Liquid detergent composition for hard surface and method for washing hard surface

Abstract

To provide a liquid detergent composition for a hard surface capable of achieving both of bactericidal activity and high temperature stability.SOLUTION: A liquid detergent composition for a hard surface, comprising (A) a silver element source or a silver ion source, (B) a disinfectant comprising an organic acid having 1 to 9 carbon atoms or a salt thereof, (C) a disinfectant comprising a phenolic compound having a phenolic hydroxyl group or a salt thereof, and (D) a surfactant, A content of the component (A) is from 4 to 15 ppm by mass, a content of the component (B) is from 0.005 to 2.2% by mass, and a content of the component (C) is from 0.03 to 0.7% by mass, with respect to a total mass of the liquid detergent composition for a hard surface, and a pH at 25 °C is from 8 to 11.5.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a liquid cleaning composition for hard surfaces and a method for cleaning hard surfaces. [Background technology]

[0002] Due to the current increasing awareness of hygiene among consumers, liquid cleaning compositions for hard surfaces are required to have disinfecting properties. Silver compounds are known to have excellent disinfecting properties. Patent Document 1 discloses a bathroom cleaner composition that contains a surfactant, an aminocarboxylic acid-type chelating agent, water-soluble silver, and polyhexamethylene biguanide, and that has excellent cleaning and disinfecting power and good inhibition of metal discoloration. Patent Document 2 discloses a hard surface cleaner composition that contains an anionic surfactant, a silver compound, a basic polyamino acid, and a chelating agent, and that has excellent cleaning and disinfecting power and excellent liquid color stability. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2018-012816 [Patent Document 2] Japanese Patent Publication No. 2020-076103 Summary of the Invention [Problem to be solved by the invention]

[0004] However, conventional bathroom cleaner compositions containing silver compounds have stability issues, such as precipitation and discoloration of the liquid in high-temperature environments. In particular, concentrated compositions are required to have high disinfecting performance so that they can maintain sufficient disinfecting performance even when diluted, but increasing the amount of disinfectant further worsens stability, making it difficult to achieve both high disinfecting performance and high-temperature stability. An object of the present invention is to provide a liquid cleaning composition for hard surfaces that can achieve both disinfecting activity and high-temperature stability. [Means for solving the problem]

[0005] The present invention has the following aspects. [1] (A) component: a source of elemental silver or silver ions; (B) Component: a disinfectant containing an organic acid having 1 to 9 carbon atoms or a salt thereof, and (C) Component: a disinfectant containing a phenolic compound having a phenolic hydroxyl group or a salt thereof, and Component (D): A liquid cleaning composition for hard surfaces containing a surfactant, Relative to the total mass of the liquid cleaning composition for hard surfaces, The content of the component (A) is 4 to 19 ppm by mass, The content of the component (B) is 0.005 to 2.2% by mass, The content of the component (C) is 0.03 to 0.7% by mass, A liquid cleaning composition for hard surfaces, having a pH of 8 to 11.5 at 25°C. [2] The liquid detergent composition for hard surfaces according to [1], wherein the mass ratio of component (B) / component (C) is 0.03 to 60. [3] A method for cleaning hard surfaces, comprising contacting an aqueous solution obtained by diluting the liquid cleaning composition for hard surfaces according to [1] or [2] with water by a ratio of 1 to 3 with an object to be cleaned. [Effects of the Invention]

[0006] According to the present invention, a liquid cleaning composition for hard surfaces that can achieve both disinfecting activity and high-temperature stability can be obtained. DETAILED DESCRIPTION OF THE INVENTION

[0007] <Liquid cleaning composition for hard surfaces> The liquid detergent composition for hard surfaces of this embodiment (hereinafter, sometimes simply referred to as "liquid detergent") is a composition containing component (A), component (B), and component (C). In this specification, a numerical range expressed by "to" means a numerical range in which the numbers before and after "to" are the lower and upper limits. In this specification, "sterilization" means removing or reducing the number of bacteria or viruses. There are no clear rules regarding the type or number of bacteria or viruses to be removed. "Antibacterial" means suppressing or inhibiting bacterial growth. "Sterilization" means killing bacteria, and there are no rules regarding the type or number of bacteria or viruses. "Sterilization" means killing or removing all bacteria, and the standard is to reduce the number of bacteria or viruses to one millionth or less compared to the pre-sterilization state. "Disinfection" means neutralizing bacteria or viruses by weakening their activity or reducing their number.

[0008] <Component (A)> Component (A) is a source of elemental silver or silver ions. In general, the fact that elemental silver and silver ions have a disinfecting effect is also described in Chemistry and Education, Vol. 53, No. 5 (2005), etc. Component (A) may be either water-soluble or fat-soluble, but is preferably water-soluble, as long as it supplies elemental silver or silver ions to the liquid detergent. In this specification, "water-soluble" means that the solubility in water at 20°C is 1 g / 100 g or more. The component (A) is preferably (1) a silver complex or (2) a silver carrier. (1) Examples of silver complexes include complexes of silver and amino acids (histidine, arginine, creatinine, etc.), complexes of silver and polymers (polymers having metal ion ligands, such as copolymers of vinylimidazole or vinylpyridine with (meth)acrylic acid esters), complexes of silver and carboxylic acids (pyruvic acid, glycolic acid, acetic acid, butyric acid, salicylic acid, etc.), complexes of silver, carboxylic acids, and amino acids, and complexes of silver and imidazole derivatives. (2) Examples of silver carriers include those in which silver salts or silver itself are supported on inorganic compounds such as phosphates such as zirconium phosphate and calcium phosphate, metal oxides such as silicon oxide, aluminum oxide, alumina silica and boron oxide, zeolites, clay minerals, and silica gel. (1) Silver complex or (2) silver carrier is commercially available.

[0009] From the viewpoint of disinfecting power and high-temperature stability, silver complexes are preferred, and silver complexes containing amino acids such as creatinine are more preferred. The component (A) may be used alone or in appropriate combination of two or more types. The content of component (A) in the liquid detergent is such that the concentration of silver derived from component (A) is 0.0004 to 0.0019% by mass (4 to 19 ppm by mass) relative to the total mass of the liquid detergent, with the silver concentration being preferably 5 to 15 ppm by mass, and more preferably 10 to 15 ppm by mass. If the concentration of silver derived from component (A) is at or above the lower limit of the above range, good disinfecting power is likely to be obtained, and if it is at or below the upper limit, good high-temperature stability is likely to be obtained.

[0010] <(B) component> Component (B) is a disinfectant containing an organic acid having 1 to 9 carbon atoms or a salt thereof. In general, the fact that organic acids having 1 to 9 carbon atoms or salts thereof have antibacterial activity is also described, for example, in Environmental Science and Pollution Research (2022) 29:32594-32604, Prospects of organic acids as a safe alternative to antibiotics in broiler chickens diet, Rifat Ullah Khan et al. Use of component (B) increases the stability of component (A) in the composition, making it easier to obtain the disinfecting effect of component (A), while also obtaining the disinfecting effect of component (B).

[0011] Component (B) is preferably water-soluble. The octanol-water partition coefficient (LogPow) of component (B) is preferably −1.00 to 3.00, more preferably −0.80 to 2.00, and even more preferably −0.60 to 1.00. When the octanol-water partition coefficient of component (B) is within the above range, the water solubility of component (B) is further improved. The molecular weight of the acid form of component (B) is preferably 46 to 290, more preferably 132 to 206. When the molecular weight of component (B) is within the above range, the disinfecting effect is further enhanced.

[0012] The component (B) has 1 to 9 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 5 carbon atoms. The number of carboxyl groups or carboxylate groups in the component (B) is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1, in one molecule.

[0013] Examples of component (B) include straight-chain fatty acids such as formic acid, acetic acid, propionic acid, butyric acid, and valeric acid; dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, fumaric acid, maleic acid, phthalic acid, isophthalic acid, and terephthalic acid; acidic amino acids such as glutamic acid and aspartic acid; oxyacids such as glycolic acid, lactic acid, hydroxyacrylic acid, α-hydroxybutyric acid, glyceric acid, tartronic acid, malic acid, tartaric acid, citric acid, salicylic acid (o, m, p), gallic acid, mandelic acid, tropic acid, and gluconic acid; and salts of these organic acids (e.g., sodium salts and potassium salts).

[0014] The component (B) may be used alone or in an appropriate combination of two or more types. The content of component (B) is preferably 0.005 to 2.2% by mass, more preferably 0.01 to 2% by mass, and even more preferably 0.05 to 0.5% by mass, based on the total mass of the liquid detergent. When the content of component (B) is at least the lower limit of the above range, the disinfecting effect derived from component (B) can be sufficiently obtained and discoloration of the liquid derived from component (A) can be suppressed, while when the content is at most the upper limit, the formation of precipitates derived from component (A) can be suppressed.

[0015] The mass ratio of component (A) / component (B) is 0.0001 to 0.2, preferably 0.00025 to 0.15, and more preferably 0.001 to 0.03. When the mass ratio is within the above range, discoloration of the liquid and formation of precipitates due to component (A) are suppressed, while the disinfecting activity of component (B) is likely to be improved.

[0016] <(C) component> Component (C) is a disinfectant containing a phenolic compound having a phenolic hydroxyl group or a salt thereof. In general, the fact that phenolic compounds having a phenolic hydroxyl group or a salt thereof have a disinfecting effect is also described in Wood Preservation, Vol. 24, 1983, pp. 3-17, by Yoshiyuki Inoue et al.

[0017] The component (C) is preferably one or more nonionic aromatic compounds selected from the group consisting of compounds represented by the following formulas (c1) and (c2).

[0018] [ka]

[0019] (In formula (c1), X is an oxygen atom or an alkylene group having 1 to 4 carbon atoms; each Y is independently a chlorine atom or a bromine atom; a, b, and c are independently 0 or an integer of 1 to 3; m is 0 or 1; and n is 0 or 1.)

[0020] [ka]

[0021] (In formula (c2), V and W each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 3 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0022] In formula (c1), -(Y) b-(Y) means that b of the hydrogen atoms bonded to the carbon atoms constituting the benzene ring are substituted with Y. c , -(OH) m and -(OH) n The same is true for . In formula (c1), X is an oxygen atom or an alkylene group having 1 to 4 carbon atoms, preferably an oxygen atom. Each Y is independently a chlorine atom or a bromine atom, preferably a chlorine atom. a, b, and c each independently represent 0 or an integer of 1 to 3. a is preferably 0 or 1. a=0 represents a single bond. At least one of b and c is preferably 1 or greater, and more preferably both are 1 or greater. The sum of b and c is preferably 2 to 6, more preferably 2 to 4, and particularly preferably 2 to 3. m is 0 or 1. n is 0 or 1. The sum of m and n is 0 to 2, preferably 0 to 1, and particularly preferably 0.

[0023] Examples of the component (c1) include monochlorohydroxydiphenyl ether, dichlorohydroxydiphenyl ether, trichlorohydroxydiphenyl ether, and benzylchlorophenol. In terms of rinsing properties, the following compounds are preferred. Dichlosan (4,4'-dichloro-2-hydroxydiphenyl ether, a compound represented by formula (c1) in which X=oxygen atom, Y=chlorine atom, a=1, b=1, c=1, n=0, and m=0), Triclosan (2,4,4'-trichloro-2'-hydroxydiphenyl ether, a compound represented by formula (c1) in which X=oxygen atom, Y=chlorine atom, a=1, b=2, c=1, n=0, and m=0).

[0024] In formula (c2), V and W each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. It is preferable that both V and W are alkyl groups having 1 to 4 carbon atoms. R 3 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom. As the component (c2), isopropylmethylphenol is preferred.

[0025] The component (C) may be used alone or in appropriate combination of two or more types. The content of component (C) is preferably 0.03 to 0.7 mass%, more preferably 0.05 to 0.5 mass%, and even more preferably 0.1 to 0.25 mass%, based on the total mass of the liquid detergent. When the content of component (C) is at least the lower limit of the above range, the disinfecting effect derived from component (C) is sufficiently obtained, while when the content is at most the upper limit, the solubility and dispersibility of component (C) is prevented from decreasing, thereby further improving high-temperature stability.

[0026] The mass ratio of component (A) / component (C) is 0.0001 to 0.04, preferably 0.001 to 0.03, and more preferably 0.002 to 0.015. When the mass ratio is within the above range, the formation of precipitates derived from component (A) can be suppressed, while the disinfecting activity of component (C) can be further improved.

[0027] The mass ratio of component (B) / component (C) is 0.03 to 60, preferably 0.04 to 50, and more preferably 0.2 to 5. When the mass ratio is within the above range, discoloration of the liquid and formation of precipitates derived from component (A) are suppressed, while a decrease in the solubility and dispersibility of component (C) is prevented, and high-temperature stability is further improved, and the disinfecting activity of components (B) and (C) can be further improved.

[0028] It is preferable that the component (C) contains one or more members selected from the group consisting of diclosan, triclosan, and isopropylmethylphenol. For example, of the total mass of component (C) contained in the liquid detergent, the sum of diclosan, triclosan, and isopropylmethylphenol is preferably more than 90 mass%, more preferably more than 93 mass%, even more preferably more than 95 mass%, and particularly preferably more than 98 mass%, or may be 100 mass%. In particular, it is preferable that component (C) contains dichrosan. For example, the proportion of dichlosan in the total mass of component (C) contained in the liquid detergent is preferably more than 90 mass%, more preferably more than 93 mass%, even more preferably more than 95 mass%, and particularly preferably more than 98 mass%, or may be 100 mass%.

[0029] <(D) component> Component (D) is a surfactant. Examples include anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, and semi-polar surfactants. Anionic surfactants are preferred as component (D). Component (D) may be used to improve the solubility and dispersibility of component (C), or to improve the cleaning power against sebum, proteinaceous stains, and other contaminants adhering to the bathroom interior. Examples of the component (D) include the following surfactants (1) to (11). (1) Linear or branched alkylbenzene sulfonate (LAS or ABS) having an alkyl group having 8 to 18 carbon atoms. (2) Alkanesulfonates having 10 to 20 carbon atoms. (3) α-olefin sulfonates (AOS) with 10 to 20 carbon atoms. (4) Internal olefin sulfonates (IOS) with carbon atoms of 16 to 24. (5) Alkyl sulfates or alkenyl sulfates (AS) having 10 to 20 carbon atoms. (6) Alkyl (or alkenyl) ether sulfates (AES) having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms, to which an average of 0.5 to 10 moles of any alkylene oxide having 2 to 4 carbon atoms or ethylene oxide and propylene oxide (molar ratio EO / PO=0.1 / 9.9 to 9.9 / 0.1) have been added. (7) Alkyl (or alkenyl) phenyl ether sulfate having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms, which is obtained by adding an average of 3 to 30 moles of any alkylene oxide having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO=0.1 / 9.9 to 9.9 / 0.1). (8) Alkyl (or alkenyl) ether carboxylate having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms, to which an average of 0.5 to 10 moles of any alkylene oxide having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO=0.1 / 9.9 to 9.9 / 0.1) have been added. (9) Alkyl polyhydric alcohol ether sulfates such as alkyl glyceryl ether sulfonic acids having 10 to 20 carbon atoms. (10) Long chain monoalkyl, dialkyl or sesquialkyl phosphates. (11) Polyoxyethylene monoalkyl, dialkyl or sesquialkyl phosphates. (12) Salts of higher fatty acids (soaps) having 10 to 20 carbon atoms.

[0030] Examples of the salts include alkali metal salts such as sodium salts and potassium salts; alkaline earth metal salts such as magnesium salts and calcium salts; alkanolamine salts such as monoethanolamine salts (monoethanolammonium), diethanolamine salts (diethanolammonium), and triethanolamine salts (triethanolammonium); and ammonium salts, with sodium salts and potassium salts being preferred.

[0031] The component (D) is preferably a linear or branched alkylbenzenesulfonate (LAS or ABS) having an alkyl group having 8 to 18 carbon atoms, an α-olefinsulfonate (AOS) having 10 to 20 carbon atoms, or an alkyl sulfate or alkenyl sulfate (AS) having 10 to 20 carbon atoms, and more preferably an α-olefinsulfonate (AOS) having 10 to 20 carbon atoms. The component (D) may be used alone or in appropriate combination of two or more types. The content of component (D) is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass, and even more preferably 2 to 10% by mass, based on the total mass of the liquid detergent composition for hard surfaces. In particular, when the liquid detergent is diluted 1 to 3 times with water to prepare a diluted liquid detergent, the content in this range is preferred.

[0032] <Water> The liquid detergent preferably contains water as a solvent from the viewpoints of ease of handling during production, solubility in water during use, etc. Examples of water include ion-exchanged water and pure water. The content of water is preferably 80 to 98 mass %, more preferably 90 to 95 mass %, based on the total mass of the liquid detergent.

[0033] <Other optional ingredients> In addition to the above components, the liquid detergent may optionally contain components that are typically used in liquid detergent compositions for hard surfaces. Examples of such optional components include glycol-based solvents (component (E)), other organic solvents, preservatives, chelating agents, bactericides, antiseptics, antifungal agents, pigments, antioxidants, thickeners, UV absorbers, solubilizers, fragrances, pH adjusters, etc.

[0034] Component (E) is a glycol-based solvent. Component (E) may be used to improve the solubility and dispersibility of component (C), or to improve the cleaning power against sebum, protein stains, and the like adhering to the bathroom interior. Component (E) preferably contains a glycol ether solvent because of its good detergency, and particularly preferably contains a glycol ether solvent represented by the following general formula (e1): R 1 -O-[(EO) x / (PO) y ]-R 2 (e1) In formula (e1), R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or a phenyl group. EO represents an oxyethylene group, PO represents an oxypropylene group, x represents the average number of repetitions of EO and is a number from 0 to 5, and y represents the average number of repetitions of PO and is a number from 0 to 5, provided that x and y are not both 0. [(EO) x / (PO) y] indicates that EO and PO may form either a random chain or a block chain.

[0035] R 1 is preferably a linear alkyl group having 1 to 4 carbon atoms, and more preferably a linear alkyl group having 2 to 4 carbon atoms. R 2 is preferably a hydrogen atom or a linear alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom. x is preferably 1 to 3, and more preferably 1 or 2. y is preferably 0 to 5, and more preferably 0 to 2.

[0036] Specific examples of component (E) include ethylene glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, ethylene glycol monohexyl ether, diethylene glycol monobutyl ether, and triethylene glycol monobutyl ether; propylene glycol ethers such as propylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, and tripropylene glycol monomethyl ether; and phenyl diglycol.

[0037] Among these, diethylene glycol monobutyl ether, propylene glycol monopropyl ether, ethylene glycol monohexyl ether, and phenyl diglycol are preferred because of their good detergency, and diethylene glycol monobutyl ether is particularly preferred.

[0038] The component (E) may be used alone or in appropriate combination of two or more types. The content of component (E) is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass, and even more preferably 2 to 10% by mass, based on the total mass of the liquid detergent composition for hard surfaces. In particular, when the liquid detergent is diluted 1 to 3 times with water to prepare a diluted liquid detergent, the content in this range is preferred.

[0039] When the content of component (E) is equal to or greater than the preferred lower limit, cleaning power is further improved. Furthermore, cleaning power is also further improved when diluted with water. Furthermore, when the content of component (E) is equal to or less than the preferred upper limit, it is more likely to become a fine mist when sprayed, and the area that can be sprayed in one go is wider.

[0040] Examples of pH adjusters include sulfuric acid, hydrochloric acid, phosphoric acid, sodium hydroxide, potassium hydroxide, alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine, and ammonia. Among these, sulfuric acid, sodium hydroxide, and potassium hydroxide are preferred, and sulfuric acid and sodium hydroxide are more preferred, from the viewpoint of ease of pH adjustment. The pH adjuster may be one type or a combination of two or more types.

[0041] <Physical properties> The pH of the liquid detergent at 25° C. is 8 to 11.5, preferably 9 to 11, and more preferably 9.5 to 10.5. When the pH is within the above range, high-temperature stability can be further improved. In this specification, the pH of the liquid detergent is a value measured by a method in accordance with JIS Z 8802:2011 "pH measurement method."

[0042] The viscosity of the liquid detergent is not particularly limited, but is preferably 1 to 50 mPa·s, more preferably 1 to 10 mPa·s. A viscosity within this range ensures good adhesion to the object to be cleaned and good dischargeability from a spray container, etc. In this specification, the viscosity of a liquid detergent is measured at a liquid temperature of 25°C using a B-type viscometer (manufactured by Tokimec Corporation) with rotor number 1 and a rotor rotation speed of 60 rpm, 60 seconds after the rotor starts rotating.

[0043] <Liquid cleaning products for hard surfaces> The liquid detergent product for hard surfaces (hereinafter sometimes simply referred to as "liquid detergent product") has a dispensing container and the liquid detergent composition for hard surfaces of the present invention contained in the dispensing container.

[0044] Examples of the dispensing container for containing the liquid detergent include a spray container, a squeeze container, etc. Among them, a spray container is preferred because of its excellent applicability to the object to be cleaned. Examples of the spray container include an aerosol spray container, a trigger spray container (direct pressure type or pressure accumulation type), a dispenser spray container, etc. These containers may be manual or electric. Examples of the aerosol spray container include those described in JP-A-9-3441 and JP-A-9-58765. When filling an aerosol spray container, propellants that can be used include LPG (liquefied propane gas), DME (dimethyl ether), carbon dioxide gas, nitrogen gas, nitrous oxide gas, etc. These propellants may be used alone or in combination of two or more. Examples of trigger spray containers include those described in JP-A Nos. 9-268473 and 10-76196. Examples of dispenser spray containers include those described in JP-A-9-256272. An example of a pressure-accumulating trigger spray container is that described in JP-A-2013-154276.

[0045] <Manufacturing method> The liquid detergent composition for hard surfaces is produced by a conventionally known production method, such as a method of adding components (A), (B), and (C), as well as optional components, to water as a solvent and mixing the mixture. The detergent product is produced by producing a liquid detergent by the above-mentioned method and storing it in a dispensing container.

[0046] <How to use> One way to use liquid detergent is to store it in a dispenser container, apply an appropriate amount of the liquid detergent from the dispenser to the object to be washed (such as a bathtub or toilet bowl), and then rinse with running water after a certain period of time, thereby performing a "rinsing" process. Another method of use is to apply an appropriate amount of liquid detergent to the object to be washed (such as a bathtub or toilet bowl) and then scrub it with a cleaning brush, known as "scrubbing." Alternatively, a liquid detergent can be applied to the object to be washed (for example, a toilet seat, floor, or wall) and then wiped off with a cloth or paper, known as "wipe-off washing."

[0047] The object to be washed may be any hard surface such as an article, for example, a hard surface in a bathroom, bathroom supplies, a hard surface in a toilet, toilet supplies, a hard surface in a kitchen, or kitchen supplies (dishes, cooking utensils, etc.). The hard surface means a surface made of a hard material such as plastic, ceramic, glass, or stainless steel. The liquid detergent of this embodiment has good high-temperature stability and is therefore particularly suitable as a liquid bathroom detergent used to clean bathrooms.

[0048] <Mechanism of action> Although it is known that components (A) to (C) all have antibacterial activity, it is unknown in the prior art that mixing these components can achieve both antibacterial activity and high-temperature stability. While the detailed mechanism is unclear, it is speculated as follows. Component (A) is generally unstable in aqueous solution and is prone to discoloration and precipitation, especially at high temperatures. However, it has been found that when a certain amount of component (B) is added in the presence of component (A), the discoloration of the solution caused by component (A) is suppressed compared to when the amount of component (B) is less than the certain amount. On the other hand, it has also been found that adding too much of component (A) or (B) to enhance antibacterial activity increases the amount of precipitates caused by component (A). Therefore, it has been found that combining components (B) and (C) in a specific ratio can achieve both antibacterial activity and high-temperature stability. Component (B) is a low-molecular-weight organic acid and therefore easily soluble in water, while component (C) contains both a phenolic hydroxyl group and an aromatic ring, making it less soluble in water than component (B). Therefore, if too much component (C) is added, high-temperature stability will actually decrease. Therefore, in the present invention, the contents of the essential components (A) to (D) are set to specific ranges. Component (D) contributes to improving the solubility and dispersibility of component (C), making component (C) more soluble in water, thereby improving the reduced high-temperature stability caused by the poor solubility of component (C). Component (B) facilitates the disinfecting effect of component (A) while also providing the disinfecting effect of component (B), and component (C) provides a high disinfecting effect even at a relatively low concentration, so the disinfecting effect can be maintained even when the liquid detergent is diluted. By using components (B) and (C) together, the liquid detergent can exhibit excellent disinfecting activity even when diluted. [Example]

[0049] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following description.

[0050] (Raw materials used) <Component (A)> Silver amino acid complex: Silver complexed with carboxylic acid and creatinine (manufactured by J Chemical Co., Ltd., product name "CF-01") (elemental silver concentration 2.5% by mass). Silver polymer complex: Silver complexed with a polymer (manufactured by Dow Chemical Japan, product name "SILVADUR 930 Antimicrobial") (elemental silver concentration: 0.1% by mass). Silver carrier: nanocolloid in which silver oxide is supported on colloidal alumina silica (JGC Catalysts and Chemicals Co., Ltd., product name "Atomy Ball UA") (silver element concentration 0.0686% by mass).

[0051] <(B) component> Citric acid (manufactured by Fuso Chemical Co., Ltd., product name "Liquid Citric Acid"). Propionic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product name "Propionic acid"). Lactic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product name "Lactic Acid").

[0052] <(C) component> Dichlosan (4,4'-dichloro-2-hydroxydiphenyl ether) (BASF Japan Ltd., trade name "Tinosan HP200"). Triclosan (5-chloro-2-(2,4-dichlorophenoxy)phenol) (Tokyo Chemical Industry Co., Ltd., trade name "Triclosan"). IPMP (isopropylmethylphenol) (Fujifilm Wako Pure Chemical Industries, trade name "4-isopropyl-3-methylphenol").

[0053] <Optional ingredients> Water: Ion-exchanged water. Surfactant: Sodium C14-alpha olefin sulfonate (AOS) (Lion Specialty Chemicals Co., Ltd., product name "Lipolan LJ441"). Water-soluble solvent: Diethylene glycol monobutyl ether (manufactured by Nippon Nyukazai Co., Ltd., trade name "Butyl Diglycol"). pH adjuster: 1N sodium hydroxide (Kanto Chemical Industry Co., Ltd.).

[0054] (Evaluation method) <sterilization performance> (1) Preparation of control samples: A control sample was prepared by autoclaving a 0.05% aqueous solution of polyoxyethylene sorbitan monooleate (Tween 80, manufactured by Tokyo Chemical Industry Co., Ltd.). (2) Preparation of test bacterial solution: Staphylococcus aureus was inoculated into NA (Nutrient Agar) medium (Difco) and pre-cultured at 37±1°C for 18 to 24 hours. Next, this bacterium was inoculated into NA medium and pre-cultured at 37±1°C for 18 to 24 hours. After that, sterilized 1 / 2NB (Nutrient Broth) medium (Difco) was used to inoculate the bacterium. 8 The concentration was adjusted to CFU / mL and mixed with an equal amount of 30 g / L bovine serum albumin (Sigma-Aldrich). (3) Preparation of deactivator: 38 g of SCDLP medium "Daigo" (Shioya MS) was dissolved in 1 L of purified water by heating, and the solution was sterilized by high-pressure steam to prepare an inactivator. (4) Antibacterial power measurement: Ten microliters of the test bacterial solution was applied to a sterilized stainless steel disk (20 mm in diameter) and allowed to stand until the test bacterial solution appeared dry. Subsequently, 0.1 mL of the evaluation sample, a 3-fold diluted evaluation sample, and the control sample were applied and allowed to stand. After 5 minutes of standing, the stainless steel disk was placed in a vial containing 10 mL of inactivator, and an appropriate amount of glass beads was added and stirred to create test solution-1. Ten-fold serial dilutions of test solution-1 were prepared with physiological saline, and the bacteria count was determined after culturing at 37±1°C for 40 to 48 hours using the pour plate culture method in NA medium. The log number of bacteria, calculated by subtracting the log number of bacteria of the evaluation sample from the log number of bacteria of the control sample, was used as the disinfection activity value, and was evaluated according to the following criteria.

[0055] [Evaluation criteria for sterilization performance] ◎: In a test using the undiluted sample for evaluation, the disinfecting activity value was 2.5 or higher. ○: In a test using the undiluted solution of the evaluation sample, the disinfecting activity value was 2.0 or more and less than 2.5. ×: In a test using the undiluted solution of the evaluation sample, the disinfecting activity value was less than 2.0.

[0056] [Sterilization performance when diluted 3 times] ◎: In a test using an evaluation sample diluted 3 times, the disinfection activity value was 2.5 or higher. ○: In a test using an evaluation sample diluted 3 times, the disinfecting activity value was 2.0 or more and less than 2.5. △: In a test using an evaluation sample diluted 3 times, the disinfecting activity value was 1.5 or more and less than 2.0. ×: In a test using an evaluation sample diluted 3 times, the disinfecting activity value was less than 1.5.

[0057] <High temperature stability (precipitation, discoloration)> 50 g of each evaluation sample was filled into a 50 mL glass bottle (Nichiden Rika Glass Co., Ltd. "SV-50A"), and after the lid was placed, the bottle was stored in a constant temperature room at 50°C for one month. One week and one month after the start of storage, the condition of the evaluation sample was visually evaluated. Evaluation was made according to the following evaluation criteria.

[0058] [Evaluation criteria for precipitation] ⊚: Almost no precipitates were observed after one week or one month. ○: Almost no precipitate was observed after one week, and slight precipitate was observed after one month. △: A slight amount of precipitate was observed after one week. ×: Clear precipitates were observed after one week.

[0059] [Evaluation criteria for discoloration] ◎: Almost no discoloration is observed after one week or one month. ○: Almost no discoloration was observed after one week, and slight discoloration was observed after one month. △: Slight discoloration observed after 1 week. ×: Obvious discoloration observed after 1 week.

[0060] <Overall rating> ◎: All sterilization performance and high temperature stability items are ○ or above. ○: One of the sterilization performance and high temperature stability items is △, and the other items are ○ or above. ×: Contains one or more × in the sterilization performance and high temperature stability items.

[0061] <Examples 1 to 25 and Comparative Examples 1 to 8> Liquid detergents were produced according to the formulations (units: mass %) shown in the table. Component (E) was added to 150 g of ion-exchanged water in a 300 ml beaker, and the mixture was stirred with a stirrer to obtain a 200 g scale composition. Next, components (A) and (B) were added and stirred with a stirrer. Next, components (C) and (D) were added and stirred, and then sodium hydroxide, a pH adjuster, was added to adjust the pH to the value shown in the table. The remaining water was added and stirred to obtain a liquid detergent. The amounts in the table are calculated as pure components. Components without a listed amount in the table were not included. The "appropriate amount" of pH adjuster is the amount required to adjust the pH of each liquid composition to a predetermined value. The "balance" water content refers to the remainder added so that the total amount (mass %) of all ingredients contained in the liquid composition becomes 100 mass %.

[0062] [Table 1]

[0063] [Table 2]

[0064] [Table 3]

[0065] [Table 4]

[0066] [Table 5]

[0067] [Table 6]

[0068] [Table 7]

[0069] As shown in Tables 1 to 7, Examples 1 to 25 were all good in disinfecting activity, disinfecting activity when diluted, and high-temperature stability. Comparative Example 1, which did not contain component (B), was found to be inferior in disinfecting activity when diluted and in high-temperature stability. Comparative Example 2, in which the content of component (B) exceeded 2 mass %, was found to be inferior in high-temperature stability. Comparative Example 3, which did not contain component (C), was found to be inferior in disinfecting activity and disinfecting activity when diluted. Comparative Example 4, in which the content of component (C) exceeded 0.5% by mass, was found to be inferior in high-temperature stability. Comparative Example 5, which did not contain component (A), was found to be inferior in disinfecting activity and disinfecting activity when diluted. Comparative Example 6, in which the content of component (A) was less than 5 ppm by mass, was found to be inferior in disinfecting activity and disinfecting activity when diluted. In Comparative Example 7, in which the content of component (A) was more than 15 ppm by mass, discoloration was observed, and it was found that the high-temperature stability was poor. Comparative Example 8, which had a pH greater than 12, was found to be inferior in high-temperature stability.

[0070] Although not described in the above examples, the following liquid detergents that have already been manufactured or will be manufactured in the future can also achieve similar effects by manufacturing them based on common technical knowledge, as in the above examples.

[0071] [Table 8]

[0072] Table 9

[0073] Table 10

[0074] Table 11

[0075] Table 12

[0076] Table 13

[0077] Table 14

[0078] Table 15

[0079] Table 16

[0080] Table 17

[0081] Table 18

[0082] Table 19

[0083] Table 20

[0084] Table 21

[0085] Table 22

[0086] Table 23

[0087] Table 24

[0088] Table 25

[0089] Table 26

[0090] Table 27

Claims

1. (A) Component: a source of elemental silver or silver ions; (B) Component: a disinfectant containing an organic acid having 1 to 9 carbon atoms or a salt thereof, and (C) Component: a disinfectant containing a phenolic compound having a phenolic hydroxyl group or a salt thereof, and Component (D): A liquid cleaning composition for hard surfaces containing a surfactant, Relative to the total mass of the liquid cleaning composition for hard surfaces, The content of the component (A) is 4 to 19 ppm by mass, The content of the component (B) is 0.005 to 2.2 mass %, The content of the component (C) is 0.03 to 0.7% by mass, A liquid cleaning composition for hard surfaces having a pH of 8 to 11.5 at 25°C.

2. 2. The liquid cleaning composition for hard surfaces according to claim 1, wherein the mass ratio of component (B) to component (C) is 0.03 to 60.

3. A method for cleaning a hard surface, comprising contacting an aqueous solution obtained by diluting the liquid detergent composition for hard surfaces according to claim 1 or 2 with water by a ratio of 1 to 3 with an object to be cleaned.

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