JP2003055121A - Disinfection solution containing hypochlorous acid, zinc or the like, disinfection method using the same, and method for controlling disease of farm crop - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an inexpensive disinfection solution hardly giving undesirable effects to the health of a human being, capable of removing many kinds of diseases and destructive fungi, and maintaining the activities, and further to provide a disinfection method and a method for controlling the disease of a farm crop. SOLUTION: The disinfection solution comprises an aqueous solution containing hypochlorous acid in a proportion of >=10 ppm expressed in terms of an effective chlorine concentration, and at least one kind of divalent metals consisting of Mn, Fe, Co, Ni, Cu and Zn ions in a proportion of >=20 ppm. The disinfection method uses the disinfection solution by a specific spraying method. The method for controlling the disease of the farm crop uses the disinfection solution and the disinfection method.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a disinfecting solution containing hypochlorous acid and a specific metal compound, a disinfecting method using the same, and a method for controlling diseases of agricultural crops.

[0002]

2. Description of the Related Art Conventionally, various and large amounts of pesticides have been used for controlling crop diseases such as cucumber spot bacterial disease, cucumber powdery mildew, cucumber downy mildew, Chinese cabbage soft rot and the like.
For these pesticides, for example, copper agents, oxytetracycline agents, kasugamycin agents, propenazole agents, and polycarbamate agents are used for cucumber spot bacterial disease, and copper agents, streptomycin agents, and oxytetracycline agents are used for Chinese cabbage soft rot. Agents etc. are used (Agricultural chemical application list 1991 version supervised by the Ministry of Agriculture, Forestry and Fisheries pesticide laboratory, published by Japan Plant Protection Association).

Some pesticides of this kind are harmful to the human body,
There are concerns about the health effects of vegetables and other consumers and producers. Particularly in greenhouse cultivation, a large amount of pesticide is used in a closed space, and thus there is a great fear of impairing the health of workers. For this reason, it is known to use an acidic aqueous solution for the purpose of reducing the amount of pesticide sprayed.
No. 194109) The effect of controlling disease bacteria was not sufficient and its sustainability was insufficient. Therefore, a more effective method for controlling diseases of agricultural crops, which has less adverse effects on health, has been desired. Further, the use of an aqueous solution of hypochlorous acid has been studied, but it has been difficult to use it because the dissociation of hypochlorous acid changes depending on the pH and the disinfection effect greatly changes. Further, although hypochlorous acid has a remarkable disinfecting effect, it has a drawback that the disinfecting effect is lost because hypochlorous acid is rapidly decomposed. There has been a demand for a disinfecting solution and a disinfecting method that exert great effects in agricultural crops, food handling sites, and medical sites, and that continue to be effective.

[0004]

[Problems to be Solved by the Invention] To provide a disinfecting solution and a disinfecting method, which have less adverse effects on human health, are capable of removing other types of diseases and harmful bacteria, maintain their effects, and are inexpensive. Is.

[0005]

The present inventor has found that hypochlorous acid has an effective chlorine concentration of 10 ppm or more, and Mn and F.
It has been found that the above object can be achieved by a disinfecting solution comprising an aqueous solution containing 20 ppm or more of at least one divalent metal consisting of e, Co, Ni, Cu and Zn ions. Further, they have found a disinfection method that can achieve the above-mentioned object by using a specific spraying method of this disinfectant solution.

The divalent metals Mn, Fe, Co, Ni, C
It is desirable that the u and Zn ions are oxides. The divalent metal content in these oxides is preferably 2 to 80% by weight. It is more preferably 20 to 80% by weight. These oxides have the following formulas (1) to (5)
Those represented by are preferably used. ^{_{N 2+ 1-x M 2+ x}} O · (Al 2 O 3) k (SiO 2) g (1) ( wherein, N represents shows the Mg or Ca, M is Mn, F
at least one divalent metal ion selected from the group consisting of e, Co, Ni, Cu and Zn, and x is 0.0
Indicates a number in the range of 01 <x <0.8, and k is 0.0 ≦ k <
The number in the range of 0.8 is shown, and g is the number in the range of 0.0 ≦ g <0.8. Mg _1-y M ²⁺ _y (OH) ₂ (2) (where M is the same as formula (1) and y is 0.001 ≦
y indicates a number in the range of y ≦ 0.9) (M ²⁺ O) _z · Al ₂ O ₃ · nSiO ₂ · aH ₂ O (3) (where M is the same as formula (1), z , n and a
Represents a number that satisfies the following ranges. 0 <z ≦ 2
4 <n <30,0 ≦ a) Ca _1-w M ²⁺ _w (OH) ₂ (4) (where M is the same as in formula (1), and w is 0.005 <
indicates the number of ranges of ^{_{w <0.4) L 1+ 2y N}} 2+ 1-x-2y M 2+ x O · (Al 2 O 3) k (SiO 2) g (5) ( wherein, L is Li, Na, K, Rb, Cs are shown, N is Mg and / or Ca, M is Mn, Fe, C
at least one of transition metal ions selected from the group consisting of o, Ni, Cu and Zn, and x is 0.00 ≦ x
Indicates a number in the range of <0.8, and y is 0.00 ≦ y <0.05
, K is a number in the range 0.0 ≦ k <0.8, and g is a number in the range 0.0 ≦ g <0.8) (the above formula (1) to In (5), M is Cu or Zn
Is more preferable, and Zn is further preferable. Mg in the formulas (1) and (5) is more preferable.

Examples of preferred oxides of the present invention are set forth below, but the present invention is not limited thereto. Numbers in parentheses are BET surface area (m ² / g) and particle size D50%
(Μm) represents the content (% by weight) of Zn or Cu. (A-1) Zn _0.14 Mg _0.86 O (15, 0.5, 19.9) (A-2) Zn _0.05 Ca _0.95 O (12, 0.6, 19.9) (A-3) Zn _0.40 Mg _0.60 O. (Al ₂ O ₃ ) _0.50 (60, 0.3, 24.3) (A-4) ZnO. (Al ₂ O ₃ ) _0.04 (30, 0.4, 76.5) (A- 5) Cu _0.05 Ca _0.95 O (18, 0.2, 5.7) (A-6) Cu _0.14 Mg _0.86 O (30, _0.3 , 19.4) (A-7) (CuO) _0.4 Al _{2 O 3 · (SiO2) 16} · 5H 2 O (15,0.2,72) (A-8) ZnO · (K 2 O) 0.005 (120,0.3,80,0.48) ( A-9) ZnO · (Na 2 O) 0.005 (90,0.3,80,0.01) (A-10) (CuO) 0.4 · Al 2 O 3 · (SiO2) 16 · 5H 2 O · (Na _{2 O) 0 005} (15,0.8,2.3,0.02) further include higher fatty acids, anionic surfactants, phosphoric acid esters, coupling agents (silane, titanate, aluminum-based) and polyhydric alcohols and fatty acids The surface-treating agent may be used with at least one surface-treating agent selected from the group consisting of the above-mentioned esters.

The following are examples of those preferably used as the surface treatment agent. Higher fatty acids having 10 or more carbon atoms such as stearic acid, erucic acid, palmitic acid, lauric acid and behenic acid; alkali metal salts of the higher fatty acids; sulfuric acid ester salts of higher alcohols such as stearyl alcohol and oleyl call; polyethylene glycol ether Sulfate ester salt, amide bond sulfate ester salt, ester bond sulfate ester salt, ester bond sulfonate, amide bond sulfonate, ether bond sulfonate, ether bond alkyl allyl sulfonate, ester bond alkyl allyl sulfonate, amide Anionic surfactants such as bound alkylallyl sulfonates; mono- or diesters of orthophosphoric acid and oleyl alcohol, stearyl alcohol, etc., or a mixture of both, in their acid form or alkali metal salt or acid Phosphoric acid esters such as emissions salt; vinyl triethoxysilane,
Vinyl-tris (2-methoxy-ethoxy) silane, gamma-methacryloxypropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, beta (3,4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-glycidoxypropyltri Silane coupling agents such as methoxysilane and gamma-mercaptopropyltrimethoxysilane; isopropyltriisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate,
Titanate coupling agents such as isopropyl tridecylbenzene sulfonyl titanate; aluminum coupling agents such as acetoalkoxyaluminum diisopropylate; esters of polyhydric alcohols and fatty acids such as glycerin monostearate and glycerin monooleate. Furthermore, for example, at least one surface treatment agent selected from the group consisting of higher fatty acids, anionic surfactants, phosphoric acid esters, coupling agents (silane-based, titanate-based, aluminum-based) and esters of polyhydric alcohols and fatty acids. May be surface-treated before use.

The following are examples of those preferably used as the surface treatment agent. Higher fatty acids having 10 or more carbon atoms such as stearic acid, erucic acid, palmitic acid, lauric acid and behenic acid; alkali metal salts of the higher fatty acids; sulfuric acid ester salts of higher alcohols such as stearyl alcohol and oleyl call; polyethylene glycol ether Sulfate ester salt, amide bond sulfate ester salt, ester bond sulfate ester salt, ester bond sulfonate, amide bond sulfonate, ether bond sulfonate, ether bond alkyl allyl sulfonate, ester bond alkyl allyl sulfonate, amide Anionic surfactants such as bound alkylallyl sulfonates; mono- or diesters of orthophosphoric acid and oleyl alcohol, stearyl alcohol, etc., or a mixture of both, in their acid form or alkali metal salt or acid Phosphoric acid esters such as emissions salt; vinyl triethoxysilane,
Vinyl-tris (2-methoxy-ethoxy) silane, gamma-methacryloxypropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, beta (3,4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-glycidoxypropyltri Silane coupling agents such as methoxysilane and gamma-mercaptopropyltrimethoxysilane; isopropyltriisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate,
Titanate coupling agents such as isopropyl tridecylbenzene sulfonyl titanate; aluminum coupling agents such as acetoalkoxyaluminum diisopropylate; esters of polyhydric alcohols and fatty acids such as glycerin monostearate and glycerin monooleate.

The particle size D50% of these oxides of the present invention is
The thickness is preferably 0.05 to 10 μm, more preferably 0.05 to 6 μm, still more preferably 0.05 to 2 μm. The particle size is a value measured by a laser scattering method after being dispersed by ultrasonic waves for 5 minutes or more. BET surface area is 1 to
Preferably 300m ² / g, more preferably 5~150m ² / g, more preferably 10 to 150 m ² / g.

The effective chlorine concentration of the disinfecting solution of the present invention is 10 to 1
000 ppm is preferable. 20 to 800 ppm is more preferable, and 30 to 300 ppm is the most preferable. Also pH
Is preferably 2.0 to 8.0, more preferably 4.0 to 7.2, and most preferably 4.5 to 6.5. It is desirable that the effective chlorine concentration is the minimum required concentration to exert the disinfection effect. If the concentration is high, there is an unfavorable effect such as chlorine odor, and if the concentration is low, a sufficient disinfecting effect cannot be obtained. The disinfection effect also varies with temperature. At temperatures near room temperature, the higher the temperature, the greater the disinfection effect. pH is an important factor that determines the concentration of undissociated hypochlorous acid. At pH 8 or higher, hypochlorous acid is dissociated and the disinfection effect is significantly reduced. When the pH is 2 or less, chlorine is generated, which is harmful to the human body. Hypochlorous acid may be supplied as a hypochlorite or a hypochlorous acid aqueous solution, or may be generated by electrolysis of a chloride ion-containing aqueous solution. The hypochlorite is not particularly limited, but sodium hypochlorite is preferable.

The pH of the disinfectant solution of the present invention is preferably adjusted by adding an inorganic acid such as hydrochloric acid, phosphoric acid, sulfuric acid or nitric acid, or an organic acid such as acetic acid, formic acid, citric acid or tartaric acid. . It is also possible to add an alkali such as sodium hydroxide. As the acid, hydrochloric acid, phosphoric acid, acetic acid, citric acid and tartaric acid are more preferable, hydrochloric acid, phosphoric acid and acetic acid are further preferable, and hydrochloric acid is particularly preferable. When adjusting these pHs, it is preferable to dilute both the acid and the alkali with water. In particular, when adjusting the pH to be between 5.0 and 7.0, it is preferable to use a sufficiently diluted acid. Also,
An aqueous solution of acid and alkali, an aqueous solution of hypochlorous acid (preferably an aqueous solution of sodium hypochlorite) and water are mixed to prepare an aqueous solution of hypochlorous acid having a predetermined concentration and pH. It does not matter whether this preparation is carried out well before use or just before use. However, since hypochlorous acid in the aqueous solution of hypochlorous acid is unstable with respect to heat, light and an oxidizing agent, it is preferable to put it in a closed container, shield it from light and store it at a low temperature. It is preferable to use a sufficiently washed container. Further, in order to accurately adjust the concentration of each composition to a predetermined value, it is preferable to use a mixing device capable of adjusting the addition amount with high precision. With this device, the hypochlorous acid aqueous solution can be prepared immediately before use. In that case, an aqueous solution of acid or alkali, an aqueous solution of hypochlorous acid (preferably an aqueous solution of sodium hypochlorite) and water can be mixed, or an aqueous solution of acid or alkali and / or It is also preferable to use an aqueous solution of chlorous acid (preferably an aqueous solution of sodium hypochlorite) after diluting it with water to a predetermined concentration. These solutions are preferably stored in a sealed container, and more preferably in the form of a cartridge that can be easily attached and detached.

The antiseptic solution of the present invention may be electrolyzed of water containing chlorine ions to prepare a hypochlorous acid aqueous solution. Further, it is preferable to electrolyze water containing sodium chloride and / or potassium chloride. It is preferable to prepare the aqueous solution of hypochlorous acid by electrolyzing water containing chlorine ions. At that time, salts such as sodium chloride and / or potassium chloride can be added. Also, electrolysis can be performed in a diaphragm electrolyzer,
It can be carried out in a non-diaphragm electrolytic cell, but the diaphragm type is more preferable. In the case of a diaphragm electrolyzer, the technique described in Patent Application No. 63-300998 is preferably used. Also, in the case of a diaphragmless electrolytic cell, patent registration 261975
The technique described in No. 6 is preferably used. Regarding these electrolysis methods, "Basics and application technology of electrolyzed water" (Masaki Matsuo, Gihodo Publishing Co., Ltd., issued January 25, 2000)
The described method can be preferably used.

The pH of the disinfecting solution of the present invention can be adjusted with a pH buffer. Also, the pH of the aqueous solution of hypochlorous acid
It is also preferred to use a pH buffer to adjust the pH. When the pH buffer solution is used, the bactericidal effect can be continued for a long period of time. The pH buffer solution is a solution in which a change in pH (hydrogen ion concentration) when an acid or a base is added to the solution is smaller than a change in pH when an acid or a base is added to pure water. The pH buffer solution can be obtained by mixing an acid, a base, or a salt thereof. Any of water-soluble acids, bases and salts are preferably used. Of course, it is necessary to consider safety depending on the application.

Any antiseptic solution of the present invention can be preferably used as long as it has the effect of reducing the above-mentioned fluctuation of pH. As examples thereof, any of those described on pages II-336 to II-339 of the 4th edition of the revised edition of the Chemical Handbook (September 1993, Maruzen Publishing Co., Ltd.) can be preferably used. Examples of preferable pH buffers will be given below, but the present invention is not limited thereto.

The pH buffer solution of the present invention is potassium chloride,
Alkali halides such as sodium chloride, amino acids such as glycine, alanine, valine, leucine, isoleucine and cystine, inorganic acids such as hydrochloric acid, boric acid and phosphoric acid, lactic acid,
Malic acid, tartaric acid, citric acid, formic acid, butyric acid, acetic acid, succinic acid, diethylparbituric acid, potassium hydrogen phthalate, potassium hydrogen phthalate, sodium hydroxide, potassium hydroxide, potassium dihydrogen phosphate, diphosphoric acid. Sodium hydrogen, dipotassium hydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, tripotassium phosphate, sodium citrate, potassium citrate, sodium dihydrogen citrate, potassium dihydrogen citrate, sodium tetraborate,
Potassium tetraborate, sodium tartrate, potassium tartrate, sodium lactate, potassium lactate, sodium acetate,
Potassium acetate, sodium dimethylparbiturate, potassium dimethylparbiturate, (2,4,6-trimethylpyridine), tris (hydroxymethyl) aminomethane, (2-amino-2-methyl-1,3-propane) Diol), tris (hydroxymethyl) aminomethane,
It is preferably an aqueous solution containing at least two kinds of compounds in (3- [4- (2-hydroxyethyl) -1-propanesulfonic acid]).

The pH buffer solution of the present invention comprises (potassium hydrogen phthalate / hydrochloric acid), (potassium chloride / hydrochloric acid), (potassium hydrogen phthalate / sodium hydroxide), (potassium dihydrogen phosphate / sodium hydroxide). , (Glycine / sodium chloride / hydrochloric acid), (glycine / sodium chloride / sodium hydroxide), (sodium citrate / hydrochloric acid),
(Sodium citrate / sodium hydroxide), (sodium tetraborate / hydrochloric acid), (potassium dihydrogen phosphate / disodium hydrogen phosphate), (potassium citrate / citric acid), (potassium dihydrogen citrate / hydrochloric acid) ), (Potassium dihydrogen citrate / sodium hydroxide), (succinic acid / sodium tetraborate), (potassium dihydrogen citrate / sodium tetraborate), (potassium dihydrogen phosphate / sodium tetraborate), (Tartaric acid / sodium tartrate), (lactic acid / sodium lactate), (acetic acid / sodium acetate), (sodium dimethylparbiturate / sodium acetate / sodium chloride / hydrochloric acid), (sodium dimethylparbiturate / hydrochloric acid), ( Disodium hydrogen phosphate / citric acid), (citric acid / potassium dihydrogen phosphate / boric acid / diethyl parbituric acid) Trisodium phosphate), (boric acid / citric acid, trisodium phosphate),

(2,4,6-trimethylpyridine / hydrochloric acid), (tris (hydroxymethyl) aminomethane / hydrochloric acid), (2-amino-2-methyl-1,3-propanediol / hydrochloric acid), (citric acid / Potassium dihydrogen phosphate /
Sodium tetraborate / tris (hydroxymethyl) aminomethane / potassium chloride / hydrochloric acid), (citric acid / potassium dihydrogen phosphate / sodium tetraborate / tris (hydroxymethyl) aminomethane / potassium chloride / sodium hydroxide), (3- [4- (2-hydroxyethyl) -1
-Propanesulfonic acid] / sodium hydroxide / sodium chloride) (the combination in () indicates the combination)
It is preferable that the aqueous solution contains at least one of the above.

The pH buffer solution of the present invention comprises (potassium hydrogen phthalate / sodium hydroxide), (potassium dihydrogen phosphate / sodium hydroxide), (sodium citrate / sodium citrate).
Sodium hydroxide), (potassium dihydrogen phosphate / disodium hydrogen phosphate), (potassium dihydrogen citrate / sodium hydroxide), (succinic acid / sodium tetraborate),
(Potassium dihydrogen citrate / sodium tetraborate),
(Potassium dihydrogen phosphate / sodium tetraborate), (lactic acid / sodium lactate), (acetic acid / sodium acetate),
(Disodium hydrogen phosphate / citric acid), (Boric acid / citric acid, trisodium phosphate), (Citric acid / potassium dihydrogen phosphate / sodium tetraborate / Tris (hydroxymethyl) aminomethane / potassium chloride / Hydrochloric acid), (citric acid / potassium dihydrogen phosphate / sodium tetraborate /
It is more preferable that the aqueous solution contains at least one kind of a combination of tris (hydroxymethyl) aminomethane / potassium chloride / sodium hydroxide (the inside of the parentheses indicates the combination).

The concentration of each component of these pH buffers is preferably any concentration as long as the required pH can be obtained. When used for a short period after opening, it is preferable that the concentration of each component of the pH buffer solution is low, and for the hand sanitizing solution used for a long period after opening, the concentration of each component is preferably high. The method of mixing the components can be used in any order.
The hypochlorous acid may be mixed either after completion of the pH buffer solution or before completion. The mixing of hypochlorous acid and pH buffer may be done at any time prior to use.

It is also preferable that the above-mentioned hypochlorous acid aqueous solution of the present invention contains a spreading agent. In the hypochlorous acid aqueous solution of the present invention, it is preferable to use a spreading agent so that the aqueous solution adheres to and spreads on leaves of agricultural products. As the spreading agent, any of anionic, cationic, nonionic and betaine surfactants and water-soluble polymers are preferably used. The concentration of the spreading agent is preferably 20 to 2000 ppm. Linear alkyl benzene sulfonate, dialkyl succinate, lignin sulfonate, polynaphthyl sulfonate, sulfonate of alkyl ester of fatty acid (JP-A-2-167202, etc.) Alkyl sulfosuccinate-based anion, etc. System surfactant. Polyacrylic acid salt, alkyl sulfate, alkyl amine oxide, cationic surfactant such as chitosan having a degree of deacetylation of 30% or more and quaternary ammonium salt are preferably used.
Among them, monoalkyl sulfate, trialkylamine-N
-Oxide, sodium fatty acid, alkyl trimethyl ammonium are particularly preferred. Although the spreading agent may be added well before use, it is preferably added just before use. In actual use, it is preferable to mix it with an acid for pH adjustment or with dilution water. It is not preferable to add it to the aqueous solution of hypochlorous acid in advance because it may accelerate the decomposition of hypochlorous acid. In that case, it is preferable to store at a low temperature and protected from light. It is preferable to attach the disinfectant of the present invention to the object to be disinfected by spraying. The droplet size when spraying is 1 to
About 50 μm is preferable.

The method for preparing the disinfecting solution of the present invention is not particularly limited, but it is preferable that the hypochlorous acid-containing solution and the metal ion-containing solution are mixed immediately before use. In the case of storing after mixing, it is preferable to block light, especially ultraviolet rays, store at low temperature, and to minimize metal ions mixed as organic substances such as proteins and alcohols or impurities. Therefore, it is preferable to use thoroughly washed containers and instruments. When the hypochlorous acid-containing aqueous solution itself is also stored, it is preferable to block light, especially ultraviolet rays, and store at low temperature. Disinfectant of the present invention, disinfection method,
Pest control methods include control of diseases of agricultural crops, reduction of pesticides, disinfection of farms for livestock such as pig farming, disinfection of agricultural equipment,
Turf management on golf courses, pesticide reduction, food processing equipment, room disinfection, restaurants, food processing equipment,
It can be used for disinfection of kitchens, rooms of medical institutions such as hospitals, and disinfection of medical instruments. In the present invention, disinfection is used as a general term for so-called disinfection, sterilization, sterilization, imparting antibacterial properties, and the like.

[0023]

Example 1 Hydrochloric acid diluted with water was added to an aqueous solution of sodium hypochlorite to adjust the pH to 5.7 to prepare an aqueous solution of hypochlorous acid of the present invention having an effective chlorine concentration of 100 ppm. 100% of the oxide compound example A-4 of the present invention was added to this solution.
Disinfecting solution-A was prepared by adding and dispersing ppm. This disinfectant-
A was sprinkled on cucumber seedlings grown in a house. Rifampicin / nalidixic acid-resistant bacterium of a cucumber spot bacterial disease bacterium of the sprayed cucumber leaf was tested as an indicator bacterium. That is, after spray-inoculating the above-mentioned drug-resistant bacteria to the sprayed leaves of the disinfectant solution-A, the leaves were washed, and the viable cell count of the drug-resistant bacteria in the cleaning liquid was counted using a selective medium. In the leaves sprayed with the disinfectant solution-A, no pathogenic bacteria survived immediately after spraying, and no survival of pathogenic bacteria was found in the leaves sprayed with the aqueous solution in the test 14 days after spraying. It was It was revealed that the disinfectant solution-A of the present invention spreads the pathogenic bacteria rapidly, and this bactericidal effect is maintained for at least 14 days after spraying.

Comparative Example Example 1 was repeated as it is, except that the oxide of the present invention was not added. Just as in Example 1, the pathogenic bacteria rapidly died immediately after spraying, but some pathogenic bacteria were detected after 14 days.

[Effect] The disinfecting solution of Example 1 maintained the disinfecting effect even after 14 days, but the disinfecting solution of the comparative example containing no oxide of the present invention had a poor sustaining effect.

[0024]

Example 2 Example 1 was repeated except that the pH was changed to 4.5, 5.5, 6.0 and 6.5, and similar results were obtained.
However, if the mixing amount of hydrochloric acid is mistaken and the pH becomes too low, chlorine gas is generated. Therefore, in this range, the pH is 5.5.
The above is safer.

[Example 3] Effective chlorine concentration of 50, 200, 300 pp
Example 1 and 2 were repeated except that m was set, and similar results were obtained.

Example 4 Spreading agent Alkylsulfosuccinate-based surface active agent is used at 100 ppm and effective chlorine concentration is 30,50 pp.
The same results were obtained by repeating Examples 1 and 2 except that m was changed.

Claims (24)

[Claims] 1. Hypochlorous acid as an effective chlorine concentration of 10 pp
m or more, and Mn, Fe, Co, Ni, Cu and Z
At least one of the divalent metals consisting of n-ion is 20
An antiseptic solution, which is an aqueous solution containing at least ppm. 2. The divalent metal Mn, Fe, Co, Ni, C
The disinfecting solution according to claim 1, wherein u and Zn ions are oxides. 3. The content of the divalent metal in the oxide is 2 to
The antiseptic solution according to claim 2, which is 80% by weight. 4. The disinfecting solution according to claim 1, wherein the oxide is represented by the following formula (1). ^{_{N 2+ 1-x M 2+ x}} O · (Al 2 O 3) k (SiO 2) g (1) ( wherein, N represents shows the Mg or Ca, M is Mn, F
at least one divalent metal ion selected from the group consisting of e, Co, Ni, Cu and Zn, and x is 0.0
Indicates a number in the range of 01 <x <0.8, and k is 0.0 ≦ k <
Indicates the number in the range of 0.8, and g indicates the number in the range of 0.0 ≦ g <0.8) 5. The disinfecting solution according to claim 1, wherein the oxide is represented by the following formula (2). Mg _1-y M ²⁺ _y (OH) ₂ (2) (where M is the same as formula (1) and y is 0.001).
Indicates a number in the range of ≤y≤0.9) 6. The disinfecting solution according to claim 1, wherein the oxide is represented by the following formula (3). (M ²⁺ O) _z · Al ₂ O ₃ · nSiO ₂ · aH ₂ O (3) (where M is the same as in formula (1), and z, n and a
Represents a number that satisfies the following ranges. 0 <z ≦ 2
4 <n <30, 0 ≦ a) 7. The disinfecting solution according to claim 1, wherein the oxide is represented by the following formula (4). Ca _1-w M ²⁺ _w (OH) ₂ (4) (where M is the same as formula (1), and w is 0.005
<Indicates the number in the range of <w <0.4) 8. The disinfecting solution according to claim 1, wherein the oxide is represented by the following formula (5). ^{_{L 1+ 2y N 2+ 1-x}} -2y M 2+ x O · (Al 2 O 3) k (SiO 2) g (5) ( wherein, L is indicated Li, Na, K, Rb, and Cs, N is Indicates Mg and / or Ca, M is Mn, Fe, C
at least one of transition metal ions selected from the group consisting of o, Ni, Cu and Zn, and x is 0.00 ≦ x
Indicates a number in the range of <0.8, and y is 0.00 ≦ y <0.05
, K is the number in the range 0.0 ≦ k <0.8, and g is the number in the range 0.0 ≦ g <0.8. 9. The disinfecting solution according to claim 1, wherein the M or divalent metal ion is Zn and / or Cu ion. 10. The M or divalent metal ion is Zn.
The disinfectant solution according to claim 9, which is an ion. 11. The M or divalent metal ion is Cu
The disinfectant solution according to claim 9, which is an ion. 12. The oxide has a particle size of D50.
%, 0.05 to 10 μm, The disinfectant solution according to claim 1, wherein 13. The effective chlorine concentration of the hypochlorous acid aqueous solution is 10 to 1000 ppm, and the pH is in the range of 2.0 to 8.0. Disinfectant solution. 14. The effective chlorine concentration is 20 to 800 pp.
The antiseptic solution according to claim 13, which is m. 15. The disinfectant solution according to claim 13, which has a pH of 4.0 to 7.2. 16. A hypochlorous acid-containing aqueous solution having a pH of an inorganic acid such as hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid, acetic acid, formic acid, citric acid,
The antiseptic solution according to any one of claims 13 to 15, which is adjusted by adding at least one kind of organic acids such as tartaric acid. 17. The disinfectant solution according to claim 16, wherein the pH of the hypochlorous acid-containing aqueous solution is adjusted by adding hydrochloric acid or acetic acid. 18. The disinfectant solution according to claim 17, wherein the pH of the hypochlorous acid-containing aqueous solution is adjusted by adding hydrochloric acid. 19. The disinfectant solution according to claim 13, wherein the hypochlorous acid aqueous solution is prepared by electrolyzing water containing chlorine ions. 20. The disinfectant solution according to claim 19, wherein water containing sodium chloride and / or potassium chloride is electrolyzed. 21. The pH of the aqueous solution containing hypochlorous acid is adjusted to pH.
The disinfectant solution according to any one of claims 13 to 20, which is adjusted with a buffering agent. 22. The disinfecting solution according to claim 1, further comprising a spreading agent. 23. A disinfecting method, characterized in that the disinfecting liquid according to any one of claims 1 to 22 is sprayed with a droplet size of 1 to 50 μm. 24. A method for controlling diseases of agricultural crops such as cucumber spot bacterial disease, cucumber powdery mildew, cucumber downy mildew, Chinese cabbage soft rot, etc. by the disinfecting solution and the disinfecting method according to any one of claims 1 to 23.