JP5036963B2 - Bactericidal detergent composition for hard surfaces - Google Patents

Description

  The present invention relates to a hard surface sterilizing detergent composition suitable for sterilizing hard surfaces such as plastics, metals, glass and tiles.

  There are many facilities where a sanitary environment is desired, such as food factories, pharmaceutical factories, hospitals, nursing homes, kitchens and toilets. In these, in order to maintain a hygienic environment, frequent sterilization treatments such as floors, walls and used tools are indispensable.

  For sterilization and cleaning of these hard surfaces, liquid or powder cleaning agents, sterilizing agents, and sterilizing cleaning agents containing surfactants and sterilizing agents are mainly used. And when incorporating a sterilization washing process into an industrial manufacturing process, processes, such as supply of an active ingredient, mixing, and application (application | coating, spraying, etc.), are often automated.

As a sterilizing detergent used for sterilizing and cleaning such hard surfaces, those containing a chlorine-based sterilizing agent are known. For example, Patent Literature 1 discloses a hard surface disinfectant cleaning composition containing hypochlorite, an amphoteric surfactant and / or a cationic surfactant, and a pH adjuster. Patent Document 2 discloses that hypochlorite can be used in an aqueous composition containing a specific long-chain amine oxide mixture.
JP-A-2001-342496 Special table hei 9-500680

  However, conventional sterilizing detergents for hard surfaces have a low sterilizing effect on spores formed by spore bacteria that are difficult to sterilize, and fungi. Processing was necessary. In food processing factories, hospitals, etc., hard surfaces such as floors, walls, equipment, and utensils are likely to be contaminated with microorganisms. Therefore, sufficient sterilization and cleaning of such hard surfaces is important.

  A hard surface disinfectant composition using an oxygen-based disinfectant is advantageous in that it has a mild impact on the environment, but the disinfection effect against microorganisms with strong drug resistance such as bacterial spores is further improved. desired. 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.

  An object of the present invention is to provide an oxygen-based bactericidal cleaning composition for hard surfaces that exhibits a higher bactericidal effect even against highly drug-resistant microorganisms such as spore-forming bacteria.

  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. Further, the present invention relates to a hard surface disinfectant cleaning composition 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. The present invention relates to a method for producing a hard surface disinfectant cleaning composition having a step of reacting in water at a pH of 8 to 12 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.

  According to the present invention, a hard surface sterilizing detergent that exhibits excellent detergency against hard surfaces and exhibits superior sterilization power against spores and molds even at low temperature and short time treatment than normal operations. A composition is obtained. In addition, the composition of the present invention has no odor problem and little influence on the working environment.

<(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 sterilizing detergent composition for hard surface of the present invention comprises (A) component and (B1) component 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, the sterilizing detergent composition for hard surface 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, as described above. 1 to less than 7, preferably 1 to 6, more preferably 1 to 5.

  The sterilizing detergent composition for hard surface of the present invention may contain a surfactant, an inorganic or organic salt, a chelating agent, a fragrance, a pigment, a dye and the like in addition to the component (A) and the component (B1). it can.

  As the surfactant used for further improving the detergency, one or more surfactants selected from amphoteric surfactants, cationic surfactants, anionic surfactants and nonionic surfactants may be used. 1 type or more chosen from anionic surfactant and a nonionic surfactant is mentioned. Surfactants can be used alone or in combination of two or more.

  Examples of amphoteric surfactants include amine oxides such as alkyldimethylamine oxide, betaines such as alkyldimethylamino fatty acid betaines, and alkylcarboxymethylhydroxyethylimidazolium betaines. Of these, alkyldimethylamine oxide having an alkyl group having 8 to 18 carbon atoms is preferable. Examples of the cationic surfactant include primary amine salts, secondary amine salts, tertiary amine salts, and quaternary ammonium salts, among which quaternary ammonium salts are particularly preferable. As the quaternary ammonium salt, at least one of the four substituents is an alkyl or alkenyl group having a total carbon number of 8 to 28, and the remainder is a benzyl group, an alkyl group having 1 to 5 carbon atoms and a carbon number of 1 to 5 Examples thereof include compounds that are groups selected from hydroxyalkyl groups. An alkyl or alkenyl group having a total carbon number of 8 to 28 may be substituted with an alkoxyl group, an alkenyloxy group, an alkanoylamino group, an alkenoylamino group, an alkanoyloxy group or an alkenoyloxy group within this carbon number range. Good. The compounding amount of the amphoteric surfactant and / or the cationic surfactant is preferably 1 ppm to 5% by weight, more preferably 5 ppm to 1% by weight, and particularly preferably 10 ppm to 0.5% by weight in the composition.

  Moreover, it is preferable to mix | blend anionic surfactant and nonionic surfactant for the permeability improvement with respect to stain | pollution | contamination, and foaming improvement. Anionic surfactants include higher fatty acid salts, higher alcohol sulfates, higher alcohol sulfonates, sulfated fatty acid salts, sulfonated fatty acid salts, phosphate ester salts, sulfate esters of fatty acid esters, and sulfones of fatty acid esters. Acid ester salt, sulfate ester salt of higher alcohol ether, sulfonate ester salt of higher alcohol ether, acetate salt of higher alcohol ether substitution, condensate of fatty acid and amino acid, alkylolated sulfate ester of fatty acid amide, alkyl of fatty acid amide Sulfonates, sulfosuccinic acid ester salts, alkylbenzene sulfonates, alkylphenol sulfonates, alkylnaphthalene sulfonates, alkylbenzimidazole sulfonates, amide ether carboxylic acids or their salts, ether carboxylic acids Or a salt thereof, N-acyl-N-methyltaurine or a salt thereof, amide ether sulfuric acid or a salt thereof, N-acyl glutamic acid or a salt thereof, N-amidoethyl-N-hydroxyethyl acetic acid or a salt thereof, acyloxyethanesulfonic acid or a salt thereof Salt, N-acyl-β-alanine or salt thereof, N-acyl-N-carboxyethyltaurine or salt thereof, N-acyl-N-carboxyethylglycine or salt thereof, and alkyl or alkenylaminocarbonylmethylsulfuric acid or salt thereof Etc. The compounding amount of the anionic surfactant is preferably 1 ppm to 5% by weight, more preferably 10 ppm to 0.5% by weight, and particularly preferably 50 ppm to 0.5% by weight in the composition.

  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. Monovalent alcohol derivative type nonionic surfactants such as ether and POE tribenzylphenyl ether; Polyhydric alcohol derivative type nonionic surfactants such as (poly) glycerin fatty acid ester, sucrose fatty acid ester, sorbitan fatty acid ester and alkylpolyglycoside Surfactant etc. are mentioned. The compounding amount of the nonionic surfactant is preferably 1 ppm to 5% by weight, more preferably 10 ppm to 1% by weight, and particularly preferably 100 ppm to 0.5% by weight in the composition.

  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 amount of water in the hard surface disinfectant cleaning composition of the present invention is 50 wt% or more and less than 100 wt%, more preferably 60 wt% or more and less than 100 wt%, particularly 70 wt% or more and 100 wt%. % Is preferred. Moreover, the bactericidal detergent composition for hard surfaces 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 sterilizing detergent composition for hard surfaces of the present invention has a sterilizing effect that the hydrogen peroxide content is 0.5% by weight or less, further 0.3% by weight or less, particularly 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.

  In the present invention, the weight ratio of the organic peracid to the surfactant is preferably surfactant / organic peracid = 0.01 to 20, more preferably 0.1 to 10, from the viewpoint of stability. ~ 5 is particularly preferred.

  Since the sterilizing detergent composition for hard surface of the present invention has a high sterilizing effect, various sterilized objects containing various microorganisms 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 bactericidal cleaning composition for hard surfaces of the present invention can provide a sufficient bactericidal effect even for such bacterial spores.

  Thus, the sterilization detergent composition for hard surfaces of the present invention has a wide sterilization spectrum and has a high effect on not only bacteria but also fungi and spores, and thus is useful for sterilization and cleaning of various hard surfaces.

  The hard surface sterilizing detergent composition of the present invention can be prepared from the following sterilizing detergent 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 sterilizing detergent (hereinafter referred to as a first composition for producing a sterilizing detergent).

(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. Disinfectant cleaning agent containing oxide (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 manufacturing a sterilizing detergent used as an aqueous solution prepared after adjusting the pH to 8 to 12 and having a pH of 1 or more and less than 7 (hereinafter referred to as a second sterilizing cleaning composition) Called things).

(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 sterilizing detergent, which is used as an aqueous solution prepared after adjusting the pH to 8 to 12 and then adjusting the pH to 1 or more and less than 7 (hereinafter referred to as a third sterilizing detergent) Called composition for production).

  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 component (B2) is solid, such as granular, powdery, etc., when the composition for producing a sterilizing detergent is liquid. In this case, percarbonate and perborate are preferable, and sodium percarbonate and sodium perborate are particularly preferable.

<The 1st composition for sterilization cleaning agent manufacture>
The first composition for producing a bactericidal cleaning 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 standpoint of maintaining the 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 bactericidal cleaning agent 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 composition for producing a sterilizing detergent 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 preferably 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 sterilization washing | cleaning agent 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 sterilizing detergent 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 2nd composition for sterilization cleaning agent manufacture>
The second composition for producing a bactericidal cleaning agent of the present invention contains the component (A) and the component (B), but the ratio of the two is a range in which the component (B1) and the component (A) react efficiently. In view of 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 sterilizing detergent according to the present invention comprises (A) component in an amount of 0.1 to 90% by weight, more preferably 0.5 to 70% by weight, particularly 1 The component (B) is preferably contained in an amount of 0.1 to 50% by weight, more preferably 0.1 to 30% by weight, and particularly preferably 0.1 to 20% by weight as the component (B1).

  In use, the second composition for producing a bactericidal cleaning agent 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. 1 to 5 (second step), an aqueous solution that is a sterilizing detergent 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 first composition for producing a sterilizing detergent according to 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 bactericidal cleaning agent as it is. In addition, these pH adjusters can be made to exist also in the above-mentioned 1st composition for sterilization cleaning agent manufacture of this invention.

  In addition to the component (A) and the component (B), the second composition for producing a bactericidal cleaning agent of the present invention is a surfactant, an inorganic or organic salt, a chelating agent, a fragrance, a pigment, and a dye. Etc. can be contained. In addition, these components can be made to exist also in the above-mentioned first composition for producing a sterilizing detergent.

  The second composition for producing a sterilizing / cleaning 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, or paste Etc. 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 cleaning agent of the present invention may be one in which all of the components are packaged together, but from the viewpoint of stability, the component (A) and the component (B) are packaged separately. A multi-drug type 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 bactericidal cleaning agent comprising a package (3) of a composition containing (an acidic pH adjusting agent 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 can be set as the composition for manufacture of a two-pack type sterilization cleaning agent which consists of package (II) of a thing.

  When the composition for producing a second sterilizing detergent of the present invention is used, an aqueous solution which is a sterilizing detergent composition containing an organic peracid is prepared by adjusting the pH in the first step and the second step. Prepared. 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 sterilizing detergent according to the present invention.

<3rd composition for sterilization cleaning agent manufacture>
The 3rd composition for sterilization cleaning agent manufacture of this invention is obtained by mix | blending the (A) component and (B) component of the said invention, and is the same as the 2nd composition for sterilization cleaning agent 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, and the pH is adjusted to 8 to 12, then the pH Is used as an aqueous solution prepared from 1 to less than 7. 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 sterilizing detergent. The third composition for producing a sterilizing detergent can also contain the surfactant, inorganic or organic salts, chelating agents, fragrances, pigments, dyes, etc., and the packaging is the same. be able to.

<Bactericidal detergent kit>
A suitable bactericidal detergent kit for obtaining a bactericidal detergent composition for hard surfaces according to the present invention, a composition for producing a bactericidal detergent according to the present invention, component (A) and (B1) provided by the composition It comprises a reaction initiator that initiates the reaction of the components (hereinafter referred to as component (C)) and a pH adjuster (hereinafter referred to as component (D)). In addition, the sterilizing detergent kit can also include (A) component, (B) component, (C) component, and (D) component.

  The sterilizing detergent kit for obtaining the hard surface sterilizing detergent composition of the present invention may be a one-pack type in which all of the ingredients are packaged in consideration of the convenience during the production of organic peracid, In consideration of stability at the time of storage, 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 the preferable dosage form of the sterilizing detergent kit, two or more of the components (A) to (D) are considered in consideration of both the convenience during the production of the organic peracid and the storage stability of the composition for production. A two-dose type containing a package in which a composition containing the same is packaged, or a multiple-dose type such as a three-dose type.

  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, since the sterilizing detergent containing organic peracid is preferably acidic in terms of sterilizing effect, the component (D) is a component that can make the pH in the alkaline region by the component (C) acidic. Is done. 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 specific dosage form of sterilization detergent kit,
(I) Package (X1) of the composition for manufacturing a sterilizing detergent containing component (A) and component (B), Package (X2) of composition containing component (C), component (D) A package (Y1), a composition (B), and a component (C) containing three or more types of dosage forms (II) and (A) including a package (X3) containing the composition Package (Y2) of composition to be used, and package (X3) of composition containing composition (D) containing three or more types (III) (A) component, (B) component and (C) component 2 or more dosage forms including the package (Z1) of the composition containing and the package (Z2) of the composition containing the component (D).

  In the dosage form (I), the form of the composition for producing a sterilizing detergent 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 sterilizing detergent 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 is selected based on the above-described usage of the first to third compositions for producing a bactericidal detergent. Can do. 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 sterilizing detergent and the sterilizing detergent kit include (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, reacting in water at pH 8 to 12, and then setting the reaction system to pH 1 or more and less than 7 It can apply to the manufacturing method of an agent composition.

  The hard surface disinfectant cleaning composition of the present invention is also suitable for systems using an automatic spray device and a spray gun. Also, foam washing and sterilization by adding a foam-increasing agent is possible.

Example 1
In the following,% means% by weight.

<Preparation of disinfectant cleaning 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. Thereafter, 75 g of a mixed acid solution consisting of 30% sulfuric acid and 6% phosphoric acid was immediately added to prepare a sterilizing detergent 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 disinfectant cleaning 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. Thereafter, 75 g of a mixed acid solution consisting of 30% sulfuric acid and 6% phosphoric acid was immediately added to prepare a sterilizing detergent 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 sterilizing detergent composition (I) or (II) prepared in a 100 mL beaker is precisely weighed, and about 50 mL of ion exchange water and a hydrogen peroxide decomposing agent (trade name: Ask Super G, manufactured by Mitsubishi Gas Chemical Co., Ltd.) 1 mL was poured and stirred well to decompose only hydrogen peroxide in the composition. 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: Collection amount of sterilizing detergent composition (g)

<Evaluation>
A test aqueous solution obtained by diluting a composition obtained using the above-described disinfectant cleaning composition (I), (II) and the components shown in Tables 1 and 2 with water so as to have the organic peracid concentration shown in Tables 1 and 2. Using, the evaluation test of the cleaning power and the bactericidal power was performed by the following methods. The results are shown in Tables 1 and 2. In addition, as a comparative product of the sterilizing detergent composition, a composition using hydrogen peroxide as a typical oxygen-based sterilizer and sodium hypochlorite as a chlorinated sterilizer as a comparative control product. And the same evaluation test was conducted.

(1) Detergency evaluation test After preparing each model stain of detergency oil stain and protein stain, each wash is performed by the improved method of rinatu test according to JIS K-3362 9.2 Detergency Evaluation Method of Synthetic Detergent for Kitchen The power was evaluated.

(1-1) Evaluation of oil stain detergency An oil stain solution is prepared by dissolving 20 g of fat and oil mixed with beef tallow and soybean oil in a volume ratio of 1: 1, 0.25 g of monoolein and 0.1 g of oil red in 60 mL of chloroform. A set of 6 clean slide glasses is used, and each mass is measured up to 1 mg. Immerse the slide glass one by one in an oil stain at 25 ± 1 ° C. to about 55 mm for about 2 seconds. The accumulation of oil stains adhering to the lower part of the slide glass is sucked up using a clean cloth or filter paper such as gauze, and the oil stains are uniformly adhered, air-dried at 25 ± 1 ° C., and the mass is measured. The model soiled glass piece is used for the test within 1 hour to 2 hours in the air drying period. At this time, the oil dirt adhesion amount per 6 pieces of model dirt glass pieces is set to 0.140 ± 0.010 g.

Six sets of this model dirt glass piece are washed for 5 minutes at 25 ± 2 ° C. using a modified Leanut washing machine, and rinsed with ion-exchanged water at 25 ± 2 ° C. for 30 seconds. The glass pieces that have been rinsed are air-dried for a day and night. The evaluation of the cleaning power is calculated from the weight of the model dirt glass piece before and after cleaning. That is, the weight difference before and after cleaning is obtained, and the cleaning rate (%) is calculated by the following formula.
Cleaning rate (%) = [(weight before cleaning−weight after cleaning) / fouling amount] × 100
The cleaning rate of each of the six glass pieces was determined, and the average value of the four cleaning rates excluding the maximum and minimum values was taken as the cleaning rate of the composition.

(1-2) Evaluation of protein dirt detergency 20 g of skim milk powder is diluted and dissolved in ion-exchanged water at 60 ° C. to make a total of 100 g to obtain a protein dirt liquid. A clean glass slide is immersed in a protein soil solution at 25 ± 1 ° C. for about 2 seconds to a point of about 55 mm. The pool of protein stains adhering to the lower part of the slide glass is blotted with a clean cloth or filter paper such as gauze, and the protein stains are uniformly adhered and air-dried at 25 ± 1 ° C. This is repeated once again, and after removing the dirt on one side completely, it is air dried and denatured at 110 ° C. for 1 hour to obtain a test piece. This test piece is used for the test within 12 hours to 24 hours. The specimens are cleaned for 5 minutes at 25 ± 2 ° C. using a Leanut modified washer and rinsed with ion exchange water at 25 ± 2 ° C. for 30 seconds. After rinsing, drying at 70 ° C. for 30 minutes, coloring with 1% by weight erythrosine solution, measuring the colored area (S ₁ ) by photographic determination, and the washing rate from the initial (before washing) protein dirt adhesion area (S ₀ ) (%) Is calculated by the following formula.
Cleaning rate (%) = [(S ₀ −S ₁ ) / S ₀ ] × 100
The cleaning rate of each of the six glass pieces was determined, and the average value of the four cleaning rates excluding the maximum and minimum values was taken as the cleaning rate of the composition.

(1-3) Evaluation of Detergency of Oil Stain by Foam 20 g of fat and oil mixed with beef tallow and soybean oil in a volume ratio of 1: 1, 0.25 g of monoolein and 0.1 g of oil red are dissolved in 60 mL of chloroform to prepare an oil stain. To do. A set of 6 clean glass slides (76 mm × 26 mm × 1 mm) is measured for each mass up to 1 mg. Immerse the slide glass one by one in an oil stain at 25 ± 1 ° C. to about 55 mm for about 2 seconds. The accumulation of oil stains adhering to the lower part of the slide glass is sucked up using a clean cloth or filter paper such as gauze, and the oil stains are uniformly adhered, air-dried at 25 ± 1 ° C., and the mass is measured. The model soiled glass piece is used for the test within 1 hour to 2 hours in the air drying period. At this time, the oil dirt adhesion amount per 6 pieces of model dirt glass pieces is set to 0.140 ± 0.010 g.

In a 300 mL beaker, put 300 mL (25 ° C) of the test aqueous solution, submerge a silicon hose with an air stone attached to the tip in the test aqueous solution, and send air with an air pump (flow rate 1.5 liter / min) to generate bubbles. . One piece of model soiled glass is brought into contact with the overflowing foam for 5 minutes, and rinsed with ion-exchanged water at 25 ± 2 ° C. for 30 seconds. The glass pieces that have been rinsed are air-dried for a day and night. The evaluation of the cleaning power is calculated from the weight of the model dirt glass piece before and after cleaning. That is, the weight difference before and after cleaning is obtained, and the cleaning rate (%) is calculated by the following formula.
Cleaning rate (%) = [(weight before cleaning−weight after cleaning) / fouling amount] × 100
The cleaning rate of each of the six glass pieces was determined, and the average value of the four cleaning rates excluding the maximum and minimum values was taken as the cleaning rate of the composition.

(2) Bactericidal evaluation test Bacillus subtilis ATCC6633, a spore-forming bacterium, was pre-cultured on an SCD agar medium (manufactured by Nippon Pharmaceutical Co., Ltd.) at 30 ° C. for about one week, and then formed on the agar medium. The colonies were scraped, suspended in 1 mL of sterile water, and examined under a microscope to confirm the formation of bacterial spores (hereinafter referred to as spores). After heat treatment at 65 ° C. for 30 minutes, centrifugal washing was performed twice, and then the concentration was adjusted to about 10 ⁸ cells / mL with an appropriate amount of sterilized water. 1.0 mL of this spore bacterial solution was prepared in the same manner as in the above (1) detergency evaluation test and uniformly inoculated on one piece of model soiled glass piece, and then air-dried to obtain a glass piece for sterilization test.

  The glass piece for sterilization test was brought into contact with the foam of the test aqueous solution generated in the same manner as in the section (1-3) of the above (1) detergency evaluation test, and immediately rinsed with sterilized water. Before the surface of the glass piece dries, a predetermined area (20 mm x 20 mm) of the glass piece is wiped with a sterilized cotton swab, and this swab is immersed in 1 mL of sterilized water (added with 3.3% sodium thiosulfate) to suspend the adhering matter. did. 100 μL of the suspension was inoculated into a sterilized test tube containing 2.0 mL of a post-culture SCD medium (manufactured by Nippon Pharmaceutical Co., Ltd.). This was cultured at 35 ° C. for 48 hours, and the growth of the fungus was observed with the naked eye.

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 The sterilizing detergent composition for hard surfaces which is -5 . The bactericidal detergent composition for hard surfaces according to claim 1, wherein the concentration of the organic peracid is 10 to 20,000 ppm. The hard acid bactericidal detergent composition according to claim 1 or 2, wherein the organic acid constituting (A) is a fatty acid having 1 to 8 carbon atoms. Furthermore, the disinfecting detergent composition for hard surfaces according to any one of claims 1 to 3, further comprising a surfactant. The hard surface bactericidal cleaning composition according to claim 4, wherein the surfactant is at least one selected from an anionic surfactant and a nonionic surfactant. (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 hard surface bactericidal detergent composition having a hydrogen peroxide content of 0.5% by weight or less, comprising a step of reacting in water at a pH of 8 to 12 and then setting the reaction system to a pH of 1 to 5 . Manufacturing method. The method for producing a hard surface sterilizing detergent composition according to claim 6, wherein the concentration of the organic peracid in the hard surface sterilizing detergent composition is 10 to 20,000 ppm. A method for sterilizing and cleaning a hard surface, wherein the hard surface sterilizing detergent composition according to claim 1 is brought into contact with the hard surface. The method for sterilizing and cleaning a hard surface according to claim 8, wherein the hard surface sterilizing and cleaning composition is any one 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 hard surface sterilizing detergent composition according to any one of claims 1 to 5, which is prepared from a composition for producing a sterilizing detergent having a molar ratio of 1 and a water content of 1 to 25% by weight. Thing .
(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. Disinfectant cleaning agent containing oxide (A) and (B1) or (B1) generated from (A) and (B2) at a molar ratio of (A) / (B1) = 1/10 to 20/1 The composition for manufacturing according to any one of claims 1 to 5, wherein the composition is prepared from a composition for manufacturing a sterilizing detergent used as an aqueous solution prepared by adjusting the pH to 8 to 12 and then adjusting the pH to 1 to 5 . The sterilizing detergent composition for hard surfaces according to 1 .
(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 composition for producing a sterilizing detergent, which is prepared from a composition for producing a sterilizing detergent used as an aqueous solution prepared with a pH of 1 to 5 after the pH is adjusted to 8 to 12. The sterilizing detergent composition for hard surfaces according to any one of the above .