JP2005305109A - Sterilizing composition and supply method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an easily decomposable sterilizing composition with high safety and a reduced environmental load, which composition can be supplied by suitable concentration and amount in a highly active composition condition matching uses and purposes. <P>SOLUTION: When this easily decomposable sterilizing composition is to be supplied, a request for supply of a sterilizing composition is received from a person to be supplied by phone, cellular phone, or a communication means via the internet. A blended sterilizing composition with a stable and highly safe composition, a valid term, suitable concentration and amount highly activated by controlling pH, etc. determined by a computer to which selections of sterilizing compositions with life extended by freezing, chemical equilibrium, etc. to be objects of the supply and decomposition rates of the sterilizing composition by sterilizing composition conditions are preliminarily inputted is supplied to the person to be supplied and the validity is monitored and reported to the person to be supplied. The person to be supplied uses the sterilizing composition within the highly active term. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a sterilizing composition capable of supplying and sterilizing a chlorine-based sterilizing agent and an oxygen-based sterilizing agent in a state of high activity in a chemical disinfection method, and a method for supplying the sterilizing composition.
More specifically, in order to supply a sterilizing composition that is easy to decompose in a state of high sterilization efficiency, the decomposition rate depending on the conditions for each composition of the sterilizing composition supplied to the supplier's computer is input in advance, Based on the demand information of the supplier using a communication system with a computer, the composition condition, concentration, supply amount and effective period of the sterilizing composition are calculated, and based on this, the sterilizing composition is prepared and delivered to the supplier. The present invention relates to a sterilizing composition and a method for supplying the sterilizing composition.

In recent years, the situation surrounding infectious diseases has changed significantly as internationalization has progressed, such as the recent increase in international exchange and the arrival of the era of rapid mass transportation by aircraft. Under these circumstances, about 30 new infectious diseases have emerged even in recent years, while existing infectious diseases that have been thought to have been overcome have recurred and threatened humanity again. Yes. These infectious diseases spread to a wide area on a global scale in a short time in the era of rapid mass transportation by aircraft.

On the other hand, with respect to infectious diseases by medical and medical advancement, improvement of public health standards, transmission of information on the onset and countermeasures of infectious diseases, transmission of information via the Internet, health awareness, racial equality, global awareness of respect for human rights, etc. Prevention and treatment are also taking place on a global scale.

In addition, there has been a change in the way of thinking about infectious diseases, and preventive measures to prevent the occurrence of infectious diseases in advance from the post-reaction type government that said to take preventive measures after the onset of infectious diseases. The government has shifted to the promotion of advanced administration, and the quarantine system is being implemented and strengthened on a global scale. As for the control of infectious diseases by disinfection and sterilization, prior actions are taken to prevent the occurrence and spread of infectious diseases.

However, if proper disinfection or sterilization is not performed in a medical site or region where a specific infection has occurred, it may cause further spread of infection or new infection.
Various methods are used for disinfection. Which treatment method is performed is determined by the purpose of use of the equipment, the degree of cleanliness requirement, the material, and the presence / absence of disinfection / sterilization facilities.

Such disinfection and sterilization methods include a physical disinfection method and a chemical disinfection method. Alcohol disinfection, which has been widely used for a long time in chemical disinfection methods, is diluted immediately in areas with high water content and immediately In addition to losing efficacy, it is known to cause fires and other disasters due to its extremely flammability.

On the other hand, chlorine-based disinfectants have long been used for bleaching and disinfecting potable water, medical equipment, cooking utensils, toilets, bathrooms, and the like. Commercially available chlorine-based disinfectants are manufactured and sold in which high-concentration chlorine gas is dissolved in a high-concentration alkaline solution in order to prevent long-term storage and generation of chlorine gas.

However, the chlorine-based disinfectant is mixed with an acidic cleaning agent, and when an acidic solution is used, a large amount of dissolved chlorine is generated as a gas, and the user may even be poisoned or intoxicated.

Although the bleaching and bactericidal effects of chlorine-based disinfectants are highly effective in the low pH region, chlorine gas is likely to be generated in the low pH region and decomposes, and the effect as a disinfectant is short. In order to compensate for the disadvantage of being lost, the bleaching and sterilizing effects are sacrificed, and the chlorine gas is prepared in a high pH region where no chlorine gas is generated, that is, a strong alkaline region. This is because it is dissolved in

In order to handle such a chlorine-based disinfectant, as described above, since the alkali concentration is high, chemical expertise such as whether the degree of dilution is appropriate and whether other detergents are acidic Even housewives who do not have eyeglasses must perform dangerous work that requires wearing glasses and gloves, as with professionals, to prevent adhesion to eyes and skin.

Recently, the cleaning effect of the hypochlorous acid water generated by electrolyzing salt water and dilute hydrochloric acid water has been recognized, and as a food additive, “strongly acidic hypochlorous acid water” and “slightly acidic hypochlorous acid water” Has been approved, and hypochlorous acid water by electrolysis has attracted attention, and various types of electrolytic sterilizers are on the market.

However, it is extremely dangerous for an amateur without electrical or chemical knowledge to handle dangerous chemicals and perform an electrochemical reaction that is electrolysis using a commercially available electrolyzer. In addition, hydrogen gas generated at the cathode by electrolysis is extremely flammable, has a wide explosion limit area by mixing with air (oxygen), and explodes due to use in places with fire such as homes, lunch centers, hospitals, The risk of fire is extremely high and is likely to lead to a major disaster.

At the same time, poisonous chlorine gas generated at the anode during electrolysis and organic chlorine compounds that are secondary carcinogenic substances, ozone gas, etc., hydrogen peroxide that co-forms other than hydrogen gas generated at the cathode, Workers handling high-concentration alkalis are placed in extremely dangerous situations.

The electrolytic reaction involves an extremely complicated and advanced operation in which a direct current is passed through the anode and cathode, electrolysis, which is an electrochemical reaction, is performed on the electrode surface, and hypochlorous acid water is generated on the anode. Become. In addition, it is difficult to produce hypochlorous acid water by electrochemical reaction while adjusting the concentration, pH and generated hypochlorous acid concentration of raw materials such as salt and hydrochloric acid, which are difficult to control even by experts. It is extremely dangerous.

Depending on the electrolysis conditions, the electrode may cause different electrode reactions, and at the same time, the electrode catalyst is consumed, the target electrode reaction of generating hypochlorous acid water does not occur, and electrode reactions other than the target occur. In addition, the electrode plate may be dissolved.

In addition, we do not know that hypochlorous acid water produced by the above electrochemical reaction is decomposed and the sterilizing ability disappears in a short time, and we do not have a means to verify, so we take measures to disinfect. However, there may be a problem that the intended disinfection is not actually performed.

On the other hand, the sterilization spectrum showing the effectiveness of the sterilizer has already been examined for each sterilizer and is recorded in Non-Patent Document 1, but the sterilizer is being disinfected using the sterilizer, for example, home, lunch center Whether or not the bactericidal agent is prepared in consideration of whether the bactericidal spectrum of the bactericidal agent used for the species to be sterilized is appropriate in fresh food sales offices, hospitals, canteens, etc. It is extremely doubtful.

Furthermore, considering the combination of the bactericides, concentration adjustment, frequency of use, etc., bactericides are not prepared, and there are few places where the results after sterilization are verified.
Furthermore, there are few studies on the bactericidal effect of the combination of bactericides.
As a result, infections caused by bacteria and viruses such as the occurrence of food poisoning patients and influenza pandemics occur every year and precious human lives are lost.
Therefore, it is considered that knowing the decomposition mechanism and decomposition rate of the bactericide is extremely important for obtaining a safe and appropriate bactericidal effect.

The most widely used chemical disinfectant is disinfection with alcohol and hypochlorous acid. Alcohol has a decrease in alcohol concentration and a decrease in disinfection action due to evaporation, but the alcohol itself is stable and chemical. It is a substance that is difficult to change.
Therefore, there is no need to consider the reduction of the bactericidal effect due to alcohol decomposition.

On the other hand, as described above, hypochlorous acid is inexpensive and has a bactericidal effect even at a low concentration, but is naturally decomposed during storage with a substance that is unstable at room temperature.
Furthermore, it is known that decomposition is accelerated by the influence of light, heating, acid, metal, and the like.

Non-patent document 2, Non-patent document 3, Non-patent document 4, and Non-patent document 5 report the oxidation-reduction reaction, reaction mechanism, and reaction rate of hypochlorous acid in an aqueous solution.
1902 Mechanisms proposed by Foerster et al. In Non-Patent Document 2, Non-Patent Document 3, and Non-Patent Document 4 are shown in Chemical Reaction Formula (1) to Reaction Formula (5).

Foersterらによって提案された上記化学反応式に対して、Listerは、非特許文献4に塩素酸イオン(ClO3-)の生成する化学反応式(4)に対して、次亜塩素酸イオン(ClO-)の分解反応速度を求めることにより、下記の化学反応式(6)、(7)を提案した。

In contrast to the above chemical reaction formula proposed by Foerster et al., Lister describes a hypochlorite ion (ClO--) in contrast to the chemical reaction formula (4) produced by chlorate ion (ClO3-) in Non-Patent Document 4. The following chemical reaction equations (6) and (7) were proposed by determining the decomposition reaction rate of).

これらの化学反応は、pHにより反応速度が変化し、律速過程が異なるため初期濃度、pHにより殺菌効果も異なってくる。

In these chemical reactions, the reaction rate varies depending on pH, and the rate-determining process varies, so the bactericidal effect varies depending on the initial concentration and pH.

Ultimately, hypochlorous acid decomposes and changes to non-bactericidal substances such as O2, Cl- and ClO3-. In order to prevent such decomposition, it is necessary to reduce the HClO concentration in the aqueous solution in order to suppress the reaction rate of the equations (6) and (7). For this purpose, the equilibrium of the equation (3) is set to the right direction, that is, the alkali is in a high pH state where ClO- can exist stably.
That is, it becomes the manufacturing method of the sodium hypochlorite aqueous solution disinfectant of the prior art of dissolving a large amount of chlorine gas in concentrated alkali.

On the other hand, regarding the bactericidal action, for example, according to Non-Patent Document 5 reported by Iwasawa et al., As the bactericidal mechanism by hypochlorous acid, “the most effective pH region of strongly acidic electrolyzed water is pH 2.7. -At pH 3.5 and below pH 2.4, the generation of chlorine gas did not establish an equilibrium relationship between hypochlorous acid and hypochlorite ions, and the bactericidal effect was reduced. " It is concluded that the bactericidal effect by acid. Among them, Iwasawa et al. Considered chlorine gas, hypochlorous acid and hypochlorite ions generated at pH 2.4 or less as chemical species that act on fungal species, and the bactericidal action of hypochlorous acid is It is expressed by the oxidative action of hypochlorous acid.

However, it has not been clarified whether the optimum pH range depending on the bacterial species is due to the difference in the antioxidant activity of the bacteria or the difference in the structure of the bacteria. Moreover, it is not described in detail as a method actually used, such as dependence on hypochlorous acid concentration, the amount of fungicide used, and the contact time with bacteria.

Further, the production and sterilization effect of “strongly acidic electrolyzed water”, that is, “strongly acidic electrolyzed water ice”, was reported by Fujiwara et al. In Non-Patent Document 7, and Koseki et al. In this report, the sterilization by electrolyzed water ice and its factors are reported in detail.

However, although the relationship between the results of residual rate of effective chlorine concentration in frozen products and freezing (formation of ice crystal structure) is explained qualitatively, the description of quantitative tests and explanations, that is, the purpose of Fujiwara et al. There is no mention of “long-term retention of characteristics by freezing strongly acidic electrolyzed water”.

Practical bactericidal effects include not only redox effects but also cell membrane solubility, washing effects, osmotic pressure effects, adsorption effects, sustainability, etc. It is necessary to evaluate safety and practicality.
Bacteria prevention handbook, 1997, Gihodo Publishing Co., Ltd. Foerster, Muller, Z. Electrochem., 8, 8, 515, 633, 721 (1902) Foerster, Muller, Z. Electrochem., 9,171 (1903) Foerster, Muller, Z. Electrochem., 10, 781 (1904) MWLister, Can. J. Chem., 30, 879 (1952) Antibacterial and antifungal magazine, 30 (10), 635-643, 2002 Agricultural Machinery Society Hokkaido Branch Bulletin No.40, 51-56 (2000) Abstracts of Annual Meeting of the Agricultural Machinery Society Vol.61st, 451-452

The present invention provides a sterilization composition that is easy to disassemble for disinfection, and replaces the supplier with a sterilization composition suitable for the purpose based on the requirements obtained from the supplier. It was made for the purpose of supplying an appropriate amount of a highly safe sterilizing composition having a high activity and a low concentration with low alkalinity.

In addition, the currently used disinfectant is a high-concentration alkali to prevent the disinfectant from being decomposed, so that the disinfection rate is slow, and therefore there is a problem of using an excessive amount of disinfectant. In addition to safety, there are concerns about the environmental impact of discarding disinfectants containing high-concentration alkalis and large amounts of chlorine.
Improving such safety and environmental impact is also a problem that the present invention can solve.

The present invention obtains information on the purpose of use, the amount of use, etc. from the supplier by telephone or computer communication means from the supplier on the sterilizing composition that is easy to decompose on behalf of the supplier intended to sterilize, Prepare a sterilizing composition according to the requirements of the recipient, or synthesize it by electrolytic reaction or chemical reaction, using a computer that has input calculation formulas such as the rate of decomposition of the product and sterilizing power according to the conditions of the sterilizing composition. The present invention provides a sterilizing composition and a method for supplying the sterilizing composition, wherein an appropriate amount of a sterilizing composition having an appropriate concentration that clearly indicates an expiration date that can be sterilized in an active state is supplied to a recipient.

In general, chlorinated bactericides exert rapid bactericidal power against bacteria even at extremely low concentrations, and also have efficacy against viruses such as AIDS virus and hepatitis B virus, and have a broad antimicrobial spectrum. It is a disinfectant.

The mechanism of action is considered to be inhibition of intracellular enzyme reaction by free chlorine, denaturation of intracellular proteins, and inactivation of nucleic acids.
An active ingredient as a bactericidal effect is considered to be hypochlorous acid, and the bactericidal effect of the bactericide is supposed to change depending on the pH of the bactericidal solution.
The concentration of hypochlorous acid in the aqueous solution is high when the pH is low due to acid dissociation of hypochlorous acid, which is a weak acid, but when the pH is high, hypochlorous acid is high. The abundance ratio of ions increases.

Hypochlorous acid easily reacts in the presence of air, heat, light (ultraviolet light), organic matter, and heavy metals, and decomposes to reduce its sterilizing power.

In addition, considering that the generation of chlorine gas increases when the acidity of the solution is pH 4 or less, commercially available chlorine-based disinfectants are solutions in which high-concentration chlorine is dissolved in a strong alkaline aqueous solution (for example, hypochlorous acid). Sodium acid solution) is commercially available. Since these commercially available chlorine-based disinfectants are strong alkaline solutions, they invade proteins and are extremely dangerous if they adhere to fingers, skin, eyes and the like. Therefore, when handling, it is essential to wear protective equipment such as gloves and glasses. In addition, considering the decrease in effectiveness such as sterilization bleaching due to decomposition during storage period, high concentration (5-12%) chlorine is dissolved in strong alkaline solution. When mixed, highly toxic chlorine gas is generated, which may lead to death due to chlorine gas poisoning.

As pointed out in “Background Technology”, in order to overcome the problems of conventional technologies such as strong alkali high-concentration sodium hypochlorite and various electrolytic sterilizers, The disinfectant to be used is a highly active disinfectant composition, and information such as the effective period of the disinfectant composition is input in advance to a computer that receives an order from a supplier, and communication such as telephone, mail by computer, and the Internet The most suitable sterilizing composition is selected from the sterilizing composition input to the computer and considering the sterilizing power, the decomposition rate for each sterilizing composition condition, and the like. After determining and preparing the effective period, appropriate concentration, and appropriate amount, the sterilizing composition is supplied to the recipient and consumed within a state where high activity is maintained, that is, within the effective period. "I came to a new proposal for the method of supplying the sterilizing compositions and their fungicidal compositions.

For example, the highly active pH range of sodium hypochlorite solution, which is widely used among chlorinated disinfectants used as chemical disinfectants, depends on the type of bacteria to be sterilized. To pH12, preferably in the range of pH2 to pH10. As described above, the pH at which hypochlorous acid exerts the most bactericidal power is preferred, but a lower pH is preferred, but if it is pH 2 or less, the bactericidal effect is said to be an area having extremely strong bactericidal power in chlorine sterilization. Simultaneously, chlorine gas is generated, and the life as a disinfectant is short. When the pH is 10 or more, it acts as an oxygen disinfectant, and the abundance of hypochlorite ions is high and stable against decomposition, but the disinfecting effect is low.

The pH of the sterilizing composition can be set in an optimum region depending on the composition of the sterilizing composition to the supplier, delivery time, degradation rate, initial concentration, expiration date, and the like.
For example, it has been found that the pH dependency of the decomposition rate of hypochlorous acid (-dC / dt) is expressed by equation (8) as an approximate expression.

図1に、次亜塩素酸水溶液中の次亜塩素酸分解速度のpH依存性を示した。
分解速度より、殺菌力を有する保証可能な有効使用期間と初期濃度を決定することが出来る。

Figure 1 shows the pH dependence of the rate of hypochlorous acid decomposition in hypochlorous acid aqueous solution.
From the decomposition rate, it is possible to determine the guaranteed effective use period and initial concentration having sterilizing power.

That is, it is possible to determine the initial concentration and effective period of the sterilizing composition to be supplied.
Furthermore, due to the pH dependence of the decomposition rate of hypochlorous acid, the chemical species involved in the bactericidal action of hypochlorous acid are not limited to chlorine gas, hypochlorous acid, and hypochlorite ions considered by Ishizawa et al. In addition, by considering other species that can coexist thermodynamically and analytically, chemical equilibrium species derived from hypochlorous acid in each pH region, which were not explained by Ishizawa et al. The optimal pH and initial concentration for the bacterial species intended for sterilization are set by considering in detail that the sterilization effect differs depending on the reaction that acts, and the sterilization mechanism for bacteria by stable chemical species at each pH, Furthermore, by clearly indicating the effective period of the disinfectant calculated from the decomposition rate at the set pH, it has an adverse effect on the dangerous and wasteful environmental impact of strong alkalis and high-concentration chlorine disinfectants / bleaching agents currently on the market. It is possible to improve the fungicide.

The chemical species equilibrium relationship for hypochlorous acid is shown in Chemical formula 3.

化3に示した化学種の存在率は、pHに依存することが大きく、特定の菌種を殺菌する好適な化学種の存在率の多いpH領域を設定し、すなわちpHを制御することにより酸素殺菌剤として作用するpH領域もしくは塩素殺菌剤として作用するpH領域が有効であるかを調査すること及び各pHにおいて存在する個々の化学種の有する酸化還元電位を算出し、評価することにより効率的な殺菌が実施できる。

The abundance ratio of chemical species shown in Chemical Formula 3 is highly dependent on pH, and a pH range with a high abundance ratio of suitable chemical species to sterilize specific bacterial species is set, that is, oxygen is controlled by controlling pH. Efficient by investigating whether the pH range acting as a fungicide or the pH range acting as a chlorine fungicide is effective, and calculating and evaluating the redox potential of each chemical species present at each pH Can be sterilized.

For example, for S. aureus and S. epidermidis, efficiency is higher than about pH 3 in the coexisting region of HClO and ClO2- in which the chlorine region and oxygen region coexist, and in P. aeruginosa in the region of pH 3 or less in the chlorine region. In T. rubrum, it has been confirmed that efficient sterilization is possible in an oxygen region of pH 7.5 or higher, which is a ClO- (HClO), ClO2- region.

As described above, the pH of the sterilizing composition is controlled to an optimum pH depending on the bacterial species to be sterilized, and the initial concentration with respect to the life and effective period of the sterilizing composition under this pH condition is defined as described above. The problems of conventional disinfectants that are not only dangerous and wasteful of commercially available strong alkalis and high-concentration chlorine disinfectants / bleaching agents but also adversely affect the environment are specifically avoided.

The fungicidal composition prepared in accordance with the present invention in Example 1 (Example 1-1-Example 1-15) and a comparative example were prepared in the same procedure as the present invention, and sodium hydroxide was added to adjust the pH to pH 10.5. And 100% diluted hypochlorous acid-based disinfectant (sodium hypochlorite concentration is 8% effective chlorine concentration, sodium hydroxide concentration is 2%, and alkylamine oxide is contained). The results of examining the bactericidal effect of 5 types of bacteria were shown.

The bactericidal effect of the bactericidal composition of the present invention was prepared in accordance with the bactericidal composition of the present invention, and the bactericidal agent of the prior art in which chlorine was dissolved at a high concentration in Comparative Example 1 having a pH of 10.5 and a high concentration of alkali. It was shown that the bactericidal effect was exhibited in a short time at a hypochlorite concentration lower than that of Comparative Example 2 which was diluted and used at a safe pH of 9 or less.

From the above results, the sterilizing composition of the present invention containing at least hypochlorous acid as the sterilizing composition has hypochlorous acid in the sterilizing composition as hypochlorous acid, and the acid concentration is hypochlorous acid. It is preferable that the pH is 9 or less, which is a region where the sterilizing power is high.

However, when the acid concentration is pH 2.5 or less, the sterilizing power of hypochlorous acid is increased, but a lot of chlorine gas is generated. As can be seen from FIG. 1, the decomposition rate of hypochlorous acid is fast and it is used due to the chlorine odor. I can't stand it.

The results regarding these pH ranges are also supported by the relationship between the pH and the abundance ratio of hypochlorous acid. Using the stability constant of hypochlorous acid (pKa = 7.2), the abundance ratio of hypochlorous acid is calculated.
Equation (9) and Equation (10) were derived from the acid dissociation equilibrium (3) of hypochlorous acid, and the abundance ratio of hypochlorous acid at pH 9, pH 10, pH 12, and pH 14 is shown in Table 1.

本発明の殺菌組成物として少なくとも次亜塩素酸を含有する殺菌組成物では、次亜塩素酸の存在比率が、pH9で約2%存在するが、本発明の領域外では、pH10でも0.2%、pH12においては0.002%となりpH10以上では、殆ど次亜塩素酸として存在せず、次亜塩素酸イオン(ClO-イオン)として存在するため、次亜塩素酸として反応し、殺菌するには次亜塩素酸濃度が低いため、反応速度が遅くなることは明白である。

In the sterilizing composition containing at least hypochlorous acid as the sterilizing composition of the present invention, the abundance ratio of hypochlorous acid is about 2% at pH 9, but outside the range of the present invention, 0.2% even at pH 10; At pH 12, it is 0.002%. At pH 10 and above, there is almost no hypochlorous acid, and it exists as hypochlorite ion (ClO-ion). It is clear that the reaction rate is slow due to the low acid concentration.

Therefore, the pH range of the bactericidal composition of the present invention which contains at least hypochlorous acid as the bactericidal composition is pH2.5-pH9.

On the other hand, the standard for sodium hypochlorite is 5% or more effective chlorine and 2% or less free alkali according to the Japanese water standard JWWA K120 1999. Other sodium hypochlorite standards are also effective chlorine 12% or more, free alkali 0.5% -2.0% (2.0% or less), pH 12 or more, high pH to ensure the stability of hypochlorous acid It is said.

The concentration of hypochlorous acid when the effective chlorine is 12% and pH 12 is derived from the formula (10) from the formulas (11) and (12), and calculated by the formula (12) is 2 ppm.

同様に、有効塩素12%、pH9における次亜塩素酸濃度は、ほぼ1000倍の2000ppmとなる。一方、実施例1の結果より、殺菌効果は、次亜塩素酸の濃度が数ppm程度より得られているが、各菌種に対して安定した殺菌効果を得られる次亜塩素酸濃度は、50ppm程度であること、図1の次亜塩素酸の分解速度のpH依存性より、pH9における次亜塩素酸の分解速度が、pH12の約2倍であることから、本発明の殺菌組成物の次亜塩素酸濃度、殺菌組成物として少なくとも次亜塩素酸を含有する殺菌組成物の供給次亜塩素酸初期濃度C0(有効塩素濃度)を算出すると式(13)となる。

Similarly, the concentration of hypochlorous acid at 12% effective chlorine and pH 9 is almost 1000 times 2000 ppm. On the other hand, from the results of Example 1, the bactericidal effect is obtained from a concentration of hypochlorous acid of about several ppm, but the concentration of hypochlorous acid that provides a stable bactericidal effect for each bacterial species is Since the decomposition rate of hypochlorous acid in FIG. 1 is about 50 ppm and the decomposition rate of hypochlorous acid at pH 9 is about twice that of pH 12, the disinfecting composition of the present invention has When the hypochlorous acid concentration and the supply hypochlorous acid initial concentration C0 (effective chlorine concentration) of the sterilizing composition containing at least hypochlorous acid as the sterilizing composition are calculated, Equation (13) is obtained.

本発明の殺菌組成物における次亜塩素酸の含有量は、殺菌組成物のpH範囲を、pH2.5-pH9と次亜塩素酸の活性が高い領域とすることにより、供給次亜塩素酸の含有量(有効塩素濃度)を0.6%と低くすることが可能である。

The content of hypochlorous acid in the sterilizing composition of the present invention is such that the pH range of the sterilizing composition is pH 2.5-pH 9 and the region of high hypochlorous acid activity is high. The content (effective chlorine concentration) can be as low as 0.6%.

Even if the acid concentration is pH9, if the concentration of hypochlorous acid exceeds 1%, it becomes unusable due to chlorine odor. Even when the concentration of hypochlorous acid is 0.6% or less in terms of effective chlorine concentration, the activity of hypochlorous acid increases as the acid concentration increases, so the concentration is reduced appropriately in proportion to the improvement in the activity. Is possible. Moreover, when a chlorine smell is strong, it can weaken by changing the raw material of a disinfection composition. Since the relationship between the chlorine odor and the acid concentration varies depending on the type of acid used in the sterilizing composition of the present invention, additives such as surfactants and alcohols, or the phase state of the sterilizing composition by freezing, It is possible to appropriately select materials, treatment methods, etc. depending on the purpose of use of the sterilizing composition, such as whether priority is given to those with less odor, priority is given to sterilizing power, or priority is given to the life of the sterilizing agent.

The sterilizing composition of the present invention makes it possible to reduce the hypochlorous acid concentration to an effective chlorine concentration of 0.6% or less, so that not only the performance of the sterilizing agent and safety in handling are improved, but also resource waste. It becomes easy to prevent wastewater treatment of hypochlorous acid after use and reduce environmental pollution of residual hypochlorous acid.

Regarding the production and sterilization effect of “strongly acidic electrolyzed water”, that is, “strongly acidic electrolyzed water ice”, Fujiwara et al. Gave a lecture at the 50th Annual Meeting of the Agricultural Machinery Society of Hokkaido (1999) and the Agricultural Machinery Society of Hokkaido It is reported in branch bulletin No. 40, 51-56 (2000). Koseki et al. Reported on the sterilization by electrolyzed water ice and its causes in Abstracts of Annual Meeting of Agricultural Machinery Society Vol.61 ^st , 451-452.

In the above report, Fujiwara et al. Concluded that strongly acidic electrolyzed water was "changed in pH and ORP values after thawing, even if freezing and thawing conditions were changed." As for the relationship between the freezing temperature and the AC (effective chlorine) residual rate, it was found that “the lower the freezing temperature, the higher the AC residual rate in the strongly acidic electrolyzed water. The qualitative explanation of associating the rate results with freezing (formation of ice crystal structure) is described qualitatively, but a description of quantitative tests and explanations, that is, the objective of Fujiwara et al. There is no mention of “long-term retention”.

The AC concentration after thawing of the “strongly acidic electrolyzed water ice” produced by Fujiwara et al. Was calculated based on the AC residual rate from the fact that the strongly acidic electrolyzed water AC concentration before freezing was approximately 40-60 mg / L. When frozen, it is at most 40 mg / L.

In the present invention, the present inventors have found a novel and highly active sterilizing composition having a higher activity and higher concentration than the “strongly acidic electrolyzed water ice” implemented by Fujiwara et al.
Furthermore, from the results of the study of the present invention, in the aqueous solution, the lower the pH of the hypochlorous acid, the faster the decomposition rate. On the other hand, in the frozen product, the lower the pH, the slower the decomposition rate. It was found to be completely different from the pH dependence.

Therefore, for chemical species that are easily degraded in the low pH region, freeze the sterilization composition, freeze the high pH freeze, or freeze the high pH sterilization composition and the low pH sterilization composition. It is possible to eliminate the degradation problem of the low pH sterilizing composition by mixing and dissolving at a ratio that makes the pH of the sterilizing composition after the target dissolution the pH that works optimally for sterilization. It becomes.

Since “freezing and thawing” is a physical phenomenon, it is a well-known thermodynamic fact that there is no change in pH and ORP due to freezing if there is no change in the material balance.
Regarding the stability of the disinfectant due to freezing, it is necessary to examine the stability accompanying the change in state at the freezing stage, the stability of the frozen product after freezing, and the stability accompanying the change in state accompanying thawing. Is a very short time compared to the storage time, and the thawing phenomenon is a phenomenon in which entropy increases without any chemical change. There are no factors that accelerate the decomposition of chlorous acid.
Fujiwara et al. Also stated that "... no difference in the AC residual rate due to the difference in thawing rate was observed." Therefore, we investigated the stability of the ice during the freezing stage and the stability of the frozen objects after freezing.

Factors affecting the decomposition of the hypochlorous acid component accompanying changes in state during the freezing stage include components and concentrations, including solvents, in the sterilizing composition prior to freezing, acid concentrations that affect hydrogen bonding during ice formation, and maximum ice crystals The generation zone transit time T is considered.

The relationship between the pre-freezing sterilization composition concentration C0, the maximum ice crystal formation zone passage time T, the sterilization composition concentration C in freezing, and the acid concentration pH of the sterilization composition and the decomposition rate v is expressed by Equation (14) to Equation (19). Indicated.

これらの依存性を検討した結果を図2、図3、図4に示した。
図2は、pHの異なる種々の氷結前殺菌組成物濃度C0が、殺菌組成物溶液の分解速度ｖに及ぼす影響を示した(T1=T、T2=T/2、T3=T/4)。
図3に、ある氷結前殺菌組成物濃度における最大氷結晶生成帯通過時間に対して氷結時の分解速度依存性を示した。
図2、図3より、分解速度ｖは、氷結前殺菌組成物濃度C0及び最大氷結晶生成帯通過時間Tにそれぞれ約1次の相関があることが示された。
すなわち、式(15)、式(19)中n1は、n1=1、式(16) 、式(19)中n2は、n2=1であった。
氷結物中の次亜塩素酸の安定性に及ぼす氷結物中の次亜塩素酸初期濃度の影響を図4に示した。
氷結物中の分解速度は、大幅に低減し氷結物中の次亜塩素酸初期濃度依存性は、1次に近い値となった。
すなわち、式(17) 、式(19)中n3は、n3=1であった。
さらに、同様に氷結物中の次亜塩素酸分解に及ばす酸濃度pHの依存性を検討した結果を図5に示した。
図5から、氷結物中の次亜塩素酸分解速度に及ぼすpHの依存性は、水溶液中の分解速度と比較して極めて遅く、低pH側で分解速度は遅く、高pH側で速くなり、水溶液中の分解速度挙動とは逆の傾向を示し、pH変化に対してほぼ1次に近い依存性が得られた。
すなわち、式(18) 、式(19)中n4は、n4=1であった。

The results of examining these dependencies are shown in FIG. 2, FIG. 3, and FIG.
FIG. 2 shows the effect of various pre-freezing sterilizing composition concentrations C0 having different pHs on the decomposition rate v of the sterilizing composition solution (T1 = T, T2 = T / 2, T3 = T / 4).
FIG. 3 shows the decomposition rate dependence during freezing with respect to the maximum ice crystal formation zone passage time at a certain pre-freezing sterilizing composition concentration.
2 and 3, it was shown that the decomposition rate v has an approximately first-order correlation between the pre-freezing sterilizing composition concentration C0 and the maximum ice crystal formation zone passage time T, respectively.
That is, n1 in the formulas (15) and (19) was n1 = 1, and n2 in the formulas (16) and (19) was n2 = 1.
Fig. 4 shows the effect of hypochlorous acid initial concentration in freezing on the stability of hypochlorous acid in freezing.
The decomposition rate in the frozen product was greatly reduced, and the initial concentration of hypochlorous acid in the frozen product was close to the first order.
That is, n3 in the formulas (17) and (19) was n3 = 1.
Furthermore, FIG. 5 shows the results of examining the dependency of the acid concentration pH on the hypochlorous acid decomposition in the frozen product.
From Fig. 5, the pH dependence on the hypochlorous acid decomposition rate in frozen products is extremely slow compared to the decomposition rate in aqueous solution, the decomposition rate is slow on the low pH side, and fast on the high pH side, It showed a tendency opposite to the decomposition rate behavior in an aqueous solution, and a dependence close to the first order on the pH change was obtained.
That is, n4 in the formulas (18) and (19) was n4 = 1.

As a result, the lifetime of the sterilizing composition in the frozen product controls the initial concentration C0 of the pre-freezing sterilized composition, the maximum ice crystal formation zone passing time T, the sterilizing composition concentration C in the frozen product, and the pH of the sterilized composition. By doing so, the expiration date can be determined from the decomposition rate, and thus the sterilization composition can be used within a period of high sterilization efficiency by notifying the recipient of the effective period of the sterilization composition to be supplied.

As a result, it has been found that the lifetime of hypochlorous acid, which has been considered to be easily decomposed, is greatly extended by freezing. Therefore, the sterilizing composition and the frozen product whose pH of the sterilizing composition is controlled are supplied with the sterilizing composition in which the decomposition rate of the sterilizing component is controlled, so that the sterilizing composition is highly active and safe even at a low concentration. Can be supplied.

Moreover, it is also possible to mix and use the sterilized compositions of different sterilizing compositions having different pHs so that the desired pH is obtained upon thawing. Furthermore, the frozen product contains a plurality of sterilizing compositions having different pHs, different compositions, and different concentrations individually adjusted to be the pH of the sterilizing composition after thawing, the composition of the sterilizing composition, and the concentration. Production and use of icing with a icing layer consisting of layers or by dispersing icing containing a plurality of individually adjusted different pH, different composition and different concentrations of sterilizing composition in the icing It is also possible.
It is also effective to use an emulsifier or an encapsulating agent as a means for dispersing a plurality of frozen products.

The bactericidal spectrum of the bactericide has a bactericidal spectrum unique to each bactericide.
The sterilizing composition of the present invention maintains the sterilizing spectrum of each sterilizing agent as a sterilizing composition to be supplied, and also provides a sterilizing effect at a lower concentration than a single use by using it together. The present inventors have found that a cooperative effect, which is an effect that cannot be obtained by using individual fungicides alone, such as expanding the sterilization spectrum, is obtained.

That is, hypochlorous acid, benzalkonium chloride, benzethonium chloride, glutaraldehyde, orthophthalaldehyde, peracetic acid, dichloroisocyanuric acid, acetic acid, acetic anhydride, an organic acid having at least one carboxyl group in the molecule, Hydrogen peroxide, ozone, alcohol having 6 or less carbon atoms, polyvinyl alcohol (PVA), hydrochloric acid, carbonic acid, carbonate, surfactant, amine, polyvinylamine (PVAM) or amide chloride salt or hydrochloride, No. 4 The bactericidal composition of the present invention, in which the secondary ammonium salt is selected from two or more chloride salts, has the bactericidal agent as a composition, and a bactericidal effect can be obtained at a lower concentration than the individual use of each bactericidal agent. The present inventors have found that cooperative effects such as a sterilizing effect can be sustained and a sterilizing spectrum expanding effect can be obtained.

The joint effect is considered to be manifested by the combination of the individual characteristics of each component and the characteristics of other components. For example, a lower alcohol is a fungicide itself, but is a good solvent for inorganic and organic compounds, and it is easy to obtain a cooperative effect with another component fungicide due to the effect of reducing interfacial tension.
In order to obtain the effect, it is liquid at room temperature and it is necessary to reduce the interfacial tension. Therefore, the carbon number is preferably 6 or less.

However, for example, when ethanol is added to hypochlorous acid in order to enhance the bactericidal effect by hypochlorous acid, hypochlorous acid is decomposed and loses the bactericidal efficacy, but there is no problem with n-propanol. In addition, the bactericidal spectrum broadening effect was observed by using ethanol in combination with peracetic acid, or by using benzalkonium chloride or benzethonium chloride alone by using ethanol in combination with benzalkonium chloride or benzethonium chloride.

In addition, alcohols that share one or more hydroxyl groups and carboxyl groups in the molecule as hydrophilic groups have solubility and pH interference action of the solution, so that the pH of the bactericidal composition of the present invention can be stabilized. Useful. The number of carbons and the number of hydroxyl groups of the alcohol are determined in consideration of the purpose of use, the place of use, the solubility with the coexisting disinfectant, and the individual disinfection spectrum.

Suitable alcohols for the present invention are ethanol, propanol, IPA, ethylene glycol, propylene glycol, glycerin, sorbitol, amyl alcohol, polyvinyl alcohol, and the like, and also polyhydric alcohols such as gluconic acid and citric acid. Also suitable are hydroxy acids which are acids.

Some surfactants have a bactericidal action per se, like alcohol, but have the function of changing the physical properties of the bactericidal composition to more effectively bring out the bactericidal power. The surfactant effect required for the bactericidal composition includes detergency, foaming power, penetrating power, adsorbing power, etc. derived from interfacial tension reducing ability, but coexistence of pH, alcohol, organic acid, etc. However, it is difficult to uniquely specify the type of surfactant because of the change in surface active ability due to the above, but HLB12 or higher having high hydrophilicity is preferable if it is an ionic surfactant or a nonionic surfactant.
When the addition amount is 1% or less, the effect as the bactericidal composition of the present invention can be achieved.

In addition, when ethanol alone, which is used for alcohol sterilization, is used, the sterilizing power of ethanol is greatly affected by the concentration, and the sterilizing power is maximized at 70-80%, and even at 80% or more, 60% or less. Is known to decline rapidly.

Similarly, in the case of hypochlorous acid, it is known that the bactericidal power varies depending on the acidity.
In many commercially available “strongly acidic electrolyzed water” generators, the pH of the produced sterilizing water is often acidic.
This is because the pH standard of “strongly acidic hypochlorous acid water” that is a food additive is pH 2.7 or less, and “slightly acidic hypochlorous acid water” is pH 5.0 to pH 6.5. It is assumed that the sterilizing power of hypochlorous acid water is designed to be effective on the acidic side.

This is because hypochlorous acid exists as ClO- ions in a strong alkaline solution having a high pH and is stable but has little effect on bactericidal activity. Conversely, in an acidic solution having a low pH, It exists as chlorous acid HClO and chlorine Cl2, and it is presumed that it is unstable but strong sterilizing power can be expected.

However, as described above in detail, for S. aureus and S. epidermidis, about pH 3 or more in the coexistence region of oxyacids HClO and ClO2-, in P. aeruginosa, pH 3 or less in the chlorine region It has been confirmed that efficient sterilization is possible in this region, and that T. rubrum allows efficient sterilization at pH 7.5 or higher, which is the ClO- (HClO), ClO2- region. Thus, even with hypochlorous acid, the acidity at which the optimum bactericidal effect is obtained differs depending on the bacterial species.

On the other hand, glutaraldehyde is known to be activated in a very acidic range of pH 7.5 to pH 8.5.

Therefore, it is speculated that the bactericidal effect of the bactericide varies depending on the mechanism in which the bactericide acts on each bacterial species.

Furthermore, the concentration, pH, etc. often change depending on the situation when acting on the object to be sterilized. In the case of alcohol sterilization on wet kitchen tables, cooking utensils, and hands, the alcohol concentration is reduced and the sterilization power is lost due to dilution of the alcohol, and sufficient sterilization cannot be performed.

Similarly, commercially available strong alkaline hypochlorous acid disinfectants become weak alkalis even when diluted with a high alkali concentration, and not only a sufficient disinfecting effect is obtained, but also damage to eyes, skin, etc. due to alkali adhesion is a threat. It becomes.

Therefore, it is important to design a bactericidal composition that can maintain a concentration and pH at which a sufficient bactericidal effect can be obtained for bacterial species intended for bactericidal purposes.
In particular, in the case of hypochlorous acid, the bactericidal power and the life of the bactericide itself change due to the change in pH.

As described above with respect to the pH dependence of the lifetime of hypochlorous acid, the selection of a pH stabilizer, that is, a pH buffering agent is important for the bactericidal activity.
In selecting a buffering agent, a buffering effect can be obtained without changing the pH, and it is safe and does not inhibit (antagonistic) the bactericidal activity, but rather increases the bactericidal activity in addition to the effect of the main agent by a cooperative effect (cooperative effect). It is preferable to use a chemical that is non-corrosive, must not be contraindicated with coexisting reagents, and is excellent in environmentally friendly disposal.

Hypochlorous acid, carbonic acid, hydrogen peroxide, organic acid, and the like in the sterilizing composition of the present invention are weak acids and can have a buffering action by the coexistence of these conjugated bases.
The carbonate ion and hydrogen peroxide ion in the aqueous solution in the present invention are added or contained as carbon dioxide injection or carbonate compound, hydrogen peroxide, organic acid or organic acid salt, or electrolysis or solution of the sterilizing composition. Ozone oxidation generates oxygen ions of chloride ions such as hypochlorous acid, oxidation power of higher-order oxides such as carbonate ions and peroxocarbonic acid, and oxidation power of ozone, and acts as a conjugate acid. It has been found that by exhibiting a pH buffering action, the buffering effect as the sterilizing composition of the present invention is exhibited and can contribute to stabilization of sterilizing power.

For example, how the oxidation-reduction potential, which is a measure of the sterilizing power of hypochlorous acid, varies depending on the pH change, and the oxidation-reduction potential of hypochlorous acid coexists with the carbonate ion of the present invention. The results compared with the case of hypochlorous acid alone are shown in Example 6.

Here, in order to clarify the contribution of carbonate ions, in the examples, carbonate ions were supplied as carbonated water injection without adding carbonate carbonate, which is a salt of a conjugate base of carbonate, and degassing of carbon dioxide gas. The graphs (FIGS. 10 and 11) show the changes in pH and redox potential.

By coexisting carbonate ions, the pH decreases, the redox potential becomes noble, the carbon dioxide gas is degassed, the carbonate ions disappear, and the same pH and redox potential as in the comparative example in which no carbon dioxide is supplied. Indicated. From this, it is clear that the bactericidal power of the fungus composition can be controlled by controlling the carbonate ion concentration in the solution.

The sterilizing composition of the present invention having a certain pH and redox potential can be obtained by coexisting a conjugate base and adjusting the acid concentration.

Similarly, the bactericidal composition of the present invention having such a buffering action includes electrolytic hypochlorite benzalkonium chloride + sodium acetate + acetic acid, peracetic acid + hydrogen peroxide + sodium acetate + ozone, peracetic acid + sodium carbonate. It is clear that it is activated by electrolysis or ozone treatment, such as + ozone, peracetic acid + hydrogen peroxide + ozone.

Therefore, the present invention provides a sterilizing composition according to the present invention, that is, by selecting a component containing a weak acid of organic acids such as hypochlorous acid, carbonic acid, hydrogen peroxide and acetic acid as a component of the sterilizing composition. By controlling the pH range where the bactericidal effect is maximized, and by subjecting them to ozone treatment and electrolytic treatment, the bactericidal effect of the bactericidal composition is derived by generating oxides having bactericidal power. This is an effective method for maintaining the sterilizing power and extending the life of the sterilizing composition.

Needless to say, in order to practically and steadily implement this technique, it is effective to control the bactericidal power and the maintenance of the bactericidal composition life by the freezing method of the present invention.
The freezing technique is described in the above-mentioned freezing technique for the bactericidal composition of the present invention.

In addition, cationic surfactants such as benzalkonium chloride and benzethonium chloride, amphoteric surfactants, amine, polyvinylamine, amide or quaternary ammonium chloride salts have surface-active ability and have bactericidal ability. Yes.

However, these disinfectants are positioned as low level disinfectants.
Cationic surfactants and amphoteric surfactants such as benzalkonium chloride and benzethonium chloride, chloride salts of amines, polyvinylamines, amides or quaternary ammoniums contain chloride ions as constituent ions and are ionized in aqueous solution. Dissociates and liberates chloride ions.

A metal or metal oxide selected from platinum group elements as electrode active catalysts on an aqueous solution containing ionized and dissociated chloride ions based on titanium, which is an insoluble anode of known technology, ie, platinum, ruthenium Electrocatalyst comprising one or more of iridium, palladium, rhodium metal or these metal oxides, and electrode catalyst selected from metal oxide or carbon selected from titanium, tantalum, tin, zirconium, aluminum, silicon Benzalkonium chloride, benzethonium chloride, etc. containing the above-described chloride ions of the present invention using an anode formed by coating a coating made of a dispersion on a titanium substrate by a method such as electroplating, thermal decomposition, or sintering Cationic surfactants and amphoteric surfactants, amines, polyvinylamines, amides or quaternary ammonium When electrolytically oxidizing an aqueous solution of a compound such as a chloride salt of the above to produce hypochlorous acid, and producing the sterilizing composition or the frozen product of these sterilized composition or the frozen product, the pH and maximum ice crystals The sterilizing composition in which the concentration and the decomposition rate are controlled by controlling the formation zone transit time becomes the sterilizing composition of the present invention in which the intrinsic sterilization spectrum of these sterilizing agents before electrolysis is extended.

Specifically, the benzalkonium chloride aqueous solution, which is a low-level disinfectant, becomes a disinfectant corresponding to a high-level disinfectant having a bactericidal effect against Mycobacterium tuberculosis by performing the electrolytic treatment according to the above-described technology of the present invention. I found.

Furthermore, it discovered that an effect was acquired with the usage-amount smaller than the case where each disinfectant was used by the cooperative effect of each disinfectant.

In addition, when sterilizing individual sterilizing compositions with different pHs and mixing them to achieve the desired pH when thawing, not only greatly expands the sterilization spectrum of the sterilizing composition, Due to the cooperative effect of the agents, the effect was obtained with a smaller amount of use than when each fungicide was used alone.

In Example 7, 0.5% -alkyl polyaminoethyl glycine hydrochloride and 0.2% -benzethonium chloride aqueous solution were respectively electrolyzed, hypochlorite aqueous solution, 0.5% -alkyl polyaminoethyl glycine hydrochloride and 0.2% -benzethonium chloride aqueous solution with hypochlorous acid. The results of investigating the bactericidal action against Mycobacterium tuberculosis with 0.5% -alkylpolyaminoethylglycine hydrochloride and 0.2% -benzethonium chloride aqueous solution as a comparative example and the aqueous solution of the present invention whose pH was adjusted after adding acid were shown.

No effect was observed in the comparative example of 0.5% -alkylpolyaminoethylglycine hydrochloride and 0.2% -benzethonium chloride aqueous solution, but the effect was seen in Examples 7-1 to 7-6 of the present invention, and the low level. It became clear that the disinfectants alkyl polyaminoethylglycine hydrochloride and benzethonium chloride acted as high-level disinfectants.

Such effects include not only the sterilizing composition of the present invention shown in Example 7 but also the frozen product of these sterilized compositions or the pH and maximum ice crystal formation zone passage time when producing the frozen product. By controlling the concentration, the concentration and decomposition rate were controlled, and it was also confirmed in the bactericidal compositions of the present invention other than the examples that could not be described in the present specification.

In addition, peracetic acid, glutaraldehyde, and orthophthalaldehyde have a broad antibacterial spectrum, but have the disadvantages of being highly toxic and vapor irritating the mucous membranes and causing chemical burns due to liquid adhesion. doing.

In the case of glutaraldehyde, it is activated by making it weakly alkaline with a pH of 7.5 to 8.5 for activation. Polymerization proceeds by this activation.
As a result, the aldehyde group, which is an active site that brings about the bactericidal action of the glutaraldehyde molecule, is lost, and therefore the activity as a bactericidal agent is lost. The period of use of glutaraldehyde is about one month at most.

Regarding this problem, the vapor pressure of the disinfectant is reduced by freezing according to the present invention, or details are unknown, but glutaraldehyde and orthophthalaldehyde can be combined with polyhydric alcohol, polyvinyl alcohol or polyvinylamine. On the other hand, in the case of peracetic acid, it is possible to reduce the vapor pressure and slow down the polymerization rate by involving an equilibrium reaction such as esterification with alcohols and salt formation in the sterilizing composition system. As a result, the present invention has been found.

In Example 8, the pH of the bactericidal composition of the present invention prepared with glutaraldehyde and polyhydric alcohols sorbitol, polyvinyl alcohol and polyvinylamine and the 3% glutaraldehyde aqueous solution of Comparative Example was adjusted to pH 7.5-pH 8.5. Later, glutaraldehyde was analyzed to compare stability.

The glutaraldehyde content of Comparative Example 8-1 was 50% or less after about 30 days, but in Example 8-2, Example 8-3, and Example 8-4, it was about 60 days after the preparation. More than 70% activity remained.

Similarly, for the purpose of extending the lifetime of peracetic acid in Example 9, each treatment of ozone gas treatment-freezing treatment, ozone gas treatment-carbonic acid treatment, hydrogen peroxide treatment-alcohol addition-freezing treatment of the present invention was performed. Example 9-1-Preparing the disinfecting composition of the present invention of Example 9-5 and stabilizing the effect of the present invention by analyzing the peracetic acid storage sample of peracetic acid of Comparative Example 9-6 and the content of peracetic acid The results of examining the sex were shown. The peracetic acid content of the sample stored at room temperature with the peracetic acid of Comparative Example 9-6 decreased to 0.1% after 30 days, but in Example 9-1 to Example 9-5 subjected to the treatment of the present invention, 0.8% The residual rate of peracetic acid was as high as% -1.8%, and it was found that it can be used as a disinfectant after 30 days.

In the sterilizing composition of the present invention, an electrolytic anodizing reaction or an oxidizing reagent produced by the anodizing reaction is used. Therefore, in this case, the raw water of the sterilizing composition of the present invention includes, for example, an electrolytic anodic reaction, an oxidizing agent such as hypochlorous acid produced by this anodic reaction, or an oxidizing agent such as ozone, peracetic acid, and hydrogen peroxide. In order to prevent the formation and diffusion of organic halides such as trihalomethane and dioxins that are carcinogenic substances generated by chemicals, the raw material water is subjected to activated carbon treatment, boiling treatment and ozone treatment in advance to remove organic matter. It is necessary to keep.

The “bactericidal composition and supply method” of the present invention freezes a short-lived bactericidal agent such as a chlorine-based bactericidal agent and an oxygen-based bactericidal agent used in a chemical disinfection method, chemical equilibrium, etc. The supply concentration by supplying a highly activated disinfectant by extending the disinfection spectrum by extending the lifespan by introducing the pH, activating based on the proper use of pH, increasing the level of the low-level disinfectant by introducing the electrolysis method Compared to conventional strong alkali / high concentration hypochlorous acid disinfectants, electrolytic sterilizers, etc., there is no risk of chemical accidents or explosions, and handling is easy and chemical. Not only can suppliers who have no knowledge be able to safely use the environment-friendly sterilizing composition, but also the rate of decomposition of the supplied sterilizing composition by the supply method of the present invention. Is the supplier Confirmation of management and effectiveness of the disinfectant composition for supplying various conditions such as the antiseptic compositions based on results calculated by the computer is grasped is facilitated. The “bactericidal composition and method for supplying the same” of the present invention using a communication system using telephones and computers can easily, safely and quickly respond to infectious diseases that are rapidly internationalized. Be expected.

Examples of the bactericidal composition of the present invention are described below.
The present invention is not limited to the following examples.
In particular, even if (freezing) is not described, considering the decomposition rate of the sterilizing composition depending on the purpose of use, freezing the sterilizing composition to control the initial concentration, and controlling the pH have already been explained. Needless to say in detail.
Hypochlorous acid-acetic acid + sodium alkyl ether sulfate, hypochlorous acid + benzalkonium chloride + carbonic acid + sodium carbonate, glutaraldehyde (pH 8) + PVA, glutaraldehyde (pH 8) + sorbitol + sodium alkylbenzene sulfonate, ortho Phthalaldehyde + IPA + lauryl N, N-dimethylaminobutyric acid, hypochlorous acid + peracetic acid, hypochlorous acid + acetic acid + benzethonium chloride, electrolytic hypochlorite benzalkonium chloride + acetic acid, hypochlorous acid + hydrochloric acid + Sodium alkylbenzenesulfonate, hypochlorous acid + benzalkonium chloride, hypochlorous acid + acetic acid, hypochlorous acid + n-propanol + peracetic acid, hypochlorous acid + gluconic acid + allyl alcohol, hypochlorous acid + Sodium carbonate + alkylamine oxide, hypochlorous acid + citric acid, hypochlorous acid + tartaric acid + ethylene glycol, (peracetic acid (40%) + hydrogen peroxide) (ice ), (Acetic anhydride + hydrogen peroxide + ozone) (freezing), (peracetic acid + ozone + carbonic acid) (freezing), benzethonium chloride + hydrochloric acid + hypochlorous acid, (peracetic acid + hydrogen peroxide) (freezing), Hydrogen peroxide + benzethonium chloride, peracetic acid + ethanol, electrolytic hypochlorite benzethonium chloride + acetic acid + sucrose laurate, glutaraldehyde + sodium citrate + polyvinylamine, hypochlorous acid + acrinol, (orthophthalaldehyde + IPA) (freezing), (orthophthalaldehyde + sodium alkylbenzene sulfonate) (freezing), hypochlorous acid + dichloroisocyanuric acid, dichloroisocyanuric acid + sodium carbonate, electrolytic hypochlorite benzethonium chloride + acetic acid, electrolytic secondary Chlorinated oxyacrinol hydrochloride + acetic acid, electrolytic hypochlorite benzalkonium chloride + acetic acid + sodium alkyl ether sulfate, electrolytic hyposalt Benzethonium chloride + acetic acid + polyoxyethylene sorbitan monooleate (20EO), electrolytic hypochlorinated tetradecyldiaminoethylglycine hydrochloride + acetic acid + polyoxyethylene (60EO) hydrogenated castor oil, electrolytic hypochlorite dodecylguanidine Examples include hydrochloride + hydrochloric acid, hypochlorous acid + hydrochloric acid + sodium lauryl sulfate, hypochlorous acid + glycine.

FIG. 12 shows a conceptual flow diagram of supplying the bactericidal composition of the present invention.
Here, only the concept is described, and since the sterilization composition specification, the product form, the recipient information, and the like are changed depending on the purpose of use, no particular details are described. Therefore, the present invention is not limited to the conceptual diagram 12. Further, the technology of the present invention will be described in detail by way of examples.

After the sterilizing composition of the present invention was produced according to the following procedure, the sterilizing effect was tested.
Titanium expanded metal dipped in hot oxalic acid, pickled and washed with water is used as an electrode substrate, and a titanium metal electrode coated with ruthenium oxide and iridium oxide as an electrode catalyst is manufactured on the electrode substrate by pyrolysis. The metal electrode is the anode, the titanium expanded metal substrate is the cathode, and a Nafion membrane made by DuPont, which is a cation exchange membrane, is used between the positive and negative electrodes, and 0.5% -saline is used as the electrolyte, and the membrane is electrolyzed by a DC power source. As an anolyte, an aqueous sodium hypochlorite solution containing an effective chlorine concentration of about 2000 ppm was produced.
Next, a sample of the bactericidal composition of the present invention was manufactured based on the aqueous sodium hypochlorite solution. Table 2 shows the sample contents.

殺菌効果：
試験方法 1.各試験菌の菌液接種後の理論菌数が1ml当たり約１０^５〜１０^６個となるように試供品100mlに対し菌液1mlを添加し、撹拌後、室温で作用を開始した。
2.試験開始5,15,30,60,120秒後の各菌の生菌数を菌数測定用培地を使用した混釈平板法(37℃、2日間培養)により測定し、各菌の不検知時間により殺菌効果を示した。
殺菌効果結果を表3に示した。

Bactericidal effect:
Test method 1. Add 1 ml of the bacterial solution to 100 ml of the sample so that the theoretical number of bacteria after inoculation of each test bacteria is about 10 ⁵ to 10 ⁶ per ml. did.
2. The number of viable bacteria of each bacterium 5, 15, 30, 60, 120 seconds after the start of the test was measured by the pour plate method (cultured at 37 ° C for 2 days) using a culture medium for microbial count. The bactericidal effect was shown by time.
The results of the bactericidal effect are shown in Table 3.

表3の結果より、本発明が、従来技術より殺菌剤の濃度が低濃度で且つ安全なpH9以下で殺菌効果が短時間で発揮されることが示された。

From the results in Table 3, it was shown that the bactericidal effect of the present invention is exhibited in a short time at a pH of 9 or less, which is a safer concentration of the bactericide than in the prior art.

A platinum-plated electrode in which a titanium expanded metal substrate was used as an electrode base material and a platinum plating coating with a thickness of about 0.5 μm was applied to the titanium base material by electroplating was produced.
Using the platinum-plated electrode as an anode, a titanium expanded metal immersed in hot oxalic acid, washed with water and washed with water as a cathode, 1% -saline solution was energized with a DC power source, electrolessly separated, and an effective chlorine concentration of about 2000 ppm. The containing hypochlorous acid aqueous solution was produced.
Next, a sample of frozen matter was produced from the hypochlorous acid aqueous solution based on the following sterilizing composition of the present invention. The frozen samples were stored frozen for 1 month, 2 months, and 3 months, then thawed and examined for changes in effective chlorine concentration and pH. In addition, these results were compared with samples stored at room temperature without freezing. Table 4 shows the sample contents.

保管試験結果：
図6に実施例2の保管方法による次亜塩素酸の安定性の関係を示した。
図7に実施例2の氷結保管によるpH経時変化の関係を示した。
さらに、添加剤を含有する本発明の試料を調製し、室温保管と氷結保管の有効塩素濃度とpHの関係を調査した。試料内容を表5に示した。

Storage test results:
FIG. 6 shows the relationship of stability of hypochlorous acid according to the storage method of Example 2.
FIG. 7 shows the relationship of changes with time in pH due to freezing storage in Example 2.
Furthermore, a sample of the present invention containing an additive was prepared, and the relationship between the effective chlorine concentration and pH in room temperature storage and ice storage was investigated. Table 5 shows the sample contents.

保管試験結果：
図8に実施例2の保管方法による次亜塩素酸の安定性の関係を示した。
図9に実施例2の氷結保管によるpH経時変化の関係を示した。
上記結果より、pHには変化が観られなかったが、有効塩素濃度に関しては、氷結保管による保管方法が、氷結を行わずに室温保管を行った保管方法より長期間安定であることが明白である。

Storage test results:
FIG. 8 shows the stability relationship of hypochlorous acid by the storage method of Example 2.
FIG. 9 shows the relationship of changes with time in pH due to freezing storage in Example 2.
From the above results, there was no change in pH, but regarding the effective chlorine concentration, it is clear that the storage method by freezing storage is more stable than the storage method by storing at room temperature without freezing. is there.

In the same manner as in Example 1, a titanium expanded metal was used as a substrate, and a titanium metal electrode on which the electrode catalyst was coated with platinum and iridium oxide among platinum group elements by a thermal decomposition method was formed on the titanium substrate. Using as a cathode, an aqueous solution containing sodium chloride and sodium carbonate was electrolyzed with a DC power source to prepare a bactericidal composition having an effective chlorine concentration of 1060 ppm and a pH of 9.10.
On the other hand, an aqueous solution containing 0.1% -ABS · Na and a 0.2M HCl aqueous solution were used to prepare a solution having the following mixing ratio and frozen. Further, the above bactericidal compositions were frozen and stored separately, and after 10 days, they were mixed and thawed so as to have the following mixing ratio. As a comparative example, a mixed solution having the same composition as in the example was prepared and stored at room temperature, and the pH and effective chlorine concentration after 10 days were measured in the same manner as in the example.
Table 6 shows the mixing composition ratio of the samples of the bactericidal composition examined.

10日後のpHと有効塩素濃度(ppm)の測定結果を表7に示した。

Table 7 shows the measurement results of pH and effective chlorine concentration (ppm) after 10 days.

表7より、本発明の氷結保存による殺菌組成物試料の有効塩素濃度に高い残存率の結果が得られたことが判る。

From Table 7, it can be seen that a result of a high survival rate was obtained in the effective chlorine concentration of the sterilizing composition sample by freezing preservation of the present invention.

In the same manner as in Example 3, an iced product of the sterilizing composition of the present invention was produced.
This was carried out in the same manner as in Example 3, except that a commercially available concentrated hypochlorous acid solution in a concentrated alkaline solution and acetic acid were used as the acid.
Sodium hypochlorite was used by diluting sodium hypochlorite (NC-S) manufactured by Tsurumi Soda Co., Ltd. having an effective chlorine concentration of 12.6% and pH 12.7. The dilution rate of sodium hypochlorite was adjusted to 500 times, and 20 times the diluted solution of acetic acid was prepared, and the mixing ratio was changed to adjust the pH. Table 8 shows the sample contents.

10日後のpHと有効塩素濃度(ppm)測定結果を表9に示した。

Table 9 shows the measurement results of pH and effective chlorine concentration (ppm) after 10 days.

表9より、実施例3と同様に、本発明の氷結保存による殺菌組成物の有効塩素濃度に高い残存率の結果が得られたことが判る。

From Table 9, it can be seen that, as in Example 3, a result of a high residual rate was obtained in the effective chlorine concentration of the sterilizing composition by freezing storage of the present invention.

Using a sodium hypochlorite (NC-S) manufactured by Tsurumi Soda Co., Ltd. and an acetic acid aqueous solution, an antibacterial composition of the present invention having an effective chlorine concentration of 482 ppm, pH 7.3, ORP 900 mV is produced, and a sample of the bactericidal composition is prepared. Freezing.
In the same manner, 4900 ml of an aqueous solution was prepared by diluting 10 ml of NC-S. After freezing the sample of the sterilizing composition, 100 ml of acetic acid was poured around the frozen matter, and freezing was effected by freezing acetic acid on the outer layer. After making the product, it was crushed. The ground frozen product was thawed, and the effective chlorine concentration, pH, and ORP were measured, and compared with the results of the sample that had been mixed frozen and thawed. The results are shown in Table 10.

表10より、どちらの試料からもほぼ同様な結果が得られた。

From Table 10, almost the same results were obtained from both samples.

A titanium metal electrode coated with platinum and iridium oxide as an electrode catalyst was used as an anode and a cathode, an aqueous solution containing 25 g / L of sodium chloride with a DC power source and pH 3 with hydrochloric acid was electrolyzed through a membrane, and effective chlorine A hypochlorous acid aqueous solution having a concentration of 3930 ppm was prepared.
The hypochlorous acid aqueous solution was diluted with carbonated water and water, respectively, and the time-dependent changes in pH and redox potential (ORP) after dilution were measured.
The results are shown in FIGS.

The pH value of the sample diluted with carbonated water dropped to pH 5.4 immediately after dilution. At the same time, the ORP value showed a value of 1000 mV or more.
After that, carbon dioxide gas is released to the atmosphere over time, and the pH value rises as the carbonic acid concentration in the solution decreases, and at the same time the ORP value decreases, and the pH and ORP of the same value as the comparative example diluted with water The value is shown.

In the same manner as in Example 1, a metal electrode coated with platinum-iridium oxide as an electrode catalyst was produced on a titanium expanded metal substrate by a thermal decomposition method, and the electrodes were used as an anode and a cathode, and a DC power source was used. A 0.5% -alkylpolyaminoethylglycine hydrochloride aqueous solution and a 0.2% -benzethonium chloride aqueous solution are respectively subjected to diaphragm electrolysis, the pH of the electrolytic solution containing an effective chlorine concentration of about 100 ppm produced at the anode is adjusted, and the bactericidal composition (7 -1 to 7-4) were produced.
On the other hand, using sodium hypochlorite (NC-S) manufactured by Tsurumi Soda Co., Ltd., hypochlorous acid aqueous solution of the present invention containing alkylpolyaminoethylglycine hydrochloride and benzethonium chloride, respectively (7-5, 7-6) Was prepared. The pH of each aqueous solution was adjusted with hydrochloric acid and acetic acid.
As comparative examples, 0.5% -alkylpolyaminoethylglycine hydrochloride aqueous solution and 0.2% -benzethonium chloride aqueous solution (7-7, 7-8) were prepared.
Using these bactericidal solutions, a bactericidal effect test was carried out on M. tuberculosis in the same manner as in Example 1 to investigate the effectiveness of the bactericidal agent. Table 11 shows the sample contents.

殺菌効果を、殺菌組成物試料に関し、10分以内に菌が死滅した試料を(-）、生存していた試料に（+）で表した。表12に殺菌効果結果を示した。

The bactericidal effect was expressed as (−) for samples in which bacteria were killed within 10 minutes and (+) for samples that were alive, with respect to the bactericidal composition samples. Table 12 shows the results of the bactericidal effect.

表12の結果より、両性界面活性剤は、低水準消毒剤であるが、本発明により両性界面活性剤の塩化物塩や塩酸塩を直流電解し、有効塩素濃度を付与することにより、あるいは次亜塩素酸を共存させることにより広範囲の殺菌スペクトルを有する高水準消毒剤となりうることが確認された。

From the results shown in Table 12, the amphoteric surfactant is a low-level disinfectant. However, according to the present invention, the chloride salt or hydrochloride of the amphoteric surfactant is subjected to direct current electrolysis to give an effective chlorine concentration, or the following. It was confirmed that the coexistence of chlorous acid can be a high-level disinfectant having a wide sterilization spectrum.

An aqueous solution containing 3% -glutaraldehyde, 6% -sorbitol, 0.5% sodium alkyl ether sulfate and 3% glutaraldehyde of the present invention, 3% polymerization degree, 5% fully saponified polyvinyl alcohol, bis- An aqueous solution containing 1% (2-hydroxyethyl) laurylamine oxide and an aqueous solution containing 3% glutaraldehyde and 5% polyvinylamine were prepared.
As a comparative example, a 3% -glutaraldehyde aqueous solution was prepared.
Buffers were added to these aqueous solutions to adjust the pH to a range of 7.5-pH8.5.
Using these pH-adjusted solutions, glutaraldehyde was analyzed, and changes with time in glutaraldehyde content were investigated. Table 13 shows the sample contents.

グルタルアルデヒド含有量の測定結果を表14に示した。

The measurement results of glutaraldehyde content are shown in Table 14.

表14の結果より、グルタルアルデヒドの殺菌作用に対する有効濃度を1.5%とすると、比較例の有効期限は30日以下であるが、本発明の方法では、60日以上の有効期間となった。

From the results shown in Table 14, when the effective concentration for bactericidal action of glutaraldehyde is 1.5%, the expiration date of the comparative example is 30 days or less, but in the method of the present invention, the effective period is 60 days or more.

Samples of examples of the present invention and samples of comparative examples shown in Table 15 were prepared, the content of peracetic acid was analyzed, and changes with time were investigated. The frozen sample was thawed immediately before analysis and subjected to analysis.

過酢酸濃度の測定結果を表16に示した。

Table 16 shows the measurement results of the peracetic acid concentration.

表16の過酢酸濃度の経時変化結果より、本発明の方法により、殺菌剤の延命化が可能となることが明白となった。

From the results of time-dependent changes in peracetic acid concentration in Table 16, it became clear that the method of the present invention can extend the life of the bactericide.

The graph which shows the pH dependence of the hypochlorous acid decomposition | disassembly rate in hypochlorous acid aqueous solution. The graph which shows the initial concentration dependence of the hypochlorous acid decomposition rate at the time of freezing. The graph which shows the maximum ice crystal formation zone passage time dependence of the hypochlorous acid decomposition rate at the time of freezing. The graph which shows the initial concentration dependence of the hypochlorous acid decomposition | disassembly rate in icing material. The graph which shows the pH dependence of the hypochlorous acid decomposition | disassembly speed | rate in icing material. 6 is a graph showing the relationship of stability of hypochlorous acid according to the storage method of Example 2. 6 is a graph showing the relationship of changes with time in pH due to freezing storage in Example 2. 6 is a graph showing the relationship of stability of hypochlorous acid according to the storage method of Example 2. 3 is a graph showing the relationship of changes with time in pH due to freezing storage in Example 2. 6 is a graph showing the relationship of changes with time in pH with and without carbonic acid addition in Example 6. 6 is a graph showing the relationship of ORP change with time depending on the presence or absence of carbonic acid addition in Example 6. The supply flow conceptual diagram of the bactericidal composition of this invention.

Claims (7)

In the method of supplying a sterilizing composition, a supplier who has received a supply request from a supplier is stuffed into a dedicated container mutually agreed upon, or a recipient of a sterilizing composition packed in a dedicated container of the supplier. Deliver and supply to a place where a supplier uses it, or supply it to a container installed at a place where the supplier uses, and collect the used container after the supplier uses the sterilizing composition. A method for supplying a sterilizing composition, characterized in that the sterilizing composition is supplied again in a container, or the unused sterilized recovered recovered sterilizing composition is reactivated and supplied. In the delivery method of the sterilizing composition, when the supplier receives a request for supplying the sterilizing composition by telephone, a mobile phone or a computer or by means of communication on the Internet from the recipient, bacteria or viruses to be sterilized Selection of the types and combinations of the drugs that make up the sterilizing composition that is effective for the sterilization composition, the decomposition rate and delivery time of the sterilizing composition, and the pH and redox potential that can maintain the activity requested by the supplier from the delivery time The sterilizing composition concentration and the required amount are calculated by a computer, and the highly active sterilizing composition is supplied in a container in which the calculated effective maintenance period is specified. A method for supplying a sterilizing composition. In the delivery method of the sterilizing composition, investigate the effect of the sterilizing composition to be supplied, report the survey result to the recipient, and continuously supply the sterilizing composition while investigating the effect of the sterilizing composition. The method for supplying a bactericidal composition according to claim 1 or 2, wherein The sterilizing composition to be supplied contains hypochlorous acid, benzalkonium chloride, benzethonium chloride, glutaraldehyde, orthophthalaldehyde, peracetic acid, dichloroisocyanuric acid, acetic acid, acetic anhydride, and at least one carboxyl group in the molecule. Has organic acid, hydrogen peroxide, ozone, alcohol having 6 or less carbon atoms, polyvinyl alcohol, hydrochloric acid, carbonic acid, carbonate, surfactant, amine chloride salt, polyvinylamine chloride salt, amide chloride salt A sterilizing composition composed of two or more selected from quaternary ammonium chloride salts, or an ice solution thereof or an aqueous solution of a chloride salt of the sterilizing composition by a direct current power source, and hypochlorite By controlling the pH and the maximum ice crystal formation zone transit time when producing the sterilized composition or these frozen products or the frozen products, The method of supplying the sterilizing compositions and their fungicidal composition according to claims 1, 2, 3, characterized in that a frost fungicidal compositions controlled solution rate. The supplied sterilizing composition contains at least one hypochlorous acid having an effective chlorine concentration of 0.6% or less as a sterilizing agent, and hypochlorous acid as a sterilizing agent within a pH range of pH 2.5 to pH 9. The sterilization composition to be actuated or the sterilization composition to which hypochlorous acid acts as a sterilizing agent in the pH range of pH 2.5 to pH 9 is icing, or the icing substance is icing the alkaline sterilizing composition. In addition, the freeze product of the sterilization composition prepared by thawing the frozen product obtained by freezing the acidic sterilization composition at the same time, and the thawed sterilization composition acts as a bactericide in the range of pH2.5-pH9, or these When producing frozen products, the concentration and decomposition rate are controlled by controlling the pH and the maximum ice crystal formation zone transit time, and the prepared frozen composition is a frozen product. , 3, 4 and the sterilization composition and their sterilization set The method of supplying the goods. The frozen sterilized composition consists of multiple layers containing different pH, different composition, different concentration of sterilizing composition individually adjusted to the pH, composition and concentration of the desired thawing sterilizing composition 6. The sterilized composition frozen product according to claims 1, 2, 3, 4, and 5, and a method of supplying the sterilized composition, wherein the sterilized composition frozen product has a frozen layer. The water used in the sterilizing composition was treated so as not to generate carcinogenic organic chlorinated substances by oxidizing agents such as hypochlorous acid, hydrogen peroxide, ozone, peracetic acid, percarbonate or salts thereof. The disinfecting composition according to claims 1, 2, 3, 4, 5, and 6, and a method for supplying the disinfecting composition, wherein the disinfecting composition is water.

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