CN110191640A - Aqueous hydrogen peroxide for sterilization solution - Google Patents

Aqueous hydrogen peroxide for sterilization solution Download PDF

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Publication number
CN110191640A
CN110191640A CN201780084068.4A CN201780084068A CN110191640A CN 110191640 A CN110191640 A CN 110191640A CN 201780084068 A CN201780084068 A CN 201780084068A CN 110191640 A CN110191640 A CN 110191640A
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China
Prior art keywords
hydrogen peroxide
aqueous solution
disinfection
mist
steam
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CN201780084068.4A
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Chinese (zh)
Inventor
野头亚理沙
井浦克弘
君塚健一
田崎贤
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Mitsubishi Gas Chemical Co Inc
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Mitsubishi Gas Chemical Co Inc
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Priority to CN202410108378.7A priority Critical patent/CN117941706A/en
Publication of CN110191640A publication Critical patent/CN110191640A/en
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N25/00Biocides, 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
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N25/00Biocides, 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
    • A01N25/02Biocides, 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 containing liquids as carriers, diluents or solvents
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N25/00Biocides, 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
    • A01N25/02Biocides, 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 containing liquids as carriers, diluents or solvents
    • A01N25/04Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • A01N25/06Aerosols
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N25/00Biocides, 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
    • A01N25/22Biocides, 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 containing ingredients stabilising the active ingredients
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N59/00Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01PBIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P1/00Disinfectants; Antimicrobial compounds or mixtures thereof
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01PBIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P3/00Fungicides
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2/00Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/16Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
    • A61L2/20Gaseous substances, e.g. vapours
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2/00Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/16Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
    • A61L2/20Gaseous substances, e.g. vapours
    • A61L2/208Hydrogen peroxide
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L9/00Disinfection, sterilisation or deodorisation of air
    • A61L9/01Deodorant compositions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L9/00Disinfection, sterilisation or deodorisation of air
    • A61L9/015Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone
    • A61L9/02Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone using substances evaporated in the air by heating or combustion
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65BMACHINES, APPARATUS OR DEVICES FOR, OR METHODS OF, PACKAGING ARTICLES OR MATERIALS; UNPACKING
    • B65B55/00Preserving, protecting or purifying packages or package contents in association with packaging
    • B65B55/02Sterilising, e.g. of complete packages
    • B65B55/04Sterilising wrappers or receptacles prior to, or during, packaging
    • B65B55/10Sterilising wrappers or receptacles prior to, or during, packaging by liquids or gases
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2101/00Chemical composition of materials used in disinfecting, sterilising or deodorising
    • A61L2101/02Inorganic materials

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Environmental Sciences (AREA)
  • Zoology (AREA)
  • Wood Science & Technology (AREA)
  • Dentistry (AREA)
  • Agronomy & Crop Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Toxicology (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Epidemiology (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Mycology (AREA)
  • Microbiology (AREA)
  • Apparatus For Disinfection Or Sterilisation (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Disinfection, Sterilisation Or Deodorisation Of Air (AREA)

Abstract

The present invention provides a kind of aqueous hydrogen peroxide solution for being easy removing residue, the sterilization used in the form of mist or steam less and then using washing to the attachment of the residue of spray nozzle.Above-mentioned technical problem can use following aqueous solution according to one embodiment and solve, the aqueous solution is the aqueous hydrogen peroxide solution of the sterilization used in the form of mist or steam, the aqueous solution contains hydrogen peroxide, 2ppm or more 8ppm orthophosphoric acid below or phosphonic acids, 10ppb or more 500ppb aluminium below and sulfate ion, and the content of above-mentioned sulfate ion is 10 times or more 20 times or less relative to the content of above-mentioned aluminium by quality ratio.

Description

Aqueous hydrogen peroxide for sterilization solution
Technical field
The present invention relates to a kind of aqueous hydrogen peroxide solutions of sterilization used in the form of mist or steam.The present invention also relates to And a kind of method for disinfection of object, the method for disinfection of the object are characterized in that, make aqueous hydrogen peroxide solution with mist or steaming The form of gas is contacted with object.
Background technique
Aqueous solution containing hydrogen peroxide is used as various fungicide.In addition, make fungicide in the form of mist or steam with it is right Before the technology sterilized as object is contacted to object is suitable for the sterilization and beverage filling of the toilet of used in electronic industry The sterilization etc. of PET bottle.Especially in recent years, popularizing with PET bottle, it is water-soluble for hydrogen peroxide used in aseptic filling Liquid, required performance improve.I.e., it is desirable that when making hydrogen peroxide and water evaporation under residue few aqueous solution or high temperature or The high aqueous solution of stability in metal storage container.
For aseptic filling using in the case where the aqueous solution containing hydrogen peroxide, it is known that utilize evaporator by peroxidating Aqueous solution of hydrogen is heated to boiling point or more and is vaporized, is sprayed the gas of hydrogen peroxide together with air to kill to container The method (referring to patent document 1) of bacterium.However, in the method, existing and adding the stabilizer in aqueous hydrogen peroxide solution A part be attached to spray nozzle, evaporator and block with pipe portion etc., hinder aseptic filling device stable operation the problem of.
In addition, being stored in canisters such as stainless steels, there are stabilitys if the stablizing effect of stabilizer is insufficient The problem of being unable to maintain that.
So far, the method as the stability for solving above-mentioned blockage problem or hydrogen peroxide, propose reduction to The additive amount of the stabilizer of aqueous hydrogen peroxide solution addition.For example, report has using aminomethy-lenephosphonic acids in patent document 2 It reduces drying residue and ensures the method for the stability of hydrogen peroxide.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 11-47242 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2013-028643 bulletin
Summary of the invention
Technical problems to be solved by the inivention
As described above, having proposed the method for solving blockage problem or stability at present.However, pair as blockage problem Plan also cannot be completely eliminated spray nozzle, attached on evaporator even if reducing the additive amount of the stabilizer in aqueous hydrogen peroxide solution The residual of object, and since the attachment of phosphonic acids system is slightly solubility, thus exist blocking with pipe portion, resistance cannot be fully solved The possibility for the problem of hindering the stable operation of aseptic filling device.
In addition, the nearest research of inventor according to the present invention is learnt, due in aqueous hydrogen peroxide solution as stablizing Phosphoric acid or chelating agent added by agent dissolve out micro metal, the stability decline of hydrogen peroxide from made of metal storage tank.Largely The interruption of service that when using stabilizer, can be avoided the decline of stability, but easily cause above-mentioned spray nozzle blocking etc., because This need to further improve.
The object of the present invention is to provide a kind of to adhere to less to the residue of spray nozzle and then utilize the easy removing of washing residual Slag, the sterilization used in the form of mist or steam aqueous hydrogen peroxide solution.
For solving the technical solution of technical problem
The present inventor studies intensively above-mentioned technical problem repeatedly, as a result, it has been found that, contain hydrogen peroxide, orthophosphoric acid Or the ratio between content of phosphonic acids, aluminium and sulfate ion and aluminium and sulfate ion can be improved peroxide in the aqueous solution of particular range Change the stability of hydrogen, reduces the attachment that attachment remains on the stabilizer in aqueous hydrogen peroxide solution of spray nozzle and evaporator Object, and residue can be easily removed using washing, so that reach the present invention.
That is, the present invention is as described below.
[1] a kind of aqueous solution, is the aqueous hydrogen peroxide solution of the sterilization used in the form of mist or steam, this is water-soluble Liquid contains:
Hydrogen peroxide;
2ppm or more 8ppm orthophosphoric acid below or phosphonic acids;
10ppb or more 500ppb aluminium below;With
Sulfate ion,
The content of above-mentioned sulfate ion is 10 times or more 20 times or less relative to the content of above-mentioned aluminium by quality ratio.
[2] aqueous solution as described in [1], wherein the concentration of above-mentioned hydrogen peroxide be 20 mass % or more, 45 mass % with Under.
[3] aqueous solution as described in [1] or [2], wherein evaporation residue amount is 10ppm or less.
[4] aqueous solution as described in any one of [1]~[3], wherein the washing removal rate in evaporator adhiesion test is 40% or more.
[5] aqueous solution as described in any one of [1]~[4], contains:
2ppm or more 5ppm orthophosphoric acid below;With
50ppb or more 250ppb aluminium below.
[6] aqueous solution as described in any one of [1]~[5] is used for the sterilization of container package material, utensil sterilization or empty Between sterilize.
[7] a kind of method for disinfection of object, which is characterized in that make aqueous solution described in any one of [1]~[6] with mist Or the form of steam is contacted with object.
[8] method for disinfection as described in [7], wherein the temperature of above-mentioned mist or steam is 30 DEG C~250 DEG C.
[9] method for disinfection as described in [7], wherein by above-mentioned mist or steam and gas mixing, gas shape fluid is formed, And contact the gas shape fluid with object.
[10] method for disinfection as described in [9], wherein above-mentioned gas be in air, nitrogen, oxygen and ozone extremely It is a kind few.
[11] method for disinfection as described in any one of [7]~[10], wherein above-mentioned object is packing container, food Machinery, PET bottle, PET bottle preform, laboratory apparatus, medical instrument, sanitary apparatus, kitchen tools or food.
[12] method for disinfection as described in any one of [7]~[10], wherein above-mentioned object is space.
[13] method for disinfection as described in [12], wherein above-mentioned space is automobile, the toilet of used in electronic industry, inhabitation Space, Medical space, kitchen, culinary art place, vehicle or aircraft.
Invention effect
Using the present invention, the stability of hydrogen peroxide be can be improved, and can be reduced attachment and be remained on spray nozzle and evaporator The stabilizer in aqueous hydrogen peroxide solution attachment, and can using washing easily remove residue.
Detailed description of the invention
Fig. 1 is the figure of the mass ratio for indicating sulfate ion content and aluminium content and the relationship of washing residue.
Fig. 2 is the figure for indicating the relationship of stabilizer total amount and stability.
Fig. 3 is the figure for indicating the relationship of aluminium content and stability.
Specific embodiment
Hereinafter, the present invention is described in detail.
1. the aqueous hydrogen peroxide solution of the sterilization used in the form of mist or steam
The aqueous hydrogen peroxide solution of the sterilization used in the form of mist or steam of the invention (in the present specification, has When be also referred to as " aqueous hydrogen peroxide solution of the invention ") containing hydrogen peroxide, orthophosphoric acid or phosphonic acids, aluminium and sulfate ion.Separately Outside, aqueous hydrogen peroxide solution of the invention can also contain other acid and/or salt is used as making to be attached to spray nozzle and steaming The additive that the washing of the evaporation residue of hair device etc. becomes easy.
The concentration of hydrogen peroxide in aquae hydrogenii dioxidi of the invention be 20 mass % or more, preferably 25 mass % with On.Concentration is higher, and bactericidal effect is also higher, peroxidating when considering safety when operation, in aquae hydrogenii dioxidi of the invention The concentration of hydrogen is preferably 45 mass % or less.Preferred concentration range is 25 mass % or more, 40 mass % or less.
Aqueous hydrogen peroxide solution of the invention contains orthophosphoric acid (chemical formula H3PO4, also referred to as " phosphoric acid ") or phosphonic acids, Content is calculated as 2ppm or more 8ppm or less with quality criteria.The lower limit value of content is preferably 3ppm, and upper limit value is preferably 6ppm, more Preferably 5ppm.It is in the numberical range by the content of orthophosphoric acid or phosphonic acids, the stabilisation effect of hydrogen peroxide can be obtained Fruit, the amount for being attached to the evaporation residue of evaporator and nozzle are suppressed.Ortho-phosphoric content can use well known method and carry out Measurement, such as can use and be measured using the chromatography of ions of the DX-500 of Dionex manufacture.
Orthophosphoric acid used in the present invention is not particularly limited, and can be used by commercially available phosphorus such as rear rattan Chemical Co., Ltd. Acid (concentration: 85%) etc..In addition, as orthophosphoric acid, it is preferable to use being designated as the substance of the specified additive of food hygiene law. In addition, orthophosphoric acid used in the present invention can also be added in aqueous solution in the form of ortho-phosphoric salt, as such salt, The dihydric phosphates such as potassium dihydrogen phosphate, sodium dihydrogen phosphate, ammonium dihydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, phosphorus can be enumerated Phosphate such as hydrophosphates, tripotassium phosphate, the tertiary sodium phosphates such as sour hydrogen diammonium etc..
Phosphonic acids used in the present invention is not particularly limited, preferably organic phospho acid.It, can be with as such organic phospho acid Enumerate aminomethylphosphonic acid, hydroxy ethylene diphosphonic acid, aminotrimethylenephosphonic acid, ethylenediamine tetramethylene phosphonic acid, two sub- second Base triamine pentamethylene phosphonic acids, hexamethylene diamine tetramethylene phosphonic acid, bis hexamethylene triamine pentamethylene phosphonic acids and the third two Amine tetramethylene phosphonic acid etc..In addition, organic phospho acid used in the present invention can also be added in aqueous solution in the form of salt.
Aqueous hydrogen peroxide solution of the invention contains 10ppb or more 500ppb aluminium below in terms of quality criteria.Aluminium contains The lower limit value of amount is preferably 50ppb, more preferably 100ppb;Upper limit value is preferably 350ppb, more preferably 250ppb.Peroxidating The content of aluminium in aqueous solution of hydrogen for example can use high-frequency inductive coupling plasma body (ICP) apparatus for analyzing luminosity iCAP 6000 (Thermo Fisher SCIENTIFIC manufactures) etc. are measured.When the content of aluminium is above range, it can obtain The stabilization effect of hydrogen oxide, the amount for being attached to the evaporation residue of evaporator and spray nozzle are suppressed.
Aluminium contained by aqueous hydrogen peroxide solution of the invention can be added in aqueous solution in the form of salt, as such The concrete example of aluminium salt is preferably listed aluminum aluminum sulfate, aluminum nitrate, aluminum sulfate, alum and oxalic acid aluminium, particularly preferably enumerates sulfuric acid Aluminium potassium.In the present invention it is preferable to use aluminum aluminum sulfate can be hydrate as 12 hydrates.Alternatively, aluminium can also be by making Pure aluminum or aluminum alloy is contacted with aqueous hydrogen peroxide solution and is added.In addition, as aluminium salt, particularly preferably used as food hygiene The specified additive of method and appointed substance.
Aqueous hydrogen peroxide solution of the invention contains sulfate ion.Sulfate ion can be added to water in the form of salt In solution, as the concrete example of such sulfate, aluminum aluminum sulfate, aluminum sulfate, alum and sodium sulphate etc. can be enumerated, but It's not limited to that.In addition, as sulfate, it is particularly preferably appointed used as the specified additive of food hygiene law Substance.The content of sulfate ion is preferably calculated as 100ppb~10,000ppb with quality criteria.
In aqueous hydrogen peroxide solution of the invention, the content of sulfate ion is by quality ratio relative to the content of aluminium 10 times or more, preferably 11 times or more, more preferably 12 times or more, and be 20 times or less, preferably 19 times or less, more preferable It is 18 times or less.It is in the range by the mass ratio of the content of sulfate ion and aluminium, the stability of hydrogen peroxide can mention Height can reduce the attachment that attachment remains on the stabilizer in aqueous hydrogen peroxide solution of spray nozzle and evaporator, and And residue can be easily removed using washing.
Decomposition ingredient as hydrogen peroxide, it is known to heavy metal classes, as the aqueous hydrogen peroxide solution industrially manufactured Contained decomposition ingredient, is substantially defined in Fe, Cr, Ni, Pd.It is preferable to use by Ni and Pd for aqueous hydrogen peroxide solution of the invention Concentration be set to 0.1ppb or less and the concentration of Fe and Cr be set to 5ppb aqueous hydrogen peroxide solution below.In this way Aqueous hydrogen peroxide solution can use well known method and obtain, can specifically enumerate and utilize distillation, ion exchange resin, absorption Material, chelating agent, the anti-method for being impregnated with film etc. and removing metal component.
Within the scope of the effect of the invention, aqueous hydrogen peroxide solution of the invention can also be containing other public The stabilizer of hydrogen peroxide known.As an example, by and with the desired amount of inorganic phosphate system stabilizer, also can further improve Stability.As concrete example, pyrophosphoric acids salts such as pyrophosphoric acid hydrogen sodium, sodium pyrophosphate etc. can be enumerated, it can be according to usage Deng requirement, contain alone or in combination.In addition, as inorganic phosphate system stabilizer, it is preferable to use finger as food hygiene law Determine additive and appointed substance.As such inorganic phosphate system stabilizer, can enumerate tripotassium phosphate, tricalcium phosphate, Tricresyl phosphate magnesium, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, calcium monohydrogenphosphate, calcium dihydrogen phosphate, phosphorus Sour disodium hydrogen, sodium dihydrogen phosphate, one hydrogen magnesium of phosphoric acid and tertiary sodium phosphate etc..
Stabilizer total amount in aqueous hydrogen peroxide solution of the invention is preferably 2,500ppb~7,000ppb, more preferably 3,000ppb~6,000ppb.
In the present invention, the washing for the evaporation residue for being attached to nozzle and rapid steamer etc. is made to become good other acid And/or salt can also be selected from the specified additive of food hygiene law.Specifically, it is preferable that L-AA and/or its salt, second Ethylenediaminotetraacetate (edetate), citric acid and/or its salt, gluconic acid and/or its salt, Pidolidone and/or its salt, silicate, nitric acid Salt, carbonate, pyrophosphate, sulfate, particularly preferred sulfate.
About aqueous hydrogen peroxide solution of the invention, evaporation residue amount be preferably 10ppm hereinafter, more preferably 8ppm with Under.Evaporation residue amount in aqueous hydrogen peroxide solution can use method documented by JIS-K1463 and be measured.
About aqueous hydrogen peroxide solution of the invention, the washing removal rate in evaporator adhiesion test be preferably 40% with On, more preferably 50% or more.It is aftermentioned in embodiment for the details of evaporator adhiesion test.
Aqueous hydrogen peroxide solution of the invention is in the form of mist or steam for sterilizing.Keep hydrogen peroxide of the invention water-soluble The method that liquid gasifies and generates mist or steam is not particularly limited.For the details of method for disinfection, in the present specification after It states.
The purposes of aqueous hydrogen peroxide solution of the invention is not particularly limited, and is preferred for the sterilization of container package material, device Tool sterilization or space sterilization.
2. the method for disinfection of object
Method for disinfection of the invention is related to the method for disinfection of object, which is characterized in that makes aquae hydrogenii dioxidi of the invention Solution is contacted in the form of mist or steam with object.About the details of aqueous hydrogen peroxide solution of the invention, institute as above It states.
The method for making aqueous hydrogen peroxide solution gasify and generating mist or steam is not particularly limited, such as can enumerate utilization The method of ultrasonic wave utilizes the method heated.It can be used alone the mist or steam of the obtained aqueous hydrogen peroxide solution, Gas shape fluid can also be formed with other gas mixings and contact with object.Preferably by evaporator by aquae hydrogenii dioxidi Solution is heated to boiling point or more and is vaporized, and the mist or steam of other gases and aqueous hydrogen peroxide solution are mixed, and is formed Gas shape fluid and use.The device of aqueous hydrogen peroxide solution heating and gasifying is set to use well known dress without particular limitation It sets.Used by mixed gas, even such as concaveconvex shape object, also can be more effectively water-soluble with hydrogen peroxide The mist or steam of liquid contact.
As the concrete example for the gas that the mist or steam with above-mentioned aqueous hydrogen peroxide solution use simultaneously, sky can be enumerated Gas, nitrogen, oxygen and ozone.In particular, since air is cheap, thus preferably.Temperature for mixed gas is preferably It is more than room temperature.
When contacting the mist of aqueous hydrogen peroxide solution or steam with object, prefers to while the gas used also carries out Heating.
The mist or steam of aqueous hydrogen peroxide solution or with the mist of the aqueous hydrogen peroxide solution after other gas mixings or The temperature of gas shape fluid as steam is preferably 30~250 DEG C, more preferably 50 DEG C~200 DEG C, further preferably 100 DEG C~150 DEG C.By using within the scope of above-mentioned temperature, sufficient sterilizing ability can be obtained, and can effectively prevent Only because of the damage of sterilization object object caused by heat.
As object, packing container, food machinery, PET bottle, PET bottle preform, laboratory apparatus, doctor may be exemplified Instrument, sanitary apparatus, kitchen tools, food and space etc. are treated, but not limited to this.
As space, automobile, the toilet of used in electronic industry, living space, Medical space, kitchen, culinary art may be exemplified Place, vehicle, aircraft etc., but not limited to this.
In the present invention, the generation device of the mist of aqueous hydrogen peroxide solution and/or steam can also be put into facility, is produced The mist and/or steam of raw aqueous hydrogen peroxide solution, reduce the bacterium number in facility.
As the facility, bathroom facility, waste treatment facilities, animal house etc. may be exemplified, but not limited to this.
Embodiment
Then, the present invention is more specifically illustrated using embodiment and comparative example.But the present invention is not limited to Under embodiment.
The stability of < hydrogen peroxide and the evaluation method > of evaporation remainder
The stability and evaporation remainder of hydrogen peroxide are evaluated using the method for JIS-K1463 defined.
The measurement > of < phosphoric acid and sulfate ion concentration
Phosphoric acid and sulfate ion concentration in aqueous hydrogen peroxide solution utilize ion chromatograph DX-500 (Dionex system Make) it is measured.
< aluminum concentration >
Aluminum concentration in aqueous hydrogen peroxide solution utilizes 6000 (Thermo Fisher of ICP apparatus for analyzing luminosity iCAP SCIENTIFIC manufacture) it is measured.
The evaluation > of < evaporator adhesion amount and washing property
Simulation evaporator is used so that well known evaporator is reference and reduces the evaporator simulated.Concentration of hydrogen peroxide 35% Aqueous hydrogen peroxide solution sample mixed with air in the simulation evaporator for being heated to 300 DEG C on one side, on one side with certain speed Liquor charging simultaneously gasifies, and test within 80 hours.When concentration of hydrogen peroxide is 25%, it is set as 112 hours.Simulation after measurement test is steamed Send out the amount of thinking highly of, using with the weight difference before test as adhesion amount (mg).Then, it washed with ion exchange water, dried, Measure weight again, using with the weight difference before test as residual quantity (mg).According to adhesion amount and residual quantity, calculated based on following formula Removal rate (%) is washed in water outlet.
Wash removal rate (%)=[1- { residual quantity (mg)/adhesion amount (mg) }] × 100
(simulation evaporator construction)
Material: SUS304L
Size:The front end of cylinder-shaped vaporizer is equipped with the conical nozzle of height 17mm.Circular cone Shape nozzle is provided with using front endHole nozzle.
(condition)
The liquor charging flow of aqueous hydrogen peroxide solution sample: 1.25mL/min
Air mass flow: 2.1L/min
Ion exchange water flow: 500ml/1.5min
The gaseous fluid temperature of jet hole: 100~120 DEG C
< SUS immersion test >
The test film (30mm × 30mm × 2mm) 2 of SUS304L is put into hydrogen peroxide water sample 300ml, 45 DEG C stand 24 hours.
1 > of < embodiment
After distillation purification, orthophosphoric acid (rear rattan chemistry strain is added into 35% aquae hydrogenii dioxidi to pure water adjustment concentration The manufacture of formula commercial firm, phosphoric acid (concentration 85.0%)) 3 mass ppm, aluminum aluminum sulfate (Wako Pure Chemical Industries, Ltd.'s manufacture, aluminum sulfate 12 hydrate of potassium (concentration 96.5%)) 1 mass ppm, sodium sulphate (Wako Pure Chemical Industries, Ltd.'s manufacture, the hydration of sodium sulphate 10 Object (concentration 99.0%)) 0.5 mass ppm.Sulfate ion at this time/Al ratio is 14.The steaming of the aqueous hydrogen peroxide solution sample Hair remainder is 6 mass ppm, and evaporator adhesion amount is 12.3mg, and the washing removal rate of attachment is 59%.
< embodiment 2-4 >
Change concentration of hydrogen peroxide, aluminum aluminum sulfate additive amount, sodium sulphate additive amount respectively, carries out same as Example 1 Experiment.Respective content is as described in Table 1.The sulfate ion of these aqueous hydrogen peroxide solution samples/Al ratio is 10~20 Range.The washing removal rate of evaporator attachment is 60% or so.
< comparative example 1-5 >
Change concentration of hydrogen peroxide, aluminum aluminum sulfate additive amount, sodium sulphate additive amount respectively, carries out same as Example 1 Experiment.Respective content is as described in Table 1.The sulfate ion of these aqueous hydrogen peroxide solution samples/Al ratio departing from 10~ 20 range.The evaporator adhesion amount of these aqueous hydrogen peroxide solution samples sees deterioration in sample segment, in addition, washing Removal rate becomes the result substantially reduced in whole samples.In addition, when stabilizer is phosphoric acid, the increase of adhesion amount and SUS Stability decline after dipping is significant.
6 > of < comparative example
For comparative example 6, also respectively change concentration of hydrogen peroxide, aluminum aluminum sulfate additive amount, sodium sulphate additive amount, carry out with The identical experiment of embodiment 1.Respective content is as described in Table 1.The sulfate radical of the aqueous hydrogen peroxide solution sample of comparative example 6 from Son/Al ratio is in the range of 10~20, but ortho-phosphoric content has been more than 8ppm.In the sample, evaporator adhesion amount and water Removal rate is washed to be degrading.
The results obtained are shown in table 1 and Fig. 1~3.
[table 1]
According to above-mentioned result it is found that passing through sulfate ion even if the total content of Al or the total content of stabilizer are few Content is 10 times or more 20 times hereinafter, being also able to maintain that the stability of hydrogen peroxide, energy relative to the content of aluminium by quality ratio Adhesion amount is enough reduced, washing removal rate (such as embodiment 1 and comparative example 2) is improved.
Industrial availability
Using the present invention, the stability of the hydrogen peroxide in aqueous hydrogen peroxide solution be can be improved, and is reduced attachment and is remained on The attachment of the stabilizer in aqueous hydrogen peroxide solution of spray nozzle and evaporator etc., and can be using washing easily Residue is removed, therefore, the thin of nonchoking nozzle etc. matches pipe portion, and aseptic filling device being capable of stable operation.

Claims (13)

1. a kind of aqueous solution is the aqueous hydrogen peroxide solution of the sterilization used in the form of mist or steam, the aqueous solution It is characterized in that, contains:
Hydrogen peroxide;
2ppm or more 8ppm orthophosphoric acid below or phosphonic acids;
10ppb or more 500ppb aluminium below;With
Sulfate ion,
The content of the sulfate ion is 10 times or more 20 times or less relative to the content of the aluminium by quality ratio.
2. aqueous solution as described in claim 1, it is characterised in that:
The concentration of the hydrogen peroxide is 20 mass % or more, 45 mass % or less.
3. aqueous solution as claimed in claim 1 or 2, it is characterised in that:
Evaporation residue amount is 10ppm or less.
4. aqueous solution according to any one of claims 1 to 3, it is characterised in that:
Washing removal rate in evaporator adhiesion test is 40% or more.
5. aqueous solution as described in any one of claims 1 to 4, which is characterized in that contain:
2ppm or more 5ppm orthophosphoric acid below;With
50ppb or more 250ppb aluminium below.
6. such as aqueous solution according to any one of claims 1 to 5, it is characterised in that:
For the sterilization of container package material, utensil sterilization or space sterilization.
7. a kind of method for disinfection of object, it is characterised in that:
Contact aqueous solution according to any one of claims 1 to 6 in the form of mist or steam with object.
8. method for disinfection as claimed in claim 7, it is characterised in that:
The temperature of the mist or steam is 30 DEG C~250 DEG C.
9. method for disinfection as claimed in claim 7, it is characterised in that:
By the mist or steam and gas mixing, gas shape fluid is formed, and contacts the gas shape fluid with object.
10. method for disinfection as claimed in claim 9, it is characterised in that:
The gas is at least one kind of in air, nitrogen, oxygen and ozone.
11. the method for disinfection as described in any one of claim 7~10, it is characterised in that:
The object is packing container, food machinery, PET bottle, PET bottle preform, laboratory apparatus, medical instrument, health Utensil, kitchen tools or food.
12. the method for disinfection as described in any one of claim 7~10, it is characterised in that:
The object is space.
13. method for disinfection as claimed in claim 12, it is characterised in that:
The space be automobile, the toilet of used in electronic industry, living space, Medical space, kitchen, culinary art place, vehicle or Aircraft.
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