Created

Sep 13, 2023 12:23 AM

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patent

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Summary

This document is a patent for a stable composition of HOCl, and includes information on its production and uses.

Key Points

- A composition of hypochlorous acid (HOCl) and its uses are described in this patent. - The composition can be used for medical and veterinary purposes, as well as for sterilizing materials and objects. - The patent also describes methods for producing the composition. - The composition is stable and can be used to treat biofilms and wounds. - The patent also mentions the use of the composition in preventing microbial growth and treating skin trauma.

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https://patents.google.com/patent/CN103501605B/en?q=(stabilizing+HOCl)&oq=stabilizing+HOCl

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This is from CN103501605B in 2015 at https://patents.google.com/patent/CN103501605B/en?q=(stabilizing+HOCl)&oq=stabilizing+HOCl

Keywords

Keywords: stable composition, HOCl, production, uses, patent

Created time

Sep 13, 2023 12:23 AM

A stable composition of HOCl, processes for its production and uses thereof Download PDF

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Publication number CN103501605B CN201280012861.0A CN201280012861A CN103501605B CN 103501605 B CN103501605 B CN 103501605B CN 201280012861 A CN201280012861 A CN 201280012861A CN 103501605 B CN103501605 B CN 103501605B Authority Prior art keywords 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.) Expired - Fee Related

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Bionical Health Industry Co Ltd

Biomimetics Health Industries Ltd

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Bionical Health Industry Co Ltd

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Priority claimed from GB1104180.3 external-priority

2012-03-08 Application filed by Bionical Health Industry Co Ltd filed Critical Bionical Health Industry Co Ltd

2014-01-08 Publication of CN103501605A publication Critical patent/CN103501605A/en

2015-07-22 Application granted granted Critical

2015-07-22 Publication of CN103501605B publication Critical patent/CN103501605B/en

Status Expired - Fee Related legal-status Critical Current

2032-03-08 Anticipated expiration legal-status Critical

Classifications

A—HUMAN NECESSITIES
A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group

A—HUMAN NECESSITIES
A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds

A—HUMAN NECESSITIES
A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
A61K33/00—Medicinal preparations containing inorganic active ingredients
A61K33/20—Elemental chlorine; Inorganic compounds releasing chlorine

A—HUMAN NECESSITIES
A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
A61K45/00—Medicinal preparations containing active ingredients not provided for in groups A61K31/00 - A61K41/00
A61K45/06—Mixtures of active ingredients without chemical characterisation, e.g. antiphlogistics and cardiaca

A—HUMAN NECESSITIES
A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
A61L2/0005—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor for pharmaceuticals, biologicals or living parts
A61L2/0082—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor for pharmaceuticals, biologicals or living parts using chemical substances
A61L2/0088—Liquid substances

A—HUMAN NECESSITIES
A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
A61L2/18—Liquid substances or solutions comprising solids or dissolved gases

C—CHEMISTRY; METALLURGY
C01—INORGANIC CHEMISTRY
C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
C01B11/00—Oxides or oxyacids of halogens; Salts thereof
C01B11/04—Hypochlorous acid
C01B11/06—Hypochlorites

C—CHEMISTRY; METALLURGY
C01—INORGANIC CHEMISTRY
C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
C01B11/00—Oxides or oxyacids of halogens; Salts thereof
C01B11/04—Hypochlorous acid
C01B11/06—Hypochlorites
C01B11/064—Hypochlorites of alkaline-earth metals

C—CHEMISTRY; METALLURGY
C01—INORGANIC CHEMISTRY
C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
C01B11/00—Oxides or oxyacids of halogens; Salts thereof
C01B11/04—Hypochlorous acid
C01B11/06—Hypochlorites
C01B11/068—Stabilisation by additives other than oxides, hydroxides, carbonates of alkali or alkaline-earth metals; Coating of particles; Shaping; Granulation

Abstract

A stable antimicrobial aqueous hypochlorous acid solution that retains its activity for at least three months and can be provided with high levels of hypochlorous acid (more than 500ppm), the aqueous hypochlorous acid composition having low chloride concentrations (maximum chloride levels of 1:3 chloride to hydrochlorous acid) and a pH between 3.5 and 7.0 to stabilise the composition without the need for additional stabilisers. A solid composition is also provided for producing the stable solution.

Description

The stable composition of HOCl, it produces and using method

The present invention relates to stable hypochlorous acid (HOCl), its production method and the various application for the described composition of use.

Fully set up in this area and use sterilizing and antiseptic solution except degerming, virus or fungal contamination.Sterile solution, disinfectant and bleaching agent are routinely for providing aseptic or the environment of sterilization.Such as wherein patient and/or environment to infect and cross-infection sensitivity environment (such as medical treatment, animal doctor, agricultural, food processing and dentistry) in, such application particular importance.Be used for surgical intervention or human or animal's health when equipment other get involved and crop process, fresh food produce and water treatment time, need pathogene to destroy.

Recognize, due to the common environmental infection (such as methicillin resistant Staphylococcus aureus (MRSA that hospital brings, Methicillin-resistant Staphylococcus aureus) and Clestridium difficile (Clostridium difficile)) raising of incidence, provide aseptic and the environment of sterilization and equipment have become more important.

Hypochlorous acid (HOCl) has been known as the effective antimicrobial of activity with directed toward bacteria, virus, fungi and spore in the art.It is particularly advantageous for medical treatment, animal doctor, agricultural and commercial Application, because it is not containing oral toxicity, skin sensitivity or stimulation (comprising Ocular irritation) and for non-mutagenic.

But, there is many problems relevant to using hypochlorous acid.Particularly, the solution of HOCl is very unstable, has the short half life period of about 48 hours.Therefore, solution loses their antimicrobial acivity fast, therefore loses their effect.The current solution of this problem is the electrolysis utilizing saline solution, and original position prepares HOCl solution as required.This needs field apparatus to prepare solution, obtains the nonactive lean solution that the high cost relevant to preparing HOCl solution is relevant with the half life period short with it.Electrolysis is also a kind of slow and expensive method, and it may change, and is difficult to (if not can not) and comes into force.

Oxidant (such as chlorine, bromine and chlorine dioxide) is widely used as highly effective antimicrobial, but shortcoming is extended storage stability in aqueous solution.When chlorine and bromine, pH also has material impact to general active species, and it affects both effect and bleaching properties.

United States Patent (USP) 2,438, relates to the stable of hypochlorite solutions 781 (on March 30th, 1948) and quotes the product be suitable for used as stabilizers in the solution of alkali metal hypochlorite, because herein is provided the shelf life of prolongation.Based on weight, prove that benzene N sodium-sulfonamide provides maximum stability.The antimicrobial efficacy with various degree that stable halogen forms like this produces certain limit instead of the halogen of the combination of microorganism thing class clearly limited.

For the control of microorganism and bleaching, at United States Patent (USP) 3,749, the solution using buffer to carry out stable N-halogenated compound was described in 672 (on July 31st, 1973), wherein by adding hypochlorite in some N-hydrogen compound (such as sulfamic acid), preparation pH is the aqueous solution of 4-11.PH stablized by buffer is 4-11, and in alkaline pH, dominant class is hypochlorite anion instead of highly effective hypochlorous acid.

United States Patent (USP) 6,162, relate to the aqueous solution of the source of single positive chlorion (unipositivechloride ion), chlorine stabilizing agent, acid buffer agent 371 (on December 19th, 2000), with stable pH for 2.0-6.5, wherein the mol ratio in the source of chlorine stabilizing agent and single positive chlorion is greater than 1:1.But can release chlorine in acid condition according to the Raman spectrum said composition such as (D Cherney people, 2006), and not attempt to control chlorite level, owing to using clorox, chlorite level is high inherently.

The another kind of mode improving the shelf life is the composition forming drying regime, as described in WO/1991/003936, wherein, said composition contains water-soluble inorganic halide, strong oxidizer, in aqueous solution, described strong oxidizer and halide reaction, to produce hypohalogenous acids radical ion and enough sulfamic acids being used as halogen acceptor.Water soluble carbonate or bicarbonate and excess of ammonia base sulfonic acid react and are used for effervesce (effervescence) to produce carbonic acid gas.But, do not require that aqueous solution is steady in a long-term.

Compared with unstable halogen, the derivative of N-hydrogen compound (such as 5,5-dimethyl hydantoins) and their chlorination has proved the stability with improvement, and this technology is widely used in such as mucus control field in paper mill.The form of combination and intermediate (such as monochloro hydantoins) discharge halogen according to demand instead of use high-purity hypochlorite solution based on preparation.United States Patent (USP) 6,471, relate to for 974 (on June 29th, 1999) via buffering and use enhancing adulterant (such as 5,5-dimethyl hydantoin), there is the N-chloro amido sulfonate composition (N-chlorosulfamate compositions) of the microbial activity of enhancing, it causes the halogen thing class of certain limit, and from the angle of end user and management, halogen thing class is less desirable.In addition, low pH can cause producing chlorine, and does not attempt chloride ion content is minimized.

Hypochlorous acid (HOCl) is weak acid, there is hypochlorous acid when chlorine is dissolved in the water.In aqueous solution, HOCl partial solution is from becoming anion hypochlorite OCl -.

Cl 2+H 2O<------>HOCl+H ++Cl -

Under pH7.5, there is HOCl and OCl of comparable sodium -, exceed this pH, dominant class is OCl -, and total ionization is there is under pH9.5.

HOCl has been accredited as main biocidal activity thing class.Therefore, owing to falling low-level HOCl, in alkaline environment more, biocidal efficacy reduces (Rideal and Evans1921) and Johns (1934).

By chlorine, liquid sodium or lithium hypochlorite, or HOCl can be produced by powder calcium hypochlorite, dehydration sodium dichloro cyanurate and trichlorocyanuric acid.In clorox and calcium hypochlorite solution, that main existence is hypochlorite ion, and as disinfectant, hypochlorite ion is lower than hypochlorous validity up to 120 times, and by Kapoor, S.K, (1968) prove.

With the little molecular dimension of the HOCl of electroneutral charged couple can rapid osmotic to microbial cell, via the inhibitory enzyme (people such as Knox, 1948), the ATP hydrolysis (people such as Barrette in cell, 1987) DNA replication dna (people such as Rosen, is suppressed, 1998) and the induced protein aggregation (people such as J Winter, 2008), HOCl makes the survivability rapid deactivation of microbial cell.

Fully quote HOCl as proof and kill spore activity (Rudolf and Levine1941), wherein under the pH level of certain limit, use the effective solutions of chlorine of 25ppm, and the B.metiens spore measuring generation 99% kills the required time.Result display is 2.5 minutes for pH6, and being 3.6 minutes for pH7, is 5 minutes for pH8, is 19.5 minutes for pH9, is 35.5 minutes for pH9.35, is 131 minutes for pH10, is 465 minutes for pH12.86.

As mentioned above, generate HOCl by electrochemistry, but its major defect lacks stability required on generator at the scene and pH retentivity.Usually due to very high brine content, also there is perchloride residue, this can cause residual and improve corrosion.

U.S. Patent Application Publication US2009/0258083A1 (on October 15th, 2009) describes a kind of method for the preparation of stable antimicrobial hypochlorite solution, the method, by diluting aging raw material with under the pH scope of 2.8-4.0, provides the HCl solution of 50-7000ppm.Under these pH levels, exist and produce the possibility of chlorine, and be less desirable from the high chloride level of clorox and hydrochloric acid about stability, burn into purity and remnants.

Unpub U.K application number 1021287.6 (people such as Mallet, C) describes containing hypochlorous aqueous solution and salt M nx ythe preparation of stable HOCl solution, wherein M is hydrogen or metal, and X has the conjugate base that pKa is the acid of 4-7, and wherein n and y is 1,2 or 3 independently, and salt M nx yhave overall neutral electric charge, the pH of described composition is 4-7.By keeping the pH of solution in specific scope, said composition has shown its antimicrobial acivity of maintenance and has reached many months.But really need in the composition to comprise salt, this may not always expect.Further preferably can the solution of administration measure, and without the need to halogen stabilizer, such as sulfamic acid.

An object of the present invention is to provide the stable solution of HOCl, it keeps it active in long period section.

Another object of the present invention is to provide the more stable solution of HOCl, it keeps its microbial activity in standard procedure (such as bottling and other industrial processes) period, and the rational change can experienced in environmental condition and not degrading, thus can pack, bottle, carry and store the longer time period before use.

Another object of the present invention is to provide the more stable solution of HOCl, its can fast, large volume produce and more cheap than the art methods of electrolysis.

Therefore, a first aspect of the present invention is to provide a kind of composition containing hypochlorous stable solution, wherein, chloride: hypochlorous acid ratio is about 1:3, more preferably at least 1:5, more preferably 1:10, and the pH of solution remains on the pH of 3.5-7.0, thus stable HOCl keeps its antimicrobial acivity to reach the time period of at least one month, preferably at least three months, especially at least six months.

Find solution to be buffered within the scope of the pH of 3.5-7, HOCl can have been made to keep stable in the solution and reach remarkable long period section, more than three months, in fact usually more than six months.This solution also can have the activity more much higher than prior art, more than 600ppm.

When pH is 5.5-6.5, HOCl has Cmax in the solution.A first aspect of the present invention one preferred embodiment in, the pH of composition is 5-6.8, more preferably 5.5-6.5, especially 6-6.5.

For concrete application requirement, can limit and control hypochlorous level is 10-130,000ppm, more preferably 60-50,000ppm.

With regard to the object of a first aspect of the present invention, the halogen source of HOCl is preferably calcium salt, such as calcium hypochlorite, and wherein calcium removes from solution.But, other halogen source can be used.In aqueous solution, HOCl partial solution from, to form hypochlorite anion OCl -.Do not need to prove now chemically, because it is common.

The degree of dissociating depends on the pH of solution.There is no the constraint of scientific theory, it should be understood that the active species in the composition of the application is HOCl.The solution with subchloride level is provided to cause having more substantial active HOCl thing class in the solution.

By adding the source of chlorine in water, the aqueous solution of preparation HOCl, to obtain cl concn for 1ppm-10, the solution of 0000,000ppm concentration.Ideally, deionized water is used as solvent.

The composition of first aspect can optionally containing additional component.Particularly, can acid or alkalescence be joined in composition, to keep the critical pH range of pH at 3.5-7 of solution.The example comprises phosphoric acid or sodium hydroxide.

Composition of the present invention can, containing other additional component, make it be more suitable for the purposes of expecting.Additional component like this includes but not limited to humectant (such as Moisturiser Surfacare ARM HE), surfactant, spices, softening agent, chelating agent, colouring agent, optical enhancer, additional antimicrobial or adjuvant and/or chlorite donor.Should be realized that, it is stable that additional component should be halogen, do not have halogen demand, and should not be oxidized HOCl, such as, by removing chloride.

Described composition also can contain halogen releasing agent, such as dimethyl hydantoin, to provide the controlled release more of halogen.Also balance and stability agent (such as sodium chlorate) can be comprised to extend storage stability.

When compared with the solution of the known HOCl by electrolytic preparation, composition according to a first aspect of the invention presents the stability of improvement.Particularly, composition is enough stable, so that it can be packed, stores and carry.Avoid the current requirement preparing HOCl as requested like this, thus provide HOCl with convenient and highly effective form.As the result of the stability improved, do not require that original position prepares HOCl.Therefore, solution of the present invention does not pass through electrolytic preparation.

A second aspect of the present invention provides a kind of method for the production of hypochlorous stable Aquo-composition, said method comprising the steps of: Xiang Shuizhong adds the source of chlorine, adjustment chloride level is the chloride of 1:3 to the maximum: hypochlorous acid, and the pH controlling solution is 3.5-7.More preferably, this ratio is 1:5, more preferably 1:8, especially the chloride of 1:10: hypochlorous acid.

In context disclosed herein, " stable " refers to when storing in airtight container at ambient temperature, and composition keeps its antimicrobial acivity to reach the time period of at least 3 months, more preferably at least 6 months.

Be that the example of the suitable non-oxide acid of 5-6.8 comprises organic acid for controlling the pKa of the pH of solution, such as acetic acid, N-(2-acetamido)-2-iminodiacetic acid (ADA), benzoic acid, 1, two [three (methylol) methylamino] propane (BIS-TRIS propane) of 3-, carbonic acid, citrate, 2-(N-morpholino) ethyl sulfonic acid (MES), two (2-ethanesulfonic acid) (PIPES) of piperazine-N-N'-, succinic acid, formic acid, lactic acid, carbonic acid, tartaric acid, benzoic acid, phosphoric acid, phosphorous acid, oxalic acid, boric acid, maleic acid, adipic acid, citric acid.Preferred example comprise in citric acid, adipic acid or phosphoric acid one or more.Described acid can also be inorganic acid, such as HCl or HNO 3.

Recognize, the amount of acid to be added becomes according to the initial pH of solution and sour concentration.The acid of any concentration can be used for acidifying HOCl solution, such as, can use the acid solution of 10mM, 100mM, 1M or 10M.Acid can add in batches, or adopts mode dropwise to add, and preferably monitors the pH of solution.Add acid, until the pH of solution is in required scope, that is, pH3.5-7.

If excessive acid joined in solution, thus make the pH of solution be reduced to lower than pH3.5, should alkali be joined in solution, to improve the pH to 3.5-7 of solution.The example of such alkali comprises caustic soda and similar alkali.

According to the present invention, the composition of form of foam can be provided.For this reason, a third aspect of the present invention provides a kind of composition according to first aspect in addition containing surfactant.Surfactant causes disinfectant to foam, and it may be useful for some application, such as, for making HOCl be fixed on time period that skin (such as hand) reaches prolongation.

The amount of the surfactant provided in a third aspect of the present invention depends on the application of the expection of composition, as discussed below.With regard to object of the present invention, surfactant exists with the amount of 0.5-2.5 volume %.Preferably, surfactant can exist with the amount of 1-1.5 volume %.Surfactant must not have halogen demand (that is, they must be that chlorine is stable) and must not be oxidized HOCl.The example of suitable surfactant comprises N-methyl-N-(1-oxododecyl)-glycine sodium salt, N-alkyl " butter " Ν, Ν-bis-hydroxyethyl amine oxide, lauryl amine oxide, Surfac A030 (Ammonyx Lo, C12-C18 alkyl dimethyl N-oxide, CAS NO68955-55-5EINECS273-218-2), nutmeg base amine oxide, sodium N-lauroyl sarcosinate, PEG-7 glyceryl cocounut oil acid esters, N'N-dimethyl tetradecyl amine N-oxide and lauryl ether sulfates be Steol CS230KE AES96 (lauryl (polyoxyethylene) ether sodium sulfate) such as.Preferably, surfactant is amine oxide, but also can use other surfactant.

A fourth aspect of the present invention provides a kind of method of hypochlorous aqueous solution for the preparation of having subchloride level, and described method comprises and add solid calcium hypochlorite and at least one phosphate buffer in deionized water.Component directly can add or add via filter (perforated bag be such as added to the water).

Preferably, use ultralow chloride calcium hypochlorite in the method, to provide required subchloride level.More preferably, use the pure calcium hypochlorite of analysis of at least 70%, more preferably use even purer calcium hypochlorite.

Regulate the pH of the solution of the hypochlorite ion of gained to about 5-6, to precipitate any remaining calcium, can remove subsequently; With

PH is regulated by suitable acid or acid (such as phosphoric acid or sodium hydroxide).Compared with other chlorine source (such as clorox), calcium hypochlorite is used to originate the chloride level that can reduce.Such as, when use calcium hypochlorite prepare time, the HOCl solution of 5000ppm usually containing being less than 500ppm chloride, by comparison, if use clorox, usually containing 2500ppm chloride of having an appointment.

Optimize via control chloride content, removing calcium and pH, method according to a forth aspect of the invention provides a kind of new route to produce high-purity, HOCl solution steady in a long-term, and without the need to stabilizing agent.The pH of the solution obtained preferably remains on the pH of 3.5-7.0, to optimize the level of HOCl and to prevent chlorine, more preferably 5.5-6.5.The subchloride level of the composition formed according to described method, lack additional stabilizing agent and pH scope is the process and application characteristic expected.

Second chlorination stage can comprise in the process, to strengthen hypochlorite concentration, comprises and makes the solid from the stage above again disperse and react with more chlorine, then remove calcium chloride subsequently.

Hypochlorous aqueous solution prepared by a fifth aspect of the present invention method related to according to a forth aspect of the invention.

Solution according to the first, the 3rd and the 5th aspect of the present invention can suitably dilute.Dilution should use deionized water to carry out, to prevent by chloride ion contamination.As required additional component can be joined in composition.Such as, magnesium sulfate can be comprised for medical benefit.

The combination of selective crystallization clorox or electrochemical method and membrane technology can be used as alternative route to produce according to subchloride HOCl solution of the present invention.

A sixth aspect of the present invention provides a kind of solid composite for the preparation of hypochlorous stable solution according to a first aspect of the invention, described composition contains solid halogen source and independent solid acid, and described halogen source and acid jointly or are individually required halogen-free coating (non-halogendemanding coating) encapsulating.

The solid composite of encapsulating according to a sixth aspect of the invention prevents halogen source and acid reaction to form hypochlorous acid, until contact with water or other aqueous solution.More preferably, composition is anhydrous.

Halogen source comprises ultralow chloride calcium hypochlorite ideally, and preferably at least 70%, the more preferably pure calcium hypochlorite of the analysis of at least 75%.Solid acid preferably includes citric acid or adipic acid, but is not limited to this.Such as, other acid spendable includes but not limited to dicarboxylic acids or tricarboxylic acids, such as oxalic acid, malonic acid, succinic acid, glutaric acid, pimelic acid and suberic acid.Can also anhydrous phosphoric acid be used, but there is the restriction of the low melting point of 42 DEG C really, make it not be suitable for warm weather.

Any suitable encapsulating method well known in the art may be used for encapsulating halogen source and acid.Halogen source and acid can in single coating coencapsuiation or encapsulate separately.Preferably, use water miscible coating, such as gelatin or gelatin replacer.The coating of encapsulating can be water-soluble polymer, and it can be selected based on needing release of active ingredients (that is, halogen and acid source) immediately still to need to postpone (that is, time dependence) release when contacting with water.It should be understood that any standard method that can use encapsulating, such as air suspension methods, centrifugally to extrude, vibrating nozzle, spraying dry, Ionic gelation method, cohesion, interfacial polycondensation or crosslinked or original position or matrix polymerisations.

In another preferred embodiment of a sixth aspect of the present invention, use by Hull, England Sporomex Co., Ltd (Sporomex Limited of Hull, U.K) technology developed, is encapsulated in active component in the shell obtained by the spore of plant or adventitia.Have their inside genetic stocks from the plant pollen of thing class (such as lycopodium) or spore, it is by chemistry or enzyme method removing, with stay the porous that is called adventitia, inertia, elastic housing.Active ingredient migration is in spore, and it is protected subsequently until discharged afterwards.When jointly mixing with water, their inclusion of spores release, makes acid and hypochlorite mixing, to produce HOCl under given pH and ppm.Because shell can stand the temperature of alkali and acid treatment and at least 250 DEG C, shell is useful especially.Center gap relatively large in the enclosure means can realize top load level, such as, for 40 micron diameter particles, realizes 4:1 (active component: adventitia, w:w).

Further details about the method for the preparation of such spore is described in the PCT publication No. WO2005/000280 of University of Hull (University of Hull).Briefly, by permeable adventitia removing genetic stocks, with the migration of relief active component passing hole, optionally (such as vacuum) is helped by filling reinforcing agent (such as ethanol) or physics.

Preferably, the solution that the powder by hypochlorite and acid is formed is filtered, more particularly by pliable and tough fine filtrator (such as, 1-5 micrometer diameter orifice), with other fragment any trapping calcium, calcium citrate, slaked lime or obtained by chemical reaction.

Encapsulating solid constituent can by fine filtrator around, with formation hypochlorous acid after, retain any solid deposits, fragment, adventitia etc.

Should be realized that, the anhydrous pattern of composition according to a sixth aspect of the invention can be made into any suitable solid shape, such as tablet form, powder or briquet.The hypochlorite be included in composition will determine the hypochlorous ppm produced in specific volume under given pH with the ratio of acid, thus make the concentration of composition be suitable for concrete application.

The stable character of HOCl composition of the present invention makes composition can provide with multiple different form, makes them suitably be sent to treatment sites.Such as, these can include but not limited to wet tissue (wipe), lotion, gel, powder and foam.The method transmitting composition of the present invention also can change, but comprise topple over, inject, pumping, dipping, coating, spraying, sprinkling and atomization.

The application of wide region is can be used for according to various stable HOCl composition provided by the invention.The example of such application at following detailed description, but should be realized that, application of the present invention is not limited to this.

Described composition is particularly suitable for sterilization or sterilizing crust, organism and environment usually.Particularly, the main application of described composition is as antimicrobial.Described composition can be used as antibacterial agent, antivirotic, antifungal agent or anti-spore agent (antisporal agent).Described composition can be used as microorganism agent (that is, killing microorganisms) or conduct suppresses microorganism agent (suppress or prevent growth of microorganism).Composition is by complete eradicate bacteria, virus, fungi and/or spore or can reduce bacterium, virus, the quantity of fungi and/or spore (particularly pathogene bacterium, virus, fungi and/or spore) or activity, makes them no longer have harmful effect.

There is provided described composition as the agent for one or more Clestridium difficile (Clostridium difficile) especially, comprise variant 027, staphylococcus aureus (Staphylococcusaureus), Pseudomonas aeruginosa (Pseudomonas aeruginosa), uncommon Laplace enterococcus (Enterococcus hirae), Candida albicans (Candida albicans), aspergillus niger (Aspergillusniger), Escherichia coli (Escherichia coli), Friedlander's bacillus (Klebsiella pneumoniae) or acinetobacter calcoaceticus (Acinetobacter sp).

Described composition can be provided for medicine (that is, processing patient infection) or make equipment or environment sterilizing.Particularly, described composition can be used for killing bacterium on surface or equipment, virus, fungi and/or spore, such as, in family, medical institutions such as hospital, doctors surgery, veterinary operating room or dental operation room or workplace.Described composition is particularly suitable for family and uses, and such as, to bathroom and/or kitchen sterilizing, is specially adapted to sterilizings such as the surfaces of preparing food such as workbench, or to equipment (such as chopping board, cutter, the baby bottles etc.) sterilizing for the preparation of food.

Described composition, also can be used for Medical Instruments sterilizing, comprises those Medical Instruments used for medical treatment, dentistry or animal doctor.Described composition may be used for the instrument of body contact (such as introscope, fixture, suture, scalpel etc., be especially difficult to those of sterilizing, such as can not autoclaved those) sterilizing.For this reason, a sixth aspect of the present invention provides a kind of by the method for object sterilizing, and described method comprises and being contacted by the composition of object with the first, the 3rd or the 5th aspect of the present invention.For purposes of the present invention, can by object dipping in the composition, or or can use applicator (such as cloth, brush, gauze or mop) that composition is applied to object by spraying, sprinkling etc.

Described composition can be used for medicine.Described composition is provided to infect for the treatment of the bacterium of (that is, on skin or in mouth) on body exterior face, virus, fungi or spore especially.Therefore, provide described composition for topical especially.Find that described composition is suitable for processing wound, wound or ulcer.Described composition directly can be applied to site of injury, and by making site of injury sterilizing (that is, by killing all types of microorganism) contribute to wound healing.Particularly, described composition can be used as wound lavage solution (wound irrigant) provides.Described composition may be used for treatment burn, post-surgical trauma and ulcer, such as static ulcer, pressure ulcers, chronic ulcer, venous ulcer and diabetic ulcer.When there is pathogene and for target, other medical conditions in both people and animal also can be treated.

When providing first, the 3rd or the composition of fourth aspect for such medical applications time, the pH of adjustable solution, to avoid any stimulation to patient or discomfort.The pH of solution can be adjusted to pH5-6, preferred pH5.4-5.8, to avoid such stimulation.

Therefore, composition of the present invention may be used for processing topical microbial infections, comprises to infection site topical composition.Recognize, composition can directly be used or be immersed on pad, gauze or bandage, and cream frost or gel are applied to infection site.Composition can allow process anti-microbial infection needed for time period in disposable or repetitive administration.

Composition impregnation of fibers of the present invention element paper or pad can not be used.Need to use described composition impregnated nonwoven material.For this reason, a seventh aspect of the present invention provide a kind of be impregnated with according to of the present invention first, the 3rd or the non-woven material of composition of fourth aspect.

Preferred wet tissue is polypropylene nonwoven wet tissue.More preferably, halogen stabilizer comprises the composition of this aspect.

The other application of composition of the present invention makes food sterilizing.Food is such as meat, fish, dairy products, vegetables or fruit.Find to use described compositions-treated food significantly improve the shelf life of food and reduce the risk of pollution.For vegetables (such as salad vegetables), vegetables can be made to contact with described composition with the fragility improving vegetables, shelf life and outward appearance.Recognize, composition of the present invention can be used as the antimicrobial for the microorganism causing disease such as to poison by food, Salmonella, Li Site Bordetella etc.Alternatively and/or in addition, described composition can be used as antimicrobial for the microorganism causing food spoilage.For meat, such as, cut chicken, beef, lamb meat and venison, contact with described composition significantly can improve them shelf life, softness and outward appearance.

Composition of the present invention also may be used for making liquid (such as water) sterilizing.There is provided described composition for making drinking water sterilizing especially.Or described composition may be used for making the water sterilizing in swimming pool, decoration pond, fountain etc.In a preferred embodiment, composition can with the metering of predetermined speed in water surge tank (water break tank).Or, composition can be added at source place.

Another important application of the present invention relate to containing of the present invention first, the 3rd or the ice of composition of fourth aspect.For this reason, a eighth aspect of the present invention by containing first, the 3rd or the composition of fourth aspect freezing, to provide ice.Ice can use with multiple medical treatment and commercial system, includes but not limited to the organ or other biological organization that store transplanting, and preserves food, such as fish (comprising marine food), meat, vegetables or dairy products.

Owing to being derived from the saline solution that HOCl produces, be difficult to freezing by the form of the HOCl of electrolysis production.Composition of the present invention does not use brine production, therefore, ideally for generation of ice.

The Another application of composition of the present invention comprises laundry disinfectant (laundry sanitiser).Laundry and clothes are the breeding places of many bacteriums, virus and pathogene.Therefore, their sterilization is crucial in consumer, medical treatment and industrial site.At present, by washings, the temperature be heated to more than 60 DEG C is mainly used in disinfecting washing.This heating needs a large amount of energy, and in many cases, because many pathogene have become resistance to higher wash temperature, does not provide the effect of expectation.Composition of the present invention provides a kind of laundry disinfectant, for making fabric sterilizing, described fabric includes but not limited at home, medical treatment, animal doctor, dentistry or industry washer or hand-wash the clothes, sheet, mop, towel, carpet, mat, footwear, cap, gloves and other article that wash in warm air drier.For purposes of the present invention, moisture or anhydrous composition of the present invention will be in the suds distribution during wash cycle.One of the present invention preferred embodiment in, after clothing washs, during final rinse cycle, add described composition.In a kind of alternate embodiment, described composition can containing can the surfactant of both cleaning and disinfection clothings and wetting agent and conditioner.

The Another application of composition of the present invention is as the sensitizing range of disinfectant for health.Use prior art be difficult at present maybe can not by below lip, inner ear and external ear, mouth, tooth, tongue, pin, arm and sexual organ sterilize log paramount and reduce (being greater than log6).The disinfectant of many prior aries is not suitable for or the dangerous sensitizing range for health.Therefore, composition height of the present invention is applicable to these regions.Composition of the present invention provides a kind of sensitizing range disinfectant, for making aforementioned areas sterilizing.

Composition of the present invention also can be used as deodorant.Smell is usually relevant to airborne bacterium, and it may be difficult to eradicate in room, refrigerator, cabinet, kitchen, industrial equipment, region or unlimited space and control smell.As high activity antimicrobial, composition of the present invention can spray, sprays or be atomized in region, to eradicate and to control smell.This can carry out continuously or carry out as required.One of the present invention preferred embodiment in, the composition of 100ppm-5000ppm is used for this application.

The Another application of the application uses composition in fresh cut-flowers, to extend their life-span.Bacterium and other microorganism are generally spends cause that is withered or degraded.Composition of the present invention can be joined holds in colored water wherein, to destroy bacterium and other pathogene, therefore extends the colored life-span, and in growth source place and the level reducing cross pollution in packaging.Or, can the described composition of sprinkling taken, or stem or head can soaked in the composition.One of the present invention preferred embodiment in, the composition of 1ppm-100ppm is used for this application.

In addition, when such as gutstring, intestines and colon treatment, stable HOCl composition of the present invention can be used as antibiotic alternative or supplementary, but is not limited to the treatment of these situations.As previously mentioned, the present invention is a kind of very strong oxidant, therefore destroys DNA and RNA of pathogen cells.Therefore, not by follow-up pathogene accumulation immunity, this is normally in the situation that the pathogene by antibiotic therapy experiences.Non-toxic character of the present invention also means that it can be used as disinfectant (such as in canalis radicis dentis dentistry (root canal dentistry) or when antibiotic is the normal processes of further preventive measure) in mammal surgical field and uses.

Composition of the present invention can be used in the preoperative with in postoperative both surgery agreements.By spraying, be atomized or pass through washing methods, surgical patients can be exposed to the present invention.This protocol procedure will make the risk minimization of cross pollution in theater context.The present invention is atomized or is sprayed in unlimited wound area by expection during surgical procedure, and when adopting stitching or other method, therefore makes entering of deleterious pathogens in both four limbs and body cavity area minimize further.

The hand that the invention provides a kind of containing composition of the present invention is used or skin antiseptic.There is provided hand disinfectant on the surface at hand or skin as microbicide or as suppression microorganism agent, thus completely eradicate bacteria, virus, fungi and/or spore or reduce bacterium, virus, the quantity of fungi and/or spore (particularly pathogene bacterium, virus or fungi) or activity, make them no longer have harmful effect.Preferably, hand with or the surfactant level of skin antiseptic be 0.1-2.5%, therefore solve needs deoiling to a certain degree and make the effective Polluted area of sterilization method height.

Surfactant also causes disinfectant to foam, its time period keeping HOCl extending on hand.Such raising effect and prevent solution from falling from hand, this is the problem that this area is relevant.When by hand-wrist bones, best practices and control need the fluid of 3ml-5ml volume.The standard liquid of the HOCl of this volume will cause significant loss of liquid to floor and clothes, and this is less desirable effect.The foaming effect of surfactant prevent this point and guarantee to exist enough HOCl solution with guarantee palm, back and finger clean.

When providing the composition of first aspect as hand use or skin antiseptic, the wetting agent of described composition preferably containing 0.1-1.0 volume % level.In this embodiment, the volume of surfactant is preferably 1-1.5 volume %.

When providing the composition of first aspect for such purposes, the pH of adjustable solution, to avoid any stimulation or the discomfort of user.The pH of solution can be adjusted to pH5-6, preferred pH5.4-5.8, to avoid such stimulation.

The present invention can be the surface cleaner form of sterilization.There is provided surface cleaner at home especially, medical treatment, animal doctor, crust in dentistry and industrial environment sterilization.With regard to object of the present invention, cleaning agent or can use applicator (such as cloth, brush, gauze or mop) to be directly applied to surface by spraying, atomization etc.This embodiment, preferably containing the surfactant of 0.1-2.5% level, therefore solves needs deoiling to a certain degree and makes the effective Polluted area of sterilization method height.

The present invention also may be used for processing cereal crops, such as with wheat, barley, corn, oat, salad, soft water fruit, vegetables as an example, it is important for wherein controlling spore, virus, bacterium, mould and fungi, to guarantee the having healthy crop of improving yield.Agricultural chemicals company develops new antimicrobial for agricultural tillage in whole world consumption huge fund, but in many cases, target pathogene in section sometime to these antimicrobial accumulation innate immunitys.By reducing the surface tension of target plant and allowing HOCl more effectively to adhere to, permission peasant is sprayed crop by this aspect of the invention in a more effective manner, thus provide the larger reduction of all aforementioned pathogene, make the immune problem relevant to current antimicrobial be no longer problem simultaneously.

The present invention also may be used for being sterilized in poultry, milk cow, pig, goat, sheep and other animal colony house, farmyard, room of milking, standing area, and there is no the corrosion that obtain relevant to product current on market and hazardous gas, such as hypochlorite and quaternary ammonium (quat ammoniums) are as an example.

Treatment is tanned severely, the skin of sun exposure damage, freckle, liver spotting, wart, proud flesh and acne.

Treatment trichophytosis and eczema, herpes labialis, the ringworm of the foot, spot and skin ulcer, canker sore, gingivitis and general periodontal health.

Reduce via atomization and eliminate airborne pathogene, and treatment humans and animals tuberculosis comprises pulmonary tuberculosis.

Now by means of only the mode of citing, by following examples, the present invention is described, wherein, Example 1 describes the preparation stable HOCl solution with subchloride level according to a first aspect of the invention and evaluated its stability a month period, and examples 2 describing the stable HOCl solution prepared and prepared by the Powdered calcium hypochlorite encapsulated and monohydrate potassium; And with reference to accompanying drawing, wherein:

Fig. 3 and 4 illustrates to reduce chloride content to the distribution curve of the impact that chlorine thing class distributes.

Embodiment 1: the research according to the present invention with the stable HOCl composition of subchloride level

The present invention relates to hypochlorous true stable.Many proposition uses the additive combined with hypochlorite or hypochlorous acid, to form different compounds or compound.These materials it is said stabilizing solution.Therefore, this solution is not pure hypochlorous acid, but has the hypochlorous balance of additive.

Usually there is the chlorine of high percentage as the chlorine combined instead of free chlorine, the hypochlorous acid do not combined that wherein free chloro table is total and hypochlorite.For some additives, the chlorine thing class of combination has slight microbiological activity, for other additives, does not then have microbiological activity.

Add other component and there is obvious result; In some applications, the solids content improving dissolving simply may be harmful to; Some additives are harmful to, and hinder them in the application of water contacting foodstuff or food-contacting surface; If water is used for drinking, medical applications or agricultural application, some is unacceptable.Therefore, the hypochlorite solution that there is pure hypochlorite solution or only there is low-level additive is expected.

Cl 2+H 2O<------>HOCl+H ++Cl -

At the Cl of some fixed concentrations -under, Cl 2, HOCl and OCl -relative scale can be expressed as:

Utilize the formula of the equilibrium constant in equation (1) and equation (2) and pH to equal the relation of the negative logarithm of hydrogen ion concentration, we obtain following formula:

The ratio of each chlorine thing class can be drawn for pH.Fig. 1 of accompanying drawing shows the common distribution of chlorine thing class under the effect of pH.The key feature of this distribution map is:

3) under pH5.5, there is the little but Cl of significance level 2(solution (aq)).

4) time lower than pH5.5, Cl 2(solution (aq)) level improves.Chlorine will be overflowed.

Notice to there is chlorine ion concentration in the equation for generating distribution curve.By setting chlorine ion concentration as variable, the impact that it distributes on chlorine thing class can be observed.Fig. 2 of accompanying drawing describes the impact that chloride concentration improves 10 times.The key feature of this distribution map is:

This figure shows, and in perchloride solution (such as, the hypochlorous acid that electrochemistry produces), hypochlorous acid level is restricted and more easily produces chlorine.

These figure show, and can more easily produce stable hypochlorous acid in subchloride solution.This figure shows, and there is less chlorine, even if at a low ph in subchloride solution; Therefore, the effusion of chlorine is greatly reduced.How low the effusion of chlorine is the critical path that hypochlorite solution decomposes, and can limit the pH of adjustment on sour direction.The present invention has shown can limit the decomposition of this route.

Make pH value of solution be offset to lower pH, reduce hypochlorite concentration, be conducive to hypochlorous acid.Hypochlorous acid can be stablized as mentioned above.Because hypochlorite concentration is much lower, the loss produced because these two hypochlorites decompose route reduces.

Due to for all solutions of chlorine, decomposable process is accelerated by the existence of light, high temperature and metal ion.Therefore, the purity of the raw material of suitably packaging and storage is still important.

If we can reduce chloride content, be only conducive to the stability of hypochlorous improvement in subchloride solution.When the solution of chlorine is by preparation of chlorine, chlorine is dissolved in the water, and hypochlorous acid and the hydrochloric acid of stoichiometric amount such as to obtain.

When producing clorox, chlorine is dissolved in sodium hydroxide, clorox and the sodium chloride of stoichiometric amount such as to obtain.This means, for 14/15% industrial liquor natrii hypochloritis, to there is about 11% sodium chloride.When the chlorine stable by organic procedures is used as the source of chlorine, chloride level is low, but organic backbone molecule may present difficulty in preparation.The phosphate of chlorination also can obtain subchloride solution, but they have high phosphate and chlorine ratio, and this presents the difficulty of himself.They also have high pH.

The present invention preferably utilizes high chlorine and chloride ratio in calcium hypochlorite.Calcium hypochlorite production method relates to the reaction of chlorine and calcium hydroxide slurry.With etc. stoichiometric amount form calcium hypochlorite and calcium chloride.Compared with calcium hypochlorite, calcium chloride is more solvable, is therefore mainly present in saline fluid.Removing saline fluid, to reduce chloride content.Carry out the second chlorination stage, to strengthen hypochlorite concentration, comprise and the solid from the stage is above disperseed again and itself and more chlorine are reacted.When being separated with salt solution by solid, again remove calcium chloride.The method obtains the solid product containing 6-8% calcium chloride and 60-65% calcium hypochlorite.

When calcium hypochlorite is dissolved in the water subsequently, form the alkaline solution of calcium and hypochlorite ion.If prepare solution by sodium hydroxide, chlorine and chloride ratio much higher.Some calcium are as calcium hydroxide precipitation.Removed by isolated by filtration.This solution is still containing the high-caliber calcium needing removing.Use phosphoric acid that pH is adjusted to about 5-6, obtain calcium phosphate precipitation.Again passed through to filter.

Product is intimate pure hypochlorous solution.Use phosphoric acid or sodium hydroxide further as required, pH can be adjusted to the value of expectation.It is beneficial that there is low-level phosphate in the solution to be used as pH buffer.Stability test illustrates any hypochlorite ion that low-level calcium stable exists.

Liquid storage can be used for preparing various product, describes in detail about of the present invention first and the third aspect as above.It is necessary that use deionized water to dilute.Running water and softening running water contain chlorion.Although only exist with relatively low level, subchloride level makes low-intensity hypochlorite solution instability (destabilising).

During one month, test the stability of the present composition, starting composition contains 5000ppm chlorine.The results are summarized in following table 1:

Result display 80% is retained in HOCl, far above the aqueous solution of the non-stable electrolysis-preparation of prior art.

Embodiment 2: prepare stable HOCl solution by the anhydrous composition of the pure calcium hypochlorite of the analysis with 75% and citric acid.

The pure calcium hypochlorite of analysis (such as Arch Chemicals sells) of " x " gram 75% is mixed with " y " gram citric acid, is placed on subsequently in water-soluble non-halogen requirement coating (such as gelatin or gelatine replacement).When with have the water of given volume " z " with pH " A " contact time, under concrete ppm and pH, produce HOCl, as shown in table 2 below.Deionized water is used to realize the pH of 5.5.

3the ppm of the chlorine measured via DPD (diethyl-p-phenylenediamine tablet) (DPD (diethyl-p-phenylenediamine tablets)).

Claims (51)

1. the method for the preparation of hypochlorous stable aqueous solution, said method comprising the steps of: Xiang Shuizhong adds the source of chlorine, adjustment is 1 chloride to the maximum in the Chlorine in Solution compound level of gained: 3 hypochlorous acid, and the pH controlling solution is 3.5-7.0, wherein, the pure calcium hypochlorite of analysis of at least 70% is contained in the source of described chlorine.

Regulate the pH to 5-6 of the solution of the hypochlorite ion of gained, to precipitate any remaining calcium, can remove subsequently; With

4. by the hypochlorous stable aqueous solution that the method in claim 1-3 described in any one prepares, wherein, stable HOCl keeps its antimicrobial acivity to reach the time period of at least one month.

5. stable aqueous solution according to claim 4, wherein, one or more the additional components in the group of this stable aqueous solution also containing the surfactant selecting free halogen stable, humectant, spices, softening agent, chelating agent, colouring agent, optical enhancer, antimicrobial or adjuvant, chlorite donor, halogen releasing agent and balance stabilizing agent composition.

6. the solid composite for the preparation of hypochlorous stable solution, described composition contains solid halogen source and independent solid acid, described halogen source and acid jointly or are individually required halogen-free coating encapsulation, wherein, described halogen source contains the pure calcium hypochlorite of analysis of at least 70%.

9. according to the solid composite in claim 6-8 described in any one, wherein, described halogen source and acid are encapsulated individually.

10. according to the solid composite in claim 6-8 described in any one, wherein, described halogen source and acid are jointly encapsulated.

11. according to the solid composite in claim 6-8 described in any one, and wherein, described coating is water miscible.

14. according to the solid composite in claim 6-8 described in any one, and wherein, described halogen source and acid are encapsulated in the adventitia that obtained by spore or pollen.

Solid composite in 30. claim 6-8 described in any one is as the application of cleaning agent or bactericidal agent.

50. 1 kinds of methods making abiotic object or the sterilizing of body exterior face, described method comprises makes this object or body exterior face contact with hypochlorous stable aqueous solution according to claim 4.

51. 1 kinds of methods making abiotic object or the sterilizing of body exterior face, described method comprises makes this object or body exterior face contact with hypochlorous stable aqueous solution according to claim 5.

CN201280012861.0A 2011-03-11 2012-03-08 A stable composition of HOCl, processes for its production and uses thereof Expired - Fee Related CN103501605B (en)

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PCT/GB2012/000228 WO2012123695A2 (en)	2011-03-11	2012-03-08	A stable composition of hoci, processes for its production and uses thereof

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US20040256330A1 (en) *	2003-05-12	2004-12-23	Tatsuo Okazaki	Method of preparing sterile water containing hypochlorous or chlorous acid, package of sterile source materials, sterile water preparation kit, method and apparatus for spatial sterilization
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US8945630B2 (en) *	2008-04-11	2015-02-03	Aquilabs S.A.	Method of producing and applications of composition of hypochlorous acid

2012

2012-03-08 CN CN201280012861.0A patent/CN103501605B/en not_active Expired - Fee Related
2012-03-08 EP EP12712138.2A patent/EP2683240A2/en not_active Withdrawn
2012-03-08 MX MX2013010362A patent/MX2013010362A/en not_active Application Discontinuation

Patent Citations (2)

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Date	Code	Title	Description
2014-01-08	C06	Publication
2017-05-03	CF01	Termination of patent right due to non-payment of annual fee	Granted publication date: 20150722 Termination date: 20160308

process for preparing an aqueous solution, aqueous solution, composition, use of an aqueous solution, nonwoven material, and method for sterilizing an animate or inanimate object

Info

BR112013023170A2 BR112013023170A BR112013023170A BR112013023170A2 BR 112013023170 A2 BR112013023170 A2 BR 112013023170A2 BR 112013023170 A BR112013023170 A BR 112013023170A BR 112013023170 A BR112013023170 A BR 112013023170A BR 112013023170 A2 BR112013023170 A2 BR 112013023170A2 Authority Prior art keywords Prior art date

Application number

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Inventor

Christopher Mallet

Original Assignee

Biomimetics Health Ind Ltd

Priority date (The priority date 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 date listed.)

Filing date

Publication date

2012-03-08 Application filed by Biomimetics Health Ind Ltd filed Critical Biomimetics Health Ind Ltd

2016-07-26 Publication of BR112013023170A2 publication Critical patent/BR112013023170A2/en

Classifications

A—HUMAN NECESSITIES
A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds

A—HUMAN NECESSITIES
A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group

A—HUMAN NECESSITIES
A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
A61K33/00—Medicinal preparations containing inorganic active ingredients
A61K33/20—Elemental chlorine; Inorganic compounds releasing chlorine

A—HUMAN NECESSITIES
A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
A61K45/00—Medicinal preparations containing active ingredients not provided for in groups A61K31/00 - A61K41/00
A61K45/06—Mixtures of active ingredients without chemical characterisation, e.g. antiphlogistics and cardiaca

A—HUMAN NECESSITIES
A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
A61L2/0005—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor for pharmaceuticals, biologicals or living parts
A61L2/0082—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor for pharmaceuticals, biologicals or living parts using chemical substances
A61L2/0088—Liquid substances

A—HUMAN NECESSITIES
A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
A61L2/18—Liquid substances or solutions comprising solids or dissolved gases

C—CHEMISTRY; METALLURGY
C01—INORGANIC CHEMISTRY
C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
C01B11/00—Oxides or oxyacids of halogens; Salts thereof
C01B11/04—Hypochlorous acid
C01B11/06—Hypochlorites

C—CHEMISTRY; METALLURGY
C01—INORGANIC CHEMISTRY
C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
C01B11/00—Oxides or oxyacids of halogens; Salts thereof
C01B11/04—Hypochlorous acid
C01B11/06—Hypochlorites
C01B11/064—Hypochlorites of alkaline-earth metals

C—CHEMISTRY; METALLURGY
C01—INORGANIC CHEMISTRY
C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
C01B11/00—Oxides or oxyacids of halogens; Salts thereof
C01B11/04—Hypochlorous acid
C01B11/06—Hypochlorites
C01B11/068—Stabilisation by additives other than oxides, hydroxides, carbonates of alkali or alkaline-earth metals; Coating of particles; Shaping; Granulation

BR112013023170A 2011-03-11 2012-03-08 process for preparing an aqueous solution, aqueous solution, composition, use of an aqueous solution, nonwoven material, and method for sterilizing an animate or inanimate object BR112013023170A2 (en)

Applications Claiming Priority (2)

Publications (1)

Family

ID=43980865

Family Applications (1)

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JP6230079B1 (en) *	2016-06-14	2017-11-15	淳一熊倉	Method and apparatus for producing or preparing hypochlorous acid aqueous solution
CN106386850A (en) *	2016-11-23	2017-02-15	沐康源科技（北京）有限公司	Preparation method and preparation apparatus of slightly-acidic hypochlorous acid water
KR20200100525A (en)	2017-01-13	2020-08-26	파모콘 엘엘씨	Materials and methods for buffering active chlorine solutions
KR20210039450A (en) *	2018-09-06	2021-04-09	후지필름 가부시키가이샤	Chemical solution, substrate treatment method
RU2711189C1 (en) *	2018-10-12	2020-01-15	Федеральное государственное бюджетное научное учреждение "Федеральный научный центр - Всероссийский научно-исследовательский институт экспериментальной ветеринарии имени К.И. Скрябина и Я.Р. Коваленко Российской академии наук" (ФГБНУ ФНЦ ВИЭВ РАН)	Method of veterinary supervision objects disinfection
RU2710600C1 (en) *	2018-10-12	2019-12-30	Федеральное государственное бюджетное научное учреждение "Федеральный научный центр - Всероссийский научно-исследовательский институт экспериментальной ветеринарии имени К.И. Скрябина и Я.Р. Коваленко Российской академии наук" (ФГБНУ ФНЦ ВИЭВ РАН)	Method of veterinary supervision objects disinfection
CN110074133A (en) *	2019-05-08	2019-08-02	上海滤郎科技发展有限公司	A kind of preparation method of subacidity hypochlorite solution
CN110123834A (en) *	2019-05-08	2019-08-16	山东消博士消毒科技股份有限公司	A kind of hypochlorous acid thimerosal and preparation method thereof
AU2020291943A1 (en) *	2019-06-14	2022-02-10	Collidion, Inc.	Compositions, kits, methods and uses for preventing microbial growth
CN112374464A (en) *	2020-08-10	2021-02-19	中山市原域企业投资有限公司	Method and equipment for preparing hypochlorous acid by combining ion exchange method with electrolysis method
CN112499800A (en) *	2020-08-10	2021-03-16	中山市原域企业投资有限公司	Method and equipment for preparing hypochlorous acid by combining two-liquid synthesis and ion exchange method
CN112499591A (en) *	2020-08-10	2021-03-16	中山市原域企业投资有限公司	Method and equipment for preparing hypochlorous acid by combining two-liquid synthesis with microporous molecular sieve
CN112501638A (en) *	2020-08-10	2021-03-16	中山市原域企业投资有限公司	Process and equipment for preparing hypochlorous acid by combining two-liquid method with electrolysis method
CN112586506A (en) *	2020-12-26	2021-04-02	深圳市疆河生物科技有限公司	High-stability molecular-state hypochlorous acid aqueous solution and preparation method thereof
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US20040226894A1 (en) *	2003-05-12	2004-11-18	Tatsuo Okazaki	Method of preparing a sterile water containing hypochlorous or chlorous acid, package of sterile source materials, and sterile water preparation kit
US20040256330A1 (en) *	2003-05-12	2004-12-23	Tatsuo Okazaki	Method of preparing sterile water containing hypochlorous or chlorous acid, package of sterile source materials, sterile water preparation kit, method and apparatus for spatial sterilization
KR20060015581A (en) *	2003-05-12	2006-02-17	다츠오 오카자키	Method for forming bactericidal water containing hypochlorous acid or chlorous acid, raw bactericidal material package and kit for forming bactericidal water, and method and apparatus for sterilizing space
JP2005000238A (en) *	2003-06-09	2005-01-06	Hiromaito Co Ltd	Method for manufacturing vessel filled with disinfectant aqueous solution
JP5059402B2 (en) *	2003-06-27	2012-10-24	ユニバーシティオブハル	Formulation comprising sporopolenin-containing outer membrane skin and method of using the formulation in the manufacture of a therapeutic drug
JP2004337582A (en) *	2003-10-27	2004-12-02	Tatsuo Okazaki	Sterilizing liquid preserving method, container for sterilization and nozzle with opening/closing valve used for this
US8945630B2 (en) *	2008-04-11	2015-02-03	Aquilabs S.A.	Method of producing and applications of composition of hypochlorous acid
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2012

2012-03-08 CN CN201280012861.0A patent/CN103501605B/en not_active Expired - Fee Related
2012-03-08 MX MX2013010362A patent/MX2013010362A/en not_active Application Discontinuation
2012-03-08 BR BR112013023170A patent/BR112013023170A2/en not_active IP Right Cessation

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Date	Code	Title	Description
2017-01-17	B08F	Application dismissed because of non-payment of annual fees [chapter 8.6 patent gazette]	Free format text: REFERENTE A 5A ANUIDADE.
2017-05-23	B08K	Patent lapsed as no evidence of payment of the annual fee has been furnished to inpi [chapter 8.11 patent gazette]
2021-06-01	B350	Update of information on the portal [chapter 15.35 patent gazette]

Publication	Publication Date	Title
BR112013023170A2 (en)	2016-07-26	process for preparing an aqueous solution, aqueous solution, composition, use of an aqueous solution, nonwoven material, and method for sterilizing an animate or inanimate object
BR112013007955A2 (en)	2016-06-21	surfactant composition, personal care cleaning composition, and method for thickening an aqueous surfactant
BR112014003681A8 (en)	2018-01-23	compound, pharmaceutical composition, pharmaceutical combination product, use of a compound, and method for treating diseases or conditions
BR112013020352A2 (en)	2017-08-08	compound, pharmaceutical composition, use of a compound and method for treating median rorgamat disease or condition in an individual
BR112013029203A2 (en)	2016-08-09	method for preparing one or more human milk oligosaccharides, and use of human milk oligosaccharides
CL2013001282A1 (en)	2013-09-27	Dimethyl amide succinate salt of 7-cyclopentyl-2- (5-piperazin-1-yl-pyridin-2-yl-amino) -7h-pyrrolo- [2,3-d] -pyrimidin-6-carboxylic acid; pharmaceutical composition that includes it and processes for its preparation.
BR112013029208A2 (en)	2017-02-14	method for preparing one or more human milk oligosaccharides or derivatives or precursors therefor, use of oligosaccharides, and, compound
BR112014011671A2 (en)	2017-05-30	compound, pharmaceutical composition, method for treating a disease or condition, and use of a compound
BRPI0906673A2 (en)	2016-07-26	aqueous dispersion, process for preparing an aqueous dispersion, use of an aqueous dispersion, and, product
BR112012031981A2 (en)	2015-09-15	aqueous composition of active ingredient, process, use, method for controlling phytopathogenic fungi and seed

A stable composition of HOCl, processes for its production and uses thereof (CN103501605B)

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