Method for producing chlorous acid aqueous solution using raw material obtained by electrolysis of salt

Abstract

To provide a method for producing a chlorous acid aqueous solution using a product obtained by electrolyzing a salt as a raw material.SOLUTION: The present invention provides a method for producing a chlorous acid aqueous solution using a salt as a raw material. The present invention provides a method for producing a chlorous acid aqueous solution, comprising the steps of: 1) electrolyzing a salt to obtain a chlorate or an aqueous solution thereof; and 2) reducing the chlorate or the aqueous solution thereof to produce an aqueous solution containing chlorous acid. The method for producing the chlorous acid aqueous solution includes a step of mixing any single substance or two or more single substances of an inorganic acid or an inorganic acid salt, and then mixing any single substance or two or more single substances of an inorganic acid, an inorganic acid salt, an organic acid, or an organic acid salt.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing chlorous acid water using a raw material obtained by electrolyzing salt. [Background technology]

[0002] Chlorous acid water is attracting attention as an antibacterial agent, bactericide, disinfectant, antiseptic, antiviral agent, and food additive: disinfectant.

[0003] The present inventors have discovered chlorous acid water and a method for producing it, and have confirmed its bactericidal effect on Escherichia coli, and have filed a patent application (Patent Document 1). Patent Document 1 discloses that sodium chlorate is used as a raw material for chlorous acid water. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2008 / 026607 Summary of the Invention [Means for solving the problem]

[0005] The present inventors have been studying intensively about the new method for producing chlorous acid water, which can replace the conventional method that uses chlorate such as sodium chlorate as raw material, and have found a technology for the method for producing chlorous acid water, which uses chlorate as raw material by electrolyzing salt, which is cheaper and more stable than chlorate.Compared with conventional method, although the electrolysis step is increased by one step, it is possible to produce not only the chlorous acid water that has conventional functions of antibacterial effect, bactericidal effect, disinfecting effect, and even antiviral effect, but also the chlorous acid water that has high antibacterial power, bactericidal power, disinfecting power, and even antiviral power.

[0006] The present invention also provides the following items. (Item 1) A method for producing chlorous acid water, comprising: 1) electrolyzing a salt to obtain a chlorate or an aqueous solution thereof; and 2) reducing the chlorate or the aqueous solution thereof to obtain an aqueous solution containing chlorous acid. (Item 2) The method according to the preceding item, wherein the salt is sodium chloride. (Item 3) The method according to any one of the preceding items, wherein the sodium chloride complies with the Japanese Pharmacopoeia sodium chloride standard or an equivalent standard. (Item 4) The method according to any one of the preceding items, wherein the chlorate or aqueous solution thereof contains at least about 45% (w / v) sodium chlorate and may also contain sodium hypochlorite and unreacted substances. (Item 5) The electrolysis is carried out by passing a saturated sodium chloride aqueous solution through a membraneless electrolysis tank at a voltage of about 2.75 to about 3.5 V and a current density of about 600 to about 5000 A / m 2 The method according to any one of the preceding items, wherein the pH of the electrolyte solution is adjusted to about 5.9 to about 7.5 while applying current at a liquid temperature of about 70°C to about 90°C for about 15 hours or more. (Item 6) Item 10. The method of any one of the preceding items, wherein the voltage is about 3 V. (Item 7) The current density is about 2500 A / m 2 The method according to any one of the preceding items, wherein (Item 8) The method according to any one of the preceding items, wherein the pH of the electrolyte solution is adjusted to about 5.9 to about 7.0. (Item 9) Item 10. The method of any one of the preceding items, wherein the pH of the electrolyte solution is adjusted to about 6.0. (Item 10) The method according to any one of the preceding items, wherein at least one acid selected from the group consisting of sulfuric acid, phosphoric acid, and nitric acid is used in the reduction step. (Item 11) The method according to any one of the preceding items, wherein the concentration of the sulfuric acid, phosphoric acid, or nitric acid is about 60% (w / w) to about 90% (w / w). (Item 12) The method according to any one of the preceding items, wherein the concentration of the sulfuric acid, phosphoric acid or nitric acid is about 70% (w / w). (Item 13) The method according to any one of the preceding items, wherein the acid comprises acid thiosulfate or a salt thereof. (Item 14) The method according to any one of the preceding items, wherein the concentration of the acidic thiosulfate is about 0% (w / v) to about 1.3% (w / v). (Item 15) The method according to any one of the preceding items, wherein the concentration of the acidic thiosulfate is about 0.5% (w / v) to about 0.7% (w / v). (Item 16) The method according to any one of the preceding items, comprising a step of obtaining a gasified product containing chlorous acid. (Item 17) The method according to any one of the preceding items, wherein an oxoacid having a reducing effect is used in combination in the reduction step. (Item 18) The method according to any one of the preceding items, wherein the oxoacid having a reducing effect is acidic thiosulfate, dithionous acid, peroxomonosulfate, peroxodisulfate, peroxophosphoric acid, peroxochromic acid, or manganese oxide. (Item 19) The method according to any one of the preceding items, wherein the oxoacid having a reducing effect is acidic thiosulfate or dithionous acid. (Item 20) The method according to any one of the preceding items, wherein the oxoacid having a reducing effect is generated from a salt of the oxoacid having a reducing effect in the reduction step. (Item 21) The method according to any one of the preceding items, wherein the salt of an oxoacid having a reducing effect is an acid thiosulfate, a dithionite, a peroxomonosulfate, a peroxodisulfate, a peroxophosphate, a peroxochromate, or a permanganate. (Item 22) The method according to any one of the preceding items, wherein the salt of an oxoacid having a reducing effect is sodium dithionite or sodium thiosulfate. (Item 23) The method according to any one of the preceding items, wherein the oxoacid having a reducing effect is used in combination with hydrogen peroxide. (Item 24) The method according to any one of the preceding items, wherein the oxoacid having a reducing effect is acidic thiosulfuric acid or dithionous acid, and when the acidic thiosulfuric acid or dithionous acid is used in combination with hydrogen peroxide, the concentration of the acidic thiosulfuric acid or dithionous acid is about 0.5% to about 1.5%. (Item 25) The method according to any one of the preceding items, wherein the concentration of the acidic thiosulfuric acid or dithionous acid is about 0.5% to about 1.0%. (Item 26) The method according to any one of the preceding items, further comprising generating a first reaction gas using the acid and the oxoacid having a reducing action in step 2). (Item 27) The method according to any one of the preceding items, comprising generating a second reaction gas in step 2) using hydrogen peroxide and the oxoacid having a reducing action. (Item 28) The method according to any one of the preceding items, comprising a step of capturing the first reaction gas in an aqueous solution containing chlorous acid using a neutralizing agent in step 2). (Item 29) The method according to any one of the preceding items, comprising a step of capturing the second reaction gas in an aqueous solution containing chlorous acid using a neutralizing agent in step 2). (Item 30) The method of any one of the preceding items, wherein the pH of the neutralizing agent is about 6.0 or higher. (Item 31) The method according to any one of the preceding items, wherein the pH of the neutralizing agent is about 10.3 to about 10.7. (Item 32) The method according to any one of the preceding items, wherein the TAL of the neutralizing agent is about 20 or greater. (Item 33) The method of any one of the preceding items, wherein the neutralizing agent has a TAL of about 2000. (Item 34) The method according to any one of the preceding items, wherein the neutralizing agent has a high buffering power in the pH range of about 4.5 to about 7.5. (Item 35) The method according to any one of the preceding items, wherein the neutralizing agent includes any one or more of an inorganic acid, an inorganic acid salt, an organic acid, and an organic acid salt. (Item 36) The method according to any one of the preceding items, further comprising mixing any one or more of an inorganic acid, an inorganic acid salt, an organic acid, or an organic acid salt with the aqueous solution containing chlorous acid. (Item 37) The method according to any one of the preceding items, comprising a step of mixing one or more of an inorganic acid or an inorganic acid salt with the aqueous solution containing chlorous acid. (Item 38) The method according to any one of the preceding items, comprising a step of mixing any one or more of an inorganic acid or an inorganic acid salt with the aqueous solution containing chlorous acid, and then mixing any one or more of an inorganic acid, an inorganic acid salt, an organic acid, or an organic acid salt. (Item 39) The method according to any one of the preceding items, wherein the inorganic acid is carbonic acid, phosphoric acid, boric acid, or sulfuric acid. (Item 40) Item 10. The method according to any one of the preceding items, wherein the inorganic acid salt is a carbonate, hydroxide, phosphate, or borate. (Item 41) Item 10. The method according to any one of the preceding items, wherein the carbonate is sodium carbonate, potassium carbonate, sodium bicarbonate, or potassium bicarbonate. (Item 42) Item 10. The method according to any one of the preceding items, wherein the hydroxide salt is sodium hydroxide or potassium hydroxide. (Item 43) The method according to any one of the preceding items, wherein the phosphate is disodium hydrogen phosphate, sodium dihydrogen phosphate, trisodium phosphate, tripotassium phosphate, dipotassium hydrogen phosphate, or potassium dihydrogen phosphate. (Item 44) Item 10. The method according to any one of the preceding items, wherein the borate is sodium borate or potassium borate. (Item 45) Item 10. The method according to any one of the preceding items, wherein the organic acid is succinic acid, citric acid, malic acid, acetic acid, or lactic acid. (Item 46) The method according to any one of the preceding items, wherein the organic acid salt is sodium succinate, potassium succinate, sodium citrate, potassium citrate, sodium malate, potassium malate, sodium acetate, potassium acetate, sodium lactate, potassium lactate, or calcium lactate. (Item 47) Chlorous acid water produced by the method according to any one of the preceding items. (Item 48) An apparatus for producing chlorous acid water, comprising: 1) an electrolysis tank for electrolyzing a salt to obtain a chlorate or an aqueous solution thereof; and 2) a reaction tank for reducing the chlorate or the aqueous solution thereof to obtain an aqueous solution containing chlorous acid. (Item 49) An agent for adjusting the reactivity of hypochlorous acid water containing oxoacids with reducing properties.

[0007] It is contemplated that the present invention may provide one or more of the above-described features in combination with or in addition to the combinations explicitly stated. Still further embodiments and advantages of the present invention will be recognized by those skilled in the art upon reading and understanding the following detailed description, if necessary. [Effects of the Invention]

[0008] According to the present invention, a novel method for producing a useful chemical agent, chlorous acid water, using a so-called chlorate, obtained by electrolyzing a salt, is provided, and the possibility of widespread use of the agent in the food industry, medical settings, nursing care and childcare, educational settings, and other daily necessities for antibacterial, sterilizing, disinfecting, and even antiviral purposes is further increased.

[0009] The method for producing chlorous acid water of the present invention is different from the conventional method described in Patent Document 1 in that: (1) It is safer because chlorate is not directly handled as a raw material. (2) Use cheaper table salt as a raw material, (3) By directly using the reaction solution obtained from the electrolysis reaction in the next step, it is now possible to produce hypochlorous acid water with various functions in addition to hypochlorous acid water, which has previously been the main active ingredient.

[0010] Regarding (1), chlorates such as sodium chlorate are classified as Class 1 hazardous materials under the Fire Service Act. Hypochlorous acid is designated as a deleterious substance under the Poisonous and Deleterious Substances Control Act, and because it is a strong oxidizing agent, it must be stored away from organic compounds and substances that are easily oxidized, making it a substance that is not easy to handle and requiring care when handling. However, in the production method of the present invention, chlorate is generated in the electrolysis reaction system and transferred directly to the next step, making it possible to produce hypochlorous acid water more safely than conventional production methods.

[0011] Regarding (2), the manufacturing method of the present invention uses sodium chloride that conforms to the Japanese Pharmacopoeia standard. This is because salt is used as a raw material, and bromate (BrO3 - ) bromide (Br - Although we do not wish to be bound by theory, the Japanese Pharmacopoeia sodium chloride standard (bromide (Br - ) concentration: 100μg / g or less) by using sodium chloride that matches the - It has become possible to keep the amount of chlorine produced below the tap water quality standards.

[0012] Regarding (3), the chlorine acid-containing aqueous solution produced in the electrolysis reaction system using sodium chloride that meets the specifications of the Japanese Pharmacopoeia sodium chloride as a raw material is used directly in the next manufacturing process. This not only makes it possible to produce hypochlorous acid water, which is primarily slow-acting and which was previously possible with previous manufacturing patents, but also makes it possible to produce hypochlorous acid water with various functions, such as significantly improved reactivity, by using it in combination with oxo acids that have reducing properties, such as acidic thiosulfate and dithionous acid, which were previously limited to hydrogen peroxide as a reducing agent. [Brief explanation of the drawings]

[0013] [Figure 1] Figure 1 shows a schematic diagram of a manufacturing plant in which the membraneless electrolysis tank and the mixing tanks for each solution are separated. The respective symbols are as follows: 1: Salt dissolution tank, 2: Saturated brine filtration device, 3: Pump 1, 4: Control panel, 5: Rectifier and power supply, 6: Electrolysis tank, 7: Storage tank, 8: Measuring instrument, 9: Pump 2, 10: Cooling device, 11: Hydrochloric acid titration device, 12: Reaction tank, 13: Agitator, 14: Acid feeder, 15: Hydrogen peroxide feeder, 16: Pump 3, 17: Neutralization tank, 18: Gas scrubbing tank, 19: Waste liquid treatment tank, 20: Condenser, 21: Jacket, A: Saturated salt water discharge valve, B: Electrolysis tank discharge valve, C: Air valve, D: Circulation on / off cock, E: Ricker discharge valve, F: Sulfuric acid inlet valve, G: Hydrogen peroxide inlet valve, H: Air pump cock, I: Three-way cock, J: Reaction liquid discharge valve, K: Air valve, L: Sample valve. [Figure 2] Figure 2 shows the UV spectrum of chlorous acid water A. The vertical axis represents absorbance, and the horizontal axis represents wavelength (nm). [Figure 3] Figure 3 shows the UV spectrum of chlorous acid water B. The vertical axis represents absorbance, and the horizontal axis represents wavelength (nm). [Figure 4] 4 is a graph showing the relationship between the phenol coefficient and the oxidizing power of each chlorine oxide measured in Example 4. The vertical axis represents the oxidizing power, and the horizontal axis represents the phenol coefficient. [Figure 5]5 is a graph showing the change over time in the oxidizing power and the phenolic coefficient for chlorous acid water A and ASC measured in Example 4. The vertical axis represents the oxidizing power, and the horizontal axis represents the phenolic coefficient. DETAILED DESCRIPTION OF THE INVENTION

[0014] The present invention will now be described with reference to the best mode thereof. Throughout this specification, singular expressions should be understood to include the plural concept unless otherwise specified. Therefore, singular articles (e.g., "a," "an," "the," etc. in English) should be understood to include the plural concept unless otherwise specified. Furthermore, terms used in this specification should be understood to have the meaning commonly used in the art unless otherwise specified. Therefore, unless otherwise defined, all technical and scientific terms used in this specification have the same meaning as commonly understood by those skilled in the art to which this invention belongs. In the event of conflict, the present specification (including definitions) will prevail.

[0015] (Definition of terms) The terms used in this specification are explained below.

[0016] In this specification, "chlorous acid water" refers to an aqueous solution containing chlorous acid (HClO2) that is used as an antibacterial agent, bactericide, disinfectant, antiviral agent, and even as a food additive or sterilant. The chlorous acid water of the present invention creates a transition state and delays the decomposition reaction, thereby stably maintaining chlorous acid (HClO2) for a long period of time. When a sample of chlorous acid water is measured using a spectrophotometer, dissociated chlorous acid (HClO2) is detected, which shows a peak at around 260 nm in the UV spectrum between 240 and 420 nm wavelengths. + ClO2 -When two absorption regions, one containing HClO2 and the other containing aqueous chlorine dioxide (ClO2 in water phase) with a peak at around 350 nm, are simultaneously observed, i.e., when a double nodule is observed, the presence of chlorous acid can be indirectly confirmed. In this case, chlorous acid (HClO2) and dissociated chlorous acid (H + ClO2 - ) equilibrium relationship (HClO⇔H + ClO2 - ) as the main component, it receives electrons from the acidic aqueous solution via aqueous chlorine dioxide (ClO2 in water phase) and dissociates chlorous acid (H + ClO2 - ) and return to the original state.

[0017] In this specification, the term "chlorous acid water" can include "chlorous acid water preparations." A chlorous acid water preparation can be produced by adding a specific buffer to the chlorous acid water produced by the method of the present invention. A typical composition of a chlorous acid water formulation, although not limited to, is a blend of 14.500% (w / v) chlorous acid water (4% product), 1.000% (w / v) potassium dihydrogen phosphate, 0.014% (w / v) sodium hydroxide, and 86.500% (w / v) purified water (sold by the applicant under the name "Careforpis"). In this blend, the chlorous acid water may be 0.25% (w / v) to 75% (w / v), the potassium dihydrogen phosphate may be 0.70% (w / v) to 13.90% (w / v), and the sodium hydroxide may be 0.01% (w / v) to 5.60% (w / v). Sodium dihydrogen phosphate may be used instead of potassium dihydrogen phosphate, and potassium hydroxide may be used instead of sodium hydroxide.

[0018] In this specification, the term "stable" for chlorous acid water refers to a state in which chlorous acid (HClO2) is maintained.

[0019] As used herein, the term "antibacterial (activity)" refers to inhibiting the growth of pathogenic, harmful, or infectious microorganisms such as molds and bacteria. Substances that have antibacterial activity are called antibacterial agents.

[0020] In this specification, the term "sterilization (action)" refers to the destruction of pathogenic, harmful, or infectious microorganisms such as molds and bacteria. A substance having a bactericidal action is called a bactericide.

[0021] In this specification, the term "sterilization (action)" refers to the elimination of pathogenic, harmful, or infectious microorganisms such as molds and bacteria. A substance having a sterilizing action is called a disinfectant.

[0022] In this specification, the term "disinfection (action)" refers to the sterilization of pathogenic, harmful, or infectious microorganisms such as molds and bacteria. A substance that has a disinfecting action is called a disinfectant.

[0023] As used herein, the term "antiviral (action)" refers to the inactivation of viruses, etc. An agent having an inactivating effect (action) is called an antiviral agent.

[0024] Those with antibacterial properties are called antibacterial agents, those with bactericidal properties are called disinfectants, those with disinfecting properties are called sanitizers, those with disinfecting properties are called disinfectants, and those with antiviral properties are called These are called antiviral agents, and in this specification, they must be expressed separately. Anything not specified here does not fall under this category. When these terms are normally used in this specification, they are understood to refer to drugs that also have antibacterial, bactericidal, disinfectant, or viral inactivation effects.

[0025] In this specification, the article to be used with the produced chlorous acid water is any article that can be impregnated with chlorous acid water to have antibacterial, bactericidal, sterilizing, disinfecting, or even antiviral effects, including medical devices, such as sheets, films, patches, brushes, nonwoven fabrics, paper, cloth, absorbent cotton, sponges, etc., but is not limited thereto.In addition, any material can be used as long as it can be impregnated with chlorous acid water.

[0026] In this specification, "TAL" refers to the alkalinity of a sample, which is measured by titrating the sample with 0.1 mol / L hydrochloric acid-acid standard solution until the pH reaches 4.0. When 1 mL of 0.1 mol / L hydrochloric acid is required to bring the pH of 100 g of sample to 4.0, the alkalinity (TAL) is defined as 1. pH 4.0 is the second neutralization point of sodium carbonate. Note that the specifications for high-grade bleaching powder are wide, and differ from company to company in the formulation of pH adjusters, etc., so the TAL is usually not included in the specifications.

[0027] In this specification, the term "reducing oxoacid" refers to an acid in which a hydrogen atom that can dissociate as a proton is bonded to an oxygen atom, and has the general formula XO n (OH) m (X is a metal atom or a non-metallic atom other than oxygen, and n and m are integers of 1 or greater.) Representative oxoacids with reducing properties include thiosulfuric acid, dithionous acid, peroxomonosulfuric acid, and peroxodisulfuric acid.

[0028] As used herein, "Liquor" refers to the liquid obtained after electrolysis. (See Encyclopedia of Chemical Processing and Design, eds. John J. McKetta and Guy E. Weismantel, Vol. 51, pp. 148-151.) In this specification, "acidic thiosulfate" refers to "thiosulfate in an acidic state" obtained by mixing thiosulfate with a strongly acidic substance such as sulfuric acid to form thiosulfate.

[0029] When a numerical value is modified by the word "about" in this specification, the numerical value indicates a range obtained by rounding the stated numerical value to the nearest digit. For example, about 5 is understood to mean 4.5 to less than 5.5, and about 0.5 is understood to mean 0.45 to less than 0.55.

[0030] (Chlorous acid water and its manufacturing example) The chlorous acid water used in the present invention has characteristics and functions discovered by the present inventors.

[0031] The present invention relates to a method different from known manufacturing methods such as those described in Patent Document 1.

[0032] That is, in the conventional method for producing hypochlorous acid water, the aqueous solution of sodium chlorate has strong oxidizing effect, and when organic matter, sulfur, metal powder, etc. are mixed, the property of exploding under heating, friction or impact is added with sulfuric acid or its aqueous solution in an amount and concentration that can maintain the pH value of this aqueous solution within 2.3 to 3.4, and react to generate hypochlorous acid, and then add hydrogen peroxide in an amount equal to or greater than the amount required for the reduction reaction of this hypochlorous acid.The hypochlorous acid water obtained by this method can indirectly maintain unstable hypochlorous acid. It forms a "cyclic reaction" in which oxidation power is replenished when it comes into contact with organic matter or microorganisms, and has the ability to maintain the same antibacterial, bactericidal, disinfectant, and even antiviral powers indefinitely. It is known to have characteristics that are clearly different from the antibacterial, bactericidal, disinfectant, and antiviral powers possessed by sodium hypochlorite, which, although strong, are immediately lost when it comes into contact with organic matter or microorganisms.

[0033] In contrast, in the present invention, instead of using chlorate as a raw material, an inexpensive and easy-to-handle salt is electrolyzed to obtain chlorate or an aqueous solution containing chlorate. Acidic thiosulfate or dithionous acid acidified with sulfuric acid is then added to this aqueous solution to carry out the first reaction. During this process, chlorine gas containing chlorous acid is generated, and then hydrogen peroxide containing acidic thiosulfate or dithionous acid is added to carry out the second reaction. During this process, chlorine dioxide gas containing chlorous acid is generated, and each gas is adsorbed onto a neutralizing agent with a high TAL and buffering power in the neutral range. In some cases, the gases generated in the first reaction and the gases generated in the second reaction may be adsorbed onto separate neutralizing agents and then combined. By adding a buffer as needed to the chlorous acid water produced by adsorbing the first and second reaction gases, the pH is maintained (pH 3.2 to pH 8.5), thereby achieving the development of a method for producing chlorous acid water with various functions, such as high reactivity, compared to conventional production methods.

[0034] DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below. The embodiments provided below are provided for a better understanding of the present invention, and it is understood that the scope of the present invention should not be limited to the following description. Therefore, it is clear that those skilled in the art can make appropriate modifications within the scope of the present invention in light of the description in this specification. It is also understood that the following embodiments of the present invention can be used alone or in combination.

[0035] In one aspect, the present invention provides a method for producing chlorous acid water, which comprises: 1) electrolyzing salt to obtain chlorate or its aqueous solution; and 2) reducing this chlorate or its aqueous solution to produce an aqueous solution containing chlorous acid.Preferably, the present invention provides a method for producing chlorous acid water, which comprises: 1) electrolyzing salt to obtain chlorate or its aqueous solution; and 2) reducing this chlorate or its aqueous solution with one or more oxoacids having reducing action to produce an aqueous solution containing chlorous acid.Without wishing to be bound by theory, this method is because it can produce more versatile chlorous acid water compared to the conventional method that uses chlorate such as sodium chlorate as raw material.

[0036] In a conventional method for producing an aqueous solution containing chlorous acid (HClO2) (chlorous acid water), which can be used as an antibacterial agent, bactericide, disinfectant, antiseptic, and even antiviral agent, sulfuric acid (H2SO4) or its aqueous solution is added to an aqueous solution of sodium chlorate (NaClO3) to create acidic conditions, and then the resulting chloric acid (HClO3) is reduced to chlorous acid by adding the amount of hydrogen peroxide (H2O2) required to produce chlorous acid (HClO2).The basic chemical reactions in this production method are represented by the following formulas A and B.

[0037] [ka]

[0038] In the A method, the amount of sodium chlorate (NaClO3) solution that can maintain the pH value within the acidic range is Equation B shows that adding sulfuric acid (H2SO4) or its aqueous solution of a certain concentration produces chloric acid while simultaneously removing sodium ions. Next, equation B shows that chloric acid (HClO3) is reduced with hydrogen peroxide (H2O2) to produce chlorous acid (HClO2).

[0039] [ka]

[0040] At that time, chlorine dioxide gas (ClO2) is generated (formula C), but when it coexists with hydrogen peroxide (H2O2), chlorous acid (HClO2) is generated through reactions D to F. Conventional inventions utilize the reactions that occur after the production of chlorine dioxide gas (ClO2).

[0041] Therefore, the method for producing chlorous acid water in the present invention begins with electrolyzing salt as a raw material. This reaction is a known method and is carried out according to the G formula. NaCl+3H2O→NaClO3+3H2 (G formula) However, if the pH conditions are not optimal or if the current density is insufficient when applying electricity, a side reaction such as reaction type H may occur. NaCl + H2O → NaClO + H2 (H formula) In one preferred embodiment, the salt is sodium chloride. Without wishing to be bound by theory, the use of sodium chloride as a raw material makes it possible to safely produce chlorous acid water.

[0042] In a further preferred embodiment, the sodium chloride complies with the Japanese Pharmacopoeia sodium chloride specification. Without wishing to be bound by theory, the Japanese Pharmacopoeia sodium chloride specification (bromide (Br - ) concentration: 100μg / g or less) by limiting the use of sodium chloride that meets the - This is because it is possible to keep the amount of chlorine produced below the tap water quality standards.

[0043] In one preferred embodiment, the electrolysis is performed by passing a saturated aqueous sodium chloride solution through a membraneless electrolysis cell, adding about 0.3% hydrochloric acid (approximately 0.1N-HCl), and applying current so as to maintain the pH in the range of about 5.9 to about 7.5.

[0044] The pH during electrolysis is preferably, but not limited to, about pH 5.9 to about 7.5, about pH 6.0 to about 7.5, about pH 6.1 to about 7.5, about pH 6.2 to about 7.5, about pH 6.3 to about 7.5, about pH 6.4 to about 7.5, about pH 6.5 to about 7.5, about pH 6.6 to about 7.5, about pH 6.7 to about 7.5, about pH 6.8 to about 7.5, about pH 6.9 to about 7.5, about pH 7.0 to about 7.5, about pH 7.1 to about 7.5, about pH 7.2 to about 7.5, about pH 7.3 to about 7.5, and about pH 7.4 to about 7.5. More preferably, the pH is about pH 5.9 to about 7.5, but is not limited thereto. More preferably, the pH range is about 5.9 to about 7.0, but is not limited thereto, and most preferably, the pH range is about 6.0, but is not limited thereto.

[0045] The electrolysis is carried out at a voltage of about 2.75 to about 3.5 V and a current density of about 600 to about 5000 A / m 2 The condition is that the liquid temperature is about 70°C to about 90°C and current is applied. Without wishing to be bound by theory, it is possible to obtain sodium chlorate with a relatively high purity, and as a result, it is possible to obtain a chlorous acid solution equivalent to that obtained by the conventional production method such as that in Patent Document 1. This becomes:

[0046] Preferred voltages include, but are not limited to, about 2.8 to about 3.5 V, about 2.9 to about 3.5 V, about 3.0 to about 3.5 V, about 3.1 to about 3.5 V, about 3.2 to about 3.5 V, about 3.3 to about 3.5 V, and about 3.4 to about 3.5 V. The optimum voltage is, but is not limited to, about 3 V.

[0047] Preferably, the current density is about 600 to about 5000 A / m 2 , about 700~5000A / m 2 , about 800~5000A / m 2 , about 900~5000A / m 2 , about 1000~5000A / m 2 , about 1100~5000A / m2 Approximately 1200~5000A / m 2 Approximately 1300~5000A / m 2 Approximately 1400~5000 A / m 2 Approximately 1500~5000A / m 2 Approximately 1600~5000A / m 2 Approximately 1700~5000 A / m 2 Approximately 1800~5000 A / m 2 Approximately 1900~5000 A / m 2 Approximately 2000~5000A / m 2 Approximately 2100~5000A / m 2 Approximately 2200~5000A / m 2 Approximately 2300~5000A / m 2 Approximately 2400~5000A / m 2 Approximately 2500~5000A / m 2 Approximately 600~5000A / m 2 Approximately 600~4900A / m 2 Approximately 600~4800A / m 2 Approximately 600~4700A / m 2 Approximately 600~4600A / m 2 Approximately 600~4500A / m 2 Approximately 600~4400A / m 2 Approximately 600~4300A / m 2 Approximately 600~4200A / m 2 Approximately 600~4100 A / m 2 Approximately 600~4000A / m 2 Approximately 600~3900A / m 2 Approximately 600~3800A / m 2 Approximately 600~3700A / m 2 Approximately 600~3600A / m 2 Approximately 600~3500A / m 2 Approximately 600~3400A / m 2 Approximately 600~3300A / m 2 Approximately 600~3200A / m 2 Approximately 600~3100A / m 2 Approximately 600~3000A / m 2 Approximately 600~2900 A / m 2, about 600~2800A / m 2 , about 600~2700A / m 2 , about 600~2600A / m 2 , about 600~2500A / m 2 The optimum current density is about 2500 A / m 2 However, the present invention is not limited to these.

[0048] The liquid temperature is about 70°C to about 90°C, and preferred examples include about 75°C to about 90°C, about 80°C to about 90°C, about 85°C to about 90°C, about 70°C to about 85°C, about 70°C to about 80°C, and about 70°C to about 75°C, but are not limited to these.

[0049] The concentration of the sulfuric acid, phosphoric acid, or nitric acid is about 60% (w / w) to about 90% (w / w), more preferably about 65% (w / w) to about 90% (w / w), about 70% (w / w) to about 90% (w / w), about 60% (w / w) to about 85% (w / w), about 60% (w / w) to about 80% (w / w), about 60% (w / w) to about 75% (w / w), and even more preferably about 70% (w / w), but is not limited to these.

[0050] The acid solution contains acidic thiosulfuric acid. Without wishing to be bound by theory, the acid solution contains acidic thiosulfuric acid, which allows the production of chlorous acid water having significantly improved reactivity compared to conventional solutions.

[0051] The concentration of the acidic thiosulfate is preferably about 0% (w / v) to about 1.3% (w / v), more preferably about 0.1% (w / v) to about 1.3% (w / v), about 0.2% (w / v) to about 1.3% (w / v), about 0.3% (w / v) to about 1.3% (w / v), about 0.4% (w / v) to about 1.3% (w / v), about 0.5% (w / v) to about 1.3% (w / v), The preferred range is about 0% (w / v) to about 1.2% (w / v), about 0% (w / v) to about 1.1% (w / v), about 0% (w / v) to about 1.0% (w / v), about 0% (w / v) to about 0.9% (w / v), about 0% (w / v) to about 0.8% (w / v), or about 0% (w / v) to about 0.7% (w / v), and more preferably about 0.5% (w / v) to about 0.7% (w / v). But it is not limited to this.

[0052] In one preferred embodiment, in reduction step, oxoacid or its salt is used in combination with reducing action.Without being bound by theory, in reduction step, by using oxoacid or its salt in combination with reducing action, not only can produce the chlorous acid water that is mainly based on the conventional delayed action, but also can produce the chlorous acid water that has various functions such as significantly improved fast-acting and high reactivity.As the reducing agent used in reduction step, hydrogen peroxide is generally used, and oxoacid with reducing action is also used or used in combination.

[0053] In one preferred embodiment, the oxoacid containing hydrogen peroxide includes, in addition to hydrogen peroxide, the following oxoacids with reducing properties: dithionous acid, acidic thiosulfuric acid, peroxomonosulfuric acid, peroxodisulfuric acid, peroxophosphoric acid, peroxochromic acid, and manganic acid. While not wishing to be bound by theory, conventional reduction reactions using hydrogen peroxide only generate chlorine dioxide gas, but the use of hydrogen peroxide in combination with these oxoacids with reducing properties generates chlorous acid, allowing the production of a gas containing chlorous acid. Preferably, the oxoacid with reducing properties is acidic thiosulfuric acid or dithionous acid, but is not limited to these.

[0054] When the oxoacid having a reducing effect is acidic thiosulfuric acid or dithionous acid, and the acidic thiosulfuric acid or dithionous acid is used in combination with hydrogen peroxide, the concentration of the acidic thiosulfuric acid or dithionous acid is about 0.5% to about 1.5%, preferably about 0.5% to about 1.4%, about 0.5% to about 1.3%, about 0.5% to about 1.2%, about 0.5% to about 1.1%, or about 0.5% to about 1.0%, and more preferably about 0.5% to about 1.0%, but is not limited to these.

[0055] In this manufacturing method, two types of gases are generated: the first reaction gas contains chlorine and chlorous acid (hereinafter referred to as the first reaction gas), and the second reaction gas contains chlorous acid and chlorine dioxide (hereinafter referred to as the second reaction gas).

[0056] In one preferred embodiment, the pH of the neutralizing agent for adsorbing the first and second reactant gases is preferably, but not limited to, about 6.0 or higher, about 6.5 or higher, about 7.0 or higher, about 7.5 or higher, about 8.0 or higher, about 8.5 or higher, about 9.0 or higher, about 9.5 or higher, about 10.0 or higher, about 11.0 or higher, about 12.0 or higher, or about 13.0 or higher. If possible, the pH may be about 6.0 to about 11.0 or lower, more preferably about 6.5 to about 11.0 or lower, about 7.0 to about 11.0 or lower, about 7.5 to about 11.0 or lower, about 8.0 to about 11.0 or lower, about 8.5 to about 11.0 or lower, about 9.0 to about 11.0 or lower, about 9.5 to about 11.0 or lower, about 10.0 to about 11.0 or lower, or about 10.5 to about 11.0 or lower. The optimum pH may be, but is not limited to, about 10.3 to about 10.7. The TAL may be, but is not limited to, about 20 or more, about 30 or more, about 40 or more, about 50 or more, about 60 or more, about 70 or more, about 80 or more, about 90 or more, about 100 or more, about 200 or more, about 300 or more, about 400 or more, about 500 or more, about 600 or more, about 700 or more, about 800 or more, about 900 or more, about 1000 or more, about 1100 or more, about 1200 or more, about 1300 or more, about 1400 or more, about 1500 or more, about 1600 or more, about 1700 or more, about 1800 or more, or about 1900 or more. The optimum TAL may be, but is not limited to, 2000. Also, pH is about 4.5 or more and about 7.5 or less, pH is about 4.6 or more and about 7.5 or less, pH is about 4.7 or more and about 7.5 or less, pH is about 4.8 or more and about 7.5 or less, pH is about 4.9 or more and about 7.5 or less, pH is about 5.0 or more and about 7.5 or less, pH is about 5.1 or more and about 7.5 or less, pH is about 5.2 or more and about 7.5 or less, pH is about 5.3 or more and about 7.5 or less, pH is about 5. pH 4 or higher, pH 5.5 or higher, pH 5.6 or higher, pH 5.7 or higher, pH 5.8 or higher, pH 5.9 or higher, pH 5.5 or higher, pH 6.0 or higher, pH 6.1 or higher, pH 6.2 or higher, pH 6.3 or higher, pH 6.4 or higher, pH 6.5 or higher, pH 6.6 or higher, pH 6.7 or higher, pH 6.8 or higher, pH 6.9 or higher, pH 7.0 or higher, pH 7.5 , pH about 7.1 to about 7.5 pH about 7.2 to about 7.5 pH about 7.3 to about 7.5 pH about 7.4 to about 7.5, pH about 4.5 to about 7.4, pH about 4.5 to about 7.3, pH about 4.5 to about 7.2, pH about 4.5 to about 7.1, pH about 4.5 above about 7.0, pH about 4.5 to about 6.9, pH about 4.5 to about 6.8, pH about 4.5 to about 6.7, pH about 4.5 to about 6.6, pH about 4.5 to about 6.5, pH about 4.5 to about 6.4, pH about 4.5 to about 6.3, pH about 4.5 to about 6.2 Highly buffered in the range of pH about 4.5 to about 6.1, pH about 4.5 to about 6.0, pH about 4.5 to about 5.9, pH about 4.5 to about 5.8, pH about 4.5 to about 5.7, pH about 4.5 to about 5.6, pH about 4.5 to about 5.5, pH about 4.5 to about 5.4, pH about 4.5 to about 5.3, pH about 4.5 to about 5.2, pH about 4.5 to about 5.1, pH about 4.5 to about 5.0, pH about 4.5 to about 4.9, pH about 4.5 to about 4.8, pH about 4.5 to about 4.7, pH about 4.5 to about 4.6 Neutralizing agents that retain their potency, i.e., have an acid dissociation constant of about 4.5 or more and about 7.5 or less, pH about 4.6 or more and about 7.5 or less, pH about 4.7 or more and about 7.5 or less, pH about 4.8 or more and about 7.5 or less, pH about 4.9 or more and about 7.5 or less, pH about 5.0 or more and about 7.5 or less, pH about 5.1 or more and about 7.5 or less, pH about 5.2 or more and about 7.5 or less, pH about 5.3 or more and about 7.5 or less, pH about 5.4 or more and about 7.5 or less, pH about 5.5 or more and about 7.5 or less, pH about 5.6 or more and about 7.5 or less, pH about 5.7 or more and about 7.5 or less, pH about 5.8 or more and about 7.5 or less, pH about 5.9 or more and about 7.5 or less, pH about 6.pH 6.0 or higher, pH 7.5 or lower, pH 6.1 or higher, pH 6.2 or higher, pH 6.3 or higher, pH 6.5 or lower, pH 6.4 or higher, pH 6.5 or lower, pH 6.6 or higher, pH 6.7 or higher, pH 6.8 or higher, pH 6.9 or higher, pH 7.0 or lower, pH 7.5 or lower 1 or more and about 7.5 or less pH about 7.2 or more and about 7.5 or less pH about 7.3 or more and about 7.5 or less pH about 7.4 or more and about 7.5 or less, pH about 4.5 or more and about 7.4 or less, pH about 4.5 or more and about 7.3 or less, p H about 4.5 to about 7.2, pH about 4.5 to about 7.1, pH about 4.5 to about 7.0, pH about 4.5 to about 6.9, pH about 4.5 to about 6.8, pH about 4.5 to about 6 .7 or less, pH about 4.5 or more and about 6.6 or less, pH about 4.5 or more and about 6.5 or less, pH about 4.5 or more and about 6.4 or less, pH about 4.5 or more and about 6.3 or less, pH about 4.5 or more and about 6.2 or less, pH about 4.5 or more and about 6.1 or less, pH about 4.5 or more and about 6.0 or less, pH about 4.5 or more and about 5.9 or less, pH about 4.5 or more and about 5.8 or less, pH about 4.5 or more and about 5.7 or less, pH about 4.5 or more and about 5.6 Neutralizers with a pH range of about 4.5 to about 5.5, about 4.5 to about 5.4, about 4.5 to about 5.3, about 4.5 to about 5.2, about 4.5 to about 5.1, about 4.5 to about 5.0, about 4.5 to about 4.9, about 4.5 to about 4.8, about 4.5 to about 4.7, or about 4.5 to about 4.6 are preferred.

[0057] Basically, it conforms to the contents of the international application number PCT / JP2014 / 006379, but the conditions of the neutralizer are pH The pH is 6.0 or higher, and preferably, the pH is between 6.0 and 11.0, with the optimum pH being 10.3 to 10.7, and the TAL is preferably 20 or higher, with the optimum TAL being 2000. More important than these conditions is that the neutralizer must have a high buffering power in the pH range of 4.5 to 7.5.

[0058] The neutralizing agent may be, without wishing to be bound by theory, an inorganic acid, an inorganic acid salt, an organic acid, Organic acid salts, hydroxide salts, etc. can be used, but the satisfaction of the above conditions is of paramount importance.

[0059] The reason is that the neutralizer used is at a pH higher than that specified in the international application PCT / JP2014 / 006379. If the neutralizing agent is used, the adsorbed chlorine dioxide gas and chlorous acid may all be converted into sodium chlorite, and this must be prevented. For the above reasons, if an inappropriate neutralizing agent is used, there is a possibility that the implementation of the characteristic production method of the present invention will be meaningless, and care must be taken, but this does not necessarily apply as long as the complete conversion of chlorine dioxide gas and chlorous acid into sodium chlorite can be prevented.

[0060] The aqueous solution containing chlorate obtained by electrolysis may also contain hypochlorite as a by-product, so an acid containing thiosulfate is added little by little to the solution. At this time, the hypochlorite reacts with the sulfuric acid to produce chlorine gas (Equation I). However, the acidic thiosulfate desalted under acidic conditions converts some of the chlorate into chlorous acid (Equation J), which is then gasified and trapped in the neutralization solution. 2NaClO+H2SO4→Cl2+Na2SO4+O2 (Formula I) H2S2O3+4HClO3+H2O→4HClO2+2H2SO4 (J formula) It is most desirable to use sulfuric acid as the acid, but phosphoric acid or nitric acid may also be used.

[0061] The amount of the acid and acidic thiosulfate to be added is preferably about 0% (w / v) to about 1.3% (w / v) of an approximately 70% (w / w) aqueous solution of the acid to be added, and the optimum concentration of acidic thiosulfate is preferably about 0.5% to about 0.7%.

[0062] Next, after adding sulfuric acid containing thiosulfate, the violent reaction ceases, bubbles disappear, and it is confirmed that the first reaction gas has ceased to be generated. Next, add hydrogen peroxide containing acidic thiosulfate or dithionous acid little by little. At this time, the second reaction gas (type C, type J, or type K) is generated, which is trapped in the neutralizing solution. H2S2O4+3HClO3+H2O→3HClO2+2H2SO4 (K formula) In addition to acidic thiosulfuric acid or dithionous acid, peroxomonosulfuric acid, peroxodisulfuric acid, peroxophosphoric acid, peroxochromic acid, and manganese oxide may also be used.

[0063] 35% hydrogen peroxide is used, and acidic thiosulfuric acid or dithionous acid is mixed with it at about 0% to about 1.5% (preferably about 0.5% to about 1.0%). This mixture is added to the reaction solution so that the total amount is about 3% to about 5% (w / w) of the mixture, thereby initiating the second reaction.

[0064] The two types of gases containing chlorous acid (first reaction gas and second reaction gas) generated in the two-stage reaction are trapped in a neutralizing agent.

[0065] The aqueous solution obtained with the neutralizing agent is called chlorous acid water.

[0066] In this case, if a large amount of the first reaction gas is adsorbed, a highly reactive chlorous acid solution can be obtained. On the other hand, if the second reaction gas is mainly adsorbed, a chlorous acid solution having the conventional characteristics obtained by the production method such as that of Patent Document 1 can be obtained.

[0067] Solutions in which the first reactive gas and the second reactive gas are adsorbed on separate neutralizing agents can be mixed together to form a single chlorous acid solution.

[0068] The neutralizing agents may be of the same composition, or neutralizing agents of different compositions may be used as long as they meet the above conditions.

[0069] By the way, the generated chlorous acid (HClO2) undergoes a decomposition reaction between multiple chlorous acid molecules, and chloride ions (Cl - In the presence of chlorous acid (HClO), hypochlorous acid (HClO), and other reducing substances, it quickly decomposes into chlorine dioxide gas and chlorine gas. Therefore, to be useful as an antibacterial agent, bactericide, disinfectant, antiseptic, and even antiviral agent, it must be prepared in a way that allows it to maintain its chlorous acid (HClO) state for a long time.

[0070] In a preferred embodiment, a step of adding a buffer to the aqueous solution containing chlorous acid after production is completed to maintain the cycle reaction is included. A single or a mixture of two or more of an inorganic acid, an inorganic acid salt, an organic acid, or an organic acid salt is used. By adding this additional step, the pH and other parameters are adjusted to create a transition state, which slows the decomposition reaction and allows chlorous acid (HClO) to be stably maintained for a long period of time.

[0071] Furthermore, in a preferred embodiment, a step of mixing one or more of an inorganic acid or an inorganic acid salt with the aqueous solution containing chlorous acid is included to maintain the cycle reaction, because adding such an additional step makes it possible to adjust the pH and the like and to control the transition state.

[0072] Furthermore, in a preferred embodiment, in order to maintain the cycle reaction, the method further comprises the step of mixing any one or more of an inorganic acid or an inorganic acid salt with the aqueous solution containing chlorous acid, and then mixing any one or more of an inorganic acid, an inorganic acid salt, an organic acid, or an organic acid salt with the aqueous solution containing chlorous acid, because the addition of such an additional step makes it possible to adjust the pH and the like and to control the transition state.

[0073] In another embodiment, the inorganic acid in the above method can be carbonic acid, phosphoric acid, boric acid or sulfuric acid, but phosphoric acid is preferred.Without wishing to be bound by theory, the present invention has shown that by using phosphoric acid in particular, within an appropriate pH range, it can have a high buffer effect, and in the state of chlorous acid, it can maintain antibacterial effect, bactericidal effect, disinfecting effect, disinfecting effect, and even antiviral effect.

[0074] Furthermore, in another embodiment, inorganic acid salt can be carbonate, hydroxide, phosphate or borate, and phosphate is preferred.In this specification, hydroxide is included in the category of inorganic acid salt.Without being bound by theory, the present invention has shown that by using phosphate in particular, within an appropriate pH range, buffer effect is high, and in the state of chlorous acid, antibacterial effect, bactericidal effect, disinfecting effect, disinfection effect, and even antiviral effect can be maintained.

[0075] In another embodiment, sodium carbonate, potassium carbonate, sodium bicarbonate, or potassium bicarbonate can be used as the carbonate salt. Preferably, sodium carbonate can be used because it has a buffering effect in two pH ranges, namely, the weakly alkaline range and the weakly acidic range, and can more advantageously stabilize chlorous acid in these ranges.

[0076] In addition, in another embodiment, hydroxide salt can include inorganic hydroxide, for example, sodium hydroxide or potassium hydroxide, calcium hydroxide, barium hydroxide can be used.Potassium hydroxide or sodium hydroxide is preferred.Not wanting to be bound by theory, these hydroxide salts can be used to increase chlorite content.On the other hand, if divalent salt is used, it can be desalted by being used in combination with phosphoric acid, and the amount of salt relative to chlorite and chlorite ion can be reduced, so it can be advantageous.

[0077] In a preferred embodiment, the sodium hydroxide and potassium hydroxide are 0.1 N to 1.0 N, and the buffer pH of the sodium phosphate and potassium phosphate is 5.0 to 7.5, particularly 5.0 to 7.0. This is because, at these compositions and pHs, the solution is stable for a longer period than previously expected, and its effect is improved.

[0078] In a further embodiment, disodium hydrogen phosphate, sodium dihydrogen phosphate, trisodium phosphate, tripotassium phosphate, dipotassium hydrogen phosphate, or potassium dihydrogen phosphate can be used as the phosphate salt. Without wishing to be bound by theory, this is because these phosphate salts can have buffering properties between pH 5 and pH 6, which is the useful pH range in which they exhibit the most antibacterial, bactericidal, disinfecting, and even antiviral activity. This pH range can be advantageous because it allows chlorous acid to exist stably. Furthermore, without wishing to be bound by theory, the present invention has shown that using potassium salts (potassium hydroxide, potassium phosphate salts (e.g., tripotassium phosphate, dipotassium hydrogen phosphate, or potassium dihydrogen phosphate)) as the metal can create a longer, more stable transition state than using sodium salts (e.g., sodium hydroxide, sodium phosphate salts (disodium hydrogen phosphate, sodium dihydrogen phosphate, trisodium phosphate)) as the metal, and furthermore, by delaying the decomposition reaction, chlorous acid (HClO) can be maintained for a longer period of time. Preferably, dipotassium hydrogen phosphate can be used.

[0079] In another embodiment, the borate salt may be sodium borate or potassium borate, with potassium salts being preferred but not limited thereto.

[0080] Furthermore, in another embodiment, succinic acid, citric acid, malic acid, acetic acid, or lactic acid can be used as the organic acid. Preferably, succinic acid can be used. Without wishing to be bound by theory, succinic acid can have a buffering effect between a pH of 5 and a pH of 4. Within this pH range, rapid gasification of chlorine dioxide can be suppressed. However, when the pH falls below the pH of 5, the pH tends to drop rapidly. In such cases, it is desirable to use an organic acid, such as citric acid, that has a buffering effect at a pH of 3.

[0081] Furthermore, in another embodiment, the organic acid salt may be sodium succinate, potassium succinate, sodium citrate, potassium citrate, sodium malate, potassium malate, sodium acetate, potassium acetate, sodium lactate, potassium lactate, or calcium lactate.

[0082] When acid and / or its salt is added, Na + +ClO2 - ⇔Na-ClO2 and K + +ClO2 - ⇔K-ClO2 and H + +ClO2 - This creates a transition state such as H-ClO2, slowing the progression of chlorous acid (HClO2) to chlorine dioxide (ClO2). This allows chlorous acid (HClO2) to be maintained for a long period of time, making it possible to produce an aqueous solution containing chlorous acid with little generation of chlorine dioxide (ClO2). While not wishing to be bound by theory, the present invention has shown that the use of a phosphate buffer enhances this maintenance effect. Furthermore, while not wishing to be bound by theory, the present invention has shown that the use of a potassium salt further enhances this maintenance effect compared to the use of a sodium salt or the like.

[0083] The decomposition of chlorite in acidic solution, as shown in Chemical Formula 2 above, is shown below.

[0084] [ka]

[0085] As shown in this equation, the decomposition rate of a chlorite aqueous solution at a given pH increases as the pH decreases, i.e., the acidity increases. In other words, the absolute rates of reactions (a), (b), and (c) in the above equation increase. For example, the proportion of reaction (a) decreases as the pH decreases, but the total decomposition rate fluctuates significantly, i.e., increases. Therefore, the amount of chlorine dioxide (ClO2) generated also increases as the pH decreases. Therefore, the lower the pH value, the faster the bleaching power, as well as the antibacterial, bactericidal, disinfectant, and even antiviral power, but the irritating and harmful chlorine dioxide gas (ClO2) makes work difficult and has adverse effects on human health. Furthermore, the reaction of chlorous acid to chlorine dioxide proceeds rapidly, making chlorous acid unstable, and the time it maintains its antibacterial, bactericidal, disinfectant, and even antiviral power is extremely short.

[0086] Therefore, when the inorganic acid, inorganic acid salt, organic acid, or organic acid salt is added to an aqueous solution containing chlorous acid (HClO), the pH value is adjusted within a range of about 3.2 to about 8.5, or, depending on the purpose, within a preferred range such as about 3.2 to about 7.0 or about 5.0 to about 7.0, from the viewpoint of the balance between the inhibition of chlorine dioxide generation and the bactericidal activity.

[0087] When the sample is measured using a spectrophotometer, the acidic chlorite ion (H ) is detected, which has a peak at around 260 nm between wavelengths of approximately 240 and 420 nm. + +ClO2 - When two absorption parts, one containing chlorine dioxide (ClO2) and the other containing a peak at around 350 nm, are simultaneously confirmed, the presence of the chlorous acid water of the present invention can be confirmed. In other words, the presence of chlorous acid (HClO2) can be confirmed. This is because, as shown in the following chemical formula 4, the water is composed mainly of chlorous acid (HClO2), chlorine dioxide (ClO2), and acidic chlorous acid ions (H + +ClO2 - ) cycle reactions are occurring simultaneously.

[0088] [ka]

[0089] When chlorous acid (HClO2) is converted to chlorine dioxide (ClO2), a single peak appears at approximately 350 nm.

[0090] It has previously been found that the pH can be further stabilized by adding a buffer directly or by adjusting the pH once with sodium carbonate or the like and then adding another buffer.

[0091] Without wishing to be bound by theory, the present invention relates to a method for treating a chlorite (HClO2), chlorine dioxide gas (ClO2), or an aqueous solution containing these, with an inorganic acid, an inorganic acid salt, an organic acid, or an organic acid salt, either alone or in combination. By combining these, it is possible to create a transition state and delay the decomposition reaction, thereby stabilizing and maintaining chlorous acid (HClO2) for a long period of time. As a result, it was unexpectedly discovered that the antibacterial, bactericidal, disinfecting, and antiseptic effects, as well as the antiviral effects, can be maintained stably for a long period of time. Preferred pH ranges include 3.2 or higher and lower than 7.0, about 5.0 to about 7.5, about 5.0 to about 7.0, about 5.5 to about 7.0, and about 5.0 to about 6.0, with lower limits of about 5.0, about 5.1, about 5.2, about 5.3, about 5.4, and about 5.5, and upper limits of about 7.5, about 7.4, about 7.3, about 7.2, about 7.1, about 7.0, about 6.9, about 6.8, about 6.7, about 6.5, about 6.4, about 6.3, about 6.2, about 6.1, about 6.0, about 5.9, about 5.8, about 5.7, about 5.6, and about 5.5, but are not limited thereto. An optimal pH is about 5.5, but is not limited thereto. In this specification, when the term "about" is used in reference to a pH value, it means a range of about 0.05, with one decimal place being the significant figure. For example, about 5.5 is understood to mean 5.45 to 5.55. In terms of clearly distinguishing it from sodium chlorite, the pH of the present invention is preferably less than 7.0, but is not limited to this.

[0092] Preferred metal hydroxides include sodium hydroxide and / or potassium hydroxide, and preferred metal phosphates include sodium phosphate (e.g., disodium hydrogen phosphate, sodium dihydrogen phosphate, trisodium phosphate) and / or potassium phosphate (e.g., tripotassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate; particularly potassium dihydrogen phosphate), and more preferably potassium hydroxide and potassium phosphate (e.g., tripotassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate; particularly potassium dihydrogen phosphate), but are not limited to these.

[0093] In one aspect, the present invention provides an apparatus for producing chlorous acid water, comprising: 1) an electrolysis tank for electrolyzing a salt to obtain a chlorate or an aqueous solution thereof; and 2) a reaction tank for reducing the chlorate or the aqueous solution thereof to obtain an aqueous solution containing chlorous acid.

[0094] In one aspect, the present invention provides an article impregnated with the antibacterial agent, bactericide, disinfectant, disinfectant, or even antiviral agent of the present invention. The article that can be used as the article of the present invention is any article that can be impregnated with chlorous acid water and used for antibacterial, bactericidal, disinfectant, disinfectant, or even antiviral purposes, including medical devices, such as sheets, films, patches, brushes, nonwoven fabrics, paper, cloth, absorbent cotton, sponges, etc., but is not limited to these.

[0095] (Example of general production of chlorous acid water by electrolysis) A salt solution is obtained by adding tap water to a salt dissolution tank until the salt no longer dissolves. This salt solution is then transferred to and filled into the electrolysis tank and storage tank. At this time, filtration is performed to remove any undissolved salt. A diluted solution of approximately 0.3% hydrochloric acid is placed in the hydrochloric acid titration apparatus, and titration begins. The pH value is adjusted while the salt solution is circulating. The cooling device is turned on, and cooling water is circulated. The control panel is used to generate electricity, which is then passed through a rectifier to begin powering up. The powered solution is then transferred to the reaction tank. The neutralization tank is pre-filled with neutralizing solution, and the gas scrubbing device is pre-filled with gas scrubbing solution. The reaction tank's agitator is then turned on, and the acid solution is gradually added to the powered solution. After confirming that no first reaction gas is being generated in the reaction tank, the remaining acid solution is added. Hydrogen peroxide solution is then slowly added, gradually generating second reaction gas, which is then absorbed by the neutralization solution in the neutralization tank. This process is repeated as many times as necessary, and production is terminated when the specifications are met.

[0096] All references cited herein, including scientific literature, patents, patent applications, and the like, are incorporated by reference in their entirety to the same extent as if each were specifically set forth.

[0097] The present invention has been described above by showing preferred embodiments for ease of understanding. The present invention will be described below based on examples. However, the above description and the following examples are provided for illustrative purposes only and are not intended to limit the present invention. Therefore, the scope of the present invention is not limited to the embodiments or examples specifically described herein, but is limited only by the claims. [Example]

[0098] The present invention will be described in more detail with reference to the following examples and comparative examples. However, the present invention is not limited to these examples, and examples obtained by appropriately combining the technical means disclosed in each example are also included in the scope of the present invention.

[0099] Where necessary, the handling of animals used in the following examples was in accordance with the Declaration of Helsinki. The specific reagents used were those listed in the examples, but equivalent products from other manufacturers (Sigma, Wako Pure Chemical Industries, Nakarai, etc.) can also be used. In this specification, chlorous acid water may be abbreviated to "chlorous acid water," but this is synonymous.

[0100] (Method for evaluating chlorous acid water) The main active ingredient in hypochlorous acid water is hypochlorous acid, but due to its properties, hypochlorous acid is often mistaken for the same thing as chlorine dioxide or sodium chlorite. Of course, it is also different from acidified sodium chlorite (ASC).

[0101] Therefore, in order to distinguish it from similar chlorine oxides, ensure the effectiveness of chlorous acid water, and manage it, we propose the following measurement method.

[0102] (Chlorite concentration) The chlorous acid concentration can be determined by the known iodometric titration method, and is the value expressed by converting the total amount of chlorine contained in the chlorous acid water into the chlorous acid concentration. This is not patented, but the principle is as follows. Using the oxidizing power of chlorous acid, iodine is liberated from potassium iodide under sulfuric acid acidity. HClO2+2H2SO4+4KI→HCl+2K2SO4+2H2O+2I2 The liberated iodine molecules are then reduced with sodium thiosulfate solution, and the point at which the solution loses color is taken as the endpoint of the titration. 2I2+4Na2S2O3→2Na2S4O6+4NaI Near the titration endpoint, starch is added as an indicator to produce a blue color (iodine-starch reaction), and the point at which this blue color becomes colorless is the titration endpoint. The concentration of chlorous acid is calculated from the amount of sodium thiosulfate solution required to reduce the liberated iodine molecules.

[0103] (Adjustment of reagents) Approximately 10 w / w% potassium iodide solution: Add approximately 20 g of potassium iodide to approximately 180 g of water.

[0104] *Adjust as needed, discard any remaining solution on the day, and never carry it over to the next day. Approximately 10 w / w% sulfuric acid: Add approximately 100 g of sulfuric acid to approximately 900 g of water. *Be sure to add the sulfuric acid to the water little by little while running the glass rod down the pipe. 1 w / w% starch solution: Add approximately 5.0 g of soluble starch and approximately 0.5 g of sodium azide to approximately 494.5 g of water, heat in a microwave oven (or electric heater), and occasionally stir with a glass rod to dissolve the soluble starch. When the solution becomes clear, stop heating, cool, and store in the refrigerator. Approximately 0.1 mol / L sodium thiosulfate solution: Dissolve 24.82 g of sodium thiosulfate pentahydrate in water to make approximately 1000 mL. Standardization: Take exactly 10 mL of approximately 1 / 60 mol / L potassium iodate, add 10 mL of approximately 10 w / w% potassium iodide solution and 10 mL of approximately 10 w / w% sulfuric acid, leave in a dark place for approximately 10 minutes, and titrate with approximately 0.1 mol / L sodium thiosulfate solution until the solution turns pale yellow. Next, add approximately 1 mL of 1 w / w% starch solution, and titrate with approximately 0.1 mol / L sodium thiosulfate solution until the solution turns colorless. Calculate the factor (f) of the 0.1 mol / L sodium thiosulfate solution using the following formula. Factor (f) = 10 / v v: Titration volume of 0.1 mol / L sodium thiosulfate solution (mL) 1 / 60 mol / L potassium iodate solution: Dissolve 1.783 g of potassium iodate, which has been preheated and dried at approximately 120°C for approximately 2 hours, in water to make 500 mL.

[0105] (How to operate) (1) Place approximately 20 g of the sample solution in a 300 mL Erlenmeyer flask with a ground stopper and add water to make approximately 200 mL. (2) Add approximately 10 mL of approximately 10 w / w% potassium iodide solution and approximately 10 mL of approximately 10 w / w% sulfuric acid and leave in a dark place for 15 minutes. (3) Add approximately 0.1 mol / L sodium thiosulfate solution until the solution turns pale yellow. Next, add approximately 1 mL of 1 w / w% starch solution, and then add approximately 0.1 mol / L sodium thiosulfate solution until the solution turns colorless. However, the approximately 0.1 mol / L sodium thiosulfate solution should be placed in a 100 mL glass beaker and added using droppers (large and small). The weight (g) added should be recorded. (CAW)=(1.7115×10 -3 ×V×f / w)×1000000×k (CAW); Chlorite concentration (ppm) V: Titration volume of 0.1 mol / L sodium thiosulfate solution (mL) f: Factor of 0.1 mol / L sodium thiosulfate solution w: Weight (g) of the sample solution measured in step (1) k: Dilution factor 1.7115×10-3 ;Weight (g) of chlorous acid equivalent to 1 mL of 0.1 mol / L sodium thiosulfate solution (Oxidizing power: sodium hypochlorite equivalent concentration) The amount of chlorine in sodium hypochlorite is not only expressed as the effective chlorine concentration calculated by iodometric titration, but also as the amount of activated chlorine contained in sodium hypochlorite that is involved in the bactericidal effect, that is, the oxidizing power, expressed as free chlorine.It is well known that the effective chlorine concentration and free chlorine of sodium hypochlorite show the same value.However, in the case of chlorous acid water, the amount of activated chlorine involved in the antibacterial effect, bactericidal effect, sterilization effect, disinfection effect, and even antiviral effect contained in chlorous acid water does not match the value of the chlorous acid concentration obtained by the above-mentioned measurement method.Therefore, it is necessary to confirm the oxidizing power of chlorous acid water using the same method as the free chlorine of sodium hypochlorite, and it can be quantified by the following method.

[0106] The oxidizing power of hypochlorous acid water: The basis and principles for measuring the sodium hypochlorite equivalent concentration are based on those described in "Water Supply Act Enforcement Regulations, Appendix 3, Spectrophotometric Method" and the Japanese Pharmacopoeia (General Test Methods) 2.24.

[0107] The oxidizing power of chlorous acid water: The sodium hypochlorite equivalent concentration is calculated using the following method.

[0108] 1. Equipment and Adjustment Method A spectrophotometer is used as the measuring device. After adjusting the device in advance using the operating instructions attached to the spectrophotometer, the wavelength and transmittance are checked assuming that they are suitable for the test. The wavelength is measured using an optical filter for wavelength calibration under the test conditions in the test report attached to each filter, near the wavelength of the reference value shown in the test report. The transmittance is measured and the wavelength at which this transmittance shows its minimum value is read. However, when conducting the test, the deviation between the measurement wavelength and the reference wavelength must be within ±0.5 nm, the measurement must be performed three times, and all measurements must be within the average value ±0.2 nm. The transmittance or absorbance is read using an optical filter for transmittance calibration under the test conditions in the test report attached to each filter, at the reference wavelength shown in the test report. Furthermore, when conducting the test, the deviation between the measured transmittance and the reference transmittance must be within 1% of the upper and lower limits of relative accuracy shown in the test report, and the measurement must be performed three times. It must be confirmed that the measured absorbance (or the value converted from the measured transmittance) is within ±0.002 of the average value when the absorbance is 0.500 or less, and within ±0.004 of the average value when the absorbance is greater than 0.500. It is desirable to use a plurality of optical filters for transmittance calibration, each having a different transmittance at the same wavelength, to confirm that the transmittance forms a straight line.

[0109] 2.Operation method Using a pre-adjusted device, select and set the light source, detector, device measurement mode, measurement wavelength or measurement wavelength range, spectral width, wavelength scanning speed, etc. Next, start the device and leave it for a certain period of time to confirm that the device is operating stably. Then, close the shutter in the sample light path to block the light and adjust so that the transmittance reading at the measurement wavelength or measurement wavelength range is 0%. Next, remove the shutter and adjust so that the transmittance reading at the measurement wavelength or measurement wavelength range is 100% (or the absorbance is 0%), and then place a cell containing a control solution, etc., in the light path. Place the cells containing the control solution, etc., in the sample light path and the control light path and adjust the transmittance reading to 100% (or the absorbance is 0%). In addition to the specified solution, use the solvent used in the test as the control solution.

[0110] 3. How to create a calibration curve 《DPD method (Sankei method)》 Grind 1.0 g of N,N-diethyl-p-phenylenediamine sulfate in a mortar and add 24 g of anhydrous sodium sulfate. Mix uniformly without crushing the crystal grains to make the "indicator." Dissolve potassium dihydrogen phosphate in ion-exchange water (or distilled water) to make a 1.6 M solution to make the "potassium dihydrogen phosphate solution." Dissolve dipotassium hydrogen phosphate in ion-exchange water (or distilled water) to make a 1.6 M solution to make the "dipotassium hydrogen phosphate solution." Mix the potassium dihydrogen phosphate solution and the dipotassium hydrogen phosphate solution, and adjust the pH to 6.5 using a pH meter. This solution is called the "phosphate buffer solution." Prepare chlorine water by adding sulfuric acid (1 + 4) dropwise to sodium hypochlorite, and allowing the generated chlorine gas to be absorbed into purified water. Use this chlorine water to adjust the free chlorine concentration to 100 ppm, and use this chlorine water to make the "reference solution." (At this time, it is important to confirm that the diluted solution is 100 ppm.) Accurately measure this standard solution and add ion-exchanged water (or distilled water) to it to create a solution containing 0.01 mL, 0.02 mL, 0.05 mL, and 0.10 mL per mL, which will be used as the "standard solution." Also, measure 9.5 mL of this standard solution, add 0.5 mL of phosphate buffer, mix uniformly, add 0.1 g of indicator, mix, and perform the test using the ultraviolet-visible absorbance measurement method [Japanese Pharmacopoeia [General Testing Methods] 2.24]. Measure the absorbance at a wavelength of 510 nm, measure 9.5 mL of ion-exchanged water (or distilled water), add 0.5 mL of phosphate buffer, and mix uniformly. This solution will be used as the "blank solution." Next, test this blank solution using the ultraviolet-visible absorbance measurement method [Japanese Pharmacopoeia [General Testing Methods] 2.24] and measure the absorbance at a wavelength of 510 nm. Repeat the above procedure three times and use the value obtained by subtracting the absorbance of the blank solution from that of the standard solution to calculate the average absorbance for each concentration. Using these calculated values, plot the oxidizing power (≒ free chlorine concentration) on the horizontal axis and the absorbance on the vertical axis (Y) to create a "calibration curve" within one hour of creating the standard solution.

[0111] 4. Measurement method using a calibration curve DPD Method (Sankei Method): Oxidizing power using a calibration curve: Calculation method for free chlorine concentration (converted to sodium hypochlorite concentration) Grind 1.0 g of N,N-diethyl-p-phenylenediamine sulfate in a mortar, add 24 g of anhydrous sodium sulfate, and mix evenly without crushing the crystal grains to form the "indicator." Dissolve potassium dihydrogen phosphate in ion-exchange water (or distilled water) to make a 1.6 M solution to form the "potassium dihydrogen phosphate solution." Dissolve dipotassium hydrogen phosphate in ion-exchange water (or distilled water) to make a 1.6 M solution to form the "dipotassium hydrogen phosphate solution." Mix the potassium dihydrogen phosphate solution and the dipotassium hydrogen phosphate solution, and adjust the pH to 6.5 using a pH meter. This solution will form the "phosphate buffer solution." Then, adjust the chlorous acid water to a chlorous acid concentration of 300 ppm using ion-exchange water (or distilled water) to form the "test solution." Next, measure out 9.5 mL of this test solution, add 0.5 mL of phosphate buffer solution, mix, then add 0.1 g of indicator and mix. Immediately measure the absorbance at a wavelength of 510 nm using a spectrophotometer, and use the calibration curve created using the DPD method to determine the "concentration of sodium hypochlorite" from the relationship (Y = aX a: coefficient).

[0112] (Carbolic Acid Coefficient Method) The antibacterial, bactericidal, disinfecting, and antiviral effects of chlorous acid water can only be accurately determined by comparing and evaluating them with the antibacterial, bactericidal, disinfecting, and antiviral effects of phenol against E. coli. The operating method is as follows:

[0113] Required reagents Phenol, nutrient broth, deoxycholate medium, sodium chloride, sterilized water Required equipment Kitchen timer, gas stove, pot, various test tubes and glassware, pipetter (10 ml), pipetter (1 ml), test tube (dry heat sterilized), gas burner, pipetter tip (dry heat sterilized), platinum loop, cotton swab Reagent preparation 5% phenol solution: Dissolve phenol in approximately 70°C water, measure out 25 mL, and add water (40°C) to make exactly 500 mL. Confirm that the specific gravity at 20°C is within the range of 1.000 ± 0.005. *It is not a problem if the solution becomes cloudy.

[0114] Liquid medium (1 L capacity): In a 1000 mL stoppered Erlenmeyer flask, add 18.0 g of normal bouillon medium to 1 L of water, mix and dissolve at room temperature for approximately 30 minutes, and after confirming that it is fully dissolved, autoclave (121°C, 15 minutes).

[0115] Liquid medium (200 mL volume): Add approximately 18.0 g of normal bouillon medium to 1 L of water, mix and dissolve at room temperature for approximately 30 minutes, and after confirming that it is fully dissolved, dispense 200 mL into a 300 mL stoppered Erlenmeyer flask and autoclave (approximately 121°C, approximately 15 minutes).

[0116] Liquid medium (test tube): Add approximately 18.0 g of normal bouillon medium to 1 L of water, mix and dissolve at room temperature for approximately 30 minutes, and after confirming that it is fully dissolved, dispense 10 mL into test tubes, put on aluminum caps, and autoclave (approximately 121°C, approximately 15 minutes).

[0117] Physiological saline: Dissolve approximately 8.5 g of sodium chloride in approximately 500 ml of water, and then add water to make 1 L. Autoclave the solution (approximately 121°C, approximately 15 minutes).

[0118] Bacterial solution (E. coli): i) E. coli is smeared onto a freshly prepared doxycholate medium (plate) and cultured at approximately 37°C for approximately 24 hours. ii) A single colony that has appeared on the medium is suspended in 10 ml of physiological saline. One loopful of the suspension is inoculated into a liquid medium (200 ml volume) and cultured at approximately 37°C for approximately 24 hours. iii) The E. coli will grow and the liquid medium (test tube) will turn cloudy. At this point, the number of E. coli contained in the liquid will be approximately 10^8 bacteria. iv) When using the bacterial solution prepared in iii), dilute it 10 times with saline and mix it with a vortex mixer before use. The number of E. coli bacteria contained in the solution at this time should be approximately 10^7 bacteria. Desoxycholate medium (plate): Add approximately 45 g of desoxycholate medium to 1 L of water, heat in an autoclave (105°C, 5 minutes), then cool to approximately 50°C. After that, spread approximately 20 mL of the medium onto a petri dish and solidify it to make a plate medium.

[0119] Sterilized water: Put an appropriate amount of distilled water into a gallon bottle and autoclave (approximately 121°C, approximately 15 minutes).

[0120] ·How to operate

[0121] [Table 1]

[0122] [Table 2]

[0123] For each sample, adjust the oxidizing power to the following values ​​and prepare the required volume for each sample.

[0124] [Table 3]

[0125] The sample prepared according to the above formulation is dispensed into dry heat sterilized test tubes.

[0126] Approximately 1 mL of bacterial solution is added to each sample, and the contact time is set to 0 minutes. At this time, the number of E. coli bacteria contained in the bacterial solution is set to approximately 10^6 bacteria.

[0127] After the specimen and the bacterial solution have come into contact, a sterilized white fungal loop is immersed in the liquid medium (test tube) 5 minutes and 10 minutes later, creating a water film on the ring at the tip of the platinum loop, and inoculating the liquid medium (test tube) in this state.

[0128] Place the inoculated test tube in a vortex mixer, seal tightly, and leave to stand at 37°C for 24 hours. After standing, test sections that show turbidity are recorded as "+," and test sections that show no turbidity are recorded as "-." However, for test sections evaluated as "+," dip a cotton swab into the liquid medium and smear a straight line from the center to the outside on a desoxycholate medium (plate). Write the name of the sample on the back of the dish where the smeared area was, and culture at 37°C for 24 hours.

[0129] After incubation for the specified time, if a typical red colony is confirmed in the smear, the specimen is evaluated as "+." If no red colony is confirmed, the specimen is evaluated as "-" and the record is corrected. Confirm that the evaluations for the 5-minute contact time and the 10-minute contact time are either "+" "+", "+" "-", or "-" "-", and if the evaluation is "+" "-", calculate the average value within that range.

[0130] If there are no test plots with a "+" or "-" mark, the intermediate value between "+" and "+" and "-" and "-" is used.

[0131] The dilution ratio of the adopted values ​​is calculated from the stock solution of chlorous acid water and the stock solution of phenol, and these are set as the "dilution ratio of the sample solution" and the "dilution ratio of phenol," respectively. These are applied to the following formula to calculate the phenol coefficient (PC).

[0132] [Table 4]

[0133] [Table 5]

[0134] In this case, the set concentration to be adopted is determined to be 0.75%, and the dilution ratio is 133. In the case of hypochlorous acid water, the phenolic coefficient is evaluated as shown in the results table below.

[0135] [Table 6]

[0136] (Indicator of hypochlorous acid water) It is known that the antibacterial, bactericidal, disinfecting, and antiviral effects of chlorine oxide vary depending on the type of main active ingredient, and the antibacterial, bactericidal, disinfecting, and antiviral effects that can be exerted per oxidizing power of 1. If this is quantified using the "carbonic acid coefficient per oxidizing power (100)", the hypochlorous acid contained in hypochlorous acid water can be calculated as follows: They are classified into chloric acid, chlorine dioxide, sodium chlorite, and ASC, and their antibacterial effects, It can have bactericidal, disinfectant, antiseptic and even antiviral effects.

[0137] (Example 1: Differences in the relationship between the oxidizing power of chlorous acid water, sodium chlorite, and chlorine dioxide and the phenolic coefficient) The following samples were prepared, and the oxidizing power: sodium hypochlorite equivalent concentration and phenolic coefficient were measured for each chlorine oxide.

[0138] [Table 7]

[0139] Using these samples, the oxidizing power: sodium hypochlorite equivalent concentration and the phenolic coefficient were measured while diluting them with ion-exchanged water as appropriate.

[0140] The results are shown below. This table and Figure 4 show the oxidizing power at each phenol coefficient: sodium hypochlorite equivalent concentration.

[0141] [Table 8]

[0142] Sodium chlorite maintains an available chlorine concentration of 25% (w / v), which corresponds to the saturated concentration. Despite this, the oxidizing power value and the phenolic coefficient value were both "0".

[0143] The relationship between the oxidizing power and the phenolic coefficient of chlorine dioxide and dissolved chlorine dioxide was consistent, but only chlorous acid water A showed a high phenolic coefficient with low oxidizing power, showing a tendency that was clearly different from the relationship between the oxidizing power and the phenolic coefficient of sodium chlorite and chlorine dioxide.This proves that the oxidizing power of chlorous acid water A has a higher antibacterial, bactericidal, disinfecting, and antiviral effect than the oxidizing power of chlorine dioxide and sodium chlorite.

[0144] In addition, since hypochlorous acid water and ASC contain the same bactericidal component, hypochlorous acid, they are completely compatible. Many experts believe that they are essentially the same thing and confuse the two when evaluating them. Therefore, we decided to create an ASC that faithfully reproduces WO99 / 18805 by Kross and compare it with the chlorous acid water A produced in Example 2.

[0145] The following samples were prepared and the oxidizing power and phenolic coefficient were measured immediately after production and on the fifth day.

[0146] [Table 9]

[0147] Dissolved chlorine dioxide was used as a control for comparison.

[0148] [Table 10]

[0149] The relationship between the oxidizing power and the phenolic acid coefficient of hypochlorous acid water A did not change even after five days. On the other hand, ASC showed a relationship between oxidizing power and the phenolic acid coefficient similar to that of hypochlorous acid water immediately after adjustment. However, after 5 days, the oxidizing power and phenolic coefficient of the dissolved chlorine dioxide (control) were found to be completely consistent. This shows that ASC is more effective against chlorine dioxide than chlorous acid water. It has been found that it is an antibacterial, bactericidal, disinfectant, antiseptic, and even antiviral agent with properties similar to those of the cereals (Figure 5). Using the actual measured values ​​obtained from the above results, the phenolic coefficients of dissolved chlorine dioxide and chlorine dioxide were divided by the oxidizing power, and then multiplied by the ratio 100 (phenolic coefficient per oxidizing power (100)). The value was maintained within a narrow range of 0.71 to 0.72. The phenolic coefficient per oxidizing power (100) of sodium chlorite was 0. On the other hand, the phenolic coefficient per oxidizing power (100) of chlorous acid water A was high, at around 1.37 to 1.87, but this was not significant. Because the range of values ​​shown is wide, in a broad sense, if the phenol coefficient per oxidizing power (100) is 0.72 or more, it can be said that it is not chlorine dioxide, and with this index, it can be said that it is chlorine oxide. It is possible to determine whether the antibacterial, bactericidal, disinfectant, and even antiviral components contained in the product are chlorite ions, chlorous acid, or chlorine dioxide. Furthermore, it is desirable for the phenolic acid coefficient per oxidizing power (100) of chlorous acid water to be maintained at 1.0 or higher, if possible.

[0150] Furthermore, when using chlorous acid water as an antibacterial agent, bactericide, disinfectant, or even antiviral agent, it is desirable to understand the amount of activated chlorine, i.e., the oxidizing power, involved in the antibacterial, bactericidal, disinfectant, and even antiviral effects, relative to the total amount of chlorine contained in the chlorous acid water. This value can be managed as the oxidizing power value per 100 ppm of chlorous acid concentration.

[0151] Furthermore, the true antibacterial, bactericidal, disinfecting, and disinfecting effects of the chlorous acid contained in the hypochlorous acid water As a result, it is desirable to control the value of the phenolic acid coefficient per 10,000 ppm of chlorous acid concentration in order to control the antiviral effect.

[0152] Therefore, the antibacterial, bactericidal, disinfecting, and antiviral effects of hypochlorous acid water are different from those of sodium hypochlorite, and are determined by three factors: "oxidizing power per 100 ppm of hypochlorous acid concentration," "phenolic acid coefficient per oxidizing power (100)," and "phenolic acid coefficient per 10,000 ppm of hypochlorous acid concentration." By managing these three items, it is possible to ensure the antibacterial, bactericidal, disinfectant, and even antiviral properties of the product.

[0153] (Example 2: Production of chlorous acid water having the conventional bactericidal effect produced in Patent Document 1 using a diaphragm-less electrolyzer-reactor integrated production plant) (Example of a manufacturing plant) An example of the integrated manufacturing plant used is shown in Figure 1. In Figure 1, the numbers represent the components shown in the table below.

[0154] [Table 11]

[0155] [Table 12]

[0156] The raw materials used and their compositions are as follows:

[0157] [Table 13]

[0158] [Table 14]

[0159] [Table 15]

[0160] [Table 16]

[0161] [Table 17]

[0162] [Table 18]

[0163] [Table 19]

[0164] [Table 20]

[0165] (Outline of the production of chlorous acid water by electrolysis) Add salt that meets the Japanese Pharmacopoeia sodium chloride standard to a salt dissolution tank filled with tap water until it no longer dissolves, and this will be called saturated salt water. Operate pump 1 to transfer this saturated salt water to the electrolysis tank and storage tank, filling them up. At this time, remove any undissolved sodium chloride crystals by passing it through a saturated salt water filtration device. Place a 0.3% diluted hydrochloric acid solution in the hydrochloric acid titration device. Start the titration. Start pump 2 and circulate the saturated saline solution while adjusting the pH to 6.0. Start the pH and liquid temperature monitors and record the values ​​at that time. Cooling The device is operated and the cooling water is circulated. The control panel is operated to generate electricity, which is passed through a rectifier and energized (voltage 3V, current 100A, current density 2500A / m 2 , 80°C ± 5°C, 78 hours 30 minutes). The electrodes connected to the electrolysis tank are made of anode (platinum-iridium coated titanium) and cathode (high purity steel), and these electrodes are arranged in parallel with a 5 mm gap without a diaphragm. The saturated salt water passes through the gap and circulates between the electrolysis tank and the storage tank. The sodium chlorate concentration of the resulting liquor is 50% (w / v), and the available chlorine concentration is 0 ppm. Pump 2 is stopped and the liquor is transferred to the reaction tank. The neutralization tank is filled with neutralizing liquid and the gas scrubbing device is filled with gas scrubbing liquid in advance, and then the agitator for the reaction tank is operated and the acid solution is added little by little to about 1 kg of liquor in the tank. After confirming that no reaction gas is being generated, add the remaining acid solution. Then slowly add the hydrogen peroxide solution, little by little generating a second reaction gas, which is then absorbed by the neutralizing solution in the neutralization tank. This process is repeated twice, and production is completed when the product meets the specifications.

[0166] The chlorous acid solution was prepared as follows. (1. Settings) The settings were as follows: 1. Check that A is tightly sealed. 2. Put recipe A into 1 3. Add recipe B to 11 4. B and D were opened, and E was confirmed to be sealed. 5 A was opened and 3 was activated 6. Transfer the liquid from 1 until 6 and 7 are full. 7. 9 was operated and each pipe was filled with the liquid 1. 8 A was sealed and 3 was stopped. 9 8 was started and pH and temperature measurements were started. 10 11 was operated and the flowing solution in 1 was adjusted to pH 6.0. 11 Started up 10 and circulated cooling water to 21 12. 4 and 6 were put into operation and power was turned on. 13 Stopped 4 and 5 14 L was released and sampled. Closed 15 L 16 Circulate until the liquid temperature falls below 25°C. 17. Conduct quality inspections and if the product meets the standards, stop step 9. Stopped 18 11 19 B and D closed 20 14 added recipe c 21 15 added recipe d 22 17 added recipe F 23 18 contains the formula g 24 Confirmed that F, G, K, H, J, and I were closed 25 Unlocked C and K 26 E was opened and 7 licker liquid was transferred. 27 E closed 28 Check the amount of licker liquid transferred 29 C and K closed 30 I was opened in the direction of 12 → I → 17 31 13 was put into operation Release 32 F, press syringe 14, and add recipe c to 12 little by little. 33 After confirming that the first chlorous acid gas was not generated, all of the ingredients in the formula c were added to 12. 34 F closed 35 G released 36 Press the syringe 15 and add the formula d to 12 little by little. 37 A violent reaction occurred, and once the foaming subsided, 16 was started and H was released. 38 Press syringe 15 and add all ingredients listed in recipe d to syringe 12. 39 G closed 40 After the reaction was completed, H was closed and 16 was stopped. 41 Stopped 13 42 I was opened in the direction of 19 → I → 17 43 K has been released 44 J was released and transferred to 19 45 Performed steps 25 to 44 twice 46 19 was neutralized by adding the formula h and discarded. 47 18 was brought to normal pressure 48 17 is brought to normal pressure, and 17 is taken out and used as hypochlorous acid water A for quality inspection. went The results of the quality inspections carried out during manufacturing are listed below.

[0167] [Table 21]

[0168] [Table 22]

[0169] [Table 23]

[0170] Hydrous Acid Water A Ingredient Analysis Table

[0171] [Table 24]

[0172] Using the above-mentioned hypochlorous acid water A as a raw material, the following ingredients were added to maintain the cycle reaction, to prepare hypochlorous acid water preparation A.

[0173] [Table 25]

[0174] [Table 26]

[0175] Example 3: Highly reactive chlorous acid produced by a membrane-less electrolysis tank-reaction tank integrated production plant Water production) The raw materials used and their compositions are as follows:

[0176] [Table 27]

[0177] [Table 28]

[0178] [Table 29]

[0179] [Table 30]

[0180] [Table 31]

[0181] [Table 32]

[0182] [Table 33]

[0183] [Table 34]

[0184] (Outline of the production of chlorous acid water by electrolysis) Add salt that meets the Japanese Pharmacopoeia sodium chloride standard to a salt dissolution tank filled with tap water until it no longer dissolves, and this will be called saturated salt water. Operate pump 1 to transfer this saturated salt water to the electrolysis tank and storage tank, filling them up. At this time, remove any undissolved sodium chloride crystals by passing it through a saturated salt water filtration device. Place a 0.3% diluted hydrochloric acid solution in the hydrochloric acid titration device. Start the titration. Start pump 2 and circulate the saturated saline solution while adjusting the pH to 6.5. Start the pH and liquid temperature monitors and record the values ​​at that time. Cooling The device is operated and the cooling water is circulated. The control panel is operated to generate electricity, which is passed through a rectifier and energized (voltage 3V, current 100A, current density 2500A / m 2 , 85°C ± 5°C, 78 hours 30 minutes). The electrodes connected to the electrolysis tank are made of anode (platinum-iridium coated titanium) and cathode (high purity steel), and these electrodes are arranged in parallel with a 5 mm gap without a diaphragm. Saturated saline passes through the gap and circulates between the electrolysis tank and the storage tank. The sodium chlorate concentration of the licker solution obtained at this time was 49% (w / v), and the available chlorine concentration was 9889 ppm. Pump 2 was stopped and the licker solution was transferred to the reaction tank. The neutralization tank was filled with neutralizing solution and the gas scrubbing device was filled with gas scrubbing solution in advance, and then the agitator for the reaction tank was operated. An acid solution was added little by little for approximately 1 kg of licker solution, and the first reaction gas was generated in the reaction tank. The acid is absorbed into the neutralizing solution in the neutralization tank. After adding the remaining acid solution and confirming that no first reaction gas or bubbles are generated, the hydrogen peroxide solution is then slowly added, gradually generating the second reaction gas, which is then absorbed into the neutralizing solution in the neutralization tank. This process is repeated twice, and production is completed when the product meets the specifications.

[0185] Chlorous acid water was produced as described below. (1. Settings) The settings were as follows: 1. Check that A is tightly sealed. 2. Put recipe A into 1 3. Add recipe B to 11 4. B and D were opened, and E was confirmed to be sealed. 5 A was opened and 3 was activated 6. Transfer the liquid from 1 until 6 and 7 are full. 7. 9 was operated and each pipe was filled with the liquid 1. 8 A was sealed and 3 was stopped. 9 8 was started and pH and temperature measurements were started. 10 11 was operated and the flowing solution in 1 was adjusted to pH 6.5. 11 Started up 10 and circulated cooling water to 21 12. 4 and 6 were put into operation and power was turned on. 13 Stopped 4 and 5 14 L was released and sampled. Closed 15 L 16 Circulate until the liquid temperature falls below 25°C. 17. Conduct quality inspections and if the product meets the standards, stop step 9. Stopped 18 11 19 B and D closed 20 14 added recipe table j 21 15 added recipe d 22 17 added recipe F 23 18 contains the formula g 24 Confirmed that F, G, K, H, J, and I were closed 25 Unlocked C and K 26 E was opened and 7 licker liquid was transferred. 27 E closed 28 Check the amount of licker liquid transferred 29 C and K closed 30 I was opened in the direction of 12 → I → 17 31 13 was put into operation Open 32 F, press syringe 14, and add recipe j to 12 little by little. 33 The first reaction gas generated was adsorbed onto the formula f in 17. 34 16 was activated and H was opened 35 After confirming that no first reaction gas was being generated, close H and stop 16. 36 Press the syringe 14 and pour all of the ingredients in the recipe j into 12. 37 F closed 38 G released 39 Press the syringe 15 and add the formula d to the syringe 12 little by little. 40 A violent reaction occurred, and once the foaming subsided, 16 was started and H was released. 41 Press syringe 15 and add all ingredients listed in formula d to syringe 12. Closed 42 G 43 After the reaction was completed, H was closed and 16 was stopped. 44 Stopped 13 45 I was opened in the direction of 19 → I → 17 46 K unlocked 47 J was released and transferred to 19 48 Performed steps 25 to 44 twice 49 19 was neutralized by adding the formula h and discarded. 50 18 at normal pressure 51 17 was brought to normal pressure, and 17 was taken out and used as hypochlorous acid water B for quality testing. The results of the quality inspections carried out during manufacturing are listed below.

[0186] [Table 35]

[0187] [Table 36]

[0188] [Table 37]

[0189] Hydrous Acid Water B Ingredient Analysis Table

[0190] [Table 38]

[0191] Using the above-mentioned hypochlorous acid water B as a raw material, the following ingredients were added to maintain the cycle reaction, to produce hypochlorous acid water formulation B.

[0192] [Table 39]

[0193] [Table 40]

[0194] (Example 4: High reactivity verification test of reactivity-maintained chlorous acid water) The hypochlorous acid water A produced in Example 2 and its formulation, hypochlorous acid water formulation A, and further, Example A comparative test was carried out in the absence of organic matter between the chlorous acid water B produced in 3 and its formulation, chlorous acid water formulation B. As a control, chlorous acid water produced by the manufacturing process patent of Patent Document 1 was used.

[0195] The chlorous acid concentration, oxidizing power, and phenolic acid coefficient of chlorous acid water, chlorous acid water A, chlorous acid water preparation A, chlorous acid water B, and chlorous acid water preparation B in Patent Document 1 were determined. Furthermore, 1 ml of Escherichia coli solution (10^7 bacteria) was added to 8 ml of physiological saline, and the mixture was stirred well. 1 ml of each chlorous acid water or chlorous acid water preparation adjusted to a chlorous acid concentration of 200 ppm was added, and the mixture was stirred for 15 seconds, 30 seconds, 1 minute, and 5 seconds. After contact for 10 minutes and 10 minutes, the reaction was stopped by adding 0.1N sodium thiosulfate, and 1 ml of the culture was inoculated onto a bouillon plate and cultured at 35°C for 1 day. This was repeated immediately after production, and on the 10th and 30th days. The chlorous acid water and chlorous acid water formulations were stored at room temperature of 25°C in a dark place.

[0196] The results are shown immediately after production.

[0197] [Table 41]

[0198] [Table 42]

[0199] The results for day 10 are shown.

[0200] [Table 43]

[0201] [Table 44]

[0202] The results for day 30 are shown.

[0203] [Table 45]

[0204] [Table 46]

[0205] Hypochlorous acid water A produced by this method is obtained by electrolyzing salt as a raw material, resulting in an aqueous solution containing chlorate salts of various concentrations as a liquor solution. This makes it possible to produce hypochlorous acid water with a wider range of hypochlorous acid concentrations and oxidizing power than hypochlorous acid water produced by conventional methods.

[0206] Because the main active ingredient in hypochlorous acid water is hypochlorous acid, the hypochlorous acid water produced by the process patent of Patent Document 1 is characterized by retaining the conventional functions of antibacterial, bactericidal, disinfectant, and antiviral effects. It was found that hypochlorous acid water A produced by this patented process, and furthermore hypochlorous acid water A in which a cyclic reaction is maintained by using hypochlorous acid water A as a raw material and a buffer, also exhibits the conventional characteristics of antibacterial, bactericidal, disinfectant, and antiviral effects, just like the hypochlorous acid water produced by the process patent of Patent Document 1.

[0207] On the other hand, compared to hypochlorous acid water A, hypochlorous acid water B and hypochlorous acid water formulation B possess highly reactive antibacterial, bactericidal, disinfectant, and even antiviral properties, enabling high reactivity against E. coli within a contact time of 15 seconds, something that was not possible with previous hypochlorous acid waters.

[0208] Although further research is needed, this phenomenon is thought to be due to the chloride ions contained in the first reaction gas accelerating the reaction rate from undissociated chlorous acid to aqueous chlorine dioxide. As a result, high reactivity was added to the gradual and sustained antibacterial, bactericidal, disinfectant, and even antiviral effects that result from the slow cyclic reaction.

[0209] The reason for this is that when sodium hypochlorite and sodium chlorite are mixed under acidic conditions, they immediately decompose into chlorate ions and chloride ions, rapidly losing their antibacterial, bactericidal, disinfectant, and even antiviral effects. In other words, they cannot be stored in this state long enough to be distributed. For this reason, a mixture of sodium hypochlorite and sodium chlorite must be adjusted to a strong alkaline state in order to store it for a long period of time. In other words, it can be said that the factor that stabilizes such a mixture depends on the pH. Therefore, it is clear that the high reactivity of chlorous acid water B is not due to the sodium hypochlorite, since it maintains its antibacterial, bactericidal, disinfectant, and even antiviral properties in the weak acid range.

[0210] Furthermore, after 10 days, the antibacterial, bactericidal, disinfectant, and antiviral properties of hypochlorous acid water B had significantly decreased, and it now only exhibited the same antibacterial, bactericidal, disinfectant, antiseptic, and antiviral properties as conventional hypochlorous acid water.

[0211] On the other hand, even after 30 days, it was found that chlorous acid water formulation B maintained its highly reactive antibacterial, bactericidal, disinfectant, and even antiviral properties. From the above, it was found that by maintaining the cyclic reaction, it is possible to maintain not only the antibacterial, bactericidal, disinfectant, and even antiviral effects of chlorous acid water, which have the conventional characteristics, but also the highly reactive antibacterial, bactericidal, disinfectant, and even antiviral effects for a long period of time. From these results, it can be said that the highly reactive antibacterial, bactericidal, disinfectant, and even antiviral effects are not derived from sodium hypochlorite.

[0212] As described above, the present invention has been illustrated using preferred embodiments thereof, but it should be understood that the scope of the present invention should be interpreted solely by the claims. This application claims priority to Japanese Patent Application No. 2016-70264 (filed March 31, 2016), the contents of which are incorporated herein by reference in their entirety. It is understood that the patents, patent applications, and other publications cited herein are incorporated by reference into this specification in their entirety as if the contents were specifically set forth herein. [Industrial Applicability]

[0213] From the above, the aqueous solution containing chlorous acid water obtained by the present invention can be used as an antibacterial agent, a bactericide, a disinfectant, an antiseptic, and also as an antiviral agent, a bleaching agent, a blood-removing agent, etc.

Claims

[Claim 1] The method described herein.

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