JP2004315518A - Composition for producing bactericidal agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a composition for producing a bactericidal agent, capable of giving the bactericidal agent which exhibits highly bactericidal activity not only on common bacteria but also on spores or mildew sporozoites whose chemical resistance is high. <P>SOLUTION: This composition for producing the bactericidal agent contains (A) an ester of a polyhydric alcohol with an organic acid having a hydrocarbon residue which may have a hydroxy group and (B1) hydrogen peroxide, wherein the composition contains water in an amount of 1-25 wt%. The composition gives the bactericidal agent as an aqueous solution containing an organic peracid. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a composition for producing a disinfectant, a disinfectant composition, and a disinfecting method.

At present, there are various agents known to be effective in bleaching, disinfecting, disinfecting, etc., but in particular, hypochlorites such as sodium hypochlorite as chlorine disinfectants, and peroxides Sodium percarbonate, sodium perborate, and the like, which generate hydrogen peroxide in hydrogen or water, are mainly used. However, these disinfectants have various problems, for example, hypochlorite has a problem of corrosion to metals and the like and a problem of chlorine gas generation due to misuse, and hydrogen peroxide has a high disinfecting effect. In order to obtain it, there is a problem that use at a high concentration or long contact is required. In the case of using hydrogen peroxide, in order to solve these problems, measures such as enhancing the bactericidal effect by using an activator in combination to generate an organic peracid during use have been taken. As such a disinfectant composition, Patent Document 1 discloses a disinfectant composition containing an inorganic peroxide, an incomplete ester of an organic acid of a polyhydric alcohol, and an alkaline earth metal salt. There is no description of its use in spores, and the bactericidal effect on spores and mold spores having higher drug resistance still needs to be improved. Further, as a method of applying an organic peracid as a disinfectant, Patent Literatures 2 and 3 are cited, and these are based on a concentrated combination of peracetic acid, acetic acid, and hydrogen peroxide as a disinfectant composition. It is difficult to handle with a strong pungent odor. Further, Patent Document 4 proposes a method of improving the bleaching effect by adjusting the pH in an organic peracid generating system, but cannot improve the bactericidal activity of spores and mold spores having higher chemical resistance. Patent Document 5 discloses that a composition containing hydrogen peroxide, carboxylic acid, and a specific ratio of percarboxylic acid to hydrogen peroxide exhibits an antibacterial effect on spores or spore-forming microorganisms. However, as in Patent Documents 2 and 3, it is accompanied by a pungent odor, and there is a problem in handleability.
JP-A-6-305920 Japanese Patent Publication No. Hei 8-500843 JP-A-8-311495 JP-A-5-25497 International Publication No. 01/70030 pamphlet

  The present invention is to efficiently and stably generate a high concentration of organic peracid when used, a bactericidal composition for obtaining a bactericide composition having high bactericidal activity, and a bactericidal composition having high bactericidal activity. The purpose is to provide.

  The present invention contains (A) an ester of a polyhydric alcohol and an organic acid having a hydrocarbon group which may have a hydroxyl group, and (B1) hydrogen peroxide, and has a water content of 1 to 25% by weight. The present invention relates to a composition for producing a fungicide (hereinafter, referred to as a first composition for producing a fungicide).

  Further, the present invention provides (A) an ester of a polyhydric alcohol and an organic acid having a hydrocarbon group which may have a hydroxyl group, and (B1) hydrogen peroxide or (B2) releasing hydrogen peroxide in water. (A) and (B1) or (B1) generated from (A) and (B2) in a molar ratio of (A) / (B1) = 1/10 to 20/1. A fungicide-producing composition, which is used as an aqueous solution prepared at a pH of 1 to less than 7 after the pH is adjusted to 8 to 12 (hereinafter, a second fungicide-producing composition) Thing).

  Further, the present invention provides (A) an ester of a polyhydric alcohol and an organic acid having a hydrocarbon group which may have a hydroxyl group, and (B1) hydrogen peroxide or (B2) releasing hydrogen peroxide in water. And (B1) generated from (A) and (B1) or (A) and (B2) at a molar ratio of (A) / (B1) = 1/10 to 20/1. A bactericide-producing composition obtained as described above, wherein the pH is adjusted to 8 to 12, and then the bactericide-producing composition is used as an aqueous solution prepared to have a pH of 1 or more and less than 7 (hereinafter, a third bactericide). (Referred to as a production composition).

  In addition, the present invention relates to a method for preparing (A) / (B1) an ester of (A) a polyhydric alcohol and an organic acid having a hydrocarbon group which may have a hydroxyl group, and (B1) hydrogen peroxide in water. A) a fungicidal composition containing an organic peracid obtained by reacting at a molar ratio of 1/10 to 20/1 and a pH of 8 to 12 and water and having a pH of 1 or more and less than 7 at 25 ° C. (Hereinafter, referred to as a first germicidal composition).

  In addition, 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 and (B1) hydrogen peroxide, wherein (A) / (B1) = 1 The reaction is carried out at a pH of 8 to 12 in water at a molar ratio of / 10 to 20/1, and then an aqueous solution containing an organic peracid obtained by setting the reaction system to a pH of 1 or more and less than 7 is brought into contact with an object to be sterilized. About the method.

  In the following, (A) an ester of a polyhydric alcohol and an organic acid having a hydrocarbon group which may have a hydroxyl group is used as a component (A), (B1) hydrogen peroxide is used as a component (B1), and (B2) The inorganic peroxide that releases hydrogen peroxide in water will be referred to as component (B2), and the components (B1) and (B2) will be referred to as component (B).

  In the component (B), the number of moles of hydrogen peroxide generated from the component (B2) refers to the hydrogen peroxide concentration (% by weight) in the component (B2) determined by the permanganate titration method. It is a value obtained by multiplying the blending amount (g) of the component (B2) in the product and dividing by 34, which is the molecular weight of hydrogen peroxide.

  The germicidal composition obtained from the bactericide-producing composition of the present invention or the germicidal composition of the present invention has a high bactericidal effect and is excellent in its persistence. ADVANTAGE OF THE INVENTION According to this invention, the sterilization method which shows the outstanding sterilization effect in a wide field | area from industrial sterilization of a food factory etc. to home sterilization is provided.

<(A) component>
The ester of the polyhydric alcohol of the component (A) and the organic acid having a hydrocarbon group which may have a hydroxyl group reacts with hydrogen peroxide to generate an organic peracid.

  As the polyhydric alcohol for constituting the component (A), those having 2 to 12 carbon atoms are preferable, and glycerins such as glycerin, diglycerin and triglycerin, glucose, sucrose, fructose, sorbitol, pentaerythritol, and alkyl Sugars such as polyglycosides and alkylfuranosides are exemplified.

  Examples of the organic acid for constituting the component (A) include aliphatic monocarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, and octanoic acid, oxalic acid, malonic acid, succinic acid, and maleic acid. , An aliphatic dicarboxylic acid such as fumaric acid, a hydroxycarboxylic acid having a hydroxyl group such as citric acid, tartaric acid, and malic acid; and the like, preferably a saturated or unsaturated aliphatic mono- or dicarboxylic acid having 1 to 8 carbon atoms. And more preferably a saturated or unsaturated aliphatic monocarboxylic acid having 1 to 8 carbon atoms, more preferably a fatty acid having 1 to 8 carbon atoms, and particularly preferably a fatty acid having 2 to 8 carbon atoms. Fatty acids. The degree of esterification of the component (A) is not limited.

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

<(B) component>
The component (B) is hydrogen peroxide of the component (B1) or an inorganic peroxide that releases hydrogen peroxide in water of the component (B2). When the composition is in a liquid state, the hydrogen peroxide is in the form of particles, In the case of a solid such as a powder, a percarbonate and a perborate are preferred, and sodium percarbonate and sodium perborate are particularly preferred.

<First bactericide production composition>
Although the first composition for producing a fungicide of the present invention contains the component (A) and the component (B1), the reaction between the component (A) and the component (B1) during storage is suppressed, and From the viewpoint of maintaining stability, the water content in the composition is 1 to 25% by weight, preferably 5 to 20% by weight, particularly preferably 5 to 15% by weight.

  Since the first composition for producing a disinfectant of the present invention is a one-part liquid composition containing a component for obtaining an organic peracid, for example, the first disinfectant composition of the present invention described below It is suitable for producing an aqueous solution for sterilization used in the sterilization method of the present invention. The content of the component (A) in the composition for producing a first fungicide 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 (B1) is , 1 to 30% by weight, more preferably 5 to 25% by weight, particularly preferably 10 to 25% by weight. The molar ratio of the component (A) to the component (B1) is (A) / (B1) = 1/10 to 20/1, further 1/10 to 10/1, particularly 1/5 to 10/1. Preferably, there is. The molar ratio of the component (B1) to one ester group of the component (A) is preferably not more than twice the molar ratio from the viewpoint of efficiently generating an organic peracid and reducing unreacted hydrogen peroxide. It is preferably, especially 0.3 to 2 times mol.

  In addition, the first composition for producing a bactericide can contain a chelating agent, a pH adjuster, a solvent, and the like, if necessary. A chelating agent is useful for suppressing catalytic decomposition due to a trace amount of metal ions such as Fe and Cr. The stock solution pH (20 ° C.) of the first composition for producing a fungicide is preferably from 0.5 to 6, more preferably from 1 to 5, and particularly preferably from 1 to 4, from the viewpoint of storage stability. Those having both the function as a pH adjuster and the function as a chelating agent are preferable, and specifically, phosphoric acid, polymerized phosphoric acid, organic phosphonic acid, aminocarboxylic acid, hydroxycarboxylic acid, or salts thereof are preferable. Especially, organic phosphonic acid or its salt is preferable. As the solvent, a polyhydric alcohol solvent is preferable, and a glycol solvent such as propylene glycol is particularly preferable.

<Second fungicide-producing composition>
The second composition for producing a fungicide of the present invention contains the component (A) and the component (B), and the ratio of the two is within a range in which the component (B1) and the component (A) efficiently react. It is preferable that the molar ratio of the component (A) to the component (B1) is (A) / (B1) = 1/10 to 20 in consideration of the organic peracid generation efficiency, the bactericidal effect, the preparation stability, and the like. / 1, 1/10 to 10/1, and more preferably 1/5 to 10/1. The molar ratio of the component (B1) to one ester group of the component (A) is preferably not more than twice the molar ratio from the viewpoint of efficiently generating an organic peracid and reducing unreacted hydrogen peroxide. It is preferably, especially 0.3 to 2 times mol. When the component (B2) is used, it is preferable to blend the component (B1) in the above range in an amount that generates the component.

  Preferably, after satisfying this molar ratio, the second composition for producing a disinfectant of the present invention contains the component (A) in an amount of 0.1 to 90% by weight, more preferably 0.5 to 70% by weight, particularly It is preferable that the component (B) is contained in an amount of 0.1 to 50% by weight, more preferably 0.1 to 30% by weight, particularly 0.1 to 20% by weight, as the component (B1).

  When used, the second composition for producing a fungicide of the present invention has a pH of 8 to 12, preferably 9 to 11 (first step), and then has a pH of 1 or more and less than 7, preferably 1 to 6, more preferably By setting it as 1 to 5 (second step), an aqueous solution which is a bactericide composition is prepared. It is preferable to use an alkaline pH adjuster in the first step and an acidic pH adjuster in the second step. This pH may be the value at the time of use, but preferably satisfies the above pH at 25 ° C. The above-mentioned composition for producing a first fungicide of the present invention can be used in the same manner.

  Examples of the alkaline pH adjuster include alkali metal hydroxides or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide and barium hydroxide, and silicic acids such as sodium silicate and potassium silicate. Alkali metal salts, alkali metal phosphates exhibiting alkalinity such as trisodium phosphate and the like, and alkali metal carbonates such as sodium carbonate and potassium carbonate are exemplified. From the viewpoint of alkalinity and water solubility, sodium hydroxide and potassium hydroxide are used. And the like, alkali metal phosphates such as trisodium phosphate and tripotassium phosphate, and alkali metal carbonates such as sodium carbonate and potassium carbonate are preferred. 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. Preferred are liquid inorganic acids such as phosphoric acid and phosphoric acid, and highly water-soluble organic acids such as citric acid and acetic acid. These can be used alone or in combination of two or more. In addition, these pH adjusters may be present as they are in the second composition for producing a fungicide of the present invention. Note that these pH adjusters can also be present in the above-mentioned composition for producing a first fungicide of the present invention.

  The composition for producing a second fungicide of the present invention contains, in addition to the component (A) and the component (B), a surfactant, an inorganic or organic salt, a chelating agent, a fragrance, a pigment, a dye, and the like. Can be. These components can also be present in the first composition for producing a bactericide of the present invention described above.

  Surfactants include nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants. Examples of the nonionic surfactant include polyoxyethylene (hereinafter, referred to as POE) alkyl ether, POE alkyl phenyl ether, polyoxypropylene / POE (block or random) alkyl ether, POE aryl phenyl ether, POE styrenated phenyl ether. , POE tribenzyl phenyl ether and other monohydric alcohol derivative type nonionic surfactants; (poly) glycerin fatty acid ester, sucrose fatty acid ester, sorbitan fatty acid ester, alkylpolyglycoside etc. nonionic surfactant Activators and the like. Examples of the anionic surfactant include lignin sulfonate, alkylbenzene sulfonate, alkyl sulfonate, POE alkyl sulfonate, POE alkylphenyl ether sulfonate, POE alkylphenyl ether phosphate, POE arylphenyl. Examples include ether sulfonates, POE aryl phenyl ether phosphates, naphthalene sulfonates, naphthalene sulfonic acid formalin condensates, POE tribenzyl phenyl ether sulfonates, POE tribenzyl phenyl ether phosphates, and the like. Examples of the cationic surfactant include mono-long-chain alkyl (8 to 18 carbon atoms) trimethylammonium chloride, di-long-chain alkyl (8 to 18 carbon atoms) dimethyl ammonium chloride, benzalkonium chloride, benzethonium chloride and the like. . Examples of the amphoteric surfactant 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 composition for producing a second fungicide of the present invention in an amount of 0 to 20% by weight, 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, succinic acid, malonic acid, citric acid, gluconic acid, metal salts of carboxylic acids such as glutaric acid, etc. And inorganic salts such as metal salts of phosphate compounds such as tripolyphosphoric acid, hexametaphosphoric acid, and phosphoric acid, and 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, and salts thereof.

  The second fungicide-producing composition of the present invention can take various forms. In the case of a liquid, a liquid having high fluidity is preferable, and in addition to an aqueous solution, a fluid, slurry, gel, paste, etc. It may be. In the case of a solid, a shape such as a granule, a powder, a granule, and a pellet may be used.

  The second composition for producing a disinfectant of the present invention may be one in which all of the components are packaged together, but from the viewpoint of stability, a plurality of components (A) and (B) separately packaged. Dosage form is preferred. For example, a package (1) of the composition containing the component (A), a package (2) of the composition containing the component (B), and a pH adjuster for finally adjusting the pH to 1 or more and less than 7 (A acidic pH adjuster such as citric acid) and a package (3) of a composition containing the composition. In this case, it is preferable to mix an alkali agent in the package (2) and adjust the mixture of the package (1) and the package (2) to have a pH of 8 to 12. In particular, in the case of a powder composition, the component (A) and the component (B) can coexist in a single package. A package containing a composition (I) containing an alkaline agent for adjusting the pH to 12, and a composition containing a pH adjuster (an acidic pH adjuster such as citric acid) for finally adjusting the pH to 1 or more and less than 7. The composition can be a two-part disinfectant-producing composition comprising a product package (II).

  At the time of use, the second composition for producing a disinfectant of the present invention is prepared by adjusting the pH in the first step and the second step to prepare an aqueous solution which is a disinfectant composition containing an organic peracid. You. The organic peracid concentration in the aqueous solution is preferably 10 to 20,000 ppm (weight ratio, the same applies hereinafter), and more preferably 10 to 10,000 ppm. Further, the content of hydrogen peroxide in the aqueous solution 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 from the viewpoint of the sterilizing effect. These findings are the same in the first composition for producing a fungicide of the present invention described above.

<Third bactericide-producing composition>
The third fungicide-producing composition of the present invention is obtained by blending the above-mentioned components (A) and (B) of the present invention. The molar ratio of the component (A) to the component (B1) derived from the component (B) is (A) / (B1) = 1/10 to 20/1. It is used as an aqueous solution prepared as less than 7 or more. Specific compounds of the components (A) and (B), and the preferred molar ratio of (A) / (B1) are also the same as those of the second composition for producing a fungicide. In addition, the third fungicide-producing composition can also contain the above-mentioned surfactant, inorganic or organic salts, chelating agents, fragrances, pigments, dyes, and the like. Can be.

<First fungicide composition>
The first fungicide composition of the present invention comprises the component (A) and the component (B1) in water at a molar ratio of (A) / (B1) = 1/10 to 20/1 and a pH of 8 to 10. It contains an organic peracid obtained by the reaction at 12, and water, and has a pH of 1 or more and less than 7 at 25 ° C. As described above, the first fungicide composition of the present invention reacts the component (A) with the component (B1) in water at a specific molar ratio and at a pH of 8 to 12, and then adjusts the pH to 1 or more. It is adjusted to less than 7, preferably 1 to 6, more preferably 1 to 5. The specific compounds of the components (A) and (B), and the preferable molar ratio of (A) / (B1) are the same as those of the above-mentioned second composition for producing a fungicide of the present invention. Further, the first fungicide composition can also contain the above-mentioned surfactant, inorganic or organic salts, chelating agent, fragrance, pigment, dye, and the like. The amount of water in the composition is preferably from 50% by weight to less than 100% by weight, more preferably from 60% by weight to less than 100% by weight, particularly preferably from 70% by weight to less than 100% by weight. Like the aqueous solution obtained from the composition for producing a fungicide of the present invention, the first fungicide composition of the present invention is an aqueous solution containing an organic peracid, and the concentration of the organic peracid in the aqueous solution is 10%. It is preferably from 20,000 ppm, more preferably from 10 to 10,000 ppm. In addition, the first fungicide composition of the present invention has a hydrogen peroxide content of 0.5% by weight or less, more preferably 0.3% by weight or less, and particularly preferably 0.2% by weight or less, for the sterilizing effect. It is preferred in that respect. This hydrogen peroxide content is preferably achieved immediately after the preparation of the composition, and more preferably at the time of use.

<Sterilization method>
In the sterilization method of the present invention, the component (A) and the component (B1) are reacted at a molar ratio of (A) / (B1) = 1/10 to 20/1 in water at pH 8 to 12, An aqueous solution containing an organic peracid (hereinafter, referred to as an aqueous solution for sterilization) obtained by setting the reaction system to a pH of 1 or more and less than 7, preferably pH 1 to 6, and more preferably pH 1 to 5, is brought into contact with an object to be sterilized. For this purpose, the bactericide composition of the present invention or the aqueous solution obtained from the bactericide-producing composition of the present invention is suitably used.

The sterilization method of the present invention,
(I) The component (A) and the component (B1) are reacted at a molar ratio of (A) / (B1) = 1/10 to 20/1 in water at pH 8 to 12 to contain an organic peracid. Step (II) of obtaining an aqueous solution Next, the pH of the aqueous solution is adjusted to 1 or more and less than 7, preferably pH 1 to 6, and more preferably pH 1 to 5 to obtain an aqueous solution for sterilization (III) The aqueous solution for sterilization is brought into contact with an object to be sterilized. Steps may be included.
In the step (I), for example, predetermined amounts of the component (A), the component (B1), and a pH adjuster (alkali agent) that gives a pH of 8 to 12 are added to water at 5 to 50 ° C. The reaction can be carried out by reacting the component (B1). The step (II) can be performed by adding a pH adjuster (acid agent) that gives a pH of 1 to less than 7 to the mixed system.

  Examples of the method of bringing the aqueous solution for sterilization into contact with the object to be sterilized include methods such as spraying, dipping, filling, and applying the aqueous solution. When spraying, it is preferable to spray. Alternatively, the object may be wiped off by impregnating a suitable carrier with the aqueous solution. Although the contact time is not limited, depending on the material to be sterilized, a sufficient effect can be obtained even within a short time of 30 seconds or less, particularly 10 seconds or less. The temperature of the aqueous solution at the time of contact is not limited, but is preferably 10 to 90 ° C, more preferably 15 to 80 ° C.

  The disinfectant (aqueous solution for disinfectant) and the disinfecting method obtained from the disinfectant composition or the disinfectant-producing composition of the present invention have a high disinfecting effect. Can be sterilized. For example, in bacteria, Escherichia coli, Salmonella, Staphylococcus aureus, bacteria causing food poisoning such as Staphylococcus and hospital-acquired infections, fungi such as Aspergillus niger, Candida fungi, and Bacillus subtilis having strong resistance to fungicides. Fungal spores such as bacterial spores and Aspergillus niger can be mentioned. Of these, bacterial spores are durable, dormant cells created in an environment unsuitable for growth, and have multiple layered outer shells outside the cells. Such bacterial spores have extremely high durability against drugs, heat, and the like, and it is difficult to completely kill them by general sterilization. However, according to the bactericide composition and the bactericidal method of the present invention, a sufficient bactericidal effect can be obtained even for such bacterial spores.

  As described above, the disinfectant (aqueous solution for disinfection) and the disinfecting method obtained from the disinfectant composition or the disinfectant-producing composition of the present invention have a wide disinfecting spectrum, and are useful not only for bacteria but also for fungi and spores. Since it is highly effective, it is useful for sterilization in a wide range of fields. For example, it is used for sterilization of walls, floors, windows, etc. of hospitals, nursing homes, food processing factories, cleaning facilities, kitchens and the like, or instruments, equipment, and product (eg, beverage) containers used therefor.

<Disinfectant kit>
A suitable disinfectant kit for obtaining the disinfectant composition of the present invention is a reaction for initiating the reaction between the composition for producing a disinfectant of the present invention and the components (A) and (B1) provided by the composition. It comprises an initiator [hereinafter, referred to as component (C)] and a pH adjuster [hereinafter, referred to as component (D)]. Further, the disinfectant kit can also be configured to include the components (A), (B), (C) and (D).

  The disinfectant kit for obtaining the disinfectant composition of the present invention may be a one-drug type in which all of the components are packaged together in consideration of the simplicity in the production of organic peracid, but the stability upon storage is In consideration of the above, a multiple dosage form in which the component (A), the component (B), the component (C), and the component (D) are individually packaged may be used. Preferred dosage forms of the disinfectant kit include two or more of the components (A) to (D) in consideration of both the simplicity during production of the organic peracid and the storage stability of the composition for production. Or a two-pack type or three-pack type containing a package in which the composition is packaged.

  The component (A) and the component (B1) react in water under alkaline conditions (preferably at a water temperature of 5 to 50) to produce an organic peracid, and therefore, a component giving such a pH is used as the component (C). it can. Specifically, alkali metal hydroxides or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide and barium hydroxide exemplified as alkaline pH adjusters, sodium silicate, and silicic acid Examples thereof include alkali metal silicates such as potassium, alkali metal phosphates exhibiting alkalinity such as trisodium phosphate, and alkali metal carbonates such as sodium carbonate and potassium carbonate. Preferred are alkali metal hydroxides such as sodium and potassium hydroxide, alkali metal phosphates such as trisodium phosphate and potassium triphosphate, and alkali metal carbonates such as sodium carbonate and potassium carbonate.

  On the other hand, since the bactericide containing an organic peracid is preferably acidic from the viewpoint of the bactericidal effect, the component (D) is a component capable of changing the pH in the alkaline region to the acidic region by the component (C). You. Specific 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, liquid inorganic acids such as sulfuric acid and phosphoric acid and highly water-soluble organic acids such as citric acid and acetic acid are preferred.

As a specific dosage form of the disinfectant kit,
(I) A package (X1) of the composition for producing a disinfectant containing the components (A) and (B), a package (X2) of the composition containing the component (C), and the component (D). Package (Y1) of the composition containing the three or more dosage forms (II) and (A) containing the package (X3) of the containing composition, containing the components (B) and (C) Three or more dosage forms (III), (A) component, (B) component, and (C) component including the composition package (Y2) and the composition package (X3) containing the component (D). And two or more dosage forms including a package (Z1) of a composition containing (A) and a package (Z2) of a composition containing the component (D).

  In the dosage form of (I), the form of the composition for producing a bactericide is not limited to powder, solid, liquid or the like, but liquid is more preferable from the viewpoint of simplicity. In the case of a liquid form, the water content in the liquid composition is preferably 1 to 25% by weight in order to suppress the reaction between the components (A) and (B) during storage and maintain stability. , More preferably 5 to 20% by weight, and even more preferably 5 to 15% by weight. If necessary, a chelating agent and a solvent can be added to the liquid composition. A chelating agent is useful for suppressing catalytic decomposition due to a trace amount of metal ions such as Fe and Cr. Further, the undiluted solution pH (20 ° C.) of the liquid composition is preferably 0.5 to 6, more preferably 1 to 5, and still more preferably 1 to 4, because it is involved in storage stability. As described above, it is preferable to use a component having both a function as a pH adjuster and a function as a chelating agent, specifically, phosphoric acid, polymerized phosphoric acid, organic phosphonic acid, aminocarboxylic acid, hydroxycarboxylic acid, Alternatively, these salts are preferable. Especially, organic phosphonic acid or its salt is preferable. As the solvent, a polyhydric alcohol solvent is preferable, and a glycol solvent such as propylene glycol is particularly preferable.

  When the composition for producing a bactericide is in the form of powder or solid in the dosage form of (I), it is preferable to use sodium percarbonate, sodium perborate, or the like as the component (B). Similarly, in the dosage form of (II) and the dosage form of (III), the composition containing the component (B) uses sodium percarbonate or sodium perborate as the component (B) from the viewpoint of storage stability. Powdered and solid forms are preferred.

  The content of the components (A) to (D) in each of these dosage forms can be selected in an appropriate range based on the usage of the first to third fungicide-producing compositions of the present invention. it can. The components other than the components (A) to (D) may be incorporated in any package containing the components (A) to (D), or may be incorporated in another package. .

Example 1
The components (A) and (B) in the amounts shown in Tables 1 to 5 and 50 g of ion-exchanged water and an appropriate amount of an alkaline pH adjuster [sodium carbonate] were stirred and mixed in a 200 mL beaker for 20 minutes. At that time, the pH was adjusted to 8 to 12. Thereafter, the pH was further adjusted to a target pH using an acidic pH adjuster [citric acid] to obtain a disinfectant composition. The change of the organic peracid concentration with time at that time was measured. The organic peracid concentration was measured by the following method. The results are shown in Tables 1 to 5.

(1) Method of Measuring Organic Peracid Concentration (1-1) Determination of Hydrogen Peroxide In a 200 mL conical beaker, ₁ g ( _{1 to} 50 g as a guide) of the bactericide composition is precisely weighed, and 10 mL of a 20% aqueous sulfuric acid solution is added. And 2 to 3 pieces of ice are added to cool the solution. After adding 1 to 2 drops of a saturated aqueous solution of manganese sulfate as a catalyst, the mixture is titrated with a 0.1 mol / L (1 / 2N) aqueous solution of potassium permanganate. The end point is where the solution exhibits a pale pink color for 1 to 10 seconds. The hydrogen peroxide concentration is calculated by the following equation (1-1).

T ₁ : required titration amount (mL) of 0.1 mol / L aqueous solution of potassium permanganate
F ₁ : Factor of 0.1 mol / L aqueous solution of potassium permanganate w ₁ : Weight (g) of fungicide composition

(1-2) Determination of Organic Peracid Into a 300 mL Erlenmeyer flask with a stopper, bactericide composition w ₂ g (1 to 50 g as a guide) is precisely weighed, and 10 mL of a 20% aqueous sulfuric acid solution, 20 mL of pure water, and saturated iodide. After addition of 2 mL of an aqueous potassium solution and sealing, the flask is gently shaken. This is allowed to stand in a cool dark place for 5 minutes, and then titrated with a 0.2 mol / L (1 / 5N) aqueous sodium thiosulfate solution. When the solution shows a pale yellow color, a few drops of a 2% aqueous starch solution are added and the titration is continued. The point at which the blue-violet color of the solution has disappeared is regarded as the end point. The organic peracid concentration is calculated by the following equation (1-2).

T ₂ : Required titration amount (mL) of 0.2 mol / L sodium thiosulfate aqueous solution
F ₂ : Factor of 0.2 mol / L sodium thiosulfate aqueous solution H: Hydrogen peroxide concentration (% by weight) determined by equation (1-1)
w ₂ : weight (g) of the fungicide composition

(Note) The numerical value in parentheses of the components is the number of moles, and the molar number in parentheses of the component (B) is the amount as hydrogen peroxide (the same applies hereinafter). The (A) / (B) molar ratio is the molar ratio of the component (A) to hydrogen peroxide (the same applies hereinafter). The residual rate of the organic peracid is calculated by (organic peracid concentration immediately after pH adjustment) / (organic peracid concentration after 120 minutes of pH adjustment) × 100 (the same applies hereinafter). 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). Note that sodium percarbonate contained 22% by weight of hydrogen peroxide, and sodium perborate contained 20% by weight of hydrogen peroxide.

Example 2
The components (A) and (B) in the amounts shown in Tables 6 to 9, 50 g of ion-exchanged water, and an appropriate amount of an alkaline pH adjuster [sodium carbonate] were stirred and mixed in a 200 mL beaker for 20 minutes. At that time, the pH was adjusted to 8 to 12. Thereafter, the pH was further adjusted to a target pH using an acidic pH adjuster [citric acid] to obtain a disinfectant composition. The bactericidal effect was measured by the following method using the obtained bactericide composition. The results are shown in Tables 6-9.

(1) Killing Effect of Bacterial Spores Bacillus subtilis ( Bacillus subtilis var. Niger ) and circulans ( Bacillus circulans IFO3967), which are spore-forming bacteria, are each added to an SCD agar medium (manufactured by Nippon Pharmaceutical Co., Ltd.) for 30 minutes. After pre-cultivation at about 4 ° C. for about 4 weeks, an appropriate amount of the colony formed on the agar medium was scraped, suspended in 1 mL of sterile water, and examined by microscopy to confirm the formation of bacterial spores (hereinafter referred to as spores). After the suspension twice centrifugally washed, and adjusted to a cell concentration of about 10 ⁸ ~10 ⁹ cell / mL in an appropriate amount of sterile water (spore solution 1). 0.1 ml of the spore fluid 1 was inoculated into 2 mL of the bactericide composition shown in Tables 6 to 9 and allowed to act at 25 ° C for 120 seconds. Immediately thereafter, 0.1 mL of the germicidal composition containing spore fluid 1 was added to SCDLP medium (Nippon Pharmaceutical Co., Ltd.) supplemented with 1.0% sodium thiosulfate to disinfect the germicidal composition. Activated (spore fluid 2). 0.2 mL of the spore fluid 2 was spread on a standard agar medium having a diameter of 9 cm, cultured at 35 ° C. for 36 hours, and the number of colonies formed on the medium was counted to confirm the number of residual bacteria.

(2) Killing effect of mold spores Black Aspergillus niger ( Aspergillus niger IFO6341) was pre-cultured on a potato dextrose agar medium (Nippon Pharmaceutical Co., Ltd.) at 25 ° C. for about 4 weeks. The cells generated on the medium were scraped and suspended in 5 ml of sterilized water, and the suspension was homogenized using a glass homogenizer. The suspension was centrifugally washed twice, and 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 the spore solution 1 was inoculated into 2 ml of the fungicide composition shown in Tables 6 to 9, and allowed to act at 25 ° C for 120 seconds. Immediately thereafter, 0.1 ml of the disinfectant composition containing the spore liquid 1 was added to an SCDLP medium (Nippon Pharmaceutical Co., Ltd.) supplemented with 1.0% sodium thiosulfate to disinfect the disinfectant composition. Activated (spore fluid 2). 0.2 mL of the spore liquid 2 was spread on a potato dextrose agar medium having a diameter of 9 cm, cultured at 25 ° C. for 3 to 4 days, and the number of colonies formed on the medium was counted to confirm the number of residual bacteria. .

Example 3
The components (A) and (B), the organic phosphonic acid [trade name: Dequest 2010 (manufactured by Sorcia Japan Co., Ltd.)], and the alkaline pH adjuster in the weights shown in Table 10 and ion-exchanged water were added to the components to obtain a total amount. The weight was 100 g. This was stirred and mixed in a 200 mL beaker for about 10 minutes. The pH at that time was 8-12. Thereafter, the pH was immediately adjusted to the target pH using an acidic pH adjuster having the weight shown in Table 10, and ion-exchanged water was added to bring the total amount to 110 g. At this time (just after the preparation), the concentration of the organic peracid and the concentration of hydrogen peroxide were measured, and the sterilizing aqueous solution about 30 minutes after the stirring was adjusted to 3000 ppm of the organic peracid to confirm the sterilizing effect. . The method for measuring the concentration of hydrogen peroxide and the concentration of organic peracid was in accordance with the method for measuring the concentration of organic peracid in Example 1. In addition, the sterilization test method followed the killing effect of the bacterial spores of Example 2, but in this example, the contact temperature and contact time between the aqueous solution for sterilization and the bacteria were 60 ° C for 20 seconds, and Bacillus cereus IFO13494 and Bacillus were used as the target bacteria. subtilis var. niger was used. Table 10 shows the results.

Example 4
A composition for producing a fungicide having the composition shown in Table 11 was prepared, and the storage stability was evaluated by the following method. Table 11 shows the results.

<Storage stability test method>
A glass bottle (colorless and transparent) having a capacity of 200 ml is filled with 150 ml of the composition for producing a disinfectant, covered, and stored at 50 ° C. After a lapse of 4 weeks, the concentration of hydrogen peroxide in the composition is measured according to the method for measuring the concentration of organic peracid in Example 1, and is defined as the concentration of hydrogen peroxide after storage. The residual ratio of hydrogen peroxide was determined by the following equation and used as an index of storage stability. The concentration of hydrogen peroxide immediately after the adjustment can be the concentration in the composition based on the charged amount of hydrogen peroxide.
Hydrogen peroxide residual ratio (%) = [(hydrogen peroxide concentration after storage) / (hydrogen peroxide concentration immediately after preparation)] × 100

Claims (10)

(A) Production of a disinfectant containing an ester of a polyhydric alcohol and an organic acid having a hydrocarbon group which may have a hydroxyl group and (B1) hydrogen peroxide and having a water content of 1 to 25% by weight. Composition. (A) an ester of a polyhydric alcohol and an organic acid having a hydrocarbon group which may have a hydroxyl group, and (B1) hydrogen peroxide or (B2) an inorganic peroxide which releases hydrogen peroxide in water. A composition for producing a fungicide, containing (A) and (B1) or a molar ratio of (B1) generated from (A) and (B2) at (A) / (B1) = 1/10 to 20/1. A composition for producing a bactericide used as an aqueous solution prepared by adjusting the pH to 8 to 12 and then adjusting the pH to 1 or more and less than 7. (A) an ester of a polyhydric alcohol and an organic acid having a hydrocarbon group which may have a hydroxyl group, and (B1) hydrogen peroxide or (B2) an inorganic peroxide which releases hydrogen peroxide in water. , (A) and (B1) or (B1) generated from (A) and (B2) in a molar ratio of (A) / (B1) = 1/10 to 20/1. A composition for producing a disinfectant, which is used as an aqueous solution prepared by adjusting the pH to 1 to less than 7 after adjusting the pH to 8 to 12. (A) An ester of a polyhydric alcohol and an organic acid having a hydrocarbon group which may have a hydroxyl group, and (B1) hydrogen peroxide in water, (A) / (B1) = 1/10 to 10 A disinfectant composition containing an organic peracid obtained by reacting at a molar ratio of 20/1 and pH 8 to 12 and water, and having a pH of 1 or more and less than 7 at 25 ° C. The fungicide composition according to claim 4, which is obtained using the composition for producing a fungicide according to claim 1. The disinfectant composition according to claim 4 or 5, wherein the content of hydrogen peroxide is 0.5% by weight or less. The composition according to any one of claims 1 to 6, wherein the organic acid constituting (A) is a fatty acid having 1 to 8 carbon atoms. The composition according to any one of claims 2, 3 and 7, wherein (B2) is an inorganic peroxide selected from sodium percarbonate and sodium perborate. (A) an ester of a polyhydric alcohol and an organic acid having a hydrocarbon group which may have a hydroxyl group, and (B1) hydrogen peroxide, (A) / (B1) = 1/10 to 20/1 A sterilization method comprising reacting an aqueous solution containing an organic peracid obtained in water at a pH of 8 to 12 at a molar ratio of 1 and then having the reaction system at a pH of 1 or more and less than 7 with an object to be sterilized. The sterilization method according to claim 9, wherein the aqueous solution is obtained using the composition according to any one of claims 1 to 8.