TW202204588A - Detergent composition for hard surfaces - Google Patents

Abstract

The present invention is a detergent composition for hard surfaces containing a metal sequestering agent, a surfactant, and water, wherein: the metal sequestering agent contains (a) a carboxylic acid-type metal sequestering agent ('component (a)' below) and (b) one or more types of metal sequestering agents ('component (b)' below) selected from phosphonic acid-type metal sequestering agents and phosphoric acid-type metal sequestering agents, and (a)/(b), which is the mass ratio of the content of component (a) and the content of component (b), is 0.20 to 40, inclusive; and the surfactant contains (c) a cationic surfactant ('component (c)' below), and the portion of content of component (c) relative to the total content of the surfactant is 20 mass% to 100 mass%, inclusive.

Description

Cleaner compositions for hard surfaces

The present invention relates to a cleaning composition for hard surfaces and a method for cleaning hard surfaces.

There are various hard surfaces made of ceramic tiles, plastics, metals, etc. in the living environment equipment around us, and these hard surfaces are exposed to various stains in the living scene. Among them, the hard surfaces used in bathrooms, kitchens, etc. are also surfaces that people touch on a daily basis. Therefore, they are easy to remain and accumulate a lot of stains, which are difficult to clean and remove. Generally speaking, as bathroom cleaners used in bathrooms such as bathtubs, bathroom walls and floors, detergents containing surfactants, solvents, metal ion chelating agents, etc. are used to remove metal soaps, especially calcium salts of fatty acids. stains. Also, in bathrooms or kitchens, the silicic acid contained in the water aggregates and accumulates on hard surfaces, depositing in scaly patterns, forming scale stains. This limescale stain is also known to be a very difficult stain to remove.

Japanese Patent Laid-Open No. 11-256198 describes a liquid detergent composition containing a specific glycerol ether, a cationic surfactant, a builder, and water under predetermined conditions. Japanese Patent Laid-Open No. 2003-183698 describes a bathroom cleaning composition containing at least a surfactant, a chelating agent, a polymer compound, a solvent and a fragrance. Japanese Patent Laid-Open No. 2019-48963 describes a liquid cleaning composition for hard surfaces, which contains 0.2% by mass to 10% by mass of (a) selected from a phosphonic acid-based chelating agent and a phosphoric acid-based chelating agent One or more, 0% by mass to 10% by mass (b) chelating agents other than (a), (c) surfactants and water, and the viscosity at 25°C exceeds 6 mPa·s and is 1000 mPa·s s or less, the liquid cleaning composition for hard surfaces is used for cleaning in contact with hard surfaces and standing for more than 1 minute. Japanese Patent Laid-Open No. 61-283697 discloses a bathroom cleaning composition containing predetermined amounts of a cationic surfactant, a nonionic surfactant, and a water-soluble solvent, respectively. Japanese Patent Laid-Open No. 10-204480 describes a liquid cleaning composition for kitchen surroundings, which contains (a) 0.01 to 10% by weight of a cationic surfactant, (b) 1 to 20% by weight of a metal chelating agent, (c) 0.5-10 weight% of water-soluble solvent and (d) 0.01-3 weight% of thickening polysaccharides, and pH is 6-8.

The present invention provides a cleaning composition for hard surfaces that exhibits excellent cleaning power on both soap scum stains and limescale stains.

The present invention relates to a cleaning composition for hard surfaces, which contains a metal chelating agent, a surfactant and water, and The metal chelating agent contains (a) a carboxylic acid type metal chelating agent [hereinafter referred to as (a) component], and (b) at least one metal selected from the group consisting of a phosphonic acid type metal chelating agent and a phosphoric acid type metal chelating agent A chelating agent [hereinafter referred to as (b) ingredient], The mass ratio of the content of the component (a) to the content of the component (b), that is, (a)/(b) is 0.20 or more and 40 or less, As the surfactant, it contains (c) a cationic surfactant [hereinafter referred to as (c) component], The ratio of the content of the component (c) to the total content of the surfactant is 20% by mass or more and 100% by mass or less.

Furthermore, the present invention relates to a method for cleaning a hard surface, comprising contacting the above-mentioned cleaning composition for a hard surface of the present invention with a hard surface for a predetermined time, and then washing the hard surface with water.

According to the present invention, there is provided a cleaning composition for hard surfaces which exhibits excellent cleaning power against both soap scum stains and limescale stains.

In the present invention, by combining the two metal chelating agents of (a) component and (b) component with (c) component, the ratio of (c) component in the surfactant is used so that the ratio of the (c) component becomes a specific amount ratio. , which more effectively removes both soap scum stains and limescale stains. Although the details of the mechanism of the effect of the present invention are unknown, it is presumed as follows: (c) Component weakens the bond between Ca and fatty acid ions in soap scum stains, and two metal chelating agents (a) and (b) are It works to capture Ca and help dissolve soap scum. Moreover, it is presumed that the reason for this is that the two metal chelating agents of (a) component and (b) component act on SiO ₂ of scale stains and contribute to dissolving the scale stains.

[Cleaner composition for hard surfaces] [Metal chelating agent] The cleaning composition for hard surfaces of this invention contains a metal chelating agent, and contains following (a) component and (b) component as a metal chelating agent.

<(a) Component> (a) Component is a carboxylic acid type metal chelating agent. The carboxylic acid type metal chelating agent may, for example, have one or more carboxyl groups and four or less carboxyl groups. Moreover, as a carboxylic acid type metal chelating agent, the carbon number of 3 or more and 9 or less can be mentioned. For example, as the component (a), one or more metal chelating agents selected from the group consisting of hydroxycarboxylic acid and its salt, and aminocarboxylic acid and its salt can be mentioned.

Examples of hydroxycarboxylic acids and salts thereof include citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, gluconic acid, diglycolic acid, oxydisuccinic acid, carboxymethylsuccinic acid, and carboxymethoxysuccinic acid. One or more of carboxymethyltartaric acid and its salts. Specifically, an alkali metal salt, an ammonium salt, or an alkanolamine salt is mentioned as a salt.

From the viewpoint of cleaning power, the hydroxycarboxylic acid and its salt are preferably one selected from the group consisting of hydroxycarboxylic acids having 2 or more carbon atoms, further 3 or more, and 9 or less, and further 8 or less, and their salts. Above, more preferably at least one selected from the group consisting of citric acid, malic acid, and salts thereof.

Examples of aminocarboxylic acids and salts thereof include nitrotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, hydroxyethylenediamineacetic acid, diethylenetriaminepentaacetic acid, and glycol ether diacetic acid. One or more of amine tetraacetic acid, hydroxyethylimino diacetic acid, beetleic acid and salts thereof. Specifically, an alkali metal salt, an ammonium salt, or an alkanolamine salt is mentioned as a salt.

From the viewpoint of cleaning power, the component (a) is preferably a polyvalent carboxylic acid type metal chelating agent having 2 or more and 4 or less carboxyl groups. More preferably, it is one or more metal chelating agents selected from the group consisting of hydroxy polycarboxylic acid and its salt, and amino polycarboxylic acid and its salt. In addition, from the viewpoint of cleaning power, the component (a) is preferably at least one selected from hydroxycarboxylic acids having 3 to 8 carbon atoms and their salts, and more preferably selected from citric acid, malic acid and their salts. One or more of such salts, more preferably citric acid or a salt thereof.

<(b) Component> The component (b) is one or more metal chelating agents selected from the group consisting of phosphonic acid-type metal chelating agents and phosphoric acid-type metal chelating agents.

The phosphonic acid-type metal chelating agent may, for example, be selected from the group consisting of ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, and ethane-1-hydroxy-1,1-diphosphine acid, ethanehydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, aminopoly(methylenephosphonic acid), One or more of phosphonic acids such as polyethylene polyamine poly(methylene phosphonic acid) and salts thereof. Examples of the salt include alkali metal salts such as sodium and potassium; ammonium salts; and alkanolamine salts such as monoethanolamine and triethanolamine. Preferred are hydroxyphosphonic acids such as ethane-1-hydroxy-1,1-diphosphonic acid and salts thereof.

The phosphoric acid-type metal chelating agent may, for example, be one or more selected from the group consisting of orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid, hexametaphosphoric acid, and salts thereof.

From the viewpoint of cleaning power, the component (b) is preferably a phosphonic acid-type metal chelating agent, more preferably one or more selected from hydroxyphosphonic acid and salts thereof, and more preferably ethane-1-hydroxy- 1,1-bisphosphonic acid or a salt thereof.

[surfactant] The cleaning composition for hard surfaces of this invention contains a surfactant, and contains following (c) component as a surfactant.

<(c) Ingredient> (c) Component is a cationic surfactant. The cationic surfactant is preferably a mono-long-chain alkyl type quaternary ammonium salt. The component (c) is preferably a cationic surfactant having sterilization properties. The cationic surfactant is preferably one or more cationic surfactants selected from the group consisting of the compound represented by the following general formula (c1) and the compound represented by the general formula (c2), and more preferably selected from the group consisting of the general formula (c2). (c2) One or more cationic surfactants among the compounds represented by (c2).

[hua 1]

[In the formula, R ^1c represents a long-chain alkyl group, a long-chain alkenyl group or a long-chain hydroxyalkyl group having 8 to 16 carbon atoms, and R ^2c , R ^3c and R ^4c are the same or different, and each represents a carbon number of 1 or more and 3 or less The alkyl group, the hydroxyalkyl group with 1 to 3 carbon atoms, or the polyoxyethylene group with the average added molar number of 10 or less, Y ^- represents a halogen atom, or a sulfonate or sulfuric acid with 1 to 5 carbon atoms. Anionic residue of ester] In the general formula (c1), R ^1c is preferably a straight-chain alkyl group having 8 or more carbon atoms, preferably 12 or less, more preferably 10 or less, R ^2c , R ^3c , R ^4c is preferably methyl or ethyl, respectively, more preferably methyl. Y ^- is preferably a halide ion, more preferably a chloride ion (Cl ^- ).

[hua 2]

[In the formula, R ^5c represents a long-chain alkyl group, a long-chain alkenyl group or a long-chain hydroxyalkyl group with a carbon number of 8 to 16, and R ^6c and R ^7c are the same or different, and represent an alkyl group with a carbon number of 1 to 3 or less, respectively , a hydroxyalkyl group with 1 to 3 carbon atoms, or a polyoxyethylene group with an average added molar number of 10 or less, and R ^8c represents an alkylene group with 1 to 3 carbon atoms. Z ^- represents a halogen atom, or an anionic residue of a sulfonic acid ester or a sulfate ester having 1 to 5 carbon atoms.] In the general formula (c2), R ^5c is preferably a straight-chain alkyl group having 8 to 14 carbon atoms, R ^6c and R ^7c are each preferably a methyl group, and R ^8c is preferably a methylene group. Z ^- is preferably a halide ion, more preferably a chloride ion (Cl ^- ). In the present invention, the general formula (c2) is preferred from the viewpoint of cleaning power, especially soap scum stain cleaning power.

[Composition, other ingredients, etc.] The cleaning composition for hard surfaces of the present invention is a composition for hard surfaces containing a metal chelating agent and a surfactant, and as a metal chelating agent, it contains (a) component and (b) component, and the content of (a) component is the same as (b) The mass ratio of the content of the component (a)/(b) is 0.20 or more and 40 or less, and the surfactant contains the (c) component, and the ratio of the content of the (c) component to the total content of the surfactant It is 20 mass % or more and 100 mass % or less.

From the viewpoint of high cleaning power, the cleaning composition for hard surfaces of the present invention preferably contains more than 0 mass %, more preferably 0.2 mass % or more, preferably 8 mass % or less, more preferably 7 mass % % or less of (a) component. In addition, in this invention, the quantity of (a) component uses the acid form conversion value.

From the viewpoint of cleaning power, the cleaning composition for hard surfaces of the present invention preferably contains 0.3 mass % or more, more preferably 0.4 mass % or more, and preferably 8 mass % or less, more preferably 6 mass % The following (b) component. In addition, in this invention, the quantity of (b) component uses the acid form conversion value.

Regarding the cleaning composition for hard surfaces of the present invention, from the viewpoint of cleaning power, the mass ratio of the content of the component (a) to the content of the component (b), that is, (a)/(b), is preferably 0.20 or more. 0.30 or more, more preferably 0.50 or more, still more preferably 0.80 or more, still more preferably 1.0 or more, and 40 or less, preferably 30 or less, more preferably 25 or less, still more preferably 10 or less, and still more Preferably it is 8 or less, More preferably, it is 5 or less, More preferably, it is 4 or less.

Regarding the cleaning composition for hard surfaces of the present invention, from the viewpoint of cleaning power, the ratio of the content of the component (c) to the total content of the surfactant is 20 mass % or more, preferably 30 mass % or more, More preferably 35 mass % or more, still more preferably 40 mass % or more, still more preferably 45 mass % or more, still more preferably 50 mass % or more, still more preferably 60 mass % or more, and 100 mass % or less , preferably 95 mass % or less, more preferably 90 mass % or less. Here, the total content of the surfactant is the total content of the (c) component, the following (d) component, (e) component, and other surfactants.

The cleaning composition for hard surfaces of this invention may further contain (d) an amphoteric surfactant [henceforth (d) component] as a surfactant.

As the amphoteric surfactant as the component (d), at least one amphoteric surfactant selected from the group consisting of amine oxides, sulfobetaines and carbonyl betaines may, for example, be mentioned. The (d) component is preferably carbonyl betaine. It is preferable that the cleaning composition for hard surfaces of this invention contains carbonyl betaine as (d) component.

The amine oxide is preferably a compound of the following general formula (d1).

[hua 3]

[In the formula, R ^1d represents a hydrocarbon group with 8 to 22 carbon atoms, preferably an alkyl group or an alkenyl group, more preferably an alkyl group, R ^2d and R ^3d are the same or different, and represent an alkyl group with 1 to 3 carbon atoms . D represents a -NHC(=O)- group or a -C(=O)NH- group, and E represents an alkylene group having 1 to 5 carbon atoms. m and p denote m=0 and p=0 or m=1 and p=1]

In the above general formula (d1), R ^1d is preferably an alkyl group having 10 to 18 carbon atoms, more preferably an alkyl group having 12 to 16 carbon atoms, from the viewpoint of cleaning power to solid fats and oils, and further It is preferably an alkyl group having 12 or more carbon atoms and 14 or less carbon atoms, and more preferably an alkyl group having 12 carbon atoms. From the viewpoint of cleaning power, R ^2d and R ^3d are each preferably a methyl group having 1 carbon atoms.

Examples of sulfobetaines include N-alkyl-N,N-dimethyl-N-sulfonic acid having an alkyl group of preferably 10 or more, preferably 18 or less, and more preferably 14 or less carbon atoms. Propylammonium sulfobetaine; N-alkyl-N,N-dimethyl-N-(2-alkyl-N,N-dimethyl-N-(2- Hydroxysulfopropyl) ammonium sulfobetaine; the carbon number of the alkanoyl group is preferably 10 or more, preferably 18 or less, more preferably 14 or less N-alkanoylaminopropyl-N,N- Dimethyl-N-sulfopropylammonium sulfobetaine; N-Alkylaminopropyl- N,N-Dimethyl-N-(2-hydroxysulfopropyl)ammonium sulfobetaine.

Examples of carbonyl betaine include: N-alkyl-N,N-dimethyl-N-carboxymethyl, preferably the carbon number of the alkyl group is 10 or more, preferably 18 or less, more preferably 14 or less Ammonium betaine; a compound represented by the following general formula (d2). From the viewpoint of cleaning power, a compound represented by the following general formula (d2) is preferred.

[hua 4]

[In the formula, R ^4d represents an alkyl group or an alkenyl group having 7 to 21 carbon atoms, and R ^5d and R ^6d each independently represent an alkyl group having 1 to 3 carbon atoms.]

In the general formula (d2), R ^4d is preferably 9 or more, more preferably 11 or more, and preferably 15 or less, more preferably 13 or less alkyl or alkenyl, preferably nonyl, decyl, Undecyl, dodecyl, tridecyl. In the general formula (d2), R ^5d and R ^6d are each independently preferably a methyl group.

From the viewpoint of cleaning power, the cleaning composition for hard surfaces of the present invention preferably contains 0.01 mass % or more, more preferably 0.05 mass % or more, still more preferably 0.1 mass % or more, and preferably 5 mass % % or less, more preferably 3 mass % or less, and still more preferably 2 mass % or less of the component (d).

When the cleaning composition for hard surfaces of the present invention contains the component (d), the quality of the content of the component (c) and the content of the component (d) from the viewpoint of the cleaning power of soap scum and the cleaning power of scale and stains The ratio (c)/(d) is preferably 0.2 or more, more preferably 0.4 or more, still more preferably 0.6 or more, still more preferably 1.0 or more, and preferably 20 or less, more preferably 15 or less.

The cleaning composition for hard surfaces of the present invention may contain (e) an anionic surfactant [hereinafter referred to as (e) component], but since there is a possibility of impairing the effect of (c) component, it is considered from the viewpoint of cleaning power. In other words, the content is preferably less. In this invention, 50 mass % or less is preferable with respect to content of (c) component, 30 mass % or less is more preferable, and 20 mass % or less is still more preferable. This ratio may be 0 mass %, that is, the cleaning composition for hard surfaces of this invention may not contain (e) component.

Here, the anionic surfactant system as the component (e) is usually used by the industry, for example, a hydrocarbon group having a carbon number of 7 or more and 22 or less, and a sulfate group, a phosphate group, a phosphonic acid group, a sulfonic acid group, or Carboxyl anionic surfactant.

Specifically, the anionic surfactants are alkyl benzene sulfonates, alkane sulfonates, alkyl sulfate ester salts, polyoxyethylene alkyl ether sulfate ester salts, α-olefin sulfonates, α-sulfo fatty acid methyl esters Ester salt, polyoxyethylene alkyl (or alkenyl) ether carboxylate, polyoxyethylene amide alkyl (or alkenyl) ether carboxylate, fatty acid salt, alkyl phosphate ester salt, polyoxyethylene alkyl ether Phosphate salts and the like include salts such as alkali metal salts such as sodium and potassium; inorganic salts such as ammonium salts and magnesium salts; and organic salts such as monoethanolammonium, diethanolammonium, and triethanolammonium.

In the cleaning composition for hard surfaces of the present invention, from the viewpoint of cleaning power, the content of the anionic surfactant is preferably 3 mass % or less, more preferably 2 mass % or less, and still more preferably 1 mass % Hereinafter, it is more preferably 0.5 mass % or less, still more preferably 0.1 mass % or less, and preferably 0 mass % or more, or may be 0 mass %. In addition, in this invention, the quantity of an anionic surfactant uses the acid type conversion value.

In the cleaning composition for hard surfaces of the present invention, the content of the surfactant is preferably 0.1 mass % or more, more preferably 0.2 mass % or more, more preferably 0.5 mass % or more, and still more preferably 1.0 mass % It is more than or equal to 8 mass % or less, More preferably, it is 7 mass % or less, More preferably, it is 5 mass % or less, More preferably, it is 4.5 mass % or less. The content of the surfactant is the total content of the (c) component, (d) component, (e) component and other surfactants other than these. As other surfactants other than (c) component, (d) component, and (e) component, nonionic surfactants, such as polyoxyalkylene alkyl ether, are mentioned.

The cleaning composition for hard surfaces of this invention may further contain (f) a water-soluble solvent [henceforth (f) component]. The water-soluble solvent is preferably a water-soluble organic solvent having a carbon number of preferably 2 or more, more preferably 3 or more, and preferably 10 or less, more preferably 8 or less. Propanol, Ethylene Glycol, Propylene Glycol, Diethylene Glycol, Dipropylene Glycol, Glycerin, Isopentyl Glycol, Propylene Glycol Monomethyl Ether, Propylene Glycol Monoethyl Ether, 3-Methyl-3-Methoxybutanol, Benzyl Alcohol, Benzene One or more water-soluble organic solvents among oxyethanol, phenylethylene glycol, phenoxyisopropanol, diethylene glycol butyl ether (diethylene glycol monobutyl ether), dibutylene glycol and benzyl alcohol. Among them, at least one water-soluble organic solvent selected from benzyl alcohol, diethylene glycol butyl ether, ethanol, and propylene glycol is more preferable. Here, the water-soluble organic solvent refers to a solvent having an octanol/water partition coefficient (LogPow) of 3.5 or less.

When the cleaning composition for hard surfaces of the present invention contains the component (f), the composition contains preferably 0.2 mass % or more, more preferably 0.5 mass % or more, and preferably 8 mass % or less, more Preferably it is 5 mass % or less of (f) component.

The cleaning composition for hard surfaces of the present invention may contain (g) a tackifier [hereinafter referred to as (g) component] from the viewpoint of improving the cleaning power on hard surfaces such as vertical surfaces that are difficult to stay on. The tackifier is preferably at least one selected from bentonite-type clay minerals, natural polymers, and synthetic polymers, and more preferably selected from nonionic polysaccharides, natural polymers, and synthetic polymers One or more of these, more preferably one or more selected from nonionic polysaccharides. Specifically, it is preferably at least one selected from the group consisting of hydroxyethyl cellulose, Sanxianjiao and polyvinylpyrrolidone, and more preferably hydroxyethyl cellulose.

When the cleaning composition for hard surfaces of the present invention contains (g) component, the composition contains preferably 0.05 mass % or more, more preferably 0.1 mass % or more, and preferably 3 mass % or less, more Preferably it is 2 mass % or less of (g) component.

From the viewpoint of cleaning power, the pH of the cleaning composition for hard surfaces of the present invention at 25° C. is preferably 6 or more, more preferably 6.5 or more, further preferably 6.8 or more, and preferably 9.5 or less, More preferably, it is 9 or less, and still more preferably 8.5 or less.

The cleaning composition for hard surfaces of this invention contains water. The cleaning composition for hard surfaces of the present invention contains preferably 80% by mass or more, more preferably 85% by mass or more, preferably 95% by mass or less, more preferably 93% by mass or less of water.

From the viewpoint of improving the cleaning power on hard surfaces that are difficult to stay on, such as vertical surfaces, the cleaning composition for hard surfaces of the present invention may contain a tackifier as a component (g), and the cleaning composition for hard surfaces of the present invention The viscosity at 25°C is preferably 10 mPa·s or more and 450 mPa·s or less. The viscosity is the value measured after 1 minute at 60 rpm using a B-type rotational viscometer using an appropriate rotor.

In the cleaning composition for hard surfaces of the present invention, fragrances, pigments, preservatives, antioxidants, etc. can be arbitrarily formulated to increase the added value of the product.

The hard surface which is the object of the cleaning composition for hard surfaces of the present invention may be a hard surface of ceramic tile, glass, stainless steel, plastic or ceramics. The cleaning composition for hard surfaces of the present invention is suitable for cleaning hard surfaces such as bathrooms, bathtubs, washbasins, tiles, powder rooms, washbasins, mirrors, sinks around kitchens, countertops, and around water pipes. The cleaning composition for hard surfaces of the present invention is suitable for use in bathrooms. Here, bathroom use refers not only to bathrooms, but also to other hard-surfaced items that exist in bathrooms, such as bathtubs and washbasins. The present invention preferably targets a hard surface to which scale stains and soap scum stains are attached.

[Cleaning method of hard surface] According to the present invention, there is provided a method for cleaning a hard surface, wherein the hard surface cleaning agent composition of the present invention is brought into contact with the hard surface for a predetermined time, and then the hard surface is washed with water. Further, according to the present invention, there is provided a method for removing scale stains and soap scum stains, wherein the hard surface cleaning composition of the present invention is brought into contact with a hard surface for a predetermined time, and then the hard surface is washed with water. That is, to provide a method for removing scale stains and soap scum stains on hard surfaces, wherein the hard surface cleaning composition of the present invention is brought into contact with the hard surfaces to which the scale stains and soap scum stains are attached for a predetermined period of time, followed by washing with water hard surface. In these methods, the matters described in the cleaning composition for hard surfaces of the present invention can be appropriately applied. The preferred form of the composition is also the same as the above-mentioned cleaning composition for hard surfaces of the present invention.

Specifically, the cleaning method of the present invention is preferably a cleaning method in which the above-mentioned cleaning agent composition for hard surfaces is brought into contact with the hard surface as a stock solution, or the cleaning agent composition for hard surfaces is not diluted with a stock solution. Hard surface contact means contacting the hard surface without diluting the above-mentioned cleaning composition for hard surfaces. Furthermore, the cleaning method of making it contact with the hard surface to which the limescale stain|pollution|contamination and the soap scum stain|pollution|contamination adhered without diluting the said hard surface cleaning composition for a hard surface can be mentioned. Furthermore, as a method of contacting with a hard surface, the method of coating on a hard surface is preferable.

The fact that the above-mentioned cleaning composition for hard surfaces is not diluted and brought into contact with a hard surface means that the cleaning composition is not intentionally diluted with water or the like and then brought into contact with a hard surface. For example, when the above-mentioned cleaning composition for hard surfaces is brought into contact with a hard surface to which water droplets or the like are attached, or when water droplets are attached to a hard surface after the above-mentioned cleaning composition for hard surfaces is brought into contact with a hard surface, it can be understood that it is incorrect. The above-mentioned cleaning composition for hard surfaces is diluted and brought into contact with the hard surfaces.

In this invention, for example, the undiluted|stock solution of the said cleaning composition for hard surfaces is made to adhere to a hard surface as it is, without changing a composition. For example, the above-mentioned cleaning composition for hard surfaces is not attached to a water-containing absorbent cotton, but is brought into contact with a hard surface to which scale stains and soap scum stains are attached. The composition of the above-mentioned cleaning composition for hard surfaces can be changed after contact with the hard surface. That is, the composition of the above-mentioned cleaning composition for hard surfaces may be diluted or concentrated after contact with the hard surface.

In the cleaning method of this invention, in order to make the said hard surface cleaning agent composition contact with a hard surface as a stock solution, it can apply|coat directly from a bottle. As a bottle, a squeeze bottle etc. are mentioned, for example.

In the present invention, a thick composition containing the components (a), (b), and (c) of the present invention can be prepared in advance, and the thick composition can be diluted with water to prepare the hard surface cleaning agent combination of the present invention. object so that it comes into contact with hard surfaces. That is, it can be a method for cleaning hard surfaces as follows: dilute the thick composition containing the components (a), (b), and (c) of the present invention with water to prepare the cleaning composition for hard surfaces of the present invention. The hard surface cleaning composition is diluted and brought into contact with the hard surface.

From the viewpoint of cleaning power, the time for allowing the cleaning composition for hard surfaces of the present invention to be in contact with hard surfaces is preferably 1 minute or more, preferably 2 minutes or more, more preferably 3 minutes or more, and more It is preferably more than 3 minutes, more preferably 4 minutes or more, more preferably 5 minutes or more, and from the viewpoint of efficient cleaning, preferably 60 minutes or less, more preferably 30 minutes or less, still more preferably It is 15 minutes or less, and more preferably 10 minutes or less. The temperature at the time of standing may be room temperature, for example, 10°C or more and 30°C or less.

Moreover, in this invention, the hard surface can be cleaned by the cleaning article which carries the cleaning agent composition for hard surfaces of this invention on a base|substrate. As an example, the following method for cleaning a hard surface is provided: after applying the cleaning composition for a hard surface of the present invention to a hard surface, it is left to stand for a predetermined time, and then wipe-cleaned. For wiping cleaning, dishcloths, rags, non-woven cloths, etc. are preferably used to remove the composition applied to the hard surface from the hard surface.

Moreover, the cleaning composition for hard surfaces of this invention can also be used as a cleaning product by impregnating a base. The cleaning article in which the hard surface cleaning agent composition of the present invention is impregnated in the substrate is preferable from the viewpoint of the workability of the cleaning operation.

The substrate used for the cleaning article impregnated with the cleaning composition for hard surfaces is flexible, can be impregnated with the cleaning composition for hard surfaces, and has sufficient strength during use without generating chips or the like. It is preferable to use a substrate that can be impregnated with the following amount of the cleaning composition for hard surfaces without a load.

As such a substrate, a fibrous structure including a fibrous material, such as various kinds of paper, nonwoven fabric, woven fabric, or woven fabric, can be exemplified. As a fibrous material which comprises these fibrous structures, a cellulose type fiber, a modified cellulose type fiber, a synthetic fiber, a mixture of 2 or more types of these, etc. are mentioned, for example.

Moreover, the porous structure (for example, a sponge-like structure) obtained by disperse|distributing air bubbles in resin can also be used as the said base|substrate.

Moreover, the cleaning method of wiping off a hard surface using the cleaning product impregnated with the cleaning agent composition for hard surfaces of this invention is suitable for easy cleaning of a hard surface from a viewpoint of the workability|operativity of a cleaning operation. The cleaning product impregnated with the cleaning composition for hard surfaces may be any of those formed by impregnating a base with the cleaning composition beforehand, or those formed by impregnating a dry base with the cleaning composition for hard surfaces immediately before use. In addition, the cleaning article impregnated with the cleaning composition for hard surfaces may be attached to a mop-like cleaning tool and used, or may be directly held by hand and used for wiping and cleaning.

In the case of pre-impregnating the cleaning composition for hard surfaces, from the viewpoint of cleaning properties, the amount of the cleaning composition for hard surfaces is relative to the mass of the substrate [that is, the quality standard of the substrate in an unimpregnated state (dry state)]. The impregnation ratio is preferably 100 mass % or more, more preferably 150 mass % or more, and preferably 1000 mass % or less, more preferably 400 mass % or less, and still more preferably 350 mass % or less. When the impregnation ratio is 100 mass % or more, sufficient cleaning power can be obtained. If the impregnation ratio is 1000 mass % or less, the release amount of the cleaning composition for hard surfaces to the surface to be cleaned will be appropriate, no stains or dust will remain on the surface to be cleaned, and it can be used for various materials including wood-based materials without any influence. The clean side of the material. From the viewpoint of further improving the cleaning performance, when the substrate is a sheet, from the viewpoints of the retention of the cleaning composition for hard surfaces required for cleaning a certain area, and the workability or cost of the sheet, The basis weight before impregnation with the cleaning composition for hard surfaces is, for example, preferably 40 g/m ² or more, more preferably 50 g/m ² or more, and preferably 200 g/m ² or less, more preferably 150 g/m m ² or less.

When using the cleaning product impregnated with the cleaning agent composition for hard surfaces, the cleaning agent composition for hard surfaces of the present invention can be separately sprayed on the object to be cleaned or the cleaning materials mentioned above and used. By using this method, a larger area can be cleaned.

In the present invention, the cleaning composition for a hard surface of the present invention is allowed to contact a hard surface for a predetermined time, and then it is cleaned if necessary, and then the hard surface is washed with water. When washing, external force (physical force) such as hand washing may be applied, or only water flow may be used for washing.

[Form of the present invention] Embodiments of the present invention are exemplified below. In these forms, the matters described in the cleaning composition for hard surfaces of the present invention and the cleaning method for hard surfaces can be appropriately applied. In addition, the matters described in each form can be appropriately applied to each other. In addition, this invention is not limited to these forms.

<1> A cleaning composition for hard surfaces, comprising a metal chelating agent, a surfactant and water, and The metal chelating agent contains (a) a carboxylic acid type metal chelating agent [hereinafter referred to as (a) component], and (b) at least one metal selected from the group consisting of a phosphonic acid type metal chelating agent and a phosphoric acid type metal chelating agent A chelating agent [hereinafter referred to as (b) ingredient], The mass ratio of the content of the component (a) to the content of the component (b), that is, (a)/(b) is 0.20 or more and 40 or less, As the surfactant, it contains (c) a cationic surfactant [hereinafter referred to as (c) component], The ratio of the content of the component (c) to the total content of the surfactant is 20% by mass or more and 100% by mass or less.

<2> The cleaning composition for hard surfaces as described in <1> wherein the component (a) is a polyvalent carboxylic acid type metal chelating agent having 2 or more and 4 or less carboxyl groups.

<3> The cleaning composition for hard surfaces as described in <1> or <2>, wherein the component (a) is at least one selected from the group consisting of hydroxycarboxylic acids having 3 to 8 carbon atoms and their salts, and further selected from One or more of citric acid, malic acid, and salts thereof, and further citric acid or a salt thereof.

<4> The cleaning composition for hard surfaces according to any one of <1> to <3>, which contains preferably more than 0 mass %, more preferably 0.2 mass % or more, and preferably 8 mass % or less, More preferably, it is 7 mass % or less of (a) component.

<5> The cleaning composition for hard surfaces according to any one of <1> to <4>, wherein the phosphonic acid-type metal chelating agent as the component (b) is selected from the group consisting of ethane-1,1-diphosphonic acid, Ethane-1,1,2-triphosphonic acid, Ethane-1-hydroxy-1,1-diphosphonic acid, Ethane-1,1,2-triphosphonic acid, Ethane-1,2-diphosphonic acid One or more of carboxyl-1,2-diphosphonic acid, methanehydroxyphosphonic acid, amino poly(methylenephosphonic acid), polyethylene polyamine poly(methylenephosphonic acid), and salts thereof.

<6> The cleaning composition for hard surfaces according to any one of <1> to <5>, which contains preferably 0.3 mass % or more, more preferably 0.4 mass % or more, and preferably 8 mass % or less, More preferably, it is 6 mass % or less of (b) component.

<7> The cleaning composition for hard surfaces according to any one of <1> to <6>, wherein the component (c) is selected from the group consisting of compounds represented by the following general formula (c1) and general formula (c2) One or more cationic surfactants in the compound.

[hua 5]

[In the formula, R ^1c represents a long-chain alkyl group, a long-chain alkenyl group or a long-chain hydroxyalkyl group having 8 to 16 carbon atoms, and R ^2c , R ^3c and R ^4c are the same or different, and each represents a carbon number of 1 or more and 3 or less The alkyl group, the hydroxyalkyl group with 1 to 3 carbon atoms, or the polyoxyethylene group with the average added molar number of 10 or less, Y ^- represents a halogen atom, or a sulfonate or sulfuric acid with 1 to 5 carbon atoms. anionic residue of ester]

[hua 6]

[In the formula, R ^5c represents a long-chain alkyl group, a long-chain alkenyl group or a long-chain hydroxyalkyl group with a carbon number of 8 to 16, and R ^6c and R ^7c are the same or different, and represent an alkyl group with a carbon number of 1 to 3 or less, respectively , a hydroxyalkyl group with 1 to 3 carbon atoms, or a polyoxyethylene group with an average added molar number of 10 or less, and R ^8c represents an alkylene group with 1 to 3 carbon atoms. Z ^- represents a halogen atom, or an anionic residue of a sulfonic acid ester or a sulfuric acid ester having 1 to 5 carbon atoms]

<8> The cleaning composition for hard surfaces as described in any one of <1> to <7> which further contains (d) an amphoteric surfactant [hereinafter referred to as (d) component] as a surfactant.

<9> The cleaning composition for hard surfaces as described in <8>, wherein the component (d) is at least one selected from the group consisting of compounds represented by the following general formula (d1) and compounds represented by the following general formula (d2). The amphoteric surfactant.

[hua 7]

[In the formula, R ^1d represents a hydrocarbon group with 8 to 22 carbon atoms, preferably an alkyl group or an alkenyl group, more preferably an alkyl group, R ^2d and R ^3d are the same or different, and represent an alkyl group with 1 to 3 carbon atoms . D represents a -NHC(=O)- group or a -C(=O)NH- group, and E represents an alkylene group having 1 to 5 carbon atoms. m and p denote m=0 and p=0 or m=1 and p=1]

[hua 8]

[In the formula, R ^4d represents an alkyl group or an alkenyl group having 7 to 21 carbon atoms, and R ^5d and R ^6d each independently represent an alkyl group having 1 to 3 carbon atoms.]

<10> The cleaning composition for hard surfaces as described in <8> or <9>, which contains preferably 0.01 mass % or more, more preferably 0.05 mass % or more, still more preferably 0.1 mass % or more, and preferably 5 mass % or less, More preferably, it is 3 mass % or less, More preferably, it is the (d) component of 2 mass % or less.

<11> The cleaning composition for hard surfaces as described in any one of <8> to <10>, wherein the mass ratio of the content of the (c) component to the content of the (d) component, that is, (c)/(d) is preferred It is 0.2 or more, more preferably 0.4 or more, still more preferably 0.6 or more, still more preferably 1.0 or more, and preferably 20 or less, more preferably 15 or less.

<12> The cleaning composition for hard surfaces as described in any one of <1> to <11>, wherein the surfactant optionally contains (e) an anionic surfactant [hereinafter referred to as (e) component], and ( The content of the component e) is 50 mass % or less with respect to the content of the component (c).

<13> The cleaning composition for hard surfaces as described in <12>, wherein the content of the component (e) is preferably 3 mass % or less, more preferably 2 mass % or less, still more preferably 1 mass % or less, still more preferably It is 0.5 mass % or less, more preferably 0.1 mass % or less, and preferably 0 mass % or more, or 0 mass %.

<14> The cleaning composition for hard surfaces according to any one of <1> to <13>, wherein the content of the surfactant is preferably 0.1 mass % or more, more preferably 0.2 mass % or more, and still more preferably 0.5 mass % or more The mass % or more is more preferably 1.0 mass % or more, and is preferably 8 mass % or less, more preferably 7 mass % or less, still more preferably 5 mass % or less, and still more preferably 4.5 mass % or less.

<15> The cleaning composition for hard surfaces as described in any one of <1> to <14> which further contains (f) water-soluble solvent [henceforth (f) component].

<16> The cleaning composition for hard surfaces as described in <14>, wherein the component (f) is water-soluble with preferably 2 or more, more preferably 3 or more, preferably 10 or less, more preferably 8 or less carbon atoms. Organic solvents.

<17> The cleaning composition for hard surfaces as described in <15> or <16>, which contains preferably 0.2 mass % or more, more preferably 0.5 mass % or more, preferably 8 mass % or less, more preferably 5 mass % (f) component below mass %.

<18> The cleaning composition for hard surfaces as described in any one of <1> to <17> which further contains (g) a tackifier [henceforth (g) component].

<19> The cleaning composition for hard surfaces as described in <18>, which contains preferably 0.05 mass % or more, more preferably 0.1 mass % or more, preferably 3 mass % or less, more preferably 2 mass % or less (g) Ingredients.

<20> The cleaning composition for hard surfaces according to any one of <1> to <19>, wherein the hard surfaces are ceramic tiles, glass, stainless steel, plastic or ceramics.

<21> The cleaning composition for hard surfaces as described in any one of <1> to <20>, wherein the mass ratio of the content of the component (a) to the content of the component (b), that is, (a)/(b) is 0.20 more preferably 0.30 or more, more preferably 0.50 or more, still more preferably 0.80 or more, still more preferably 1.0 or more, and 40 or less, preferably 30 or less, more preferably 25 or less, still more preferably 10 Hereinafter, it is more preferably 8 or less, still more preferably 5 or less, and still more preferably 4 or less.

<22> The cleaning composition for hard surfaces according to any one of <1> to <21>, wherein the ratio of the content of the component (c) to the total content of the surfactants is 20% by mass or more, preferably 30% mass % or more, more preferably 35 mass % or more, still more preferably 40 mass % or more, still more preferably 45 mass % or more, still more preferably 50 mass % or more, still more preferably 60 mass % or more, and 100 mass % or less, preferably 95 mass % or less, more preferably 90 mass % or less.

<23> A method for cleaning a hard surface, comprising contacting the hard surface cleaning composition as described in any one of <1> to <22> with a hard surface for a predetermined time, and then washing the hard surface with water.

<24> The method for cleaning hard surfaces as described in <23>, wherein the predetermined time is 1 minute or more, preferably 2 minutes or more, more preferably 3 minutes or more, still more preferably more than 3 minutes, still more preferably 4 minutes or more , more preferably 5 minutes or more, more preferably 60 minutes or less, more preferably 30 minutes or less, still more preferably 15 minutes or less, and still more preferably 10 minutes or less.

<25> The method for cleaning a hard surface as described in <23> or <24>, wherein the hard surface is a hard surface to which scale stains and soap scum stains are attached.

Example The cleaning composition for hard surfaces shown in Tables 1-5 was prepared, and the following items were evaluated. The results are shown in Tables 1 to 5.

＜Cleaning power＞ (1) Evaluation method for cleaning power of soap scum stains (1-1) Production of model soap scum stains The cleaning power of model soap scum stains obtained by compounding soap and sebum was evaluated. The production method of the model soap scum stain is shown below. 90 mass % of solid soap (Kao White) and 10 mass % of model sebum stains were mixed at 50-60 degreeC, and it heat-retained, and the obtained solution was made into A solution. Furthermore, the composition of the model sebum stain was 40% by mass of linoleic acid, 20% by mass of oleic acid, 20% by mass of palmitic acid, 10% by mass of cholesterol, and 10% by mass of liquid paraffin. The calcium chloride solution with German hardness of 10゜dH was kept at 20-30°C, and the obtained solution was designated as B solution. On a polypropylene plate (50 mm × 100 mm × 2 mm), apply solution A as thinly and evenly as possible. After natural drying at 20-30 °C for 5 minutes, apply solution B as thinly and evenly as possible. Dry naturally at 20-30°C for 5 minutes. The operation of applying the A solution → natural drying → applying the B solution → natural drying was repeated 30 to 50 times to produce a model soap scum stain.

(1-2) Evaluation of soap scum cleaning power A Place the flat plate with the model soap scum stain made in (1-1) horizontally so that the surface with the stain becomes the upper surface, and add 1 drop (about 0.3 mL) to the model soap scum stain with a dropper. Each cleaning composition for hard surfaces was left to stand for the predetermined time described in the table, and then washed sufficiently with ion-exchanged water, and the cleaning power was judged according to the following criteria. As for the specific method, under the same photographing conditions such as brightness, the flat plate without stains, the flat plate before cleaning after applying the stain, and the flat plate after cleaning were photographed, and the gray scale of each plate was measured from the obtained images. Set the cleaning rate of the plate before stain cleaning as 0%, and set the plate without stain as 100%, and calculate the cleaning rate of the plate after cleaning. Image processing software ImageJ 1.47v was used for gray scale determination.

(1-3) Evaluation of soap scum cleaning power B Vertically stand the flat plate with the model soap scum stains made in (1-1) upright, apply 1 mL of each hard surface cleaning agent composition on the model soap scum stains with a dropper and leave it for 10 minutes, then use a dropper. The ion-exchanged water was sufficiently washed, and the cleaning power was judged according to the following criteria. Under the same photographing conditions such as brightness, the flat plate without stain, the plate before cleaning after applying the stain, and the plate after cleaning were photographed, and the gray scale of each plate was measured from the obtained images. Set the cleaning rate of the plate before stain cleaning as 0%, and set the plate without stain as 100%, and calculate the cleaning rate of the plate after cleaning. Image processing software ImageJ 1.47v was used for gray scale determination.

(2) Evaluation method for cleaning power of scale stains (2-1) Fabrication of model scale stains 0.3 mL of 300 ppm SiO ₂ /300 ppm CaCl ₂ aqueous solution was applied as uniformly as possible on a glass slide (76 mm × 26 mm ) at the lower 25 mm portion, dried on a hot plate heated to 140°C, and washed with ion-exchanged water. The operations of applying the solution and drying on the glass slide were repeated 3 times to make model scale stains.

(2-2) Scale and stain cleaning power evaluation A Place the glass slide with the scale stains on the model made in (2-1) horizontally so that the surface with the stains becomes the upper surface, and place a absorbent cotton (Cure) cut into the size of the scale stains on the slide glass. Let, 4 cm × 4 cm, manufactured by Kawamoto Sangyo Co., Ltd., dropwise add 1 mL of each cleaning composition for hard surfaces, leave it for the specified time in the table, and reciprocate 5 times with light force (about 200 g) re) wipe the entire slide. After that, the slide glass was sufficiently washed with ion-exchanged water, and then the cleaning power was judged according to the following criteria. Regarding the specific method of the evaluation criteria, under the same photographing conditions such as brightness, photograph the unstained glass slides, the stained glass slides before cleaning, and the cleaned glass slides. The image measures the gray scale of each slide. The cleaning rate of the glass slide before cleaning was set to 0%, and the cleaning rate of the unstained glass slide was set to 100%, and the cleaning rate of the plate after cleaning was calculated. Image processing software ImageJ 1.47v was used for gray scale determination.

(2-3) Scale and stain cleaning power evaluation B Vertically stand the glass slide with the model scale stains made in (2-1) upright, apply 1 mL of each hard surface cleaning agent composition on the model scale stains with a dropper and leave it for 10 minutes, then use Absorbent cotton (Cure Let, 4 cm x 4 cm, manufactured by Kawamoto Sangyo Co., Ltd.) was wiped back and forth 5 times with light force (about 200 g in weight) to wipe the contact portion of each detergent composition. Then, after sufficiently washing with ion-exchanged water, the cleaning power was judged according to the following criteria. Under the same photographing conditions such as brightness, photograph the unstained glass slides, the stained glass slides before cleaning, and the cleaned glass slides, and measure each glass slide from the obtained images. of grayscale. The cleaning rate of the glass slide before cleaning was set to 0%, and the cleaning rate of the unstained glass slide was set to 100%, and the cleaning rate of the plate after cleaning was calculated. Image processing software ImageJ 1.47v was used for gray scale determination.

<Adhesion> Apply 1 mL of each hard surface cleaning composition to the upper part of the vertically erected 15 cm ² tile, and after 5 seconds, measure the quality of the cleaning solution remaining on the tile, and measure the quality of the cleaning solution on the vertical surface according to the following standards. Adhesion was evaluated. : 0.80 g or more of cleaning solution remaining (more than 80% remaining) △: 0.5 g-0.79 g remaining cleaning solution (50%-79% remaining) ×: 0.49 g or less remaining cleaning solution (49% or less remaining) Also, The viscosity of the composition was measured after 1 minute at 60 rpm using a B-type rotational viscometer (at 25°C), and the obtained value is shown in the table. Furthermore, in the case of low viscosity, rotor No. 1 is used, and if necessary, rotor No. 2 or 3 is used so that it falls within the measurement range of viscosity.

[Table 1] Example 1-1 1-2 1-3 1-4 1-5 1-6 1-7 1-8 1-9 1-10 Liquid cleaner compositions for hard surfaces Compounding composition (mass %) (a) citric acid 5 5 5 5 5 5 5 5 5 Sodium EDTA 3 (b) Ethane-1-hydroxy-1,1-diphosphonic acid 2 2 2 2 2 2 2 2 2 2 Amino trimethylene phosphonic acid Tripolyphosphate Surfactant (c) benzyl octyl dimethyl ammonium chloride 0.3 0.5 0.6 0.8 1 1.3 1.4 1 1 1 Benzyldecyldimethylammonium chloride benzyl lauryl dimethyl ammonium chloride Octyltrimethylammonium chloride Decyltrimethylammonium chloride (d) Lauroaminopropyl Betaine 1.2 1.0 0.9 0.8 0.5 0.2 0.1 0.5 0.5 0.5 Lauryl Hydroxy Sultaine Lauryl Dimethylamine Oxide (e) Sodium alkyl ether sulfate Polyoxyethylene (7) alkyl ether (f) Diethylene glycol monobutyl ether 2 2 2 2 2 2 2 2 2 2 benzyl alcohol spices 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 sodium hydroxide 3.5 3.5 3.5 3.5 3.5 3.5 3.5 0.5 3.5 3.5 Ion exchanged water margin margin margin margin margin margin margin margin margin margin total 100 100 100 100 100 100 100 100 100 100 (a)/(b) (mass ratio) 2.5 2.5 2.5 2.5 2.5 2.5 2.5 1.5 2.5 2.5 Ratio (mass %) of (c) component in all surfactants 20 33 40 50 67 87 93 67 67 67 pH(25℃) 7 7 7 7 7 7 7 7 7 7 Putting time (minutes) 10 10 10 10 10 10 10 10 5 3 Soap scum cleaning power evaluation A (%) 70 80 80 90 95 95 95 95 85 80 Scale and stain cleaning power evaluation A (%) 80 85 85 90 90 90 90 90 80 75

[Table 2] Example 1-11 1-12 1-13 1-14 1-15 1-16 1-17 1-18 1-19 1-20 Liquid cleaner compositions for hard surfaces Compounding composition (mass %) (a) citric acid 5 5 5 5 5 5 5 5 5 5 Sodium EDTA (b) Ethane-1-hydroxy-1,1-diphosphonic acid 2 2 2 2 2 2 2 2 Amino trimethylene phosphonic acid 2 2 Tripolyphosphate Surfactant (c) benzyl octyl dimethyl ammonium chloride 1 2 3 1 1 Benzyldecyldimethylammonium chloride 1 1 1 1 1 benzyl lauryl dimethyl ammonium chloride Octyltrimethylammonium chloride Decyltrimethylammonium chloride (d) Lauroaminopropyl Betaine 0.5 1.0 1.5 0.5 0.5 0.5 Lauryl Hydroxy Sultaine 0.5 0.5 Lauryl Dimethylamine Oxide 0.5 0.5 (e) Sodium alkyl ether sulfate 0.4 Polyoxyethylene (7) alkyl ether 1 (f) Diethylene glycol monobutyl ether 2 2 2 2 2 2 2 2 2 2 benzyl alcohol spices 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 sodium hydroxide 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 Ion exchanged water margin margin margin margin margin margin margin margin margin margin total 100 100 100 100 100 100 100 100 100 100 (a)/(b) (mass ratio) 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Ratio (mass %) of (c) component in all surfactants 67 67 67 40 67 67 67 53 67 67 pH(25℃) 7 7 7 7 7 7 7 7 7 7 Putting time (minutes) 2 5 5 10 10 10 10 10 10 10 Soap scum cleaning power evaluation A (%) 75 90 95 70 95 95 85 80 95 95 Scale and stain cleaning power evaluation A (%) 70 80 80 80 90 90 90 85 90 90

[table 3] Example Comparative example 1-21 1-22 1-23 1-24 1-25 1-26 1-27 1-28 1-1 1-2 1-3 1-4 1-5 Liquid cleaner compositions for hard surfaces Compounding composition (mass %) (a) citric acid 5 5 5 5 5 5 5 5 5 5 5 7 Sodium EDTA (b) Ethane-1-hydroxy-1,1-diphosphonic acid 2 2 2 2 2 2 2 Amino trimethylene phosphonic acid 2 2 Tripolyphosphate 2 2 Surfactant (c) benzyl octyl dimethyl ammonium chloride 1 0.1 1 1 1 Benzyldecyldimethylammonium chloride 1 1 2 1 benzyl lauryl dimethyl ammonium chloride 1 Octyltrimethylammonium chloride 1 Decyltrimethylammonium chloride 1 (d) Lauroaminopropyl Betaine 0.5 0.5 0.5 0.5 0.5 0.5 0.5 1.5 1.4 0.5 0.5 0.5 Lauryl Hydroxy Sultaine Lauryl Dimethylamine Oxide 0.5 (e) Sodium alkyl ether sulfate Polyoxyethylene (7) alkyl ether (f) Diethylene glycol monobutyl ether 2 2 2 2 2 2 2 2 2 2 2 2 2 benzyl alcohol 1 spices 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 sodium hydroxide 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3 3 1 Ion exchanged water margin margin margin margin margin margin margin margin margin margin margin margin margin total 100 100 100 100 100 100 100 100 100 100 100 100 100 (a)/(b) (mass ratio) 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 - - 0 Ratio (mass %) of (c) component in all surfactants 67 67 67 67 67 67 80 67 0 6.7 67 67 67 pH(25℃) 7 7 7 7 7 7 7 7 7 7 7 7 7 Putting time (minutes) 10 10 10 10 10 10 10 10 10 10 10 10 10 Soap scum cleaning power evaluation A (%) 85 90 90 90 90 90 95 95 50 60 65 65 60 Scale and stain cleaning power evaluation A (%) 90 90 90 90 90 90 90 90 75 75 40 40 80

[Table 4] Example 2-1 2-2 2-3 2-4 2-5 2-6 2-7 2-8 2-9 2-10 Liquid cleaner compositions for hard surfaces Compounding composition (mass %) (a) citric acid 5 5 5 5 5 5 5 5 Sodium EDTA 3 3 (b) Ethane-1-hydroxy-1,1-diphosphonic acid 2 2 2 2 2 2 Amino trimethylene phosphonic acid 2 2 Tripolyphosphate 2 2 Surfactant (c) benzyl octyl dimethyl ammonium chloride 1 1 1 1 1 Benzyldecyldimethylammonium chloride 1 1 1 1 benzyl lauryl dimethyl ammonium chloride 1 (d) Lauroaminopropyl Betaine 0.5 0.5 0.5 0.5 0.5 0.5 Lauryl Hydroxy Sultaine 0.5 0.5 Lauryl Dimethylamine Oxide 0.5 0.5 (e) Sodium alkyl ether sulfate 0.4 Polyoxyethylene (7) alkyl ether 0.5 (f) Diethylene glycol monobutyl ether 2 2 2 2 2 2 2 2 2 2 benzyl alcohol 1 (g) Hydroxyethyl cellulose ether 0.3 0.3 0.3 0.3 Sanxianjiao 0.5 Polyvinylpyrrolidone 0.3 spices 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 sodium hydroxide 3.5 0.5 3.5 3.5 3.5 3.5 3.5 0.5 3.5 3.5 Ion exchanged water margin margin margin margin margin margin margin margin margin margin total 100 100 100 100 100 100 100 100 100 100 (a)/(b) (mass ratio) 2.5 1.5 2.5 2.5 2.5 2.5 2.5 1.5 2.5 2.5 Ratio (mass %) of (c) component in all surfactants 67 67 67 67 50 53 67 67 67 67 Viscosity(25℃)(mPa・s) 35 35 35 35 420 90 2 2 2 2 pH(25℃) 7 7 7 7 7 7 7 7 7 7 Soap scum cleaning power evaluation B (%) 95 95 90 90 90 90 75 75 75 75 Scale and stain cleaning power evaluation B (%) 90 90 90 90 90 90 70 70 70 70 adhesion △ △ △ △

[table 5] Comparative example Example Comparative example Example 3-1 3-1 3-2 3-3 3-4 3-2 3-5 3-6 3-7 3-8 3-9 3-10 3-11 3-12 3-13 Cleaner compositions for hard surfaces Compounding composition (mass %) (a) citric acid 1 2 4 5 6 6.85 2 2.5 1 0.5 5 5 5 5 5 (b) Ethane-1-hydroxy-1,1-diphosphonic acid 6 5 3 2 1 0.15 0.5 1 0.4 0.2 2 2 2 2 2 Surfactant (c) benzyl octyl dimethyl ammonium chloride 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.5 0.5 0.5 0.3 0.5 0.6 0.8 1 (d) Lauroaminopropyl Betaine 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 1.2 1.0 0.9 0.8 0.5 (f) Diethylene glycol monobutyl ether 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 spices 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 sodium hydroxide 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 Ion exchanged water margin margin margin margin margin margin margin margin margin margin margin margin margin margin margin total 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 (a)/(b) (mass ratio) 0.17 0.4 1.3 2.5 6 45.7 4 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Ratio (mass %) of (c) component in all surfactants 61.5 61.5 61.5 61.5 61.5 61.5 61.5 50 50 50 20 33.3 40 50 66.7 pH(25℃) 7 7 7 7 7 7 7 7 7 7 7 7 7 7 7 Putting time (minutes) 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Soap scum cleaning power evaluation A (%) 65 85 95 95 95 95 85 85 80 75 70 80 85 90 95 Scale and stain cleaning power evaluation A (%) 90 90 90 90 80 50 80 80 75 60 80 85 90 90 90

The ingredients in the table are as follows. In addition, each component represents the mass % in a table|surface based on the quantity converted from an active ingredient.・Lauramidopropyl betaine: amphoteric surfactant, in general formula (d2), R ^4d is an alkyl group having 11 carbon atoms, and R ^5d and R ^6d are methyl groups, Amphitol 20AB, manufactured by Kao Co., Ltd.・Sodium alkyl ether sulfate: anionic surfactant, the carbon number of the alkyl group is 12 to 16, the average molar number of ethylene oxide added is 4.0, ES-4K, manufactured by Kao Co., Ltd. ・Polyoxyethylene ( 7) Alkyl ether: Nonionic surfactant, Softanol 70H, manufactured by Kao Co., Ltd., () is the average number of added moles of oxyethylidene. Hydroxyethyl cellulose ether: Nonionic polysaccharide natural Polymer, HEC DAICEL SE850K, Daicel FineChem Co., Ltd. ・Sanxianjiao: Anionic polysaccharide natural polymer, KELZAN, manufactured by Sanjing Co., Ltd. ・Polyvinylpyrrolidone: Synthetic polymer, PVP K-90, Manufactured by ISP TECHNOLOGIES, INC

Claims (8)

A cleaning composition for hard surfaces, comprising a metal chelating agent, a surfactant and water, and The metal chelating agent contains (a) a carboxylic acid type metal chelating agent [hereinafter referred to as (a) component], and (b) at least one metal selected from the group consisting of a phosphonic acid type metal chelating agent and a phosphoric acid type metal chelating agent A chelating agent [hereinafter referred to as (b) ingredient], The mass ratio of the content of the component (a) to the content of the component (b), that is, (a)/(b) is 0.20 or more and 40 or less, As the surfactant, it contains (c) a cationic surfactant [hereinafter referred to as (c) component], The ratio of the content of the component (c) to the total content of the surfactant is 20% by mass or more and 100% by mass or less. The cleaning composition for hard surfaces according to claim 1, which further contains (d) an amphoteric surfactant as a surfactant. The cleaning composition for hard surfaces as claimed in claim 1 or 2, wherein as the surfactant, any (e) anionic surfactant is contained, and the content of the (e) anionic surfactant relative to the content of the (c) component is 50 mass % or less. The cleaning composition for hard surfaces according to any one of claims 1 to 3, which further contains (f) a water-soluble solvent. The cleaning composition for hard surfaces according to any one of claims 1 to 4, wherein the hard surfaces are ceramic tiles, glass, stainless steel, plastic or ceramics. A method for cleaning a hard surface, comprising contacting the hard surface cleaning agent composition according to any one of Claims 1 to 5 with the hard surface for a predetermined time, and thereafter washing the hard surface with water. The cleaning method for hard surfaces as claimed in claim 6, wherein the specified time is more than 1 minute. The method for cleaning a hard surface as claimed in claim 6 or 7, wherein the hard surface is a hard surface with scale stains and soap scum stains attached.