JP5036962B2 - Disinfectant composition for automatic washing machine - Google Patents

Description

  The present invention relates to a disinfectant composition for an automatic washing machine.

  Automatic dishwashers are becoming increasingly popular in places where hotels, restaurants, lunch centers, office lunches, and other large-scale dishes are washed, and there are various types of automatic types such as conveyor type, door type, and under counter type. A dishwasher has been introduced. Although these apparatuses have different appearances, basically, the cleaning agent is ejected from the spray nozzle, and the food residue on the tableware is washed away.

Cleaning agents used in such dishwashers include: fats and oil stains that are food residue on tableware, alkaline agents that promote decomposition and solubilization of protein stains, polymer compounds that disperse stains, etc. It is basically composed of a metal ion sequestering agent that promotes dissolution and dispersion in an alkaline detergent solution by capturing metal ions. In a dishwasher, since rinsing is usually performed after washing with such a cleaning agent, a sterilization process may be performed by introducing a sterilization step between washing and rinsing. A chlorine-based disinfectant is used as the disinfectant. For example, Patent Document 1 discloses a method for disinfecting bacterial spores that can be applied to an automatic dishwasher using a hypochlorite solution. Patent Document 2 discloses a disinfectant composition for an automatic washing machine containing hypochlorite, an amphoteric surfactant and / or a cationic surfactant, and a pH adjuster. Patent Document 3 discloses that hypochlorite can be used in an aqueous composition containing a specific long-chain amine oxide mixture.
JP 5-317391 JP 2001-288018 A Special table hei 9-500680

  Unlike the chlorine-based disinfectant such as sodium hypochlorite, the disinfectant composition for the automatic cleaning machine using the oxygen-based disinfectant mainly composed of hydrogen peroxide has no risk of generating toxic gas. Although it is advantageous in that the influence on the environment is mild, there is almost no bactericidal effect on drug-resistant microorganisms such as bacterial spores. In particular, if spore-forming bacteria remain, germination and growth will eventually occur, which may lead to food poisoning, and thus it is necessary to sufficiently sterilize. For spore-forming bacteria, it is known that a bactericide containing peracetic acid has some effect, but it is difficult to use in terms of odor and has a problem such as a poor working environment. Since automatic washing machines are often used at high temperatures, this odor problem is particularly noticeable.

  An object of the present invention is to provide an oxygen-based disinfectant composition for an automatic cleaning machine that exhibits a higher disinfecting effect even on highly drug-resistant microorganisms, such as spore-forming bacteria, and has no toxic gas generation or odor problems It is to be.

  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 (B1) hydrogen peroxide [hereinafter referred to as (B1 The organic peracid obtained by reacting at a molar ratio of (A) / (B1) = 1/10 to 20/1 and pH 8 to 12 and water. The present invention relates to a disinfectant composition for an automatic washing machine having a pH of 1 or more and less than 7 at 25 ° C.

  Further, the present invention provides (A) / (B1) = 1 with (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. It is related with the manufacturing method of the disinfectant composition for automatic washing machines which has the process made to react by pH 8-12 in water by the molar ratio of / 10-20 / 1, and then making the said reaction system 1 or more and less than 7.

  The composition of the present invention is suitable for use in an automatic washing machine used for washing dishes and the like, and exhibits high bactericidal power even against highly resistant bacteria such as spore-forming bacteria under normal operation.

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

  The disinfectant composition for an automatic washing machine of the present invention comprises a component (A) and a component (B1) in water at a molar ratio of (A) / (B1) = 1/10 to 20/1, and pH 8 The organic peracid obtained by making it react in -12, and water are contained, and pH in 25 degreeC is 1 or more and less than 7. That is, as described above, the disinfectant composition for an automatic cleaning machine of the present invention reacts the component (A) and the component (B1) in water at a specific molar ratio and at a pH of 8 to 12, and then the pH. 1 to less than 7, preferably 1 to 6, more preferably 1 to 5.

  The disinfectant composition for an automatic washing machine of the present invention may contain a surfactant, an inorganic or organic salt, a chelating agent, a fragrance, a pigment, a dye, etc. in addition to the component (A) and the component (B1). it can.

  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 from the viewpoint of low foaming property, and a polyhydric alcohol derivative type nonionic surfactant is more preferable. Moreover, it is preferable that 0-20 weight% of surfactant is contained in the disinfectant composition for automatic washing machines of this invention, and also 0-10 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.

  Further, the amount of water in the disinfectant composition for automatic washing machine of the present invention is 50% by weight or more and less than 100% by weight, more preferably 60% by weight or more and less than 100% by weight, particularly 70% by weight or more and 100% by weight. % Is preferred. Moreover, the disinfectant composition for automatic washing machines of the present invention is an aqueous solution containing an organic peracid, and the organic peracid concentration in the composition is 10 to 20,000 ppm, more preferably 10 to 10,000 ppm. Is preferred. Further, the disinfectant composition for an automatic washing machine 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. This is preferable. This hydrogen peroxide content is preferably achieved immediately after preparation of the composition and further upon use.

  Since the disinfectant composition for an automatic washing machine of the present invention has a high disinfecting effect, it is possible to disinfect various objects to be sterilized in which various microorganisms exist. 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, according to the germicidal composition for an automatic washing machine of the present invention, a sufficient germicidal effect can be obtained even for such bacterial spores.

  As described above, the disinfectant composition for an automatic washing machine of the present invention has a wide sterilization spectrum and has a high effect on not only bacteria but also fungi and spores. Therefore, it is useful for sterilizing dishes and the like using an automatic washing machine. It is.

  The disinfectant composition for an automatic washing machine of the present invention can be prepared from the following disinfectant manufacturing composition.

(1) It contains 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, and has a water content of 1 to 25% by weight. A composition for producing a bactericidal agent (hereinafter referred to as a first composition for producing a bactericidal agent).

(2) (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 that releases hydrogen peroxide in water. Production of bactericides containing oxides in a molar ratio of (B1) generated from (A) and (B1) or (A) and (B2) (A) / (B1) = 1/10 to 20/1 A composition for manufacturing a bactericide used as an aqueous solution prepared with a pH of 1 to less than 7 after adjusting the pH to 8 to 12 (hereinafter referred to as a second composition for manufacturing a bactericide) .

(3) (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 that releases hydrogen peroxide in water. An oxide is obtained by blending (A) and (B1) or (B1) generated from (A) and (B2) at a molar ratio of (A) / (B1) = 1/10 to 20/1. A composition for producing a bactericide, which is 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 (hereinafter, the third composition for producing a bactericide) Called things).

  Hereinafter, (B2) the inorganic peroxide that releases hydrogen peroxide in water will be referred to as the component (B2), and the components (B1) and (B2) will be described as the component (B).

  In addition, among the (B) component, the number of moles of hydrogen peroxide generated from the (B2) component is the composition of the hydrogen peroxide concentration (% by weight) in the (B2) component 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.

<(B) component>
Among the components (B), the inorganic peroxide that releases hydrogen peroxide in the water of the component (B2) is a solid, such as granular or powdery hydrogen peroxide when the composition for producing a bactericide is liquid. In this case, percarbonate and perborate are preferable, and sodium percarbonate and sodium perborate are particularly preferable.

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

  The first composition for producing a bactericide of the present invention is a one-component liquid composition containing a component for obtaining an organic peracid. The content of the component (A) in the first fungicidal 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 (B1) is 1 to 30% by weight, more preferably 5 to 25% by weight, and 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, more preferably 1/10 to 10/1, particularly 1/5 to 10/1. Preferably there is. In addition, the molar ratio of the component (B1) per one 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, the 1st composition for fungicide manufacture 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 first composition for producing a bactericide 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.

<Second composition for producing a bactericide>
The second composition for producing a fungicide of the present invention contains the component (A) and the component (B), but the ratio of both is within the range in which the component (B1) and the component (A) react efficiently. Preferably, considering the organic peracid production efficiency, bactericidal effect, formulation stability, etc., the molar ratio of the component (A) to the component (B1) is (A) / (B1) = 1 / 10-20. / 1, preferably 1/10 to 10/1, more preferably 1/5 to 10/1. In addition, the molar ratio of the component (B1) per one 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. Even when the component (B2) is used, it is preferably blended in an amount that generates the component (B1) within the above range.

  Preferably, after satisfying this molar ratio, the second composition for producing a fungicide of the present invention comprises (A) component in an amount of 0.1 to 90% by weight, further 0.5 to 70% by weight, particularly 1 to It is preferable to contain 50% by weight of component (B) as component (B1) in an amount of 0.1 to 50% by weight, further 0.1 to 30% by weight, particularly 0.1 to 20% by weight.

  In use, 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 a pH of 1 or more and less than 7, preferably 1 to 6, more preferably. By setting it as 1-5 (2nd process), the aqueous solution which is a disinfectant composition is prepared. 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 may be that at the time of use, but preferably satisfies the above pH at 25 ° C. The above-described first composition for producing a bactericide of the present invention can also be used in the same manner.

  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 be present in the second composition for producing a bactericide as it is. In addition, these pH adjusters can also be made to exist also in the above-mentioned 1st composition for fungicide manufacture of this invention.

  In addition to the (A) component and the (B) component, the second composition for producing a bactericide of the present invention includes the above-described surfactants, inorganic or organic salts, chelating agents, fragrances, pigments, dyes, and the like. Can be contained. In addition, these components can also be present in the first composition for producing a bactericide of the present invention.

  The second composition for producing a bactericidal agent of the present invention can take various forms, but in the case of a liquid, a highly fluid one is preferable. In addition to an aqueous solution, a fluid slurry, gel, paste, etc. It may be. Moreover, in the case of solid form, shapes, such as a granular form, a powder form, a granular form, a pellet form, are mentioned.

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

  When the composition for producing a second bactericide of the present invention is used, an aqueous solution which is a bactericide composition containing an organic peracid is prepared by adjusting the pH in the first step and the second step. The 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. In addition, the hydrogen peroxide content 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 in view of the bactericidal effect. These findings are the same in the first composition for producing a fungicide of the present invention.

<3rd composition for fungicide manufacture>
The 3rd composition for fungicide manufacture of this invention is obtained by mix | blending the (A) component and (B) component of the said invention, and like the 2nd composition for fungicides manufacture, 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 above 7 or less. Specific compounds of component (A) and component (B) and a preferred molar ratio of (A) / (B1) are the same as those in the second composition for producing a bactericide. Moreover, the above-mentioned surfactant, inorganic or organic salts, chelating agents, fragrances, pigments, dyes, and the like can also be contained in the third composition for producing a bactericide, and the packaging mode is the same. Can do.

<Disinfectant kit>
A suitable disinfectant kit for obtaining a disinfectant composition for an automatic washing machine according to the present invention comprises a composition for producing a disinfectant according to the present invention, and (A) component and (B1) component provided by the composition. A reaction initiator for starting the reaction [hereinafter referred to as component (C)] and a pH adjuster [hereinafter referred to as component (D)] are included. Moreover, a disinfectant kit can also be comprised including (A) component, (B) component, (C) component, and (D) component.

  The disinfectant kit for obtaining the disinfectant composition for an automatic washing machine of the present invention may be a one-part type packaged with all of the blended components packaged in consideration of the convenience during the production of organic peracid, In consideration of time stability, 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. As a preferable dosage form of the disinfectant kit, two or more of the components (A) to (D) are used in consideration of both the convenience during the production of the organic peracid and the storage stability of the composition for production. It is a multi-dose type such as a two-drug type or a three-drug type containing a package in which a composition containing the same is packaged.

  Since the component (A) and the component (B1) react under alkaline conditions (preferably a water temperature of 5 to 50) in water to produce an organic peracid, a component giving such 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 adjusting agents, sodium silicate, silicic acid Examples include alkali metal silicates such as potassium, alkali metal phosphates such as trisodium phosphate, and alkali metal carbonates such as sodium carbonate and potassium carbonate. From the viewpoint of alkalinity and water solubility, hydroxylation is possible. Alkali metal hydroxides such as sodium and potassium hydroxide, alkali metal phosphates such as trisodium phosphate and tripotassium phosphate, and alkali metal carbonates such as sodium carbonate and potassium carbonate are preferred.

  On the other hand, the disinfectant containing an organic peracid is preferably acidic in terms of bactericidal effect, so that the component (D) is a component capable of bringing the pH in the alkaline region to the acidic region by the (C) component. The Specific examples include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid exemplified as acidic pH adjusters, 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 preferable.

As a specific dosage form of the disinfectant kit,
(I) A package (X1) of a composition for producing a bactericide containing (A) component and (B) component, a package (X2) of a composition containing (C) component, and (D) component A package (Y1), a component (B), and a component (C) containing three or more types of dosage forms (II) and (A) components including the package (X3) of the contained composition Three or more types of dosage forms (III), (A) component, (B) component, and (C) component including the package body (Y2) of the composition and the package body (X3) of the composition containing the component (D) 2 or more dosage forms including the packaging body (Z1) of the composition containing, and the packaging body (Z2) of the composition containing the component (D).

  In the dosage form (I), the form of the composition for producing a bactericide is not limited to powder, solid, liquid, etc., but liquid is more preferable from the viewpoint of simplicity. In the case of taking 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 component (A) and the component (B) during storage and maintain stability. More preferably, it is 5 to 20 weight%, and 5 to 15 weight% is still more preferable. Moreover, a chelating agent and a solvent can be added to the said liquid composition as needed. A chelating agent is useful for suppressing catalytic decomposition due to a small amount of metal ions such as Fe and Cr. Moreover, since the undiluted | stock solution pH (20 degreeC) of the said liquid composition is concerned with storage stability, 0.5-6 are preferable, More preferably, it is 1-5, 1-4 are still more preferable. As described above, it is preferable to use a component that has both an action as a pH adjuster and an action as a chelating agent. Specifically, phosphoric acid, polymerized 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.

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

  The content of the components (A) to (D) in each of these dosage forms can be selected based on the above-described usage of the first to third fungicidal composition of the present invention. it can. In addition, components other than the components (A) to (D) may be blended in any package containing these components (A) to (D), or may be blended in other packages. .

  The composition for producing a bactericide or the bactericide kit includes (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 molar ratio for reaction in water at pH 8 to 12, and then the reaction system is adjusted to pH 1 or more and less than 7 for the automatic washing machine of the present invention It is applicable to the manufacturing method of a disinfectant composition.

  In general, an automatic washing machine for tableware performs washing (washing with an alkaline detergent), rinsing, drying, and the like. The sterilizing composition for an automatic washing machine of the present invention performs a sterilization process between washing and rinsing. It is preferably used as sterilized water that is introduced and added to water for sterilization. The organic peracid concentration in the sterilized water at that time is preferably in the same range as the aqueous solution. In general, the temperature during sterilization is 40 to 70 ° C. and the sterilization time is 5 to 20 seconds, and the disinfectant composition for an automatic washing machine of the present invention exhibits a sufficient sterilizing effect even when used in such a short time treatment. .

Example 1
In the following,% means% by weight.
<Preparation of disinfectant composition (I)>
(A) 50 g of triacetin (manufactured by Cognis Japan, effective content 100%) and (B) 25 g of hydrogen peroxide (manufactured by Ube Chemilla, 60% effective) are mixed with 850 g of ion-exchanged water, and sodium hydroxide is mixed therein. 75 g of an alkaline aqueous solution containing 27% and 1.3% of organic phosphonic acid (trade name: Diquest 2010, manufactured by Solusia) was poured and mixed and stirred for 5 minutes. Immediately thereafter, 75 g of a mixed acid solution consisting of 30% sulfuric acid and 6% phosphoric acid was added to prepare an antibacterial composition (I) containing an organic peracid. The pH of the composition (I) (25 ° C.) was about 2, and the hydrogen peroxide content was about 1500 ppm.

<Preparation of assemblage fungicide composition (II)>
(A) 50 g of D-glucose-O-pentaacetate (reagent: manufactured by Tokyo Chemical Industry Co., Ltd., 100% effective), (B) 25 g of hydrogen peroxide (manufactured by Ube Chemilla Co., Ltd., 60% effective) and 850 g of ion-exchanged water Into this, 75 g of an alkaline aqueous solution containing 27% of sodium hydroxide and 1.3% of organic phosphonic acid (trade name: Diquest 2010, manufactured by Solusia) was poured and mixed and stirred for 5 minutes. Immediately thereafter, 75 g of a mixed acid solution consisting of 30% sulfuric acid and 6% phosphoric acid was added to prepare an antibacterial composition (II) containing an organic peracid. The pH of the composition (II) (25 ° C.) was about 2, and the hydrogen peroxide content was about 1500 ppm.

<Measurement of organic peracid concentration>
About 1 g of the fungicide composition (I) or (II) prepared in a 100 mL beaker is precisely weighed, and about 50 mL of ion-exchanged water and a hydrogen peroxide decomposing agent (trade name: Ask Super G, manufactured by Mitsubishi Gas Chemical Co., Ltd.) And hydrogen peroxide in the composition was decomposed. Thereafter, 5 mL of 20% sulfuric acid and 5 mL of 10% potassium iodide aqueous solution were poured and stirred, and titrated with a 0.1 mol / L sodium thiosulfate aqueous solution, and the organic peracid concentration (peracetic acid concentration) was determined by the following formula. .
Organic peracid (peracetic acid) concentration (%) = T × 38 / W / 100
T: Required titration amount of 0.1 mol / L sodium thiosulfate aqueous solution (mL)
W: Amount of collected fungicide composition (g)

  As a result, the organic peracid concentration (as peracetic acid concentration) in the bactericidal composition (I) was about 2.6%, and the organic peracid concentration (as peracetic acid concentration) in the bactericidal composition (II) was about 2.6%. It was 3.0%.

<Evaluation>
Using a test aqueous solution obtained by diluting the composition obtained using the above-mentioned fungicide composition (I), (II) and the components shown in Table 1 with water so as to have the organic peracid concentration shown in Table 1, the following A test was conducted. The results are shown in Table 1.

(1) After culturing Bacillus cereus NBRC13494, which is a spore-forming bacterium, on an SCD agar medium (manufactured by Nippon Pharmaceutical Co., Ltd.) at 30 ° C. for about one week, the colonies formed on the agar medium are scraped off, It was suspended in 1 mL of sterilized water and microscopically confirmed to form bacterial spores (hereinafter referred to as spores). After heat treatment at 65 ° C. for 30 minutes, centrifugal washing was performed twice, and then the bacterial concentration was adjusted to about 10 ⁹ to 10 ¹⁰ cells / mL with an appropriate amount of sterilized water.

(2) About 300 g of soft cooked cooked rice is placed in a plastic lunch box (170 mm x 120 mm x 43 mm), allowed to cool at room temperature for 2 hours, and then cooked. In the lunch box, 1 mL of the Bacillus cereus spore suspension prepared in (1) was uniformly sprayed with a mist generating spray to create a fungus-contaminated lunch box.

(3) This contaminated lunch box was washed, sterilized and rinsed under the following conditions using an automatic dishwasher DW-2000R manufactured by Sanyo Electric Co., Ltd., and the number of spores before and after washing were compared. Here, the number of spores before and after washing was determined by wiping a predetermined area (50 mm x 50 mm) of the lunch box with a sterilized cotton swab, suspending it in 1 mL sterilized water, serial dilution, and standard agar medium (manufactured by Nippon Pharmaceutical Co., Ltd.) After smearing 100 μL and culturing at 35 ° C. for 24 hours, the number of colonies was counted.

  In addition, as a comparative product of the bactericidal composition, a composition using hydrogen peroxide, which is a representative oxygen-based bactericide, and sodium hypochlorite, which is a chlorine-based bactericide, is prepared, and the same bactericidal performance evaluation is performed. A test was conducted.

<Cleaning conditions>
Cleaning temperature: 60 ° C ± 2 ° C
Cleaning time: 15 seconds Cleaning agent: Axal manufactured by Kao Corporation, cleaning agent concentration: 0.15%
<Sterilization conditions>
Sterilization temperature: 60 ° C
Sterilization time: 10 seconds <rinsing conditions>
Rinsing temperature: 60 ° C
Rinse time: 5 seconds

The concentration of hydrogen peroxide in the table indicates the effective concentration of hydrogen peroxide, and the sodium hypochlorite concentration indicates the effective chlorine concentration. The surfactant is as follows.
(1): The effective concentration was adjusted to the numerical values shown in Table 1 using EMAL 20C [manufactured by Kao Corporation, 25% effective content].
(2): Amphital 20N [manufactured by Kao Corporation, effective content 35%] was used so that the effective concentration was the value shown in Table 1.
(3): Sanisole C [manufactured by Kao Corporation, effective amount 50%] was used so that the effective concentration was the value shown in Table 1.
(4): Mydol 12 [manufactured by Kao Corporation, effective content 40%] was used so that the effective concentration was the value shown in Table 1.
(5): Emulgen 106 (manufactured by Kao Corporation, 100% effective component) was used so that the effective component concentration was the value shown in Table 1.

Claims (9)

(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 It contains an organic peracid obtained by reacting at a molar ratio of 20/1 and at pH 8-12, and water, the hydrogen peroxide content is 0.5% by weight or less, and the pH at 25 ° C. is 1 A disinfectant composition for an automatic washer that is ~ 5 . The disinfectant composition for an automatic washing machine according to claim 1, wherein the concentration of the organic peracid is 10 to 20,000 ppm. The disinfectant composition for an automatic washing machine according to claim 1 or 2, wherein the organic acid constituting (A) is a fatty acid having 1 to 8 carbon atoms. (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 are (A) / (B1) = 1/10 to 20/1. The disinfectant composition for an automatic washing machine having a hydrogen peroxide content of 0.5% by weight or less, having a step of reacting in water at pH 8 to 12 and then setting the reaction system to pH 1 to 5 Manufacturing method. The manufacturing method of the germicidal composition for automatic washing machines of Claim 4 whose density | concentration of the organic peracid in the germicidal composition for automatic washing machines is 10-20,000 ppm. When washing dishes with an automatic washing machine, the dishes are washed with a sterilization time of 5 to 20 seconds using the germicidal composition for automatic washing machines according to any one of claims 1 to 3. Method. The tableware washing | cleaning method of Claim 6 which performs a sterilization process at 40-70 degreeC. A sterilization process including a washing process, a rinsing process, and a drying process, in which a sterilization process is introduced between the washing process and the rinsing process, and in the sterilization process, the sterilizing composition for the automatic washing machine is added to water for sterilization treatment. The method for washing tableware according to claim 6 or 7, which is used as water. The dishwashing method according to any one of claims 6 to 8, wherein the disinfectant composition for an automatic washing machine is the disinfectant composition for an automatic washing machine of any of the following (i) to (iii) : .
(I) (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 / The germicidal composition for an automatic washing machine according to any one of claims 1 to 3, which is prepared from a composition for producing a germicidal agent having a molar ratio of 1 and a water content of 1 to 25% by weight . .
(Ii) (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 that releases hydrogen peroxide in water. Production of bactericides containing oxides in a molar ratio of (B1) generated from (A) and (B1) or (A) and (B2) (A) / (B1) = 1/10 to 20/1 A composition for use in a fungicide, wherein the composition is prepared as an aqueous solution prepared by adjusting the pH to 8 to 12, and then adjusting the pH to 1 to 5. The germicide composition for automatic washing machines as described.
(Iii) (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 that releases hydrogen peroxide in water. An oxide is obtained by blending (A) and (B1) or (B1) generated from (A) and (B2) at a molar ratio of (A) / (B1) = 1/10 to 20/1. a fungicide composition for producing, after 8 to 12 the pH, was prepared from fungicides for producing composition used as an aqueous solution prepared to pH as 1-5, any of claims 1 to 3 The disinfectant composition for automatic washing machines according to claim 1.