JP5794954B2 - Disinfectant manufacturing method - Google Patents

Description

The present invention relates to a disinfecting solution produced by diluting a sodium hypochlorite high-concentration stock solution with water and a method for producing the same, and more particularly to a disinfecting solution producing method capable of withstanding long-term storage.

  For disinfection of fingers, clothes, door knobs, furniture, cooking utensils and other items, a disinfectant obtained by diluting sodium hypochlorite with water is often used and has been commercialized for a long time. This disinfectant is usually prepared by diluting a stock solution of sodium hypochlorite (an aqueous solution having an effective chlorine concentration of about 1 to 12%) with water to an effective chlorine concentration of 0.02 to 0.1% (1000 mg / L). Spread to the extent. In addition, there are some to which a small amount of a surfactant is added. In small baths such as public baths and aqua park facilities, pharmaceutical preparations that are diluted about 10 times to about 1% (10,000 mg / L) and the flow rate of the chemical injection pump is easily adjusted are frequently performed. Yes.

  Since the sodium hypochlorite stock solution usually has residual alkali of about 0.3% in order to avoid generation of chlorine gas in the distribution stage, most of them are strongly basic with a pH exceeding 10. In addition, the sodium hypochlorite stock solution itself is not always stable because it is strongly basic and cannot withstand long-term storage. Therefore, it is recommended to use it as soon as possible after preparation.

In addition, when the sodium hypochlorite stock solution is diluted, fine particles such as metal oxides contained in the diluted water or adhering to the container have many pores that increase the adsorption surface area. It is a well-known fact that oxygen is generated by decomposing chlorous acid as well as hydrogen peroxide.
Therefore, the decrease in the effective chlorine concentration that becomes conspicuous with the passage of time is considered to be because hypochlorous acid generates oxygen and decomposes it, or converts it into chloric acid (the same ion in water). Moreover, the increase in pH accompanying the use of a strong basic disinfectant also causes a decrease in sterilizing power.
Therefore, conventionally, as described in Patent Document 1, attempts have been made to add bromide to an aqueous sodium hypochlorite solution to improve its stability.

Japanese Patent Laid-Open No. 01-164701 JP 2002-249407 A Japanese Patent Laid-Open No. 10-81610 International Publication No. 2006-057311 JP 2002-363017 A

  However, in the technique described in Patent Document 1, although a certain effect is recognized with respect to the stability of hypochlorous acid itself at a high concentration of sodium hypochlorite stock solution level, the stability of the disinfectant solution diluted with the stock solution is improved. Is known to have no effect.

  In the tap water disinfection stock solution, for example, if it is produced at a slightly high concentration of 12 to 13% to guarantee an effective chlorine concentration of 12% and consumed immediately upon arrival, the intended purpose can be achieved. However, with the disinfecting solution having the effective chlorine concentration of 0.02 to 0.1%, it is very rare to consume the entire amount immediately, and in some cases, the storage period may be more than half a year. is there. The farther from the field of use that specializes in disinfection and consumes a large amount of disinfectant, there is an unavoidable tendency for the disinfectant storage period to become longer and expire.

  In recent years, virus-related diseases such as norovirus, rotavirus, and new influenza virus have been increasing, while legionella infections associated with larger amoeba and protozoan infections such as Cryptosporidium or Giardia, which are larger than previously known pathogens Diseases are reported to the country by doctors in line with the enforcement of the law, and this disease is also increasing.

The disinfectant contains various components, but the top of disinfectants that are effective regardless of the size of pathogens, from viruses, bacteria, amoeba to protozoa, is chlorinated. Hypochlorous acid (HOCl) is used as the chemical. ) And hypochlorite ions (OCl ⁻ ) as the main component will dominate the market. This is because the efficacy of alcohol-based or quaternary ammonium salt-based disinfectants is limited to bacteria.

On the other hand, in industries that consume a large amount of sodium hypochlorite solution such as water purification plants, chlorate ions (ClO ₃ ⁻ ), which increase in proportion to the decrease in available chlorine, are regarded as a problem in terms of toxicity. In the water quality standard, regulation was set to 0.6 mg / L or less. Therefore, each facility has begun measures such as installing a cooling device for the purpose of low-temperature storage and systematic early consumption.

Regardless of the effective chlorine concentration of the disinfectant, the concentration of chlorate ions increases with time as the pH rises above 6.0. Of course, it has already been found that the gradual increase in the chlorate ion concentration increases as the amount of light irradiated to the disinfectant increases and as the solution temperature increases.
Through the inventor's long-standing research, disproportionation reaction in which the outer shell electrons of three molecules of hypochlorite ion move slowly and convert into one molecule of chlorate ion and two molecules of chloride ion (Cl ⁻ ). It has also been found that it will expire.
On the other hand, if the pH of the sodium hypochlorite solution is set to the acidic range, the formation of chlorate ions can be suppressed, but if the pH buffering power of the disinfectant solution is weak, the pH will drop suddenly when mixed with a strong acid and chlorine gas will be lost. The risk of falling below 4.0, the pH boundary that generates (Cl ₂ ), increases. Therefore, it is not necessary to neutralize the chlorinating agent so that it becomes weakly acidic.

A known technique for producing a weakly acidic disinfectant with an increased pH buffering capacity for the purpose of reducing the risk of chlorine gas generation is a method of adding a disinfectant to the pH buffer. The buffer solution having a pH of 5 to 6 is prepared by mixing an aqueous solution of aromatic potassium hydrogen phthalate (C ₆ H ₄ (COOK) (COOH)) and sodium hydroxide (NaOH) in accordance with a known specification, It is common to prepare.

  However, when free effective chlorine such as hypochlorous acid is present in the disinfecting solution, there are overwhelmingly many cases where effective chlorine as a medicinal component disappears when the conventional technique is applied as it is. Aromatic carboxylic acids are usually expensive, and instead of being unsaturated, that is, fumaric acid having a double bond in the molecule (HOOCCH = CHCOOH) or the like, it is oxidized by effective chlorine even if it becomes cheap. Cannot fulfill its purpose. These characteristics are well known. Nevertheless, in the field of disinfectant-related art, there has been a lack of studies on the reactivity between chlorine agents and pH buffer components.

  Therefore, in Patent Document 2, succinic acid and salicylic acid are used. In Patent Document 3 and Patent Document 4, succinic acid, glycolic acid, maleic acid, and inorganic acids having no pH buffering power are used as components for stabilizing the effective chlorine concentration. Listed. In any case, effective chlorine is consumed and oxidized even under complete light shielding. In addition, Patent Document 5 states that “all pH buffering agents listed in chemical manuals that are publicly known documents can be used”, which is a typical substance that rapidly reacts with hypochlorous acid to generate and decompose chloramine. Certain glycines are also claimed. Therefore, nothing can be learned as prior art from the techniques described in these documents regarding the present invention.

When phthalate, phosphate and borate are prepared individually in a pH buffer solution, it is impossible to constantly maintain the pH in the region of 5-6. Further, even when a commercially available sodium hypochlorite solution having residual alkali is neutralized with hydrochloric acid, sulfuric acid, or nitric acid having no buffering power to have a pH of 5 to 6, each acid and each salt It is also a known fact that the dissociation equilibrium value (dissociation constant) pKa is greatly deviated from the pH range, and a buffering force cannot be obtained.
Moreover, in the disinfectant formulation, if there is residual alkali, intentional salt addition is unnecessary.

In order to enhance the microorganism inactivation effect, that is, the so-called “bactericidal power” of effective chlorine, the disinfecting solution adopted based on the prior art is a basic chlorine water made neutral or weakly acidic. If the disinfectant is consumed at an early stage, a highly basic neutral sodium hypochlorite concentrate diluted with water and neutralized by adding diluted acetic acid to neutral or A weakly acidic desired disinfectant can be easily obtained.
Even if inorganic acids and organic acids other than acetic acid listed in Patent Document 2 to Patent Document 5 are not selected, they are formed from acetic acid and non-dissociated acetate formed from alkali in the stock solution and ionized acetate ions. This is because the pH is relatively stable due to the dissociation equilibrium, that is, the pH buffer effect.

However, when it is prepared for the purpose of commercializing a disinfectant solution, it is effective in the disinfectant solution under storage conditions much longer than 3 days (72 hours) listed in the examples of Patent Document 2 to Patent Document 5. It is required to maintain the chlorine concentration without reducing it.
This purpose cannot be achieved only by neutralizing with an organic acid having a pKa of pH 6 or lower. In addition, it is difficult to completely eliminate the possibility that a very small amount of foreign matter such as rust is mixed during preparation, or the possibility of light entering the storage container by opening / opening the storage container, etc. There is no possibility that inorganic acids will consume chlorine in the stock solution.

Even if such abuse conditions occur, it is possible to suppress the decomposition of the metal oxide, which is deeply related to the oxygen generation decomposition of the chlorine-based disinfectant, by dissolving it into metal ions. The fact that aqueous solutions of dicarboxylic acids such as oxalic acid (HOOCCOOH) and ketocarboxylic acids (HOOCCO-R) also dissolve iron oxide, also known as “red rust”, is useful for the formulation of pharmaceutical formulations. This is a well-known finding.
Next, the inventors have found that the dicarboxylic acids and ketocarboxylic acids consume very little chlorine even under light irradiation except for oxalic acid. In exceptional cases, oxalic acid is known to be completely decomposed into carbon dioxide and water by hypochlorous acid under UV irradiation, so care must be taken when formulating.

The purpose of the present invention is to avoid the risk of conversion from available chlorine to chlorate ions and the risk of chlorine gas generation at the same time to maintain the effective chlorine concentration for several months or more, and is indispensable for the growth of unspecified pathogens Another object of the present invention is to provide a disinfectant that exhibits a high degree of disinfecting ability by adding a trace amount of a substance that breaks the substance metabolism balance of glycogen glycolysis and citric acid cycle in addition to effective chlorine.
A pH buffer solution composed of a plurality of organic acids exhibits a buffering effect due to the dissociation equilibrium between each acid ion and each acid salt, so that it acts more complicatedly than a single acid, and also suppresses disproportionation of effective chlorine.

Means for solving the above-described problems are as follows.
(1) A method for producing a disinfectant solution comprising chlorinated water in which a high-concentration sodium hypochlorite aqueous solution having at least basicity is added to water so that the effective chlorine concentration is 1 mg / L to 10000 mg / L,
Of the pyruvic acid, oxalic acid, oxalic acetic acid, and adipic acid, the total amount corresponding to 0.1% by weight to 1% by weight of acetic acid as a neutralizing and pH buffering agent and further acetic acid as a disinfection aid. A method for producing a disinfectant solution comprising a step of adding a mixed solution prepared by pre-mixing at least one organic acid (hereinafter abbreviated as an organic acid mixed solution) so that the pH becomes approximately 5 to 6.
As the chlorinating agent stock solution, a sodium hypochlorite solution having a free alkali of 2% or less that conforms to the standards of the Japan Water Works Association is used. Thereby, a free alkali concentration is restrict | limited and the production | generation of a chlorate ion is suppressed as much as possible. In addition, the number of days required for distribution and storage is shortened as much as possible to dilute, followed by neutralization to facilitate the handling of the disinfectant solution.
Furthermore, as dilution water for the stock solution, tap water with a stipulated regulation of residual chlorine concentration is filtered through a hollow fiber membrane to remove fine foreign substances, or the water filtered through a reverse osmosis membrane is sterilized and treated with tap water. Use water that allows detection of equivalent free residual chlorine concentration. In addition, an oxidation treatment with hypochlorous acid is performed on a transfer pipe and a storage container for diluting water such as tap water to prevent adhesion and residue of oxides.
However, there is no major problem even if the total organic acid concentration of the premixed organic acid mixture is not strictly determined, but the concentration is about 5% which is easy to handle during the process operation.
(2) When pre-preparing the organic acid mixture, lactic acid is prepared instead of pyruvic acid, and lactic acid is converted to pyruvic acid by a chemical reaction with hypochlorous acid in chlorinated water to obtain a disinfection aid (1 The manufacturing method of the disinfection liquid as described in).
(3) An organic acid mixed solution or an alkali agent is added again to the disinfectant so that the pH of the disinfectant finally becomes 5.0 to 6.0, and an organic acid salt is not intentionally added. (1) The method for producing a disinfectant solution according to (1).
However, since the highly basic chlorine solution stock solution described in (1) is used for fine adjustment of the effective chlorine concentration, the chlorine solution stock solution may be used as an alkaline agent for fine adjustment of pH.

According to the above-mentioned means (1), a disinfectant having a concentration suitable for a wide range of applications from a small bathtub to a general household can be obtained. In addition, even if some oxide remains in the diluted water or inside the container, remarkable chlorine consumption can be avoided, and contamination by foreign substances can be suppressed as much as possible by membrane filtration.
Furthermore, even if the phenomenon of hypochlorous acid, which is free effective chlorine, decomposes for some reason and lowers the pH, acetic acid works particularly reliably among the components of the organic acid mixture that acts as a buffering agent to buffer pH fluctuations. It suppresses decomposition by suppressing.
In addition, the organic acid added to the mixture of organic acids as a disinfectant aid is dissolved at the same time into a metal ion even if the metal oxide that can cause decomposition is not completely removed. Can be lost at the same time.
Therefore, if the disinfectant is filled in a light-shielding container that does not use a metal that catalyzes the decomposition of effective chlorine or a plastic containing additives as a liquid contact material, the effective chlorine concentration can be stabilized and maintained for a long period of time. It becomes possible, and commercialization and distribution become easy.

According to the above means (2), when lactic acid (CH ₃ CH (OH) COOH) is substituted for pyruvic acid, lactic acid is easily oxidized by hypochlorous acid. Lactic acid is similarly oxidized by an oxidizing agent such as potassium permanganate not used in the present invention.
However, since the inventor's research has shown that the product is only converted to pyruvic acid (CH ₃ COCOOH) and does not decompose to carbon dioxide and water, lactic acid is a substitute for pyruvic acid.
Moreover, since the total amount of the disinfectant auxiliary agent is extremely small compared to the neutralization and acetic acid of the pH buffer agent, the effective chlorine concentration immediately after the addition of the organic acid mixed solution is slightly reduced.
On the other hand, no chlorine is consumed in the disinfecting solution under complete light shielding, but pyruvic acid, oxalic acetic acid (HOOCCOCH ₂ COOH) belonging to ketocarboxylic acid, or oxalic acid, oxalic acetic acid, adipic acid (HOOC (CH ₂ ) belonging to dicarboxylic acid. _By adding a small amount of (4COOH), it becomes possible to inactivate by disrupting the substance metabolism balance of the glycogen glycolysis system and the citric acid cycle, which is indispensable when various pathogens of disinfecting partners that cannot be identified grow.
In addition, since the enzyme possessed by the microorganism is inactivated by a chemical reaction with hypochlorous acid, the metabolic circuit does not work, and all the organic acid species that are components of the disinfectant aid remain and remain toxic as waste products. That is, it demonstrates the disinfection ability as an auxiliary.
Incidentally, pyruvic acid is a substance located in the early stage of gluconeogenesis from lactic acid in the previous stage of the citric acid cycle or in the liver. Oxalacetic acid (also referred to as oxaloacetate in biochemistry) is a substance located next to the above-described pyruvate in the circulation stage of the citric acid cycle or in gluconeogenesis. Therefore, the organic acid below pyruvic acid used as a disinfection aid is not metabolized without an enzyme, and thus exerts an effect of inhibiting the growth of microorganisms and the like.
Naturally, the organic acid mixed solution is different from a mere neutralizing agent. Even if the total content of the disinfecting auxiliary agent is 0.1% by weight to 1% by weight with respect to acetic acid, dissolution of metal oxides and inactivation of microorganisms The amount of response is sufficient for conversion. Moreover, the disproportionation reaction of effective chlorine is suppressed by the interaction of a plurality of organic acids.

  According to the above-mentioned means (3), the manufacturing standard of the disinfecting solution is defined, and when making fine adjustments so that the effective chlorine concentration and pH conform to the standard, the chlorine solution stock solution can also be used as an alkaline agent. In addition, an organic acid mixed solution can also be used as an acid agent without separately preparing an inorganic acid or the like.

It is explanatory drawing of the manufacturing method of the disinfection liquid concerning embodiment of this invention. It is explanatory drawing of the manufacturing method of the disinfection liquid concerning embodiment of this invention. It is the figure which compared the pH buffer power of the disinfection liquid concerning embodiment of this invention.

  1 and 2 are explanatory diagrams of a method for producing a disinfectant according to Example 1 of the present invention. Moreover, FIG. 3 is the figure which compared the disinfecting liquid of this invention and the disinfectant prepared by the well-known method regarding pH buffering power. Hereinafter, a method for producing a disinfectant according to an embodiment of the present invention will be described with reference to these drawings.

The manufacturing method of the disinfection liquid concerning the form of Example 1 starts with the manufacture of water used for cleaning of dilution water and containers. In order to prevent waste of effective chlorine, it is best to use tap water as the raw water for dilution. However, if untreated water such as groundwater must be used, the water filtered through the reverse osmosis membrane should be disinfected with chlorine. The free residual chlorine concentration equivalent to tap water is detected.
First, as shown in FIG. 1, tap water from the tap tap 1 is introduced into the hollow fiber membrane filtration device 2 and filtered, and the filtered water is stored in the diluted water storage container 3. Of course, the dilution water storage container 3 has been pre-cleaned with chlorine water. Membrane filtration is performed in the diluting water production process because the decomposition is accelerated by porous microparticles with high adsorption capacity of hypochlorous acid and enzyme-containing microorganisms (biological organisms) such as algae spores. Things need to be thoroughly removed.

Next, an organic acid mixed solution used for pH adjustment is prepared in advance. Based on the recognition that the composition ratio of each acid is more important than the concentration of the organic acid, Table 1 shows Example 1 for the formulation of the organic acid mixture. Since pure organic acids include solids such as crystals at room temperature and pressure, a plurality of types of organic acids are prepared as aqueous solutions.

Table 2 shows the content ratios of Example 1 and disinfection aids changed.

Table 3 shows the content ratios of Examples 1 and 2 and disinfection aids changed.

The inventor uses acetic acid as a neutralizing and pH buffering agent, and ketocarboxylic acid that consumes little hypochlorous acid for the purpose of inactivating foreign substances such as accelerating algae and rust that can occur under unexpected conditions. By formulating at least one organic acid among pyruvate, oxalacetate and dicarboxylic acid belonging to oxalic acid, oxalic acid and adipic acid, the disinfecting solution of the present invention is more effective than the disinfecting solution of the prescription using acetic acid alone. Furthermore, it discovered that the outstanding disinfection effect was exhibited.
The inventor has confirmed that organic acids below oxalic acetic acid do not consume hypochlorous acid under complete light shielding. In any case, disinfection aids below pyruvic acid are indispensable to the organic acid mixture regardless of the amount of addition.

  Next, as shown in FIG. 2, the opening / closing valve 7 of the dilution water storage container 3 is opened, and a predetermined amount of dilution water is put into the disinfectant preparation container 6. Next, the on / off valve 8 of the sodium hypochlorite stock solution storage container 4 is opened, and the sodium hypochlorite stock solution is added to the diluted water in the disinfectant preparation container 6. close up.

Next, while driving the agitator 10, the on-off valve 9 of the organic acid mixed solution storage container 5 is opened,
An organic acid mixture such as Table 1 formulation that satisfies the conditions of claim 1 is added to the diluted solution in the disinfectant preparation container 6, and the on-off valve 9 is closed when the pH becomes approximately 5 to 6 while viewing the pH meter 11.

Next, the open / close valve 8 of the sodium hypochlorite stock solution storage container 4 is slightly opened to finally prepare the effective chlorine concentration to be a predetermined concentration. At the same time, it is confirmed that the pH is 5.0 to 6.0. If it is slightly off, the organic acid mixed solution in the organic acid mixed solution storage container 5 or the hypochlorite in the sodium hypochlorite stock solution storage container 4 A small amount of sodium acid stock solution is added to make a final preparation to obtain a disinfectant solution for manufacturing purposes. By giving priority to strict pH adjustment, even if the effective chlorine concentration may be slightly increased, there will be no trouble related to the intended purpose.
In addition, the effective chlorine concentration and residual alkalinity of the sodium hypochlorite stock solution have an allowable range for each lot. In addition, not only the effective chlorine concentration but also the chlorate ion concentration changes in the distribution stage until acquisition, and the amount of acid added to make it weakly acidic cannot be determined until the preparation work is completed. Therefore, since it is meaningless to show the addition amount of the organic acid mixed solution, the pH value is described in the following description instead. The disinfection efficacy is uniquely determined by the effective chlorine concentration and pH value at the time of disinfection, and the rough efficacy can be predicted by showing both condition values.

表４の硫酸滴定量の倍率単位は〔ｍＬ／ｍＬ〕である。
表４の結果は、本願実施例１の有機酸混液を用いて調製した消毒液（３）には、無機酸中和品と比較して７〜１０倍のｐＨ緩衝力が備わっていることを証明している。 FIG. 3 shows the disinfection solution (3) prepared by mixing the disinfecting solution (1) and disinfecting solution (2) neutralized with hydrochloric acid having no pH buffering power and the organic acid mixture of Example 1 of the present application as a comparison target. A 01 mol / L sulfuric acid was dropped, and the relationship between the titration amount and the pH change was measured and compared.
However, the pH of the disinfecting solution during preparation storage is around 7 in which the disinfecting solution (1) and the disinfecting solution (2) are substantially neutral in view of the actual situation of similar commercial products, and the disinfecting solution (3) prepared in Example 1 is It was set to 5.4. Moreover, until it used for experiment, all disinfectants were completely shaded and preserve | saved at normal temperature, and the conditions were aimed at.
For comparison of the three types of disinfectants, the same 0.01 mol / L sulfuric acid was added to the substantially neutral disinfectant until the pH reached 5.4, and the pH values at the start of titration were matched. Further, the end of the titration was set at the time when the pH dropped below 4.0 and reached 3.5.
Hypochlorous acid (HOCl) starts to change into the form of molecular chlorine (Cl ₂ ) when the pH is about 4 or less, so it is necessary for the pH to reach 4.0 on the premise of avoiding the risk of chlorine gas generation. The results were as shown in Table 4 by comparison with the sulfate titration.

The unit of magnification for sulfuric acid titration in Table 4 is [mL / mL].
The results in Table 4 show that the disinfecting solution (3) prepared using the organic acid mixed solution of Example 1 of the present application has a pH buffering power 7 to 10 times that of the inorganic acid neutralized product. Prove that.

表５の結果は、本願実施例１の有機酸混液を用いて調製した消毒液（３）が、虐待条件を課しても有効塩素濃度の減少を不都合な程に生じていないことを証明している。一方、塩酸で中和した消毒液は双方ともに希硫酸の添加により急激にｐＨ低下し、分子状の塩素が気相に拡散する等により、１３〜１８％もの有効塩素濃度の減少をみた。 The above experiment means that in order to maintain the effective chlorine concentration, that is, the disinfecting effect, it is essential to stabilize the pH of the disinfecting solution, but by adding the sulfuric acid solution until the pH becomes 3.5, It is also a kind of abuse test. Based on the inventor's experience, even if the solvent is not water and acetic acid is in an anhydrous state, both solid chlorine and powdered manganese dioxide are added to hydrochloric acid. Generate gas. Since there is a subtle cause for the reduction of available chlorine, simply neutralizing does not guarantee the safety of the disinfectant.
Therefore, first, the reduction rate of the effective chlorine concentration after the abuse test was calculated.Next, the chlorate ion and free effective chlorine in the disinfectant solution that contributed to the decrease were calculated. In the latter case, the conversion was calculated by substituting the initial concentration into the calculation formula. The reduction rate and conversion rate were sufficient to predict the efficacy of the disinfectant solution under abuse conditions.
Table 5 shows the reduction rate obtained by dividing the effective chlorine concentration [mg / L] reduction amount at the end of the experiment by the initial concentration. The sterilizing power of the chlorine agent is roughly determined by the multiplier (CT value) between the effective chlorine concentration and the contact time if the pH is kept constant.

The results in Table 5 prove that the disinfectant solution (3) prepared using the organic acid mixture of Example 1 of the present application did not cause an inconvenient decrease in the effective chlorine concentration even when the abuse condition was imposed. ing. On the other hand, both of the disinfectants neutralized with hydrochloric acid rapidly decreased in pH by the addition of dilute sulfuric acid, and the effective chlorine concentration decreased by 13 to 18% due to the diffusion of molecular chlorine into the gas phase.

本願実施例１の有機酸混液を用いて調製した消毒液（３）は、測定前の生成濃度を考慮し計算の補正をしなくても、僅か３％が塩素酸イオンに転化したにすぎない。画期的な安定度といえる。表６の結果は、塩酸中和の消毒液（１）及び塩酸中和の消毒液（２）に比し、該（３）が塩素酸イオンへの転化を十分抑えていることを明確に証明する。
一方、塩酸で中和した消毒液は、調製時のｐＨが略中性の７前後であったことで、有効塩素の１５〜２０％もが保管中に塩素酸イオンに転化済みであったことを示唆する。 Table 6 shows the conversion ratio (weight ratio) to chlorate ions obtained by dividing the chlorate ion concentration [mg / L] in the disinfectant solution at the end of the experiment by the initial concentration of effective chlorine. As a matter of course, the measured chlorate ion concentration includes those already generated during disinfectant storage.

In the disinfectant solution (3) prepared using the organic acid mixture of Example 1 of the present application, only 3% was converted to chlorate ions even without correction of calculation in consideration of the generated concentration before measurement. . This is an epoch-making stability. The results in Table 6 clearly demonstrate that (3) sufficiently suppresses the conversion to chlorate ions compared to the hydrochloric acid neutralized disinfectant (1) and the hydrochloric acid neutralized disinfectant (2). To do.
On the other hand, the disinfectant neutralized with hydrochloric acid had a pH of about 7 at the time of preparation, and 15-20% of the effective chlorine had been converted to chlorate ions during storage. To suggest.

表７は本発明の消毒液の長期間（１年超）安定性をみたものである。
保存条件：ダンボール内ポリエチレン製容器保存、容器２０Ｌ、液温２８〜３２℃
尚、表７上段記載数値で５６日経過時のｐＨ５．２は測定誤差範囲内にある。
比較として、中和及びｐＨ緩衝として５％の酢酸のみを使用した場合を示す。

また、本比較例とは別ロット調製品で、稀ではあるが、３ヶ月〜１年の室温保存で有効塩素の濃度が極度に低下し失効するものがあった。原因を追及したところ、一例では緑藻の一種が観察され、また錆とみられる微小異物が含まれていたためと判明した。
中和及びｐＨ緩衝に酢酸を単独で用いても３〜４ヶ月の保存期間であれば有効塩素濃度減少は約２％で、商品流通に支障はないとみることもできる。しかし、使用前に失効が確認された返品率を無視できない事態になれば、長期安定性を保証するため別種の有機酸を添加・混合することが不可欠となる。
表８の結果は、実施例１乃至実施例３の有機酸混液を用いて調製した消毒液が１年を経過しても、有効塩素濃度及びｐＨ値に変化は殆どなく安定であることを証明する。
また、調製に用いた原液の同様実験では、ｐＨ値は１２前後で安定しているものの、８ヶ月後の有効塩素濃度は初期濃度の約３０％まで低下した事例が殆どであった。
５％の酢酸のみを使用した比較例と対照すれば、酢酸がｐＨ緩衝の主役であることに相違はないが、酢酸に塩素を消費しないケトカルボン酸又はジカルボン酸を混合した方が有効塩素並びにｐＨの安定化が増す。実施例１でピルビン酸等の酢酸に対する総混合率は０．５％強、実施例２で同０．９％強、実施例３で同０．１％強にすぎないが、稀に混入し早期分解の原因となる藻の増殖を抑え、また、錆を溶解して吸着による触媒作用を阻止するには十分な含量である。そこで、混合し調製する該有機酸の酢酸に対する該有機酸総含量０．１重量％を有意の下限とし、実施例２を根拠に同１％を上限とした。
但し、酢酸に対する該有機酸総含量が１重量％を超えて処方された場合でも、調整後の消毒液効能や化学的特性に大きな差異が生じるとは考えられない。しかし、原液の残留アルカリを中和しｐＨ緩衝力の事前算定が容易な酢酸の特性に大きく影響する高い総含量では、調整後の消毒液につき成分表示等品質保証の再検討を余儀なくされる。
表５及び表６の結果も併せ考察すると、ｐＨを５．０〜６．０に厳格な調製を行い、ｐＨの変動を抑え、且つ有効塩素消失の原因を徹底的に除かないと、有効塩素濃度が短時間のうちに初期濃度の１０％を超えて低下した不良品がでることが明白になった。 The above-mentioned experiment is nothing but to show that stabilization of the pH value of the disinfecting solution is indispensable in order to maintain the effective chlorine concentration, that is, the disinfecting effect. Moreover, unless it is a long-term storage experiment, the difference from the case of a single component when an organic acid is mixed is not clearly shown. Therefore, apart from the acid titration experiment, an efficacy evaluation experiment was also conducted in the case where the disinfectant prepared using the organic acid mixed solution of the present example was stored in a container for a long period of time. In addition, efficacy evaluation is enough to look at transition of effective chlorine concentration and pH value. Table 7 shows the results of light shielding, chemical amount and liquid temperature conditions related to chlorate ion generation, which should be kept as storage conditions. The pH value varies slightly from lot to lot.

Table 7 shows the long-term (over 1 year) stability of the disinfecting solution of the present invention.
Storage conditions: Polyethylene container storage in cardboard, container 20L, liquid temperature 28-32 ° C
In addition, as shown in the upper part of Table 7, pH 5.2 after 56 days is within the measurement error range.
As a comparison, the case where only 5% acetic acid is used as neutralization and pH buffer is shown.

Moreover, although it was a different lot preparation from this comparative example, there was a rare product that expired due to extremely low concentration of available chlorine when stored at room temperature for 3 months to 1 year. When the cause was investigated, in one example, a kind of green algae was observed, and it was found that it contained minute foreign matter that appeared to be rust.
Even if acetic acid is used alone for neutralization and pH buffering, if the storage period is 3 to 4 months, the decrease in effective chlorine concentration is about 2%, and it can be considered that there is no problem in the distribution of goods. However, if it becomes impossible to ignore the return rate that has been confirmed to expire before use, it is essential to add and mix different organic acids to ensure long-term stability.
The results in Table 8 prove that the disinfectant prepared using the organic acid mixture of Examples 1 to 3 is stable with little change in effective chlorine concentration and pH value even after one year. To do.
In the same experiment of the stock solution used for the preparation, although the pH value was stable at around 12, the effective chlorine concentration after 8 months was almost lowered to about 30% of the initial concentration.
In contrast to the comparative example using only 5% acetic acid, there is no difference that acetic acid is the main role of pH buffering, but acetic acid and dicarboxylic acid that do not consume chlorine in acetic acid are more effective chlorine and pH. Increased stabilization. In Example 1, the total mixing ratio of acetic acid such as pyruvic acid was just over 0.5%, in Example 2 was just over 0.9%, and in Example 3 was just over 0.1%, but rarely mixed. The content is sufficient to suppress the growth of algae that cause premature degradation and to dissolve rust and prevent catalytic action by adsorption. Therefore, the total organic acid content of 0.1% by weight of the organic acid mixed and prepared with respect to acetic acid was made a significant lower limit, and the upper limit was made 1% based on Example 2.
However, even when the total organic acid content with respect to acetic acid is prescribed to exceed 1% by weight, it is not considered that a great difference is produced in the disinfectant solution efficacy and chemical characteristics after adjustment. However, with a high total content that neutralizes residual alkali in the stock solution and greatly affects the characteristics of acetic acid, which allows easy pre-calculation of pH buffering power, it is unavoidable to reexamine quality assurance such as component display for the adjusted disinfectant solution.
Considering the results of Table 5 and Table 6 together, if the pH is strictly adjusted to 5.0 to 6.0, the fluctuation of the pH is suppressed, and the cause of the loss of effective chlorine must be thoroughly removed, the effective chlorine It became clear that there was a defective product whose concentration fell below 10% of the initial concentration in a short time.

検体は、実施例１処方の有効塩素濃度が８０ｍｇ／Ｌ、ｐＨが５．２の調製消毒液。
尚、Ｈ１Ｎ１ウイルスの不活性化試験では、該消毒液添加１５秒後から「不検出」の結果が出た。従って、不活性化力は極めて高く、前記ＣＴ値を約２０と算定できた。 Table 9 shows the test results of the inactivation effect of microorganisms using the disinfecting solution of the present invention. In addition, the inspection method of Norovirus was based on the RT-PCR method, and the new influenza virus (H1N1) was based on the method of measuring a virus infectivity value using a test cell.
Only the results that were submitted to the specialized inspection organization and reported in an appropriate manner are shown below.

The specimen is a prepared disinfectant solution having an effective chlorine concentration of 80 mg / L and a pH of 5.2 according to the formulation of Example 1.
In the H1N1 virus inactivation test, a “not detected” result was obtained 15 seconds after the addition of the disinfectant solution. Therefore, the deactivation power was extremely high, and the CT value was calculated to be about 20.

検体は、実施例１処方の有効塩素濃度が８０ｍｇ／Ｌ、ｐＨが５．２の調製消毒液。
検査機関が選択した試験方法により、試料１ｍＬ当たりの生菌数〔ｃｆｕ／ｍＬ〕を測定した。菌種毎に該消毒液との接触時間が異なるので、後尾に時間を記載してある。
但し、この効果試験は、各菌種を培養後、遠心分離、検体接種後に放置、培地に回収し４段階希釈して生菌数測定の各工程を経ており、消毒液の実用実態と同じではない。
表９及び表１０の結果は、本発明の消毒液がウイルス、細菌及びカビ等の病原体種を問わず不活性化の著効を示し、所望の効果が得られることを証明している。
また、実施例２及び実施例３の処方による有機酸混液を用いて調製した本発明消毒液の効果試験でも同じ結果を得ており、有効塩素濃度を維持すれば効果にも差異はない。 Furthermore, Table 10 shows the results of an effect test when the disinfecting solution of the present invention is used for pathogenic bacteria and molds mainly causing food poisoning.
Only the results that were submitted to the specialized inspection organization and reported in an appropriate manner are shown below.

The specimen is a prepared disinfectant solution having an effective chlorine concentration of 80 mg / L and a pH of 5.2 according to the formulation of Example 1.
The number of viable bacteria per mL of sample [cfu / mL] was measured by the test method selected by the inspection organization. Since the contact time with the disinfectant varies depending on the bacterial species, the time is written at the tail.
However, in this effect test, each bacterial species is cultured, centrifuged, left after inoculation of the specimen, collected in a medium, diluted in four stages, and subjected to each step of measuring the number of viable bacteria. Absent.
The results in Table 9 and Table 10 demonstrate that the disinfecting solution of the present invention exhibits a remarkable effect of inactivation regardless of pathogen species such as viruses, bacteria, and molds, and a desired effect can be obtained.
Moreover, the same result was obtained in the effect test of the disinfectant of the present invention prepared using the organic acid mixed solution according to the formulation of Example 2 and Example 3, and there is no difference in the effect as long as the effective chlorine concentration is maintained.

表１１の試験は、本発明による実施例１乃至実施例３処方の有機酸混液を用いて調製した、有効酸素濃度が８０ｍｇ／Ｌ、ｐＨが５．３の消毒液を使用し、手動式噴霧器で対象物に噴霧して１分間接触させる方法で行った。

野菜等の食品を消毒する場合、学校給食施設等では前記の次亜塩素酸ナトリウム液市販品（表中では「次亜ソー」と略）を水道水等で希釈し、該塩素水に野菜等を浸漬するのが一般的である。従って、該次亜ソーと実施例１の本発明消毒液の効果を比較すれば、次亜塩素酸の効能が単に濃度だけで決まるものではないことが明白である。
また、本発明の消毒液が著効を示す一事例として、パセリについては浸漬だけでなく全体に噴霧した場合の結果も表１２に載せた。因みに、パセリやホウレン草等の青物野菜は特に根の部分に、本発明の消毒補助剤処方の一つに挙げるシュウ酸を多く含んでいる。消毒補助剤処方に挙げる一連の有機酸は、動植物の代謝で産生される老廃物であるから、微量の含有を殊更警戒する必要はない。
ヒト皮膚一次刺激性試験のパッチテストでも被験者全員「反応なし」、衣服への影響試験でも特別視される悪影響は「なし」となったから、安全面での問題もない。
ここまでの効果試験の結果を総括すれば、本発明の消毒液は、細菌からウイルスに至るまで、その大小を問わずほぼ完ぺきに不活性化できることを証明している。 Therefore, tests were performed under conditions close to the practical use of the disinfectant, and the results are shown in Tables 11 and 12.

The test of Table 11 uses a disinfectant having an effective oxygen concentration of 80 mg / L and a pH of 5.3, prepared using the organic acid mixture of the formulations of Examples 1 to 3 according to the present invention. The method was carried out by spraying the object and contacting it for 1 minute.

When disinfecting foods such as vegetables, dilute the sodium hypochlorite liquid commercial products (abbreviated as “hyposo” in the table) with school water at school lunch facilities, etc. Is generally immersed. Therefore, comparing the effects of the hyposodium and the disinfectant of the present invention of Example 1 , it is clear that the efficacy of hypochlorous acid is not determined solely by the concentration.
Moreover, as an example in which the disinfecting solution of the present invention is highly effective, the results of spraying parsley as well as dipping the whole are listed in Table 12. Incidentally, green vegetables such as parsley and spinach contain a large amount of oxalic acid listed as one of the disinfectant adjuvant formulations of the present invention, particularly in the root portion. The series of organic acids listed in the disinfection aid formulation is a waste product produced by the metabolism of animals and plants, so there is no need to be particularly wary of the inclusion of trace amounts.
In the patch test of the human skin primary irritation test, all subjects were “no response”, and the adverse effect that was regarded as special in the influence test on clothes was “none”, so there was no safety problem.
Summarizing the results of the effect tests so far, it has been proved that the disinfecting solution of the present invention can be almost completely inactivated from bacteria to viruses regardless of its size.

Capacity used in small tub plurality of disinfection of 1 m ³ to 20 m ^3, the effective chlorine concentration is at about 1% sodium hypochlorite solution, it is described below the present invention Example 4.
The water was diluted by adding 10 L of a 12% sodium hypochlorite solution conforming to the standards of the Japan Water Works Association, and the amount of the solution was made less than 100 L. Next, hydrochloric acid was added to neutralize residual alkali in the stock solution, and the pH was adjusted to about 7. Further, 4 L of an acidity 4.3% / organic acid mixture described in Example 1 was added to adjust the pH to 5.8, and the total amount of the disinfectant was adjusted to 100 L.
The disinfectant solution was stored in a chemical tank, and the conventional water quality control was performed by driving the metering pump so that the free residual chlorine concentration in the bath water was maintained at 0.4 to 1.0 mg / L. The problems of “exceeding the bath water pH of 8.0” and “sporadic detection of Enterobacter cloacae, one of the coliforms” that occurred with the chlorinating agent disappeared, and the issue was resolved . That is, the bath water pH can be maintained at 7 to 8 at all times, and by suppressing the decrease in the sterilizing power of free chlorine, the results of “negative” were improved every time in the E. coli test.
In addition, in the application as in Example 4, since the addition operation of the organic acid mixed solution is performed every time it is used, it is not stored for a long period of one week or more. Accordingly, the disinfection solution having an effective chlorine concentration of 1% (10,000 mg / L) can be easily implemented.

The present invention relates to chlorine water for disinfection by adding a mixed solution formulated with a plurality of organic acids to give weak acidity and pH buffering property to chlorine water containing hypochlorous acid as a main disinfecting component. Enables long-term storage. In addition, the disinfectant has a strong pH buffering power that does not become pH 4 or less even when mixed with an acidic substance by mistake in the process of distribution, storage, and use, and the quality of safety can be guaranteed. Become.
Therefore, the disinfectant according to the present invention is used for doors, windows, floors, kitchens, etc. that are touched to disinfect foods such as vegetables and fruits and dishes and cooking utensils in order to prevent infection by pathogenic microorganisms and viruses. It can be widely used not only for the surface of building fixtures, furniture, home appliances and clothes, but also for disinfection of small bathtubs. Moreover, it is also possible to dilute and use the disinfecting solution according to the present invention as appropriate according to the application.

DESCRIPTION OF SYMBOLS 1 Water supply tap 2 Hollow fiber membrane filtration apparatus 3 Diluted water storage container 4 Sodium hypochlorite stock solution storage container 5 Organic acid mixed solution storage container 6 Disinfectant preparation container 7-9 Open / close valve connected to each container 10 Stirrer 11 pH Total

Claims (3)

A method for producing a disinfectant solution comprising chlorinated water in which an aqueous solution of at least basic sodium hypochlorite having at least basicity is added to water so that the effective chlorine concentration is 1 mg / L to 10,000 mg / L,
Acetic acid as a neutralizing and pH buffering agent, and pyruvic acid, oxalic acid, oxalic acetic acid and adipic acid having a total content corresponding to 0.1% by weight to 1% by weight with respect to acetic acid as a disinfecting aid. A method for producing a disinfecting solution, comprising a step of adding a preliminarily prepared mixed solution to adjust the pH to about 5 to 6.   The lactic acid is blended in place of pyruvic acid for the purpose of generating the disinfectant pyruvic acid by a chemical reaction with hypochlorous acid in the chlorinated water when preparing the organic acid mixture. Of manufacturing disinfectant solution. A mixture of organic acids or a high-concentration sodium hypochlorite aqueous solution having at least basicity is added again to the disinfectant so that the pH of the disinfectant finally becomes 5.0 to 6.0. The method for producing a disinfectant solution according to claim 1, wherein an acid salt is not intentionally added.

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