TW505499B - A sustained release, transparent or translucent composition, a terpolymer, a multilayered composite for providing sustained release of chlorine dioxide, the processes for preparing the compositions, and a method of using the compositions - Google Patents

Abstract

A composition for retarding bacterial, fungal and viral contamination and mold growth containing an acid releasing polymer, a hydrophilic material, and chlorite anions. Each component of the composition has a particle size of not more than about 1,000 angstroms. The composition is substantially free of water and capable of releasing chlorine dioxide upon hydrolysis of the acid releasing polymer. Also disclosed are a terpolymer having the formula; a multilayered composition for providing sustained release of chloride dioxide; and the process for preparing the above compositions.

Description

V. Description of the Invention (1) Related Cases This case is a part of consecutive US patent cases 60 / 00,144 filed on June η, 1995. Back of the invention The present invention relates to an optically transparent or translucent biocidal composition which releases chlorine dioxide upon activation and a method for using the composition. Dioxide gas (ClO2) is an excellent oxidant and is widely used as a bleach, disinfectant, fumigant or deodorant. It can penetrate the cell walls or membranes (at concentrations below 丄 ppm) of mold spores, bacteria and other microbial contaminants and destroy them. An 'oxidizing gas or sub-gas red steel has also been incorporated into food packaging. Studies have shown that residual amounts of preservatives for children do not pose a significant genetic or carcinogenic risk to humans. Meier et al. Studied the effects of subchronic and acute oral administration of gas, dioxide, sodium chlorite, and sodium chlorate on chromosomal disorders and sperm head abnormalities in rats [Environ, Mutagenesis, 2_, 201 (1985)]. Only highly reactive hypochlorite has a weakly positive effect on mutation potential. Other compounds, including dioxide and sodium chlorite, will not blame mouse chromosomal disorders or increase the number of small nuclei in the bone marrow. Vilagines and others believe that the harmless effect of chlorine dioxide is that it cannot produce methyl halide, unlike hypochlorite and gas [proc. Printed by AWWA Disinfect · Semin ·, 24 pp. (1 977) ); Chem. Abs. 93, 1 73 5 1 3 f]. Recently, Richardson et al. Reported that an EPA study of the reaction of dioxide with water-containing organic compounds confirms this observation [Environ. Sci. Technol., 592 (1 994)] 〇 Japanese Publications 63/2 96,758, 63/2 74,434 and 5 7 / 168,977 Reveals that deodorant containing chlorine dioxide is incorporated into the polymer, ceramic beads, or broken -4-This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) 505499 V. Description of the invention (2 Acid is wrapped in a non-woven fabric. Gels that produce chlorine dioxide for topical disinfection applications are disclosed in Kenyon et al., Am · J · Vet. Res ·, () Chlorine monoxide-generating gels are generally composed of Suspended gel of chlorite steel is mixed with lactic acid-containing gel before use to prevent the release of chlorine dioxide prematurely. Gels that release chlorine dioxide have been used in food preservatives. Encapsulation method It has been used in the source of preparing chlorine dioxide. Canadian Patent 9 5 9,23 8 Rev. π: The generation of oxidizing gas is produced by encapsulating sodium aerobic acid and lactic acid in polyvinyl alcohol, mixing capsules and water to produce Chlorine dioxide σ Tice et al. U.S. Patent 4,585,482 discloses Instead, poly (vinyl fluorenyl ether-maleic anhydride) or poly (lactic acid_glycolic acid) is gradually hydrolyzed to produce acid, which can release sodium dioxide from chlorine dioxide. Polyalcohol wetting agent and water to Polyanhydride or lactic acid is encapsulated in a nylon coating. After sodium chlorite diffuses through the nylon wall into the capsule, an impermeable polystyrene layer surrounds the nylon capsule gel to retain water in the capsule. The capsule can be coated on The surface releases chlorine dioxide. Although the capsule is said to provide biocidal effects for several days to months, chlorine dioxide begins to release immediately after the capsule is prepared. The batch method used to prepare the capsule also involves many chemical reactions and physical methods, among which For some issues related to environmental treatment, please read the I matter first and then fill in this page. It is printed by the Central Consumers Bureau of the Ministry of Economic Affairs and printed by the Consumer Cooperative.

Wellinghoff et al. Have formulated compositions including a hydrophobic phase containing an acid releasing agent and a hydrophilic phase containing a chlorite anion. The composition is substantially free of water until it is exposed to water. Upon exposure to water, acids and hydronium ions are generated in the hydrophobic phase. Hydrogen ions move into the hydrophilic phase and react with anion chlorite to release chlorine dioxide from the composition. These compositions only include and 5-This paper size applies to Chinese National Standard (CNS) A4 specifications (210X297 mm) i 505499 A7 B7 ----------------- V. Invention Explanation (3) Produces FDA-approved substances or substances that are generally considered safe. The composition can be used in food packaging and other applications, such substances can be digested by humans or come into contact with humans. These compositions are described in U.S. Patent 5,360,609, and U.S. Patent 08 / 465,358, 08 / 465,086, 08/462, 164, 08 / 461,716, and 08/46 1,304.

Wellinghoff et al. U.S. Patent No. 08 / 462,039 discloses a composition formulated to maximize the release of dioxide gas, in which a hydrophilic substance contains an α-amino ether and a nitrosate (from imine chlorite And alkali reaction formation). The nucleophilic attack of chlorite anions against chlorite anions is unstable. ~ However, when the imine chlorite reacts with the test, the more stable amine ether and chlorite are formed. Printed by the Consumers' Cooperative of the Central Bureau of Standards, the Ministry of Economic Affairs \ ¥ 611 丨 1 ^ 11〇 ££, et al. U.S. Patent Case No. 08 / 461,706, revealing that the largest amount of dioxide released from an amine-containing composition In the method, the chlorite source is provided only when the composition is applied to the surface. After application, the composition is exposed to a dioxide gas ' which reacts with the amine as% • to form imine chlorite, or dissolve in the amine to provide a chlorite anion. The composition is then activated in the presence of moisture to release dioxide gas. During handling, storage and application, the composition may be exposed to high temperatures ' because the hydrophilic substance does not contain nitrosyl imine or any anion which may decompose at that temperature. This method also precludes the premature release of chlorine dioxide from the composition.

Barenberg et al. U.S. Patent No. 08 / 465,087 describes many uses of the compositions disclosed by Wellingoff et al. To prevent bacterial, fungal, and viral contamination and the growth of mold on food, meat, and other materials, as well as felts, etc. Stinky way. — ________ _ 6 -____ Zhang scale is applicable to China National Standard (CNS) 8 4 specifications (210X 297 mm) ~-505499 Printed by A7 B7, Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of invention (4) Although We e 11 The composition of ingh ff et al. is an effective biocide, but a biocidal composition that releases an acid and a chlorite-containing component to form an optically clear or translucent single-phase mixture is still required. SUMMARY OF THE INVENTION Therefore, for the purpose of the present invention, it may be mentioned that an optically transparent or translucent composition is provided, which releases chlorine dioxide at a concentration sufficient to eliminate bacteria, fungi, molds and viruses; The concentration of chlorine dioxide is several months after activation; the composition provided. The increase in the release rate of chlorine dioxide is proportional to the increase in temperature and humidity (promote the growth of mold and bacteria); the composition provided only releases Substances permitted for human exposure or digestion; and the provision of inexpensive compositions that do not adversely affect the appearance and mechanical properties of the substrates to be applied. The present invention relates to a composition for preventing the contamination of bacteria, fungi and viruses and the growth of mold Contains acid release polymer, hydrophilic substance and chlorite anion. Each component of the composition has a particle size of not more than about 1,000 angstroms, is substantially free of water, and can release dioxide gas when the acid release polymer is hydrolyzed. Another specific embodiment of the present invention relates to a composition for preventing the contamination of bacteria, fungi, and viruses and the growth of molds, which contains ammonium amine, a gas acid anion, and polyethylpyrrolidone, lactic acid, and Acid release trimer formed by glycolic acid. Each component of the composition has a particle size of no more than about 1,000 angstroms. It is substantially free of water and can release chlorine dioxide when the acid-releasing polymer is hydrolyzed. Another specific embodiment of the present invention relates to a terpolymer, which has the following formula. Please read it first, read the back δ winter, and note the matter before filling out this page-7 This paper size applies to China National Standard (CNS) Α4 specification (210X297 Mm) JU5499 A7 B7 V. Description of Invention (5)

H〇f PVNP_CH ^ 〇 ^ CH2y_〇WX〇R x 7yX 4 where PVNP has the following formula: --CH 2- C Η-- R is a low-carbon or low-carbon base grease 'n is 5 to 50Q-, J is 1 To 5,000, y is 0 to 5, 0 0 0 'z is 0 to 5, 0 0 0, but y or z must be at least 1. Another embodiment of the present invention relates to a multilayer composition for providing sustained release chlorine dioxide. The composition contains a water-soluble layer including an acid-releasing polymer, a hydrophilic substance, and a chlorite anion, an upper water-conditioning layer contacts the upper surface of the water-soluble layer, and a lower water-conditioning layer contacts the lower surface of the water-soluble layer . The water-soluble layer is substantially free of water, and the components of the layer have a particle size of not more than about 1,000 angstroms. The moisture-regulating layer is water-insoluble, so that water penetrates the moisture-regulating layer, water interprets the acid polymer, and triggers the release of chlorine dioxide from the multi-layer composition. Another specific embodiment of the present invention printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economics is related to a method for preparing a composition and composition, which is composed of mixing a hydrophilic substance, a gaseous acid salt, a release polymer, and an organic solvent to form each component. A mixture having a particle size of not more than about 1,000 angstroms. The mixture is substantially free of water and can release chlorine dioxide when the acid release polymer is hydrolyzed. Another embodiment of the present invention relates to a method for preparing acid release polymerization.物 之 -8-This paper size is in accordance with Chinese national standard (0 ^ 7 A, see the standard (210X297) ^ --- B7 V. Description of the invention (6) Method 'By biting copper with mixed polyethylene pbiha: ^ Zhangxinlai, Lactic Acid, Glycolic Acid and Water, and mixed in the presence of an esterification catalyst in a ampoule, w ... this mouthpiece to form a polyethylenyl eleol with an acid end group -Lactic acid-glycolic acid terpolymer. The polymer is dissolved in an organic solvent, and neutralizes the acid terminal group of the self-defined terpolymer, β to form an acid release polymer. The embodiment of the m-body of the present invention is -A species that prevents bacteria, roundworms and viruses / defective and roundworms from growing Method for deodorizing on the surface and / or surface, treating the surface of the 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 Into the atmosphere around the surface. Each component of the composition has a particle size of not more than about 1,000 angstroms. Another specific embodiment of the present invention is a method for preventing the contamination of bacteria, fungi and viruses and the growth of mold on the surface of a substance. And / or a method for deodorizing a substance by exposing the surface of the substance to a composition that does not release chlorine dioxide in the absence of water, and the composition is exposed to water damage so that the monoxide is released from the composition into the surroundings of the substance Atmosphere. Each component of the composition has a particle size of no more than about 1000 angstroms. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, another specific embodiment of the present invention is a method for preventing the contamination of bacteria, fungi and viruses and A method for mold growth on a substance and / or deodorization of a substance by incorporating a composition that does not release chlorine dioxide in the absence of water into the substance, and the substance is exposed to the water so that the oxidized milk is controlled by the group The substance is released into the atmosphere around the substance. Each component of the composition has a particle size of not more than about 1,000 angstroms. Other objects and advantages of the present invention can be understood from the following detailed description. The paper dimensions are applicable to the Chinese National Standard (CNS) ) A4 specification (2 丨 0X297 mm) 505499 A7 __ —_ B7____ 7. Description of the invention (7) Brief description of the drawing 1 Figure 1 is a diagram of a multilayer composition for providing sustained release chlorine dioxide In the present invention, it has been found that a sustained release of chlorine dioxide can be produced when a liquid containing a chlorite anion is exposed to water. Although compositions that release chlorine dioxide are known, this The solution is unique because it is optically transparent or translucent and is substantially invisible when applied to the substrate. When the solution is applied to the substrate, the substrate can be clearly seen through the film formed on the substrate. For example, if the solution is coated on a cardboard box (() 〇11 仏 111 lamp 11〇 & 1 ^ 1) 〇 ^ :), the graphics are kept clearly visible through the coating. Although the coating releases chlorine dioxide oxidants, the coating does not change the graphics or affect the color of the graphics. The solution can also be applied to the surface of a transparent or translucent substrate to provide a biocidal effect while maintaining the "see-through" nature of the substrate. If the solution is applied on a transparent plastic food container, consumers can see the container food before purchasing the food. Biocidal solutions protect food from microbial contamination and allow consumers to inspect food without opening the container. Therefore, the solution can be visually inspected for substances while releasing chlorine monoxide to sterilize, deodorize or protect the substance from contamination or spread. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs for the purpose of the present invention, the solution is a mixture of ingredients, each with a particle size of not more than about 1,000 Angstroms, preferably not more than about 500 Angstroms, more preferably More than about 100 Angstroms, measured by a microscope or light scattering method known in polymer technology. The solution of the present invention may also be a mixture in which the particle size of each component is not greater than 2,000 angstroms, when the refractive indices of the components of the mixture are the same or substantially similar. The solution including the above particle size components is transparent or semi-transparent in appearance, and is regarded as a single-phase mixture because the diameter of the phase microstructure is less than that which can be _ ___ ~ 10-

Said the scale standard (CNS) A4 specification (21Gx2977j ^-~ ---__ I 505499 A7-~~ -------___ 5. Description of the invention (8) '~ See the wavelength of light. When at least about 80. Light, preferably at least about 90% of light. When the solution is transmitted, the solution is optically transparent, which is the purpose of the present invention. The solution does not scatter the light source, and for crystal stabilization, it produces particles larger than ^^ ㈧. The particle size of the solution is relatively large. It is small enough to uniformly disperse the ingredients. When the acid-releasing polymer in the composition interprets the acid and hydrostone hydrogen ions from the absorbed water, chlorine monoxide is released from the composition. Hydrogen ions diffuse from the polymer. It reacts with the chlorite anion in the composition and releases the chlorine dioxide gas m. The monoxide gas diffuses out of the composition into the atmosphere for a period of about 6 months' to prevent bacteria, molds, fungi, and viruses from growing on the material. The single-phase composition provides a more complete conversion to the dioxide gas than the two-phase composition, because the acid release polymer and the chlorite anion are closer than the two-phase composition. Release to about y · 〇χ 106 Ear dioxide / cm2 at least ^ weeks, {months Or the composition for 6 months can be formulated for various end uses by the method of the present invention. The composition preferably contains about 0.1% to about 20% by weight of chlorite anion and counter ion, about 10% to about 70% by weight Hydrophilic substance, and about 1.0% to about 50% by weight acid release polymer; more preferably about 10% to about 20% by weight chlorite anion and counter ion, about 10% to about 50% by weight % Hydrophilic substance, and about 10% by weight to about 30% by weight, acid-releasing polymer, the Consumer Standards Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs, prints any solution that forms a solution with chlorite anions, counterions, and hydrophilic substances and can The acid release polymer hydrolyzed by the surrounding water is the object of the present invention. The release is preferred: the polymer preferably does not ooze or enter the environment. The acid release polymer preferably has an average degree of polymerization of about 10 to about 1 〇〇〇〇〇, more preferably about 50 to about 10,000, the best about 100 to about 300. This paper size applies the Chinese National Standard (CNS) A4 specifications (210X297 mm) 505499 A7 B7 Ό-f CH.

〇No I Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. 5. Description of the invention (9. Acid-releasing polymers are better than hydrophilic oligomers. Acid anions and hydrophilic substances can be as low as T phase. Preferred acid release polymers are phase compatible oligomers such as polyvinylpyrrolidone 1 vinyl alcohol, polyacrylic acid or polypropylene amine and acids such as lactic acid. , Glycolic acid, or other copolymers of silk acid or a mixture of these acids. Preferred polyacids have the following formula: 〇〇 — (^ R -COC-^ — where R is: and seven,--(〇) ~ (Or m is 1 or 2, η is 4 to 12, X is 0 or N-CH3. A particularly good release acid polymer is a terpolymer of polyacetylene, bilo copper, lactic acid and glycolic acid. Each of the polymers of lactic acid and glycolic acid and polyvinylpyrrolidone = parts preferably have an average degree of polymerization of about i to about 5,000, more preferably about 5 to about optimal about 10 to about 30. The acid polymer has the following formula: Η0 Let PVNP—CH Jd— (〇II -CH, C—〇- CHr -CH-

) 0R-12 This paper is suitable for financial and economic standards (CNS publication) 505499 A7 B7

V. Description of the invention (1G where PVNP has the following formula: R is a low-carbon or low-carbon ester, η is 5 to 500, X is 1 to 5, 000, y is 0 to 5,000, and z is 0 to 5, 〇〇, but 7 or 2 must be at least j. R is preferably methyl, η Chevron is 5 to 100, x, 7 and 2 are preferably ^ 100. Lactic acid in the trimer, The optimal ratio of glycolic acid and polyvinylpyrrolidone is selected based on the adhesion, hardness, or other properties required for the intended use of the composition. Skilled artisans of ice hydrates should know how to make lactic acid and ethanol in copolymers The ratio of acid to polyvinylpyrrolidone is most suitable to obtain the desired properties of the composition. Any hydrophilic substance that forms a solution with a chlorite anion as a counterion and a hydrophobic substance I. A hydrophilic substance is acceptable for the purposes of the present invention. The sexual substance is preferably amine, amine or polyhydric alcohol. When the source of nitrosic acid is chlorite, the salt dissolves in the hydrophilic substance to form the chlorite anion to balance the ions. However, 'if hydrophilic The substance is amine and the gas source is chlorine dioxide, and the economy is dioxin. The imprinted gas reacts with the amine on the spot to form imino acid imine, if the oxidation potential of the amine is low enough to oxidize the amine. The composition of the present invention preferably includes ammonium as a hydrophilic substance to provide the composition with dry properties. Pyridamine is preferably selected from urea or oligomers. Pyridamine. Urea is the best 'because of its high hydrogen binding density which can improve the absorption and release efficiency of the chlorine dioxide of the composition' and it is soluble in polyvinylpyrrolox Ketone is neutralized and plasticized, it does not react with acid-releasing polymer, and it provides greater viscosity of the composition. The composition can be 13-this paper rule ^ (210X297 mm) 505499 A7 B7 V. Description of the invention (11 including multiple Up to about 30% by weight of amidine, preferably from about 5 to about 20% by weight. Acetamide, more preferably from about 10 to about 15% by weight of amide. Please read the back of the page first. Chlorite anions generally do not react with hydrophilic substances or acid-releasing polymers, but are surrounded by hydrogen bonds provided by nitrogen or hydroxide in the hydrophilic substance or acid-releasing polymers. Suitable for incorporation into the compositions of the present invention Chlorite sources include alkali metal chlorites such as sodium chlorite or chlorite Potassium acid, alkaline earth metal chlorites such as calcium chlorite, chlorites of transition metals, or chlorites of protonated primary, primary, secondary or quaternary amines or imines. Many chlorites Salt sources, such as sodium argonite, are stable at treatment temperatures in excess of about ^^^, and can be treated at quite south temperature. Each component of the composition is substantially free of water to avoid significant release of chlorine dioxide before the composition is used For the purpose of the present invention, if the amount of water in the composition does not provide a pathway for the transfer of hydrated hydrogen ions from the acid-releasing polymer to the arginic acid anion, the composition is substantially free of rhenium. Each component of the composition may generally include up to about 1.0% by weight of f% water without providing a transport route for hydrated hydrogen ions. Each component preferably contains less than about 0.1% by weight of water, more preferably about 0.001% by weight and about 0% by weight of 1% water. Non-real-quality water can hydrolyze a portion of the acid-releasing polymer to generate acid and hydronium ions in the composition. However, hydrated hydrogen ions will not expand. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs will disperse to chlorite anions until free water is available to fully transport the hydrated hydrogen ions. A preferred composition of the present invention comprises from about 10% to about 30.% by weight of a polyvinylpyrrolidone-lactic-glycolic acid terpolymer, from about 10% to about 30% by weight. /. Urea, about 10% to about 20% by weight of chlorite anion, and about 10% by weight. /. To about J0 weight. /. Polyvinylpyrrolidone homopolymer. -14-This paper standard is suitable for financial standards (CNS) A4 specification (505499, 'A7 ___B7 V. Description of the invention (12) The composition may also include a compatibilizer to make the acid-releasing polymer in the composition hydrophilic and hydrophilic The substance is compatible with the chlorite anion. When the acid-releasing polymer does not include a significant hydrophilic oligomer portion, it is preferred to add a compatibilizer to make the polymer compatible with the other ingredients of the composition. Better compatibility Agents include homopolymers of polyvinylpyrrolidone, or copolymers thereof with olefin oligomers. Polyethylenepyrrolidine 嗣 is a preferred compatibilizer 'and can also be used to increase the mechanical strength of the composition. Polyvinyl The pyrrolidone preferably has an average degree of polymerization of from about 1 to about 10,000, more preferably from about 100 to about 10,000, and most preferably from about 3,000 to about 5,000. A plasticizer may be added to the composition to soften the acid release adduct. The plasticizer is preferably any monomer or oligomer ammonium such as succinimidine, generally known in the polymer arts as a plasticizer. Formamidine, N-methylformamide, N-methylacetamide and isopropylpropenamide-propanamine g. Amine and N_ Carbamate toxic is not good in applications involving human contact. If the polymer amine center is sufficiently mobile, no plasticizer is required. Glassy polymers can be added by at least about 10% by weight, preferably about 10 wt.% To about 30 wt.% Plasticizer in the polymer to reduce the glass transition temperature below the reaction temperature and soften to increase mobility. It can be used as a plasticizer for the acid release polymer of the present invention Other amines include 1 > 10: (0) ((: 1 * 12 (: 1120) 11〇 ^ 2 (^ 20: (0 ”1 " 12, where 11 is 1 to 10) employee consumption of the Central Standards Bureau of the Ministry of Economic Affairs Printed by the cooperative, H2NC (0) (CH2CH20) nCH ((0CH2CH2) mC (0) NH2) 2 where η is 1 to 5 and m is 1 to 5, and N (CH2CH20) nCH2CH2 (0) NH2) 3 where η 1 to 100. Moisture scavengers, such as sodium sulfate, calcium sulfate, silica gel, alumina, zeolite, and calcium chloride, can be added to the composition to prevent premature hydrolysis of acid release polymers. Wetting agents can be added to Make the composition more hydrophilic and increase the acid release polymer. The size of the paper is suitable for the Chinese National Standard (CNS) A4 specification (2 丨 〇297mm) 5 05499 A7 B7 V. Description of the invention (13 Printing resolution of the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs. The conventional film-forming additives can also be added to the composition, if necessary. The additives include cross-linking agents, fire retardants, emulsifiers And compatibilizers. If the composition is optically transparent or translucent, these additives must be hydrophilic and soluble in the composition. Preferred amines for use as hydrophilic substances include urea, amidine, and acrylamide _ Isopropylacrylamide, formamide and copolymers of acrylamide-isopropylacrylamide, and acrylamide, isopropylpropanamide, or N, N-methylenebisacrylamide And copolymers of primary or secondary amines. Before being exposed to the dioxide gas, amidine can be used as a carrier for the cast film, which does not react with polymerizable, electron-deficient alkenes (such as allylamine). Suitable amines for use as a hydrophilic substance include primary amines, secondary amines, and tertiary amines having pendant hydrogen bonding groups. Electron-substituted amines are preferred, which provide electrons to convert chlorine dioxide to chlorite. The electron-drawing group concentrates the electron density on the group, so it is difficult for chlorine dioxide to pull one electron from the amine. Tertiary amines with non-hydrogen-bonded side groups that are soluble in hydrophilic solvents are also acceptable. Representative amines include: alkanolamines; copolymers of aminoalkanes and enedipropenamide; alkylaminopyridines; enediamines; alkylaminocycloalkanes; alkylaminocarbamidines dissolved in diluents Alkanes; amines having the formula R3-XNHX ;; dissolved N (CH2CH2OH) 3-xHx, R3N (NCH2CH2C (0) NH2) 2, (CH3) 2N (CH2) zN (CH3) 2, r5r6n (ch2) nhc (o) nh2, n (ch2ch2nhc (o) nh2) 3, or 16 This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) Please read it in nr first. 5 Things to fill in this page% Order 505499 A7 B7 V. Description of the invention (14 0 ^ II 丨 丨 .NH-c CH2] nNH — CH2CH2C — NHCH2NHCCH2CH2- hn

NH

HnN 2n —cch2] 3a '^ —cch ^ —- nh2

〇 II 'CH2CHT' C-NH-C CH 23 2 N-CChi3]

•,or

H2 N f .N N- 乂 n〉 = 0

c / \ ^ / VNH

H-, N where: R substituents are each-(CH2CHzO) yH, -0 (^ 3) 2 (0 ^) ^,-(CE2) ^ m {CK2c} i2〇) ziit -ch (ch3) 2, • CCh2] 2—n —C CH2 ^ 2—Ministry of Economic Affairs ^^ Standards Bureau Employees ’Cooperative Cooperatives printed alkyl, cycloalkyl, benzyl, propylamine, or pyridyl; R !, R2, R · 5 and R6 are alkyl groups; R3 is methyl or ethyl; m is 1-100; η is 2 or 3; X is 0, 1, or 2; y is 1 or 2; ζ is 1, 2 or 3. The above compounds are generally soluble in amidine, isopropylacrylamide-acrylamide or other conventional plasticizers. Preferred amines include copolymers of monoethanolamine, diethanolamine, triethanolamine, 1,3-diaminopropane or 1,2-diaminoethane and N, N-methylenebispropenamide, 4-diamine Methylaminopyridine, tetramethyleneethylenediamine, N, N-diamidinocyclohexane, dissolved 1- (N-dipropylamino) -2-carboxamidoethane or 1- (N -17-This paper size is in accordance with Chinese National Standard (CNS) A4 specification (21 × 297 mm) 505499 Μ B7 V. Description of the invention (15 dimethylamino group) -2-Si: Amino ethyl sintered, first grade Amine, secondary amine of formula R2R3NH, N (CH2CH2OH) 3,

H2N f · N Ν-0- χ-f \ —ΝΗ ΗΝ ΝΗ) = 0 Η2Ν-C CH23 3—Ν Ν-C CH2 ^ 3—ΝΗ2 dissolved nr5r6r7, (ch3) 2nch2ch2n (ch3) 2, r8r9nch2ch2c (o ) nh2, rur12n (ch2) 3nhc (o) nh2 n (ch2ch2nhc (o) nh2) 3,

〇 II NH-C CH2] nNH— CH2CH2C- NHCH2NHCCH2CH2 or

〇II CH2CHT ~ C_NH_ch2ch2ch2n_c ch3] 'Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs where: Ri is -ch2ch2〇ch2ch2oh, -c (ch3) 2ch2〇h, -ch2ch2nhch2ch2〇h, -CH ( CH3) 2 / -ch2ch2〇h, • CCH2] 2—N NH; 18 This paper size applies Chinese National Standard (CNS) A4 (210x297 male thin) • CCH2] 2— N- or 505499, A7 B7 V. Invention Note (16) R2 and R3 are each n-propyl, isopropyl, acrylamide, or -CH2CH2Oh; R5 and R6 are methyl; R7 is 4-P biphenyl; and Han 9 is each methyl , N-Propyl or isopropyl; Rii and Ri2 are each methyl'ethyl, n-propyl, or isopropyl whose '· m is 1 to 100; n is 2 or 3. Suitable diluents include formamidine or acrylamide-isopropylacrylamide. The oligomer or polymer secondary amine and acrylamide are converted into acrylamide substituted tertiary amine by Michael reaction, because the amido group does not react with the acid releasing agent. Polyols, including glycerol, sorbitol, polyvinyl alcohol, and polyalcohols, can be used as hydrophilic substances. However, when a hydroxy compound is incorporated into the composition, the release of the dioxide gas can occur relatively quickly, and the composition can be restricted from being used in a rapid release system of the dioxide gas. The composition of the present invention is prepared by mixing a hydrophilic substance, chlorite, an acid release polymer, and an organic solvent to form a mixture having a particle size of not more than about 1,000 angstroms. The mixture is substantially free of water and releases chlorine dioxide when the acid release polymer is hydrolyzed. Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs, acid-releasing polymers are prepared by mixing oligomers, carboxylic acids, and water to form a mixture. The mixture is heated in the presence of an esterification catalyst to form a copolymer having an acid end group. The copolymer is dissolved in an organic solvent and neutralizes the acid end group in g to form an acid-releasing polymer. Preferred acid release terpolymers: A mixture of polyvinylpyrrolidone oligomer, lactic acid, glycolic acid, and water is mixed to form a mixture, and the mixture is heated in the presence of an esterification catalyst to form a polyacetamate having an acid end group. Pyrrolidone · lactic acid-glycolic acid terpolymer. The terpolymer is dissolved in an organic solvent, and the terpolymer is neutralized to esterify the acid end group of the trimer to form an acid release polymer. The preparation of this trimer is described in Example 2. _________ _ 19-Ben Du Shi Cai Guan Jia Pi (, Secret (21 () > < 297 public director) " " " " " " " " " Or other strong + acid (even if the pH of the aqueous solution is not greater than 1). If the chlorite is substantially soluble in the organic solvent and the solvent is substantially free of water, the organic compound is suitable for preparing the composition of the present invention. Organic The solvent is preferably methanol or ethanol, and most preferably methanol. The preferred solution includes about 10% by weight to about 30% by weight of a polyvinylpyrrolidone lactic acid-glycolic acid terpolymer, and about 5% by weight to About 30% by weight of urea, about 10% by weight!% To about 30% by weight of chlorite anion, and about 100% by weight of about 30% by weight of polyvinylpyrrolidone homopolymer. 30% by weight to weight / methanol. Methanol in the solution evaporates when a film is formed on the surface of the solution or some other end product is formed. For example, when the composition is exposed to water, chlorine dioxide is released from this preferred composition. Water and water Explain the acid trimer, forming polyvinyl pyrrolidone oligomer, lactic acid in the composition And glycolic acid. Lactic acid and glycolic acid react with water to form hydronium ions. Hydronium ion reacts with chlorite to form dioxide gas and metal salts of lactic acid or glycolic acid. The hydrolysis is described as follows: 〇H〇- (lpvNP —CH.C —〇〇CH p C — 〇- CH. 〇 丨 丨 丨 \ C Η * -C —7 0 C Η-Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

0 HO—PVNP—CH ^ COH several days to ► several weeks V hoch'cLoh

CH-, 0 I 3 II Z HOCH—c—OH " cc 20-This paper size applies to China National Standard (CNS) A4 (210X 297 mm) Exhaust 499 'A7 _______B7 V. Description of the invention (18) 〇 〇

II II cl〇 + M * 0 " CCH20H η- m + o cchoh 2 ch3 The release rate of chlorine dioxide from the composition can be changed by changing the viscosity of the composition when preparing the composition, and changing the concentration of the acid-releasing polymer in the composition. Change the crystallinity of the composition 'and control it by adding a desiccant or wetting agent to the composition to control the release of an emulsified milk from the composition when the composition is exposed to moisture. Compositions of the invention containing amines can form chlorinimines rather than dissolved oxynite anions. When the amine hydrophilic substance is in contact with the hydrophobic acid-releasing polymer, the ‘imine 1¾ • imine is formed. An emulsified gas (C102) is reduced by an amine on an electron to form an ammonium cation and a gas acid equilibrium ion (C1CV). Ammonium cations are quickly converted to imine cations, which lose one proton from adjacent carbon atoms and oxidize with another chlorine dioxide molecule. The mechanism of the above reaction in the water system is described in Rosenbatt et al., J 0 rg. C he m., 2790 (1963); J. Amer. Chem. Soc. Heart 5), 1 158, 1 1 63 (1 967 ) ○ Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. If the nitrosic acid anion and / or imine cation generated by the initial electron transfer of the amine is rapidly compounded and stabilized with a hydrophilic molecule, high chlorine dioxide is converted into chlorine Acid salt. In some formulations, uncomplexed nitrosic acid anions can be consumed by reacting with imine counterions at temperatures above about 60 ° F. Nitrous acid can also disproportionate to gaseous and chlorate. An amine with a high 1)] ^^ is preferred because it reacts more rapidly with chlorine monoxide and is a more effective proton sink, which can maintain the alkaline pH required for the stability of the chlorite ion. This paper size applies to the Chinese National Standard (CNS) A4 (210x297 mm) 505499 A7 B7 V. Description of the invention (19) When water contacts the composition, chlorine dioxide is released by imine chlorite. Hydrolysis of the acid-releasing polymer provides a hydronium cation (h3o +), which reacts with imine chlorite to release chlorine dioxide gas. The decomposition products of the reaction are ammonium (aminium) salts and organic acid salts. These products remain in the composition. It has been found that in some cases, if the composition is exposed to more than about 60. At the temperature of 〇, the imino acid can be decomposed, reducing the chlorite and salt that can be converted into chlorine dioxide; In order to maximize the release of chlorine dioxide from the composition, it has been found that when the hydrophilic substance in the composition is an amine, the chlorite source can provide the composition only when the composition is applied to the surface. After application ... the composition is exposed to chlorine dioxide, which reacts with the amine to form imine chlorite on the spot, or is dissolved in the amine to provide the oxy acid anion. The composition is then activated in the presence of moisture to release chlorine monoxide. During processing, preservation, and application, the composition may be exposed to high temperatures' because the hydrophilic substance does not contain nitrosyl imine or any chlorite anion that may decompose at that temperature. This method also precludes the premature release of chlorine dioxide from the composition. Chlorine dioxide can be provided by the composition through a dioxide gas generator. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs to make amines in the pure form of imine chlorite or in the presence of plasticizers, the amine must be sufficiently rich in Electrons, and the nitrogen of the amine must be locally mobile. The electron-drawing group should be separated from the amine center than at least two methylene groups, so that the dioxide will draw electrons from the amine. Each bond moves around the nitrogen center of the amine required for the formation of ammonium. If the amine is frozen into a glassy matrix, the nitrogen of the amine cannot be moved and the amine cannot be converted to imine chlorite. The glassy amine may be added to the amine by at least about 10% by weight of a plasticizer (such as low molecular weight ammonium amine) to reduce the glass transition temperature below the reaction temperature and be modified to increase mobility. Other suitable plasticizers are polymer technology. The paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 505499 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, A7 -----___ B7 V. Invention Description (20) is well known. Mouth, released a large amount of chlorine dioxide can be stabilized by chlorite anion. The nucleophilic attack of chlorite anion against chlorite anion is unstable. It has been found that the room temperature life of the chlorite anion is substantially prolonged when pure (e.g., Jin Gusong) is present in the substrate containing the imidate. The mechanism by which the acidic counterion is stabilized by an alkoxide is shown below. K 2N'CR2-Op. · ^ NaC, 〇2 where R'2 and R2 are the groups corresponding to the selected amine 'R " is a fluorenyl group. In the absence of water, the imine ions immediately decompose into amine ether and the more stable sodium chlorite. If water is present during the tertiary amine oxidation, the formation of unstable amino alcohols can attack the chlorite anion unless the chlorite anion is effectively complexed with a hydrophilic solvent. After the chlorite anion is solvated, the addition of water is not harmful. Acceptable strong bases for stabilizing chlorites include metal alkoxides such as methanol, ethanol, propanol or sodium butoxide, potassium or calcium, metal oxides such as alumina or oxide pins, metal ions such as Na +, methanol The three aspects of hydrazone, hydrazone, acetic acid salts such as sodium acetate, substituted acetic acid salts, or other substances that can produce a strong base reaction to attack the nitrogen center of imine chlorite. The composition of the invention can be formulated in a variety of ways to suit a wide range of end uses. The composition can be formulated as an extrudate (such as a film or pellet) or powder, using conventional extrusion and spray-drying methods, respectively. The composition of the present invention can be formulated into a powder. Although the powder is not optically transparent, -23-This paper size applies to China National Standard (CNS) A4 (210X297 mm)

1T ----- (Please read the precautions on the back before filling in this hundred C d II-· I-, 505499 ， A7 ————____ Β7 ___ V. Description of the invention (21) Compared with chlorite particles, it provides a low concentration of chlorine dioxide at the release rate. To prepare powder, anhydrous particles are added to the fluidized bed. The acid release polymers, hydrophilic substances, and chlorite anions in the organic detergent are as described above. The solution enters the chamber of the fluidized bed through a small-diameter nozzle and gelatinizes the water-free particles that can impact the flow. When it comes into contact with the flowing particles, the falling liquid solidifies to form an acid release core, with a layer of water-free particles embedded in the outer surface Forming a powder that releases chlorine dioxide. Because the anhydrous particles are hard inorganic substances, the aggregation effect is minimized. The particles can be packed in a dry and sealed container.,---... In the formation of powders that release dioxide gas, the anhydrous particles are delayed Atmospheric moisture catalyzes the release of chlorine dioxide. Suitable anhydrous substances include anhydrous sulfuric acid steel, Tibetan acid medicine, magnesium sulfate, and water-depleted silicone. Other anhydrous particles can also interact with The powder that releases monoxide is post-mixed to delay the release of the dioxide. In addition to forming a powder composition, the composition of the present invention can be formulated in a solvent for casting a film or other methods of use. The composition can be used Well-known thermal dissolution

, Sub-coating, spray coating, curtain coating, dry wax, wet wax, co-extrusion and layers are legally applied to form a film 10, including a water-soluble optically transparent or translucent layer 12 'contains an acid release polymer, a gas acid anion and a hydrophilic = substance' as shown in FIG. 1. The water layer 12 is prepared on the moisture regulating layer 14 on the substrate 16, and then the water layer 18 is cast on the water-soluble layer 12. Moisture adjustment The layers 14 and 18 are water-insoluble water-permeable films, which can prevent the water-soluble layer 12 from degrading in the presence of water. This arrangement can provide chlorine dioxide atmosphere for several days, number 499, .A7 _______ B7______ Invention description (22) weeks or months. The moisture regulating layer can also control the rate of moisture entering the water-soluble layer to control the release of chlorine dioxide when the multilayer composition is activated with moisture. Suitable water-insoluble, water-permeable membranes may consist of poly (ethylene_propylene) or poly (acrylate) copolymers or their ionomers (such as poly (ethylene_propane) sulfonate). Hydroxyethyl methacrylate, oxyethyl methacrylic acid @, that is, a copolymer of at least one hydrophilic component and at least one hydrophobic component, and other water-insoluble water-permeable membranes known in the art are also suitable. The laminated composition of the present invention can maintain the desired chlorine dioxide release rate (mole / second / cm 2 film) in the presence of atmospheric moisture on the surface, adsorb the dioxide on the surface and kill bacteria and other microorganisms. Time required for contamination. Loss from the container or exposed surface can reduce the concentration of chlorine dioxide on the surface because the emulsified chlorine diffuses into the atmosphere. The concentration of monoxide released by the film at a certain time can be calculated, if the leakage rate and absorption rate on the surface are given. Therefore 'after measuring the leak rate, formulate the composition so that it contains a sufficient amount of nitrosate to respond at a rate sufficient to compensate for the leak rate during the desired sustained release. 0 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. Several aspects must be considered in the design of the chlorine dioxide-releasing composition used to control the release and biocidal effect in the container, that is, to control the chlorine dioxide production rate of the release film, and the chlorine dioxide can be reversible (absorbed) or irreversible (reacted). The method is distributed between the phases in the container, and the gas leakage rate from the container. The design of this composition is described in Example 15 of U.S. Patent No. 461/304. The preferred extended release system of the present invention preserves chlorite reservoirs. 'A series of periodic pulsed releases (pUlsed releases) combined with bacteria, viruses, or bacillus. Suspicious time of deficient infection or typical of interested biology. Cultivation time. -25-This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) 505499 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs • A7 B7 V. Invention Description (23) The system design can be optimized to The loss rate of atmospheric chlorine dioxide applied can maintain the desired killing concentration for the necessary time. A typical controlled release multilayer composition includes a water-soluble layer A, each layer being formed from a composition of the invention. Each layer typically has a thickness of about 5 mils and is separated from each other by a water-swellable intermediate layer C. The intermediate layer C may be composed of a wide variety of substances because chlorine dioxide can be equally diffused in the hydrophobic and hydrogen-bonded matrix. Optically transparent or translucent substances include copolymers of at least one hydrophilic monomer or oligomer and at least one hydrophobic monomer or oligomer, polyionic polymers (polyiano.mers) such as protonated and neutralized sulfonated Or phosphorylated oligoenes or polyenes (such as polyethylene, polypropylene), alkyl acrylates, hydroxyethyl methacrylates, methoxyethylfluorenyl acrylates, and copolymers thereof. Fatty substituted polyhydric alcohol phosphates and phosphosilicates and their mixtures with olefinic polymers and oligomers can be used without forming optically transparent compositions. Finely divided anhydrous salts or desiccants can be added to any layer to prevent water-catalyzed reactions to form chlorine dioxide. It has been found that the structure of a multilayer composition, in which the arrangement of each layer is defined by the formula C (ACA) nC (where η is the number of pulses desired), can provide periodic pulses to release high concentrations of chlorine dioxide for weeks or months . The pulse release can be adjusted with the growth, cultivation, and pollution of viruses, molds, maggots, and bacteria. The cycle time and spike concentration of chlorine dioxide can be controlled by layer thickness, chlorite and acid release polymer loading, and water and ion permeability characteristics of the A and C layers. When each layer (ACA)! Is continuously penetrated by water vapor and hydronium ions, pulsed release occurs. For A and C films with a thickness of 5 mils, the pulse release of chlorine dioxide is from about 1 day to the paper size. The Chinese National Standard (CNS) A4 specification (210X 297 mm) is applicable. 505499 Employees' Cooperatives, Central Standards Bureau, Ministry of Economic Affairs Printing A7_B7 V. Description of the invention (24) The change in about 200 days can be achieved by separating the layer a with the intermediate layer C which can support the change of the transport rate of the hydronium ion. The pulse release capability of the multilayer film can be calculated as provided in Example 16 of U.S. Patent No. 08 / 461,304. There are many uses for the composition of the present invention. The water-soluble composition can be used in most environments exposed to moisture. It is required that the composition be protected from degradation or incorporation of the substance as a component with a water-insoluble water-permeable substance. The composition can be used to prevent the growth of molds, fungi, viruses and bacteria on the surface of the substance, deodorize the substance, or inhibit the spread. The surface of the substrate is treated with the composition, which does not release dioxide in the absence of moisture Gas, the treated surface is blasted with water to release chlorine dioxide from the composition into the atmosphere around the surface. The release of chlorine dioxide prevents bacterial, fungal and virus contamination and mold growth on the surface, deodorizes the surface, and inhibits spread. Each component of the composition has a particle size of no more than about 1,000 angstroms. The surface can be treated by the coating, extrusion, lamination, and impregnation methods of the composition of the present invention well known in this art. The treated surface is generally part of the container, part of the substrate placed in the container, or packaging film, or other packaging forms. When the optically transparent composition of the present invention is applied to a substrate, the surface of the substrate can be seen by a film formed on the surface. For example, if the composition is applied to a container board box printed with graphics, the graphics are still clearly visible. The container or substrate may be protected by a coating of the biocidal composition, although the composition is transparent and substantially imperceptible to the consumer. The biocidal atmosphere generated in the container or other packaging can be used to store foods, including monitor berries, raspberries, strawberries, and other ground beef pies (pattie is too secret. The inflammation scale applies the Chinese National Standard (CNS) Α · 4 specifications ( 210X 297 public chrome (please read the precautions of back cloud before filling out this page ▼ Order ^ 05499 'A 7 —-------- B7 _ V. Description of the invention (25), filets) , And other meats, fortified foods, pet foods, dry foods, cereals, grains, or most foods that are susceptible to bacterial contamination or mold growth. It can also protect fertilizer cakes, laundry detergents, stored paper documents, clothes , Coatings, seeds, footwear and their packaging are free of mold growth, mildew, fungi and algae. Medical appliances, devices and supplies, disposable or non-disposable personal care products after use And soil can be sterilized to prevent microbial contamination. Medical, biological or biological hazardous waste in hospitals, laboratories and clinics can also be sterilized to kill microorganisms in the waste. Sports shoes, footweaj and disposable shoes and socks (footweaj) and Slag Packed in a treated container, the odor can also be minimized. Think or photographic equipment and supplies, such as VCRs, videotapes, loudspeakers, cameras, photographic negatives, camera lenses, Lenses and medical monitors in medical devices, and other medical devices can also be treated with the composition or exposed to the composition to prevent mold, mildew, pinworm, and algae (growth. Biocidal compositions can be incorporated to make devices and One of the supplies is a polymer melt (such as a cartridge or a device box) (%)). The box or box may also include a film of the composition attached to the inside. Ministry of Economy Central Standard The biocidal composition printed by the bureau's consumer cooperative can replace the silicone bag commonly used in the shipping and storage of electronic and photographic devices. The composition of the present invention is particularly suitable for use in or incorporated into transparent or translucent products. It can also be applied to the surface of a transparent or translucent substrate to provide biocidal action while maintaining the "see through" of the substrate. For example, if the solution is applied to a transparent plastic food container, consumers can Before buying food, you can see the food in the container; the material; ^ Liquid protection food is free of microorganisms (defective, while keeping the paper size of the consumer at the same time.) '一 —_______ B7 ______ 5. Description of the invention (26) Do not open Container to inspect food. Therefore, the solution can be visually inspected for the substance 'while simultaneously releasing chlorine dioxide to sterilize, deodorize or protect the substance from contamination or spread. When the composition is applied to a transparent surgical bandage, the wound is sterilized with chlorine dioxide And it can be seen by the terminal V that the wound can be inspected without removing the bandages and causing the wound to be exposed to pollution. The Consumer Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs, printed transparent or translucent products that can be processed with the composition of the invention, including transparent packaging such as "clam -shell) "type container, transparent packaging film such as plastic packaging paper for food, disposable tableware, plates and cups, food supply products, food packaging 'food storage containers, and other food packaging, camping, shipping, travel Or portable water filters for treating water during first aid, waste containers or bags for medical or biological hazardous waste. The packaging can be processed to preserve long-term wild foods, such as processed foods stored at room temperature on a "fresh" shelf, including tortillas, cakes or other baked goods, energy bars, Sugar, snack food, etc. Transparent biodegradable and non-decomposable sutures for humans and animals can be treated to prevent infection at the site of use. 'Maintain the sterilization of the sutures during storage, replacing steam, ethylene oxide and r-rays for sutures. Sterilize. Transparent "see through" end bands, band-aids, and surgical dressings can also be treated with the above-mentioned multilayer composition to reduce microbial contamination and infection. The composition of the present invention is also particularly suitable for providing transparent, invisible coatings on products, such as furniture and flooring used in environments susceptible to microbial contamination, such as hospitals. The composition can also be incorporated into or applied to beneficial or heating, ventilating and air-conditioning pipes 'to prevent microbial contamination' to reduce "sick building syndrome" and prevent Legiononella prem〇philiMsi bacteria-29- This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) 505499 • A7 ----——____ B7 V. Description of the invention (27) _ '" ~ ------ The disease of veterans occur. Can use conventional containers, such as cardboard or cardboard boxes, corrugated, non-woven, plastic, foam or polymer multilayer containers, generally used in the "clamshell" type container of the fast food industry, fiber, plastic Or paper bags, seed bags, or waste containers. The treated surface can also be reusable or disposable pads or sheets, including tray coverings, surgical tray covers, woven box tape materials, meat cutting boards, drawer or shelf pads, Sports bag or sports cabinet lockers) inserts, food wrapping paper, paper sheets that separate Chinese food, packaging trays, overpouches (such as those used for packing intravenous bags), fresh fruit separators or box linings, poultry, meat , Absorbent pads for seafood or products, or absorbent layers for diapers. Such pads or sheets are generally made of paper, cellulose, polymers, woven fibers or non-woven materials. This method can also be used to coat the surface of the seed to protect the seed from mold or tadpole growth during storage and to protect the seed against tadpole growth during planting. Printed by the Consumer Cooperative of the Central Waxun Bureau of the Ministry of Economic Affairs. When the coating is activated with water ’, a micro-atmosphere of chlorine dioxide is generated in the soil near the seeds, which inhibits the growth of Pseudomonas sp. Seeds in storage need not be coated for protection, but can be enclosed in a container (tea bag) containing the active substance or coated on a container. The paper impregnated with the composition produces sufficient dioxide to protect the seeds. Although any seed can be protected with a coating, edible seeds (such as corn kernels, sunflower seeds, or soybeans) are still coated for human consumption. Therefore, after seed coating, the coated seeds are ready for planting or human consumption. The optically transparent composition of the present invention can be applied to seeds, so that the appearance of the seeds is not changed by the composition. -30 ~ ^ 5 " Ruler ^ Applicable to Chinese National Standard (〇) \ 5) 8.4 Specifications (210/297 mm) " Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 505499 A7 B7 V. Description of Invention (2S ) Another specific embodiment of the present invention is a method for preventing the growth and / or deodorization of fungi, bacteria, or emblems on a surface, and treating the surface with a composition that does not release chlorine dioxide in the absence of water, And the treated surface is exposed to moisture to release chlorine dioxide from the composition into the atmosphere around the surface. Preferred uses include foot powder to prevent Hong Kong feet and other fungi. The powder can be applied directly to the foot surface or can be incorporated into the shoe insert. The powder can be applied between the cloth cover of the shoe insert and the foam pad, soaked in the foam pad, or impregnated or applied to the heel or upper lining. Dioxide gas generated by the water in the shoes diffuses into the surrounding atmosphere from the composition to kill the inside of the shoes, fungi and deodorization. -The powder can be blended with conventional ingredients such as talc, corn starch, flavor, miconazole nitrate, tolnaftate silica, boric acid, aluminum hydroxide, salicylic acid and cellulose. The powder can also be blended with other ingredients used in bath powders or powders used to treat jock itching. Powder can also be used on carpets to remove the odor of carpets. Ingredients generally incorporated into powdered carpet deodorants or cleaners can be blended with the powders of the present invention. The composition can also be formulated into microcapsules, which will rupture after being stepped on and then activated by moisture. The microcapsules can be dipped into floor mats, showers or bath mats, or can be used to deodorize carpets. The powder can also be wrapped in a spice bag and placed in the ship's environment, such as the ship's deck, sump, or storage area, to prevent mold and mold from growing in these areas. , And another use of the mouthpiece is to provide automatic sterilization packaging, especially for the medical industry. The composition can be applied to pipes, connecting pipes, fittings or other parts.内 # (in dwelllng) catheters, needles, peritoneal dialysis, percutaneous devices, percutaneous access, transvenous bags, colostomy bags, and other medical devices--31 _ -(Please read the precautions on the back before filling out this page) ▼, 1T 505499 A7 B7 V. Description of the invention (29 Accessories 5F can be processed in accordance with the method of the present invention to sterilize the device and prevent insertion of bite infection, sinus traek ) Infections, etc. In addition, the seal on the packaging also = automatic sterilization packaging processed to provide medical devices, equipment, and supplies. The composition of the present invention is expected to kill bacteria on the surface of meat. However, it is "expected to penetrate ground beef Patty. It has been found that the chlorine oxide released by the paper treated with the composition can effectively penetrate the entire thickness of the meatloaf, killing cold-stained E. coli and Salmonella during meat processing. Large intestine cups in cold-stained meat Bacteria 0157: H7 cause death and serious diseases, especially for cooking, fermentation and drying. Meat patUes (typical operating towels), which are sold commercially, are ground, squeezed, and made into cakes. , Separate the paper pieces to prevent money from sticking. After packaging, the minced meat is exposed to chlorine dioxide in the refrigerator for a period of time to kill and inhibit the growth of bacteria. The following examples are used to illustrate the advantages of the present invention. Specific examples and uses are not intended to limit the present invention, except as described in the scope of the following patents. Example 1 Consumers' cooperation with the Central Bureau of Commerce of the Ministry of Economic Affairs, printed polyvinyl pyrrolidone oligomers are made of vinyl Pyrrolidone is prepared in water using free radical initiation to polymerize hydrogen peroxide and ammonia catalysts, such as £.

As described by Barabas, Encyl. Poly. Sci. Eng., YT ^ 1 98 (1 989), 3 g of acetamyl piracetam was dissolved in 7 g of water at 3,000 ml. Hydrogen peroxide and 0.3 ml of concentrated ammonia were polymerized at 55 ^ for 5 hours. The reaction products were polyvinyl pyrrolidone oligomer and 2-pyrrolidone. At the end of the reaction, 2 l of < 30% argon peroxide was added to oxidize the terminal aldehyde or carboxylic acid groups. After the solvent was pumped out and the product was dried at 60 ° C, the hard polyvinylpyrrolidone oligomer was recovered. The standard size was SS, family standard 32-(CNS) A4 size (210X297 mm) ---- 505499 A7

5. Description of the invention (30) The substance 'has a hydroxyl group and a carboxyl group as terminals. The reaction is as follows: Η I Ν \ Z0

CHp = CH 50e C, 1 ° 2

NH ^ OH

r CH ^ -CH2C00H Human V dry at 60 ° c

II

HO—PVNP—CH2CO.H —-— where PVNP represents polyvinylpyrrolidone and has the following formula: rN, p0 [__ | d · J gate where η is 5 to 500. Example 2 A multi-block polyester copolymer of polyethylene vinyl tolridone printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economics was prepared by mixing 0.46 g of polyvinylpyrrolidone oligomer prepared in Example 1, 0.23 G of glycolic acid and -see M lactic acid with 1.5 ml of water and 0.005 g of p-benzoic acid hydration catalyst. The mixture was slowly heated to 120 ° C under a dynamic vacuum at 20 J to remove the esterified water. A terpolymer with a sour stage is recovered. For the esterification of acid end groups, the copolymer is dissolved in Dali-Li methanol and neutralized with ammonia. Alternatively, the acid end groups may be methanolated in excess. The terminal radical (not called 0 terminal group) shown in the following reaction diagram can be used by the polymer dissolved in excess alcohol or by the polymer dissolved in alcohol and neutralized with ammonia.-China -——: 9 49 5 5 A7 B7 31 Description of the invention (formation. The alcohol has the formula ROH, where R is ethyl, n-propyl or isopropyl. The resulting polyvinyl pyrrolidone-polylactate-glycolate (pvnp_PlgA) is polymerized The product contains 34 mol% polyvinyl pyrrolidone, 32 mol% glycolate and 24 mol./lactate. The PVNP-PLGA trimer is prepared as shown below: 0 × HO-PVNP-CH CQH II? H3,9

2 〇H + y H〇CH2C-OH. 2 HoinJc'-OH Toluene acid

0 II H〇 (-PVNP-CH2C-〇AZLCH JCL (1:11) 〇H 2 methanol

HO

〇II -f pvnp-ch2c-〇 ^^ CH2IcL (fH3 〇.L π x 1 ^ c-4〇CH. Example printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 3 PVNP-PLGA trimer prepared according to Example 2 30% by weight in methanol. Each solution was neutralized with diethylamine, and a solution of sodium nitrosene (recrystallized from methanol), urea and polyvinylpyrrolidone (360,000 MW) in methanol (1 〇wt% total solids), so that the total solids mixture contains 51 wt. 0 / 〇1 > ¥ 1 ^ 1) _1 ^ (3 octatrimer, 3 4 wt.%) Polyethylpyrrolidone Weight, 9 weight., Urea and 6 weight Έ:% air-saving private steel. The solution was washed and formed into a film to keep uniform and dispersed and transparent.-34 A paper size applies Chinese National Standard (CNS) A4 specification (2ΐ〇). χ 297 mm) 505499 'A 7 ____________ B7 V. Description of the invention (32) Example 4 A solution of PLGA copolymer in chloroform was added with sodium chlorite (re-added from methanol, "." ε) urea (10% by weight total Solid) and polyvinyl-pyrrolidone (36,000,000 MW) t methanol solution (10% by weight of total solids), the solution remained turbid and was cast into It is separated into a PLGA phase and a polyvinylpyrrolidone_urea · chlorite phase. The present invention can be modified and replaced in various forms. Specific embodiments have been shown in the drawings as examples and have been described in detail herein. It should be understood, however, that it is not intended to limit the invention to the particular form disclosed, but, on the contrary, is intended to include all modifications and equivalents falling within the spirit and scope of the invention as defined by the scope of the patent Printed on a piece of paper with an appropriate degree of paper by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, 4 I ¾ 4 Λ4 SNC i, '

Claims (1)

A B c D 505499 Patent Application No. 085108976 Amended Application for Patent Scope (August 91 1. Slow-release, transparent or translucent biocidal composition for preventing bacterial, fungal and virus pollution and mold growth, containing acid-releasing polymer, hydrophilic substance and chlorite anion, each component of the composition With a particle size of up to L000 Angstroms, the composition is substantially free of water and can release chlorine dioxide when the acid release polymer is hydrolyzed. 2. The composition according to item 丨 of the patent application, wherein the hydrophilic substance is ammonium 'acid-releasing polymer is a terpolymer formed from a polyethylene ether molybdenum phase, lactic acid, and glycolic acid. 3. The composition according to item 1 or 2 of the scope of patent application, wherein the composition is optically transparent. 4. The composition according to item 1 or 2 of the scope of patent application, wherein the composition is a single phase. 5. The composition according to item 1 or 2 of the scope of patent application, wherein the composition is a film. 6. The composition according to item i of the patent application, wherein the hydrophilic substance is ammonium amine, amine or polyalcohol. 7. The composition according to item 2 or 6 of the scope of the patent application, wherein the fermented amine is urea or oligomer amidine. 8. A composition according to item 7 of the scope of patent application, wherein the composition includes polyethylene glycol leaf 1: Luodiangang. 9. The composition according to item 8 of the scope of patent application, wherein the polyethynyl exidoridone has an average degree of polymerization of 1 to 10,000 ^ 10. The composition according to item 7 of the patent scope, wherein the composition includes Hydrophilic or oligoplasticizers are selected from succinamide, methylamine, and N_ This paper size is applicable. China National Standard (CNS) A4 specification (210 X 297 mm) 505499 ------ ~ --- VI. Patent Application Range 8 8 8 8 Αβ c D where the acid release polymer is the acid release polymer and the acid polymer is methylformamide, N-methylacetamide and Isopropylpropylamine _ amidine. Cloth 11. The composition according to item 2 or 6 of the scope of the patent application, wherein the nitrosic acid anion is from imine chlorite, or is selected from alkali metal chlorite, alkaline earth metal chlorite and transition metal ions. Chlorate of chlorite, or protonated primary, secondary, tertiary or quaternary amines. R 12. The composition according to item 1 of the scope of patent application has an average degree of polymerization of 10 to 10,000. 13. The composition according to item 2 of the patent application has an average degree of polymerization of 10 to 10,000. 14. The composition according to item 12 of the scope of the patent application, wherein the acid release polymer is a polymer formed of polyvinyl pyrrolidone, polyvinyl alcohol, polyurethane or polyacrylamide and one or more α-hydroxy acids This thing. ^ 15. According to the composition according to item 14 of the scope of the patent application, the dane tau copolymer is formed from 4 vinylpyrrolidone, lactic acid and glycolic acid. 16. The combination according to item 2 or 15 of the scope of the patent application, wherein each part of the polymer i lactobismuth, glycolic acid, and polyvinylpyrrolidone preferably has an average degree of polymerization of 1 to 5,000. 17. Composition according to item 2 or 16 of the scope of patent application H ^ Initial ′ where the copolymerization has the following formula: -2- This paper size is suitable for domestic use (CNS) A4 specification (210X297 public director) 505499 A8 B8 C8 _ D8 VI. Patent Application Range 0 0 CH 0 / 丨 丨 X / II \ / I II X 〇H〇Z-P '/ NP — c H 2 C — G —CH, C — 0 —X ·-· CH — · C- ^ OR \ / x, _ y Z where PVNP has the following formula: f —CCH, -CH-- — IM / 0 CT. L-π / R is lower alkyl or lower alkyl Esters, n is 5 to 500, x is 1 to 5,000, y is 0 to 5,000, z is 0 to 5,000, and the restriction is that Y or Z must be 1 or more. 18. A composition according to item 1 or 2 of the scope of patent application, wherein at least 1.0 X 1 (T6 mole chlorine dioxide / cm 2 is released from the composition for at least 1 week. 19. According to item 1 or 2 of the scope of patent application A composition of which at least 1.0 X 1 (T6 mole chlorine dioxide / cm 2 is released from the composition for at least 1 month. 20. A composition according to item 1 or 2 of the scope of patent application, wherein at least 1.0 X 10_6 Mo Ear chlorine dioxide / cm 2 is released from the composition for at least 6 months. 21. A trimer having the formula: -3- This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) 505499 505499 AB c D, the scope of patent application where PVNP has the following formula: -Xc: * R is low-burning group or low alkyl ester , Η is 5 to 500, \ is! To 5,000, y is 0 to 5,000,000, 2 is 0 to 5,000, and the restriction is that ah or 2 must be 1 or more. 22 · —a multi-layer composition for providing sustained release of chlorine dioxide, comprising: a water-soluble layer comprising an acid-releasing polymer, a hydrophilic substance and a gas acid anion, the layer is substantially free of water, and each of the layers Cheng Ling has a particle size of up to 1,000 angstroms; ', an upper moisture regulating layer contacts the upper surface of the water-soluble layer, a lower moisture regulating layer contacts the lower surface of the water-soluble layer, and L and one layer are water-insoluble, so Moisture Permeation Moisturizing Layer: Regulates acid polymers, triggering the release of chlorine dioxide from a multilayer composition. 7 interpretation 23, a substance for providing time-pulsed release of chlorine dioxide, comprising: ^ hip combination two or more water-soluble layers, including acid-releasing polymer, nitrogen and chlorite anion, each layer is substantially free of water, Each of the seven properties has a particle size of up to about 1,000 angstroms; and each of the -4 paper ruler _ specifications (21GX297 ^ i7 505499 A BCD VI. Patent application scope Three or more layers of water-insoluble water permeable barrier layer, In order to control the diffusion of water, or the hydrated hydrogen ions produced by the hydrolysis of acid-releasing polymers, diffuse into the water-soluble layer. The arrangement of the layers in the composition is defined by the formula C (ACA) nC, where c is the barrier layer and A is the water-soluble layer. , N is an integer from 1 to 10. 24. A method for preparing a transparent or translucent biocidal composition, comprising: mixing a hydrophilic substance, chlorite, an acid release polymer and an organic solvent to form each component having A mixture with a particle size of up to 1,000 angstroms, the mixture is substantially free of water, and can release dioxide gas when the acid-releasing polymer is hydrolyzed. 25. The method according to item 24 of the scope of patent application, further comprising the preparation of acid-releasing Polymer step: mixing polyvinylpyrrolidone oligomer, lactic acid, glycolic acid, and water; heating the mixture in the presence of an esterification catalyst to form a polyvinylpyrrolidone-lactic acid having an acid terminal group -Glycolic acid terpolymer; the terpolymer is dissolved in an organic solvent; and the terpolymer is neutralized to esterify the acid end group of the terpolymer to form an acid release polymer. 26. According to item 25 of the scope of patent application The method, wherein the S catalyst is p-toluenesulfonic acid. 27. The method according to item 25 of the patent application, wherein the organic solvent is selected from methanol and ethanol. 28. The method according to item 24 of the patent application, and Including the step of applying the composition to the substrate to form a film. 29. The method according to item 28 of the scope of patent application, including the exposure of the film to -5- This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) ) 505499 AB c D 6. The scope of patent application Moisture Explains the steps of acid polymer and release of chlorine dioxide from the composition by water. 30. The method according to item 28 of the patent application scope, wherein the composition is below the group The temperature at which the chlorite decomposes is applied as a viscous hot melt. 31. The method according to item 28 of the scope of patent application, wherein at least 1.0 X 10 · 6 mol of chlorine dioxide / cm 2 is released from the film for 1 week. 32. The method according to item 28 of the scope of patent application, wherein at least 1.0 X HT6 mole of chlorine dioxide / cm 2 is released from the membrane for 1 month. 33. The method according to item 28 of the patent application zone, of which at least 1.0XHT6 Mole chlorine dioxide / cm 2 is released from the film for 6 months. 34 —A method for preparing a transparent or translucent biocidal composition comprising: mixing an amine and an acid release polymer to form a mixture; and exposing the mixture to two Chlorine oxide, which reacts with an amine to form imine chlorite in a mixture. The mixture has a particle size of up to 1,000 angstroms and can release chlorine dioxide when the acid release polymer is hydrolyzed. 35. The method according to item 34 of the scope of patent application, wherein the mixture includes a base, and when exposed to chlorine dioxide, the chlorine dioxide reacts with the amine to form an imine chlorite, which is decomposed to form chlorite in the mixture. Inside. 36. The method according to item 34 of the application, wherein chlorine dioxide is dissolved in the amine to form a chlorite anion in the mixture. -6-This paper is fully compliant with National Standards (CNS) A4 specifications (210X 297 mm) 505499 Λ8 B8 C8 D8 VI. Application for patents ^ 37.-Prevents bacteria, fungi and virus pollution and mold from growing on the surface A method for deodorizing the surface and / or the surface, including treating the surface of the substrate with a composition such as the one in the scope of patent application; and exposing the treated surface to moisture to release chlorine dioxide from the composition into the atmosphere around the surface In order to prevent bacterial, fungal and viral contamination and emblem growth on the surface and / or surface deodorization. 38. A method for preventing bacterial, fungal and viral contamination and mold growth on the surface of a substance and / or deodorization of the substance, including treating the surface of the substance with a composition such as the one in the scope of patent application; and Exposure to moisture to release chlorine dioxide from the composition into the atmosphere surrounding the substance to prevent bacterial, fungal and viral contamination and mold growth on the surface of the substance and / or deodorization of the substance. 39. A method for preventing bacterial, fungal and viral pollution and mold growth on a substance and / or deodorization of a substance, including incorporating the composition as described in the scope of patent application item 1 into the substance; and exposing the substance to water to Chlorine dioxide is released from the composition into the atmosphere surrounding the substance to prevent bacterial, fungal and viral pollution and mold growth on the substance and / or deodorization of the substance. 40. The method according to item 37 of the scope of patent application, wherein the substrate is flooring, furniture, seeds, biodegradable sutures, non-decomposable sutures, end bands, surgical dressing, in-dwelling catheters , Disposable tableware, plates or cups, food supply products, food packaging paper size applicable to the Chinese Standard (CNS) A4 specification (210κ 297 sounds) Application for patent scope paper loaded 'food storage, packaging containers, portable water filter Devices, waste containers or bags for medical or biological hazardous waste, filters for heating, ventilating, and cleaning the soil, shoes (f00twear), or photographs or electronic devices or supplies (supplies). 41. The method according to item 37, 38 or 39 of the scope of patent application, wherein the composition is optically transparent. 42. The method according to claim 37, 38 or 39, wherein the composition is a packaging film. 43. The method according to item 37, 38, or 39 of the scope of the patent application, wherein the composition includes an acid release polymer; a hydrophilic substance and an anion ion of chlorite. 44. The method according to item 38 of the scope of patent application, wherein the substance is seeds' meat, poultry, seafood, fresh food or processed food, disposable tableware, dishes or cups, soil, footwear, or Photographs or electronic devices or supplies. 45. The method according to item 44 of the scope of patent application, wherein the meat, poultry or seafood is patty or filet, bacteria, fungi and virus contamination, and emblem bacteria grow on the surface and the pie or meat slice 46. The method according to item 39 of the scope of patent application, wherein the substance is biodegradable suture, non-decomposable suture, bandage, surgical dressings, in-dwelling catheter, disposable Tableware, plates or cups, food supply products, food wrapping paper, food storage, packaging containers, portable water filters, waste of medical or biological hazardous waste -8- 9 49 05 5 8 8 8 8 A BCD patent application container or bag for heating, ventilation and air conditioning; filter, soil, footwear, or supplies ° or electronic device or supply The paper size applies to China National Standard (CNS) A4 (210X 297 mm)