on carpet to remove odors from the carpet. The ingredients commonly incorporated in deodorizers of carpet powders or cleaners can be mixed with the powder of the present invention. The mixed body can also be formulated in microcapsules that break after being stepped on and are then activated by hunger. These microcapsules can be impregnated in floor, bath mats or can be used in the deodorization of carpet. The powders can also be packed in a bag and placed in marine environments, such as the deck, well or storage areas in boats, to prevent mildew and mold growth in these areas. Another use for mixed bodies is to provide 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 the hydrophobic or hydrophilic material in sep- arated components that are activated when press-fitted together. Pipe fittings used with intravenous bags, for example, can be treated so that one 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 film. Hydrophilic material containing chlorite, and the treated surfaces of the fittings are interconnected in the presence of moisture to initiate the release of chlorine dioxide from the treated surfaces in the atmosphere surrounding the material. Adjustments for permanent catheters, needles, peritoneal dialysis, percutaneous devices, percutaneous accesses, colostomy bags and other medical devices can also be treated according to this method. Additionally, closures in a package can be treated to provide self-sterilization packaging for devices, instruments and medical supplies. It is expected that the mixed body of the present invention can kill bacteria on the surface of meats. However, it is not expected to penetrate a ground beef steak. It has been discovered that chlorine dioxide arising from paper treated with the instant body can p > Effectively infiltrate the total thickness of a steak and kill bacteria such as E. coli and Salrnonella that result from contamination during meat processing. E. coli 0157: H7 in rotten flesh has caused death and severe disease and appears to be especially resistant to cooking, fermentation and drying. In a typical operation that produces beef steak for commercial consumption, the meat is ground, extruded and formed into steaks that are separated by sheets of coated paper that prevent adhesion of the individual steaks. After packing, the ground meat can be exposed to chlorine dioxide for a period when it is in refrigerated storage to kill and inhibit it. growth of the bacteria. The following examples are presented to describe the preferred embodiments and utilities of the present invention and not to limit the present invention unless otherwise specified in the claims appended thereto.

EXAMPLE 1 A polyvinylpyrrolidone oligomer was prepared by polymerizing vinyl pyrrolidone in water using a free radical initiation with hydrogen peroxide and ammonia catalyst, as described in E.S. Barabas, Encyl. Poly. Sci. Eng., 17., 198 (1989). Three grams of vinylpyrrolidone were dissolved in 7 grams of water and polymerized with 0.03 ml of 30% hydrogen peroxide and 0.3 ml of concentrated ammonia water for 5 hours at 55 ° C. The reaction products were oligomer of polyvinylpyrrolidone and 2-pyrrolidone. At the end of the reaction, 2 additional rnl of 30% hydrogen peroxide were added to oxidize any terminal aldehyde group to carboxylic acid groups. After the solvent was removed by pumping and the product was vacuum dried at 60 ° C, a hard, clear polyvinylpyrrolidone oligornero, terminated with hydroxyl and carboxyl groups, was recovered. The reaction is illustrated below: Dry under vacuum at 60 ° C HO- PVNP CHjCOH where PVNP polyvinylpyrrolidone represeta, which has the formula: where n = 5 to 500.

EXAMPLE 2 A multi-block polyester polyvinylpyrrolidone copolymer was prepared by mixing 0.46 g of polyvinylpyrrolidone oligornero prepared in example 1, 0.23 g of glycolic acid and 0.225 ml of 85% lactic acid with .5 ml of water and 0.005 g of catalyst of esterification of p-toluene sulphonic acid. The mixture was heated slowly for 20 hours at 120 ° C under a dynamic vacuum to remove the esterification water. A multi-block terpolymer having acid terminal groups was recovered. To enterify the acid terminal groups, the copolymer was dissolved in a large excess of methanol and neutralized with ammonia. Alternatively, the acid terminal groups can be esterified with excess ethanol. Terminal groups OR- rather than the terminal group CH3O- shown in the reaction scheme below, can be formed by dissolving the polymer in an excess of alcohol or by dissolving the polymer in an alcohol and neutralizing with ammonia. The alcohol has the formula ROH wherein R is ethyl, n-propyl, or isopropyl. The resulting terpolymer polyvinylpyrrolidone-polylactate glycolate (PVNP-PLGA) contained 34 mole% polyvinylpyrrolidone, 32% glycollate and 24% lane%. The PVP-PLGA terpolymer preparation is below: TOUBq? H - dN? D? H 02H- ootuojtnst? Snto ?. opto? HO - 3 - HDOH Z - HO - DZHDOH r H03 HD dN? D- OH x II E I II II O HD OR O EXAMPLE 3 A 30% solution in peeo of the PVP-PLGA terpolymer prepared in accordance with Example 2 in methanol is neutralized with triethylamine and added to a solution of rnetanol (10% by weight total solids) of sodium chlorite (recrystallized from methanol). ), urea and polyvinylpyrrolidone (360,000 MW) so that the total solids mixture contained 51% by weight of the terpolymer PVNP-PLGAn 34% by weight of the polyvinylpyrrolidone homopolymer, 95 by weight of urea and 6% by weight of chlorite of sodium. The solution melts into a film and remains uniformly dispersed and indefinitely transparent.

EXAMPLE 4 A solution of the PLGA copolymer in chloroform is added to a solution in methanol (10% by weight of total solids) of sodium chlorite (recrystallized from methanol), urea (10% by weight of total solids) and polyvinylpyrrolidone (360,000 MW). The solution remains cloudy and separated in a PLGA phase and a polyvinylpyrrolidone-urea-chlorite phase when melted in a film. Although the invention is susceptible to different modifications and alternative forms, specific embodiments thereof have been shown by way of example in the drawings which are described herein in detail. However, it should be understood that they are not intended to limit the invention to the particular form described but rather, on the contrary, the intention is to cover all modifications, equivalent and alternative that fall within the spirit and scope of the invention as defined by means of the attached claims.

Claims (9)

NOVELTY OF THE INVENTION CLAIMS

1. - A composition for retarding contamination by bacteria, fungi and viruses and oho growths comprising an acid releasing polymer, a hydrophilic material, and chlorite anions, each component of the composition having a particle size of no more than about 1,000 angstroms, and the composition is substantially free of water and capable of liberating chlorine dioxide by hydrolysis of the acid releasing polymer.

2. A composition for retarding contamination by bacteria, fungi and viruses and growth of molds comprising an amide, chlorite anions, and an acid-releasing terpolymer formed from polyvinylpyrrolidone, lactic acid and glycolic acid, each component of the composition having a particle size of no more than about 1,000 angstroms, and the composition is substantially free of water and is capable of liberating chlorine dioxide by hydrolysis of the acid liberating polymer

3. A terpolymer having the formula: R where PVNP has the formula: and R is a lower alkyl group or a lower alkyl ester, n is 5 500, x is from 1 to 5,000, and is from 0 to 5,000, and z is from 0 to 5,000, provided that either of the two yoz must be at least 1.

4. A mixed multilayer body to provide sustained release of chlorine dioxide comprises, a water soluble layer comprised of an acid-releasing polymer, a hydrophilic material and chlorite anions, the layer is substantially free of water and each component of the layer has a particle size of no more than about 1,000 angstroms; and an upper moisture regulation layer in contact with an upper surface of the water soluble layer, and a lower moisture regulation layer in contact with a lower surface of the water soluble layer, the moisture regulating layers are insoluble in water, so that the moisture penetrating any of the moisture regulating layers hydrolyzes the acid releasing polymer to initiate chlorine dioxide release from the multi-layered mixed body.

5. - A mixed multi-layered body for providing time-pulsed release of chlorine dioxide comprising at least 2 water-soluble layers comprising an acid-releasing polymer, a hydrophilic material and chlorite anions, the layers are readily free of charge. water and each of the components of the layer has a particle size of no more than about 1,000 angstroms e; and at least three water-insoluble, water-permeable barrier layers for controlling the diffusion of water or the diffusion of hydronium ions produced by hydrolysis of the acid-releasing polymer to the water-soluble layer, the arrangement of the layers in the body mixed is defined by the formula C (ACA) nC where C is a barrier layer, A is a water soluble layer, and n is an integer ranging from 1 to 10. 6.- A process for the preparation of a composition comprising mixing a hydrophilic material, a chlorite salt, an acid liberating polymer and an organic solvent to form a mixture in which each of the components has a particle size of no more than about 1,000 angstroms, the mixture is substantially free of water and capable of liberating chlorine dioxide by hydrolysis of the acid releasing polymer. 7. A process for the preparation of an acid-releasing polymer comprising mixing a polyvinylpyrrolidone oligornero, lactic acid, glycolic acid and water, heating the mixture in the presence of a sizing catalyst to form a terpolymer of polyvinylpyrrolidone-lactic acid -glycolic acid having acid terminal groups; Dissolve the lime grain in an organic solvent; and neutralizing the terpolymer to esterify the acid end groups of the terpolymer to form the acid releasing polymer. 8. A process for the preparation of a composition comprising, mixing an amine and an acid-releasing polymer to form a mixture; and exposing the mixture to chlorine dioxide which reacts with the amine to form iminium chlorite within the mixture, the mixture has a particle size of not more than about 1,000 angstrorns and is capable of liberating chlorine dioxide by hydrolysis of the polymer acid liberator. 9. A process for the preparation of a composition comprising, mixing an amine, a base and an acid releasing polymer to form a mixture; and exposing the mixture to chlorine dioxide which reacts with the amine to form iminium chlorite which decomposes with the base to form a chlorite salt within the mixture, the mixture has a particle size of no more than about 1,000 angstroms and is capable of of releasing chlorine dioxide exposing the material to moisture to release chlorine dioxide from the composition in the atmosphere surrounding the material to retard contamination by bacteria, fungi and viruses, and growth of molds in the material and / or deodorize the material.