JPH1081610A - Production of sterilizing antispetic solution and sterilizing disinfectant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To extremely simply produce a sterilizing antiseptic solution having performances and properties equal to those of acidic electrolytic water at a low cost by compounding a medicine comprising a specific chlorine agent, an acidic substance or hydrogen peroxide therein. SOLUTION: This sterilizing antiseptic solution is prepared by dissolving a chlorine agent selected from the group of sodium dichloroisocyanurate, sodium hypochlorite, high test hypochlorite and chloramine T, an acidic substance or hydrogen peroxide in water. An acidic aqueous solution at pH <=5.5 having >=30ppm content of residual chlorine and >=+800mV oxidation-reduction potential(ORP) is obtained by the preparation. Citric acid, malic acid, tartaric acid, maleic acid, succinic acid, etc., are cited as the acidic substance and a powdery mixture obtained by mixing the chlorine agent powder with an organic or/and an inorganic acid in a powdery form may be used as the sterilizing and disinfectant. The sterilizing antispectic solution or sterilizing and disinfectant is used for washing of hands in medical institutions, various recreational facilities or kitchens, washing of various apparatuses or materials or equipment, washing of linen, dishcloths, clothes or footwear, cleaning of walls or floors, washing, etc., of dental impression materials.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to hand washing in medical institutions, various welfare facilities, kitchens, general households, etc., washing of various equipment and fixtures, washing of linen, fukin, clothes and footwear, cleaning of walls and floors, The present invention relates to a method for producing a disinfectant and a disinfectant used for washing dental impressions, artificial dialysis lines, and the like.

[0002]

2. Description of the Related Art In general, if a saline solution is electrolyzed between both electrodes through a membrane such as an ion exchange membrane, high-pH alkaline electrolyzed water is produced on the cathode side with the generation of hydrogen, and the anode side is produced. Is known to produce low pH acidic electrolyzed water containing active chlorine and oxygen. However, the latter acidic electrolyzed water has a strong bactericidal action, is less toxic than conventional general-purpose disinfectants, is less likely to cause rough skin even when used for hand washing, and has been used. Wastewater has attracted attention for sterilization because it does not require special treatment. In recent years, various electrolyzed water generators configured to add a trace amount of sodium chloride to tap water to perform electrolysis and take out acidic electrolyzed water generated on the anode side are commercially available.

The acidic electrolyzed water has a pH of 2.7 or less and a residual chlorine content of 30 to 40 pp obtained by ordinary electrolysis.
m, oxidation-reduction potential (hereinafter referred to as ORP) +1100 m
V or higher, strongly acidic electrolyzed water, PH 4.5 to 5.5 obtained by diluting the water immediately after electrolysis, residual chlorine amount 50 to
There is 80 ppm, ORP +800 to +1000 mV weakly acidic electrolyzed water, and the latter weakly acidic electrolyzed water has an advantage of being excellent in storage stability. The bactericidal action of acidic electrolyzed water is said to be based on the destruction of the microbial habitat by high ORP and the bactericidal effect by hypochlorous acid.

[0004] That is, as for the ORP, the facultative aerobic microorganism is +200 to +820 mV as the ORP, and the anaerobic microorganism is -700 to +100 mV. But
In the acidic electrolyzed water, the environment of high ORP almost deviating from the region A is exceeded, so that the membrane potential of the organelle exceeds the stabilization limit,
It is understood that energy metabolism and respiration are obstructed, making it difficult to live. Further, the chlorine gas generated by the electrolysis of the salt changes so that the compound form in water shifts to the right side of the following formula as the pH becomes higher, but Cl ₂ + H ₂ O ← → HCl + HOCl ← → HCl + H ⁺
In the PH region of + OCl ⁻ acidic electrolyzed water, as shown in FIG. 2, most of the water is present as hypochlorous acid (HOCl), which is active chlorine. It is thought that denaturation (inactivation of enzyme activity due to oxidation of the N-terminal amino group) occurs and death occurs.

[0005]

As described above, acidic electrolyzed water generated on the anode side by electrolysis of a saline solution is considered to be highly useful for sterilization and disinfection. Is very expensive, so it is not economically feasible to introduce it into small-scale facilities or ordinary households that do not require a large amount of disinfectant, Even facilities with high consumption and high consumption have a large burden on equipment costs, so it has been difficult to install them in all necessary locations.

Therefore, in order to promote the use of acidic electrolyzed water for sterilization and disinfection, the emergence of an inexpensive electrolyzed water generator is expected. However, the construction of the electrolysis section, piping, electrical and fluid control, and the like are required. There is naturally a limit in reducing the manufacturing cost of the device, and the cost of maintenance such as replacement due to the life of the electrode is unavoidable, so it is difficult to solve the economic problem, especially when the frequency of use and consumption are small. Can not respond to.

[0007]

SUMMARY OF THE INVENTION In view of the above-mentioned situation, the present inventors have conducted intensive studies in order to provide inexpensively acidic electrolyzed water having high utility for sterilization and disinfection. The idea was changed 180 degrees from the idea of lowering the cost of sterilization, and a sterilizing and disinfecting solution having the same performance and properties as acidic electrolyzed water could be prepared very easily and inexpensively by mixing chemicals without depending on the method of electrolysis of saline solution. And found that the present invention can be provided.

[0008] That is, the method for producing a disinfecting solution according to claim 1 of the present invention comprises the steps of: a) dissolving in water a chlorine selected from the group consisting of sodium dichloroisocyanurate, sodium hypochlorite, high-grade salami powder, and chloramine T; PH5. By dissolving an agent and b) an acidic substance or hydrogen peroxide.
The method is characterized in that an acidic aqueous solution having a residual chlorine content of 30 ppm or less and an ORP (oxidation-reduction potential) of +800 mV or more is prepared. Thus, according to this method,
By adjusting the pH to 5.5 or less by the b component, the residual chlorine based on the chlorinating agent of the a component dissolved in water becomes a form that exists as active hypochlorous acid, and is set to ORP + 800 mV or more by the b component. Therefore, a highly useful disinfectant solution having the same performance and properties as the acidic electrolyzed water generated by the conventional electrolysis of saline can be easily and inexpensively obtained. The hydrogen peroxide of the component b has an effect of lowering the pH of the aqueous solution by reacting with the chlorine of the chlorine agent of the component a to generate hydrochloric acid.

According to a second aspect of the present invention, in the method for producing a germicidal disinfectant according to the first aspect, since the chlorine agent is sodium dichloroisocyanurate, the disinfectant has a high stability of residual chlorine. Can be prepared inexpensively and easily.

According to the third aspect of the present invention, the first or second aspect is provided.
The method for producing a disinfectant solution of
Since the composition is adjusted to 4.5 to 5.5, the residual chlorine amount to 50 to 80 ppm, and the oxidation-reduction potential to +800 to 1000 mV, the obtained disinfectant solution is generated by the conventional electrolysis of saline. It is equivalent to weakly acidic electrolyzed water.

According to a fourth aspect of the present invention, in the method for producing a germicidal disinfectant according to the third aspect, the component b) is selected from the group consisting of citric acid, malic acid, tartaric acid, maleic acid, succinic acid, oxalic acid, glycolic acid, and acetic acid. Weak acid electrolysis by conventional electrolysis of salt water because it employs at least one acidic substance selected from hydrochloric acid, sulfuric acid, nitric acid, sodium hydrogen sulfate, sulfamic acid, phosphoric acid, or hydrogen peroxide A disinfectant solution corresponding to water can be easily prepared.

According to the fifth aspect of the present invention, the first or second aspect is provided.
The method for producing a disinfectant solution of
2.7 or less, the residual chlorine amount is 30 to 40 ppm, and the oxidation-reduction potential is adjusted to +1100 mV or more. Therefore, the obtained disinfectant solution is obtained by the strong acid electrolysis generated by the conventional electrolysis of saline. It is equivalent to water.

According to a sixth aspect of the present invention, in the method for producing a germicidal disinfectant according to the fifth aspect, the component a is selected from sodium dichloroisocyanurate, sodium hypochlorite, and high-grade powder. The component b) is:
Strongly acidic electrolyzed water obtained by electrolysis of conventional saline is used because it employs at least one acidic substance selected from maleic acid, succinic acid, acetic acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and sodium hydrogen sulfate. Can be easily prepared.

[0014] The germicidal disinfectant according to claim 7 of the present invention comprises a chlorine agent powder selected from the group consisting of sodium dichloroisocyanurate, high-grade salad powder, and chloramine T;
Since it is composed of a powder mixture of an organic acid and / or an inorganic acid in the form of a powder, by simply setting the chlorine agent powder and the organic acid and / or the inorganic acid in a predetermined mixing ratio in advance, it can be simply dissolved in water. The above disinfectant can be supplied as a pack product in powder form that can be easily prepared.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, a chlorinating agent of component a and an acidic substance or hydrogen peroxide of component b may be simply dissolved in water when producing a disinfectant solution. 5 or less, residual chlorine amount 30 ppm or more, ORP
The amounts of the components a and b and the mixing ratio thereof are set so that an acidic aqueous solution of +800 mV or more is obtained. That is, the amount of residual chlorine depends on the amount of the chlorinating agent used, and the PH and ORP depend on the amount of the b component used, respectively. What is necessary is just to set each usage amount according to the kind and combination of both a and b components so that the above-mentioned conditions of PH and ORP may be satisfied. Thus, the obtained disinfecting solution has the same performance and properties as the acidic electrolyzed water generated by the conventional electrolysis of saline, and has an excellent disinfecting effect.

Further, as described above, the conventional acidic electrolyzed water obtained by the electrolysis of salt water is classified into a strongly acidic solution and a weakly acidic solution. The amounts of the components a and b and the mixing ratio thereof may be set so as to be an acidic aqueous solution corresponding to the PH, the residual chlorine amount, and the ORP in each of the acidic electrolyzed water. That is, in a strongly acidic aqueous solution, the pH is 2.7 or less and the residual chlorine amount is 30.
４０40 ppm, oxidation-reduction potential +1100 mV or more, PH 4.5 to 5.5 in weakly acidic aqueous solution, residual chlorine amount 50 to 8
0 ppm, ORP + 800 to 1000 mV.

The chlorine agent of the component a includes sodium dichloroisocyanurate (hereinafter abbreviated as SDCI), sodium hypochlorite, high-grade powder [Ca (OCl) ₂ ],
Chloramine T (CH ₃ C ₆ H ₄ SO ₂ NClNa · 3H
₂ O), and other chlorine agents are unsuitable. For example, trichloroisocyanuric acid, which is structurally similar to SDCI, is a chlorinating agent having a high effective chlorine content of 90%, but it is difficult to prepare a target disinfectant solution because it is hardly soluble in water. In addition, chlorine dioxide (Cl
In O ₂ ) and sodium chlorite (NaClO ₂ ), even if the residual chlorine amount is set to about 80 ppm and the pH is adjusted to 5.5 to 2.7 by adding an acidic substance, the ORP is +75.
It is only 0 mV or less, and the target disinfectant cannot be adjusted.

However, among the above four chlorine agents, SDCI is particularly recommended as the most suitable one. That is, the SDCI indicates that the effective chlorine concentration is 60% or more (theoretical value 6).
(4.5%) as well as excellent stability of the amount of residual chlorine in the aqueous solution, and is easily soluble in water and the aqueous solution is almost neutral (1%).
% Aqueous solution having a pH of 6.0 to 7.0) has the advantage that an acidic aqueous solution of the required residual chlorine amount and PH can be easily prepared with a small amount of the component b.

On the other hand, sodium hypochlorite is the most widely used alkaline chlorinating agent. There are ordinary products and low-salt products, both of which have different alkalinities. Since there is a difference in alkalinity and available chlorine concentration, it is necessary to measure alkalinity and available chlorine concentration in advance for each type of varieties used in order to prepare a disinfectant solution with the required PH and residual chlorine, and it is unstable Therefore, the residual chlorine amount must be measured successively at the time of use to confirm that the amount is within an appropriate range, and these labors are very complicated. There is a drawback that it increases.

In the case of advanced salad powder, the effective chlorine concentration is 60%.
% Or more, but the use of component b is also large because of its alkalinity. In addition, powdery products having good water solubility are class 1 hazardous substances and have a hygroscopic property and chlorine. There is a problem that granular products which are inferior in stability and do not correspond to dangerous substances are hardly soluble in water and cannot be used. Further, chloramine T is a powder that is easily soluble in water, but has a low effective chlorine concentration of 25% and is more expensive than SDCI.
There is a drawback that the amount of components used increases, and it is not particularly suitable for preparing a strongly acidic aqueous solution corresponding to strongly acidic electrolyzed water.

The acidic substance of the component (b) can be used without limitation as long as the pH and ORP of the acidic aqueous solution obtained in combination with the chlorinating agent of the component (a) can be adjusted to a predetermined range. Things. That is, PH 4.5 to 5.5, residual chlorine amount 50 to 80 pp
m, ORP + 800 to 1000 mV for preparing a weakly acidic aqueous solution include citric acid, malic acid, tartaric acid, maleic acid, succinic acid, oxalic acid, glycolic acid, acetic acid, hydrochloric acid,
Sulfuric acid, nitric acid, sodium hydrogen sulfate, sulfamic acid, phosphoric acid and the like are preferred. Alternatively, for preparing a strongly acidic aqueous solution having a pH of 2.7 or less, a residual chlorine amount of 30 to 40 ppm, and an ORP of 1100 mV or more, maleic acid, succinic acid, acetic acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, sodium hydrogen sulfate and the like can be mentioned. However, succinic acid and acetic acid for preparing a strongly acidic aqueous solution are somewhat inferior in that the amounts used are considerably larger than those of the others.

Citric acid, malic acid, tartaric acid, maleic acid, oxalic acid, glycolic acid, and sulfamic acid are all unsuitable for preparing a strongly acidic aqueous solution.
This is because RP cannot be set to +1100 mV or more. Further, as another acidic substance, for example, boric acid is not suitable because an acidic aqueous solution having a pH of 5.5 or less cannot be prepared. It should be noted that sodium dihydrogen phosphate has a drawback that the amount of use is increased because it is an acidic aqueous solution of pH 5.5 or less.
On the other hand, chloramine T, which is a chlorine component of the component a, cannot be used for preparing a strongly acidic aqueous solution because the ORP cannot be increased to +1100 mV or more.

Hydrogen peroxide as the component (b) has an effect of lowering the pH of the aqueous solution by reacting with the chlorine of the chlorine agent of the component (a) to generate hydrochloric acid, and therefore can be used in place of the above acidic substance. . However, in order to lower the pH of the aqueous solution to 2.7 or less, it is necessary to add a large amount of hydrogen peroxide, and in order to compensate for the accompanying large consumption of chlorine, the amount of the chlorine agent used will be extremely large. Therefore, hydrogen peroxide is not suitable for preparing a strongly acidic aqueous solution.

In the present invention, the chlorine agent as the component a and the acidic substance or the hydrogen peroxide as the component b are dissolved in water, and a weakly acidic aqueous solution or a strongly acidic aqueous solution satisfying the above-mentioned residual chlorine amount, PH and ORP is prepared. The water to be prepared can be purified water such as ion-exchanged water or ordinary tap water.

The obtained strongly acidic and weakly acidic aqueous solutions are each disinfected with a sterilizing disinfectant having the same action and properties as those of the weakly acidic electrolyzed water and the strongly acidic electrolyzed water produced by the conventional electrolyzed water generator. Therefore, it can be used for various sterilization and disinfection applications in place of the electrolyzed water. Its uses include:
For example, hand washing water for disinfection in medical institutions, various welfare facilities, kitchens, households, etc., cleaning of medical and cooking utensils, portable toilets, wagons, shelves, shelves, sinks, etc., and cleaning of walls and floors Examples include wiping, washing of clothing such as linen, fukin, eblon, white robe, and footwear such as slippers. Furthermore, in addition to the above-mentioned general uses, if both weakly acidic and strongly acidic disinfectants are used for disinfecting and cleaning the alginate impression material after obtaining the tooth profile in dentistry, the shape change and surface roughness of the impression material are almost eliminated. There is an advantage that sterilization of bacteria transferred from the mouth of the patient can be carried out without occurrence, and if the artificial dialysis line is used for washing, the calcium carbonate adhering to the line can be removed in a short time together with the sterilization.

In general, a disinfectant solution is prepared by dissolving both the components a and b in water at a ratio specified in a manual provided by the manufacturer on the user side. In order to save the trouble of weighing the components a and b, and setting the use ratio, for example,
If a disinfectant is provided in which the components a and b are packaged in an amount and a ratio corresponding to a unit amount of disinfectant such as 5, 10 liters, and the user dissolves it in a predetermined amount of water, Good.

When the above-mentioned disinfectant is used, particularly, a, b
If both components are powdered, both components can be mixed in a predetermined ratio in advance to provide a product in the form of a powder mixture, which is convenient for transportation and storage, and a disinfectant solution for the user. Has the advantage that the preparation of is also easier. In addition, what can be obtained as a powder form is, for the component a, SDCI, high-grade salad powder, chloramine T,
In component b, citric acid, malic acid, tartaric acid, maleic acid,
Examples include succinic acid, oxalic acid, sodium hydrogen sulfate, and sulfamic acid.

[0028]

【Example】

[Manufacturing Example 1 of Disinfectant Solution] Ion-exchanged water was used as dilution water, and citric acid, malic acid, tartaric acid, succinic acid, maleic acid, oxalic acid, glycolic acid (70% aqueous solution), acetic acid, and hydrochloric acid were used as acidic substances. (1N aqueous solution), sulfuric acid (1N aqueous solution), nitric acid (1N aqueous solution), sodium hydrogen sulfate, sulfamic acid, phosphoric acid (85% aqueous solution), sodium dihydrogen phosphate, and boric acid. 12 of SDCI (measured value of available chlorine 62.0%)
In addition to an aqueous solution having a concentration of 0 mg / liter, pH 4.5,
Disinfecting solutions composed of the weakly acidic aqueous solutions of 5.0 and 5.5 were respectively prepared, and the ORP of each disinfecting solution was measured. Table 1 shows the amount of the acidic substance (the amount as a liquid in the form of an aqueous solution) and the measured value of ORP required for the preparation of each disinfectant solution. However, boric acid has too little PH lowering ability,
Even at an addition amount of 5 g / liter, the pH could not be reduced to 5.7 or less, and was not suitable for preparing a disinfectant solution corresponding to the target weakly acidic electrolyzed water. The amount of residual chlorine immediately after the preparation of each disinfectant was 74.4 ppm.

[Production Example 2 of Disinfectant Solution] Tap water is used as dilution water, and citric acid, malic acid, tartaric acid, succinic acid, maleic acid, oxalic acid, glycolic acid (70% aqueous solution), hydrochloric acid are used as acidic substances. (1N aqueous solution), sulfuric acid (1N aqueous solution), sodium hydrogen sulfate, sulfamic acid, and phosphoric acid (85% aqueous solution) were used, and each acidic substance was subjected to SDCI (measured value of available chlorine 62.0%) of 12%.
In addition to an aqueous solution having a concentration of 0 mg / liter, pH 4.5,
Disinfecting solutions composed of the weakly acidic aqueous solutions of 5.0 and 5.5 were respectively prepared, and the ORP of each disinfecting solution was measured. The results are shown in Table 2 together with the amount of the acidic substance (the amount of the solution in the form of an aqueous solution) required for the preparation of each disinfecting solution. The amount of residual chlorine immediately after the preparation of each disinfectant was 74.4 ppm.

[0030]

[Table 1]

[0031]

[Table 2]

From the results of Tables 1 and 2, when tap water is used as the dilution water, the required amount of the acidic substance is slightly larger than when the ion-exchanged water is used. PH4.5 corresponding to the weakly acidic electrolyzed water obtained by the conventional electrolyzed water generator from the acidic substance of
~ 5.5, residual chlorine amount 50 ~ 80ppm, ORP + 80
It turns out that a sterilizing solution of 0 to 1000 mV can be easily prepared. However, sodium dihydrogen phosphate is used in the above P
There is a drawback that the amount of addition required for adjusting to the range of H and ORP is very large, and therefore, it was not used in Production Example 2. The acetic acid and nitric acid used in Production Example 1 were:
Although the use in Production Example 2 is simply omitted, even when tap water is used as dilution water, it can be used without any inconvenience.

[Time-dependent change of disinfectant solution 1] According to Production Example 1, ion exchanged water was used
A variety of acidic substances are added to an aqueous solution having a concentration of 0 mg / liter so that the pH becomes approximately 5 to prepare a disinfectant solution composed of a weakly acidic aqueous solution. Immediately after preparation of each disinfectant solution (elapsed time 0), 24 hours later , 72 hours later, PH, ORP and residual chlorine amount were measured, and the results shown in Table 3 were obtained. Similarly, according to Production 2, PH immediately after preparation and 24 hours after preparation of each disinfectant solution prepared using tap water as dilution water,
When the ORP and the residual chlorine content were measured, the results shown in Table 4 were obtained.

[0034]

[Table 3]

[0035]

[Table 4]

From the results shown in Table 3, according to the method of the present invention, a weakly acidic sterilizing and disinfecting solution prepared by adjusting the pH to approximately PH5 with various acidic substances using ion-exchanged water as a dilution water and SDCI as a chlorinating agent was obtained. Even after 72 hours, a pH of 4.5 to 4.5 corresponding to the weakly acidic electrolyzed water obtained by the conventional electrolyzed water generator.
5.5, residual chlorine amount 50-80 ppm, ORP + 800
It is clear that the range of １０００1000 mV is maintained and the storage stability is excellent. Also, from the results in Table 4, in the same manner, the weakly acidic disinfectant prepared at approximately PH5 using tap water as the dilution water tends to have a slightly higher PH when oxalic acid is used as the acidic substance. However, it can be seen that most of them can be used without any trouble as a disinfectant solution showing the same pH, residual chlorine amount and ORP as weakly acidic electrolyzed water by an electrolyzed water generator even 24 hours after preparation.

[Manufacturing Example 3 of Disinfectant Solution] While using ion-exchanged water as dilution water, citric acid,
Malic acid, tartaric acid, succinic acid, maleic acid, oxalic acid,
Glycolic acid (70% aqueous solution), acetic acid, hydrochloric acid (1N aqueous solution), sulfuric acid (1N aqueous solution), nitric acid (1N aqueous solution), sodium hydrogen sulfate, sulfamic acid, phosphoric acid (85% aqueous solution) The substance was added to an aqueous solution of SDCI (measured value of available chlorine amount: 62.0%) having a concentration of 60 mg / liter to prepare a sterilizing and disinfecting solution composed of a strongly acidic aqueous solution of pH 2.7 and 2.65. The ORP of the sterilizing solution was measured. The results are shown in Table 5 together with the amount of the acidic substance (the amount of the solution in the form of an aqueous solution) required for the preparation of each sterilizing solution. The amount of residual chlorine immediately after the preparation of each disinfectant was 37.2 ppm.

[Manufacturing Example 4 of Disinfectant Solution] Tap water was used as dilution water, and citric acid, malic acid, tartaric acid, succinic acid, maleic acid, oxalic acid, glycolic acid (70% aqueous solution), hydrochloric acid were used as acidic substances. (1N aqueous solution), sulfuric acid (1N aqueous solution), sodium hydrogen sulfate, sulfamic acid, and phosphoric acid (85% aqueous solution) were used, and each acidic substance was subjected to 60% of SDCI (measured value of available chlorine 62.0%).
In addition to the aqueous solution having a concentration of mg / liter, disinfecting solutions each consisting of a strongly acidic aqueous solution of pH 2.7 and 2.65 were prepared, and the ORP of each disinfecting solution was measured. The results are shown in Table 5 together with the amount of the acidic substance (the amount of the solution in the form of an aqueous solution) required for the preparation of each sterilizing solution. The amount of residual chlorine immediately after the preparation of each disinfectant solution was 37.2 pp.
m.

[0039]

[Table 5]

From the results shown in Table 5, when inexpensive tap water is used as the diluting water, the required amount of the acidic substance is slightly larger than when ion-exchanged water having a small buffering property is used. As maleic acid, succinic acid,
By using acetic acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and sodium hydrogen sulfate, a pH of 2.7 or less corresponding to strongly acidic electrolyzed water obtained by a conventional electrolyzed water generator, a residual chlorine amount of 30 to 40 ppm, It turns out that a disinfectant solution of ORP + 1100 mV or more can be easily prepared. However, citric acid, malic acid, tartaric acid, oxalic acid,
ORP using glycolic acid or sulfamic acid
Is below +1100 mV, so that it cannot be replaced with strongly acidic electrolyzed water. When the acidic substance is acetic acid, the strongly acidic P
In setting the H range, it is necessary to use a very large amount. Acetic acid and nitric acid used in Production Example 3 were used in Production Example 4
Is simply omitted, but even if tap water is used as dilution water, it can be used without any inconvenience.

[Time-dependent change of disinfectant solution 2] According to Production Example 3, ion-exchanged water was used
Various acidic substances are added to an aqueous solution having a concentration of mg / liter so as to have a pH of about 2.6 to 2.7 to prepare a disinfecting solution composed of a strongly acidic aqueous solution. ) And 24 hours later, PH, ORP and residual chlorine amount were measured. Similarly, in accordance with Production 4, PH, ORP, and residual chlorine amounts were measured immediately after and 24 hours after the preparation of each strongly acidic sterilizing disinfectant prepared using tap water as dilution water. Table 6 shows the results.

[0042]

[Table 6]

From the results shown in Table 6, according to the method of the present invention, ion exchange water or tap water was used as dilution water, SDCI was used as a chlorinating agent, and the pH was adjusted to about 2.6 to 2.7 with various acidic substances. Strongly acidic disinfectants are especially acidic substances, acetic acid,
In the case of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and sodium hydrogen sulfate, even after 24 hours from the preparation, the pH, the residual chlorine amount, and the ORP are the same as those of the strongly acidic electrolyzed water obtained by the conventional electrolyzed water generator. It can be seen that it can be used without any trouble. However, a strongly acidic aqueous solution using succinic acid, maleic acid, or phosphoric acid as an acidic substance can be said to be desirably used with little time after adjustment because the amount of residual chlorine is greatly reduced with time. Table 6 also shows the change with time when glycolic acid and sulfamic acid are used as the acidic substances for reference. However, these are not suitable as a substitute for strongly acidic electrolyzed water since the ORP of the prepared aqueous solution is lower than +1100 mv. is there.

[Preparation Example 5 of Disinfectant Solution] While ion-exchanged water was used as dilution water, tartaric acid and hydrochloric acid (1N aqueous solution) were used as acidic substances, and these acidic substances were treated with sodium hypochlorite (effective chlorine). 600 mg of amount 12%)
PH 5.5, PH
Disinfectants containing 5.0 and PH 4.5 weakly acidic aqueous solutions were prepared.

[Production Example 6 of Disinfectant Disinfectant] In addition to using ion-exchanged water as dilution water, each of malic acid and hydrochloric acid (1N aqueous solution) was used as an acidic substance, and these acidic substances were treated with advanced salad powder (Nankai Chemical Industry). Manufactured, available chlorine 6
(3.8%) of 114 mg / liter, and a disinfectant solution consisting of a weakly acidic aqueous solution having a pH of 5.5, 5.0, or 4.5 was prepared.

[Manufacturing Example 7 of Disinfectant Solution] In addition to using ion-exchanged water as dilution water, citric acid and hydrochloric acid (1N aqueous solution) were used as acidic substances, and these acidic substances were treated with chloramine T (effective chlorine amount 25%). %), A pH of 5.5, 5.0, and 288 mg / liter.
Disinfectants containing 4.5 weakly acidic aqueous solutions were prepared.

The amount of residual chlorine and the ORP immediately after the preparation of each of the disinfecting solutions obtained in Production Examples 5 to 7 were measured. The results are shown in Table 7 together with the amount of acidic substance (the amount of hydrochloric acid) required for the preparation of each disinfectant solution.

[0048]

[Table 7]

From the results in Table 7, it can be seen that the use of any of sodium hypochlorite, high-grade powder and chloramine T as the chlorinating agent corresponds to the weakly acidic electrolyzed water obtained by the conventional electrolyzed water generator. PH 4.5-5.5, residual chlorine amount 50
It can be seen that a germicidal disinfectant of 〜80 ppm, ORP + 800-1000 mV can be easily prepared. However, in the preparation of these germicidal disinfectants, the amount of the acidic substance used is larger than when SDCI is used as the chlorine agent. In the case of a germicidal disinfectant using chloramine T, S
The ORP has a lower value as compared with the case where DCI is used.

[Time-dependent change of disinfectant solution 3] Production Examples 5 to 7
Use ion-exchanged water as the dilution water, sodium hypochlorite, high-grade powder, chloramine T as the chlorinating agent, and citric acid and hydrochloric acid (1N aqueous solution) as the acidic substances. Was added to adjust the pH to about 5.0 to prepare a disinfectant solution composed of a weakly acidic aqueous solution. In addition, sodium hypochlorite and high-grade salad powder were used as the chlorinating agent, and hydrochloric acid (1N aqueous solution) was used as the acidic substance, and the concentration of the chlorinating agent aqueous solution was approximately 略 of those in Production Examples 5 and 6, and the PH was 2.65. A disinfectant solution consisting of a strongly acidic aqueous solution of was prepared. Then, PH, ORP, and residual chlorine amounts were measured immediately after preparation (elapsed time 0) and after 24 hours of each of these disinfectants. Table 8 shows the results.

[0051]

[Table 8]

From the results in Table 8, it can be seen that the weakly acidic germicidal disinfectant prepared by the method of the present invention using sodium hypochlorite, high-grade salad powder and chloramine T as the chlorinating agent was obtained at the time of 24 hours after the preparation. However, PH corresponding to the weakly acidic electrolyzed water obtained by the conventional electrolyzed water generator, the residual chlorine amount,
It can be seen that the sterilizing solution showing ORP is maintained. Further, according to the method of the present invention, even in the case of a strongly acidic disinfecting solution prepared using sodium hypochlorite and high-grade salad powder as the chlorine agent, respectively, at the time of 24 hours after preparation, when the chlorinated agent is high-grade salad powder It can be seen that the residual chlorine content is slightly lower, but the properties are maintained substantially the same as the strongly acidic electrolyzed water obtained by the conventional electrolyzed water generator. The strongly acidic disinfectant solution having a pH of 2.7 or less, in which the chlorinating agent is chloramine T, was prepared using hydrochloric acid as an acidic substance. However, since the ORP was below +1100 mv and the formation of precipitates was observed, the strong acid was used. It was not suitable as a substitute for electrolyzed water.

[Production Example 8 of Disinfectant Solution] As shown in Table 9 below, hydrogen peroxide was added to aqueous solutions of SDCI at various concentrations.
CI / H ₂ O ₂ was added at a molecular ratio of 8/1, 8/2, or 8/3 to prepare each disinfectant solution comprising a weakly acidic aqueous solution. The PH, ORP and residual chlorine content of these disinfecting solutions were measured, and a 140 mg / l SD
With respect to the germicidal disinfectant obtained by adding hydrogen peroxide to the CI aqueous solution at a molecular ratio of 8/2, the change over time at the time of 24 hours and 72 hours after preparation was examined, and the results shown in Table 9 were obtained. Was.

[0054]

[Table 9]

From the results shown in Table 9, it can be seen that the pH is lowered by the addition of hydrogen peroxide. This is because one molecule of hydrogen peroxide consumes the chlorine contained in one molecule of SDCI, and hydrochloric acid is thereby produced. It is thought to be. Thus, PH 4.5 to 5.5 corresponding to weakly acidic electrolyzed water, residual chlorine amount 50
The molecular ratio of SDCI / H ₂ O ₂ is 4/1 in order to make a weakly acidic aqueous solution of ８０80 ppm, ORP + 800-1000 mV, and to reduce the consumption of SDCI by hydrogen peroxide.
Near is preferred. In addition, from the time-dependent change shown in Table 9, even a weakly acidic disinfectant obtained by adjusting the pH with hydrogen peroxide can be obtained with a conventional electrolyzed water generator even after 72 hours from its preparation. It can be seen that properties equivalent to the weakly acidic electrolyzed water are maintained, and excellent storage stability is provided.

[Sterilization Test 1] P prepared in Production Example 1
H5.0 germicidal disinfectant (see Table 1, 15 kinds excluding those in which the acidic substance is boric acid), PH 2.65 prepared using ion-exchanged water in Production Example 3, ORP +1100 mv or more germicidal disinfectant (Table 1) 5; 8 kinds); PH5.0 germicidal disinfectants prepared in Production Examples 5 to 7 (see Table 7; 6 varieties); (See Table 8 ... 2 types), 140 mg in Production Example 8
/ L concentration of SD2 aqueous solution with hydrogen peroxide at a molecular ratio of 8/2
10 ml of each of the germicidal disinfectants (see Table 9 ... 1 type) obtained by adding in 3 test tubes,
1 ml of each bacterial solution of Staphylococcus aureus and Pseudomonas aeruginosa (number of bacteria about 10 ⁶
Was added to each test tube and shaken for 1 minute. Then, 50 μl of the mixture was collected, applied to the entire surface of a petri dish medium, and cultured at 37 ° C. for 24 hours. When the surfaces of these media were observed, no colonies were found. In addition, the SCDLP agar medium for measurement of the number of viable preservative-inactivated bacteria "DAIGO" was used as the medium.

[Sterilization Test 2] P prepared in Production Example 1
H5.0 germicidal disinfectant solution (see Table 1, 15 kinds except for the case where the acidic substance is boric acid) is sprayed from the height of 20 cm on the floor of the sickroom, and 5 minutes later with a food stamp for general viable bacteria. The center of each sprayed surface was stamped and cultured at 37 ° C. for 2 days. As a result, colonies were formed on the floor surface which was not sprayed with the disinfectant solution in the same manner, but colonies were not found on any of the stamped floor surfaces.

[Effect test on dental impression material] Production example 1
Three kinds of disinfecting solutions of pH 5.0 prepared by adding citric acid, succinic acid and sodium dihydrogen phosphate to an aqueous solution of SDCI at a concentration of 120 mg / l respectively, and 60 mg / l in Production Example 3
Maleic acid, glycolic acid,
Each of sodium hydrogen sulfate was added, and three kinds of disinfecting solutions of pH 2.65 prepared using tap water as dilution water. In Preparation Example 8, hydrogen peroxide was added to a 140 mg / l SDCI aqueous solution at a molecular ratio of 8/2. The alginate impression material (diameter 2) used in dentistry to obtain a patient's tooth model was used in each solution using the disinfectant solution obtained by addition.
(5 mm, 10 mm height pellet) was immersed for 30 minutes, and the change in diameter was measured. The alginate impression material after the immersion was transferred to a gypsum impression, and after 40 minutes, the alginate impression material was removed and the state of the gypsum surface was examined. The results are shown in Table 10 together with the results of immersion in tap water instead of the sterilizing solution.

[0059]

[Table 10]

From the results shown in Table 10, it can be seen that the disinfectants and disinfectants according to the method of the present invention show little change in shape due to the immersion of the alginate impression material, and the gypsum surface except for those using sodium dihydrogen phosphate as the acidic substance. Since there is no roughness, it can be seen that the tooth impression can be suitably used for sterilization of the dental impression material after obtaining the impression.

[Applicability test for disinfection washing of artificial dialysis line] A sterilization disinfectant of pH 5.0 prepared by adding citric acid to a 120 mg / l SDCI aqueous solution in Production Example 1, 140 mg / l in Production Example 8 Disinfectant obtained by adding hydrogen peroxide to a concentrated SDCI aqueous solution at a molecular ratio of 8/2,
Using a 130 mg / l aqueous solution of SDCI alone as a disinfecting and washing test solution, a dialysate solution of 10 μl, 25 μl, and 50 μl was dropped on a stainless steel plate and air-dried for 24 hours. Prepare only the number,
Each of these samples was immersed in each of the test solutions described above, pulled up every 30 minutes, and determined by the OCPC method (orthocresol phthalein complexone method) to determine whether calcium remained on the plate. The immersion time (30 minutes unit) required for the removal of the resin was examined. Table 11 shows the results.

[0062]

[Table 11]

From the results shown in Table 11, the weakly acidic disinfectant obtained by using the SDCI as the chlorinating agent in the method of the present invention can remove calcium carbonate precipitated from the dialysate, and is used for disinfection and cleaning of the artificial dialysis line. It turns out that it can be used conveniently. In addition, as a result of conducting a similar applicability test for disinfection and cleaning of the artificial dialysis line for a strongly acidic disinfectant solution,
Calcium removal was higher than in the case of weak acid, and complete removal was possible within 30 minutes. Therefore, when the artificial dialysis line is to be used for disinfecting and cleaning as described above, one of the sterilizing and disinfecting solutions must be prepared in advance.
A concentrated solution having a concentration of about 5 to 50 times may be prepared, and may be diluted to a required concentration for disinfecting and washing.

[0064]

According to the first aspect of the present invention, a highly useful sterilizing and disinfecting solution having the same performance and properties as acidic electrolyzed water generated by conventional electrolysis of saline is provided. And can be obtained easily and inexpensively without using expensive equipment such as

According to the second aspect of the present invention, the above sterilizing and disinfecting solution, which is particularly excellent in the stability of residual chlorine, can be easily prepared at low cost.

According to the third aspect of the present invention, it is possible to prepare, as the above-mentioned germicidal disinfectant, a solution corresponding to weakly acidic electrolyzed water generated by conventional electrolysis of saline.

According to the fourth aspect of the present invention, the above-mentioned sterilizing and disinfecting solution can be reliably and easily prepared as a solution corresponding to a weakly acidic electrolyzed water obtained by electrolysis of a conventional saline solution.

According to the invention of claim 5, as the above-mentioned disinfectant solution, a solution corresponding to strongly acidic electrolyzed water generated by conventional electrolysis of saline can be prepared.

According to the sixth aspect of the present invention, the above-mentioned disinfectant can be reliably and easily prepared as a solution corresponding to the conventional strongly acidic electrolyzed water obtained by electrolysis of a saline solution.

According to the eighth aspect of the present invention, a disinfectant capable of easily preparing the above disinfectant by simply dissolving it in a predetermined amount of water can be supplied as a pack product in powder form.

[Brief description of the drawings]

FIG. 1 is a correlation diagram of redox potential and PH showing a living sphere of a microorganism.

FIG. 2 is a correlation diagram between effective chlorine abundance ratio and PH showing a change in the form of available chlorine in water.

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[Procedure amendment]

[Submission date] November 8, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0028

[Correction method] Change

[Correction contents]

[0028]

EXAMPLES [Manufacturing Example 1 of Disinfectant Solution] Ion-exchanged water is used as dilution water, and citric acid, malic acid, tartaric acid, succinic acid, maleic acid, oxalic acid, and glycolic acid (70% aqueous solution) are used as acidic substances. Acetic acid, hydrochloric acid (1N aqueous solution), sulfuric acid (1N aqueous solution), nitric acid (1N aqueous solution), sodium hydrogen sulfate, sulfamic acid, phosphoric acid (85% aqueous solution), sodium dihydrogen phosphate, boric acid, Each acidic substance was subjected to SDCI (measured value of available chlorine 62.0%) of 12
In addition to an aqueous solution having a concentration of 0 mg / liter, pH 4.5,
Disinfecting solutions composed of the weakly acidic aqueous solutions of 5.0 and 5.5 were respectively prepared, and the ORP of each disinfecting solution was measured. The amount of acidic substance and O required for preparation of each disinfectant
Table 1 shows the measured values of RP. However, boric acid has too little ability to lower the pH, so even if it is added in an amount of 5 g / liter, the pH is lowered.
Was not reduced to 5.7 or less, which was unsuitable for preparing a disinfectant solution corresponding to the target weakly acidic electrolyzed water. The amount of residual chlorine immediately after the preparation of each disinfectant was 74.4 ppm.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0029

[Correction method] Change

[Correction contents]

[Production Example 2 of Disinfectant Solution] Tap water is used as dilution water, and citric acid, malic acid, tartaric acid, succinic acid, maleic acid, oxalic acid, glycolic acid (70% aqueous solution), hydrochloric acid are used as acidic substances. (1N aqueous solution), sulfuric acid (1N aqueous solution), sodium hydrogen sulfate, sulfamic acid, and phosphoric acid (85% aqueous solution) were used, and each acidic substance was subjected to SDCI (measured value of available chlorine 62.0%) of 12%.
In addition to an aqueous solution having a concentration of 0 mg / liter, pH 4.5,
Disinfecting solutions composed of the weakly acidic aqueous solutions of 5.0 and 5.5 were respectively prepared, and the ORP of each disinfecting solution was measured. Both are shown in Table 2 with the amount of the acidic substance required results for the preparation of the disinfectant. The amount of residual chlorine immediately after the preparation of each disinfectant was 74.4 ppm.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0030

[Correction method] Change

[Correction contents]

[0030]

[Table 1]

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0031

[Correction method] Change

[Correction contents]

[0031]

[Table 2]

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0034

[Correction method] Change

[Correction contents]

[0034]

[Table 3]

[Procedure amendment 6]

[Document name to be amended] Statement

[Correction target item name] 0035

[Correction method] Change

[Correction contents]

[0035]

[Table 4]

[Procedure amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0037

[Correction method] Change

[Correction contents]

[Manufacturing Example 3 of Disinfectant Solution] While using ion-exchanged water as dilution water, citric acid,
Malic acid, tartaric acid, succinic acid, maleic acid, oxalic acid,
Glycolic acid (70% aqueous solution), acetic acid, hydrochloric acid (1N aqueous solution), sulfuric acid (1N aqueous solution), nitric acid (1N aqueous solution), sodium hydrogen sulfate, sulfamic acid, phosphoric acid (85% aqueous solution) The substance was added to an aqueous solution of SDCI (measured value of available chlorine amount: 62.0%) having a concentration of 60 mg / liter to prepare a sterilizing and disinfecting solution composed of a strongly acidic aqueous solution of pH 2.7 and 2.65. The ORP of the sterilizing solution was measured. Both are shown in Table 5 the amount of acidic substance required results for the preparation of the disinfectant. The amount of residual chlorine immediately after the preparation of each disinfectant solution was 37.
It was 2 ppm.

[Procedure amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0038

[Correction method] Change

[Correction contents]

[Manufacturing Example 4 of Disinfectant Solution] Tap water was used as dilution water, and citric acid, malic acid, tartaric acid, succinic acid, maleic acid, oxalic acid, glycolic acid (70% aqueous solution), hydrochloric acid were used as acidic substances. (1N aqueous solution), sulfuric acid (1N aqueous solution), sodium hydrogen sulfate, sulfamic acid, and phosphoric acid (85% aqueous solution) were used, and each acidic substance was subjected to 60% of SDCI (measured value of available chlorine 62.0%).
In addition to the aqueous solution having a concentration of mg / liter, disinfecting solutions each consisting of a strongly acidic aqueous solution of pH 2.7 and 2.65 were prepared, and the ORP of each disinfecting solution was measured. The results are shown in Table 5 together with the amount of acidic substance required for preparing each disinfectant solution. The amount of residual chlorine immediately after the preparation of each disinfectant was 37.2 ppm.

[Procedure amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0039

[Correction method] Change

[Correction contents]

[0039]

[Table 5]

[Procedure amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0042

[Correction method] Change

[Correction contents]

[0042]

[Table 6]

Claims (7)

[Claims] 1. dissolving in water a) a chlorinating agent selected from the group consisting of a) sodium dichloroisocyanurate, sodium hypochlorite, high-grade powder, and chloramine T; and b) an acidic substance or hydrogen peroxide. PH 5.5 or less, residual chlorine amount 30 ppm or more, oxidation-reduction potential +800
A method for producing a disinfecting and disinfecting solution, comprising preparing an acidic aqueous solution of mV or more. 2. The method according to claim 1, wherein the chlorine agent is sodium dichloroisocyanurate. 3. An acidic aqueous solution having a pH of 4.5 to 5.5, a residual chlorine amount of 50 to 80 ppm, and an oxidation-reduction potential of +800 to 1
The method for producing a disinfectant / disinfectant according to claim 1 or 2, wherein the disinfectant is adjusted to 000 mV. 4. The method according to claim 1, wherein the component (b) is citric acid, malic acid,
4. The compound according to claim 3, which is at least one acidic substance selected from tartaric acid, maleic acid, succinic acid, oxalic acid, glycolic acid, acetic acid, hydrochloric acid, sulfuric acid, nitric acid, sodium hydrogen sulfate, sulfamic acid and phosphoric acid, or hydrogen peroxide. Method for producing a disinfectant solution of the present invention. 5. The method according to claim 1, wherein the acidic aqueous solution is adjusted to a pH of 2.7 or less, a residual chlorine content of 30 to 40 ppm, and an oxidation-reduction potential of +1100 mV or more. 6. The component (a) is selected from sodium dichloroisocyanurate, sodium hypochlorite, and high-grade powder, and the component (b) is maleic acid.
The method for producing a germicidal antiseptic according to claim 5, wherein the method is at least one acidic substance selected from succinic acid, acetic acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and sodium hydrogen sulfate. 7. A sodium dichloroisocyanurate,
A germicidal disinfectant comprising a powder mixture of a powder of a chlorine agent selected from the group consisting of advanced salami powder and chloramine T, and a powdered organic acid and / or inorganic acid.