Cleaning agent composition for hard surfaces

Abstract

The present invention provides a cleaning agent composition for hard surfaces that exhibits excellent sustained effectiveness in suppressing the occurrence of urine scale stains and yellow stains derived from urine on hard surfaces, and a method for cleaning hard surfaces using the same. [Solution] A cleaning agent composition for hard surfaces, comprising the following components (a), (b), (c), and water, wherein the mass ratio (c) / [(a)+(b)] of the content of component (c) to the total content of components (a) and (b) is 0.005 or more and 0.3 or less. (a) Ingredients: Metal chelating agent (b) Component: Foaming surfactant (c) Component: Water-soluble polymer

Description

Technical Field

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

Background Art

[0002] Generally, for cleaning the dirt inside a toilet bowl, a cleaning agent composition or a bleaching agent composition is applied to the target surface, and a cleaning brush or the like is used in combination for physical removal. Since this operation requires applying force in a forward-bent posture for a certain period of time, it places a heavy physical burden, especially on the elderly, who find it particularly strenuous work. In addition, in the peripheral back part of the bowl of a flush toilet, it is difficult for a cleaning brush to reach due to its uneven shape, so once dirt accumulates, it becomes difficult to remove even with physical force. Representative examples of such dirt that accumulates easily include urinary calculus dirt and yellowing dirt derived from urine. The durability of the effect of preventing the generation of these dirt is strongly desired by users.

[0003] Patent Document 1 discloses an antifouling cleaning agent composition containing a specific polysiloxane, a specific surfactant, a metal chelating agent, and water, which is excellent in detergency and the durability of the antifouling effect. Patent Document 2 discloses an antifouling cleaning agent for hard surfaces that can impart excellent antifouling properties using a high molecular weight polymer having a group selected from an amino group and a quaternary ammonium group, and does not cause recontamination even when repeatedly used. Patent Document 3 discloses a liquid cleaning agent composition for toilets containing a specific surfactant, a specific glycol-based compound, an aminocarboxylic acid-based chelating agent, and a polycarboxylic acid-based chelating agent, which is excellent in the detergency of urine stains. Patent Document 4 discloses a liquid cleaning agent article for toilets containing a specific surfactant, a specific glycol-type solvent, and one or more polymers selected from polyvinyl alcohol-based polymers and cellulose-based polymers, which is excellent in the detergency of urine stains and has good dischargeability and retention from the container.

Prior Art Documents

Patent Documents

[0004] [Patent Document 1] Japanese Unexamined Patent Application Publication No. 2004-162041 [Patent Document 2] Japanese Unexamined Patent Application Publication No. 2003-238991 [Patent Document 3] Japanese Unexamined Patent Application Publication No. 2020-100774 [Patent Document 4] Japanese Unexamined Patent Application Publication No. 2020-105388 [Summary of the Invention] [Problems to be Solved by the Invention]

[0005] Yellowing and urinary calculi, which are typical stains in the toilet bowl, are considered to be caused by urine stains and water scale and are visually recognized when a certain number or more accumulate in the toilet bowl. These stains occur throughout the toilet bowl and are likely to occur, for example, in the back of the periphery of the bowl of a flush toilet, where the washing water flows, and near the water seal. In order to clean dried urine stains that occur in places such as the back of the periphery of the bowl of a flush toilet where a brush cannot reach, it is necessary to keep the cleaning agent in that place for a long time. However, it has been confirmed that there are problems with the cleaning effect in places such as the back of the periphery of the bowl of a flush toilet where the cleaning agent is difficult to stay. In response to this problem, the above-mentioned patent documents disclose a technique for enhancing the antifouling effect by leaving a specific polymer compound on a hard surface. However, from the perspective of the sustainability of the effect of preventing the occurrence of accumulated urinary calculus stains and yellowing stains derived from urine, the inventors believe that there is room for further improvement.

[0006] The present invention provides a cleaning agent composition for a hard surface, which is excellent in the sustainability of the effect of suppressing the occurrence of urinary calculus stains and yellowing stains derived from urine on a hard surface, and a method for cleaning a hard surface using the same composition. [Means for Solving the Problems]

[0007] The present invention relates to a cleaning agent composition for hard surfaces, comprising the following components (a), (b), (c), and water, wherein the mass ratio (c) / [(a)+(b)] of the content of component (c) to the total content of components (a) and (b) is 0.005 or more and 0.3 or less. (a) Ingredients: Metal chelating agent (b) Component: Foaming surfactant (c) Component: Water-soluble polymer

[0008] The present invention also relates to a method for cleaning hard surfaces, comprising bringing the hard surface cleaning agent composition of the present invention into contact with the hard surface.

[0009] The present invention also relates to a method for suppressing the occurrence of urine scale stains and yellow stains derived from urine on a hard surface, by bringing the hard surface cleaning agent composition of the present invention into contact with the hard surface. [Effects of the Invention]

[0010] The present invention provides a cleaning agent composition for hard surfaces that exhibits excellent sustained effectiveness in suppressing the occurrence of urine scale stains and yellow stains derived from urine on hard surfaces, and a method for cleaning hard surfaces using the same. [Modes for carrying out the invention]

[0011] The reason why the cleaning agent composition for hard surfaces of the present invention and the cleaning method for hard surfaces using the same exhibit superior sustained effectiveness in suppressing the occurrence of urine scale stains and yellow stains derived from urine on hard surfaces is not entirely clear, but it is presumed to be as follows. Urine scale stains and yellow stains originating from urine occur, for example, on the upper part of the water seal and the underside of the rim of the bowl of a flush toilet. It is believed that this is caused by the accumulation of waste-derived dirt and metal ions in a porous material formed from urine scale and limescale from tap water. In order to suppress the occurrence of these urine scale stains and yellow stains originating from urine and maintain the effect, it is considered that the challenge is not only to remove the urine and limescale stains that cause the stains, but also to continue suppressing the accumulation of stains even after treatment. However, even if a cleaning agent composition is applied to the upper part of the water seal and the underside of the rim of the bowl of a flush toilet, the active ingredient is easily washed away by the water after use, and the active ingredient is easily diluted by contact with water, resulting in insufficient effectiveness. The cleaning agent composition for hard surfaces of the present invention contains components (a), (b), and (c) in specific ratios, allowing component (a), which is effective against yellow stains on hard surfaces, particularly above the water seal of flush toilets, to remain and act on the hard surface, especially above the water seal, for a long time without being diluted. In particular, when the cleaning agent composition for hard surfaces of the present invention is applied to a hard surface in foam form, components (b) and (c) can form stable foam, allowing component (a) to remain and act on the hard surface, especially above the water seal of flush toilets, for a long time. Furthermore, it is believed that the presence of component (c) on the hard surface after flushing makes the surface hydrophilic, thereby suppressing the generation of limescale and urine stains. It is presumed that these actions suppress the generation of urine scale and yellow stains derived from urine, and that the effect is long-lasting.

[0012] [Cleaning agent composition for hard surfaces] <(a) Ingredients> The cleaning agent composition for hard surfaces of the present invention contains a metal chelating agent as component (a).

[0013] (a) Specific examples of components include one or more chelating agents selected from (a1) to (a3) ​​below. (a1) Amino acids such as aspartic acid, glutamic acid, and glycine, and their alkali metal salts or alkanolamine salts (a2) Aminocarboxylic acids such as ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, hydroxyethyliminodiacetic acid, nitrilotriacetic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, triethylenetetraminehexaacetic acid, diencholic acid, and their alkali metal salts or alkanolamine salts (a3) Organic acids such as diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, oxydisuccinic acid, gluconic acid, carboxymethylsuccinic acid, carboxymethyltartaric acid, etc. (excluding component (b) described later), and their alkali metal salts or alkanolamine salts

[0014] (a) The component is preferably one or more selected from hydroxycarboxylic acids such as citric acid and malic acid, aminocarboxylic acids such as ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, hydroxyethyliminodiacetic acid, and salts thereof, from the viewpoint of cleaning performance for urinary scale stains and yellow stains derived from urine (hereinafter simply referred to as yellow stains), more preferably one or more selected from citric acid, ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, hydroxyethyliminodiacetic acid, and salts thereof, and even more preferably one or more selected from citric acid, ethylenediaminetetraacetic acid, and salts thereof. The form of the salt is preferably a sodium salt, potassium salt, ammonium salt, or alkanolamine salt.

[0015] <(b) Component> The cleaning agent composition for hard surfaces of the present invention contains a foaming surfactant as component (b). Component (b) of the present invention is prepared by adding a surfactant and deionized water to a standard No. 11 wide-mouth bottle (mouth diameter × body diameter × height: φ31.9 × φ51.5 × 95.5 mm) to prepare 50 mL of a 1% by mass surfactant aqueous solution. A foaming surfactant is defined as a surfactant that generates foam immediately after shaking for 10 seconds with a vertical shaking amplitude of 10 cm (length from top to bottom) and a shaking cycle of 3 times / second.

[0016] (b) Component (b) is preferably one or more selected from (b1) amine oxide type surfactant (hereinafter referred to as (b1) component), (b2) betaine type surfactant (hereinafter referred to as (b2) component), (b3) alkyl (poly) glycoside (hereinafter referred to as (b3) component), (b4) alkyl glyceryl ether (hereinafter referred to as (b4) component), (b5) anionic surfactant (hereinafter referred to as (b5) component), and (b6) cationic surfactant (hereinafter referred to as (b6) component), more preferably one or more selected from component (b1), component (b2), component (b3), component (b4), and component (b5), even more preferably one or more selected from component (b2), component (b3), and component (b4), and even more preferably component (b2).

[0017] As the amine oxide type surfactant of component (b1), a compound of the following general formula (b1) is preferred.

[0018] [ka]

[0019] [In the formula, R 11b R represents an alkyl group or alkenyl group having 7 to 22 carbon atoms, more preferably an alkyl group. 12b and R 13b represents an alkyl group having 1 to 3 carbon atoms, either identical or different. D represents a -NHC(=O)- group or a -C(=O)NH- group, and E represents an alkylene group having 1 to 5 carbon atoms. q and p represent either q=0 and p=0 or q=1 and p=1.

[0020] In the above general formula (b1), when q=1 and p=1, R 11b From the viewpoint of sustained yellowing stain suppression effect, the hydrocarbon group is preferably an alkyl group, having 9 or more carbon atoms, preferably 11 or more, and 18 or fewer carbon atoms, preferably 16 or fewer, more preferably 14 or fewer carbon atoms. Also, if q=0 and p=0, R 11bFrom the perspective of the persistence of the yellowing stain suppression effect, it is a hydrocarbon group having 10 or more carbon atoms, preferably 12 or more carbon atoms, and 18 or less carbon atoms, preferably 16 or less carbon atoms, more preferably 14 or less carbon atoms, preferably an alkyl group. In the present invention, q = 0 and p = 0 are preferred. R 12b 、R 13b is preferably a methyl group having 1 carbon atom.

[0021] (b2) component includes a betaine-type surfactant having one or more, preferably one alkyl group or alkenyl group having 7 to 22 carbon atoms, preferably a sulfobetaine-type surfactant, or a carbobetaine-type surfactant. As the betaine-type surfactant, a compound of the following general formula (b2) is suitable.

[0022]

Chemical formula

[0023] [In the formula, R 21b is an alkyl group or alkenyl group having 7 to 18 carbon atoms, and R 22b is an alkylene group having 1 to 6 carbon atoms. A is a group selected from -COO-, -CONH-, -OCO-, -NHCO-, -O-, and r is a number of 0 or 1. R 23b 、R 24b is an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms, and R 25b is an alkylene group having 1 to 5 carbon atoms which may be substituted with a hydroxy group. B is -SO3 - 、-OSO3 - 、-COO - . ] <000019>

[0024] In the general formula (b 21b <00000[016>From the perspective of the persistence of the yellowing stain suppression effect, it is an alkyl group or alkenyl group having 7 or more carbon atoms, preferably 10 or more carbon atoms, and 18 or less carbon atoms, preferably 14 or less carbon atoms, more preferably 12 or less carbon atoms, preferably an alkyl group. A is preferably -COO- or -CONH-, and more preferably -CONH-. R 22b The number of carbon atoms is preferably 2 or 3. r is preferably 0. R 23b , R 24b Preferably, it is a methyl group. R 25b The number of carbon atoms is preferably 1. B is preferably -COO - That is the case.

[0025] Specifically, betaine-type surfactants include one or more selected from alkylcarboxybetaine, alkylamidecarboxybetaine, alkylsulfobetaine, alkylhydroxysulfobetaine, alkylamidehydroxysulfobetaine, and alkylamino fatty acid salts. From the viewpoint of sustained yellowing stain suppression effect, preferably one or more selected from alkylamidopropyl-N,N-dimethylcarboxybetaine and alkyl-N,N-dimethylacetic acid betaine. These alkyl groups have 7 or more carbon atoms, preferably 10 or more, and 18 or less, preferably 14 or less, and more preferably 12 or less.

[0026] As the alkyl(poly)glycoside of component (b3), compounds of the following general formula (b3) are preferred. R 31b -(OR 32b ) p G q (b3) [In the formula, R 31b R is an alkyl group having 8 to 16 carbon atoms. 32b R is an alkylene group with 2 to 4 carbon atoms, G is a residue derived from a reducing sugar, and p is a number between 0 and 6 that indicates the average number of moles of oxyalkylene groups added, and p R 32b These can be the same or different. q represents the average degree of condensation of G, and is a number between 1 and 10.

[0027] In general formula (b3), R 31bFrom the viewpoint of sustained yellowing stain suppression, the alkyl group has 8 or more carbon atoms, preferably 9 or more, and 16 or fewer carbon atoms, preferably 14 or fewer. R 32b This is an alkylene group having 2 to 4 carbon atoms, preferably an ethylene group or a propylene group, more preferably an ethylene group. p represents the average number of moles of oxyalkylene groups added, and is 0 or greater, and 6 or less, preferably 3 or less, more preferably 1 or less, and even more preferably 0. q represents the average degree of condensation of G, and from the viewpoint of formulation stability, it is a number between 1 and 10, preferably 5 or less, and more preferably 2 or less. Examples of G include residues derived from monosaccharides such as glucose, galactose, xylose, mannose, lyxose, arabinose, fructose, or mixtures thereof, and residues derived from disaccharides or more such as maltose, xylobiose, isomaltose, cellobiose, gentibiose, lactose, sucrose, nigerose, turanose, raffinose, gentianose, menditose, or mixtures thereof. Of these, preferred raw materials from the viewpoint of formulation stability are glucose and fructose among monosaccharides, and maltose and sucrose among disaccharides or more.

[0028] (b4) Specifically, the component may be an alkylglyceryl ether having one alkyl group with 8 to 18 carbon atoms, preferably 8 to 14 carbon atoms, and more preferably 8 to 12 carbon atoms. The alkyl group of component (b4) may be a branched alkyl group having 8 to 12 carbon atoms, preferably 8 to 10 carbon atoms, and from the viewpoint of sustained yellowing stain suppression effect, a 2-ethylhexyl group, an isononyl group, or an isodecyl group is preferred, and a 2-ethylhexyl group is more preferred. (b4) Specifically, the component may be an alkylglyceryl ether having one alkyl group with 8 to 12 carbon atoms, and a 2-ethylhexylglyceryl ether is more preferred.

[0029] (b5) The anionic surfactant of component (b5) can be one or more selected from alkylbenzene sulfonates, polyoxyalkylene alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, olefin sulfons, alkanesulfons, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfo fatty acid salts, N-acyl amino acids, phosphate mono or diesters, and sulfosuccinates. The number of carbon atoms in the alkyl or alkenyl group of the anionic surfactant is, for example, 8 to 22 carbon atoms, preferably 10 to 16 carbon atoms, and more preferably 12 to 14 carbon atoms. In the polyoxyalkylene group of the anionic surfactant, the oxyalkylene group is preferably one or more groups selected from the oxyethylene group and the oxypropylene group, with the oxyethylene group being preferred. In the polyoxyalkylene group, the average number of added moles of oxyalkylene groups is, for example, 0 to 10, and preferably 1 to 3. Examples of counterions to the anionic groups of these anionic surfactants include alkali metal ions such as sodium ions and potassium ions; alkaline earth metal ions such as calcium ions and magnesium ions; ammonium ions; and alkanolamines having 1 to 3 alkanol groups with 2 or 3 carbon atoms (e.g., monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, etc.).

[0030] (b5) The component is preferably one or more selected from alkylbenzene sulfonates, alkyl or alkenyl ether sulfates, and alkyl or alkenyl sulfates, from the viewpoint of sustained yellowing stain suppression effect. The alkyl group of the alkylbenzene sulfonate has 10 or more carbon atoms, preferably 12 or more, and 18 or less, preferably 14 or less, and the alkyl group is preferably linear. The alkyl or alkenyl ether sulfate salt is preferably a polyoxyalkylene alkyl or alkenyl ether sulfate salt. The polyoxyalkylene alkyl or alkenyl ether sulfate salt has an alkyl or alkenyl group with 8 or more carbon atoms, preferably 10 or more, and 18 or less, preferably 14 or less. The polyoxyalkylene alkyl or alkenyl ether sulfate salt has an oxyalkylene group with preferably 2 or 3 carbon atoms, more preferably 2 carbon atoms, and an average number of added moles of oxyalkylene groups of 0.5 or more, more preferably 1.0 or more, and 4.0 or less, preferably 3.0 or less. The number of carbon atoms in the alkyl or alkenyl sulfate salt is 10 or more, preferably 12 or more, and 18 or less, preferably 14 or less.

[0031] (b6) From the viewpoint of the persistence of the yellowing stain suppression effect, component (b61) is preferably one or more selected from the compounds represented by the following general formula (b61) (hereinafter referred to as component (b61)) and the compounds represented by the following general formula (b62) (hereinafter referred to as component (b62)).

[0032] [ka]

[0033] [In the formula, R 61b R is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, 62b R is a group selected from aliphatic hydrocarbon groups having 8 to 18 carbon atoms, alkyl groups having 1 to 3 carbon atoms, and hydroxyalkyl groups having 1 to 3 carbon atoms. 63b and R 64b Each of these is independently selected from alkyl groups having 1 to 3 carbon atoms and hydroxyalkyl groups having 1 to 3 carbon atoms, X - It is an anion.

[0034] [ka]

[0035] [In the formula, R 65b R is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, 66b and R 67b Each of these is independently selected from alkyl groups having 1 to 3 carbon atoms and hydroxyalkyl groups having 1 to 3 carbon atoms, X - It is an anion.

[0036] In general formula (b61), R 61b The number of carbon atoms is 8 or more, preferably 10 or more, more preferably 12 or more, preferably 18 or less, more preferably 16 or less, and even more preferably 14 or less, from the viewpoint of the sustained effect of suppressing yellowing stains. 61b The group is preferably an alkyl group or an alkenyl group, with alkyl groups being preferred. In general formula (b61), R 62b This group is selected from aliphatic hydrocarbon groups having 8 to 18 carbon atoms, alkyl groups having 1 to 3 carbon atoms, and hydroxyalkyl groups having 1 to 3 carbon atoms. R 62b However, if it is an aliphatic hydrocarbon group with 8 to 18 carbon atoms, R 62b From the viewpoint of the sustained effect of suppressing yellowing stains, alkyl or alkenyl groups with a value of 8 or more, preferably 10 or more, more preferably 12 or more, and preferably 18 or less, more preferably 16 or less, and even more preferably 14 or less are preferred, with alkyl groups being preferred.

[0037] In general formula (b61), R 63b and R 64b Each of these groups is independently selected from alkyl groups having 1 to 3 carbon atoms and hydroxyalkyl groups having 1 to 3 carbon atoms. 63b and R 64bEach of these is preferably an alkyl group having 1 to 3 carbon atoms. Examples of alkyl groups having 1 to 3 carbon atoms include a methyl group, an ethyl group, and a propyl group. Examples of hydroxyalkyl groups having 1 to 3 carbon atoms include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.

[0038] In general formula (b61), X - It is an anion. Examples of anions include halogen ions, such as chlorine ions, bromoions, and iodide ions. Also, examples of alkyl sulfate ions having 1 to 3 carbon atoms include methyl sulfate ions, ethyl sulfate ions, and propyl sulfate ions.

[0039] Preferred compounds of the general formula (b61) include one or more selected from N-alkyl-N,N,N-trimethylammonium salts having 12 to 18 carbon atoms in the alkyl group, N,N-dialkyl-N,N-dimethylammonium salts having 8 to 16 carbon atoms in the alkyl group, and N-alkyl-N,N-dimethyl-N-ethylammonium salts having 12 to 16 carbon atoms in the alkyl group.

[0040] In general formula (b62), R 65b R is an aliphatic hydrocarbon group having 8 to 18 carbon atoms. 65b The number of carbon atoms is preferably 8 or more, more preferably 10 or more, even more preferably 12 or more, and preferably 18 or less, more preferably 16 or less, and even more preferably 14 or less, from the viewpoint of the sustained effect of suppressing yellowing stains. 65b The group is preferably an alkyl group or an alkenyl group, with alkyl groups being preferred.

[0041] In general formula (b62), R 66b and R 67b Each of these groups is independently selected from alkyl groups having 1 to 3 carbon atoms and hydroxyalkyl groups having 1 to 3 carbon atoms. 66b and R 67bEach of these is preferably an alkyl group having 1 to 3 carbon atoms. Examples of alkyl groups having 1 to 3 carbon atoms include a methyl group, an ethyl group, and a propyl group. Examples of hydroxyalkyl groups having 1 to 3 carbon atoms include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.

[0042] In general formula (b62), X - It is an anion. Examples of anions include halogen ions, such as chlorine ions, bromoions, and iodide ions. Also, alkyl sulfate ions with 1 to 3 carbon atoms, such as methyl sulfate ions, ethyl sulfate ions, and propyl sulfate ions.

[0043] Specific examples of compounds with general formula (b62) include N-octyl-N,N-dimethyl-N-benzylammonium salt, N-decyl-N,N-dimethyl-N-benzylammonium salt, N-dodecyl-N,N-dimethyl-N-benzylammonium salt, N-tridecyl-N,N-dimethyl-N-benzylammonium salt, N-tetradecyl-N,N-dimethyl-N-benzylammonium salt, N-pentadecyl-N,N-dimethyl-N-benzylammonium salt, N-hexadecyl-N,N-dimethyl-N-benzylammonium salt, N-dodecyl-N,N-diethyl-N-benzylammonium salt, and N-tridecyl-N,N-diethyl-N-benzylammonium salt. Examples include one or more compounds selected from nium salts, N-tetradecyl-N,N-diethyl-N-benzylammonium salt, N-pentadecyl-N,N-diethyl-N-benzylammonium salt, N-hexadecyl-N,N-diethyl-N-benzylammonium salt, N-dodecyl-N-methyl-N-ethyl-N-benzylammonium salt, N-tridecyl-N-methyl-N-ethyl-N-benzylammonium salt, N-tetradecyl-N-methyl-N-ethyl-N-benzylammonium salt, N-pentadecyl-N-methyl-N-ethyl-N-benzylammonium salt, and N-hexadecyl-N-methyl-N-ethyl-N-benzylammonium salt.

[0044] <(c) component> The cleaning agent composition for hard surfaces of the present invention contains a water-soluble polymer as component (c). Component (c) of the present invention refers to a polymer compound that can dissolve in 10 g or more of water at 25°C.

[0045] (c) Examples of components include water-soluble natural polymer compounds, water-soluble modified natural polymer compounds in which the hydroxyl groups of natural polymer compounds such as cellulose and starch are modified (or "substituted" in this invention) with alkyl groups having 1 to 3 carbon atoms, hydroxyalkyl groups, cationic groups, alkylcarborsi groups, etc., and water-soluble synthetic polymer compounds such as unsaturated carboxylic acid polymers, polyvinyl alcohol, and polyalkylene glycol.

[0046] Examples of water-soluble natural polymer compounds and water-soluble modified natural polymer compounds include gum arabic, color ginan, guar gum, starch, xanthan gum, water-soluble modified cellulose (e.g., ethylcellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, cationized cellulose), cationized starch, sodium alginate, and cationized guar gum. The weight-average molecular weight of the water-soluble natural polymer compound, the water-soluble modified natural polymer compound, and the water-soluble synthetic polymer compound is preferably 1000 or more, preferably 3 million or less, and more preferably 2 million or less, from the viewpoint of the sustained effect of suppressing yellowing stains. (c) The weight-average molecular weight of the polymer compound of component (c) is determined by gel permeation chromatography (GPC) using a mixed solution of acetonitrile and water (phosphate buffer) as the developing solvent, with polyethylene glycol as the standard.

[0047] (c) Component is preferably one or more selected from water-soluble modified cellulose and polyvinyl alcohol, more preferably one or more selected from hydroxyethylcellulose, carboxymethylcellulose and polyvinyl alcohol, and even more preferably hydroxyethylcellulose, from the viewpoint of the persistence of the yellowing stain suppression effect, foaming ability and foam stability.

[0048] The weight-average molecular weight of carboxymethylcellulose is preferably 50,000 or more, more preferably 100,000 or more, preferably 500,000 or less, more preferably 300,000 or less, and even more preferably 150,000 or less, from the viewpoint of the persistence of the yellowing stain suppression effect and foaming properties. The degree of substitution (degree of etherification) of the carboxymethyl groups in carboxymethylcellulose is preferably 0.01 or higher, more preferably 0.1 or higher, even more preferably 0.5 or higher, and preferably 10 or lower, more preferably 5 or lower, even more preferably 1.2 or lower, and even more preferably 0.8 or lower, from the viewpoint of the persistence of the yellowing stain suppression effect and foaming properties.

[0049] The weight-average molecular weight of hydroxyethylcellulose is preferably 500,000 or more, more preferably 1,000,000 or more, even more preferably 1,250,000 or more, and preferably 3,000,000 or less, more preferably 2,000,000 or less, and even more preferably 1,750,000 or less, from the viewpoint of the persistence of the yellowing stain suppression effect and foaming properties. The degree of substitution of the hydroxyethyl group in hydroxyethylcellulose is preferably 0.01 or higher, more preferably 0.1 or higher, even more preferably 0.5 or higher, even more preferably 0.8 or higher, and preferably 10 or lower, more preferably 5 or lower, even more preferably 3 or lower, even more preferably 2 or lower, and even more preferably 1.5 or lower, from the viewpoint of the persistence of the yellowing stain suppression effect and foaming ability.

[0050] The weight-average molecular weight of polyvinyl alcohol is preferably 5,000 or more, more preferably 10,000 or more, preferably 250,000 or less, more preferably 200,000 or less, and even more preferably 150,000 or less, from the viewpoint of the persistence of the yellowing stain suppression effect and foaming properties. The degree of saponification of polyvinyl alcohol is preferably 70 mol% or more, more preferably 80 mol% or more, preferably 100 mol% or less, and more preferably 90 mol% or less, from the viewpoint of the persistence of the yellowing stain suppression effect and foaming properties. Furthermore, the polyvinyl alcohol may be copolymerized with an unsaturated compound that can copolymerize with vinyl alcohol.

[0051] <Composition, etc.> The cleaning agent composition for hard surfaces of the present invention contains component (a) in an amount of preferably 0.5% by mass or more, more preferably 1.0% by mass or more, even more preferably 1.5% by mass or more, and preferably 5.0% by mass or less, more preferably 4.0% by mass or less, and even more preferably 3.0% by mass or less, from the viewpoint of suppressing yellowing stains. In the present invention, the mass of component (a) shall be the value obtained by converting it to acid.

[0052] The cleaning agent composition for hard surfaces of the present invention contains component (b) in an amount of preferably 0.5% by mass or more, more preferably 1.0% by mass or more, even more preferably 1.5% by mass or more, even more preferably 2.0% by mass or more, and preferably 10.0% by mass or less, more preferably 7.0% by mass or less, even more preferably 5.0% by mass or less, and even more preferably 4.0% by mass or less, from the viewpoint of sustained yellowing stain suppression effect. In the present invention, if component (b) includes component (b5), the mass of component (b5) shall be the value obtained by converting it to a sodium salt.

[0053] The hard surface cleaning agent composition of the present invention contains component (c) in an amount of preferably 0.001% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.03% by mass or more, even more preferably 0.05% by mass or more, and preferably 1.0% by mass or less, more preferably 0.8% by mass or less, even more preferably 0.5% by mass or less, even more preferably 0.25% by mass or less, even more preferably 0.1% by mass or less, and even more preferably 0.08% by mass or less, from the viewpoint of the persistence of the yellowing stain suppression effect and the stability of the foam.

[0054] In the hard surface cleaning agent composition of the present invention, the mass ratio (c) / [(a)+(b)] of the content of component (c) to the total content of components (a) and (b) is 0.005 or more, preferably 0.007 or more, more preferably 0.01 or more, and 0.3 or less, preferably 0.25 or less, more preferably 0.20 or less, even more preferably 0.10 or less, even more preferably 0.05 or less, and even more preferably 0.025 or less.

[0055] The cleaning agent composition for hard surfaces of the present invention preferably further contains a water-soluble solvent as component (d) from the viewpoint of sustained yellowing stain suppression effect and foaming properties. With respect to component (d), "water-soluble" means that 5 g or more dissolves in water at 20°C.

[0056] (d) The water-soluble solvent for component (d) can be one or more water-soluble solvents selected from ethanol, isopropyl alcohol, 2-methyl-2-propanol, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monoethyl ether (methylpropylene glycol), propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monohexyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, triethylene glycol monobutyl ether, 3-methyl-3-methoxybutanol, phenoxyethanol, phenyl glycol, phenyl diglycol, phenoxyisopropanol, dibutylenediglycol, and benzyl alcohol. (d) Component is preferably one or more water-soluble solvents selected from ethanol, diethylene glycol monobutyl ether, benzyl alcohol, phenoxyethanol, isopropyl alcohol, and propylene glycol monoethyl ether, from the viewpoint of the persistence of the yellowing stain suppression effect and foaming properties, and more preferably one or more water-soluble solvents selected from diethylene glycol monobutyl ether and benzyl alcohol.

[0057] If the cleaning agent composition for hard surfaces of the present invention contains component (d), component (d) is preferably contained in an amount of 1.0% by mass or more, more preferably 3.0% by mass or more, even more preferably 5.0% by mass or more, and preferably 10.0% by mass or less, more preferably 8.0% by mass or less, and even more preferably 7.5% by mass or less, from the viewpoint of the persistence of the yellowing stain suppression effect and foaming properties.

[0058] The cleaning agent composition for hard surfaces of the present invention may optionally contain fragrances, dyes, preservatives, enzymes, pH adjusters, antioxidants, etc., in order to increase the added value of the product (except for components (a) to (d) above).

[0059] The hard surface cleaning agent composition of the present invention contains water. That is, the remainder other than the components (a) to (c) and any optional components is water. The hard surface cleaning agent composition of the present invention contains water in an amount of preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, and preferably 99% by mass or less, and more preferably 95% by mass or less. It is preferable to use ion-exchanged water, sterilized ion-exchanged water, etc.

[0060] The pH of the hard surface cleaning agent composition of the present invention at 25°C is preferably 5.0 or higher, more preferably 6.0 or higher, even more preferably 6.5 or higher, even more preferably 8.0 or higher, even more preferably 9.5 or higher, and preferably 13.0 or lower, more preferably 12.0 or lower, and even more preferably 11.0 or lower, from the viewpoint of sustained effectiveness in suppressing urine scale and yellowing stains. The pH value shall be the value measured by the glass electrode method.

[0061] The cleaning agent composition for hard surfaces of the present invention exhibits excellent sustained effectiveness in suppressing the occurrence of urine scale and yellow stains derived from urine on hard surfaces such as toilets. Therefore, the cleaning agent composition for hard surfaces of the present invention is suitable for use on the hard surfaces of toilets, and is particularly suitable for use in areas where the cleaning agent is less likely to accumulate, such as the underside of the rim of the bowl of a flush toilet, the area where flushing water flows, and the area near the water seal, where urine scale and yellow stains derived from urine are likely to occur.

[0062] The hard surface cleaning agent composition of the present invention is preferably used by spraying or applying it in droplet or foam form and bringing it into contact with the hard surface, and more preferably by spraying or applying it in foam form and bringing it into contact with the hard surface. A spraying device can be used for spraying or applying. The present invention provides a hard surface cleaning agent article in a spray container, which is obtained by filling the hard surface cleaning agent composition of the present invention into a container equipped with a sprayer.

[0063] The container equipped with a sprayer for filling the hard surface cleaning agent composition of the present invention in the hard surface cleaning agent article in a spray container of the present invention includes manual spraying devices that do not use propellants, such as trigger-type spray containers and pump-type spray containers, and aerosols that use propellants. The container equipped with the sprayer is preferably a trigger-type spray that can spray or apply the contents in droplet or foam form, and more preferably a trigger-type spray equipped with a mechanism for spraying the contents in droplet form or a trigger-type spray equipped with a mechanism for forming foam (foam-forming mechanism).

[0064] In the hard surface cleaning agent article in a spray container of the present invention, when a trigger-type spray equipped with a mechanism for spraying the hard surface cleaning agent composition of the present invention in droplet form is used, the nozzle diameter of the spray nozzle of the spray container containing the composition is preferably in the range of 0.1 mm or more, more preferably 0.3 mm or more, and preferably 2 mm or less, and more preferably 1 mm or less, in order to ensure ease of spraying, that the sprayed droplets are not rough, that the spray is not linear, and that the sprayable area does not become extremely narrow. When using a trigger-type spray equipped with a mechanism for spraying in droplet form, the cleaning agent article for hard surfaces in a spray container of the present invention sprays, preferably 0.1 mL or more, more preferably 0.3 mL or more, and preferably 5 mL or less, and more preferably 2 mL or less of the composition in a single operation.

[0065] Furthermore, in the hard surface cleaning agent article in a spray container of the present invention, when a trigger-type spray equipped with a foam-forming mechanism is used, it is preferable that the spray container has a spin element and a liquid passage plate in which several rod-shaped protrusions are installed in a circular space with a diameter of 4 to 8 mm. Here, the spin element is a mechanism that imparts spin to the flow of a liquid through the spin element and finally ejects it from the nozzle. For detailed structure, refer to Figure 4(b) of Japanese Patent Publication No. Hei 8-332422 and Japanese Patent Publication No. Hei 8-108102, and Figure 1 of Japanese Patent Publication No. 2002-68265.

[0066] When using a trigger-type spray equipped with a foam-forming mechanism, the hard surface cleaning agent article in the spray container of the present invention sprays, preferably 0.5 mL or more, more preferably 1 mL or more, preferably 30 mL or less, more preferably 15 mL or less, and even more preferably 5 mL or less of the composition in a single operation.

[0067] Another component of the foam formation mechanism, the liquid passage plate, has a circular space with a diameter of 5 to 7 mm, in which rod-shaped protrusions are preferably placed, preferably 3 to 8 rod-shaped protrusions. When the plate is viewed in plan view, rectangular rod-shaped protrusions with a width of 0.8 to 1.2 mm and a length of 2 to 4 mm are preferable. Furthermore, the area occupied by the rod-shaped protrusions in the space excluding the rod-shaped protrusions is preferably 30% or more, more preferably 40% or more, preferably 90% or less, more preferably 80% or less, and even more preferably 70% or less. By installing such a liquid passage plate, the adhesion and retention of foam on the vertical surface is improved.

[0068] When the hard surface cleaning agent composition of the present invention is used to be applied to a hard surface in foam form using a trigger-type spray equipped with a foam-forming mechanism, the foam specific volume (volume of foam per unit mass (g) (ml)) of the hard surface cleaning agent composition of the present invention 5 minutes after foam formation is preferably 5 ml / g or more, more preferably 10 ml / g or more, even more preferably 15 ml / g or more, even more preferably 20 ml / g or more, even more preferably 30 ml / g or more, and more preferably 50 ml / g or less, even more preferably 45 ml / g or less, and even more preferably 40 ml / g or less, from the viewpoint of the persistence of the yellow stain suppression effect. The foam specific volume can be measured by the method described in the evaluation of foam specific volume in the examples.

[0069] When the hard surface cleaning agent composition of the present invention is used to be applied to a hard surface in a foamy form using a trigger-type spray equipped with a foam-forming mechanism, the ratio B / A of the foam specific volume (volume of foam per unit mass (g) (ml)) (hereinafter referred to as A) 30 seconds after foam formation and the foam specific volume (volume of foam per unit mass (g) (ml)) (hereinafter referred to as B) 10 minutes after foam formation is preferably 0.05 or higher, more preferably 0.1 or higher, even more preferably 0.15 or higher, even more preferably 0.2 or higher, and even more preferably 0.9 or lower, even more preferably 0.8 or lower, and even more preferably 0.7 or lower, from the viewpoint of the persistence of the yellowing stain suppression effect. The foam specific volume can be measured by the method described in the evaluation of the foam specific volume in the examples.

[0070] The container for the hard surface cleaning agent article in a spray bottle of the present invention can be a commonly used container. For example, it can be obtained from polyethylene, polypropylene, or polyethylene terephthalate as a raw material and can be manufactured by blow molding or the like. The wall thickness of the container may differ between the bottom and sides, preferably 0.01 to 2 mm, and the capacity of the container is preferably 100 to 1000 mL. The amount of hard surface cleaning agent composition filled into the container is preferably 200 to 500 mL for ease of handling. The liquid should be filled while leaving a reasonable amount of empty space.

[0071] The cleaning agent composition for hard surfaces of the present invention contains component (a) and water, and when used with a trigger-type spray equipped with a foam-forming mechanism, the foam specific volume (volume of foam per unit mass (g) (ml)) 5 minutes after foam formation is 5 ml / g or more and 50 ml / g or less, and the ratio B / A of the foam specific volume (volume of foam per unit mass (g) (ml)) 30 seconds after foam formation (hereinafter referred to as A) to the foam specific volume (volume of foam per unit mass (g) (ml)) 10 minutes after foam formation (hereinafter referred to as B) is 0.05 or more and 0.9 or less is preferable in terms of the sustained effect of suppressing the occurrence of urine scale stains and yellow stains derived from urine on hard surfaces. In other words, in one embodiment, the present invention provides a hard surface cleaning agent composition containing component (a) and water, wherein, using a trigger-type spray equipped with a foam-forming mechanism, the foam specific volume (volume of foam per unit mass (g) (ml)) 5 minutes after foam formation is 5 ml / g or more and 50 ml / g or less, and the ratio B / A of the foam specific volume (volume of foam per unit mass (g) (ml)) (hereinafter referred to as A) 30 seconds after foam formation to the foam specific volume (volume of foam per unit mass (g) (ml)) (hereinafter referred to as B) 10 minutes after foam formation is 0.05 or more and 0.9 or less. The hard surface cleaning agent composition of the embodiment described above can be appropriately adapted to the embodiments described in the hard surface cleaning agent composition of the present invention. The preferred range of foam specific volume and ratio B / A 5 minutes after foam formation, and the measurement method are also the same as those described in the hard surface cleaning agent composition of the present invention.

[0072] [Method for cleaning hard surfaces] The present invention relates to a method for cleaning hard surfaces, comprising bringing the hard surface cleaning agent composition of the present invention into contact with the hard surface. The cleaning method for hard surfaces of the present invention uses the cleaning agent composition for hard surfaces of the present invention. A preferred embodiment of the composition is the same as the cleaning agent composition for hard surfaces of the present invention described above. The target hard surface is the same as that described in the hard surface cleaning agent composition of the present invention. The cleaning method for hard surfaces of the present invention can be suitably implemented as a cleaning method for hard surfaces, in which the cleaning agent composition for hard surfaces of the present invention is brought into contact with the hard surface, and then rinsed without scrubbing.

[0073] In the cleaning method for hard surfaces of the present invention, the cleaning agent composition for hard surfaces is brought into contact with the hard surface. Specifically, the cleaning method involves contacting the hard surface cleaning agent composition undiluted with the hard surface, or contacting the hard surface cleaning agent composition undiluted with the hard surface, that is, contacting the hard surface cleaning agent composition with the hard surface without dilution. To contact the hard surface cleaning agent composition without dilution means not to intentionally dilute the hard surface cleaning agent composition with water or the like before contacting the hard surface. For example, if the hard surface cleaning agent composition comes into contact with a hard surface that has water droplets on it, or if water droplets adhere to the hard surface after the hard surface cleaning agent composition has come into contact with the hard surface, this can be understood as contacting the hard surface cleaning agent composition without dilution. In the present invention, it is preferable to bring the undiluted hard surface cleaning agent composition into contact with the hard surface as is, that is, without altering its composition. For example, the hard surface cleaning agent composition is brought into contact with the hard surface without adhering it to a water-soaked sponge. After contact with the hard surface, the composition of the hard surface cleaning agent composition may change. That is, after contact with the hard surface, the composition of the hard surface cleaning agent composition may be diluted or concentrated.

[0074] Furthermore, the present invention provides a method for cleaning hard surfaces, which involves bringing the hard surface cleaning agent composition into contact with the hard surface and then rinsing it without scrubbing, preferably by bringing it into contact with the hard surface, leaving it for a predetermined time, and then rinsing it without scrubbing. In other words, it is a cleaning method in which the hard surface cleaning agent composition is brought into contact with the hard surface without scrubbing using a flexible material such as a sponge or fingers, and then left without applying any external force. After contact with the hard surface cleaning agent composition, if necessary, a predetermined time is left, and then the hard surface is rinsed with water. When rinsing, external force (physical force) may be applied with hands or other means, or it may simply be rinsed with a stream of water.

[0075] The method of bringing the hard surface cleaning agent composition into contact with the hard surface is preferably by spraying or coating, more preferably by spraying in droplet form or coating in foam form, and even more preferably by coating in foam form. The hard surface cleaning method of the present invention preferably uses the hard surface cleaning agent article in a spray container of the present invention described above.

[0076] In the present invention's method for cleaning hard surfaces, the hard surface cleaning agent composition is applied to a hard surface with an area of ​​100 cm². 2 The substance is brought into contact with the material in a ratio of preferably 0.1g or more, more preferably 0.3g or more, even more preferably 0.4g or more, and preferably 5g or less, more preferably 3g or less, and even more preferably 2g or less.

[0077] In the hard surface cleaning method of the present invention, when the hard surface cleaning agent composition is applied to the hard surface in the form of foam, the hard surface cleaning agent composition is applied to the hard surface as foam, where the foam specific volume (volume of foam per unit mass (g) (ml)) 5 minutes after foam formation is preferably 5 ml / g or more, more preferably 10 ml / g or more, even more preferably 15 ml / g or more, even more preferably 20 ml / g or more, even more preferably 30 ml / g or more, and more preferably 50 ml / g or less, even more preferably 45 ml / g or less, and even more preferably 40 ml / g or less, from the viewpoint of the persistence of the yellow stain suppression effect. The foam specific volume can be measured by the method described in the evaluation of foam specific volume in the examples.

[0078] In the hard surface cleaning method of the present invention, when the hard surface cleaning agent composition is applied to the hard surface in the form of foam, the hard surface cleaning agent composition is applied to the hard surface as foam in which the ratio B / A of the foam specific volume (volume of foam per unit mass (g) (ml)) (hereinafter referred to as A) 30 seconds after foam formation to the foam specific volume (volume of foam per unit mass (g) (ml)) (hereinafter referred to as B) 10 minutes is preferably 0.05 or higher, more preferably 0.1 or higher, even more preferably 0.15 or higher, even more preferably 0.2 or higher, and more preferably 0.9 or lower, even more preferably 0.8 or lower, and even more preferably 0.7 or lower, from the viewpoint of the persistence of the yellowing stain suppression effect. The foam specific volume can be measured by the method described in the evaluation of the foam specific volume in the examples.

[0079] In the cleaning method for hard surfaces of the present invention, from the viewpoint of sustained yellowing stain suppression effect, the cleaning agent composition for hard surfaces is left to stand for preferably 30 seconds or more, more preferably 50 seconds or more, even more preferably 60 seconds or more, even more preferably 3 minutes or more, even more preferably 5 minutes or more, and from the same viewpoint, preferably 15 minutes or less, even more preferably 10 minutes or less, after contact with the hard surface. In this case, the start of the standing period may be defined as the time when the composition first comes into contact with the hard surface. The predetermined time may be within this range. The temperature at which the product is left to stand is room temperature, for example, between 10°C and 30°C.

[0080] Furthermore, in the hard surface cleaning method of the present invention, from the viewpoint of the persistence of the yellowing stain suppression effect, the hard surface cleaning agent composition is preferably brought into contact with the hard surface for 30 seconds or more, more preferably 50 seconds or more, even more preferably 60 seconds or more, even more preferably 3 minutes or more, even more preferably 5 minutes or more, and from the same viewpoint, preferably 15 minutes or less, more preferably 10 minutes or less.

[0081] In the cleaning method for hard surfaces of the present invention, the cleaning agent composition for hard surfaces of the present invention is brought into direct contact with the hard surface. Since it is sufficient to leave the cleaning agent composition in contact with the hard surface, there is no need to apply external force during cleaning, such as scrubbing with a flexible material like a sponge. Furthermore, the cleaning method for hard surfaces of the present invention involves applying the hard surface cleaning agent composition of the present invention, preferably in foam form, to the hard surface and leaving it there, thus allowing the composition to remain on the hard surface for a long time. The present invention provides a method for cleaning hard surfaces, which involves contacting the hard surface cleaning agent composition with the hard surface, and then rinsing the hard surface with water, preferably after leaving it for a predetermined time.

[0082] In the cleaning method for hard surfaces of the present invention, it is preferable to apply a cleaning agent composition for hard surfaces containing component (a) and water using a trigger-type spray equipped with a foam-forming mechanism, wherein the foam specific volume (volume of foam per unit mass (g) (ml)) 5 minutes after foam formation is 5 ml / g or more and 50 ml / g or less, and the ratio B / A of the foam specific volume (volume of foam per unit mass (g) (ml)) 30 seconds after foam formation (hereinafter referred to as A) to the foam specific volume (volume of foam per unit mass (g) (ml)) 10 minutes after foam formation (hereinafter referred to as B) is 0.05 or more and 0.9 or less to the hard surface with foam, from the viewpoint of sustained effect in suppressing the occurrence of urine scale stains and yellow stains derived from urine on hard surfaces. In other words, in one embodiment, the present invention provides a method for cleaning hard surfaces, wherein a cleaning agent composition for hard surfaces containing component (a) and water is applied to the hard surface using a trigger-type spray equipped with a foam-forming mechanism, wherein the foam specific volume (volume of foam per unit mass (g) (ml)) 5 minutes after foam formation is 5 ml / g or more and 50 ml / g or less, and the ratio B / A of the foam specific volume (volume of foam per unit mass (g) (ml)) 30 seconds after foam formation (hereinafter referred to as A) to the foam specific volume (volume of foam per unit mass (g) (ml)) 10 minutes after foam formation (hereinafter referred to as B) is 0.05 or more and 0.9 or less. The hard surface cleaning method of the embodiment described above can appropriately apply the embodiments described in the hard surface cleaning method of the present invention. The hard surface cleaning agent composition used in the hard surface cleaning method of the embodiment is the same as the hard surface cleaning agent composition of the present invention, and the embodiments described in the hard surface cleaning agent composition of the present invention can appropriately apply. The hard surface to be cleaned is the same as the embodiment described in the hard surface cleaning agent composition of the present invention. The foam specific volume after 5 minutes from foam formation, the preferred range of the ratio B / A, and the measurement method are also the same as the embodiments described in the hard surface cleaning method of the present invention.

[0083] [Method for suppressing the occurrence of urine scale stains and yellow stains derived from urine on hard surfaces] The present invention relates to a method for suppressing the occurrence of urine scale stains and yellow stains derived from urine on a hard surface, by bringing the hard surface cleaning agent composition of the present invention into contact with the hard surface. By bringing the cleaning agent composition for hard surfaces of the present invention into contact with a hard surface, the occurrence of urine scale stains and yellow stains derived from urine can be suppressed. In the method for suppressing the occurrence of urine scale stains and yellow stains derived from urine on hard surfaces according to the present invention, the manner in which the hard surface cleaning agent composition of the present invention is brought into contact with the hard surface is the same as the manner described in the hard surface cleaning method of the present invention. The present invention provides a method for suppressing the occurrence of urine scale stains and yellow stains derived from urine on hard surfaces, and the embodiments described in the present invention's method for cleaning hard surfaces can be appropriately applied. The present invention provides a method for suppressing the occurrence of urine scale stains and yellow stains derived from urine on hard surfaces, using the hard surface cleaning agent composition of the present invention. A preferred embodiment of the composition is the same as the hard surface cleaning agent composition of the present invention described above. The target hard surface is the same as that described in the hard surface cleaning agent composition of the present invention.

[0084] In the present invention's method for suppressing the occurrence of urine scale stains and yellow stains derived from urine on hard surfaces, it is preferable to apply a hard surface cleaning agent composition containing component (a) and water to the hard surface using a trigger-type spray equipped with a foam-forming mechanism, where the foam specific volume (volume of foam per unit mass (g) (ml)) 5 minutes after foam formation is 5 ml / g or more and 50 ml / g or less, and the ratio B / A of the foam specific volume (volume of foam per unit mass (g) (ml)) 30 seconds after foam formation (hereinafter referred to as A) to the foam specific volume (volume of foam per unit mass (g) (ml)) 10 minutes after foam formation (hereinafter referred to as B) is 0.05 or more and 0.9 or less, in order to maintain the effect of suppressing the occurrence of urine scale stains and yellow stains derived from urine on hard surfaces. In other words, the present invention provides a method for suppressing the occurrence of urine scale stains and urine-derived yellow stains on hard surfaces, wherein in one embodiment, a hard surface cleaning agent composition containing component (a) and water is applied to a hard surface using a trigger-type spray equipped with a foam-forming mechanism, wherein the foam specific volume (volume of foam per unit mass (g) (ml)) 5 minutes after foam formation is 5 ml / g or more and 50 ml / g or less, and the ratio B / A of the foam specific volume (volume of foam per unit mass (g) (ml)) 30 seconds after foam formation (hereinafter referred to as A) to the foam specific volume (volume of foam per unit mass (g) (ml)) 10 minutes after foam formation (hereinafter referred to as B) is 0.05 or more and 0.9 or less. The method for suppressing the occurrence of uric acid stains and yellow stains derived from urine on a hard surface according to the embodiment of the present invention can appropriately apply the embodiments described in the method for suppressing the occurrence of uric acid stains and yellow stains derived from urine on a hard surface according to the present invention. Furthermore, the hard surface cleaning agent composition used in the method for suppressing the occurrence of uric acid stains and yellow stains derived from urine on a hard surface according to the embodiment of the present invention is the same as the hard surface cleaning agent composition according to the present invention, and the embodiments described in the hard surface cleaning agent composition according to the present invention can appropriately apply. The target hard surface is the same as the embodiments described in the hard surface cleaning agent composition according to the present invention. The foam specific volume 5 minutes after foam formation, the preferred range of the ratio B / A, and the measurement method are also the same as the embodiments described in the hard surface cleaning method according to the present invention. [Examples]

[0085] The components used in the examples and comparative examples are shown below. <(a) Ingredients> • Ethylenediaminetetraacetate tetrasodium: Manufactured by Chubu Kirest Co., Ltd. • Hydroxyethylenediaminetriacetic acid: Manufactured by Chubu Kirest Co., Ltd. • Dihydroxyethylglycine: Manufactured by Chubu Kirest Co., Ltd. • Hydroxyethyleneiminodiacetic acid: Manufactured by Chubu Kirest Co., Ltd. Sodium citrate: Manufactured by Showa Chemical Co., Ltd.

[0086] <(b) Component> • Lauryldimethylamine oxide: (b1) component, in general formula (b1), R 11b is an alkyl group with 12 carbon atoms, R 12b and R 13b This compound has a methyl group, q=0, and p=0. Product name: Anchitol 20N, manufactured by Kao Corporation. • Lauryldimethylaminoacetic acid betaine: (b2) component, in general formula (b2), R 21b is an alkyl group with 12 carbon atoms, r is 0, R 23b , R 24b is a methyl group, R 25b B is a methylene group, B is -COO - The compound, product name: Anchitol 20AB, manufactured by Kao Corporation. • Sodium lauryl sulfate: (b5) ingredient, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. • Benzalkonium chloride: (b6) component, in general formula (b62), R 65b is an alkyl group with 12 carbon atoms, R 66b and R 67b is a methyl group, X - This is a chlorion compound, product name: Sanizol B-50, manufactured by Kao Corporation. • 2-Ethylhexylglyceryl ether: (b4) Ingredient, Product name: Penetol GE-EH, manufactured by Kao Corporation • Alkyl polyglycoside: (b3) component, in general formula (b3), R 31b A compound with an alkyl group having 10 to 14 carbon atoms, p = 0, q = 1.4, product name: AG124, manufactured by Kao Corporation.

[0087] <(c) component> • Hydroxyethylcellulose: Weight-average molecular weight 1.56 million, degree of substitution of hydroxyethyl groups 1.0-1.3, Daicel HEC SE850, manufactured by Daicel Corporation. • Polyvinyl alcohol: weight-average molecular weight 10,000-200,000 (average degree of polymerization 1750), degree of saponification 70-100 mol%, Kuraray Poval PVA-217, manufactured by Kuraray Co., Ltd.

[0088] <(d) component> • Diethylene glycol monobutyl ether: Manufactured by Nippon Emulsifier Co., Ltd. • Benzyl alcohol: Manufactured by Tokyo Chemical Industry Co., Ltd. Phenoxyethanol: Manufactured by Nippon Emulsifier Co., Ltd. • Ethanol: Traceable 95, manufactured by Japan Alcohol Industry Co., Ltd. <Other ingredients> ·Fragrance

[0089] [Preparation of cleaning agent compositions for hard surfaces] Using the components shown in Tables 1 and 2, hard surface cleaning agent compositions with the compositions shown in Tables 1 and 2 were prepared by the method described below. To obtain the hard surface cleaning agent compositions shown in Tables 1 and 2, components (a) to (d) and fragrance were first added to deionized water in the amounts shown in Tables 1 and 2, and dissolved at room temperature (25°C). After mixing, hydrochloric acid and / or sodium hydroxide were added as pH adjusters to adjust the pH to the values ​​shown in Tables 1 and 2. The pH was measured using the glass electrode method. Note that the amounts of each ingredient listed in Tables 1 and 2 are all effective amounts.

[0090] [Evaluation of foam volume] The hard surface cleaning agent compositions shown in Table 1 were filled into a dispensing container (TA-F, manufactured by Yoshino Kogyosho Co., Ltd.), and 5 g of foam from the composition was dispensed towards a conical liquid volume meter (model No. 1423, manufactured by PMP, capacity 250 mL, manufactured by Kartell). After standing for 30 seconds, 5 minutes, or 10 minutes from foam formation, the foam specific volume was measured. The foam specific volume was calculated using the following formula. The results are shown in Table 1. Foam specific volume (mL / g)=foam volume (mL) / discharge amount (g) Furthermore, the foam stability index was calculated from the foam specific volume after 30 seconds and after 10 minutes using the following formula. The results are shown in Table 1. A value closer to 1 indicates better foam stability. Foam stability = (Foam specific volume after 10 minutes (mL / g) / Foam specific volume after 30 seconds (mL / g))

[0091] [Evaluation of foam retention] Three white ceramic tiles (LIXIL Misty Palette, 100mm x 100mm) were joined vertically and propped against a vertical wall so that the tile was at a 60° angle to the horizontal contact surface. 100g of water was poured from the top tile to recreate the ceramic surface after flushing. Next, the hard surface cleaning agent composition shown in Table 1 was filled into a dispensing container (TA-F, manufactured by Yoshino Kogyosho Co., Ltd.), and foam was dispensed towards the center of the top tile. The time required for the liquid or foam flowing down the tile to contact the contact surface of the bottom tile was measured three times, and the average value was evaluated according to the evaluation criteria below. A score of 3 or higher was considered a pass. The results are shown in Table 1. A higher number indicates greater effectiveness. <Evaluation Criteria> 5 points: 90 seconds or more 4 points: 60 seconds or more and 89 seconds or less 3 points: 30 seconds or more and 59 seconds or less 2 points: 10 seconds or more and 29 seconds or less 1 point: 9 seconds or less

[0092] [Evaluation of the sustained effect of suppressing urinary stones and yellowing] <Sustained effectiveness test for inhibiting urinary stones and yellowing (1)> A durability test was conducted on household flush toilets (such as the Neorest RH1 with integrated bidet function (material: ceramic, model number: TCF9768, manufactured by TOTO Ltd., 2022) and the NEW Arauno V (material: organic glass, model number: CH3010W, manufactured by Panasonic Corporation, 2016)) that are cleaned once a week, to test the effectiveness of suppressing the occurrence of urine scale and yellow stains derived from urine. The hard surface cleaning agent compositions shown in Table 1 were filled into a pressurized discharge container (TA-F, manufactured by Yoshino Kogyosho Co., Ltd.). On the first day of the test, (1) 10 ml of the hard surface cleaning agent composition was applied in a foamy manner to cover the entire inside of the bowl of the flush toilet, left for 5 minutes, and then flushed with water from the toilet's water tank. Subsequently, on the 7th day, (1) was performed again. The above procedure was performed for one month (4 cycles), and the degree of soiling inside the bowl of the flush toilet was observed visually and under a black light one month after the start of the test. The household flush toilets being evaluated were used daily throughout the test period. Five expert panelists evaluated the toilets visually according to the following criteria, with a score of 3 or higher considered a pass. A higher score indicates superior durability in suppressing the occurrence of urine scale and yellowing stains caused by urine. The results are shown in Table 1. 5 points: Compared to one month ago, there are absolutely no urine scale stains or yellow stains caused by urine. 4 points: Compared to one month ago, there is almost no urine scale or yellow stains from urine. 3 points: Compared to one month ago, there are some urine scale stains and yellow stains from urine, but they are not very noticeable. Points 2: Compared to a month ago, urine scale stains and yellow stains from urine are slightly more noticeable. 1 point: Compared to one month ago, urine scale and yellow stains from urine are more noticeable.

[0093] <Sustained effectiveness test for inhibiting urinary stones and yellowing (2)> The hard surface cleaning agent compositions shown in Table 2 were filled into squeeze containers (Toilet Hyter containers, manufactured by Kao Corporation). On the first day of testing, (1) 10 mL of the hard surface cleaning agent composition was applied in liquid form to cover the entire inside of the bowl of a flush toilet, left for 5 minutes, and then flushed with water from the toilet's water tank. The test was conducted in the same manner as the sustained effect test for inhibiting urine scale and yellowing (1). The results are shown in Table 2.

[0094] <Sustained effectiveness test for inhibiting urinary stones and yellowing (3)> The hard surface cleaning agent compositions shown in Table 2 were filled into a pressurized discharge container (TA-F, manufactured by Yoshino Kogyosho Co., Ltd.). On the first day of testing, (1) 10 ml of the hard surface cleaning agent composition was applied in a foamy manner to cover the entire inside of the bowl of a flush toilet, left for 1 minute, and then flushed with water from the toilet's water tank. The test was conducted in the same manner as the sustained effect test for inhibiting urine scale and yellowing (1). The results are shown in Table 2.

[0095] [Table 1]

[0096] [Table 2]

Claims

1. A cleaning agent composition for hard surfaces, comprising the following components (a), (b), (c), and water, wherein the mass ratio (c) / [(a)+(b)] of the content of component (c) to the total content of components (a) and (b) is 0.005 or more and 0.3 or less. (a) Ingredients: Metal chelating agent (b) Component: Foaming surfactant (c) Component: Water-soluble polymer

2. (c) The hard surface cleaning agent composition according to claim 1, wherein component (c) is water-soluble modified cellulose.

3. (b) The hard surface cleaning agent composition according to claim 1, wherein component (b) is one or more selected from amine oxide type surfactants, betaine type surfactants, alkyl (poly) glucosides, alkyl glyceryl ethers, anionic surfactants, and cationic surfactants.

4. Furthermore, the hard surface cleaning agent composition according to claim 1 further contains a water-soluble solvent as component (d).

5. A hard surface cleaning agent composition according to claim 1, for use on the hard surface of a toilet.

6. A method for cleaning a hard surface, comprising bringing a hard surface cleaning agent composition according to any one of claims 1 to 5 into contact with the hard surface.

7. The method for cleaning a hard surface according to claim 6, wherein the cleaning agent composition for hard surfaces is left in contact with the hard surface for 30 seconds or more.

8. The method for cleaning a hard surface according to claim 6, wherein the cleaning agent composition for hard surfaces is applied to the hard surface as foam having a specific volume of 5 ml / g or more five minutes after foam formation.

9. A method for suppressing the occurrence of urine scale stains and yellow stains derived from urine on a hard surface, comprising bringing a hard surface cleaning agent composition according to any one of claims 1 to 5 into contact with the hard surface.

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