JP2003048804A - Fungicide and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fungicide having a high fungicidal effect and sustaining the fungicidal effect for a long period. SOLUTION: This fungicide 6 is obtained by mixing an aqueous solution 4 of ammonium chloride with an aqueous solution 5 of sodium hypochlorite. In the fungicide 6, the sodium hypochlorite is mixed in a ratio of 0.5-2 equivalents based on 1 equivalent of the ammonium chloride. The sum total of the molar concentration of the ammonium chloride in the fungicide 6 and the molar concentration of the sodium hypochlorite is <=0.1 mol/L. The oxidation-reduction potential of the fungicide 6 is measured with an ORP meter 2 and the oxidation-reduction potential is regulated within the range of +300 to +700 mV relatively to a silver/silver chloride electrode.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a bactericide and a method for producing a bactericide. This bactericide is suitable for use in preventing the generation of slime in industrial cooling water and industrial water for paper manufacturing processes.

[0002]

2. Description of the Related Art A lot of water such as cooling water, process water, and washing water is used in association with industrial activities. The water used for these industrial activities is contaminated with microorganisms existing in the atmosphere and microorganisms contained in industrial raw materials, etc., so that various problems caused by the proliferation of microorganisms in water are problematic in this water. Become.

For example, in cooling water, viscous substances secreted by microorganisms may entrap dirt, iron rust, organic matter and the like in the water to form a mud-like substance called slime. Since this slime has a large viscosity, it has a property of being easily attached. Therefore, the slime may adhere to the inside of the strainer or the cooling pipe provided in the middle of the cooling pipe to make water passage difficult, or may adhere to the pipe of the heat exchanger to reduce the cooling efficiency. Moreover, when slime adheres to the metal surface, the metal may be corroded.

Particularly in recent years, the degree of circulation and reuse of cooling water has advanced, and the amount of water discharged to the outside of the system has been reduced as much as possible. Therefore, nutrients of microorganisms are accumulated in the cooling water and the microorganisms easily grow. ing.

When slime is generated in the process water used in the paper mill, white water pits, flow boxes,
Slime will adhere to the walls of pipes and the like. Then, when the slime becomes large to some extent, it is peeled off from the wall surfaces and mixed into the pulp. Therefore, the strength of the final product, paper, is reduced, or the surface of the paper is colored, spots, etc., and the product value is significantly reduced.

For this reason, when water has been conventionally used in industrial activities, various bactericides such as chlorine bactericides, organic halogen bactericides and bactericides composed of hypohalite are added to the water. , Often prevent the growth of microorganisms.

However, among the above germicides, the chlorine germicides are dangerous to handle. Further, the organic halogen-based bactericide has the drawbacks that it is highly toxic to the human body and the manufacturing cost is high. On the other hand, the disinfectant composed of hypohalite has a drawback that it has a low disinfecting power, although it has a low handling risk and low toxicity to the human body.

Therefore, in recent years, attempts have been made to solve the above problems by combining these bactericidal agents or by mixing chemicals for increasing the bactericidal power. Among these, an ammonium salt such as ammonium chloride and a bactericide produced by mixing a hypohalous acid-generating compound such as sodium hypochlorite capable of generating hypohalous acid when dissolved in water are highly sterilized. In addition to having power, the danger to the human body is not so great, and the manufacturing cost is low (JP-A-5-14).
6785).

[Problems to be Solved by the Invention]

However, according to the inventor's earnest research, in the bactericidal agent in which the above ammonium salt and the hypohalous acid generating compound are mixed, the bactericidal power is large depending on the mixing ratio of the ammonium salt and the hypohalous acid generating compound. fluctuate. Further, the aqueous solution of the hypohalous acid generating compound has a property of gradually decomposing during storage.

Therefore, the residual chlorine concentration of the aqueous solution of the hypohalous acid generating compound as the raw material is measured by the method of JIS K0101, and the residual chlorine concentration is converted into the concentration of the hypohalous acid generating compound. It is also conceivable to mix the ammonium salt and the hypohalous acid generating compound based on different concentrations.

However, the concentration of the hypohalous acid generating compound converted from the residual chlorine concentration does not exactly match the concentration of the true hypohalous acid generating compound in the bactericide. In addition, there is a time lag between the measurement of the residual chlorine concentration and the mixing of the hypohalous acid generating compound. Therefore, it is difficult to strictly control the mixing ratio, and the bactericidal ability of the bactericide produced in this way is not always sufficient. Further, there is also a problem that the bactericidal power of the bactericide thus produced is lost in a short time.

The present invention has been made in view of the above-mentioned conventional problems, and it is an object to be solved to provide a bactericide having a high bactericidal power and the bactericidal power lasting for a long time. Further, it is also a problem to be solved to provide a manufacturing method in which manufacturing control is easy and a bactericide showing high bactericidal power can be manufactured.

[0013]

Means for Solving the Problems The inventor has conducted diligent research to solve the above problems, and a hypohalous acid generating compound is mixed at a ratio of 0.5 to 2 equivalents to 1 equivalent of a water-soluble ammonium salt. The total concentration of the ammonium salt and the hypohalous acid generating compound is 0.1 m.
It has been found that when the sterilizing power is not more than ol / L, the sterilizing power of the obtained bactericidal agent is high and the sterilizing power is maintained for a long time, and the present invention has been completed.

That is, according to the test results of the inventor, the bactericide produced by mixing the conventional ammonium salt and the hypohalous acid-generating compound salt is the water-soluble ammonium salt of the hypohalous acid-generating compound. 0.5-2 for 1 equivalent
It shows high bactericidal power when mixed in an equivalent ratio.
However, even if the mixing ratio is within the above range, the bactericidal activity of the obtained bactericide becomes low with time. Further, the smaller the total of the molar concentration of the ammonium salt contained in the germicide and the molar concentration of the hypohalous acid generating compound, the longer the germicidal activity is maintained. Then, the hypohalous acid generating compound is 0.5 to 2 with respect to 1 equivalent of the water-soluble ammonium salt.
If they are mixed in an equivalent ratio and the total of the molar concentration of the ammonium salt and the molar concentration of the hypohalous acid generating compound is 0.1 mol / L or less, the obtained bactericide has high bactericidal activity. The required sterilizing power can be maintained for a practically sufficient time.

That is, the disinfectant of the present invention is a disinfectant containing water as a solvent, a water-soluble ammonium salt, and a hypohalous acid-generating compound capable of generating hypohalous acid by dissolving in the water. In the bactericide, the hypohalous acid-generating compound is mixed in a ratio of 0.5 to 2 equivalents to 1 equivalent of the water-soluble ammonium salt, and the water-soluble ammonium salt contained in the bactericide is The total of the molar concentration and the molar concentration of the hypohalous acid generating compound contained in the bactericide is 0.1 mol / L or less.

According to the test results of the inventor, when the hypohalous acid generating compound is mixed in the bactericidal agent at a ratio of 0.5 to 2 equivalents to 1 equivalent of the water-soluble ammonium salt, the bactericidal activity becomes high. Furthermore, if the total of the molar concentration of the water-soluble ammonium salt contained in the germicide and the molar concentration of the hypohalous acid generating compound contained in the germicide is 0.1 mol / L or less, Sufficient sustainability.
Therefore, the disinfectant of the present invention has a high disinfecting power, and the disinfecting power is maintained for a long time.

In the bactericide of the present invention, the hypohalous acid generating compound is 0.5 to 1 equivalent to 1 equivalent of the water-soluble ammonium salt.
It is preferable that they are mixed in a ratio of 1 equivalent. According to the test results of the inventor, when ammonium bromide and sodium hypochlorite are mixed to produce a bactericide, for example, if they are mixed in a ratio within this range, the bactericidal power is particularly high.

The bactericide of the present invention has a redox potential of silver /
It is preferably in the range of +300 to +700 mV with respect to the silver chloride electrode. According to the test results of the inventor, the bactericidal power of the bactericide of the present invention changes depending on the mixing ratio of the water-soluble ammonium salt and the hypohalous acid generating compound, and decreases with the passage of time. The bactericidal power can be grasped by the redox potential, and the redox potential of the bactericide is +300 to +700 relative to the silver / silver chloride electrode.
Within the range of mV, it has a sufficiently high bactericidal activity as a bactericide.

In the bactericide of the present invention, as the water-soluble ammonium salt, both an organic acid ammonium salt and an inorganic acid ammonium salt can be used. As the ammonium salt of an organic acid, for example, ammonium acetate, ammonium propionate, ammonium oxalate or the like can be used. As the ammonium salt of an inorganic acid, for example, ammonium chloride, ammonium bromide, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium nitrate, ammonium sulfate and the like can be used. Also, a mixture of these can be used. Of these, at least one of ammonium chloride and ammonium bromide is preferable. This is because these compounds are safe, easy to handle, and easily available.

Further, in the disinfectant of the present invention, as the hypohalous acid generating compound, any compound can be used as long as it can be dissolved in water to generate hypohalous acid. Among these, especially, sodium hypochlorite, calcium hypochlorite, potassium hypochlorite, sodium hypobromite, potassium hypobromite, trichloroisocyanuric acid, sodium dichloroisocyanurate, potassium dichloroisocyanurate, bromo It is preferably at least one of chlorodimethylhydantoin, dibromodimethylhydantoin and dichlorodimethylhydantoin. Sodium hypochlorite, calcium hypochlorite,
Since potassium hypochlorite, sodium hypobromite, potassium hypobromite, trichloroisocyanuric acid, sodium dichloroisocyanurate and potassium dichloroisocyanurate are relatively inexpensive, these are used as the hypohalous acid generating compound. Thus, it is possible to reduce the manufacturing cost of the germicide. In addition, bromochlorodimethylhydantoin, dibromodimethylhydantoin and dichlorodimethylhydantoin have the advantage of being safe because they are not toxic to the human body. In addition, these hypohalous acid generating compounds may be mixed and used.

Further, according to the test results of the inventor, the bactericidal activity of the mixed solution of the water-soluble ammonium salt and the hypohalous acid generating compound decreases with the passage of time, but the redox potential of the mixed solution is low. The sterilizing power decreases and increases. Therefore, if the redox potential of the mixed liquid is grasped, the sterilizing power of the mixed liquid can be grasped.

That is, in the method for producing a bactericide of the present invention, at least water as a solvent, a water-soluble ammonium salt, and
In the method for producing a bactericide from a mixed solution obtained by mixing a hypohalous acid-generating compound capable of generating hypohalous acid when dissolved in water, the redox potential of the mixed solution is grasped. The above-mentioned bactericidal agent is produced by

In the production method of the present invention, the bactericide is produced by grasping the redox potential of the mixed solution. Therefore, the mixing ratio of the ammonium salt and the hypohalous acid generating compound can be set to a mixing ratio required for having high bactericidal activity.

Further, by grasping the redox potential of the mixed solution, it becomes possible to grasp whether or not the bactericidal activity has decreased after the bactericidal agent has been manufactured, and it is possible to obtain a bactericidal agent having a bactericidal activity of a certain level or more. Can be supplied.

Further, as described above, according to the test results of the inventor, there is a certain correlation between the bactericidal activity and the redox potential in the bactericide of the present invention. That is, when the mixing ratio of the hypohalous acid generating compound to the ammonium salt is increased, the redox potential once decreases and then increases again. Then, in the range of the mixing ratio where the redox potential decreases, the bactericidal power becomes high. Therefore, if the ammonium salt and the hypohalous acid generating compound are mixed so that the range of the redox potential of the bactericide matches the range in which the bactericidal power becomes high, a bactericide having a high bactericidal power can be continuously produced. Is possible.

That is, it is preferable that the redox potential of the mixed solution be in the range of +300 to +700 mV with respect to the silver / silver chloride electrode. According to the test results of the inventor, the bactericidal power of the bactericide is particularly high in this range.

In the production method of the present invention, the hypohalous acid generating compound is added in an amount of 0.5 to 1 equivalent to 1 equivalent of the water-soluble ammonium salt.
It is preferable to mix them in a ratio of 1 equivalent. According to the test results of the inventor, for example, when ammonium bromide and sodium hypochlorite are mixed to produce a bactericide, if they are mixed at a ratio within this range, particularly high bactericidal power is exhibited.

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, Test Examples 1 to 12 and Comparative Examples 1 to 13 embodying the present invention will be described with reference to the drawings.

(Test Example 1) In Test Example 1, first, the bactericide manufacturing apparatus 1 shown in FIG. 1 is prepared. This disinfectant manufacturing device 1
Is provided with a first tank 1a for storing the ammonium chloride aqueous solution, a second tank 1b for storing the sodium hypochlorite aqueous solution, and a reaction tank 1c. The first tank 1a, the second tank 1b, and the reaction tank 1c are pipes 1d and 1e, respectively.
The metering pumps 1f and 1g are provided in the middle of the pipes 1d and 1e. A supply pipe 1h for supplying the manufactured germicide is connected to the side surface of the reaction tank 1c. The reaction tank 1c is equipped with a stirrer 1i. The reaction tank 1c is provided with an ORP meter 2 for measuring the redox potential. The ORP meter 2 is composed of an ORP electrode 2a in which a silver / silver chloride electrode and a platinum electrode are combined, and an electrometer 2b,
The ORP electrode 2a is installed inside the reaction tank 1c.
The metering pumps 1f, 1g and the electrometer 2b are connected to the controller 3, and the controller 3 can control the metering pumps 1f, 1g so that the redox potential becomes a set potential. .

The bactericide manufacturing apparatus 1 configured as described above
The bactericidal agent 6 is manufactured as follows according to the process shown in FIG. First, ammonium chloride (reagent manufactured by Kanto Kagaku Co., Ltd.) was prepared and dissolved in water to a concentration of 0.008 mol / L to obtain an ammonium chloride aqueous solution 4, which was placed in the first tank 1a shown in FIG. Store.

Water was added to an aqueous solution of sodium hypochlorite (reagent manufactured by Asahi Denka Kogyo Co., Ltd.) having an effective chlorine concentration of 12% by mass to obtain an aqueous solution of sodium hypochlorite 5 having a concentration of 0.008 mol / L. , Which is stored in the second tank 1b.

Next, as the mixing step S1 shown in FIG. 2, the metering pump 1f shown in FIG. 1 is driven to put a certain amount of the ammonium chloride aqueous solution 4 into the reaction tank 1c. Then, the metering pump 1g is driven while stirring with the stirrer 1i, and the sodium hypochlorite aqueous solution 5 is gradually added until the ammonium chloride aqueous solution 4 becomes 1 equivalent to the sodium hypochlorite aqueous solution 5 at 1 equivalent. In addition, the fungicide 6 of Test Example 1
To get

Test Example 2 In the bactericide of Test Example 2, the concentrations of the ammonium chloride aqueous solution 4 and the sodium hypochlorite aqueous solution 5 were both 0.017 mol / L. Other manufacturing conditions are the same as in the case of Test Example 1.

Test Example 3 In the bactericide of Test Example 3, the concentrations of the ammonium chloride aqueous solution 4 and the sodium hypochlorite aqueous solution 5 were both set to 0.056 mol / L. Other manufacturing conditions are the same as in the case of Test Example 1.

Test Example 4 In the bactericide of Test Example 4, the concentrations of the ammonium chloride aqueous solution 4 and the sodium hypochlorite aqueous solution 5 were both 0.084 mol / L. Other manufacturing conditions are the same as in the case of Test Example 1.

Test Example 5 In the bactericide of Test Example 5, the concentrations of the ammonium chloride aqueous solution 4 and the sodium hypochlorite aqueous solution 5 were both 0.017 mol / L, and sodium hypochlorite was added to 1 equivalent of ammonium chloride. Mix to 0.5 equivalents. Other manufacturing conditions are the same as in the case of Test Example 1.

Test Example 6 In the bactericide of Test Example 6, the concentrations of the ammonium chloride aqueous solution 4 and the sodium hypochlorite aqueous solution 5 were both 0.017 mol / L, and sodium hypochlorite was added to 1 equivalent of ammonium chloride. Mix to give 2 equivalents. Other manufacturing conditions are the same as in the case of Test Example 1.

(Test Example 7) In the bactericide of Test Example 7, instead of the ammonium chloride aqueous solution 4, the concentration was 0.017 m.
Using an ol / L ammonium bromide aqueous solution, sodium hypochlorite was mixed in an amount of 0.5 equivalent to 1 equivalent of ammonium bromide. Other manufacturing conditions are the same as in the case of Test Example 1.

(Test Example 8) In the bactericide of Test Example 8, instead of the ammonium chloride aqueous solution 4, the concentration was 0.017 m.
Using an ol / L aqueous solution of ammonium bromide, 1 equivalent of sodium hypochlorite was mixed with 1 equivalent of ammonium bromide. Other manufacturing conditions are the same as in the case of Test Example 1.

(Test Example 9) In the bactericide of Test Example 9, instead of the ammonium chloride aqueous solution 4, the concentration was 0.017 m.
Using an ol / L ammonium bromide aqueous solution, sodium hypochlorite was mixed in an amount of 2 equivalents relative to 1 equivalent of ammonium bromide. Other manufacturing conditions are the same as in the case of Test Example 1.

Test Example 10 With the bactericide of Test Example 10,
Instead of the aqueous solution 5 of sodium hypochlorite, the concentration was 0.
A 017 mol / L bromochlorodimethylhydantoin (Kanto Chemical Co., Inc. reagent) aqueous solution was used. Other manufacturing conditions are the same as in the case of Test Example 1.

Test Example 11 With the bactericide of Test Example 11,
Instead of the aqueous solution 5 of sodium hypochlorite, the concentration was 0.
A 017 mol / L dibromodimethylhydantoin (Kanto Chemical Co., Inc. reagent) aqueous solution was used. Other manufacturing conditions are the same as in the case of Test Example 1.

Test Example 12 With the bactericide of Test Example 12,
Instead of the aqueous solution 5 of sodium hypochlorite, the concentration was 0.
An 017 mol / L sodium dichloroisocyanurate (Kanto Chemical Co., Inc. reagent) aqueous solution was used. Other manufacturing conditions are the same as in the case of Test Example 1.

Comparative Example 1 In Comparative Example 1, the concentrations of both the ammonium chloride aqueous solution 4 and the sodium hypochlorite aqueous solution 5 were 0.169 mol / L. Other manufacturing conditions are the same as in the case of Test Example 1.

Comparative Example 2 In Comparative Example 2, the concentrations of the ammonium chloride aqueous solution 4 and the sodium hypochlorite aqueous solution 5 were both 0.338 mol / L. Other manufacturing conditions are the same as in the case of Test Example 1.

Comparative Example 3 In Comparative Example 3, the concentrations of the ammonium chloride aqueous solution 4 and the sodium hypochlorite aqueous solution 5 were both 0.845 mol / L. Other manufacturing conditions are the same as in the case of Test Example 1.

Comparative Example 4 In Comparative Example 4, the concentrations of both the ammonium chloride aqueous solution 4 and the sodium hypochlorite aqueous solution 5 were 1.126 mol / L. Other manufacturing conditions are the same as in the case of Test Example 1. Comparative Example 5 In Comparative Example 5, the concentrations of the ammonium chloride aqueous solution 4 and the sodium hypochlorite aqueous solution 5 were both 1.69.
It was set to 0 mol / L. Other manufacturing conditions are the same as in the case of Test Example 1.

Comparative Example 6 In Comparative Example 6, a test was conducted without adding anything.

Comparative Example 7 In Comparative Example 7, the ammonium chloride aqueous solution 4 and the sodium hypochlorite aqueous solution 5 both had a concentration of 0.017 mol / L and ammonium chloride 1
Sodium hypochlorite was mixed to 0.25 equivalent to the equivalent. Other manufacturing conditions are the same as in the case of Test Example 1.

(Comparative Example 8) In Comparative Example 8, the concentrations of both ammonium chloride aqueous solution 4 and sodium hypochlorite aqueous solution 5 were 0.017 mol / L, and ammonium chloride 1
Sodium hypochlorite was mixed in an amount of 4 equivalents per equivalent. Other manufacturing conditions are the same as in the case of Test Example 1.

(Comparative Example 9) In Comparative Example 9, the concentration was 0.01
It is a 7 mol / L ammonium chloride aqueous solution.

(Comparative Example 10) In Comparative Example 10, the density was 0.
It is a 017 mol / L sodium hypochlorite aqueous solution.

Comparative Example 11 In Comparative Example 11, instead of the ammonium chloride aqueous solution 4, the concentration was 0.017 mol /
Using an aqueous ammonium bromide solution of L, sodium hypochlorite was mixed in an amount of 0.25 equivalent to 1 equivalent of ammonium bromide. Other manufacturing conditions are the same as in the case of Test Example 1.

Comparative Example 12 In Comparative Example 12, instead of the ammonium chloride aqueous solution 4, the concentration was 0.017 mol /
Using an aqueous ammonium bromide solution of L, sodium hypochlorite was mixed with 4 equivalents per 1 equivalent of ammonium bromide. Other manufacturing conditions are the same as in the case of Test Example 1.

Comparative Example 13 In Comparative Example 13, the density was 0.
It is an ammonium bromide aqueous solution of 017 mol / L.

(Evaluation method) For each bactericidal agent of Test Examples 1 to 12 and each solution of Comparative Examples 1 to 13, measurement of redox potential and sterilizing power tests 1 and 2 after a lapse of a certain time after production were performed. went.

<Measurement of oxidation-reduction potential> The measurement of the oxidation-reduction potential was conducted by adding ORP to the bactericide of each test example and the solution of each comparative example.
The electrode 2a is dipped to measure the potential difference between the silver / silver chloride electrode and the platinum electrode which form the ORP electrode 2a.
This was done by measuring in b.

<Sterilizing Power Test 1> Test Examples 1 to 6 and 10 to 1
For 2 and Comparative Examples 1 to 10, the following sterilizing power test 1
I went.

A sterilizing power test was conducted using white water under the wire of the paper machine in the papermaking process of neutral neutral papermaking using newspaper waste paper raw material. This white water has a pH of 7.2 and a temperature of 4
At 0 ° C., the viable cell count is 8 × 10 ⁸ cells / mL. 100 mL of this white water was sampled in a 300 mL Erlenmeyer flask, and the sterilizing agent of each test example or the solution of each comparative example had a total molar concentration of ammonium salt and hypohalous acid generating compound of 0.071 mmol / L. Was added. However, nothing was added to Comparative Example 6. And
After shaking for 30 minutes on a shaker, inoculate TGY medium (medium prepared by dissolving tryptone, yeast extract and glucose in ion-exchanged water and adjusting the pH to 7.0), and culturing at 32 ° C for 3 days Incubate in a container. Then, the medium was taken out from each incubator, and the number of viable bacteria per 1 mL was measured by visually counting the number of generated colonies.

<Sterilizing Power Test 2> For Test Examples 7 to 9 and Comparative Examples 6 and 10 to 13, the following sterilizing power test 2 was performed.

First, a plate medium for general bacteria having the following composition was prepared. Glucose 1.0 g / L Peptone 5.0 g / L Yeast extract 2.5 g / L Distilled water 1 L pH 6.8

Then, Pseudomonas aerug (Pseudomonas aerug) was used as a test cell.
Inosa) (IFO-12689) was cultured in this plate medium for general bacteria to obtain a culture solution.

Furthermore, in 100 mL of this culture solution, the total of the molar concentration of the ammonium salt and the molar concentration of the hypohalous acid generating compound of the fungicide of each test example or the solution of each comparative example becomes 0.071 mmol / L. So added. However, nothing was added to Comparative Example 6. And 30
After the lapse of minutes, 0.1 mL was sampled, dropped into a medium having the following composition, stretched over the entire surface of the medium with a sterilized conradi rod, and inoculated.

[0064] Glucose 1.0 g / L Peptone 5.0 g / L Yeast extract 2.5g / L Agar 18g / L Distilled water 1L pH 6.8

Then, the medium inoculated as described above was placed in a thermostatic bath and cultured in an incubator at 32 ° C. for 3 days. After that, the medium was taken out, and the number of viable bacteria per 1 mL was measured by visually counting the number of generated colonies.

(Evaluation Results) Table 1 shows the results of the bactericidal test of the bactericides of Test Examples 1 to 4 and the solutions of Comparative Examples 1 to 6.

[0067]

[Table 1]

From Table 1, nothing is added to the fungicides of Test Examples 1 to 4 in which the total molar concentration of ammonium chloride and sodium hypochlorite is 0.1 mol / L or less. Compared with Comparative Example 6 which does not have a large number of viable bacteria, the bactericidal activity is high, while 0.1 mol /
It can be seen that in Comparative Examples 1 to 5 in which L is exceeded, the sterilizing power is low. From this, in the disinfectant containing ammonium chloride and sodium hypochlorite, the total of the molar concentration of ammonium chloride contained in this disinfectant and the molar concentration of sodium hypochlorite is 0.1 mol / L or less. Then, it can be seen that the effect as a bactericide is great.

Table 2 shows the results of the redox potential and the bactericidal power test 1 of the bactericides of Test Examples 2, 5 and 6 and the solutions of Comparative Examples 7 to 10.

[0070]

[Table 2]

From Table 2, it can be seen that the bactericides of Test Examples 2, 5 and 6 in which the equivalent number of sodium hypochlorite is 0.5 to 2 equivalents to 1 equivalent of ammonium chloride have high bactericidal activity.

Further, while the redox potentials of the bactericides of Test Examples 2, 5 and 6 having high bactericidal power are in the range of +300 to +700 mV, the redox potentials of Comparative Examples 7 to 9 having low bactericidal power are as described above. Out of range. From this, the redox potential is +300 to +700 m with respect to the silver / silver chloride electrode.
It can be seen that a bactericidal agent having a high bactericidal power can be produced by controlling the sterilizing agent so that it is in the range of V. The redox potential of the solution of Comparative Example 10 is within the above range, but since Comparative Example 10 does not add ammonium chloride, sterilization is possible only by grasping whether or not ammonium chloride is added. It does not cause any problems in the manufacturing control of the agent.

Furthermore, the redox potential and sterilizing power test 2 of the bactericides of Test Examples 7 to 9 and the solutions of Comparative Examples 6 and 10 to 13
The results are shown in Table 3.

[0074]

[Table 3]

From Table 3, it can be seen that the bactericides of Test Examples 7 to 9 in which the equivalent number of sodium hypochlorite is 0.5 to 2 equivalents to 1 equivalent of ammonium bromide have high bactericidal activity.
Further, among them, it can be seen that the bactericidal activity of the bactericides of Test Examples 7 and 8 in which the equivalent number of sodium hypochlorite is 0.5 to 1 equivalent to 1 equivalent of ammonium bromide is particularly high.

The redox potentials of the bactericides of Test Examples 7 to 9 having high bactericidal power are in the range of +300 to +700 mV, whereas the redox potentials of the solutions of Comparative Examples 6 and 10 to 13 having low bactericidal power are low. Is outside the above range. From this, the oxidation-reduction potential is + 300-
It can be seen that a bactericide having a particularly high bactericidal power can be produced by controlling it within the range of +700 mV.

Table 4 shows the results of the oxidation-reduction potential and sterilizing power test 1 of the bactericides of Test Examples 10 to 12 and the solutions of Comparative Examples 6 and 9.

[0078]

[Table 4]

From Table 4, it can be seen that even if bromochlorodimethylhydantoin, dibromodimethylhydantoin or dichlorodimethylhydantoin is used as the hypohalous acid generating compound, a bactericide having high bactericidal activity can be obtained. Since these hypohalous acid generating compounds are solids, they are easy to store and transport. Further, there is an advantage that toxicity to the human body is low.

Table 5 shows the results of the oxidation-reduction potential and the sterilizing power test 1 or 2 for each production time of the bactericides of Test Examples 2 and 6 to 8 and the solutions of Comparative Examples 5 to 8.

[0081]

[Table 5]

From Table 5, among the bactericides of Test Examples 5, 2 and 6 consisting of ammonium chloride and sodium hypochlorite, the equivalent number of sodium hypochlorite to 0.5 equivalent of ammonium chloride is 0.5 to 2. It can be seen that the bactericides of Test Examples 5, 2, and 6 in the range of 5 maintain a sufficiently high bactericidal power for 60 minutes after production. In particular, it can be seen that the bactericides of Test Examples 5 and 2 in which the equivalent number of sodium hypochlorite with respect to 1 equivalent of ammonium chloride is in the range of 0.5 to 1 maintain the bactericidal power for a further long time.

The bactericidal activity can be understood by using the redox potential as an index, and the redox potential is +300 to +70.
It can be seen that a bactericide in the range of 0 mV has a sufficient bactericidal power. Therefore, if the redox potential is grasped, it becomes possible to grasp whether or not the bactericidal power of the bactericidal agent is lowered, and it is possible to always supply the bactericidal agent having a bactericidal power of a certain level or more.

Also, in Test Example 8 consisting of ammonium bromide and sodium hypochlorite, sufficient bactericidal activity was maintained as a bactericidal agent for 20 minutes after production, and the bactericidal activity was determined by grasping the redox potential. You can grasp.

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram of a disinfectant manufacturing apparatus.

FIG. 2 is a process drawing for producing a bactericide of Test Example.

[Explanation of symbols]

4 ... Water-soluble ammonium salt (ammonium chloride aqueous solution,
Ammonium bromide aqueous solution) 5 ... Hypohalous acid generating compound (sodium hypochlorite aqueous solution, bromochlorodimethylhydantoin, dibromodimethylhydantoin, sodium dichloroisocyanurate) 6 ... Microbicide 1a ... 1st tank 1b ... 2nd tank 1c ... reaction tank 2 ... potential measuring means (ORP meter)

Claims (7)

[Claims] 1. A bactericide containing water as a solvent, a water-soluble ammonium salt, and a hypohalous acid-generating compound capable of generating hypohalous acid when dissolved in the water, wherein the bactericide contains The hypohalous acid generating compound is mixed in a ratio of 0.5 to 2 equivalents to 1 equivalent of the water-soluble ammonium salt, and the bactericidal agent has a molar concentration of the water-soluble ammonium salt contained in the bactericidal agent. Is 0.1 mol in total with the molar concentration of the hypohalous acid generating compound contained in
/ L or less, a bactericide characterized by being below. 2. The redox potential is + with respect to the silver / silver chloride electrode.
The bactericide according to claim 1, which is in a range of 300 to +700 mV. 3. The disinfectant according to claim 1, wherein the water-soluble ammonium salt is at least one of ammonium chloride and ammonium bromide. 4. The hypohalous acid generating compound is sodium hypochlorite, calcium hypochlorite, potassium hypochlorite, sodium hypobromite, potassium hypobromite, trichloroisocyanuric acid, dichloroisocyanuric acid. The disinfectant according to claim 1, 2 or 3, which is at least one of sodium, potassium dichloroisocyanurate, bromochlorodimethylhydantoin, dibromodimethylhydantoin and dichlorodimethylhydantoin. 5. A bactericidal agent is prepared from a mixed solution prepared by mixing at least water as a solvent, a water-soluble ammonium salt, and a hypohalous acid-generating compound which can dissolve in the water to generate hypohalous acid. In the method for producing a bactericide, the bactericide is produced by grasping the redox potential of the mixed solution. 6. The method for producing a bactericide according to claim 5, wherein the redox potential of the mixed solution is mixed so as to be in the range of +300 to +700 mV with respect to the silver / silver chloride electrode. 7. The total of the molar concentration of the water-soluble ammonium salt contained in the mixed liquid and the molar concentration of the hypohalous acid generating compound contained in the mixed liquid is 0.1 mol / L or less, 7. The compound according to claim 5, wherein the hypohalous acid generating compound is mixed in a ratio of 0.5 to 2 equivalents to 1 equivalent of the water-soluble ammonium salt.
A method for producing the disinfectant described.