CN101528035A - Solid biocide composition and sealed biocide article - Google Patents
Solid biocide composition and sealed biocide article Download PDFInfo
- Publication number
- CN101528035A CN101528035A CNA2006800523493A CN200680052349A CN101528035A CN 101528035 A CN101528035 A CN 101528035A CN A2006800523493 A CNA2006800523493 A CN A2006800523493A CN 200680052349 A CN200680052349 A CN 200680052349A CN 101528035 A CN101528035 A CN 101528035A
- Authority
- CN
- China
- Prior art keywords
- solid composite
- acid
- bromide
- solid
- salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The present invention discloses a solid composition for forming chlorine dioxide on demand and a sealed biocide article.
Description
The application requires the U.S. Provisional Patent Application 60/812,632 submitted on June 12nd, 2006 and the priority of the U.S. Provisional Patent Application 60/750,786 submitted on December 16th, 2005, and their whole disclosures are introduced by reference at this.
Technical field
The present invention relates to solid biocidal compositions.Described composition can go out chlorine dioxide by rapid release when contacting with water or moisture.The invention still further relates to sealing biocidal goods.
Background technology
Chlorine dioxide is a kind of yellow green gas of high response, at a large amount of aqueous solution that can be formed with usefulness in such as application such as sterilization, sterilization and stink controls.It is a kind of effective antimicrobial, bleaching agent, and also is accepted as bactericide in the application of urban water and drinking water treatment, cooling tower and food processing day by day.
A few days ago, the rules approval has made chlorine dioxide be accepted day by day in order to reduce pathogene in using such as the food processings such as use in fowl body chilled water tank, ox and cleaning of pig carcass and the crude agricultural product.
Therefore chlorine dioxide has the many advantages that are better than traditional chlorine class biocide because bacterial cell membrane is had better choice.Yet multiple shortcoming has also limited the use of chlorine dioxide, although its excellent security and environmental aspect will make various industries be benefited.
The solid composite of prior art
Description of the Prior Art make the method for chlorine dioxide by dry compositions, as tablet, powder and piece cake.Prior art at large is encompassed in the laid-open U.S. Patents application 2004/0135116, is introduced into by reference at this.
United States Patent (USP) 6,602,442 have described " dry compositions " that contains lithium hypochlorite, sodium chlorite and niter cake.Though find that this mixture is very easily molten and generate chlorine dioxide fast in being added to water the time, because the chlorine that generates discharges a large amount of chlorine greater than its solvability in water, this be undesirable (going in the 2nd hurdle the 55th～56 referring to this patent).In addition, the stability of described drying composite is restricted, especially in high humidity environment.These restrictions make and can't add a large amount of water that this is because excessive generation chlorine will cause the cause of described mixture " flash distillation ".
Laid-open U.S. Patents application 2004/0135116 and United States Patent (USP) 6,699,404 have been described the solid " block " that discharges chlorine dioxide, and it comprises the granular solid matter mixture of ingredients, and the size of described particle is significantly less than the size of described block.Described block forms by the mixture of compression by particulate component, and is essentially big tablet.In the time of in joining liquid water, described tablet discharges chlorine dioxide and free chlorine.The composition of the claimed chlorite of this patent, acid source and free halogen source, its preferred compositions are the sodium salts of sodium chlorite, niter cake and dichlord isocyanurice acid.
Laid-open U.S. Patents application 2005/0249658B2 has described the solid composite of the release chlorine dioxide of the temperature stability with raising.The temperature stability that is improved is released the chlorine agent by adopting two kinds: the combination of DCCNa and hypochlorite provides.This application has also been instructed and adopted pKa is that 2.8～6.0 acidulant can further improve temperature stability.
Halogen strengthens oxidising composition and the activating solvent reactor is being described among laid-open U.S. Patents application 2005/0155936A1 and the 2006/0013751A1.The solid oxidation composition that contains chlorine dioxide has wherein been described.This application has been described use metal chlorite, oxidant and chloride salt and has been generated chlorine dioxide.
U.S. Patent application 2006/0016765A1 has described the composition that is used to generate chlorine dioxide, and said composition contains reactive oxygen compounds and generates the compound (referring to the 23rd section) of chlorine dioxide.Preferred reactive oxygen compounds is the oxyacid compound (referring to the 26th section) of sulfur-bearing.The suitable precursor that is used to generate chlorine dioxide comprises chlorite, alkali metal salt or alkaline-earth halide salt (referring to the 26th section).Described preferred compositions is sodium chlorite, Potassium Monopersulfate and magnesium chloride.This communique is openly listed a lot of metal halides, and these metal halides can be used as " in order to quicken the catalyzer that chlorine dioxide generates ", have wherein listed zinc bromide (referring to the 42nd section).Yet described zinc bromide is use (referring to table 1) in 4.1 o'clock at pH.In addition, it is that 3.7 o'clock calcium bromides are " comparative example C " that this communique has been instructed pH, promptly inoperative, and it also present orange, thereby influenced the result, therefore instruction avoids using calcium bromide (referring to table 1).In addition, this communique is not taught in pH 5～9 and forms hypobromous acid or its plurality of advantages.
Existence is to can be as required generating chlorine dioxide fast in the presence of water or moisture, and do not generate the demand of the solid biocidal compositions of a large amount of chlorine or other undesirable compounds.
Summary of the invention
Goal of the invention
Employing pKa value generates chlorine dioxide as oxide species by chlorite for about 8.6 weak hypohalogenous acids.
Adopting acidity constant is 2.3 * 10
-9Weak hypohalogenous acids generate chlorine dioxide by chlorite.
When the present invention contacts with water or moisture, generate ionic species OCl
-And/or OBr
-
When the present invention contacts with water or moisture, generate ionic species HOCl and/or HOBr.
The employing oxidability is that 1.33 electron-volts weak hypohalogenous acids generates chlorine dioxide as oxide species by chlorite.
Thereby the employing oxidability is 1.44 electron-volts a monopersulfate salt oxidizing agent forms chlorine dioxide by chlorite generation hypohalogenous acids.
PH is 5.0～9.0 in reaction, adopts oxidant, chlorite and bromide salt to generate chlorine dioxide.
Thereby generate dark red brown liquid halogen and generate chlorine dioxide as the intermediate steps that forms chlorine dioxide.Described liquid halogen overweights water and is positioned at the bottom of described reaction vessel.
Generate chlorine dioxide, wherein form liquid halogen, and have 35 atomic number.
Generate chlorine dioxide, wherein before distinctive chlorine dioxide smell, form bromine sample smell.
Generate chlorine dioxide, wherein the acidulant material does not need to keep below 5.0 pH.
The solid biocidal compositions that does not have chlorine sample smell.
In described composition, do not contain the solid biocidal compositions that free halogen discharges compound.Free halogen discharges compound and is defined as: if be added in the water, this compound will produce measurable free halogen.
That only constitute or in molecular formula, do not have a solid biocidal compositions of carbon atom by inorganic chemical.
Employing generates hypobromous acid when contacting with water or seawater any compound generates chlorine dioxide.
Make not the solid biocidal goods that can degrade because of moisture, oxygen and temperature.
Make not the solid biocidal goods that can discharge chlorine dioxide and active oxygen too early because of moisture and temperature.
The structure that can keep the active o content of described composition.
Make not and can overflow or leak the biocidal goods that discharge chlorine dioxide too early because of the accident of moisture, water or other aqueous fluids.
Make the not solid biocidal goods of flavescence too early of described composition or packaging material.
Manufacturing operation safety and do not need directly to be exposed to the solid biocidal goods of skin.
Summary of the invention
When relating in joining water or moisture, an embodiment of the invention generate the solid biocidal compositions of chlorine dioxide fast.
Another embodiment of the present invention relates to the sealing biocidal goods that comprise the biocidal compositions that is sealed between the two-layer high barrier material.The described composition of described sealing biocidal goods has a detailed description hereinafter.
The present invention relates to generate the new chemical approach of chlorine dioxide by solid constituent.It has utilized adopts bromide salt or releases bromide and corresponding hypohalogenous acids product is the oxidative pathway of hypobromous acid.Thereby formed hypobromous acid provides oxidation potential to generate chlorine dioxide by its chlorite immediately.
Usually utilize intermediate reaction species hypochlorous acid chlorite to be converted into chlorine dioxide when in the prior art, generating chlorine dioxide as oxide species.Hypochlorous acid can be formed by a lot of solid constituents, these compositions be generally chlorinated isocyanurates salt, chlorinated hydantoin, alkali metal or alkaline earth metal hypochlorite or with the metal chloride salt of reactive oxygen compounds such as monopersulfate nak response.
In the present invention, when hypobromous acid substitutes as described oxide species, the situation during than use hypochlorous acid, described chlorite takes place in neutral pH (being preferably about 6.5～about 7.5) fast to the conversion of chlorine dioxide.When hypobromous acid generated in the presence of chlorition, chlorine dioxide can be with the high yield rapid release.
Because liquid is brown and overweights water, therefore the reaction of described uniqueness is high-visible, and forms immediately when described composition is added to the water.Described brown liquid accumulates in described reactor bottom, forms the thin layer that covers described solid composite.Described brown liquid is considered to halogen (being bromine).Along with reaction is proceeded, the characteristic yellow of chlorine dioxide can be seen and increase until described brown complete obiteration soon.Less than 5 minutes, described ClO 2 solution was glassy yellow and reaches its Cmax.
The chlorine dioxide releasing effect that this astonishing enhancing occurs it is believed that it is because the pKa value of described two kinds of weak acid there are differences.Than pKa is 7.5 hypochlorous acid, and the pKa that hypobromous acid has is 8.6.At pH is 7.5 o'clock, exists to be less than 50% described active oxidizer HOCl, and Comparatively speaking, HOBr is 94%.The hypochlorous acid approach reaction needed of Cai Yonging uses other acidulant material to transform fast to chlorine dioxide to guarantee chlorition in the prior art.Described hypochlorous acid delivery formulations also generates the free chlorine of failing to be converted into chlorine dioxide in solution.This is to be disadvantageous in the application of totally chlorine free requiring described reaction.
The oxidation of described two kinds of hypohalogenous acids just can conveniently be proved by the chlorine dioxide that relatively uses bromide salt and chloride salt to generate.Than oxidation chlorination sodium under the same conditions, when sodium bromide was oxidized to hypobromous acid in the presence of sodium chlorite, described reaction took place very apace and generates the chlorine dioxide that productive rate improves 2～3 times.Described astonishing result is that the productive rate of raising and the shorter maximum chlorine dioxide of acquisition discharge the required reaction time.
The chlorine dioxide productive rate occur to increase to it is believed that it also is to overweight water and accumulate in the bottom of the close described solid composite response location of described reaction vessel because described reaction intermediate is bromine and hypobromous acid.Observing the skim bromine covers on the described solid reactant that is positioned at described drag.It is believed that these phenomenons help conversion rate and the ratio of described chlorition to chlorine dioxide.Therefore, can think that than the diffusion rate of the chlorine of available technology adopting, the diffusion rate of bromine is slower, this helps the chlorine dioxide of viewed more high yield.
Can consider United States Patent (USP) 6,699,404 prior art illustrates this point.Wherein described the employing tablet and can obtain high conversion, this is because pore structure occurs and generate the anionic saturated substantially acid solution of chlorite.Wherein also described in case described reactants dissolved in solution, chlorite's anion will be very little to the further conversion of chlorine dioxide.
Therefore, do not wish to carry the baby in any theory, it is believed that in the present invention, because hypobromous acid (HOBr) plays a role under neutral pH effectively, the therefore slow diffusion rate of described intermediate bromine and do not need acid solution can help the chlorine dioxide conversion yield to improve and the quickening of speed.
The invention still further relates to the packing of described solid biocidal compositions.Found the stability problem that in many solid composites of the prior art cited above, exists.At United States Patent (USP) 6,699, " block " mentioned in 404 is found under the wet condition (humidity＞40%) and the yellow effect generally occurs.The composition of U.S. Patent application 2006/0016765A1 also is found in the wet environment even easier reaction and observe a large amount of releases of chlorine dioxide.At United States Patent (USP) 6,602, the too early release that the mixture of describing in 442 also shows chlorine dioxide.The invention solves stability problem, and described the method for the useful pot-life of the solid mixture that prolongs the chlorine dioxide precursor material and compression solid mixture.
Description of drawings
Fig. 1 has described the top view of blister package of the present invention;
Fig. 2 has described the end view of blister package of the present invention; With
Fig. 3 has described the end view of belt packing of the present invention.
Embodiment
A. composition of the present invention
Described composition comprises hypobromous acid solid source and chlorite solid source.The active component of described composition is through selecting and existing with such amount, promptly, this amount makes at 25 ℃, when having the concentration of the 1g active component of described composition to measure in the water with every 100ml, the pH of the solution that described composition dissolves is formed in water is about 5～about 9, be preferably about 5.5～about 8.5, more preferably about 6～about 8, and most preferably be about 6.5～about 7.5.Described active component is described hypobromous acid solid source and described chlorite solid source.
Described chlorite solid source comprises alkali metal or alkaline earth metal chlorite, releases bromine compounds and described hypobromous acid solid source comprises oxidant and solid.
Described alkali metal or alkaline earth metal chlorite can be any desirable chlorites, as sodium chlorite, potassium chlorite, lithium chlorite, calcium chlorite, zinc chlorite or magnesium chlorite, and their all commercially available acquisitions.
Described composition contains have an appointment 10%～about 90% hypobromous acid solid source and about chlorite solid source of 10%～about 90% usually.Except as otherwise noted, otherwise all percentages all are based on the percentage by weight of described composition total weight.
Preferred compositions contains 10%～about 90% the sodium chlorite of having an appointment, about 5～about 90% sodium bromide and about 5%～60% Potassium Monopersulfate.More preferably, described composition contains have an appointment 20%～about 60% sodium chlorite, about sodium bromide of 10%～about 40% and about Potassium Monopersulfate of 10%～about 50%.Except as otherwise noted, otherwise all percentages all are based on the percentage by weight of described composition total weight.
Oxidant is essentially acidity usually.Therefore, based on the gross weight of the compound of described oxidant, chlorite and release bromide, the amount of preferred described oxidant be described composition about 5～about 50%, more preferably about 10%～about 40%, and most preferably be about 10%～about 30%.Compound be oxidant be again to discharge under the situation of compound of bromide, then described amount is based on the gross weight of described chlorite and described compound.
The suitable example of oxidant comprises alkali metal and alkaline earth metal persulfate, monopersulfate salt and ammonium persulfate; Alkali metal and alkaline earth metal peroxide, as lithium peroxide, sodium peroxide, potassium peroxide, calper calcium peroxide, zinc peroxide or peromag, urea peroxide, percarbonate, persilicate, perphosphate (comprising slaine), and hydrogen peroxide.Preferred oxidant is a Potassium Monopersulfate.
Other examples of peroxide except that hydrogen peroxide comprise dialkyl peroxide, diacyl peroxide, pre-percarboxylic acids (performed percarboxylic acid), organic and inorganic peroxide and/or hydrogen peroxide.Organic peroxide/the hydroperoxides that are fit to comprise diacyl and dialkyl peroxide, as dibenzoyl peroxide, tert-butyl hydroperoxide, two lauroyl peroxides, dicumyl peroxide and composition thereof.
The peroxy acid that is fit to that is used in the described composition comprises diperoxy dodecanedioic acid (DPDDA), crosses magnesium phthalate, crosses lauric acid, benzylhydroperoxide, diperoxyazelaic acid and composition thereof.
The suitable example of bromide salt comprises alkali metal and alkaline earth metal bromide, as sodium bromide, lithium bromide, potassium bromide, magnesium bromide, ammonium bromide, zinc bromide, calcium bromide and aluminium bromide.
Other examples of bromide salt comprise the naturally occurring mixture that is rich in the salt of bromine usually, as Dead Sea salt (Dead Sea salt) and salt solution (brine).These mixtures contain bromide salt and other common salt, as sodium chloride, potassium chloride, magnesium chloride, zinc chloride, sodium sulphate, potassium sulphate, magnesium sulfate, sodium iodide and potassium iodide etc.The combination of any salt all can be used as described bromide source.
Other exemplary combined comprise: the combination of bromide salt and chloride salt or iodide salt.For example: bromide salt+sodium chloride, potassium chloride, lithium chloride, magnesium chloride, calcium chloride, zinc chloride, ammonium chloride or aluminium chloride.Perhaps for example also can use the iodide salt of sodium, potassium, lithium, calcium, magnesium, zinc, ammonium or aluminium.In the present invention, all these materials can be used singly or in combination.
The described halide Yanyuan that need be used for generating described hypohalogenous acids also may reside in processed water.For example, the seawater that contains 3.5% the salt of having an appointment also can be used as unique source of described halide salts.Described chlorine dioxide release composition can be reduced to two parts: chlorous acid Yanyuan and oxidant.This unpredictable consequence sees when joining sodium chlorite and Potassium Monopersulfate in the seawater (referring to tentative embodiment 6).
The wherein said bromide ion that also has that is fit to is the compound of the release bromide of suitable organic cations salt, such as, but be not limited to ammonium bromide, alkyl ammonium bromide, dialkyl group ammonium bromide, trialkyl ammonium bromide, wherein said alkyl is independently selected from has the 1～straight chain of about 24 carbon atoms or the aliphatic of branched chain, aromatic series or aromatic hydrocarbon group.
The bromide ion that also has that is suitable as the compound that discharges bromide exchanges material.Described bromide ion exchange material is can exchange the material of bromide ion when having more common chloride ion in the aqueous solution, and it typically is the water-insoluble polymerism mineral substrate that is loaded with high bromide ion content in advance.
It is desirable to, described salt should form hypobromous acid with the Potassium Monopersulfate oxidation time.The mixture of some salt or salt will form the combination of hypobromous acid, hypochlorous acid and/or hypoiodous acid.Hypochlorous acid also is strong oxidizer and extra bromide salt is converted into hypobromous acid.
Also can use the other forms of bromine compounds of releasing.Following compound provides free bromine and corresponding hypobromous acid in joining liquid water the time.They also can be used as oxidant to change bromide salt into free bromine.Be fit to provide the liquid bromine that also has element form of free bromine.This liquid bromine is adopting dark liquid under room temperature and normal pressure.
Generate the compound of hypohalite
The compound that generates hypohalite can provide the oxidation potential that sodium chlorite is oxidized to chlorine dioxide.The compound that generates hypohalite also can generate free bromine by bromide ion in the aqueous solution.The suitable combination thing that free operational halogen concentration is provided is the compound that generates hypochlorite or hypobromite.These compounds must be water solubles and to generate the reactive halogen ion in water-soluble back (be HOCl, HOBr, OCl at least in part or fully
-, OBr
-).Therefore, the compound of described generation hypohalite also can think be oxidant also be the bromide releasing agent.
Any following representative source or its mixture comprise alkali metal and alkaline earth metal hypobromite, for example: hypobromous acid lithium, sodium hypobromite, potassium hypobromite, hypobromous acid calcium, hypobromous acid magnesium and hypobromous acid zinc.
The hypochlorite that is fit to produces agent and also has Efficacious Disinfeitant, chlorination polyphosphoric acid trisodium and 12 hydration Efficacious Disinfeitants and composition thereof.
Any following representative source or its mixture comprise alkali metal and alkaline earth metal hypochlorite, and for example: lithium hypochlorite, clorox, postassium hypochlorite, calcium hypochlorite, magnesium hypochlorite and hypochlorous acid zinc also are fit to.
The halogeno-cyanogen lithate
Can use halogeno-cyanogen lithate or its mixture in any following representative source in the present invention, include but not limited to their lithium, sodium, potassium, calcium, magnesium or zinc salt.Tribromo isocyanuric acid, dibromo isocyanurate, monobromo isocyanuric acid, a bromo-dichlord isocyanurice acid, two bromo-, one symclosene and a bromo-one symclosene are used in and are added to the water or generate free bromine and corresponding hypobromous acid thereof when contacting with water.
The compound of the generation hypobromite that is fit to also comprises: 1,3,5-triazines-2,4,6 (1H, 3H, 5H)-and triketone, 1,3-two bromo-, sodium salt (dibromo isocyanurate sodium---CAS#15114-34-8); And 1,3,5-triazines-2,4,6 (1H, 3H, 5H)-and triketone, 1, the 3-dibromo, sylvite (dibromo isocyanurate potassium---CAS#15114-46-2).
The compound of the generation hypobromite that is fit to also comprises: 1,3,5-triazines-2,4,6 (1H, 3H, 5H)-and triketone, 1-bromo-3-chloro-, sodium salt (bromine symclosene sodium---CAS#20367-88-8); And 1,3,5-triazines-2,4,6 (1H, 3H, 5H)-and triketone, 1-bromo-3-chloro-, sylvite (bromine symclosene potassium---CAS#29545-74-2).
1,3,5-triazines-2,4,6 (1H, 3H, 5H)-and triketone, 1,3-two bromo-5-chloro-(bromine symclosene---CAS 666714-66-5); 1,3,5-triazines-2,4,6 (1H, 3H, 5H)-and triketone, 1,3-two bromo-(the dibromo cyanuric acid---CAS#15114-43-9); With a bromo-one chloro-sodium isocyanurate (bromine symclosene one sodium-salt hydrate---CAS#164918-61-0) also be fit to.
The organic compound of the generation hypobromite that other are fit to comprises N-bromo phthalic amide, N, N-dibromodimethyl hydantoin, N, N-dibromo diethyl hydantoins, N, the sweet uracil of N-dibromo dimethyl (N, N-dibromodimethylglycoluracil), dibromo triethylenediamine dihydrochloride and composition thereof.
The compound of the generation hypochlorite that is fit to comprises: trichlorocyanuric acid, dichlorocyanuric acid, a chlorine cyanuric acid, sodium dichloro cyanurate (dihydrate and anhydrous) and potassium dichloroisocyanurate.
The compound of the generation hypochlorite that is fit to also includes, but are not limited to N, N-two chloro-s-triazine triketones, N-chloro phthalic amide, N-two chloro-para toluene sulfonamides, 2,5-N, N-dichloro azo two carbon amidine hydrochlorides, N, N, N, the sweet uracil of N-tetrachloro (N, N, N, N-tetrachloroglycoluracil), N, N-is chlorine dioxide-based, N, N, N-trichloromelamine (N, N-dichloroyl, N, N, N-trichloromelamine), N-chloro-succinimide, methylene-two (1-chloro-5,5-dimethyl ethyl hydantoins), 1,3-two chloro-5-methyl-5-isobutyl group hydantoins, 1,3-two chloro-5-n-pentyl hydantoins, 1,3-two chloro-5, the 5-dimethyl hydantoin, 1,4-two chloro-5,5-diethyl hydantoins, 1-chloro-5, the 5-dimethyl hydantoin, N-chlorine Chloramine, the dichloro succinamide, 1,3,4, the sweet uracil (1 of 6-tetrachloro, 3,4,6-tetrachlorogylcouracil); The sylvite of the sylvite of symclosene and sodium salt, dichlorocyanuric acid and sodium salt; The sylvite and the sodium salt of the sylvite of the sylvite of the sylvite of the sylvite of N-bromination succinimide and sodium salt, N-chlorination succinimide and sodium salt, malonyl imines and sodium salt, phthalimide and sodium salt and naphthalene imines; And their mixture.
Halogenated hydantoin, as 1-bromo-3-chloro-5,5-dimethyl hydantoin (BCDMH), 1-bromo-3-chloro-5-methyl-5-ethyl-hydantoins (BCEMH), 1,3-two bromo-5,5-dimethyl hydantoin (DBDMH), 1,3-two bromo-5-methyl-5-ethyl-hydantoins (DBEMH) is fit to.
Other N-halogen amine that are fit to are trichloromelamine, tribromo melamine, dibromodimethyl hydantoin and dichlorodimethylhydantoin, chlorine bromine dimethyl hydantoin, N-Clofenamide (haloamide), chloramines (halogen amine) and composition thereof.
The compound that also has part chlorination or bromination that is fit to, comprise N-bromo-N-Chlorodimethyl hydantoins, N-bromo-N-chlorine diethyl hydantoins, N-bromo-N-chlorodiphenyl base hydantoins, N-bromo-N, the sweet uracil of N-dichloro-dimethyl (N-bromo-N, N-dichloro-dimethylglycouracil), N-bromo-N-chlorine NaDCC, bromine chlorine triethylenediamine dihydrochloride and composition thereof.
Described composition can contain other compositions as required.For example, if described composition forms tablet, as described in common composition also joins alternatively as adhesive, releasing agent, compression aid, tablet lubricant, sweller, carrier material, filler and surfactant in the composition.
B. structure
Described composition can be by well known by persons skilled in the art such as mixing, blend, granulation, Pelleting, compressing tablet or any method such as extrude and make.Preferable methods is a compressing tablet, and it can carry out according to the method that those skilled in the art were familiar with.Tablet provides the convenient form of the embodiment that shows second embodiment of the present invention, and it comprises and contains the sealing biocidal goods that are sealed in the composition required for protection in the high-barrier packing.
The present invention will further describe with regard to tablet, but the present invention is not limited to this.The stability of the composition of tablet form is decided by two factors: moisture and described tablet are isolated to prevent the too early release of chlorine dioxide.2) prevent that described oxidant (being Potassium Monopersulfate) from discharging active oxygen.
Find, in the mixture of chlorite+oxidant+halide salts (can be any two or three in the described composition) and compressed mixture, stability problem occurs.These problems comprise chlorine dioxide too early release, packaging material flavescence, powder or tablet flavescence, in closed container, generate chlorine dioxide and undesirable around the bleaching of article.When having enough pot-lives the product of (promptly＞1 year) attempting to make, described stability problem is proved to be unacceptable.
Once the various low separated packaging material that was used to encapsulate made tablet has found it is unaccommodated.Particularly low-resistance is every polymer film, and being found in the validity aspect as PE, PET and PVETOH (polyvinyl ethanol, polyvinyl alcohol) all has in various degree deficiency.The thickness of described film and porosity it is believed that it is to fail to prevent the key factor that described tablet decomposes.
When adopting high-barrier packaging material, find described tablet stability be improved significantly.Aluminium is primary high barrier material, and this is owing to it is an impermeable for moisture and gas, and the material that therefore contains aluminium lamination is preferred.Yet, also can use other high barrier materials.Aluminium polymer film from Alcan Corporation is the example of preferred material.
High blocking-up polymer film generally includes the several layer materials that are pressed into compound, and generally includes aluminium lamination.In the following material some are examples of material of lamination film forming: printed article, paper, lacquer, aluminium, PVC, PE, PET, sealant (the coextrusion thing of PE and Surlyn), CERAMIS (laminate that does not contain aluminium), binder, heat seal coating.
Preferably, thus the aluminium lamination press mold of two layers of soft is formed described sealing biocidal goods around tablet heat seal of the present invention.The packing of this type is referred to as the Al-Al packing.Than the tablet of the formation chlorine dioxide of prior art, this is the result that unanticipated arrives, because method for packing before fails to obtain suitable stability.Described film can have all kinds and function, and is called " soft laminate " or " bubble-cap lid ".
A kind of preferred sealed package that is used to wrap up described tablet is called the belt packing, and as shown in Figure 3, it is included in 12 place's heat seals, two diaphragms 10 and 11 together.Tablet composition 2a of the present invention is equipped with in inner space between two diaphragms 10 and 11.Described sealed package provides the environment that prevents that moisture and oxygen from entering around described composition.
Described tablet composition 2a also can be sealed in the bigger packaging body that is called blister package, as illustrated in fig. 1 and 2.These often use in child-resistant packaging.Bigger tablet size (as greater than 20 grams) can be packaged among the bubble-cap more easily.Blister package in Fig. 1 and 2 comprises the paper tinsel layer 3 that uses binder 8 and diaphragm 1 bonding.Described tablet composition 2a is equipped with in space 2 between paper tinsel layer 3 and diaphragm 1.The part of described paper tinsel layer 3 keeps not bonding (shown in 5 places and zone 6), with the fin (flap) that is provided for opening described blister package.Described blister package can have as the perforation shown in 7, can separate single bubble-cap.
Find yet that the environmental condition in manufacturing and packaging operation can influence the stability of described sealing compositions.Environmental temperature and humidity are most important factors.Relative moisture is preferably and remains below about 15%RH, and temperature is preferably and is lower than about 80 °F.Most preferably, it is about 10% that described relative moisture should be lower than, and temperature is lower than 70 °F.
For example, described packaging operation can carry out on automatic double-deck aluminium packing machine.Two volume soft layer jewelling films can be sent described machine to, and the temperature that seals around described tablet is 150～200 °F.The double-layer seal lamination aluminium film band that is packaged with tablet can be cut into 4 inches * 3 inches band.Described then band can be placed in the carton of tape label.
Embodiment
Test portion
All concentration readings are carried out on Hach DR 2500 spectrometers.
Embodiment 1
Sodium chlorite 1.0 grams
Potassium Monopersulfate (KMPS) 1.5 grams
Sodium bromide 0.9 gram
Join in the 300ml water.The result is after 5 minutes, at pH 6.5,1400 mg/litre (1400ppm) chlorine dioxide.
Sodium chlorite 1.0 grams
KMPS 1.2 grams
Sodium bromide 0.9 gram
Join in the 300ml water.The result is after 5 minutes, at pH 7.0,1050ppm.
Comparative examples A
Sodium chlorite 1.0 grams
KMPS 1.2 grams
Sodium chloride 0.7 gram
Join in the 300ml water.The result is after 5 minutes, at pH 7.0,420ppm.In order to use sodium chloride to obtain more high yield, pH will have to be reduced to below 4, to obtain comparatively speaking suitable with sodium bromide productive rate.
Sodium chlorite 1.0 grams
Bromine symclosene sodium 0.5 gram
Join in the 300ml water.The result is after 15 minutes, at pH 7.0,350ppm.
Embodiment 4
Sodium chlorite 1.0 grams
Bromine symclosene sodium 0.5 gram
Sodium bromide 0.5 gram
Join in the 300ml water.The result is after 15 minutes, at pH7.0, and 400ppm.
Sodium chlorite 1.0 grams
Potassium Monopersulfate 1.2 grams
Join in the 300ml fresh seawater.The result is after 20 minutes, at pH 6.0,600ppm.
Embodiment 6
Sodium chlorite 1.0 grams
Ammonium bromide 0.5 gram
Potassium Monopersulfate 1.2 grams
Join in the 300ml water.The result is after 5 minutes, at pH6.5, and 900ppm.
Embodiment 7
Sodium chlorite 1.0 grams
Potassium Monopersulfate 2.0 grams
Sodium bromide 0.9 gram
Join in the 300ml water.Form peony and maintenance immediately above 2 hours.Detect the characteristic odor of bromine.Described solution does not produce any visible or measurable chlorine dioxide.Think that pH is too low owing to there are a large amount of Potassium Monopersulfates, therefore impel reaction to form bromine.
Comparative example B
This comparative example B adopts the embodiment 4 of laid-open U.S. Patents application 2006/0016765.In this embodiment 4, in being less than every 100ml water, measure during 0.07g, at pH 4.1, in composition, use zinc bromide.Because the amount of OXONE (Potassium Monopersulfate) is present in the described composition with high percentage (72.6%), makes that thus pH is lower.The 2.6g tablet is dissolved in 3.785 premium on currency, and this changes the 0.07g that has an appointment in every 100ml water into.Because described tablet contains non-active ingredient, described active component reality exists with the amount that is less than 0.07g in every 100ml water.If the concentration of described active component is increased to 1g among every 100ml, pH even will be lower than 4.1.
On the contrary, embodiments of the invention provide scope at 6～7 pH when the 1g active component is dissolved in the water of 100ml.
Embodiment 8
Preparation has the tablet of following prescription as mentioned above:
Sodium chlorite 31%
Sodium bromide 28%
Potassium Monopersulfate 16%
Sodium sulphate 8%
Dolomol 7%
Test definite biocidal to render a service: saccharomycete (Saccharomyces), Zygosaccharomyces bacterium (Zygosaccharomyces), British mold (Brettanomyces) to following three kinds of microorganisms.The result has proved that described three kinds of microorganisms are had effective biocidal effect.
Make solution by a slice tablet is dissolved in 1 liter of deionized water, and test is to the effectiveness of microorganism.
Described biocidal test is by Modesto, and the G3 Enterprises of CA carries out.The result is presented in table 1～3.
Table 1
Table 2
Table 3
Advantage of the present invention
Generate chlorine dioxide fast in neutral pH.
The present invention avoids using dangerous chlorine-releasing compound, as hypochlorite and chlorinated isocyanuric acid salt, therefore, does not generate free chlorine in solution.
The present invention avoids adding the acidulant material in described composition, therefore improved stability and reduced corrosivity.
Generate chlorine dioxide fast and do not have remnants with high yield.
Than the composition of describing before, composition of the present invention has better security performance.Sodium dichloro cyanurate has the NFPA scoring of (3-1-2) and is categorized as oxidant by DOT.Potassium Monopersulfate has the NFPA scoring of (3-0-1) and is categorized as the corrosivity solid by DOT.
Different with the composition of describing before, composition of the present invention does not have chlorine sample smell.
High yield discharges chlorine dioxide and can only use two kinds of precursors to realize, this is different from most of preparations that there is precursor compound more than three kinds in needs.
Though with reference to the embodiment of the present invention for required protection the present invention is had been described in detail; but it will be readily apparent to one skilled in the art that and under the situation of the spirit and scope that do not deviate from the present invention for required protection, to make various modifications and improvement the present invention.
Claims (44)
1. solid composite that is used for generating as required chlorine dioxide, described composition comprises: the hypobromous acid solid source; With the chlorite solid source, wherein said hypobromous acid solid source and the existing amount of chlorite solid source make at 25 ℃, when having the concentration of the 1g active component of described composition to measure in the water with every 100ml, the pH of the solution that described composition dissolves is formed in water is 5～9, and described active component is the gross weight of described hypobromous acid solid source and described chlorite solid source.
2. solid composite as claimed in claim 1, wherein said chlorite solid source comprises alkali metal or alkaline earth metal chlorite, and described hypobromous acid solid source comprises oxidant and bromide salt.
3. solid composite as claimed in claim 2, wherein said oxidant are at least a oxidant that is selected from the group of being made up of alkali metal and alkaline earth metal persulfate, monopersulfate salt, alkali metal and alkaline earth metal peroxide, urea peroxide, percarbonate, persilicate, perphosphate and hydrogen peroxide.
4. solid composite as claimed in claim 2, wherein said bromide salt comprise at least a bromide salt that is selected from the group of being made up of alkali metal and alkaline earth metal bromide.
5. solid composite as claimed in claim 2, wherein said bromide salt comprise and are selected from least a of the group be made up of sodium bromide, lithium bromide, potassium bromide, calcium bromide, magnesium bromide, ammonium bromide and aluminium bromide.
6. the solid composite that generates chlorine dioxide as required as claimed in claim 1, wherein said chlorite solid source comprises alkali metal or alkaline earth metal chlorite, and described hypobromous acid solid source comprises the solid chemical compound of oxidant and release bromide.
7. solid composite as claimed in claim 6, the solid chemical compound of wherein said release bromide comprise and being selected from by uride in bromination hydantoins, the bromine chloroethene---group that BCDMH, dibromodimethyl hydantoin, bromination isocyanurate and bromine symclosene are formed at least a.
8. solid composite as claimed in claim 2, wherein said oxidant comprise and are selected from least a of the group be made up of dialkyl peroxide, diacyl peroxide, pre-percarboxylic acids, organic and inorganic peroxide, hydroperoxides, organic peroxide, hydroperoxides, diacyl and dialkyl peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide, two lauroyl peroxides, dicumyl peroxide and composition thereof.
9. solid composite as claimed in claim 2, this solid composite further comprise at least a peroxy acid that is selected from the group of being made up of diperoxy dodecanedioic acid (DPDDA), mistake magnesium phthalate, mistake lauric acid, benzylhydroperoxide, diperoxyazelaic acid and composition thereof.
10. solid composite as claimed in claim 2, wherein said bromide salt comprise sea salt or the salt solution that is rich in bromine.
11. solid composite as claimed in claim 6, the compound of wherein said release bromide comprises and is selected from least a of the group be made up of ammonium bromide, alkyl ammonium bromide, dialkyl group ammonium bromide, trialkyl ammonium bromide that wherein said alkyl is independently selected from has the 1～straight chain of about 24 carbon atoms or the aliphatic of branched chain, aromatic series or aromatic hydrocarbon group.
12. solid composite as claimed in claim 6, the compound of wherein said release bromide comprise bromide ion exchange material.
13. solid composite as claimed in claim 1, this solid composite further comprises the hypochlorous acid source.
14. solid composite as claimed in claim 1, this solid composite further comprises the hypoiodous acid source.
15. solid composite as claimed in claim 1, wherein said hypobromous acid source comprises the hypobromite compound.
16. comprising, solid composite as claimed in claim 15, wherein said hypobromite compound be selected from least a by the group of forming such as alkali metal such as hypobromous acid lithium, sodium hypobromite, potassium hypobromite, hypobromous acid calcium, hypobromous acid magnesium, hypobromous acid zinc and alkaline earth metal hypobromite and composition thereof.
17. further comprising at least a hypochlorite that is selected from the group of being made up of Efficacious Disinfeitant, chlorination polyphosphoric acid trisodium and 12 hydration Efficacious Disinfeitants and composition thereof, solid composite as claimed in claim 1, this solid composite produce agent.
18. further comprising, solid composite as claimed in claim 1, this solid composite be selected from least a by the group of forming such as alkali metal such as lithium hypochlorite, clorox, postassium hypochlorite, calcium hypochlorite, magnesium hypochlorite, hypochlorous acid zinc and alkaline earth metal hypochlorite and composition thereof.
19. solid composite as claimed in claim 1, wherein said hypobromous acid source comprises the salt of bromo cyanuric acid or described bromo cyanuric acid.
20. comprising, solid composite as claimed in claim 19, the salt of wherein said bromo cyanuric acid or described bromo cyanuric acid be selected from least a of the group formed by tribromo isocyanuric acid, dibromo isocyanurate, monobromo isocyanuric acid, a bromo-dichlord isocyanurice acid, two bromo-, one symclosene and a bromo-one symclosene.
21. solid composite as claimed in claim 1, wherein said hypobromous acid source comprises and is selected from least a of the group be made up of the compound that generates hypobromite that the compound of described generation hypobromite comprises 1,3,5-triazine-2,4,6 (1H, 3H, 5H)-triketone, 1,3-two bromo-, sodium salt (dibromo isocyanurate sodium---CAS#15114-34-8); 1,3,5-triazines-2,4,6 (1H, 3H, 5H)-and triketone, 1, the 3-dibromo, sylvite (dibromo isocyanurate potassium---CAS#15114-46-2); 1,3,5-triazines-2,4,6 (1H, 3H, 5H)-and triketone, 1-bromo-3-chloro-, sodium salt (bromine symclosene sodium---CAS#20367-88-8); 1,3,5-triazines-2,4,6 (1H, 3H, 5H)-and triketone, 1-bromo-3-chloro-, sylvite (bromine symclosene potassium---CAS#29545-74-2); 1,3,5-triazines-2,4,6 (1H, 3H, 5H)-and triketone, 1,3-two bromo-5-chloro-(bromine symclosene---CAS 666714-66-5); 1,3,5-triazines-2,4,6 (1H, 3H, 5H)-and triketone, 1,3-two bromo-(the dibromo cyanuric acid---CAS#15114-43-9); With a bromo-one chloro-sodium isocyanurate (bromine symclosene one sodium-salt hydrate---CAS#164918-61-0).
22. solid composite as claimed in claim 1, wherein said hypobromous acid source comprises and being selected from by N-bromine phthalic amide, N, N-dibromodimethyl hydantoin, N, N-dibromo diethyl hydantoins, N, the organic compound of at least a generation hypobromite of the group that the sweet uracil of N-dibromo dimethyl, dibromo triethylenediamine dihydrochloride and composition thereof are formed.
23. solid composite as claimed in claim 1, this solid composite further comprises and is selected from by trichlorocyanuric acid, dichlorocyanuric acid, one chlorine cyanuric acid, sodium dichloro cyanurate (two hydrations and anhydrous), potassium dichloroisocyanurate, N, N-two chloro-s-triazine triketones, N-chlore O-phthalic acid acid amides, N-two chloro-para toluene sulfonamides, 2,5-N, N-dichloro azo two carbon amidine hydrochlorides, N, N, N, the sweet uracil of N-tetrachloro, N, N-is chlorine dioxide-based, N, N, the N-trichloromelamine, N-chloro-succinimide, methylene-two (1-chloro-5,5-dimethyl ethyl hydantoins), 1,3-two chloro-5-methyl-5-isobutyl group hydantoins, 1,3-two chloro-5-n-pentyl hydantoins, 1,3-two chloro-5, the 5-dimethyl hydantoin, 1,4-two chloro-5,5-diethyl hydantoins, 1-chloro-5, the 5-dimethyl hydantoin, N-chlorine Chloramine, the dichloro succinamide, 1,3,4, the sweet uracil of 6-tetrachloro, the sylvite of symclosene and sodium salt, the sylvite of dichlorocyanuric acid and sodium salt, the sylvite of trichlorocyanuric acid and sodium salt, the sylvite and the sodium salt of N-bromination succinimide, the sylvite and the sodium salt of N-chlorination succinimide, the sylvite of malonyl imines and sodium salt, the sylvite of phthalimide and sodium salt, the compound of at least a generation hypochlorite of the group that the sylvite of naphthalene imines and sodium salt and composition thereof are formed.
24. solid composite as claimed in claim 1, this solid composite comprises at least a halogenated hydantoin.
25. solid composite as claimed in claim 1, this solid composite comprises and is selected from by such as 1-bromo-3-chloro-5,5-dimethyl hydantoin (BCDMH), 1-bromo-3-chloro-5-methyl-5-ethyl-hydantoins (BCEMH), 1,3-two bromo-5,5-dimethyl hydantoin (DBDMH), 1, at least a halogenated hydantoin of the group that 3-two bromo-5-methyl-5-ethyl-hydantoins (DBEMH) and composition thereof etc. are formed.
26. solid composite as claimed in claim 1, this solid composite comprise at least a N-halogen amine that is selected from the group of being made up of trichloromelamine, tribromo melamine, dibromodimethyl hydantoin, dichlorodimethylhydantoin, chlorine bromine dimethyl hydantoin, N-Clofenamide (haloamide), chloramines (halogen amine) and composition thereof.
27. solid composite as claimed in claim 1, this solid composite comprises and is selected from by comprising N-bromo-N-Chlorodimethyl hydantoins, N-bromo-N-chlorine diethyl hydantoins, N-bromo-N-chlorodiphenyl base hydantoins, N-bromo-N at least a part chlorination of the group that the sweet uracil of N-dichloro-dimethyl, N-bromo-N-chlorine NaDCC, bromine chlorine triethylenediamine dihydrochloride and composition thereof are formed and the compound of bromination.
28. solid composite as claimed in claim 1, this solid composite comprises the combination of bromide salt and chloride salt or iodide salt.
29. solid composite as claimed in claim 28, wherein said chloride salt or iodide salt comprise sodium chloride, potassium chloride, lithium chloride, magnesium chloride, calcium chloride, zinc chloride, ammonium chloride, aluminium chloride and composition thereof.
30. solid composite as claimed in claim 2, this solid composite comprises: the sodium chlorite of about 10 weight %～about 90 weight %; The sodium bromide of about 10 weight %～about 90 weight %; With the Potassium Monopersulfate of about 5 weight %～about 90 weight %, described percentage by weight is based on the gross weight of described composition.
31. solid composite as claimed in claim 2, described solid composite comprises: the sodium chlorite of about 20 weight %～about 60 weight %; The Potassium Monopersulfate of about 10 weight %～about 60 weight %; Sodium bromide and/or ammonium bromide with about 10 weight %～about 40 weight %.
32. solid composite as claimed in claim 2, wherein said bromide salt are the bromide salt except that calcium bromide and zinc bromide.
33. solid composite as claimed in claim 1, wherein said hypobromous acid solid source and the existing amount of chlorite solid source make at 25 ℃, when having the concentration of the 1g active component of described composition to measure in the water with every 100ml, the pH of the solution that described composition dissolves is formed in water is 6～8.
34. solid composite as claimed in claim 1, wherein said hypobromous acid solid source and the existing amount of chlorite solid source make at 25 ℃, when having the concentration of the 1g active component of described composition to measure in the water with every 100ml, the pH of the solution that described composition dissolves is formed in water is 6.5～7.5.
35. solid composite as claimed in claim 1, wherein said chlorite solid source comprises sodium chlorite, and described hypobromous acid solid source comprises the bromo cyanurate.
36. solid composite as claimed in claim 35, wherein said bromo cyanurate is the bromine chlorocyanurate.
37. solid composite as claimed in claim 1, wherein said composition comprise about 10%～about 90% described hypobromous acid solid source and about 10%～about 90% described chlorite solid source.
38. sealing biocidal goods, sealing biocidal goods comprise the tablet that is sealed in the high-barrier packing, and described tablet contains the described composition of claim 2.
39. sealing biocidal goods as claimed in claim 38, wherein said tablet is sealed in the blister package.
40. sealing biocidal goods as claimed in claim 38, wherein said tablet are sealed in the belt packing.
41. generate the method for chlorine dioxide, described method comprises: in the described composition of claim 2, add water, make the hypobromous acid and the sodium chlorite that are produced react and the generation chlorine dioxide.
42. method as claimed in claim 41, this method further are included in the step that generates hypobromous acid in the water.
43. further comprising, method as claimed in claim 41, this method utilize hypochlorous acid bromide salt to be converted into the step of hypobromous acid.
44. method as claimed in claim 41, this method further comprise sodium chlorite and Potassium Monopersulfate are joined step in the seawater.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US75078605P | 2005-12-16 | 2005-12-16 | |
| US60/750,786 | 2005-12-16 | ||
| US60/812,632 | 2006-06-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101528035A true CN101528035A (en) | 2009-09-09 |
Family
ID=41095648
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006800523493A Pending CN101528035A (en) | 2005-12-16 | 2006-12-15 | Solid biocide composition and sealed biocide article |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101528035A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104370353A (en) * | 2014-11-27 | 2015-02-25 | 田颖 | Novel disinfection and water purification powder |
| CN109122715A (en) * | 2017-06-27 | 2019-01-04 | 德州绿能水处理科技有限公司 | Potassium hydrogen peroxymonosulfate compound disinfectant |
| CN109819999A (en) * | 2019-04-04 | 2019-05-31 | 开封恩科生物科技有限公司 | Chlorine dioxide solid releasing agent and preparation method thereof |
-
2006
- 2006-12-15 CN CNA2006800523493A patent/CN101528035A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104370353A (en) * | 2014-11-27 | 2015-02-25 | 田颖 | Novel disinfection and water purification powder |
| CN109122715A (en) * | 2017-06-27 | 2019-01-04 | 德州绿能水处理科技有限公司 | Potassium hydrogen peroxymonosulfate compound disinfectant |
| CN109819999A (en) * | 2019-04-04 | 2019-05-31 | 开封恩科生物科技有限公司 | Chlorine dioxide solid releasing agent and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20080299161A1 (en) | Solid Biocide Composition and Sealed Biocide Article | |
| US20070029263A1 (en) | Multi-functional oxidizing composition | |
| US7204931B2 (en) | Stable composition with enhanced biocidal and virucidal effect | |
| US6171485B1 (en) | Process for producing a chlorine dioxide-containing disinfectant solution for water treatment | |
| EP1315422B1 (en) | Production of concentrated biocidal solutions | |
| US8252200B2 (en) | Coated calcium hypochlorite composition | |
| US20090232903A1 (en) | Biocide compositions | |
| MX2008011037A (en) | Chlorine dioxide based cleaner/sanitizer. | |
| US7993545B2 (en) | Tablet composition for the in-situ generation of chlorine dioxide for use in antimicrobial applications | |
| JP2001522773A (en) | Method and apparatus for producing an aqueous solution containing chlorine dioxide | |
| JP2009523708A5 (en) | ||
| US8017032B2 (en) | Tablet composition for the in-situ generation of chlorine dioxide for use in antimicrobial applications | |
| WO2009091854A1 (en) | Stable chlorine dioxide tablet | |
| CN101528035A (en) | Solid biocide composition and sealed biocide article | |
| MXPA03002917A (en) | Composition for generating chlorine dioxide. | |
| EP1786266B1 (en) | Concentrated aqueous bromine solutions and their preparation | |
| AU2006320788B2 (en) | Solid biocidal compositions and methods of using the same | |
| CA2545338C (en) | Multi-functional oxidizing composition | |
| US5575945A (en) | Chemical treatment system for producing odor and taste-free potable water | |
| CA3050292C (en) | Use of an encapsulated chlorine bleach particle to reduce gas evolution during dispensing | |
| US7087251B2 (en) | Control of biofilm | |
| US20110027330A1 (en) | Tablet composition for the in-situ generation of chlorine dioxide for use in antimicrobial applications | |
| US20240156099A1 (en) | Composition for generation of chlorine dioxide for use as sanitizer | |
| Sotier | The Role of Chlorine Germicides |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20090909 |