Composition for sterilization and sterilization method

Abstract

To provide a disinfection composition that is suitable for users, including general consumers, to perform bacteria eradication, antibacterial measures, sterilization, or disinfection, wherein the disinfection composition has a pH of 12 or less, tends not to roughen hand skin, and has high storage stability, and to provide a disinfection method using the disinfection composition.SOLUTION: A disinfection composition contains a bromine-based oxidizing agent, a sulfamic acid compound, and a buffer; has an effective bromine concentration that falls within the range of 0.005-1.5%; and a pH that falls within the range between 5.0 and 11.0.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a sterilizing composition for sterilizing, antibacterial, disinfecting, or sterilizing an object to be sterilized, and a sterilizing method for sterilizing, antibacterial, disinfecting, or sterilizing an object to be sterilized using the sterilizing composition.

Background Art

[0002] The novel coronavirus (CoVid-19), which has been rapidly spreading since the end of 2019 to the present, has become a historical pandemic. Due to this event, consumer behavior has changed significantly. Especially in households, restaurants, etc., consumers have taken the initiative to sterilize, antibacterial, disinfect, or sterilize all kinds of places such as the walls, doors, floors, furniture, kitchen sinks, washing machines, bathrooms, kitchens, dining tables, chairs, etc. of houses.

[0003] As effective sterilizing, antibacterial, disinfecting, or sterilizing methods, in Japan, sufficient supply is possible, and as effective chemical substances, sodium hypochlorite and ethanol can be mentioned. Furthermore, in the "Evaluation of the effectiveness of alternative disinfection methods against the novel coronavirus (Final Report)" published by the National Institute of Technology and Evaluation (NITE) in Japan in June 2020, various surfactants, soaps, hypochlorous acid water, sodium dichloroisocyanurate, etc. are also said to be effective.

[0004] However, when users including general consumers handle these substances themselves, there are various risks. For example, ethanol is effective against viruses with envelopes such as the novel coronavirus (CoVid-19), but it does not work effectively against viruses without envelopes, such as norovirus.

[0005] Regarding sodium hypochlorite, many commercially available products have an available chlorine concentration of about 6 to 12% by weight (60,000 to 120,000 mgCl / L). When users including general consumers use this, there is a risk of generating chlorine gas by mixing with an acid, and even in dilution with water, due to a concentration adjustment error, there is a risk of insufficient effect due to a low concentration or various adverse effects due to a high concentration. Adverse effects due to a high concentration include discomfort due to the odor of chlorine gas in a closed space, corrosion due to contact with metal objects, skin irritation to the human body, etc. Also, even if sodium hypochlorite can be adjusted to a concentration of 0.05% by weight (500 mgCl / L) or more recommended in the "List of Disinfection and Sterilization Methods Effective against Novel Coronavirus" announced by the Ministry of Economy, Trade and Industry of Japan on July 6, 2020, there is a risk of discomfort due to the odor of chlorine gas during wiping.

[0006] Regarding sodium dichloroisocyanurate which is a solid, essentially it has the same risks as sodium hypochlorite. Regarding hypochlorous acid water, in the above report of NITE, it is said to be effective against the novel coronavirus (CoVid-19) at an available chlorine concentration of 35 mgCl / L or more. However, it is difficult for commercially available hypochlorous acid water to stably maintain an available chlorine concentration of 35 mgCl / L or more for a long time, and there is a risk of the concentration becoming insufficient for the effect. Also, in the above report of the Ministry of Economy, Trade and Industry, for "wiping" using hypochlorous acid water, it recommends an available chlorine concentration of 80 mgCl / L or more, but in practice, there is a problem that it is very difficult to supply while maintaining an available chlorine concentration of 80 mgCl / L or more.

[0007] Although surfactants and soaps have a certain effect, the use concentration at which the effect is recognized is as high as about 0.1% by weight or more, and it is difficult to instantaneously perform sterilization, antibacterial, disinfection, or sterilization. Moreover, since their wastewater places a large environmental burden, it cannot be said that their use is preferable.

[0008] Thus, when users including general consumers use existing recommended chemical substances for the purpose of sterilization, antibacterial, disinfection, or sterilization, they have some risks or problems.

[0009] On the one hand, Patent Document 1 describes a water treatment agent composition containing water, a bromine-based oxidizing agent with an available bromine concentration of 1 to 16.5% by mass as the effective bromine concentration based on the total amount of the water treatment agent composition, sulfamic acid in an amount of 0.7 to 2.0 times the molar amount of the bromine-based oxidizing agent, and an alkali containing at least one of sodium hydroxide and potassium hydroxide, having a pH of 12.5 or higher, and a water concentration of 54% by mass or higher based on the total amount of the water treatment agent composition.

[0010] However, when the above-mentioned available bromine concentration is converted to an available chlorine concentration, it is as high as 4400 mgCl / L to 73300 mgCl / L, and the pH is 12.5 or higher. When the water treatment agent composition of Patent Document 1 is used by users including general consumers for disinfection, antibacterial, sterilization, or disinfection, there is a high risk of roughness, etc. Also, in the study by the present inventors, it was found that the water treatment agent composition of Patent Document 1 has a problem of insufficient storage stability at a pH suitable for use by users including general consumers.

[0011] In addition, in order to safely deliver to users including general consumers, it is desirable to dilute and provide such a high-concentration oxidizing agent. Further, in the diluted solution, since roughness occurs when the pH is higher than 12, it is better to adjust the pH to 12 or lower. However, oxidizing agents such as stabilized hypobromous acid and sodium hypochlorite are stable on the alkaline side, but there is a possibility of generating halogen gas when it becomes acidic, and it is not stable.

Prior Art Documents

Patent Documents

[0012]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0013] An object of the present invention is to provide a sterilizing composition suitable for use by users including general consumers for sterilization, antibacterial, disinfection, or sterilization, which is less likely to cause rough hands with a pH of 12 or less and has high storage stability, and a sterilization method using the sterilizing composition.

Means for Solving the Problems

[0014] The present invention includes a bromine-based oxidizing agent, a sulfamic acid compound, and a buffer, and the available bromine concentration is 0.005% or more 1.15 % and below, and the pH is in the range of 5.0 to 11.0 wherein the buffer contains at least one of a carbonate and a hydrogen carbonate It is a sterilizing composition.

[0015] The present invention includes a bromine-based oxidizing agent, a sulfamic acid compound, and a buffer, and the available bromine concentration is in the range of 0.007% or more and 1.15% or less, and the pH is in the range of 5.0 to 10.5 wherein the buffer contains at least one of a carbonate and a hydrogen carbonate It is a sterilizing composition.

[0017] In the sterilizing composition, the concentration of at least one of the carbonate and bicarbonate is preferably in the range of 10 mg / L to 60000 mg / L.

[0018] In the sterilizing composition, it is preferable to further include a pH adjuster.

[0019] In the sterilizing composition, it is preferable that the pH adjuster contains at least one of sodium hydroxide, sulfuric acid, hydrochloric acid, and nitric acid.

[0020] In the sterilizing composition, it is preferable to contain 1.0 to 2.0 times the equivalent amount of the sulfamic acid compound with respect to the equivalent amount of the bromine-based oxidizing agent.

[0021] In the sterilizing composition, it is preferable that the bromine-based oxidizing agent is bromine.

[0022] The present invention is a sterilization method in which the sterilizing composition is added to an object to be sterilized so that the available bromine concentration is in the range of 0.00002 to 1.5%.

Advantages of the Invention

[0023] According to the present invention, there are provided a sterilizing composition suitable for users including general consumers to perform sterilization, antibacterial, disinfection, or sterilization, less likely to cause rough hands with a pH of 12 or less, and having high storage stability, and a sterilizing method using the sterilizing composition.

Brief Description of the Drawings

[0024]

Figure 1

Modes for Carrying Out the Invention

[0025] Embodiments of the present invention will be described below. This embodiment is an example of carrying out the present invention, and the present invention is not limited to this embodiment.

[0026] <Sterilizing Composition> The sterilizing composition according to the embodiment of the present invention contains a bromine-based oxidizing agent, a sulfamic acid compound, and a buffer, and is a composition having an available bromine concentration in the range of 0.005% or more and 1.5% or less, and a pH in the range of 5.0 to 11.0. Further, the sterilizing composition according to the embodiment of the present invention contains a bromine-based oxidizing agent, a sulfamic acid compound, and a buffer, and is a composition having an available bromine concentration in the range of 0.007% or more and 1.15% or less, and a pH in the range of 5.0 to 10.5.

[0027] As a result of intensive studies, the present inventors have found that by adding a buffer to a bromine-based oxidizing agent and a sulfamic acid compound, the storage stability is remarkably improved at a predetermined available bromine concentration and pH. The composition for sterilization according to the present embodiment is a composition suitable for users including general consumers to perform disinfection, antibacterial, disinfection, or sterilization, less likely to cause rough skin with a pH of 12 or less, and having high storage stability. The composition for sterilization according to the present embodiment is a stabilized hypobromite-based solution, and can obtain long-term storage stability, which could not be achieved with a conventional aqueous sodium hypochlorite solution. In addition, it has a very high disinfection effect, antibacterial effect, disinfection effect, or sterilization effect not only against viruses having an envelope such as the novel coronavirus (CoVid-19), but also against viruses without an envelope such as norovirus, which could not be achieved with a conventional high-concentration ethanol solution.

[0028] In addition, by adding a buffer, it is possible to easily maintain a predetermined quality during productization. For example, when actually manufacturing a sterilizing composition in which the available bromine concentration of stabilized hypobromous acid, which is a bromine-based oxidizing agent, is in the range of 0.01% or more and 0.25% or less, and the pH is 5 or more and 10.5 or less. For example, when trying to produce 100 kg of a composition with an available chlorine concentration of 250 mgCl / L, it was found that after adjusting the pH to 9, the amount of 62.5% sulfuric acid required to adjust the pH to 4 is only 1.4 g. Therefore, when adjusting the pH of a stabilized hypobromous acid composition, which is a bromine-based oxidizing agent, to the neutral range, there is a possibility that the pH will fluctuate greatly due to a slight difference in the amount of acid added. Furthermore, since the amount of alkali in the stabilized hypobromous acid composition, which is a bromine-based oxidizing agent, may also vary, it has been difficult to maintain a predetermined quality during productization by controlling the pH of the stabilized hypobromous acid composition at pH 12 or less. On the other hand, by adding a buffer, the fluctuation of the pH with respect to the amount of the pH adjuster added is small, and a predetermined quality can be easily maintained during productization. Furthermore, it has been discovered that the addition of carbonate maintains storage stability at a higher available bromine concentration or a lower available bromine concentration rather than not adding carbonate. Therefore, it has been found that the effect of carbonate enables productization from a lower available bromine concentration to a higher available bromine concentration in addition to the buffering effect during production.

[0029] The phrase "containing a bromine-based oxidizing agent and a sulfamic acid compound" may include a stabilized hypobromous acid composition containing a mixture of a "bromine-based oxidizing agent" and a "sulfamic acid compound", or may include a stabilized hypobromous acid composition containing a "reaction product of a bromine-based oxidizing agent and a sulfamic acid compound".

[0030] Examples of the bromine-based oxidizing agent include bromine (liquid bromine), bromine chloride, bromic acid, bromate, hypobromous acid, etc. Hypobromous acid may be produced by reacting a bromine compound such as sodium bromide with a chlorine-based oxidizing agent such as hypochlorous acid.

[0031] Among these, a composition containing "bromine and a sulfamic acid compound (a mixture of bromine and a sulfamic acid compound)" or "a reaction product of bromine and a sulfamic acid compound" using bromine is more preferable as a sterilizing composition because it produces less by-product bromic acid and has lower corrosiveness to metals compared to a composition of "a bromine compound, hypochlorous acid, and sulfamic acid".

[0032] Examples of the bromine compound include sodium bromide, potassium bromide, lithium bromide, ammonium bromide, and hydrobromic acid. Among these, sodium bromide is preferable from the viewpoint of formulation cost and the like.

[0033] Examples of the chlorine-based oxidant include chlorine gas, chlorine dioxide, hypochlorous acid or its salts, chlorous acid or its salts, chloric acid or its salts, perchloric acid or its salts, chlorinated isocyanuric acid or its salts, and the like. Among these, examples of the salts include alkali metal hypochlorite such as sodium hypochlorite and potassium hypochlorite, alkaline earth metal hypochlorite such as calcium hypochlorite and barium hypochlorite, alkali metal chlorite such as sodium chlorite and potassium chlorite, alkaline earth metal chlorite such as barium chlorite, other metal chlorites such as nickel chlorite, ammonium chlorate, alkali metal chlorate such as sodium chlorate and potassium chlorate, alkaline earth metal chlorate such as calcium chlorate and barium chlorate, and the like. These chlorine-based oxidants may be used alone or in combination of two or more. From the viewpoint of handleability and the like, it is preferable to use sodium hypochlorite as the chlorine-based oxidant.

[0034] The sulfamic acid compound is a compound represented by the following general formula (1). R2NSO3H (1) (In the formula, R is independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.)

[0035] Examples of sulfamic acid compounds include, in addition to sulfamic acid (amidosulfuric acid) in which both of the two R groups are hydrogen atoms, sulfamic acid compounds in which one of the two R groups is a hydrogen atom and the other is an alkyl group having 1 to 8 carbon atoms, such as N-methylsulfamic acid, N-ethylsulfamic acid, N-propylsulfamic acid, N-isopropylsulfamic acid, N-butylsulfamic acid, etc., sulfamic acid compounds in which both of the two R groups are alkyl groups having 1 to 8 carbon atoms, such as N,N-dimethylsulfamic acid, N,N-diethylsulfamic acid, N,N-dipropylsulfamic acid, N,N-dibutylsulfamic acid, N-methyl-N-ethylsulfamic acid, N-methyl-N-propylsulfamic acid, etc., sulfamic acid compounds in which one of the two R groups is a hydrogen atom and the other is an aryl group having 6 to 10 carbon atoms, such as N-phenylsulfamic acid, or salts thereof. Examples of sulfamate salts include alkali metal salts such as sodium salt and potassium salt, alkaline earth metal salts such as calcium salt, strontium salt, and barium salt, other metal salts such as manganese salt, copper salt, zinc salt, iron salt, cobalt salt, and nickel salt, ammonium salt, and guanidine salt. The sulfamic acid compound and these salts may be used alone or in combination of two or more. From the viewpoint of environmental load and the like, it is preferable to use sulfamic acid (amidosulfuric acid) as the sulfamic acid compound.

[0036] The stabilized hypobromous acid composition may further contain an alkali. Examples of the alkali include alkali hydroxides such as sodium hydroxide and potassium hydroxide. From the viewpoint of product stability at low temperatures and the like, sodium hydroxide and potassium hydroxide may be used in combination. Further, the alkali may be used not in solid form but as an aqueous solution.

[0037] When a buffer is used, the storage stability of the sterilizing composition is high and the pH adjustment during production becomes easy. As the buffer, acetates, carbonates, bicarbonates, phosphate compounds, citrates, tartrates, borates, etc. can be used. In particular, when at least one buffer solution of carbonates and bicarbonates is used as the buffer, the pH adjustment during production becomes easy. Examples of carbonates include alkali metal salts such as sodium carbonate and potassium carbonate. Examples of bicarbonates include alkali metal salts such as sodium bicarbonate and potassium bicarbonate. Among these, bicarbonates with high buffering properties and a neutral pH range are preferred.

[0038] The concentration of at least one of carbonic acid and bicarbonate in the sterilizing composition is preferably in the range of 10 mg / L to 60000 mg / L, and more preferably in the range of 100 mg / L to 5000 mg / L. If the concentration of at least one of carbonic acid and bicarbonate in the sterilizing composition is less than 10 mg / L, the storage stability of the sterilizing composition may decrease. If it exceeds 60000 mg / L, the bicarbonate may precipitate as it exceeds the solubility.

[0039] The pH of the sterilizing composition is in the range of 5.0 to 11.0, or in the range of 5.0 to 10.5. Preferably, it is in the range of 5.5 to 10.7, and more preferably in the range of 6.0 to 10.5. If the pH of the sterilizing composition is less than 5.0, the storage stability decreases. If it exceeds 11.0, it becomes a factor causing roughness during handling.

[0040] The amount of halogen gas generated after storing the sterilizing composition for 1 hour at 30°C under sealed conditions is preferably 0.05 mg / L or less, and more preferably 0.025 mg / L or less.

[0041] The effective bromine concentration in the composition for sterilization is in the range of 0.005% to 1.5%, preferably in the range of 0.007% to 1.15%, and more preferably in the range of 0.007% to 1.127%. When the effective bromine concentration in the composition for sterilization is less than 0.005%, the sterilizing power may be significantly reduced and the storage stability may also decrease. When it exceeds 1.5%, the stability may be significantly reduced. The effective bromine concentration of the composition for sterilization, in terms of the equivalent effective chlorine concentration, is in the range of 20 - 6700 mgCl / L, preferably in the range of 30 - 5100 mgCl / L, and more preferably in the range of 30 - 5000 mgCl / L.

[0042] In the water treatment agent composition described in Patent Document 1, it contains a bromine-based oxidizing agent with an effective bromine concentration of 1 - 16.5% by mass. Since the molecular weight of bromine (Br2) is 159.8 and the molecular weight of chlorine (Cl2) is 70.9, when converted to the effective chlorine concentration, 1% of the effective bromine concentration results in an effective chlorine concentration of 1÷159.8×70.9 = 0.44%. Given that the effective chlorine concentration in Patent Document 1 is 0.44% and the specific gravity is 1.0 g / mL, the effective chlorine concentration of 0.44% is (0.44 wt% = 0.44 g / 100 g = 0.44(g)×1000(mg))÷((100(g) / 1.0(g / mL)) / 1000(L)) = 4400 mgCl / L (rounded to two significant figures). By performing the same calculation, an effective bromine concentration of 1 - 16.5% by mass results in an effective chlorine concentration (mgCl / L) ranging from 4400 mgCl / L to 73300 mgCl / L.

[0043] In the composition for sterilization according to this embodiment, the ratio of the equivalent of the "sulfamic acid compound" to the equivalent of the "bromine-based oxidizing agent" is preferably 1.0 or more, more preferably in the range of 1.0 or more and 2.0 or less, and even more preferably in the range of 1.05 or more and 1.5 or less. When the ratio of the equivalent of the "sulfamic acid compound" to the equivalent of the "bromine-based oxidizing agent" is less than 1.0, the bromine concentration may be significantly reduced. When it exceeds 2.0, the manufacturing cost may increase.

[0044] In the sterilizing composition according to this embodiment, a pH adjuster may be further blended. Examples of the pH adjuster include alkalis such as alkali hydroxides like sodium hydroxide and potassium hydroxide, and acids such as sulfuric acid, hydrochloric acid, and nitric acid. At least one of sodium hydroxide, sulfuric acid, hydrochloric acid, and nitric acid is preferable as the pH adjuster in terms of being a strong acid and a strong alkali and being an inorganic substance.

[0045] In view of cases where bacteria, viruses, etc. are attached to organic substances, etc., it is also effective to blend an auxiliary agent in the sterilizing composition in order to enhance the permeability of the stabilized hypobromous acid composition to organic substances, etc. A typical chemical substance of the auxiliary agent is a surfactant. By increasing the permeability of the stabilized hypobromous acid composition, the effects of disinfection, antibacterial, disinfection, sterilization, and inactivation can be enhanced.

[0046] As the surfactant to be blended, conventionally known substances can be used. Examples of the surfactant include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants, and these can be used alone or in appropriate combinations of two or more.

[0047] Examples of the anionic surfactant include those conventionally used in detergents, etc., and are not particularly limited, and various anionic surfactants can be used. For example, the following anionic surfactants can be mentioned.

[0048] Examples of anionic surfactants include fatty acid salts such as lauric acid and palmitic acid, alkyl ether carboxylic acids, acyl lactates, N-acyl amino acid salts, alkane sulfonates, α-olefin sulfonates, α-sulfo fatty acid methyl ester salts, alkyl diphenyl ether disulfonates, linear alkylbenzene sulfonates, linear alkylnaphthalene sulfonates, alkyl sulfates such as lauryl sulfate, alkyl ether sulfate esters, polyoxyethylene alkyl sulfate esters, polyoxyethylene alkyl allyl sulfate esters, polyoxyethylene alkyl phenyl ether sulfonate alkyl phosphate esters, alkyl sulfosuccinates, and the like.

[0049] Examples of cationic surfactants include, in addition to quaternary ammonium salts such as N-decyl-N-isononyl-N,N-dimethylammonium chloride, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, amine salt types such as N-methylbis(hydroxyethyl)amine fatty acid ester hydrochloride, amine salts such as alkylamine hydrochlorides and fatty acid amide amines, and alkylpyridinium salts.

[0050] Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers such as polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl allyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene sorbitan fatty acid esters, alkyl glucosides, polyoxyethylene fatty acid esters, polyoxyethylene castor oil, sucrose fatty acid esters, and polyhydric alcohol fatty acid ester types and polyhydric alcohol alkyl ether types such as sorbitan fatty acid esters, fatty acid alkanolamides, ethylene oxide / propylene oxide adducts of lower / higher alcohols, sucrose fatty acid salts esters, alkanolamides, and the like.

[0051] Examples of amphoteric surfactants include alkylamino fatty acid salts, alkyl betaines, alkyl sulfobetaines, alkyl imidazoline type betaines, and the like.

[0052] The surfactant can be used as one kind or a mixture of two or more kinds, and the addition amount of the surfactant is, for example, in the range of 0.1 to 20% by weight, preferably in the range of 0.1 to 10% by weight, more preferably in the range of 0.1 to 5% by weight, based on the total amount of the sterilizing composition.

[0053] The sterilizing composition according to this embodiment contains water as the remaining portion of the above components. Examples of water include tap water, pure water, ultrapure water, and the like.

[0054] <Method for producing a sterilizing composition> The sterilizing composition according to this embodiment can be obtained, for example, by mixing a bromine-based oxidizing agent, a sulfamic acid compound, and a buffer in water, and further, a pH adjuster such as an alkali or a surfactant may be mixed. The sterilizing composition according to this embodiment can be obtained, for example, by diluting a stabilized hypobromous acid composition obtained by mixing a bromine-based oxidizing agent, a sulfamic acid compound, and, if necessary, an alkali or the like in water with water, adding a buffer, and adding a pH adjuster if necessary, so that, for example, the available bromine concentration is in the range of 0.005% or more and 1.5% or less, and the pH is in the range of 5.0 to 11.0, or the available bromine concentration is in the range of 0.007% or more and 1.15% or less, and the pH is in the range of 5.0 to 10.5.

[0055] As a method for producing a sterilizing composition containing bromine and a sulfamic acid compound, it preferably includes a step of adding bromine to a mixed solution containing water, an alkali, and a sulfamic acid compound and reacting it in an inert gas atmosphere, or a step of adding bromine to a mixed solution containing water, an alkali, and a sulfamic acid compound in an inert gas atmosphere. By adding and reacting in an inert gas atmosphere or adding in an inert gas atmosphere, the bromate ion concentration in the sterilizing composition is reduced.

[0056] The inert gas to be used is not limited, but at least one of nitrogen and argon is preferable from the viewpoints of production and the like, and nitrogen is particularly preferable from the viewpoints of production cost and the like.

[0057] The oxygen concentration in the reactor during the addition of bromine is preferably 6% or less, more preferably 4% or less, still more preferably 2% or less, and particularly preferably 1% or less. When the oxygen concentration in the reactor during the reaction of bromine exceeds 6%, the amount of bromic acid generated in the reaction system may increase.

[0058] The addition rate of bromine is preferably 25% by weight or less based on the total amount of the composition for sterilization, more preferably 1% to 20% by weight. When the addition rate of bromine exceeds 25% by weight based on the total amount of the composition for sterilization, the amount of bromic acid generated in the reaction system may increase. When it is less than 1% by weight, the antibacterial, disinfection, or sterilization effect may be inferior.

[0059] The reaction temperature during the addition of bromine is preferably controlled in the range of 0°C to 25°C, and more preferably controlled in the range of 0°C to 15°C from the viewpoints of production cost and the like. When the reaction temperature during the addition of bromine exceeds 25°C, the amount of bromic acid generated in the reaction system may increase, and when it is less than 0°C, it may freeze.

[0060] <Sterilization method> The sterilization method according to this embodiment is a method for performing sterilization, disinfection, antibacterial, or sterilization of an object to be sterilized using the above-described composition for sterilization. In this specification, "sterilization" in "composition for sterilization", "object to be sterilized", "sterilization method", etc. includes "disinfection" for removing or reducing microorganisms from a certain substance or a limited space, etc., "antibacterial" for suppressing the growth of bacteria on the surface of products, etc., "disinfection" for killing, removing, or reducing pathogenic microorganisms among microorganisms, "sterilization" for killing microorganisms such as bacteria, and also includes "antiviral" for reducing the number of viruses on products, etc., "mold prevention" for suppressing the growth of mold, etc. Definitions and the like of each term are described in the "Guidelines for Antibacterial Processed Products, Antibacterial Product Technology Council" issued by the Ministry of International Trade and Industry, Bureau of Consumer Affairs on May 20, 1999.

[0061] The object to be sterilized is not particularly limited. For example, it can be used for sterilization, antibacterial, disinfection, or sterilization of walls, doors, floors, furniture, kitchen sinks, washing machines, bathrooms, kitchens, dining tables, chairs, office supplies, household items, food containers, fibers, indoor spaces, cleaning factories, inside and outside vehicles, food factories, meat factories, livestock farms, etc. in homes, restaurants, factories, offices, etc.

[0062] For example, the sterilization method according to the present embodiment is not particularly limited as long as it can sterilize, antibacterial, disinfect, or sterilize the object to be sterilized. For example, it can be carried out by spraying the sterilization composition onto the object to be sterilized, wiping and cleaning by impregnating a cloth for the cleaning process, or further diluting the sterilization composition and immersing equipment and objects.

[0063] In the sterilization method according to the present embodiment, the above sterilization composition may be added to the solution of the object to be sterilized so that the effective bromine concentration is in the range of 0.00002% to 1.5% (FAC 0.1 to 6700 mg / L). Here, FAC refers to the free chlorine concentration (mg / L).

Examples

[0064] Hereinafter, examples and comparative examples will be given to explain the present invention more specifically and in detail. However, the present invention is not limited to the following examples.

[0065] [Drug A: Preparation 1 of Stabilized Hypobromous Acid Composition] Under a nitrogen atmosphere, liquid bromine: 16.9 wt%, sulfamic acid: 10.7 wt%, sodium hydroxide: 12.9 wt%, potassium hydroxide: 3.94 wt%, and water: the balance were mixed to prepare a stabilized hypobromous acid composition. The pH of the stabilized hypobromous acid composition was 14, and the total chlorine concentration was 7.5 wt%. The total chlorine concentration is the value (mg-Cl2 / L) measured by the total chlorine measurement method (DPD (diethyl-p-phenylenediamine) method) using a multi-parameter water quality analyzer DR / 4000 manufactured by HACH. The detailed preparation method of the stabilized hypobromous acid composition is as follows.

[0066] While controlling the flow rate of nitrogen gas with a mass flow controller so that the oxygen concentration in the reaction vessel is maintained at 1%, 1436 g of water and 361 g of sodium hydroxide were added to a 2 L four-necked flask sealed by continuous injection and mixed. Then, 300 g of sulfamic acid was added and mixed. After that, while maintaining cooling so that the temperature of the reaction solution became 0 to 15°C, 473 g of liquid bromine was added, and further 230 g of a 48% potassium hydroxide solution was added. A target stabilized hypobromous acid composition having a sulfamic acid content of 10.7%, a bromine content of 16.9%, and an equivalent ratio of sulfamic acid to the equivalent of bromine of 1.04 based on the weight ratio to the total amount of the composition was obtained. The pH of the resulting solution was 14 as measured by the glass electrode method. The bromine content of the resulting solution was 16.9% as measured by a method of performing redox titration using sodium thiosulfate after converting bromine to iodine with potassium iodide, which was 100.0% of the theoretical content (16.9%). In addition, the oxygen concentration in the reaction vessel during the bromine reaction was measured using an "Oxygen Monitor JKO-02 LJDII" manufactured by Jiko Co., Ltd. The bromic acid concentration was less than 5 mg / kg.

[0067] The pH measurement was performed under the following conditions. Electrode type: Glass electrode type pH meter: IOL-30 type manufactured by Toa DKK Corporation Electrode calibration: Two-point calibration was performed using a neutral phosphate pH (6.86) standard solution (Type 2) manufactured by Kanto Chemical Co., Inc. and a borate pH (9.18) standard solution (Type 2) manufactured by the same company. Measurement temperature: 25°C Measured value: The electrode was immersed in the measurement solution, and the value after stabilization was taken as the measured value, which was the average value of three measurements.

[0068] [Drug B: Preparation of Stabilized Hypobromous Acid Composition 2] 0.4% by weight of water was added to 12% by weight of sodium hypochlorite as Cl2 40% by weight and mixed. 18.4% by weight of 40% by weight sodium bromide was added thereto. After completion of mixing, 40% by weight of a sodium sulfamate solution was further added and mixed. Finally, 1.2% by weight of sodium hydroxide was added and mixed.

[0069] <Example 1, Comparative Example 1> [Confirmation of storage stability] In a polyethylene sealed container, a chemical agent A (manufactured by Organo Co., Ltd.), which is a stabilized hypobromous acid composition, and sodium hydrogen carbonate or a phosphate buffer were diluted with water to the predetermined concentrations and pH shown in Table 1 (Examples 1-1 to 1-5, Comparative Example 1-1), and the pH was adjusted with sulfuric acid as a pH adjuster. Incidentally, 1 g of sodium hydrogen carbonate (molecular weight 84) was added to 1 L to prepare a 12 mM solution. The phosphate buffer refers to a solution in which 0.94 g of sodium dihydrogen phosphate dihydrate (molecular weight 156.01) and 2.15 g of disodium hydrogen phosphate hydrate (molecular weight 358.14) were added to 1 L so that each phosphate compound was added at 6 mM, and the solution was prepared so that the total amount of the phosphate compounds was 12 mM. The remaining available chlorine amount after storage at 50°C for 7 days was measured by the total chlorine measurement method (DPD (diethyl-p-phenylenediamine) method), and the available chlorine residual rate (%) was determined. The results are shown in Table 1.

[0070]

Table 1

[0071] Thus, in Examples 1-1 to 1-3 in which sodium hydrogen carbonate was blended as a buffer, the available chlorine residual rate was 90% or more, whereas when sodium hydrogen carbonate was not blended (Comparative Example 1-1), the available chlorine residual rate was 50% or less, indicating that the stability was significantly reduced. When a large amount of sodium hydrogen carbonate was blended, the available chlorine residual rate decreased slightly, but the same level of stability was maintained. Also, when a phosphate compound was blended as a buffer, the available chlorine residual rate was 69%.

[0072] <Example 2, Comparative Example 2> [Difference in required amount of hydrogen carbonate] A polyethylene sealed container was prepared with 100 kg of a drug A (manufactured by Organo), which is a stabilized hypobromous acid composition, and sodium hydrogen carbonate diluted with water to the predetermined concentrations shown in Table 2 (Examples 2-1 to 2-3, Comparative Example 2-1), and 62.5 wt% sulfuric acid required for the pH range described in Table 2 was added using sulfuric acid as a pH adjuster. The results of the required amount (g) of 62.5 wt% sulfuric acid are shown in Table 2.

[0073]

Table 2

[0074] When sodium hydrogen carbonate is used, there is an allowable range of sulfuric acid addition amounts of 96 g in Example 2-1, 16 g in Example 2-2, and 14 g in Example 2-3. In contrast, when sodium hydrogen carbonate is not used (Comparative Example 2-1), there is only an allowable range of sulfuric acid addition amount of 0.5 g, and when more acid is added than 0.5 g, the pH will deviate significantly.

[0075] <Examples 3, 4, Comparative Example 3> [Confirmation of storage stability] A polyethylene sealed container was filled with drug A and drug B (manufactured by Organo), which are stabilized hypobromous acid compositions, and sodium hydrogen carbonate diluted with water to the predetermined concentrations shown in Tables 3, 4, and 5 (Examples 3-1 to 3-27, Examples 4-1 to 4-7, Comparative Examples 3-1 to 3-25), and the pH was adjusted with sulfuric acid as a pH adjuster. The remaining available chlorine amount after storage at 50 °C for 7 days was measured by the total chlorine measurement method (DPD (diethyl-p-phenylenediamine) method), and the available chlorine residual rate (%) was determined. The results are shown in Tables 3, 4, and 5. Also, the relationship between the available bromine concentration (%) and pH in Example 3 and Comparative Example 3 is shown in Figure 1.

[0076]

Table 3

[0077]

Table 4

[0078] [Table 5]

[0079] It was found that the stabilized hypobromous acid composition A had a stability of 55% or less when the pH of the diluted drug was 12.5, and the storage stability was significantly reduced when the available bromine concentration was greater than 1.5% at pH 11.5. On the other hand, it was found that the stability was significantly improved when diluted between 0.03% and 1.5% of the available bromine concentration of the drug, especially between 0.011% and 1.13%, and the pH was in the range of 5.0 to 11.0. Also, for the drug B which is a stabilized hypobromous acid composition, the stability was significantly improved in all cases.

[0080] [Example 5] [Confirmation of generation of bromine gas and chlorine gas] 1 L of a solution prepared by diluting the drug A (manufactured by Organo Corporation) with water to a predetermined concentration shown in Table 6 (Examples 5-1 to 5-6) was placed in a 1.1-liter polyethylene sealed container filled with Sagamihara well water dechlorinated with a filter, 1000 mg / L of sodium hydrogen carbonate was added, adjusted to a predetermined pH using sulfuric acid as a pH adjuster, and stirred with a stirrer at 150 rpm. The prepared solution was placed in a 1-L volumetric flask, and after 1 hour in a constant temperature bath at 30 °C, the total chlorine concentration in the solution was measured, and immediately after opening the lid of the volumetric flask, the halogen gas concentration in the headspace was measured using Detection Tube No. 8La by the method of a detector tube type gas measuring instrument (JIS K 0804: Detector tube type gas measuring instrument). The results are shown in Table 6.

[0081] [Table 6]

[0082] The drug A using stabilized hypobromous acid was able to suppress the halogen gas odor in the range of Examples 5-1 to 5-6.

[0083] When the chemical agent adjusted to pH 7.5 and 50 mg Cl / L with hypochlorite as the available chlorine concentration was measured in the same manner as in Example 5, 0.1 mg Cl / L of halogen gas was generated with hypochlorite.

[0084] Therefore, it was found that stabilized hypobromous acid hardly generates halogen gas, can suppress the generation of unpleasant odors due to halogen gas during use, and can suppress the adverse effects of halogen gas.

[0085] <Example 6> [Confirmation of bactericidal effect] Peptone, bonito extract, phosphorus, nitrogen, etc. were added to the Sagamihara well water dechlorinated with a filter and cultured (hereinafter referred to as "culture solution"). The general bacterial count was 7.9×10 4 CFU / mL.). To 99 mL of the stabilized hypobromous acid composition (FAC 250 mg / L, pH 8.5, available bromine concentration 0.056%, sodium hydrogen carbonate 1000 mg / L, manufactured by Organo), 1 mL of the culture solution was added and mixed (hereinafter referred to as "test solution"). After 5 minutes, sodium sulfite was added to inactivate the active ingredient, and after a predetermined time, the general bacterial count (CFU / mL) in the test solution was measured using a Petrifilm AC plate (manufactured by 3M). The results are shown in Table 7.

[0086] Note that the "specimen" in Table 7 refers to a solution obtained by adding 1 mL of the culture solution (7.9×10 4 CFU / mL) to 99 mL of the stabilized hypobromous acid composition (FAC 250 mg / L, available bromine concentration 0.056%, pH 8.5, sodium hydrogen carbonate 1000 mg / L, manufactured by Organo).

[0087]

Table 7

[0088] As shown in Table 7, when 1 mL of the culture solution was added to 99 mL of pure water, 8.3×10 after 5 minutes 2While it was CFU / mL, with the stabilized hypobromous acid composition (FAC 250 mg / L, available bromine concentration 0.056%, pH 8.5, sodium hydrogen carbonate 1000 mg / L, manufactured by Organo), the sample became 4 CFU / mL after 5 minutes, confirming its bactericidal performance.

[0089] As described above, like in the examples, a bactericidal composition suitable for users including general consumers to perform disinfection, antibacterial, sterilization, or disinfection, with less likelihood of rough skin formation at pH 12 or below and high storage stability, was obtained.

Claims

1. A composition for sterilization, comprising a bromine-based oxidizing agent, a sulfamic acid compound, and a buffer, having an available bromine concentration in the range of 0.005% or more and 1.15% or less, and a pH in the range of 5.0 to 11.0, wherein the buffer contains at least one of a carbonate and a bicarbonate.

2. A composition for sterilization, comprising a bromine-based oxidizing agent, a sulfamic acid compound, and a buffer, having an available bromine concentration in the range of 0.007% or more and 1.15% or less, and a pH in the range of 5.0 to 10.5, wherein the buffer contains at least one of a carbonate and a bicarbonate.

3. The composition for sterilization according to Claim 1 or 2, wherein the concentration of at least one of the carbonate and the bicarbonate is in the range of 10 mg / L to 60000 mg / L.

4. The composition for sterilization according to any one of Claims 1 to 3, further comprising a pH adjuster.

5. The composition for sterilization according to Claim 4, wherein the pH adjuster contains at least one of sodium hydroxide, sulfuric acid, hydrochloric acid, and nitric acid.

6. The composition for sterilization according to any one of Claims 1 to 5, containing 1.0 to 2.0 times equivalent of the sulfamic acid compound with respect to the equivalent of the bromine-based oxidizing agent.

7. The composition for sterilization according to any one of Claims 1 to 6, wherein the bromine-based oxidizing agent is bromine.

8. A sterilization method, characterized in that the composition for sterilization according to any one of Claims 1 to 7 is added to an object to be sterilized so that the available bromine concentration is in the range of 0.00002% to 1.5%.

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