Cleaning composition for hard surfaces, antibacterial / antiviral treatment method

Abstract

To provide a detergent composition for hard surfaces that can readily give an antibacterial / antiviral function to the whole of a target surface and enables its function to last after water washing, and an antibacterial / antiviral treatment method using the detergent composition for hard surfaces.SOLUTION: A detergent composition for hard surfaces comprises component (A): a cationic surfactant comprising a quaternary ammonium salt with one or two C10-18 alkyl groups, component (B): a nonionic surfactant, and component (C): a water-soluble copolymer, wherein the component (C) is at least one kind selected from (C-1) a copolymer comprising a vinyl monomer having a tertiary amine structure and an anionic vinyl monomer, (C-2) a copolymer comprising a vinyl monomer having a quaternary ammonium structure and a vinyl monomer having a sulfonic acid structure, and (C-3) a betaine copolymer having a trisilanol group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a cleaning composition for hard surfaces and an antibacterial / antiviral treatment method. [Background technology]

[0002] In recent years, social awareness of toilet hygiene has increased, and there is a demand for simple cleaning that can free people from worries about invisible dirt such as bacteria and viruses. To achieve this, it is important that areas in the toilet that are difficult to reach with hands or brushes can be cleaned with daily cleaning. However, conventional detergents have not been able to provide sustained antibacterial or antiviral effects through simple treatment, including in areas of the toilet that are difficult to reach with hands or brushes.

[0003] For example, known hard surface cleaner compositions used to remove dirt adhering to hard surfaces such as toilets contain (a) a copolymer containing a specific structural unit (a1) having a betaine group and a specific structural unit (a2) having a cationic group, in which the molar ratio of structural unit (a1) to structural unit (a2), structural unit (a1) / structural unit (a2), is 30 / 70 or more and 99.9 / 0.1 or less, (b) a cationic surfactant, and (c) a chelating agent (see, for example, Patent Document 1). Furthermore, as a cleaning composition for hard surfaces, for example, one containing a cationic surfactant as component (A) and a polyoxyethylene alkyl ether-type nonionic surfactant having an HLB of 12 to 14 as component (B) is known (see, for example, Patent Document 2). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2018-199769 [Patent Document 2] Japanese Patent Application Publication No. 2018-95718 Summary of the Invention [Problem to be solved by the invention]

[0005] The hard surface cleaner composition of Patent Document 1 is capable of sustaining disinfecting performance, but has the problem of not being able to provide foaming properties or foam retention, and not being able to provide sufficient antibacterial / antiviral functions in areas that are hard to reach with hands or brushes.Furthermore, the hard surface cleaner composition of Patent Document 2 does not take into account the flushing action that occurs when cleaning hard-to-reach areas such as the underside of a toilet rim, and therefore has the problem of not being able to maintain function after flushing, and not being able to provide sufficient antibacterial / antiviral functions.

[0006] The present invention has been made in view of the above circumstances, and aims to provide a hard surface cleaner composition that can easily impart antibacterial / antiviral functions to the entire surface to be treated and that can maintain these functions even after rinsing with water, and an antibacterial / antiviral treatment method using the hard surface cleaner composition. [Means for solving the problem]

[0007] The present invention has the following aspects. [1] Component (A): a cationic surfactant containing a quaternary ammonium salt having one or two alkyl groups having 10 to 18 carbon atoms; (B) component: a nonionic surfactant; (C) component: a water-soluble copolymer; Contains A hard surface cleaner composition, wherein the component (C) is at least one selected from (C-1) a copolymer consisting of a vinyl monomer having a tertiary amine structure and an anionic vinyl monomer, (C-2) a copolymer containing a vinyl monomer having a quaternary ammonium structure and a vinyl monomer having a sulfonic acid structure, and (C-3) a betaine copolymer containing a trisilanol group. [2] The content of the component (A) is 0.05 to 2.0% by mass of the total composition, The (A) / (B) ratio is 0.5 to 50 by mass; The cleaning composition for hard surfaces according to [1], wherein the (A) / (C) ratio is 2.0 to 100 by mass. [3] An antibacterial / antiviral treatment method using the hard surface cleaner composition according to [1] or [2], by allowing foam of the hard surface cleaner composition to remain on a target surface, thereby carrying out antibacterial / antiviral treatment. [Effects of the Invention]

[0008] The present invention can provide a hard surface cleaner composition that can easily impart antibacterial / antiviral functions to the entire surface to be treated and that can maintain the functions even after rinsing with water, and an antibacterial / antiviral treatment method using the hard surface cleaner composition. DETAILED DESCRIPTION OF THE INVENTION

[0009] The present invention will be described in detail below.

[0010] The hard surface cleaner composition of the present invention is a composition containing the following components (A), (B), and (C).

[0011] <Component (A)> The component (A) is a cationic surfactant containing a quaternary ammonium salt having one or two alkyl groups having 10 to 18 carbon atoms. The quaternary ammonium salt is an alkyl ammonium salt such as a monoalkyltrimethyl type ammonium salt or a dialkyldimethyl type ammonium salt, and preferably has 12 to 18 carbon atoms. Examples of the quaternary ammonium salt include halogen ions such as chloride ions and bromide ions, sulfate ions, etc., with chloride ions and sulfate ions being preferred. Specific examples of the quaternary ammonium salt include dodecyltrimethylammonium chloride, decyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, didecyldimethylammonium chloride, stearyltrimethylammonium chloride, cetyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, benzalkonium chloride, didecyldimethylammonium chloride, trimethylstearylammonium sulfate, and dodecyltrimethylammonium sulfate, with stearyltrimethylammonium chloride, dodecyltrimethylammonium chloride, trimethylstearylammonium sulfate, and dodecyltrimethylammonium sulfate being preferred, and stearyltrimethylammonium chloride and dodecyltrimethylammonium chloride being particularly preferred.

[0012] The content of component (A) is preferably from 0.05 to 2.0 mass %, more preferably from 0.08 to 1.0 mass %, and even more preferably from 0.1 to 0.5 mass %, relative to the total mass of the hard surface cleaner composition. When the content of component (A) is equal to or greater than the above lower limit, antibacterial / antiviral properties and foaming properties are likely to be improved. When the content of component (A) is equal to or less than the above upper limit, retention is likely to be improved.

[0013] <(B) component> Component (B) is a nonionic surfactant. Examples of component (B) include polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl (or alkenyl) phenyl ethers, fatty acid alkyl ester alkoxylates in which alkylene oxide is added between the ester bonds of long-chain fatty acid alkyl esters, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene fatty acid esters, polyoxyalkylene hydrogenated castor oil, and glycerin fatty acid esters. Examples of polyoxyalkylene alkyl ethers include those in which an average of 3 to 30 moles of alkylene oxide having 2 to 4 carbon atoms are added to an aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms. Examples of aliphatic alcohols used in the synthesis include primary alcohols and secondary alcohols. The alkyl group may have a branched chain. The component (B) may be used singly or in appropriate combination of two or more. From the viewpoint of improving retention, polyoxyalkylene alkyl ethers having 12 to 18 carbon atoms in the branch and an average addition mole number of 5 to 9 of ethylene oxide carbon atoms of 2 are preferred, such as polyoxyethylene isostearyl ether (HLB=8) having an average addition mole number of 5.

[0014] The HLB of the component (B) is preferably 6 to 14. When the HLB of component (B) is within the above range, retention is likely to be improved. HLB (Hydrophilic-Lipophilic Balance) is a value that indicates the degree of affinity of a surfactant for water and oil (organic compounds insoluble in water).

[0015] The content of component (B) is preferably 0.01 to 1.0 mass %, more preferably 0.03 to 0.5 mass %, and even more preferably 0.03 to 0.2 mass %, relative to the total mass of the hard surface cleaner composition. When the content of component (B) is equal to or greater than the above lower limit, retention is likely to be improved.When the content of component (B) is equal to or less than the above upper limit, antibacterial / antiviral properties are likely to be improved.

[0016] <(C) component> Component (C) is a water-soluble copolymer, which is a polymer that dissolves transparently in 1 L of water at 25°C in an amount of 0.1 g or more. Component (C) is at least one selected from (C-1) a copolymer consisting of a vinyl monomer having a tertiary amine structure and an anionic vinyl monomer, (C-2) a copolymer containing a vinyl monomer having a quaternary ammonium structure and a vinyl monomer having a sulfonic acid structure, and (C-3) a betaine copolymer containing a trisilanol group.

[0017] Examples of vinyl monomers having a tertiary amine structure include dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate (DMAEMA), dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, dimethylaminobutyl acrylate, dimethylaminobutyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, 2-(dimethylamino)ethyl methacrylate, dimethylaminoethyl acrylamide, dimethylaminoethyl methacrylamide, dimethylaminopropyl acrylamide, dimethylaminopropyl methacrylamide, dimethylaminobutyl acrylamide, dimethylaminobutyl methacrylamide, diethylaminoethyl acrylamide, and diethylaminoethyl methacrylamide.

[0018] The anionic vinyl monomer is, for example, a vinyl monomer having an anionic functional group exhibiting acidity or a salt thereof, and examples thereof include a vinyl monomer having a sulfonic acid group or a salt thereof. Examples of vinyl monomers having a sulfonic acid group include acrylic acid, methacrylic acid (MAA), acrylamidomethanesulfonic acid, methacrylamidomethanesulfonic acid, acrylamidoethanesulfonic acid, methacrylamidoethanesulfonic acid, acrylamidopropanesulfonic acid, methacrylamidopropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, methanesulfonic acid acrylate, methanesulfonic acid methacrylate, ethanesulfonic acid acrylate, ethanesulfonic acid methacrylate, propanesulfonic acid acrylate, propanesulfonic acid methacrylate, and salts thereof. Among these, from the viewpoint of durability of antibacterial / antiviral function, acrylic acid, acrylic acid salts, methacrylic acid (MAA), methacrylic acid salts, acrylamidomethanesulfonic acid, acrylamidomethanesulfonate, methacrylamidomethanesulfonate, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonate, 2-methacrylamido-2-methylpropanesulfonate, methanesulfonic acid acrylate, and methanesulfonic acid methacrylate are preferred, and acrylic acid, acrylic acid salts, methacrylic acid (MAA), methacrylic acid salts, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonate, 2-methacrylamido-2-methylpropanesulfonate, and 2-methacrylamido-2-methylpropanesulfonate are more preferred. These compounds may be used singly or in appropriate combination of two or more.

[0019] Examples of vinyl monomers having a quaternary ammonium structure include quaternary ammonium salts. Specific examples of quaternary ammonium salts include trimethylaminoethyl acrylate chloride, trimethylaminoethyl methacrylate chloride, trimethylaminopropyl acrylate chloride, trimethylaminopropyl methacrylate chloride, trimethylaminobutyl acrylate chloride, trimethylaminobutyl methacrylate chloride, triethylaminoethyl acrylate chloride, triethylaminoethyl methacrylate chloride, trimethylaminoethyl acrylamide chloride, trimethylaminoethyl methacrylamide chloride, trimethylaminopropyl acrylamide chloride (AAPTAC), trimethylaminopropyl methacrylamide chloride (MAPTAC), trimethylaminobutyl acrylamide chloride, trimethylaminobutyl methacrylamide chloride, triethylaminoethyl acrylamide chloride, and triethylaminoethyl methacrylamide chloride. Among these, trimethylaminoethyl methacrylate chloride, trimethylaminopropyl methacrylamide chloride (MAPTAC), and trimethylaminopropyl acrylamide chloride (AAPTAC) are preferred from the viewpoint of durability of antibacterial / antiviral functions. These compounds may be used singly or in appropriate combination of two or more.

[0020] Examples of the vinyl monomer having a sulfonic acid structure include the above-mentioned vinyl monomers having a sulfonic acid group.

[0021] Trisilanol-containing betaine copolymers are hydrophilic polymers containing trisilanol groups, with a main chain consisting of a betaine-containing monomer and a hydrocarbon-chain monomer, and with a terminal trisilanol group. Examples include trisilanol-containing alkyl / N,N-dimethylammonium alkyl-α-sulfobetaine copolymers and trisilanol-containing alkyl / N,N-dimethylammonium alkyl-α-carbobetaine copolymers, and commercially available products such as "LAMBIC-771W" and "LAMBIC-1000W" (Osaka Organic Chemical Industry Ltd.). These compounds may be used singly or in appropriate combination of two or more.

[0022] From the viewpoint of durability of the antibacterial / antiviral function, the molar ratio of the anionic vinyl monomer to the tertiary amine, or the vinyl monomer having a sulfonic acid structure to the vinyl monomer having a quaternary ammonium structure, is preferably in the range of 70 / 30 to 30 / 70, more preferably 60 / 40 to 40 / 60, and particularly preferably 60 / 40 to 55 / 45.

[0023] The water-soluble copolymer may contain a hydrophobic vinyl monomer. Examples of hydrophobic vinyl monomers include propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, hexyl acrylate, hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl acrylate, octyl methacrylate, lauryl acrylate, lauryl methacrylate, propyl acrylamide, propyl methacrylamide, butyl acrylamide, butyl methacrylamide, t-butyl acrylamide, t-butyl methacrylamide, hexyl acrylamide, hexyl methacrylamide, octylacrylamide, octyl methacrylamide, lauryl acrylamide, and lauryl methacrylamide. Among these, from the viewpoint of durability of antibacterial / antiviral function, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, hexyl acrylate, hexyl methacrylate, 2-ethylhexyl acrylate, and 2-ethylhexyl methacrylate are preferred, and butyl acrylate, butyl methacrylate, t-butyl acrylate, and t-butyl methacrylate are more preferred.

[0024] Specific examples of component (C) include a copolymer of methacrylic acid (MAA) / dimethylaminoethyl methacrylate (DMAEMA) (60 / 40 (molar ratio)), a copolymer of trimethylaminopropylacrylamide chloride (AAPTAC) / acrylamidomethylpropanesulfonic acid (AMPS) / methacrylic acid (MAA) / t-butyl methacrylate (t-BMA) (48 / 43 / 6 / 3 (molar ratio)), a copolymer of trisilanol group-containing alkyl / N,N-dimethylammonium alkyl-α-sulfobetaine, and a copolymer of trisilanol group-containing alkyl / N,N-dimethylammonium alkyl-α-carbobetaine. From the viewpoint of durability of antibacterial / antiviral functions, (trimethylaminopropylacrylamide chloride / acrylamidomethylpropanesulfonic acid / methacrylic acid / t-butyl methacrylate) and methacrylic acid / dimethylaminoethyl methacrylate are preferred, and methacrylic acid / dimethylaminoethyl methacrylate is more preferred. Furthermore, specific examples of component (C) include water-soluble polymers containing and consisting of DMAEMA, MAPTAC, and methacrylic acid, specifically, commercially available products such as MIRAPOL SURF S-110 and MIRAPOL SURF S-210 (manufactured by Solvay Nicca Co., Ltd.).

[0025] The content of component (C) is preferably from 0.01 to 0.1 mass %, more preferably from 0.025 to 0.05 mass %, relative to the total mass of the hard surface cleaner composition. When the content of component (C) is at least the above lower limit, antibacterial / antiviral properties are likely to be improved, and when the content of component (C) is at most the above upper limit, foaming properties are likely to be improved.

[0026] The mass ratio of component (A) / component (B) (hereinafter also referred to as the (A) / (B) ratio) is 0.5-50, preferably 1-30, and more preferably 2-10. When the (A) / (B) ratio is equal to or greater than the lower limit, the antibacterial / antiviral properties are easily improved, and when the (A) / (B) ratio is equal to or less than the upper limit, the retention is easily improved.

[0027] The mass ratio of component (A) / component (C) (hereinafter also referred to as the (A) / (C) ratio) is 2.0-100, preferably 2.2-50, and more preferably 2.5-20. When the (A) / (C) ratio is equal to or greater than the above lower limit, the foaming property is likely to be improved. When the (A) / (C) ratio is equal to or less than the above upper limit, the durability of the antibacterial / antiviral function is likely to be improved.

[0028] <Optional ingredients> Optional components include pH adjusters and viscosity adjusters other than the components (A), (B), and (C).

[0029] As the pH adjuster, at least one of citric acid and sodium hydroxide is preferably used. By including a pH adjuster, even if the hard surface cleaning composition of the present invention comes into contact with hands, it can prevent skin damage and improve safety.

[0030] The pH of the hard surface cleaner composition of the present invention is preferably 5.0 to 9.0, more preferably 6.0 to 8.0, and even more preferably 6.5 to 7.5.

[0031] In the present invention, the pH (25° C.) of the hard surface cleaner composition refers to a value measured by a method in accordance with JIS Z 8802:1984 "pH measurement method."

[0032] Examples of viscosity modifiers include xanthan gum and guar gum.

[0033] <Method of manufacturing a hard surface cleaning composition> The hard surface cleaner composition can be obtained by mixing the components (A), (B), and (C), and, if necessary, any optional components.

[0034] <Method of using the hard surface cleaning composition> The hard surface cleaner composition of the present invention is used in a container. Examples of containers that can accommodate the hard surface cleaner composition of the present invention include containers that dispense the composition onto a target surface using a trigger-type sprayer, containers that spray a foam or mist aerosol, and containers that dispense the cleaner composition from a bottle opening. Of these, trigger-type sprayers are particularly preferred from the viewpoints of foaming ability, retention, and durability of antibacterial / antiviral functions. Examples of trigger-type sprayers include pressure-accumulation trigger sprayers and direct-pressure trigger sprayers. Of these, pressure-accumulation trigger sprayers are particularly preferred from the viewpoints of foaming ability, retention, and durability of antibacterial / antiviral functions. Examples of pressure-accumulation trigger sprayers include the trigger-type spray container described in JP 2017-214464 A, the trigger-spray foamer container described in JP 2012-131951 A, and the trigger-type spray container described in JP 2018-199771 A.

[0035] <Action and effect> The hard surface cleaner composition of the present invention described above contains the components (A), (B), and (C), and therefore can easily impart antibacterial / antiviral functions to the entire surface to be treated (target surface), and can maintain these functions even after rinsing with water.

[0036] [Antibacterial / antiviral treatment method] The antibacterial / antiviral treatment method of the present invention is a method for treating a hard surface using the hard surface cleaner composition of the present invention, in which antibacterial / antiviral treatment is performed by allowing foam composed of the hard surface cleaner composition to remain on a target surface.

[0037] The hard surface is not particularly limited, and examples thereof include solid hard surfaces such as glass, pottery, porcelain, enamel, tile, ceramics; metals such as aluminum, stainless steel, brass, etc.; synthetic resins such as polyethylene, polypropylene, melamine resin, polyamide resin, ABS resin, FRP, etc.; natural fibers such as cotton, silk, wool, etc.; and synthetic fibers such as polyester, nylon, rayon, etc. The fibers are preferably textile products having a shape and strength suitable for treatment with the hard surface cleaner composition of the present invention. The hard surface to which the hard surface cleaning composition and antibacterial / antiviral treatment method of the present invention can be applied is preferably a hydrophilic hard surface. Here, the term "hydrophilic" as used herein refers to a hard surface having a static contact angle with water of less than 70°. This static contact angle can be measured by the method described in the Examples. Suitable hard surfaces in the present invention include one or more hard surfaces selected from glass, ceramic, porcelain, plastic, stainless steel, and silicon wafers. The subject of the present invention is hard surfaces, specifically articles having hard surfaces, such as toilets, bathtubs, kitchen sinks, window panes, mirrors, faucets, etc.

[0038] Treatment of a hard surface with the hard surface cleaner composition of the present invention can be carried out by bringing foam comprising the hard surface cleaner composition into contact with the hard surface. In the present invention, from the viewpoints of antibacterial / antiviral activity and persistence, the specific foam volume of the foam produced 1 minute after spraying at a trigger pull rate of 6 g / s to 18 g / s is 15 mL / g or more, preferably 25 mL / g or more, and from the viewpoints of economy and usability (ease of defoaming), it is preferable that the foam be brought into contact with a hard surface at a volume of preferably 60 mL / g or less, more preferably 55 mL / g or less, even more preferably 50 mL / g or less, and even more preferably 45 mL / g or less. Note that the specific foam volume refers to the foam volume per unit amount calculated from the foam volume immediately after being dispensed from the container and the mass of the dispensed composition. A preferred method is to spray the foam onto a hard surface using a spray or the like and then dry it. If necessary, the foam may be rinsed with water after being sprayed. Alternatively, the foam may be thinly spread using a sponge or the like after being sprayed. The amount of foam that is brought into contact with the hard surface is, for example, 10 cm 2 The volume is preferably 10 mL or more and 160 mL or less, more preferably 20 mL or more and 120 mL or less.

[0039] The temperature when treating a hard surface is preferably 0°C or higher, more preferably 10°C or higher, even more preferably 15°C or higher, from the viewpoint of enhancing antibacterial / antiviral properties and facilitating the treatment method, and is preferably 45°C or lower, more preferably 40°C or lower, even more preferably 35°C or lower. Furthermore, it is preferable that the hard surface treated with the hard surface cleaner composition of the present invention is treated uniformly from the viewpoint of enhancing antibacterial / antiviral properties, etc. The uniformity of the surface treatment can be determined by visually observing the hard surface after treatment. [Example]

[0040] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following description. The raw materials used in this example are as follows:

[0041] "Raw materials used" The compound shown below was used as component (A) (cationic surfactant). A1-1: Dodecyltrimethylammonium chloride (trade name: Lipocard 12-37w, Lion Specialty Chemicals Co., Ltd.) A1-2: Stearyltrimethylammonium chloride (trade name: Lipocard T-800, Lion Specialty Chemicals Co., Ltd.) A2-1: Benzalkonium chloride (product name: Cation G-50, Sanyo Chemical Industries, Ltd.) A2-2: Didecyldimethylammonium chloride (trade name: Lipocard 210-80E, Lion Specialty Chemicals Co., Ltd.)

[0042] (B) component (nonionic surfactant): The following compounds were used. · B1-1: Polyoxyethylene isostearyl ether (average number of moles of ethylene oxide added: 5, trade name: Emalex 1805, manufactured by Nippon Emulsion Co., Ltd.)

[0043] (C) component (water-soluble polymer containing anionic and cationic groups): The following compounds were used. · C1-1: Methacrylic acid (MAA) / dimethylaminoethyl methacrylate (DMAEMA) = 60 / 40 (molar ratio) · C1-2: Trimethylaminopropylacrylamide chloride (AAPTAC) / acrylamidomethylpropanesulfonic acid (AMPS) / methacrylic acid (MAA) / t-butyl methacrylate (t-BMA) = 48 / 43 / 6 / 3 (molar ratio) · C1-3: Trisilanol group-containing alkyl / N,N-dimethylammonium alkyl-α-sulfobetaine copolymer (trade name: LAMBIC-771W, manufactured by Osaka Organic Chemical Industry Co., Ltd.) · C1-4: Trisilanol group-containing alkyl / N,N-dimethylammonium alkyl-α-carboxybetaine copolymer (trade name: LAMBIC-1000W, manufactured by Osaka Organic Chemical Industry Co., Ltd.) · C2-1: Dimethylammonium acrylate taurine / vinylpyrrolidone copolymer (trade name: ARISTFLEX AVC, Matsumoto Kogyo) · C2-2: Polyethyleneimine (trade name: SP-200, manufactured by Nippon Shokubai Co., Ltd.) · C2-3: Polyvinyl alcohol (trade name: PVA-117, manufactured by Kuraray Co., Ltd.)

[0044] <Synthesis of C1-1> Into a 1 L flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet tube, a dropping port for monomer, and a dropping port for initiator, 280 parts by mass of ion-exchanged water was added and stirred, and heated to 90 °C under a nitrogen stream to prepare a polymerization solvent. Next, into a 500 mL beaker, each monomer and ion-exchanged water were added so that the molar ratio of MAA / DMAEMA was 60 / 40, the pH was adjusted to 5.0 using sulfuric acid, and stirring was continued to prepare a monomer mixed solution. Also, into a 200 mL beaker, sodium persulfate as an initiator was added at 1.5 mol% by mass based on the monomer and 100 parts by mass of ion-exchanged water to make a uniform solution, and an initiator solution was prepared. While maintaining the temperature of the polymerization solvent at 90 °C, all of the initiator solution and all of the monomer mixed solution were continuously dropped over 3 hours, and further heating and stirring were continued for 5 hours to obtain a polymer copolymer (C1-1). As a result of analyzing the residual monomers in the obtained polymer aqueous solution by the second method of the acrylic residual monomer test method, a general test method for formulation components by cosmetic type, the conversion rate of the monomer was 99% or more in all cases. Also, the average molecular weight of the polymer copolymer (C1-1) was 23,600 when measured using size exclusion chromatography (SEC).

[0045] <Synthesis of C1-2> Into a separable flask equipped with a cooling reflux tube, a thermometer, a nitrogen inlet tube, and a stirring device, 25.0 g of AAPTAC, 22.5 g of AMPS, 1.25 g of MAA, 1.25 g of t-BMA, 0.69 g of sodium persulfate, and 200 g of ion-exchanged water were charged, and stirred at room temperature (about 20 °C) for 30 minutes while blowing nitrogen. Next, the reaction system was heated to 85 °C and reacted for 6 hours. Then, the product was taken out from the separable flask and reprecipitated with hexane to obtain 39 g of a solid of the polymer copolymer (C1-2). The mass average molecular weight of the obtained polymer copolymer (C1-2) was 60,000 when measured using SEC.

[0046] <Optional components> ·pH adjuster: Citric acid (Kanto Chemical Co., Inc.), Sodium hydroxide: Caustic soda (Fuso Chemical Industry Co., Ltd.) Ethanol (Japan Alcohol Sales), aminocarboxylic acid chelating agent: EDTA (Akzo Nobel Co., Ltd.), water: ion-exchanged water

[0047] <Manufacturing method> According to the formulations shown in Tables 2 to 7, 500 g of each liquid detergent composition was prepared by the following procedure. Components (A), (B), and (C) and the common components were added to water and mixed, and if necessary, a pH adjuster (citric acid or sodium hydroxide) was added to adjust the pH to 7.0 to obtain the liquid detergent composition of each example. The common compositions are as shown in Table 1. The contents are expressed as mass % in the liquid detergent composition.

[0048] [Table 1]

[0049] <Liquid treatment evaluation of liquid detergent composition> The liquid detergent compositions of the Examples and Comparative Examples were evaluated by the following evaluation methods, and the results are shown in the tables.

[0050] <Foaming property> The liquid detergent composition at 25°C was sprayed into a 200 mL measuring cylinder using a dispenser container with a trigger pull speed of 13 g / s for five consecutive strokes (approximately 0.9 g / stroke), and the amount of foam dispensed (g) was weighed. The foam height was evaluated by reading the scale and subtracting the amount of foam dispensed from the foam height, and was evaluated according to the following evaluation criteria. The evaluation results are shown in Tables 2 to 7. ◯, ⊚, and ⊚◎ were considered acceptable. [Foaming evaluation criteria] ◎◎: 30mL / g or more. ◎: 25 or more but less than 30 mL / g. ○: 20 or more but less than 25 mL / g. △: 15 or more and less than 20 mL / g. ×: Less than 15 mL / g.

[0051] <Bubble retention> A liquid detergent composition at 25°C was sprayed from a dispenser toward a 50 cm square tile (product name: Misty Kiramik, manufactured by LIXIL Corporation) tilted at 60° from a distance of approximately 10 cm at a trigger pull rate of 13 mL / s in one stroke (approximately 0.9 g / stroke). The drop speed (sec / cm) was calculated from the drop distance and drop time, and the composition was evaluated according to the following criteria. The evaluation results are shown in Tables 2 to 7. ◯, ⊚, and ⊚◎ were considered acceptable. [Evaluation criteria for retention] ◎◎: 2.0 seconds / cm or more. ◎: 1.8 or more and less than 2.0 seconds / cm ○: 1.5 or more and less than 1.8 seconds / cm. △: 1.2 or more and less than 1.5 seconds / cm. ×: Less than 1.2 seconds / cm.

[0052] <Antibacterial / antiviral> Antibacterial / antiviral properties were evaluated using a ceramic plate (50 mm long x 50 mm wide x 5 mm thick, manufactured by LIXIL Corporation). First, 0.25 mL of the liquid detergent composition was applied to the ceramic plate so as to cover the entire surface, and the applied liquid detergent composition was left for 1 minute. Thereafter, the substrate was rinsed with tap water at 25° C. for 20 seconds at a flow rate of 50 mL / s, and this was used as an evaluation substrate. Subsequently, antibacterial evaluations were conducted against Staphylococcus aureus and Escherichia coli in accordance with JIS Z2801, and antiviral evaluations against influenza virus in accordance with ISO21072, and were evaluated according to the following evaluation criteria. The evaluation results are shown in Tables 2 to 7. ○, ◎, and ◎◎ were considered pass, and the lower score for Staphylococcus aureus or Escherichia coli was used as the antibacterial evaluation score. [Evaluation criteria for durability of antibacterial / antiviral functions] ◎◎:ΔLog4 or higher. ◎: ΔLog3 or more but less than ΔLog4. ○: ΔLog2 or more and less than ΔLog3. △: ΔLog1 or more and less than ΔLog2. ×: Less than ΔLog1.

[0053] <Sustained antibacterial / antiviral properties even after foam washing> Using a ceramic plate (50mm long x 50mm wide x 5mm thick, manufactured by LIXIL Corporation), we evaluated the durability of antibacterial / antiviral properties after foam cleaning. The ceramic plate was tilted at 60° and the liquid detergent composition at 25°C was sprayed from a location approximately 10 cm away using a dispenser at a trigger pull rate of 13 mL / s, covering the entire surface of the ceramic plate in one stroke (approximately 0.9 g / stroke), and left for 1 minute. The ceramic plate was then rinsed with tap water at 25°C at a flow rate of 50 mL / s for 20 seconds, and this was used as an evaluation substrate for foam cleaning (1). The ceramic plate was also rinsed three times with tap water at 25°C at a flow rate of 50 mL / s for 20 seconds, and this was used as an evaluation substrate for foam cleaning (2). Subsequently, antibacterial evaluations were conducted against Staphylococcus aureus and Escherichia coli according to JIS Z2801, and antiviral evaluations against influenza viruses according to ISO 21072, and the evaluations were conducted according to the following evaluation criteria. The evaluation results are shown in Tables 2 to 7. ○, ◎, and ◎◎ were considered to be pass, and the lowest score for Staphylococcus aureus or Escherichia coli was used as the antibacterial evaluation score. [Evaluation criteria for durability of antibacterial / antiviral functions] ◎◎:ΔLog4 or higher. ◎: ΔLog3 or more but less than ΔLog4. ○: ΔLog2 or more and less than ΔLog3. △: ΔLog1 or more and less than ΔLog2. ×: Less than ΔLog1.

[0054] [Table 2]

[0055] [Table 3]

[0056] [Table 4]

[0057] [Table 5]

[0058] [Table 6]

[0059] [Table 7]

[0060] Examples 1 to 32 to which the present invention was applied were excellent in foaming properties, foam retention, antibacterial / antiviral properties, and durability of antibacterial / antiviral functions. Comparative Example 1, which contained ammonium dimethyltaurate acrylate / vinylpyrrolidone copolymer instead of component (C), was inferior in durability of the antibacterial / antiviral functions. Comparative Example 2, which contained polyethyleneimine instead of component (C), was inferior in durability of the antibacterial / antiviral functions. Comparative Example 3, which contained polyvinyl alcohol instead of component (C), was inferior in durability of the antibacterial / antiviral functions.

Claims

1. Component (A): a cationic surfactant containing a quaternary ammonium salt having one or two alkyl groups having 10 to 18 carbon atoms; (B) component: a nonionic surfactant; Component (C): a water-soluble copolymer; Contains The component (A) is a monoalkyltrimethyl ammonium salt having 12 to 18 carbon atoms, The component (C) is at least one selected from the following component (C-1) and the following component (C-2), Component (C-1): a copolymer composed of a vinyl monomer having a tertiary amine structure and an anionic vinyl monomer; Component (C-2): at least one selected from copolymers containing a vinyl monomer having a quaternary ammonium structure and a vinyl monomer having a sulfonic acid structure; the content of the component (A) is 0.1 to 0.5% by mass of the total composition, the content of the component (B) is 0.03 to 0.5% by mass of the total composition; the (A) / (B) ratio is 2 to 10 by mass; A hard surface cleaner composition having an (A) / (C) ratio of 2.0 to 50 by mass.

2. An antibacterial / antiviral treatment method using the hard surface cleaner composition according to claim 1, comprising retaining foam comprising the hard surface cleaner composition on a target surface to perform antibacterial / antiviral treatment.

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