Acidic disinfectant composition and cleaning sheet

Abstract

The present invention provides a disinfectant composition and cleaning sheets that maintain disinfecting and virus inactivation properties without the use of surfactants and exhibit excellent effective oxygen stability. [Solution] The present invention provides an acidic disinfectant composition comprising (A) a persulfate or persulfate salt, and (B) an acidifying agent comprising at least one selected from inorganic acids, organic sulfonic acids, and organic phosphonic acids, wherein the pH at 25°C is 0.6 or higher and 3 or lower, and the composition does not contain surfactants, and a cleaning sheet comprising a base sheet impregnated with this acidic disinfectant composition.

Description

[Technical Field]

[0001] This invention relates to an acidic disinfectant composition and a cleaning sheet. Specifically, it relates to an acidic disinfectant composition that does not contain a surfactant, contains persulfuric acid or a persulfate, and a specific acidic agent, and has a pH of 0.6 or higher and 3 or lower at 25°C, and a cleaning sheet using the same. [Background technology]

[0002] Disinfectants are used to reduce the risk of food poisoning and the spread of infection, and to maintain good hygiene in medical facilities, food factories, kitchens, and other similar facilities. Various bactericidal components are used for disinfecting medical facilities, food factories, and kitchens. As a bactericidal component, disinfectants primarily composed of cationic surfactants, such as quaternary ammonium salts, are commonly used. Furthermore, anionic and nonionic surfactants are known to have virus-inactivating properties against enveloped viruses such as coronaviruses. In addition, to prevent the proliferation of microorganisms from dirt adhering to and remaining on the surface to be disinfected, disinfectant compositions combining nonionic, anionic, and amphoteric surfactants are used to impart cleaning properties.

[0003] Regarding conventional disinfectant cleaning agents, Patent Document 1 describes a wet wipe containing a quaternary ammonium salt. Reference Document 2 describes a wet wipe containing a quaternary ammonium salt, iodide propynyl butylcarbamate, and polyaminopropyl biguanide. Patent Document 3 describes an antiviral composition containing a persulfate, a halide, sulfamic acid, a non-reducing organic acid, an acidic phosphate, and a surfactant. Patent Document 4 describes an acidic disinfectant composition containing persulfate or its salt, a surfactant such as anionic surfactants or amphoteric surfactants, and an acidifying agent. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2016-022272 [Patent Document 2] Japanese Patent Publication No. 2018-188368 [Patent Document 3] Japanese Patent Publication No. 165309 / 1983 [Patent Document 4] Japanese Patent Application No. 2024-138362 [Overview of the project] [Problems that the invention aims to solve]

[0005] Surfactants are used in detergents and disinfectants, and it is well known that these are discharged into the wastewater after use in homes and factories, negatively impacting aquatic environments. With the growing awareness of environmental issues in recent years, there is a need to develop products that avoid the use of surfactants, even for products that have traditionally used them. Furthermore, to minimize the impact on the skin when the chemical solution comes into direct contact with the skin, users prefer disinfectant compositions that do not contain surfactants. On the other hand, disinfectant compositions that do not use surfactants raise concerns about reduced disinfecting and virus inactivation effects.

[0006] This invention was discovered to solve the above-mentioned problems. Specifically, the objective is to provide a disinfectant composition and cleaning sheets that can maintain disinfecting and virus inactivation effects without using surfactants and have excellent effective oxygen stability. [Means for solving the problem]

[0007] To solve the above problems, the present inventors conducted diligent studies and found that an acidic disinfectant composition containing (A) persulfuric acid or a persulfate, and (B) an acidifying agent containing at least one selected from inorganic acids, organic sulfonic acids, and organic phosphonic acids, having a pH of 0.6 or higher and 3 or lower at 25°C, and free of surfactants, and a cleaning sheet comprising a base sheet impregnated therewith, can solve the above problems, and thus the present invention was completed.

[0008] In other words, the present invention is (1) An acidic disinfectant composition comprising (A) a persulfate or persulfate, and (B) an acidifying agent containing at least one selected from inorganic acids, organic sulfonic acids, and organic phosphonic acids, having a pH of 0.6 or higher and 3 or lower at 25°C, and free of surfactants. (2) The acidic disinfectant composition of (1), wherein component (A) contains potassium peroxobisulfate. (3) The acidic disinfectant composition of (1), wherein component (B) contains at least one selected from sulfuric acid, nitric acid, phosphoric acid, pyrophosphate, metaphosphate, m-xylenesulfonic acid, p-toluenesulfonic acid, cumenesulfonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, and 2-phosphonobutane-1,2,4-tricarboxylic acid. (4) The acidic disinfectant composition of (1) wherein component (B) contains sulfuric acid, (5) The acidic disinfectant compound of (1) wherein the mass ratio (A) / (B) of component (A) to component (B) is 0.01 or more and 500 or less. (6) A cleaning sheet comprising a base sheet impregnated with any of the acidic disinfectant compositions of (1) to (5), (7)(6) The base sheet contains synthetic fibers, and the base sheet is impregnated with an acidic disinfectant composition in an amount of 100 parts by mass or more and 600 parts by mass or less per 100 parts by mass of the fibers constituting the base sheet, for use as a cleaning sheet. This is the gist of it. [Effects of the Invention]

[0009] The acidic disinfectant composition and cleaning sheets of the present invention exhibit disinfecting and virus inactivating effects equivalent to those of compositions containing surfactants, even without the use of surfactants. [Modes for carrying out the invention]

[0010] The present invention relates to an acidic disinfectant composition and a cleaning sheet containing the above-mentioned components (A) and (B). The acidic disinfectant composition and cleaning sheet of the present invention contain persulfate or persulfate as component (A). This component (A) primarily contributes to the disinfecting effect.

[0011] (A) component can use any persulfuric acid or persulfate with a sterilizing effect. For example, as persulfates, sodium peroxydisulfate, potassium peroxydisulfate, ammonium peroxydisulfate, sodium hydrogen peroxymonosulfate, potassium hydrogen peroxymonosulfate, ammonium hydrogen peroxymonosulfate, etc. can be mentioned. From the viewpoints of commercial reasons and sterilizing properties, potassium hydrogen peroxymonosulfate is preferable as the persulfate. These oxidizing agents may be used alone or in combination of a plurality.

[0012] Incidentally, potassium hydrogen peroxymonosulfate is contained as a part of a triple complex salt (potassium peroxymonosulfate (sulfuric acid) potassium; 2KHSO5·KHSO4·K2SO4) composed of potassium hydrogen peroxymonosulfate, potassium hydrogen sulfate, and potassium sulfate, and is commercially available under the trade name of "Oxone". When the (A) component contains potassium hydrogen peroxymonosulfate, since it is preferably potassium hydrogen peroxymonosulfate derived from the triple complex salt composed of potassium hydrogen peroxymonosulfate, potassium hydrogen sulfate, and potassium sulfate, in the present application, potassium peroxymonosulfate (sulfuric acid) potassium composed of the triple complex salt is used as the (A) component.

[0013] The concentration of oxidizing substances such as persulfuric acid can be measured by the iodine titration method. <Test method> Weigh an appropriate amount of the test solution, add 10 mL of 20% sulfuric acid and 10 mL of 25% potassium iodide solution, perform titration with a 0.01 mol / L aqueous sodium thiosulfate solution, and take the point when it becomes colorless for 30 seconds as the end point. Calculate the effective oxygen concentration from the dropping amount of the 0.01 mol / L aqueous sodium thiosulfate solution up to the end point by the following formula (1). [Calculation formula] Effective oxygen concentration (ppm) = (dropping amount (mL) of 0.01 mol / L aqueous sodium thiosulfate solution × 80.00) / test solution amount (g) ····· (1)

[0014] The acidic disinfectant composition of the present invention contains an acidic agent as component (B), which includes at least one selected from inorganic acids, organic sulfonic acids, and organic phosphonic acids. This component (B) mainly contributes to the stability of component (A). Components (A) and (B) may each be a single component or a combination of multiple components.

[0015] Examples of inorganic acids include sulfuric acid, bromic acid, hydroiodic acid, nitric acid, nitrite, thiocyanic acid, phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphate, tripolyphosphate, tetrapolyphosphate, metaphosphate, pentapolyphosphate, hexametaphosphate, and ultraphosphate, which are condensed phosphoric acids. Among these, sulfuric acid, nitric acid, phosphoric acid, pyrophosphate, and metaphosphate are preferred.

[0016] Examples of organic sulfonic acids include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, hexanesulfonic acid, xylenesulfonic acid such as m-xylenesulfonic acid, toluenesulfonic acid such as p-toluenesulfonic acid, cumensulfonic acid such as p-cumensulfonic acid, and benzenesulfonic acid such as methoxybenzenesulfonic acid. Among these, methanesulfonic acid, m-xylenesulfonic acid, p-toluenesulfonic acid, and cumensulfonic acid are preferred, and m-xylenesulfonic acid, p-toluenesulfonic acid, and cumensulfonic acid are more preferred.

[0017] Examples of organic phosphonic acids include 1-hydroxyethylidene-1,1-diphosphonic acid, methylenediphosphonic acid, 1,2-ethylenediphosphonic acid, 1-hydroxypropyridene-1,1-diphosphonic acid, 1-hydroxybutylidene-1,1-diphosphonic acid, and 2-phosphonobutane-1,2,4-tricarboxylic acid. Among these, 1-hydroxyethylidene-1,1-diphosphonic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid are preferred.

[0018] From the viewpoint of effective oxygen stability and disinfection properties, and from the viewpoint of leaving no residue after wiping with the agent, sulfuric acid, nitric acid, phosphoric acid, methanesulfonic acid, pyrophosphate, metaphosphate, m-xylenesulfonic acid, p-toluenesulfonic acid, cumenesulfonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, and 2-phosphonobutane-1,2,4-tricarboxylic acid are preferred, sulfuric acid, nitric acid, and phosphoric acid are more preferred, and the use of sulfuric acid is even more preferred.

[0019] The above components (A) and (B) may each be a single component or a combination of multiple components.

[0020] The acidic disinfectant composition of the present invention may contain water as component (C). As the water, tap water, softened water, purified water, RO water, ion-exchanged water, and distilled water can be used. As an example of tap water, tap water from Arakawa Ward, Tokyo (pH=7.6, total alkalinity (calcium carbonate equivalent) 40.5 mg / L, German hardness 2.3°DH (of which calcium hardness 1.7°DH, magnesium hardness 0.6°DH), chloride ions 21.9 mg / L, sodium and its compounds 15 mg / L, nitrate nitrogen and nitrite nitrogen 1.2 mg / L, fluorine and its compounds 0.1 mg / L, boron and its compounds 0.04 mg / L, total trihalomethanes 0.016 mg / L, residual chlorine 0.4 mg / L, organic matter (total organic carbon content) 0.7 mg / L) can be used. The water in component (C) of this invention is the remainder of the total amount of components (A) and (B), or the remainder of the total amount of component (A), component (B), and any other optional component.

[0021] The concentration of component (A) in the acidic disinfectant composition is not particularly limited as long as it achieves the effects of the present invention. However, from the viewpoint of the disinfectant properties, virus inactivation properties, and effective oxygen stability of the acidic disinfectant composition, if the acidic disinfectant composition contains component (C), the concentration is preferably 0.1% by mass or more and 5% by mass or less, more preferably 0.2% by mass or more and 2% by mass or less, and even more preferably 0.3% by mass or more and 1% by mass or less, based on the total amount of the composition. Furthermore, if the acidic disinfectant composition does not contain component (C) and is in the case of a solid, the concentration is preferably 10% by mass or more and 100% by mass or less, more preferably 20% by mass or more and 95% by mass or less, and even more preferably 30% by mass or more and 90% by mass or less, based on the total amount of the composition. Potassium peroxobisulfate is present in the triple salt (2KHSO5·KHSO4·K2SO4), which consists of potassium peroxobisulfate, potassium bisulfate, and potassium sulfate, at a concentration of 42.8 to approximately 45% by mass.

[0022] The concentration of component (B) in the acidic disinfectant composition is not particularly limited as long as it achieves the effects of the present invention. However, from the viewpoint of the disinfecting properties of the acidic disinfectant composition, if the disinfectant composition contains component (C), it is preferably 0.01% by mass or more and 5% by mass or less, more preferably 0.05% by mass or more and 2% by mass or less, and even more preferably 0.1% by mass or more and 1% by mass or less, based on the total amount of the composition. Furthermore, if the acidic disinfectant composition does not contain component (C) and is in the case of a solid, it is preferably 1% by mass or more and 100% by mass or less, more preferably 5% by mass or more and 90% by mass or less, and even more preferably 10% by mass or more and 80% by mass or less.

[0023] From the viewpoint of disinfection and virus inactivation, the mass ratio of component (A) to component (B) of the acidic disinfectant composition of the present invention is preferably such that the value of (A) / (B) is 0.01 or more and 500 or less, more preferably 0.05 or more and 100 or less, still preferably 0.2 or more and 100 or less, even more preferably 0.3 or more and 50 or less, and most preferably 0.5 or more and 50 or less.

[0024] The acidic disinfectant composition of the present invention may further contain, as needed, pH adjusters, glycol-based solvents and / or glycol ether-based solvents, chelating agents, dyes, other disinfectants, defoaming agents, fragrances, corrosion inhibitors, natural extracts, thickeners, enzymes, and other salt components (such as sodium chloride and Glauber's salt).

[0025] Examples of pH adjusters include lithium hydroxide, potassium hydroxide, sodium hydroxide, cerium hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide, aluminum hydroxide, sodium carbonate, sodium acetate, potassium phosphate, sodium phosphate, sodium hydrogen phosphate, N,N-dimethylethanolamine, N,N-dibutylethanolamine, N-(β-aminoethyl)ethanolamine, N-methylethanolamine, N-methyldiethanolamine, N-ethylethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, Nt-butyldiethanolamine, Nt-butyldiethanolamine. Examples include alkalis such as ethylethanolamine, Nt-butyldiethanolamine, N-(β-aminoethyl)isopropanolamine, N,N-diethylisopropanolamine, 2-amino-2-hydroxymethyl-1,3-propanediol, aminomethylpropanol, tetrahydroxypropylethylenediamine, morpholine, N-methylmorpholine, N-ethylmorpholine, piperazine, hydroxyethylpiperazine, 2-methylpiperazine, trans-2,5-dimethylpiperazine, and cis-2,6-dimethylpiperazine, as well as acids other than component (B) (e.g., acetic acid). These may be used individually or in combination of two or more.

[0026] Examples of the glycol-based solvents include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, isoprene glycol, 1,2-butylene glycol, and 1,3-butylene glycol. These may be used individually or in combination of two or more.

[0027] Examples of glycol ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monobenzyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, triethylene glycol monohexyl ether, triethylene glycol monophenyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, propylene glycol methyl ethyl ether, and dipropylene glycol methyl ethyl ether. These may be used individually or in combination of two or more.

[0028] Examples of chelating agents include ethylenediaminetetraacetic acid, nitrilotriacetic acid, methylglycinediacetic acid, hydroxyethylenediaminetriacetic acid, diethylenetriaminopentaacetic acid, triethylenetetraaminehexaacetic acid, hydroxyethyliminodiacetic acid, dihydroxyethylglycine, glutamic acid diacetic acid, aspartic acid diacetic acid, β-alanine diacetic acid, serine diacetic acid, and alkali metal salts thereof. These may be used individually or in combination of two or more.

[0029] Examples of pigments include natural pigments, synthetic pigments, or mixtures thereof. Examples of other disinfectants include ε-polylysine, poly-γ-glutamic acid, nisin, etc. Examples of defoaming agents include silicone-based defoaming agents, polyether-based defoaming agents, higher alcohol-based defoaming agents, etc. Examples of fragrances include natural fragrances, synthetic fragrances, or blends thereof. Examples of corrosion inhibitors include polycarboxylic acids such as short-chain dicarboxylic acids or tricarboxylic acids, phosphate esters, triazoles such as benzotriazole, tolyltriazole or mercaptobenzothiazole, adipic acid, glutaric acid, succinic acid, silicates, etc. Examples of natural extracts include those derived from plants such as hemp, Rubiaceae, Brassicaceae, Poaceae, Ebenaceae, Asteraceae, Lamiaceae, Zingiberaceae, Camellia, Solanaceae, Cupressaceae, Myrtaceae, Vitaceae, Fabaceae, Rutaceae, and Liliaceae, as well as natural extracts derived from animals such as lysozyme and leek protein extract. Examples of thickeners include carrageenan, xanthan gum, guar gum, locust bean gum, gatcha gum, karaya gum, and pectin. Examples of enzymes include lipase, alkaline amylase, amylase, cellulase, protease, and pullulanase.

[0030] The pH of the acidic disinfectant composition of the present invention is preferably 0.6 or higher and 3 or lower, and more preferably 1 or higher and 2.5 or lower, from the viewpoint of the stability of component (A).

[0031] The acidic disinfectant composition of the present invention does not contain a surfactant. This is because it can exhibit the desired disinfecting and virus inactivating effects without the use of a surfactant. The surfactant is not particularly limited, but examples include amphoteric surfactants, anionic surfactants, cationic surfactants, and nonionic surfactants.

[0032] When the surfactant is an amphoteric surfactant, examples include alkylaminoacetic acid betaine, alkylamidopropyl betaine, sulfobetaine, alkylamino(mono or di)propionate salts, imidazolinium betaine, alkylamine oxide, alkylaminoethylglycine, alkyldi(aminoethyl)glycine, glycine n-(3-aminopropyl)C10-16 derivatives, alkylpolyaminoethylglycine, alkylβ-alanine, alkyldiethanolamine, polyoxyalkylenealkylamine, and oxyethylene-added surfactants of diamines.

[0033] When the surfactant is an anionic surfactant, examples include fatty acids, alkyl or alkenyl succinic acid, polyoxyalkylene alkyl or alkenyl ether carboxylic acid, alkylol sarcosine, alkyl or alkenyl sulfate, polyoxyalkylene alkyl ether sulfate, polyoxyalkylene alkenyl ether sulfate, amide ether sulfate, alkylbenzene sulfonic acid, olefin sulfonic acid, alkanesulfonic acid, alkyl diphenyl ether disulfonic acid, dialkyl sulfosuccinate, polyoxyalkylene alkyl ether sulfosuccinate half-ester, acyl tauric acid, alkyl monophosphate, alkyl triphosphate, polyoxyalkylene alkyl ether phosphate, dipolyoxyalkylene alkyl ether phosphate, tripolyoxyalkylene alkyl ether phosphate, tripolyoxyalkylene alkyl ether phosphate, and alkali metal salts and ammonium salts thereof.

[0034] When the surfactant is a cationic surfactant, examples include alkyl(alkenyl)trimethylammonium salt, dialkyl(alkenyl)dimethylammonium salt, alkyl(alkenyl)quaternary ammonium salt, mono or dialkyl(alkenyl)quaternary ammonium salt containing an ether group, ester group, or amide group, alkyl(alkenyl)pyridinium salt, alkyl(alkenyl)dimethylbenzylammonium salt, alkyl(alkenyl)isoquinolinium salt, dialkyl(alkenyl)morphonium salt, polyoxyethylenealkyl(alkenyl)amine, alkyl(alkenyl)amine salt, polyamine fatty acid derivative, amyl alcohol fatty acid derivative, benzalkonium chloride, benzethonium chloride, and the like.

[0035] Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers (the addition of ethylene oxide and propylene oxide may be random or blocky), polyethylene glycol propylene oxide adducts, polypropylene glycol ethylene oxide adducts, glycerin fatty acid esters or their ethylene oxide adducts, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, alkyl polyglucosides, fatty acid monoethanolamides or their ethylene oxide adducts, fatty acid-N-methyl monoethanolamides or their ethylene oxide adducts, fatty acid diethanolamides (e.g., coconut oil fatty acid diethanolamide) or their ethylene oxide adducts, sucrose fatty acid esters, alkyl (poly)glycerin ethers, polyglycerin fatty acid esters, polyethylene glycol fatty acid esters, and fatty acid methyl ester ethoxylates.

[0036] The acidic disinfectant composition of the present invention is generally prepared by mixing and stirring the components if they are liquids, or by dissolving the solid components in water and then adding the other liquid components and mixing and stirring them. Furthermore, if each component is solid, it can be mixed in the desired ratio. Ribbon mixers, Nauter mixers, drum mixers, etc., are suitably used for mixing, but ribbon mixers are particularly preferred. Alternatively, the mixture can be compressed into tablets using a tablet press. However, depending on the composition, the order in which each component is added, the order in which it is dissolved, and the manufacturing procedures such as heating / cooling as necessary are not particularly restricted.

[0037] The acidic disinfectant composition may be in either liquid or solid formulation form.

[0038] In the disinfection method using the acidic disinfectant composition of the present invention, the above-mentioned acidic disinfectant composition may be used as is or diluted with water and applied to the surface of the object to be disinfected as a disinfectant solution. Alternatively, the disinfectant solution can be sprayed or discharged onto the object to be disinfected using a foaming cleaning machine (spray gun or foam pump), or the object to be disinfected can be immersed in the disinfectant solution. Furthermore, it can be used as a cleaning sheet by impregnating it with the base sheet described below.

[0039] (Base sheet) The cleaning sheet of the present invention comprises a base sheet. The cleaning sheet of the present invention may be a single-layer sheet consisting substantially only of a base sheet, or it may be a laminated sheet of two or more layers formed by laminating a base sheet and any other sheet. Alternatively, the base sheet may be made of different materials.

[0040] The above-mentioned base sheet can be any sheet that can adequately hold the impregnated acidic disinfectant composition. Specifically, examples of base sheets include nonwoven fabrics, woven fabrics, and mesh fabrics made of regenerated fibers, synthetic fibers, natural fibers, or mixtures thereof.

[0041] From the viewpoint of exhibiting good effective oxygen stability, it is preferable that the base sheet is a sheet containing synthetic fibers, and it is more preferable that the proportion of synthetic fibers to the total mass of fibers constituting the base sheet is 10% by mass or more, even more preferable that it is 50% by mass or more, and even more preferable that it is a proportion exceeding 75% by mass. The amount of the acidic disinfectant composition impregnated into the base sheet can be in the range of 100 parts by mass or more and 600 parts by mass or less per 100 parts by mass of fibers constituting the base sheet, preferably 150 parts by mass or more and 500 parts by mass or less, and more preferably 200 parts by mass or more and 450 parts by mass or less.

[0042] Regenerated fibers refer to fibers produced by dissolving natural polymer compounds into a solution and then spinning it through a spinneret. Examples of natural polymer compounds include cellulose-based materials using cellulose materials such as wood and cotton, and protein-based materials using protein materials such as milk, corn, and peanuts. Examples of regenerated fibers manufactured using cellulose-based materials include rayon, polynosic, cupro, and lyocell. Examples of synthetic fibers include polypropylene, polyester, polyethylene terephthalate (PET), polystyrene, and acrylic, while examples of natural fibers include cotton and wool.

[0043] The cleaning sheets of the present invention exhibit excellent disinfecting properties despite not using surfactants. Therefore, the present invention is useful not only for cleaning various objects to be wiped in the home, providing a hygienic environment, but also for disinfection in a wide range of fields, including the medical, food, brewing, and agricultural sectors.

[0044] The cleaning sheets of the present invention are applicable to a variety of uses, and are suitable for, for example, surface disinfection excluding the surface of human skin, equipment disinfection, or disinfection and antiviral use in wet areas such as toilets, around beds, and drains. The cleaning sheets of the present invention can be formed in the form of multiple sheets stacked together, in the form of a long sheet wound into a roll, or in the form of a sheet folded to an appropriate size. [Examples]

[0045] The present invention will be described in detail below with reference to examples, reference examples, and comparative examples. The components used in the formulations of the examples, reference examples, and comparative examples are shown below. In the following examples, etc., "%" represents mass percent unless otherwise specified, and the numerical values ​​of the formulations in the examples, reference examples, and comparative examples in the table represent the mass percent of the pure content. "Remainder" indicating the water content refers to the amount of formulation adjusted so that the total amount of the final prepared acidic disinfectant composition is 100% by mass. The compounds used in the examples, reference examples, and comparative examples are listed below. Regarding the notation of alkyl groups, for example, when it is written as alkyl(C8~18), it represents a mixture having alkyl groups with 8 or more carbon atoms and 18 or less. In this application, potassium peroxysulfate (sulfate) consisting of a triple salt of potassium peroxymonosulfate, potassium bisulfate, and potassium sulfate is defined as component (A), and the numerical values ​​of its formulation are shown in the examples, reference examples, and comparative examples.

[0046] Tables 1 to 7 below show the components of the acidic disinfectant composition (hereinafter referred to as the disinfectant composition) used in the cleaning sheets of the examples, reference examples, and comparative examples. Tables 1 to 7 also show the percentage (mass%) of each constituent fiber relative to 100% mass of the base sheet. Cleaning sheets were prepared by impregnating 100 parts by mass of a nonwoven fabric base sheet containing various fibers in the proportions shown in the table with 350 to 450 parts by mass of a disinfectant composition (undiluted solution was used if the disinfectant composition was in liquid form, and a 1% diluted solution was used if it was in solid form), storing them in a sealed container for 24 hours. In addition, each cleaning sheet was squeezed with a vise under a force of 10 N·cm for 10 minutes, and the extracted solution was prepared as the extract. The following measurements and evaluations were performed using cleaning sheets and / or extracted fluids. The measurement and evaluation results are shown in Tables 1 to 7.

[0047] (A) component A-1: Potassium peroxysulfate (manufactured by Lanxess, product name "OXONE" (trademark) (a double salt consisting of potassium peroxymonosulfate, potassium bisulfate, and potassium sulfate)) A-2: Potassium peroxodisulfate A-3: Sodium peroxodisulfate A-4: Ammonium peroxodisulfate

[0048] (B) Component B-1: Sulfuric acid B-2: Nitric acid B-3: Phosphate B-4: Methanesulfonic acid B-5: Metaphosphate B-6: m-xylene sulfonic acid B-7: p-toluenesulfonic acid B-8:2-Phosphobutane-1,2,4-tricarboxylic acid

[0049] (C) Ingredients: Ion-exchanged water surfactants Octyldimethylamine oxide (manufactured by Global Amins, product name "GENAMINOX OC (trademark)") Decyldimethylamine oxide (manufactured by Global Aminze, product name "GENAMINOX K-10 (trademark)") Sodium secondary alkane (C14-C17) sulfonate (manufactured by Clariant, product name "HOSTAPUR SAS30SB (trademark)") Sodium polyoxyethylene alkyl ether sulfate (manufactured by Teika Corporation, product name: Teikapol NE-7030 (trademark)) Alkyl (C14-C18) trimethylammonium chloride (manufactured by Lion Specialty Chemicals, product name: Lipocard 16-29 (trademark)) Polyoxyalkylene alkyl (C9-C11) ether (manufactured by Oxalis Chemicals, product name: JCT Ethoxylate 91-6)

[0050] For each example, the composition was prepared by adding water (component C) to a mixing tank so that the total composition amounted to 100% by mass, then adding components (A), (B), and optionally a surfactant to the mixing tank and thoroughly mixing and stirring. For the solid, component (A), persulfuric acid or persulfate, was added to a mixing tank so that the final composition amounted to 100% by mass, then adding component (B) to the mixing tank and thoroughly mixing and stirring.

[0051] Examples 1-37, Reference Examples 1-6, Comparative Examples 1-10 The disinfectant compositions shown in Examples 1 to 37 were prepared. Disinfectant activity, virus inactivation, available oxygen stability, and storage stability were measured for each disinfectant composition. Tables 1 to 5 show the results for Examples 1 to 37, Table 6 shows the results for Reference Examples 1 to 6, and Table 7 shows the results for Comparative Examples 1 to 10.

[0052] *1: pH measurement method A pH measuring composite electrode (Standard ToupH electrode 9615S-10D, manufactured by Horiba, Ltd.) was connected to a pH meter (pH / ion meter F-72, manufactured by Horiba, Ltd.), and the power was turned on. A saturated potassium chloride aqueous solution (3.33 mol / L) was used as the internal solution for the pH electrode. Next, 100 mL beakers were filled with pH 4.01 standard solution (phthalate standard solution), pH 6.86 (neutral phosphate standard solution), and pH 9.18 standard solution (borate standard solution), and the beakers were immersed in a 25°C constant temperature bath for 30 minutes. The pH measuring electrode was immersed in the standard solutions adjusted to constant temperature for 3 minutes, and calibration was performed in the order of pH 6.86 → pH 9.18 → pH 4.01. Each disinfectant composition (the undiluted solution was used if the composition was liquid, and a 1% diluted solution was used if it was solid) was filled into a 100 mL beaker and adjusted to 25°C in a constant temperature bath. A pH measuring electrode was immersed in the sample adjusted to constant temperature for 3 minutes, and the pH of the composition was measured.

[0053] *2: Disinfection test (bacteria) The bacterial strain used for the test was Staphylococcus aureus (NBRC13276).

[0054] 2-1: Culturing of bacterial strains The test strains were streaked onto SCD agar (Nissui Pharmaceutical Co., Ltd.), incubated at 37°C for 24 hours, and then the colonies were scraped off. Each strain was then diluted in sterile phosphate-buffered saline and used as a bacterial suspension.

[0055] 2-2: Preparation of sterile neutralizing solution 10 g of soy lecithin, 30 g of Tween80, 1 g of L-histidine, and 20 g of sodium thiosulfate were dissolved in 1 L of distilled water while being heated, and then cooled while stirring. Afterward, 9 mL of each solution was dispensed into screw-cap test tubes, and sterilized by autoclaving (121°C, 20 minutes) to obtain sterile neutralized solutions.

[0056] 2-3: Disinfection Test Each 10 mL of extract contains a final concentration of 1.5 × 10 8 ~5.0×10 8 0.1 mL of each bacterial suspension was added to achieve the desired CFU / mL ratio, and the mixture was allowed to come into contact with the solution at 20°C for 1 minute to prepare the test solution. 1 mL of each test solution was added to a sterile neutralizing solution and thoroughly mixed. The mixture was mixed and solidified on SCD agar medium, and then incubated at 37°C for 2 days. After incubation, the number of viable cells was measured, and the difference from the initial number of cells was used to determine the logarithm. 10 The reduction was calculated, and the disinfecting effect was evaluated according to the following criteria.

[0057] <Evaluation Criteria> ◎: Log of the test bacteria 10 Reduction of 6 or more ○: Log of the test bacteria 10 A reduction of 4 or more, but less than 6. △: Log of the test bacteria 10 A reduction of 2 or more, but less than 4. ×: Log of the test bacteria 10 The number of days is less than 2. Items with a rating of △, ○, or ◎ were judged to be practical.

[0058] ※3: Bactericidal test (spore-forming bacteria) As the test strain, Clostridioides difficile ATCC9689 (10 8 CFU / mL level) was used.

[0059] 3-1: Cultivation of the strain The test strain was smeared on BHI agar medium supplemented with taurocholic acid (manufactured by Difco), anaerobically cultured at 37°C, and after cultivation, it was confirmed by microscopic observation that spores were sufficiently formed. 10 mL of sterilized pure water was added to the petri dish, and the colonies were scraped off to collect the suspension. The collected suspension was centrifuged and washed 3 times under the conditions of 10,000 rpm, 4°C, and 15 minutes. After centrifugation, an appropriate amount of sterilized pure water was added to adjust the bacterial count to about 2.0×10 8 ~9.0×10 8 CFU / mL, and heat treatment was carried out in a water bath at 80°C for 15 minutes to obtain a spore-forming bacteria solution for use.

[0060] 3-2: Preparation of sterilized neutralizing solution 10 g of soy lecithin, 30 g of Tween 80, 1 g of L-histidine, and 20 g of sodium thiosulfate were dissolved by heating in 1 L of distilled water, and cooled while stirring. Then, 9 mL of each was dispensed into test tubes with screw caps and sterilized by high-pressure sterilization (121°C, 20 minutes) to obtain a sterilized neutralizing solution.

[0061] 3-3: Bactericidal test To 10 mL of each squeezed juice, 0.1 mL of the test spore-forming bacteria solution was added, and the mixture contacted at 20°C for 10 minutes was used as the test solution. 1 mL of each test solution was added to the sterilized neutralizing solution and stirred well. This 1 mL was added to BHI agar medium supplemented with taurocholic acid (manufactured by Difco), and mixed culture was carried out under anaerobic conditions to measure the viable cell count. Log 10 reduction was calculated from the difference from the initial bacterial count and evaluated according to the following criteria.

[0062] <Evaluation criteria> ◎: Log of the test bacteria 10A reduction of 3 or more bacteria indicates a decrease in bacterial count. ○: Log of the test bacteria 10 Bacterial count reduction of 2 or more but less than 3 △: Log of the test bacteria 10 Bacterial count reduction of 1 or more but less than 2 ×: Log of the test bacteria 10 Bacterial count reduction of less than 1 Based on this, △, ○, and ◎ were judged as being practical.

[0063] *4: Virus inactivation test (feline calicivirus) Each test tube containing 0.9 mL of extract contains 10 8 TCID 50 0.1 mL of feline calicivirus solution, adjusted to a concentration of / mL, was added and mixed in a mixer to create a mixture, which was then allowed to react at 25°C for 1 minute. Similarly, a test was conducted using phosphate-buffered saline (PBS) instead of the extracted solution, and this was used as a control. The reaction was stopped by diluting the reaction mixture sevenfold in Dulbecco's modified Eagle's Medium (DMEM) supplemented with 2% fetal bovine serum (FBS). The stopped solution was serially diluted sevenfold in DMEM medium, and each dilution was inoculated into feline kidney cells (CRFK). The cells were then cultured for 4 days in 1% FBS-supplemented DMEM medium at 37°C in a CO2 incubator set to 5% CO2. After culturing, the cytopathic effect was observed, and the viral infectivity titer (TCID) was measured. 50 The viral titer ( / mL) was calculated. From the initial infectivity titer of the control and the infectivity titer after the test substance was applied, the logarithmic decrease in viral titer (viral titer Log) was calculated. 10 The reduction value was calculated, and the virus inactivation effect was evaluated according to the following criteria.

[0064] <Evaluation Criteria> ◎: Decrease of 4 or more in the logarithmic decrease in viral infectivity titer. ○: Decrease in the logarithmic decrease of viral infectivity titer of 3 or more and less than 4. △: Decrease in the logarithmic decrease of viral infectivity titer of 2 or more but less than 3. ×: Decrease in viral infection titer logarithm less than 2 Based on this, △, ○, and ◎ were judged as being practical.

[0065] *5: Test to reduce wiping marks caused by cleaning sheets. A 15cm x 15cm glass plate was prepared, and its surface was wiped five times vertically and five times horizontally with each cleaning sheet. After that, the glass plate was dried at room temperature for two hours, and any remaining residue on the glass plate surface was visually evaluated.

[0066] <Evaluation Criteria> ◎: No residue or streaks are noticeable at all. ○: Leaves almost no residue after wiping. △: There are some slight streaks left behind after wiping, but it's not a problem. ×: I'm concerned about the residue left behind after wiping. Based on this, △, ○, and ◎ were judged as practical.

[0067] *6: Evaluation test regarding discoloration of nonwoven fabric Test method: Ten cleaning sheets (200mm x 250mm) were used and stored at 40°C for one week. After storage, the changes in the appearance of the cleaning sheets were observed visually. <Evaluation Criteria> ◎: No discoloration or deterioration has occurred. ○: There is almost no slight discoloration or minor deterioration. △: There is some slight discoloration or significant deterioration, but it is not a problem. ×: Overall, there is significant discoloration and severe deterioration. Based on this, △, ○, and ◎ were judged as being practical.

[0068] *7: Effective oxygen stability test Test method: Each cleaning sheet (200mm x 250mm x 10 sheets) was placed in a bag made of PET and polyethylene with aluminum vapor deposition, sealed by heat sealing, and the amount of available oxygen remaining in the extracted liquid was measured after being left at 40°C for one month. <Testing Method> An appropriate amount of test solution was weighed, 10 mL of 20% sulfuric acid and 10 mL of 25% potassium iodide solution were added, and the solution was titrated with a 0.01 mol / L sodium thiosulfate aqueous solution. The endpoint was the point at which the solution became colorless after 30 seconds, and the effective oxygen concentration was calculated from the amount of 0.01 mol / L sodium thiosulfate aqueous solution added to reach the endpoint using the following formula (1). [Calculation formula] Effective oxygen concentration (ppm) = (Volume of 0.01 mol / L sodium thiosulfate aqueous solution added (mL) × 80.00) / Volume of test solution (g) ... (1)

[0069] <Evaluation Criteria> ○: Effective oxygen retention rate is 80% or higher △: Available oxygen remaining rate is 60% or more, but less than 80%. ×: Available oxygen retention rate is less than 60% Based on this, △ and ○ were judged to be practical.

[0070] *8: Storage stability test 100g of each disinfectant composition was placed in a polypropylene container and left to stand for one month at 0°C, 25°C, and 40°C, after which its appearance was observed.

[0071] <8-1: Criteria for evaluating storage stability (liquids)> ○: No separation or turbidity observed; stable. △: There is no overall separation, and slight turbidity is visible, but there are no problems with use. ×: Separation or turbidity is observed. Based on this, △ and ○ were judged to be practical.

[0072] <8-2: Criteria for evaluating storage stability (solids)> ○: Little to no moisture absorption or solidification observed. △: Some moisture absorption and solidification may be observed, but this does not affect usability. ×: Solidification occurs due to moisture absorption, and it is not fluid. Based on this, △ and ○ were judged to be practical.

[0073] [Table 1]

[0074] [Table 2]

[0075] [Table 3]

[0076] [Table 4]

[0077] [Table 5]

[0078] [Table 6]

[0079] [Table 7]

[0080] The results above demonstrate that the examples exhibit disinfecting and virus inactivating effects equivalent to those of Reference Examples 1-5, which contain surfactants, even without the use of surfactants. Furthermore, the acidic disinfectant composition of the present invention is also shown to be sufficiently useful as a cleaning sheet.

[0081] This specification discloses the following inventions. (1) An acidic disinfectant composition comprising (A) a persulfate or persulfate, and (B) an acidifying agent containing at least one selected from inorganic acids, organic sulfonic acids, and organic phosphonic acids, having a pH of 0.6 or higher and 3 or lower at 25°C, and free of surfactants. (2) The acidic disinfectant composition of (1), wherein component (A) contains potassium peroxobisulfate. (3) The acidic disinfectant composition of (1) or (2), wherein component (B) comprises at least one selected from sulfuric acid, nitric acid, phosphoric acid, pyrophosphate, metaphosphate, m-xylenesulfonic acid, p-toluenesulfonic acid, cumenesulfonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, and 2-phosphonobutane-1,2,4-tricarboxylic acid. (4) An acidic disinfectant composition of any of (1) to (3) in which component (B) contains sulfuric acid, (5) An acidic disinfectant compound of any of (1) to (4) wherein the mass ratio (A) / (B) of component (A) to component (B) is 0.01 or more and 500 or less. (6) A cleaning sheet comprising a base sheet impregnated with any of the acidic disinfectant compositions of (1) to (5), A cleaning sheet wherein the base sheet of (7)(6) contains synthetic fibers, and the base sheet is impregnated with an acidic disinfectant composition in an amount of 100 parts by mass or more and 600 parts by mass or less per 100 parts by mass of the fibers constituting the base sheet.

Claims

1. An acidic disinfectant composition comprising (A) persulfate or persulfate as component, and (B) an acidifying agent containing at least one selected from inorganic acids, organic sulfonic acids, and organic phosphonic acids, wherein the pH at 25°C is 0.6 or higher and 3 or lower, and it does not contain surfactants.

2. (A) The acidic disinfectant composition according to claim 1, wherein component (A) contains potassium peroxobisulfate.

3. The acidic disinfectant composition according to claim 1, wherein component (B) comprises at least one selected from sulfuric acid, nitric acid, phosphoric acid, pyrophosphate, metaphosphate, m-xylenesulfonic acid, p-toluenesulfonic acid, cumenesulfonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, and 2-phosphonobutane-1,2,4-tricarboxylic acid.

4. (B) The acidic disinfectant composition according to claim 1, wherein component (B) contains sulfuric acid.

5. The acidic disinfectant composition according to claim 1, wherein the mass ratio (A) / (B) of component (A) to component (B) is 0.01 or more and 500 or less.

6. A cleaning sheet comprising a base sheet impregnated with the acidic disinfectant composition described in any one of claims 1 to 5.

7. A cleaning sheet, wherein the base sheet according to claim 6 contains synthetic fibers, and the base sheet is impregnated with an acidic disinfectant composition in an amount of 100 parts by mass or more and 600 parts by mass or less per 100 parts by mass of the fibers constituting the base sheet.

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