WO2018142810A1 - 殺菌用過酸化水素水溶液 - Google Patents
殺菌用過酸化水素水溶液 Download PDFInfo
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- WO2018142810A1 WO2018142810A1 PCT/JP2017/046351 JP2017046351W WO2018142810A1 WO 2018142810 A1 WO2018142810 A1 WO 2018142810A1 JP 2017046351 W JP2017046351 W JP 2017046351W WO 2018142810 A1 WO2018142810 A1 WO 2018142810A1
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- hydrogen peroxide
- aqueous solution
- sterilization
- mist
- aluminum
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- 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
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- 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
- A01N25/02—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 containing liquids as carriers, diluents or solvents
-
- 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
- A01N25/02—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 containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
- A01N25/06—Aerosols
-
- 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
- A01N25/22—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 containing ingredients stabilising the active ingredients
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- 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
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- 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
- A61L2/20—Gaseous substances, e.g. vapours
-
- 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
- A61L9/00—Disinfection, sterilisation or deodorisation of air
- A61L9/01—Deodorant compositions
-
- 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
- A61L9/00—Disinfection, sterilisation or deodorisation of air
- A61L9/015—Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone
- A61L9/02—Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone using substances evaporated in the air by heating or combustion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65B—MACHINES, APPARATUS OR DEVICES FOR, OR METHODS OF, PACKAGING ARTICLES OR MATERIALS; UNPACKING
- B65B55/00—Preserving, protecting or purifying packages or package contents in association with packaging
- B65B55/02—Sterilising, e.g. of complete packages
- B65B55/04—Sterilising wrappers or receptacles prior to, or during, packaging
- B65B55/10—Sterilising wrappers or receptacles prior to, or during, packaging by liquids or gases
Definitions
- the present invention relates to an aqueous hydrogen peroxide solution for sterilization used as mist or steam.
- the present invention also relates to a method for sterilizing an object, characterized in that an aqueous hydrogen peroxide solution is brought into contact with the object as mist or vapor.
- Aqueous solutions containing hydrogen peroxide are used as various disinfectants. Further, a technique for sterilizing an object by bringing the sterilizer into contact with the object as mist or vapor is applied to sterilization of a clean room for electronic industry, sterilization of a plastic bottle before filling a beverage, or the like. Particularly in recent years, coupled with the widespread use of PET bottles, the required performance for aqueous hydrogen peroxide solutions used for aseptic filling has increased. That is, there are demands for a material that has little residue when hydrogen peroxide and water are evaporated, and a material that has high stability in high temperature or metal storage containers.
- Patent Document 2 reports a method of reducing dry residue and ensuring the stability of hydrogen peroxide using aminomethylene phosphonic acid.
- An object of the present invention is to provide a hydrogen peroxide aqueous solution for sterilization to be used as mist or steam, which has less residue residue on the spray nozzle and can be easily removed by washing with water.
- the inventors of the present invention contain hydrogen peroxide, orthophosphoric acid or phosphonic acid, aluminum, and sulfate ions, and the ratio of the content of aluminum and sulfate ions is within a specific range.
- the aqueous solution improves the stability of hydrogen peroxide, reduces the deposits derived from the stabilizer in the aqueous hydrogen peroxide solution remaining on the spray nozzle and evaporator, and allows the residue to be easily removed by washing with water. And the present invention has been reached.
- the present invention is as follows.
- a hydrogen peroxide aqueous solution for sterilization used as mist or steam, Hydrogen peroxide, 2 ppm or more and 8 ppm or less of orthophosphoric acid or phosphonic acid, Aluminum of 10 ppb or more and 500 ppb or less; Containing sulfate ions, The aqueous solution whose content of the said sulfate ion is 10 times or more and 20 times or less by mass ratio with respect to content of the said aluminum.
- the aqueous solution according to [1] wherein the concentration of the hydrogen peroxide is 20% by mass or more and 45% by mass or less.
- a method for sterilizing an object comprising bringing the aqueous solution according to any one of [1] to [6] into contact with the object as mist or vapor.
- the sterilization method according to [7] wherein the temperature of the mist or steam is 30 ° C to 250 ° C.
- the sterilization method according to [7], wherein the mist or vapor is mixed with gas to form a gaseous fluid and contacted with an object.
- the gas is at least one selected from the group consisting of air, nitrogen, oxygen, and ozone.
- the stability of hydrogen peroxide is improved, the stabilizer-derived deposits in the aqueous hydrogen peroxide solution remaining on the spray nozzle and the evaporator are reduced, and the residue can be easily removed by washing with water. it can.
- aqueous hydrogen peroxide solution used as mist or steam of the present invention (in this specification, sometimes referred to as “aqueous hydrogen peroxide solution of the present invention”) Hydrogen oxide, orthophosphoric acid or phosphonic acid, aluminum, and sulfate ion are included. Furthermore, the aqueous hydrogen peroxide solution of the present invention may contain other acid and / or salt as an additive for facilitating washing of the evaporation residue adhering to the spray nozzle or the evaporator.
- the concentration of hydrogen peroxide in the hydrogen peroxide solution of the present invention is 20% by mass or more, preferably 25% by mass or more.
- the concentration of hydrogen peroxide in the hydrogen peroxide solution of the present invention is preferably 45% by mass or less.
- a more preferable concentration range is 25% by mass or more and 40% by mass or less.
- the aqueous hydrogen peroxide solution of the present invention contains orthophosphoric acid (chemical formula H 3 PO 4 , also simply referred to as “phosphoric acid”) or phosphonic acid, and its content is 2 ppm or more and 8 ppm or less on a mass basis.
- the lower limit of the content is preferably 3 ppm, and the upper limit is preferably 6 ppm, more preferably 5 ppm.
- the content of orthophosphoric acid or phosphonic acid is within this numerical range, the effect of stabilizing hydrogen peroxide is obtained, and the amount of evaporation residue adhering to the evaporator or nozzle is suppressed.
- the content of orthophosphoric acid can be measured by a known method, for example, by ion chromatography using DX-500 manufactured by Dionex.
- the orthophosphoric acid used in the present invention is not particularly limited, and phosphoric acid (concentration: 85%) commercially available from Goto Chemical Co., Ltd. or the like can be used. Moreover, as orthophosphoric acid, it is preferable to use what is designated as the designated additive of the Food Sanitation Law.
- the orthophosphoric acid used in the present invention may be added to the aqueous solution in the form of a salt of orthophosphoric acid. Examples of such salts include potassium dihydrogen phosphate, sodium dihydrogen phosphate, dihydrogen phosphate.
- Examples include dihydrogen phosphates such as ammonium, dipotassium hydrogen phosphate, disodium hydrogen phosphate, hydrogen phosphates such as diammonium hydrogen phosphate, phosphates such as tripotassium phosphate, trisodium phosphate, etc. It is done.
- dihydrogen phosphates such as ammonium, dipotassium hydrogen phosphate, disodium hydrogen phosphate, hydrogen phosphates such as diammonium hydrogen phosphate, phosphates such as tripotassium phosphate, trisodium phosphate, etc. It is done.
- the phosphonic acid used in the present invention is not particularly limited, but is preferably an organic phosphonic acid.
- organic phosphonic acids include aminomethylphosphonic acid, hydroxyethylidene diphosphonic acid, aminotrimethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, hexamethylenediaminetetramethylenephosphonic acid, bishexamethylenetriaminepenta Examples include methylenephosphonic acid and propylenediaminetetramethylenephosphonic acid.
- the organic phosphonic acid used in the present invention may be added to the aqueous solution in the form of a salt.
- the aqueous hydrogen peroxide solution of the present invention contains 10 ppb or more and 500 ppb or less of aluminum on a mass basis.
- the lower limit value of the aluminum content is preferably 50 ppb, more preferably 100 ppb, and the upper limit value is preferably 350 ppb, more preferably 250 ppb.
- the content of aluminum in the aqueous hydrogen peroxide solution can be measured with, for example, a high-frequency inductively coupled plasma (ICP) emission spectrometer iCAP 6000 (Thermo Fisher SCIENTIFIC).
- ICP inductively coupled plasma
- iCAP 6000 Thermo Fisher SCIENTIFIC
- the aluminum contained in the aqueous hydrogen peroxide solution of the present invention may be added to the aqueous solution in the form of a salt.
- a salt include potassium aluminum sulfate, aluminum nitrate, aluminum sulfate, and aluminum ammonium sulfate.
- aluminum oxalate are preferable, and potassium aluminum sulfate is particularly preferable.
- the potassium aluminum sulfate preferably used in the present invention may be a hydrate such as dodecahydrate.
- aluminum may be added by bringing pure aluminum or an aluminum alloy into contact with an aqueous hydrogen peroxide solution.
- the aqueous hydrogen peroxide solution of the present invention contains sulfate ions.
- the sulfate ion may be added to the aqueous solution in the form of a salt, and specific examples of such a sulfate include potassium aluminum sulfate, aluminum sulfate, aluminum ammonium sulfate, and sodium sulfate, but are not limited thereto. Is not to be done.
- the content of sulfate ions is preferably 100 ppb to 10,000 ppb on a mass basis.
- the sulfate ion content is 10 times or more, preferably 11 times or more, more preferably 12 times or more, and 20 times or less, preferably 20 times or less, with respect to the aluminum content. 19 times or less, more preferably 18 times or less.
- the mass ratio of the sulfate ion and aluminum content is within this range, so that the stability of hydrogen peroxide is improved, and the stabilizer-derived deposits in the hydrogen peroxide solution remaining on the spray nozzle and the evaporator are removed. And the residue can be easily removed by washing with water.
- Heavy metals are known as hydrogen peroxide decomposition components, but the decomposition components contained in an aqueous hydrogen peroxide solution produced industrially are almost limited to Fe, Cr, Ni, and Pd.
- the aqueous hydrogen peroxide solution of the present invention is preferably an aqueous hydrogen peroxide solution in which the concentration of Ni and Pd is 0.1 ppb or less and the concentration of Fe and Cr is 5 ppb or less, respectively.
- Such an aqueous hydrogen peroxide solution is obtained by a known method, and specifically includes a method of removing a metal component by distillation, ion exchange resin, adsorbent, chelate, reverse osmosis membrane or the like.
- the aqueous hydrogen peroxide solution of the present invention may contain other known hydrogen peroxide stabilizers as long as the effects of the present invention are not impaired.
- the stability can be further improved by using a required amount of an inorganic phosphate stabilizer in combination.
- Specific examples include pyrophosphates such as sodium hydrogen pyrophosphate and sodium pyrophosphate, and they may be contained alone or in combination as desired for the intended use.
- the inorganic phosphate stabilizer it is preferable to use those designated as designated additives in the Food Sanitation Law.
- Such inorganic phosphate stabilizers include tripotassium phosphate, tricalcium phosphate, trimagnesium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate. , Calcium monohydrogen phosphate, calcium dihydrogen phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, magnesium monohydrogen phosphate, trisodium phosphate, and the like.
- the total amount of the stabilizer in the aqueous hydrogen peroxide solution of the present invention is preferably 2,500 ppb to 7,000 ppb, and more preferably 3,000 ppb to 6,000 ppb.
- acids and / or salts that improve the washing performance of evaporation residue adhering to a nozzle or an evaporator can also be selected from designated additives of the Food Sanitation Law.
- the aqueous hydrogen peroxide solution of the present invention preferably has an evaporation residue amount of 10 ppm or less, more preferably 8 ppm or less.
- the amount of evaporation residue in the aqueous hydrogen peroxide solution can be measured by the method described in JIS-K1463.
- the water removal rate in the evaporator adhesion test is preferably 40% or more, and more preferably 50% or more. Details of the evaporator adhesion test will be described later in Examples.
- the aqueous hydrogen peroxide solution of the present invention is used for sterilization as mist or steam.
- the method of vaporizing the aqueous hydrogen peroxide solution of the present invention to generate mist or vapor is not particularly limited. Details of the sterilization method will be described later in this specification.
- aqueous hydrogen peroxide solution of the present invention is not particularly limited, but it is preferably used for container and packaging material sterilization, instrument sterilization, or space sterilization.
- the sterilization method of the present invention relates to a method of sterilization of an object, wherein the aqueous hydrogen peroxide solution of the present invention is brought into contact with the object as mist or vapor. Details of the aqueous hydrogen peroxide solution of the present invention are as described above.
- a method for vaporizing the aqueous hydrogen peroxide solution to generate mist or vapor is not particularly limited, and examples thereof include an ultrasonic method and a heating method.
- the mist or vapor of the hydrogen peroxide aqueous solution thus obtained may be used alone, or may be mixed with another gas and contacted with the object as a gaseous fluid.
- the aqueous hydrogen peroxide solution is heated and vaporized to the boiling point or higher with an evaporator, and another gas and a mist or vapor of the aqueous hydrogen peroxide solution are mixed and used as a gaseous fluid.
- the apparatus for heating and vaporizing the hydrogen peroxide aqueous solution is not particularly limited, and a known apparatus can be used. By mixing and using the gas, for example, even an uneven object can be more efficiently brought into contact with the mist or vapor of the aqueous hydrogen peroxide solution.
- gas to be accompanied with the mist or vapor of the hydrogen peroxide aqueous solution include air, nitrogen, oxygen, and ozone.
- air is preferable because it is inexpensive.
- the temperature of the gas used for mixing is preferably room temperature or higher.
- the temperature of the gaseous fluid such as the mist or vapor of the aqueous hydrogen peroxide solution or the mist or vapor of the aqueous hydrogen peroxide solution mixed with another gas is preferably 30 to 250 ° C, more preferably 50 to 200 ° C, still more preferably Is 100 ° C. to 150 ° C.
- Examples of the object include, but are not limited to, a packaging container, a food machine, a PET bottle, a PET bottle preform, a laboratory instrument, a medical instrument, a sanitary instrument, a cooking instrument, food, and a space.
- Examples of the space include, but are not limited to, a clean room for an automobile, an electronic industry, a living space, a medical space, a kitchen, a kitchen, a vehicle, and an aircraft.
- a hydrogen peroxide aqueous solution mist and / or vapor generator may be brought into the facility to generate the hydrogen peroxide aqueous solution mist and / or vapor, thereby reducing the number of bacteria in the facility.
- Examples of such facilities include toiletries, waste disposal facilities, and barns, but are not limited to these.
- the simulated evaporator used was a simulated reduced scale with reference to a known evaporator.
- a hydrogen peroxide aqueous solution sample having a hydrogen peroxide concentration of 35% was sent to a simulated evaporator heated to 300 ° C. at a constant speed while being mixed with air and vaporized, and tested for 80 hours.
- the hydrogen peroxide concentration was 25%, the time was 112 hours.
- the weight of the simulated evaporator after the test was measured, and the weight difference from that before the test was defined as the amount of adhesion (mg).
- Water removal rate (%) [1 ⁇ ⁇ residual amount (mg) / adhesion amount (mg) ⁇ ] ⁇ 100 (Simulated evaporator structure)
- Example 2-4 Experiments similar to those of Example 1 were performed by changing the hydrogen peroxide concentration, the potassium aluminum sulfate addition amount, and the sodium sulfate addition amount. Each content is as described in Table 1. The sulfate ion / Al ratio of these aqueous hydrogen peroxide samples is in the range of 10-20. The water removal rate of the deposit on the evaporator was around 60%.
- Example 1-5 Experiments similar to those of Example 1 were performed by changing the hydrogen peroxide concentration, the potassium aluminum sulfate addition amount, and the sodium sulfate addition amount. Each content is as described in Table 1.
- the sulfate ion / Al ratio of these hydrogen peroxide aqueous solution samples is out of the range of 10-20.
- the amount of the evaporator attached to these hydrogen peroxide aqueous solution samples deteriorated in some samples, and the water removal rate greatly decreased in all samples.
- the stabilizer was phosphoric acid alone, an increase in the adhesion amount and a decrease in stability after SUS immersion were significant.
- Comparative Example 6 For Comparative Example 6, the same experiment as in Example 1 was performed by changing the hydrogen peroxide concentration, the potassium aluminum sulfate addition amount, and the sodium sulfate addition amount. Each content is as described in Table 1.
- the sulfate ion / Al ratio of the aqueous hydrogen peroxide sample of Comparative Example 6 is in the range of 10 to 20, but the orthophosphoric acid content exceeds 8 ppm. In this sample, both the amount of deposited evaporator and the water removal rate deteriorated.
- the sulfate ion content is 10 times or more and 20 times or less in terms of mass ratio with respect to the aluminum content, It can be seen that while the stability of hydrogen peroxide is maintained, the amount of adhesion can be reduced and the water washing removal rate can be increased (for example, Example 1 and Comparative Example 2).
- the stability of hydrogen peroxide in the aqueous hydrogen peroxide solution is improved, the deposits derived from the stabilizer in the aqueous hydrogen peroxide solution remaining on the spray nozzle and the evaporator are reduced, and the residue is washed with water. Therefore, the aseptic filling apparatus can be stably operated without blocking a thin pipe portion such as a nozzle.
Abstract
Description
[1]
ミスト又は蒸気として用いる殺菌用の過酸化水素水溶液であって、
過酸化水素と、
2ppm以上、8ppm以下のオルトリン酸又はホスホン酸と、
10ppb以上、500ppb以下のアルミニウムと、
硫酸イオンとを含有し、
前記硫酸イオンの含有量が前記アルミニウムの含有量に対して質量比で10倍以上、20倍以下である、水溶液。
[2]
前記過酸化水素の濃度が、20質量%以上、45質量%以下である、[1]に記載の水溶液。
[3]
蒸発残渣量が10ppm以下である、[1]又は[2]に記載の水溶液。
[4]
蒸発器付着試験における水洗除去率が40%以上である、[1]~[3]のいずれかに記載の水溶液。
[5]
2ppm以上、5ppm以下のオルトリン酸と、
50ppb以上、250ppb以下のアルミニウムとを含む、[1]~[4]のいずれかに記載の水溶液。
[6]
容器包装材料殺菌、器具殺菌又は空間殺菌に使用するための、[1]~[5]のいずれかに記載の水溶液。
[7]
[1]~[6]のいずれかに記載の水溶液をミスト又は蒸気として対象物に接触させることを特徴とする、対象物の殺菌方法。
[8]
前記ミスト又は蒸気の温度が30℃~250℃である、[7]に記載の殺菌方法。
[9]
前記ミスト又は蒸気を気体と混合してガス状流体とし、対象物に接触させる、[7]に記載の殺菌方法。
[10]
前記気体が空気、窒素、酸素、及びオゾンよりなる群から選択される少なくとも1種である、[9]に記載の殺菌方法。
[11]
前記対象物が包装容器、食品機械、ペットボトル、ペットボトルプリフォーム、実験器具、医療器具、衛生器具、調理器具又は食品である、[7]~[10]のいずれかに記載の殺菌方法。
[12]
前記対象物が空間である、[7]~[10]のいずれかに記載の殺菌方法。
[13]
前記空間が自動車、電子工業用のクリーンルーム、居住空間、医療スペース、厨房、調理場、車両又は航空機である、[12]に記載の殺菌方法。
本発明のミスト又は蒸気として用いる殺菌用の過酸化水素水溶液(本明細書において、「本発明の過酸化水素水溶液」ということもある)は、過酸化水素と、オルトリン酸又はホスホン酸と、アルミニウムと、硫酸イオンとを含む。更に、本発明の過酸化水素水溶液は、噴霧ノズルや蒸発器などに付着した蒸発残渣の水洗性を容易にするための添加剤として、その他の酸及び/又は塩を含んでもよい。
本発明の殺菌方法は、本発明の過酸化水素水溶液をミスト又は蒸気として対象物に接触させることを特徴とする対象物の殺菌方法に関する。本発明の過酸化水素水溶液の詳細については、上述のとおりである。
過酸化水素の安定性及び蒸発残分は、JIS-K1463に規定された方法で評価した。
過酸化水素水溶液中のリン酸と硫酸イオン濃度は、イオンクロマトグラフィーDX-500(Dionex製)で測定した。
過酸化水素水溶液中のアルミニウム濃度は、ICP発光分析装置iCAP 6000(Thermo Fisher SCIENTIFIC製)で測定した。
模擬蒸発器は公知の蒸発器を参考に縮小模擬したものを用いた。過酸化水素濃度35%の過酸化水素水溶液サンプルは、300℃に加熱した模擬蒸発器に、空気と混合させながら一定速度で送液して気化させ、80時間試験した。過酸化水素濃度25%の場合は112時間とした。試験後の模擬蒸発器重量を測定し、試験前との重量差を付着量(mg)とした。さらにこれをイオン交換水で水洗、乾燥して再度重量を測定し、試験前との重量差を残留量(mg)とした。付着量と残留量から、下記式に基づいて水洗除去率(%)を算出した。
水洗除去率(%)=[1-{残留量(mg)/付着量(mg)}]×100
(模擬蒸発器構造)
材質: SUS304L
サイズ:150mm×23mmφ円筒気形気化室の先端に高さ17mmの円錐形ノズルをつけたもの。円錐形ノズルは先端に2mmφの穴が開いたものを用いる。
(条件)
過酸化水素水溶液サンプルの送液流量:1.25mL/min
空気流量: 2.1L/min
イオン交換水流量: 500ml/1.5min
ノズル口のガス流体温度:100~120℃
過酸化水素水サンプル300mlにSUS304L製のテストピース(30mm×30mm×2mm)2枚を入れ、45℃にて24時間静置した。
蒸留精製し、純水で35%に濃度調整した過酸化水素水に、オルトリン酸(後藤化学株式会社製、リン酸(濃度85.0%))3質量ppm、硫酸カリウムアルミニウム(和光純薬工業株式会社製、硫酸カリウムアルミニウム12水和物(濃度96.5%))1質量ppm、硫酸ナトリウム(和光純薬工業株式会社製、硫酸ナトリウム10水和物(濃度99.0%))0.5質量ppmを添加した。このときの硫酸イオン/Al比は14であった。この過酸化水素水溶液サンプルの蒸発残分は6質量ppmであり、蒸発器付着量は12.3mg、付着物の水洗除去率は59%であった。
過酸化水素濃度、硫酸カリウムアルミニウム添加量、硫酸ナトリウム添加量をそれぞれ変えて実施例1と同様の実験をおこなった。それぞれの含有量は表1に記載のとおりである。これらの過酸化水素水溶液サンプルの硫酸イオン/Al比は、10~20の範囲である。蒸発器付着物の水洗除去率は60%前後であった。
過酸化水素濃度、硫酸カリウムアルミニウム添加量、硫酸ナトリウム添加量をそれぞれ変えて実施例1と同様の実験をおこなった。それぞれの含有量は表1に記載のとおりである。これらの過酸化水素水溶液サンプルの硫酸イオン/Al比は、10~20の範囲を外れている。これらの過酸化水素水溶液サンプルの蒸発器付着量は一部のサンプルで悪化が見られ、また水洗除去率はすべてにおいて大きく低下する結果となった。また、安定剤がリン酸のみでは、付着量の増加とSUS浸漬後の安定度低下が顕著であった。
比較例6についても、過酸化水素濃度、硫酸カリウムアルミニウム添加量、硫酸ナトリウム添加量をそれぞれ変えて実施例1と同様の実験をおこなった。それぞれの含有量は表1に記載のとおりである。比較例6の過酸化水素水溶液サンプルの硫酸イオン/Al比は、10~20の範囲内であるが、オルトリン酸の含有量が8ppmを超えている。このサンプルでは蒸発器付着量および水洗除去率のいずれも悪化した。
Claims (13)
- ミスト又は蒸気として用いる殺菌用の過酸化水素水溶液であって、
過酸化水素と、
2ppm以上、8ppm以下のオルトリン酸又はホスホン酸と、
10ppb以上、500ppb以下のアルミニウムと、
硫酸イオンとを含有し、
前記硫酸イオンの含有量が前記アルミニウムの含有量に対して質量比で10倍以上、20倍以下である、水溶液。 - 前記過酸化水素の濃度が、20質量%以上、45質量%以下である、請求項1に記載の水溶液。
- 蒸発残渣量が10ppm以下である、請求項1又は2に記載の水溶液。
- 蒸発器付着試験における水洗除去率が40%以上である、請求項1~3のいずれか一項に記載の水溶液。
- 2ppm以上、5ppm以下のオルトリン酸と、
50ppb以上、250ppb以下のアルミニウムとを含む、請求項1~4のいずれか一項に記載の水溶液。 - 容器包装材料殺菌、器具殺菌又は空間殺菌に使用するための、請求項1~5のいずれか一項に記載の水溶液。
- 請求項1~6のいずれか一項に記載の水溶液をミスト又は蒸気として対象物に接触させることを特徴とする、対象物の殺菌方法。
- 前記ミスト又は蒸気の温度が30℃~250℃である、請求項7に記載の殺菌方法。
- 前記ミスト又は蒸気を気体と混合してガス状流体とし、対象物に接触させる、請求項7に記載の殺菌方法。
- 前記気体が空気、窒素、酸素、及びオゾンよりなる群から選択される少なくとも1種である、請求項9に記載の殺菌方法。
- 前記対象物が包装容器、食品機械、ペットボトル、ペットボトルプリフォーム、実験器具、医療器具、衛生器具、調理器具又は食品である、請求項7~10のいずれか一項に記載の殺菌方法。
- 前記対象物が空間である、請求項7~10のいずれか一項に記載の殺菌方法。
- 前記空間が自動車、電子工業用のクリーンルーム、居住空間、医療スペース、厨房、調理場、車両又は航空機である、請求項12に記載の殺菌方法。
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JP2018565989A JPWO2018142810A1 (ja) | 2017-01-31 | 2017-12-25 | 殺菌用過酸化水素水溶液 |
KR1020237002665A KR20230017922A (ko) | 2017-01-31 | 2017-12-25 | 살균용 과산화수소 수용액 |
CN201780084068.4A CN110191640A (zh) | 2017-01-31 | 2017-12-25 | 杀菌用过氧化氢水溶液 |
CN202410108378.7A CN117941706A (zh) | 2017-01-31 | 2017-12-25 | 杀菌用过氧化氢水溶液 |
KR1020197017238A KR20190111904A (ko) | 2017-01-31 | 2017-12-25 | 살균용 과산화수소 수용액 |
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Cited By (3)
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WO2022190894A1 (ja) * | 2021-03-08 | 2022-09-15 | 三菱瓦斯化学株式会社 | 殺菌用過酸化水素水溶液並びにこれを用いた対象物の殺菌方法および殺菌された対象物の製造方法 |
WO2022272257A1 (en) * | 2021-06-23 | 2022-12-29 | Evonik Corporation | A process for sterilization treatment using a residue-free hydrogen peroxide |
JP7273441B1 (ja) | 2022-10-05 | 2023-05-15 | 株式会社エアレックス | 除染液、並びに、これを使用する除染装置及び除染方法 |
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KR20190111904A (ko) | 2019-10-02 |
TW201832663A (zh) | 2018-09-16 |
CN117941706A (zh) | 2024-04-30 |
CN110191640A (zh) | 2019-08-30 |
TWI789373B (zh) | 2023-01-11 |
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