JP4047300B2 - Method for producing organic peracid - Google Patents

Description

  The present invention relates to a method for producing an organic peracid used for bactericides, bleaches and the like.

  At present, there are various known chemicals that have actions such as bleaching, sterilization, and disinfection. In particular, hypochlorites such as sodium hypochlorite as chlorinated fungicides and peroxidation as oxygen-based sterilizing agents. Sodium percarbonate, sodium perborate and the like that generate hydrogen peroxide in hydrogen and water are mainly used. However, these disinfectants have various problems. For example, hypochlorite has a problem of corrosion on metals and the like and a problem of generation of chlorine gas due to misuse, and hydrogen peroxide has a high disinfecting effect. In order to obtain, there is a problem that use at a high concentration and contact for a long time are required. When hydrogen peroxide is used, in order to solve these problems, measures such as enhancing the bactericidal effect by generating an organic peracid during use in combination with an activator are taken. As such a disinfectant composition, Patent Document 1 discloses a disinfectant composition containing an inorganic peroxide, an incomplete organic acid ester of a polyhydric alcohol, and an alkaline earth metal salt, but less than pH 7 However, there is room for improvement in the bactericidal effect of spores and mold spores with higher chemical resistance. In addition, Patent Documents 2 and 3 can be cited as methods for applying organic peracid as a bactericidal agent, and these are based on a concentrated combination of peracetic acid, acetic acid and hydrogen peroxide as a bactericidal composition. It is difficult to handle with a strong pungent odor. Furthermore, Patent Document 4 proposes a method of adjusting the pH in an organic peracid generating system to improve the bleaching effect, but improvement of the bactericidal power of spores and mold spores with higher chemical resistance cannot be expected.

For example, in the case of peracetic acid, the organic peracid is produced continuously by reacting hydrogen peroxide and acetic acid under acidic conditions, and is obtained as an equilibrium mixture containing peracetic acid, acetic acid, hydrogen peroxide and water. Peracetic acid can be produced by partially oxidizing acetaldehyde in the gas phase, or by oxidizing acetaldehyde under a catalyst to produce an intermediate acetaldehyde monoperacetate, which is decomposed in a solvent. You can also. Patent Documents 5 and 6 disclose concentrates suitable for sterilization, which contain peracetic acid or acetic acid, hydrogen peroxide, water, and the like. However, it is difficult to say that conventional biocides using organic peracids are sufficiently controlled in consideration of an appropriate balance of raw materials in the production method. In addition, as described above, when the acetic acid and hydrogen peroxide are reacted, the reaction product is obtained as an equilibrium mixture containing hydrogen peroxide, so the hydrogen peroxide concentration ratio is relatively high. Therefore, the organic peracid aqueous solution produced by the conventional method tends to increase the content of the unreacted hydrogen peroxide component. When the concentration of hydrogen peroxide per unit amount increases, the concentration of organic peracid decreases, which is disadvantageous for more advanced sterilization. In addition, today, reducing the burden on the environment is a big issue, but disinfectants containing excessive hydrogen peroxide require treatment such as neutralization and decomposition before discharge, which is expensive. It becomes a burden.
JP-A-6-305920 Japanese National Patent Publication No. 8-500843 JP-A-8-311495 JP-A-5-25497 JP-A-52-25034 JP-A-52-25011

  An object of the present invention is to provide a method which can produce an organic peracid which exhibits high stability and bactericidal power and which is suitable as a bactericidal agent without excessive use of hydrogen peroxide.

  The present invention relates to (A) an ester of a polyhydric alcohol and an organic acid having a hydrocarbon group which may have a hydroxyl group (hereinafter referred to as component (A)) and (B) hydrogen peroxide [hereinafter referred to as (B ) Component] in a molar ratio of (A) / (B) = 1/10 to 20/1 in water at pH 8 to 12, and then the reaction system is adjusted to pH 1 or more and less than 7 The present invention relates to a method for producing an organic peracid.

  According to the present invention, (A) an ester of a polyhydric alcohol and an organic acid having a hydrocarbon group which may have a hydroxyl group, and (B) hydrogen peroxide are (A) / (B) = 1. Provided is a method for producing an antibacterial composition containing an organic peracid having a step of reacting at a pH of 8 to 12 in water at a molar ratio of / 10 to 20/1, and then setting the reaction system to a pH of 1 or more and less than 7. Is done.

  According to the present invention, an organic peracid having a high effect as a disinfectant can be efficiently produced without using excessive hydrogen peroxide. For this reason, since an organic peracid aqueous solution having a low hydrogen peroxide content can be obtained, for example, even when used as a disinfectant, it is possible to reduce the drainage load on the environment.

<(A) component>
The ester of the polyhydric alcohol (A) and the organic acid having a hydrocarbon group which may have a hydroxyl group is an activator of hydrogen peroxide released from the component (B). To produce an organic peracid.

  (A) As a polyhydric alcohol for comprising a component, a C2-C12 thing is preferable, Glycerines, such as glycerol, diglycerol, and triglycerol, glucose, sucrose, fructose, sorbitol, pentaerythritol, alkyl Examples include saccharides such as polyglycosides and alkylfuranosides.

  The organic acid for constituting the component (A) includes aliphatic monocarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, octanoic acid, oxalic acid, malonic acid, succinic acid, maleic acid. And aliphatic dicarboxylic acids such as fumaric acid, hydroxycarboxylic acids having a hydroxyl group such as citric acid, tartaric acid, malic acid, etc., preferably saturated or unsaturated aliphatic mono- or dicarboxylic acids having 1 to 8 carbon atoms. More preferably, a C1-C8 saturated or unsaturated aliphatic monocarboxylic acid is mentioned, More preferably, a C1-C8 fatty acid is mentioned, Especially preferably, it is C2-C8. Fatty acids are mentioned. The degree of esterification of the component (A) is not limited.

  As a specific component (A), glycerol and an ester of an aliphatic monocarboxylic acid having 1 to 8 carbon atoms are preferable, and triacetin is particularly preferable.

<(B) component>
The component (B) is hydrogen peroxide, and an inorganic peroxide that releases hydrogen peroxide in water may be dissolved in water. The inorganic peroxide is preferably a percarbonate, particularly a perborate, particularly sodium percarbonate or sodium perborate.

<Manufacturing method>
In the production method of the present invention, when the component (A) and the component (B) are reacted, the molar ratio between them is set to a specific ratio, and the pH of the reaction system is changed in two steps. Unlike the conventional method in which acetic acid and hydrogen peroxide are reacted, the production method of the present invention does not accumulate hydrogen peroxide in the system because the reaction of component (A) and component (B) is an irreversible reaction. This is advantageous when an aqueous solution containing an organic peracid having a desired concentration is produced. That is, according to the present invention, there is a step of reacting the component (A) and the component (B) in water at a pH of 8 to 12 in the specific molar ratio, and then setting the reaction system to a pH of 1 or more and less than 7. A method for producing an aqueous solution containing an organic peracid can be provided.

  The molar ratio of the component (A) to the component (B) is (A) / (B) = 1/10 to 20/1, 1/10 to 10/1, particularly 1/5 to 10/1. It is preferable from the viewpoint of the production efficiency and stability of the organic peracid. In addition, the molar ratio of the component (B) per ester group of the component (A) is 2 times or less from the viewpoint of efficiently generating organic peracid and reducing unreacted hydrogen peroxide. Particularly preferred is 0.3 to 2 moles.

  In addition, the ratio of the component (A), the component (B) and the water is preferably [(A) + (B)] / water = 1/10000 to 1/1, and preferably 1/1000 to 1/2. preferable.

  In the reaction system after satisfying the above molar ratio or weight ratio, the component (A) is 0.1 to 90% by weight, more preferably 0.5 to 70% by weight, particularly 1 to 50% by weight, and the component (B) It is preferable to add 0.1 to 50% by weight, more preferably 0.1 to 30% by weight, particularly 0.1 to 20% by weight.

  In the production method of the present invention, it is preferable to use a liquid composition containing the component (A) and the component (B) and having a water content of 1 to 25% by weight. That is, in the production method of the present invention, the component (A) and the component (B) are provided as a liquid composition containing the component (A) and the component (B) and having a water content of 1 to 25% by weight. It is preferable. The content of the component (A) in the liquid composition is preferably 20 to 90% by weight, more preferably 30 to 90% by weight, particularly preferably 40 to 80% by weight, and the content of the component (B) is 1 to 30% by weight. %, Further 5 to 25% by weight, particularly 10 to 25% by weight is preferred. The molar ratio of the component (A) to the component (B) is (A) / (B) = 1/10 to 20/1, further 1/10 to 10/1, particularly 1/5 to 10/1. Preferably there is. In addition, the molar ratio of the component (B) per ester group of the component (A) is 2 times or less from the viewpoint of efficiently generating organic peracid and reducing unreacted hydrogen peroxide. Particularly preferred is 0.3 to 2 moles.

  Moreover, this liquid composition can contain a chelating agent, a pH adjuster, a solvent, etc. as needed. A chelating agent is useful for suppressing catalytic decomposition due to a small amount of metal ions such as Fe and Cr. From the viewpoint of storage stability, the stock solution pH (20 ° C.) of the liquid composition is preferably 0.5 to 6, more preferably 1 to 5, and particularly preferably 1 to 4. What combined the effect | action as a pH adjuster and the effect | action as a chelating agent is preferable, and specifically, phosphoric acid, polymeric phosphoric acid, organic phosphonic acid, aminocarboxylic acid, hydroxycarboxylic acid, or these salts are preferable. Of these, organic phosphonic acids or salts thereof are preferred. As the solvent, a polyhydric alcohol solvent is preferable, and a glycol solvent such as propylene glycol is particularly preferable.

  The component (B) is an inorganic peroxide that releases hydrogen peroxide in water, for example, percarbonate, perborate, especially sodium percarbonate, granular containing sodium perborate, powder, etc. What was obtained from the composition of the shape can also be used.

  In the present invention, after mixing the component (A) and the component (B), the pH of the reaction system is adjusted to 8 to 12, preferably 9 to 11 (first step), and then the pH is 1 or more and less than 7, preferably 1 to 6. More preferably, it is 1 to 5 (second step). It is preferable to use an alkaline pH adjusting agent in the first step and an acidic pH adjusting agent in the second step. This pH is the one during the reaction, but preferably the final product after the reaction satisfies the pH of the second step at 25 ° C.

  The first step is a step for generating an organic peracid, and the time is not limited, but it is preferable to maintain the pH at 8 to 12 until 50% of the organic peracid is generated. The preferred reaction time for the first step is 1 to 120 minutes. The reaction temperature in the first step is preferably 5 to 50 ° C.

  The second step is a step for stabilizing the generated organic peracid, and is basically performed by adding a pH adjuster for adjusting the pH to 1 or more and less than 7 in the reaction system. That is, when the pH reaches a predetermined value, the second step is completed. The reaction temperature in the second step is preferably 5 to 50 ° C.

  According to the production method of the present invention, the organic peracid can be obtained in a form that exists in an aqueous solution. The concentration of the residual hydrogen peroxide in the aqueous solution can prevent the accumulation of hydrogen peroxide and stabilize the organic peracid. From the viewpoint of safety, 60% by weight or less of the initial charge amount of hydrogen peroxide is preferable, 50% by weight or less is more preferable, and 0.1 to 50% by weight is particularly preferable.

  Examples of alkaline pH adjusters include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, or alkaline earth metal hydroxides, sodium silicate, potassium silicate, and other silicic acids. Examples include alkali metal salts, alkali metal phosphates such as trisodium phosphate, and alkali metal carbonates such as sodium carbonate and potassium carbonate. From the viewpoints of alkalinity and water solubility, sodium hydroxide and potassium hydroxide Preferred are alkali metal hydroxides such as alkali metal phosphates such as trisodium phosphate and tripotassium phosphate, and alkali metal carbonates such as sodium carbonate and potassium carbonate. Examples of the acidic pH adjuster include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, and organic acids such as formic acid, acetic acid, citric acid, succinic acid and gluconic acid. From the viewpoint of acidity and water solubility, sulfuric acid is preferred. Liquid inorganic acids such as phosphoric acid and highly water-soluble organic acids such as citric acid and acetic acid are preferred. These can be used alone or in combination of two or more. Moreover, these pH adjusters may exist in the aqueous solution containing the organic peracid manufactured by this invention as it is.

  In the present invention, in addition to the component (A) and the component (B), surfactants, inorganic or organic salts, chelating agents, fragrances, pigments, dyes and the like can be charged into the reaction system. Thereby, a disinfectant, a bleaching agent, etc. are obtained easily.

  Surfactants include nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants. Nonionic surfactants include polyoxyethylene (hereinafter referred to as POE) alkyl ether, POE alkylphenyl ether, polyoxypropylene / POE (block or random) alkyl ether, POE arylphenyl ether, POE styrenated phenyl ether. Monovalent alcohol derivative type nonionic surfactants such as POE tribenzylphenyl ether; Polyhydric alcohol derivative type nonionic surfactants such as (poly) glycerin fatty acid ester, sucrose fatty acid ester, sorbitan fatty acid ester, alkylpolyglycoside Examples include activators. Anionic surfactants include lignin sulfonate, alkylbenzene sulfonate, alkyl sulfonate, POE alkyl sulfonate, POE alkyl phenyl ether sulfonate, POE alkyl phenyl ether phosphate ester salt, POE aryl phenyl Examples include ether sulfonate, POE arylphenyl ether phosphate, naphthalene sulfonate, naphthalene sulfonate formalin condensate, POE tribenzyl phenyl ether sulfonate, POE tribenzyl phenyl ether phosphate. Examples of the cationic surfactant include mono long chain alkyl (C8-18) trimethylammonium chloride, dilong chain alkyl (C8-18) dimethylammonium chloride, benzalkonium chloride, benzethonium chloride, and the like. . Examples of amphoteric surfactants include alkylaminotrimethylglycine, alkyldimethylamine oxide, and alkyldiaminoethylglycine hydrochloride. These can be used alone or in combination of two or more. As the surfactant, a nonionic surfactant is preferable, and a polyhydric alcohol derivative type nonionic surfactant is more preferable. Further, the surfactant is preferably contained in the reaction system in the present invention in an amount of 0 to 20% by weight, and more preferably 0 to 10% by weight.

  In addition to being used as a pH adjuster, salts are mainly used for the purpose of stabilizing a bactericidal agent. Specifically, metal salts of carboxylic acids such as succinic acid, malonic acid, citric acid, gluconic acid, glutaric acid, etc. Organic salts, phosphoric acid compound metal salts such as tripolyphosphoric acid, hexametaphosphoric acid and phosphoric acid, and inorganic salts such as sulfates such as sodium sulfate and potassium sulfate. These can be used alone or in combination of two or more.

  Examples of the chelating agent include ethylenediaminetetraacetic acid, nitrilotriacetic acid, tripolyphosphoric acid, polyhydroxyacrylic acid, organic phosphonic acid and the like or salts thereof.

  The aqueous solution containing an organic peracid obtained by the present invention can take various forms, but in the case of a liquid, it is preferably one having high fluidity, and in addition to the aqueous solution, fluid slurry, gel, paste form Etc.

  The aqueous solution containing an organic peracid produced according to the present invention preferably has an organic peracid concentration of 10 to 100,000 ppm (weight ratio, the same applies hereinafter), and further 10 to 50,000 ppm.

  For example, a bactericidal agent is useful because an organic peracid having a necessary concentration can be easily obtained by using a compounding component so that the production method of the present invention is carried out at the time of use.

  In the case of a bactericidal agent, the aqueous solution containing the organic peracid produced according to the present invention may be used as it is, but from the viewpoint of economy, it is diluted with water as appropriate, and the organic peracid concentration is 10 to 10. It is preferably used as an aqueous solution of 20,000 ppm, more preferably 10 to 10,000 ppm.

  When the organic peracid obtained by the production method of the present invention is used as a bactericidal agent, an aqueous solution containing the organic peracid (hereinafter referred to as a bactericidal aqueous solution) is brought into contact with the article to be sterilized.

  Examples of the method for bringing the aqueous solution for sterilization into contact with the article to be sterilized include methods such as spraying, dipping, filling, and applying the aqueous solution. When spraying, it is preferable to spray. Further, the object may be wiped off by impregnating a suitable carrier with the aqueous solution. The contact time is not limited, but depending on the article to be sterilized, a sufficient effect can be obtained even in a short time of 30 seconds or less, particularly 10 seconds or less. Moreover, although the temperature of the said aqueous solution at the time of making it contact is also not limited, 10-90 degreeC is preferable and 15-80 degreeC is more preferable.

  Such an aqueous solution for sterilization is a sterilizer composition, and the hydrogen peroxide content in the composition is preferably 0.5% by weight or less, more preferably 0.3% by weight or less, and particularly preferably 0.2% by weight or less. .

  Since the organic peracid produced according to the present invention has a high sterilizing effect, various sterilized objects in which various microorganisms exist can be targeted for sterilization. For example, bacteria such as Escherichia coli, Salmonella, Staphylococcus aureus, and green-condensed bacteria such as food poisoning and nosocomial infections, fungi such as black koji mold, Candida, and Bacillus subtilis having strong resistance to fungicides Examples include bacterial spores and fungal spores such as Aspergillus niger. Among these, the bacterial spore is a dormant cell having durability that is produced in an environment unsuitable for growth, and has multiple layered outer shells outside the cell. Such bacterial spores are extremely resistant to drugs and heat, and it is difficult to kill them completely by general sterilization. However, the organic peracid produced according to the present invention can provide a sufficient bactericidal effect against such bacterial spores.

  As described above, the organic peracid produced according to the present invention has a broad sterilization spectrum and has a high effect on not only bacteria but also fungi and spores, and thus is useful for sterilization in a wide range of fields. For example, it is used for the sterilization of hospitals, nursing homes, food processing factories, cleaning facilities, kitchen walls, floors, windows, etc., or appliances, fixtures, and products (for example, beverages) used in them.

Example 1 and Comparative Example 1
In the 200 mL beaker, the components (A), (B), and ion-exchanged water (indicated by the symbol (C) in the table) and an appropriate amount of alkaline pH adjuster [sodium carbonate] shown in Tables 1 to 6 are contained. And stirred for 20 minutes. The pH at that time was 8-12. Then, it adjusted to the target pH shown in a table | surface further using the acidic pH adjuster [citric acid]. The change in the organic peracid concentration over time at that time was measured. The organic peracid concentration was measured by the following method. The results are shown in Tables 1-6.

  In addition, in the 200 mL beaker, (A) component, (B) component and ion-exchanged water (indicated by the symbol (C) in the table) and an appropriate amount of acidic pH adjuster [citric acid] shown in Table 7 And stirred for 20 minutes. The pH at that time was adjusted to 3-5. The organic peracid concentration at that time was measured, but generation of organic peracid was not observed. This example corresponds to an example in which the pH of the first step is 3 to 5 and the second step is not particularly provided. The results are shown in Table 7.

(1) Measuring method of organic peracid concentration (1-1) Quantification of hydrogen peroxide Into a 200 mL conical beaker, accurately weigh the organic peracid-containing aqueous solution w ₁ g ( _{1 to} 50 g as a guide) after the second step. Then, 10 mL of 20% sulfuric acid aqueous solution and 2 to 3 pieces of ice were added to cool the solution. After adding 1-2 drops of saturated aqueous manganese sulfate solution as a catalyst, 0.1 mol / L (1/2 N) permanganate Titrate with aqueous potassium solution. The end point is where the solution exhibits a light pink color for 1 to 10 seconds. The hydrogen peroxide concentration is calculated by the following formula (1-1).

T ₁ : Titration required amount of 0.1 mol / L potassium permanganate aqueous solution (mL)
F ₁ : Factor of 0.1 mol / L potassium permanganate aqueous solution w ₁ : Weight of organic peracid-containing aqueous solution after the second step (g)

(1-2) Determination of organic peracid In a 300 mL conical flask with a stopper, an organic peracid-containing aqueous solution w ₂ g (1 to 50 g as a guide) after the second step is precisely weighed, 10 mL of 20% sulfuric acid aqueous solution, pure After adding 20 mL of water and 2 mL of a saturated aqueous potassium iodide solution and sealing the flask, the flask is shaken lightly. This is left to stand in a cool dark place for 5 minutes, and then titrated with a 0.2 mol / L (1/5 normal) sodium thiosulfate aqueous solution. When the solution shows a pale yellow color, add several drops of 2% starch aqueous solution and continue titration. The point where the blue-violet color of the solution disappears is taken as the end point. The organic peracid concentration is calculated by the following formula (1-2).

T ₂ : Required amount of titration of 0.2 mol / L sodium thiosulfate aqueous solution (mL)
F ₂ : Factor of 0.2 mol / L sodium thiosulfate aqueous solution H: Hydrogen peroxide concentration (wt%) determined by the formula (1-1)
w ₂ : Weight of organic peracid-containing aqueous solution after the second step (g)

(Note) The numerical value in () of the blending component is the number of moles, and the number of mole in () of the (B) component is the amount as hydrogen peroxide (the same applies hereinafter). The molar ratio (A) / (B) is the molar ratio of the component (A) and hydrogen peroxide (the same applies hereinafter). The term “immediately after the second step in the organic peracid concentration” means immediately after the pH in the system reaches a predetermined value, and the residual rate of organic peracid is [(organic peracid concentration immediately after the second step) / (Organic peracid concentration after 60 minutes of the second step)] x 100 (the same applies hereinafter). In addition, the hydrogen peroxide remaining rate is obtained by calculating the total hydrogen peroxide weight in the system from the hydrogen peroxide concentration calculated from the equation (1-1), and dividing this by the initial input total hydrogen peroxide weight. (The same applies hereinafter). In addition, among the components (A), the fatty acid of glycerin fatty acid ester [trade name: Homotex PT, manufactured by Kao Corporation] has 8 carbon atoms (the same applies hereinafter). Sodium percarbonate contained 22% by weight of hydrogen peroxide, and sodium perborate contained 20% by weight of hydrogen peroxide.

Reference Example 1 and Comparative Reference Example 1
An aqueous solution for sterilization containing the organic peracids produced in Example 1 and Comparative Example 1 at the concentrations shown in Tables 8 to 11 and having a pH of Tables 8 to 11 was prepared, and the sterilizing effect was measured by the following method. . The results are shown in Tables 8-11.

(1) Bacterial spore killing effect Spore-forming bacteria, Bacillus subtilis var. Niger, and circulans bacterium ( Bacillus circulans IFO3967) are each applied to SCD agar medium (manufactured by Nippon Pharmaceutical Co., Ltd.). After pre-culturing at 4 ° C. for about 4 weeks, an appropriate amount of colonies formed on the agar medium were scraped and suspended in 1 mL of sterilized water, and microscopically confirmed to form bacterial spores (hereinafter referred to as spores). This suspension was subjected to centrifugal washing twice and then adjusted to a bacterial concentration of about 10 ⁸ to 10 ⁹ cells / mL with an appropriate amount of sterile water (spore solution 1). 0.1 ml of this spore solution 1 was inoculated into 2 ml of the aqueous solution for sterilization shown in Tables 8 to 11 and allowed to act at 25 ° C. for 120 seconds. Immediately thereafter, 0.1 mL of the sterilizing aqueous solution containing the spore solution 1 was added to SCDLP medium (Nippon Pharmaceutical Co., Ltd.) supplemented with 1.0% sodium thiosulfate to inactivate the sterilizing aqueous solution. (Spore fluid 2). Spore solution 2 was smeared in 0.2 mL on a standard agar medium having a diameter of 9 cm, cultured at 35 ° C. for 36 hours, and the number of remaining colonies was confirmed by counting the number of colonies formed on the medium.

(2) Killing effect of mold spores Black Aspergillus ( Aspergillus niger IFO6341) was pre-cultured on potato dextrose agar medium (Nippon Pharmaceutical Co., Ltd.) for about 4 weeks. The microbial cells generated on the medium were scraped off and suspended in 5 ml of sterilized water, and the suspension was homogenized using a glass homogenizer. This suspension was subjected to centrifugal washing twice, and then adjusted to a bacterial concentration of about 10 ⁸ to 10 ⁹ cells / mL with an appropriate amount of sterilized water (spore solution 1). 0.1 mL of this spore solution 1 was inoculated into 2 ml of the sterilizing aqueous solution shown in Tables 8 to 11 and allowed to act at 25 ° C. for 120 seconds. Immediately after that, 0.1 ml of the sterilizing aqueous solution containing the spore solution 1 was added to SCDLP medium (Nippon Pharmaceutical Co., Ltd.) containing 1.0% sodium thiosulfate to inactivate the sterilizing aqueous solution. (Spore solution 2). Spore solution 2 was smeared on potato dextrose agar medium having a diameter of 9 cm, cultured at 25 ° C. for 3 to 4 days, and the number of remaining bacteria was confirmed by counting the number of colonies formed on the medium. .

Example 2
Component (A), component (B), organic phosphonic acid [trade name: Diquest 2010 (manufactured by Solusia Japan Co., Ltd.)] and alkaline pH adjuster with the weights shown in Table 12 were added to ion-exchanged water. The weight was 100 g (first step). This was stirred and mixed in a 200 mL beaker for about 10 minutes. The pH at that time was 8-12. Then, it adjusted to the target pH rapidly using the acidic pH adjuster of the weight shown in Table 10, and also added ion-exchange water, and made the whole quantity 110g (2nd process). The organic peracid concentration and the hydrogen peroxide concentration at this time (immediately after preparation) were measured, and the change over time in the organic peracid concentration (30 minutes, 60 minutes, and 120 minutes after the preparation) was measured. . The sterilizing aqueous solution after aging for 120 minutes was adjusted to 3000 ppm as the organic peracid concentration to confirm the sterilizing effect. In addition, the measuring method of hydrogen peroxide concentration and organic peracid concentration followed the measuring method of organic peracid concentration of Example 1. Further, a method bactericidal test in accordance with the killing effect of the bacterial spores in Reference Example 1, the contact temperature and contact time for sterilization solution and bacteria in this example a 60 ° C. 20 seconds, Bacillus as the target bacteria cereus IFO13494 and Bacillus circulans IFO3967 was provided.

Example 3
Liquid compositions having the compositions shown in Table 13 were prepared, and the stability of organic peracid production was evaluated by the following method. The results are shown in Table 13.

<Organic peracid production stability test method>
The liquid composition Xg of Table 13, 0.1 g of organic phosphonic acid, and 2 g of NaOH were prepared in a 100 mL beaker so that the total amount became 100 g by adding ion-exchanged water. After stirring and mixing for 5 minutes, the generated organic peracid concentration (%) (organic peracid production concentration immediately after preparation) was measured according to the organic peracid concentration measurement method of Example 1. Here, in Examples 3-1 to 3-3, X = 7.5 (g), and in Examples 3-4 to 3-9 and Comparative Examples 3-1 to 3-2, X = 10 (g). did.

Further, 150 ml of the liquid composition shown in Table 13 is filled in a glass bottle (colorless and transparent) having a capacity of 200 ml, covered, and stored at 50 ° C. After 4 weeks, the organic peracid production was performed in the same manner as described above, and the organic peracid production concentration (%) after storage was measured in the same manner. The organic peracid production stability was determined by the following formula.
Organic peracid production stability rate (%) = [(Organic peracid production concentration after storage) ÷ Organic peracid production concentration immediately after adjustment] × 100

Claims (9)

(A) An ester of a polyhydric alcohol and a carboxylic acid which may have a hydroxyl group and (B) hydrogen peroxide in a molar ratio of (A) / (B) = 1/10 to 20/1, A method for producing an organic peracid, comprising a step of reacting in water at pH 8 to 12, and then bringing the reaction system to pH 1 or more and less than 7. (A) and (B), (A) and (B) the manufacturing method according to claim 1 Symbol placement containing and water content is produced as a liquid composition is 1 to 25% by weight. The method according to claim 1 or 2 , wherein the carboxylic acid constituting (A) is a fatty acid having 1 to 8 carbon atoms. The process according to any one of claims 1 to 3 , wherein the reaction of (A) and (B) at pH 8 to 12 in water is carried out at 5 to 50 ° C for 1 to 120 minutes. (A) An ester of a polyhydric alcohol and a carboxylic acid which may have a hydroxyl group and (B) hydrogen peroxide in a molar ratio of (A) / (B) = 1/10 to 20/1, A method for producing a fungicide composition, comprising a step of reacting in water at pH 8 to 12, and then setting the reaction system to pH 1 or more and less than 7. The production method according to claim 5, wherein (A) and (B) are produced as a liquid composition containing (A) and (B) and having a water content of 1 to 25% by weight. The method according to claim 5 or 6, wherein the content of hydrogen peroxide in the disinfectant composition is 0.5% by weight or less. The carboxylic acid which comprises (A) is a C1-C8 fatty acid, The manufacturing method in any one of Claims 5-7. The method according to any one of claims 5 to 8, wherein the reaction of (A) and (B) at pH 8 to 12 in water is carried out at 5 to 50 ° C for 1 to 120 minutes.