WO2021251483A1

WO2021251483A1 - Detergent composition for hard surfaces

Info

Publication number: WO2021251483A1
Application number: PCT/JP2021/022289
Authority: WO
Inventors: 陽介中川
Original assignee: 花王株式会社
Priority date: 2020-06-12
Filing date: 2021-06-11
Publication date: 2021-12-16
Also published as: TW202204588A; JP2021195554A

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

Detergent composition for hard surfaces

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

Background technology There are various hard surfaces made of tiles, plastics, metals, etc. in the living environment equipment that surrounds us, and these hard surfaces are exposed to the environment where various stains adhere in daily life. In particular, the hard surface used for bathrooms, kitchens, etc. is a surface that people come into contact with on a daily basis, so that a lot of dirt remains and easily accumulates, and it is difficult to clean and remove it. There is. Bathroom cleaning agents generally used for bathrooms such as bathtubs, bathroom walls and floors include cleaning agents containing surfactants, solvents, metal ion sequestering agents, etc. in order to remove stains on metal soaps, especially calcium salts of fatty acids. Is used. Further, in a bathroom or kitchen, silicic acid contained in water is polymerized and accumulated on a hard surface, and is deposited like a scaly pattern to become scale stains. This scale stain is also known as a stain that is extremely difficult to remove.

Japanese Unexamined Patent Publication No. 11-256198 describes a liquid detergent composition containing a specific glyceryl ether, a cationic surfactant, a builder, and water under predetermined conditions.
Japanese Unexamined Patent Publication No. 2003-183698 describes a bathroom cleaner composition containing at least a surfactant, a chelating agent, a polymer compound, a solvent and a fragrance.
Japanese Patent Application Laid-Open No. 2019-48963 describes (a) one or more selected from phosphonic acid-based chelating agents and phosphoric acid-based chelating agents in an amount of 0.2% by mass or more and 10% by mass or less, other than (b) and (a). A liquid detergent composition for hard surfaces containing 0% by mass or more and 10% by mass or less of a chelating agent, (c) a surfactant and water, and having a viscosity at 25 ° C. of more than 6 mPa · s and 1000 mPa · s or less. There is described a liquid detergent composition for a hard surface, which is used for cleaning in contact with a hard surface and left to stand for 1 minute or more.
Japanese Unexamined Patent Publication No. 61-283697 describes a bathroom cleaner composition containing a predetermined amount of each of a cationic surfactant, a nonionic surfactant, and a water-soluble solvent.
Japanese Patent Application Laid-Open No. 10-204480 describes (a) 0.01 to 10% by weight of a cationic surfactant, (b) 1 to 20% by weight of a metal chelating agent, and (c) 0.5 to 10% by weight of a water-soluble detergent. % And (d) a liquid detergent composition for kitchen surroundings containing 0.01 to 3% by weight of a thickening polysaccharide and having a pH of 6 to 8.

Outline of the Invention The present invention provides a cleaning agent composition for a hard surface which exhibits excellent detergency against both soap scum stains and scale stains.

The present invention is a hard surface cleaning agent composition containing a metal sequestering agent, a surfactant, and water.
As the metal sequestering agent, one or more metal sequestering agents selected from (a) a carboxylic acid type metal sequestering agent [hereinafter referred to as (a) component], and (b) a phosphonic acid type metal sequestering agent and a phosphoric acid type metal sequestering agent. [Hereinafter referred to as (b) component] and
(A) / (b), which is the mass ratio of the content of the component (a) to the content of the component (b), is 0.20 or more and 40 or less.
As a surfactant, (c) a cationic surfactant [hereinafter referred to as (c) component] is contained.
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 present invention relates to a detergent composition for a hard surface.

The present invention also relates to a method for cleaning a hard surface, wherein the cleaning agent composition for a hard surface of the present invention is brought into contact with the hard surface for a predetermined time, and then the hard surface is rinsed with water.

According to the present invention, there is provided a cleaning agent composition for a hard surface that exhibits excellent detergency against both soap scum stains and scale stains.

Embodiment for carrying out the invention In the present invention, the two metal sequestering agents (a) and (b) are combined with the component (c), and the ratio of the component (c) in the surfactant is specified. It is possible to remove both soap scum stains and scale stains more effectively by using the amount ratio of. Although the details of the effect manifestation mechanism of the present invention are unknown, the component (c) weakens the bond between Ca and the fatty acid ion in the soap scum stain, and the two metal sequestering agents (a) and (b) are used. It is presumed that by acting, Ca is extracted and soap scum is solubilized. Further, it is presumed that the two metal sequestering agents of the component (a) and the component (b) _{act on the SiO 2 of the water stain and solubilize.}

[Cleaning agent composition for hard surface]
[Metal blockade]
The detergent composition for a hard surface of the present invention contains a metal sequestering agent, and contains the following components (a) and (b) as the metal sequestering agent.

<(A) component>
The component (a) is a carboxylic acid type metal sequestering agent. Examples of the carboxylic acid type metal sequestering agent include those having 1 or more and 4 or less carboxy groups. Further, examples of the carboxylic acid type metal sequestering agent include those having 3 or more and 9 or less carbon atoms. For example, as the component (a), one or more metal sequestering agents selected from hydroxycarboxylic acid and its salt and aminocarboxylic acid and its salt can be mentioned.

Hydroxycarboxylic acids and salts thereof include citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, gluconic acid, diglycolic acid, oxydisuccinic acid, carboxymethylsuccinic acid, carboxymethyloxysuccinic acid, carboxymethyl tartaric acid, and their salts. One or more selected from salt can be mentioned. Specific examples of the salt include alkali metal salts, ammonium salts, and alkanolamine salts.

From the viewpoint of detergency, the hydroxycarboxylic acid and its salt are one or more selected from hydroxycarboxylic acids having 2 or more carbon atoms, 3 or more carbon atoms, 9 or less carbon atoms, and 8 or less carbon atoms and salts thereof. Is preferable, and one or more selected from citric acid, malic acid and salts thereof is more preferable.

The aminocarboxylic acid and its salts are selected from nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, hydroxyethylenediamineacetic acid, diethylenetriaminetetraacetic acid, glycoletherdiaminetetraacetic acid, hydroxyethyliminodiacetic acid, gencoric acid and salts thereof. One or more types can be mentioned. Specific examples of the salt include alkali metal salts, ammonium salts, and alkanolamine salts.

The component (a) is preferably a polyvalent carboxylic acid type metal sequestering agent having 2 or more and 4 or less carboxy groups from the viewpoint of detergency. More preferably, one or more metal sequestering agents selected from hydroxy polyvalent carboxylic acid and its salt and amino polyvalent carboxylic acid and its salt can be mentioned.
Further, the component (a) is preferably one or more selected from hydroxycarboxylic acids having 3 or more and 8 or less carbon atoms and salts thereof, and is selected from citric acid, malic acid, and salts thereof1 from the viewpoint of detergency. More than seeds are more preferred, and citric acid or salts thereof are even more preferred.

<(B) component>
The component (b) is one or more metal sequestering agents selected from a phosphonic acid type metal sequestering agent and a phosphoric acid type metal sequestering agent.

Examples of the phosphonic acid type metal sequestering agent include ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid, and ethanehydroxy-1,1,2. -Selected from phosphonic acids such as triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, aminopoly (methylenephosphonic acid), polyethylenepolyaminepoly (methylenephosphonic acid) and salts thereof. One or more types can be mentioned. Examples of the salt include alkali metal salts such as sodium and potassium, ammonium salts or alkanolamine salts such as monoethanolamine and triethanolamine. Preferred are hydroxyphosphonic acids such as ethane-1-hydroxy-1,1-diphosphonic acid and salts thereof.

Examples of the phosphoric acid-type metal sequestering agent include orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid, hexametaphosphoric acid, and one or more selected from these salts.

From the viewpoint of detergency, the component (b) is preferably a phosphonic acid type metal sequestering agent, more preferably one or more selected from hydroxyphosphonic acid and salts thereof, and ethane-1-hydroxy-1,1-diphosphonic acid or. The salt is more preferred.

[Surfactant]
The detergent composition for a hard surface of the present invention contains a surfactant, and contains the following component (c) as the surfactant.

<(C) component>
The component (c) is a cationic surfactant. As the cationic surfactant, a monolong-chain alkyl type quaternary ammonium salt is preferable. The component (c) is preferably a cationic surfactant having a sterilizing property. As the cationic surfactant, one or more cationic surfactants selected from the compound represented by the following general formula (c1) and the compound represented by the general formula (c2) are preferable, and the general formula (c2). More preferably, one or more cationic surfactants selected from the compounds represented by.

[In the formula, R ^1c represents a long-chain alkyl group having 8 or more and 16 or less carbon atoms, a long-chain alkenyl group or a long-chain hydroxyalkyl group, and R ^2c , R ^3c and R ^4c are the same or different, respectively. 1 or 3 carbon atoms an alkyl group, a polyoxyethylene group having 1 to 3 hydroxyalkyl group or an average addition mole number of 10 or less carbon atoms, Y ^- is a halogen atom, or a number of 1 to 5 sulfonic carbon Anion residue of acid ester or sulfate ester is shown. ]
In the general formula (c1), R ^1c preferably has a linear alkyl group having 8 or more carbon atoms, preferably 12 or less, more preferably 10 or less, and R ^2c , R ^3c , and R ^4c have a methyl group, respectively. Alternatively, an ethyl group is preferable, and a methyl group is more preferable. Y ⁻ is preferably a halogen ion and further preferably a ^{chloride ion (Cl −).}

[In the formula, R ^5c represents a long-chain alkyl group having 8 or more and 16 or less carbon atoms, a long-chain alkenyl group or a long-chain hydroxyalkyl group, and R ^6c and R ^7c have the same or different carbon atoms, respectively. An alkyl group having 3 or more carbon atoms, a hydroxyalkyl group having 1 or more carbon atoms or 3 or less carbon atoms, or a polyoxyethylene group having an average addition molar number of 10 or less is shown, and R ^8c indicates an alkylene group having 1 or more carbon atoms and 3 or less carbon atoms. Z ⁻ indicates a halogen atom or an anion residue of a sulfonic acid ester or a sulfuric acid ester having 1 or more and 5 or less carbon atoms. ]
In the general formula (c2), R ^5c is preferably a linear alkyl group having 8 or more carbon atoms and 14 or less, R ^6c and R ^7c are preferably methyl groups, and R ^8c is preferably a methylene group. Z ⁻ is preferably a halogen ion and further preferably a ^{chloride ion (Cl −).}
In the present invention, the general formula (c2) is suitable from the viewpoint of detergency, particularly soap scum stain detergency.

[Composition, other ingredients, etc.]
The hard surface cleaning agent composition of the present invention is a hard surface composition containing a metal sequestering agent and a surfactant, and contains (a) component and (b) component as a metal sealing agent. (A) / (b), which is the mass ratio of the content of the component (a) to the content of the component (b), is 0.20 or more and 40 or less, and the component (c) is contained as a surfactant. 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.

From the viewpoint of high detergency, the cleaning agent composition for a hard surface of the present invention contains the component (a) in an amount of preferably more than 0% by mass, more preferably 0.2% by mass or more, and preferably 8% by mass. Hereinafter, it is more preferably contained in an amount of 7% by mass or less. In the present invention, the acid type conversion value is used as the amount of the component (a).

From the viewpoint of detergency, the cleaning agent composition for a hard surface of the present invention contains the component (b) in an amount of preferably 0.3% by mass or more, more preferably 0.4% by mass or more, and preferably 8% by mass. Hereinafter, it is more preferably contained in an amount of 6% by mass or less. In the present invention, the acid type conversion value is used as the amount of the component (b).

In the hard surface cleaning agent composition of the present invention, from the viewpoint of detergency, (a) / (b), which is the mass ratio of the content of the component (a) to the content of the component (b), is 0. 20 or 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. Below, it is more preferably 10 or less, still more preferably 8 or less, still more preferably 5 or less, still more preferably 4 or less.

From the viewpoint of detergency, the ratio of the content of the component (c) to the total content of the surfactant is 20% by mass or more, preferably 30% by mass or more, more preferably. Is 35% by mass or more, more preferably 40% by mass or more, still more preferably 45% by mass or more, still more preferably 50% by mass or more, still more preferably 60% by mass or more, and further preferably 100% by mass or less, preferably 100% by mass or less. It is 95% by mass or less, more preferably 90% by mass or less. Here, the total content of the surfactant is the total content of the component (c), the component (d) described later, the component (e), and other surfactants.

The hard surface detergent composition of the present invention can further contain (d) an amphoteric surfactant [hereinafter referred to as (d) component] as a surfactant.

Examples of the amphoteric surfactant of the component (d) include one or more amphoteric surfactants selected from amine oxides, sulfobetaines and carbobetaines. The component (d) is preferably carbobetaine. The hard surface detergent composition of the present invention preferably contains carbobetaine as the component (d).

As the amine oxide, the compound of the following general formula (d1) is suitable.

[In the formula, R ^1d represents a hydrocarbon group having 8 or more carbon atoms and 22 or less carbon atoms, preferably an alkyl group or an alkenyl group, more preferably an alkyl group, and R ^2d and R ^3d have the same or different carbon atoms and have 1 or more carbon atoms. Shows 3 or less alkyl groups. D represents an -NHC (= O) -group or a -C (= O) NH- group, and E represents an alkylene group having 1 or more carbon atoms and 5 or less carbon atoms. m and p indicate 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 or more and 18 or less carbon atoms, and more preferably an alkyl group having 12 or more and 16 or less carbon atoms, from the viewpoint of detergency against solid fat. It is more preferably an alkyl group having 12 or more carbon atoms and 14 or less carbon atoms, and even more preferably an alkyl group having 12 carbon atoms. From the viewpoint of detergency, R ^2d and R ^3d are each preferably a methyl group having 1 carbon atom.

As the sulfobetaine, N-alkyl-N, N-dimethyl-N-sulfopropylammonium sulfobetaine and an alkyl group having an alkyl group having preferably 10 or more carbon atoms and preferably 18 or less, more preferably 14 or less carbon atoms. N-alkyl-N, N-dimethyl-N- (2-hydroxysulfopropyl) ammonium sulfobetaine, having an alkanoyl group having a carbon number of preferably 10 or more, preferably 18 or less, and more preferably 14 or less. N-alkanoylaminopropyl-N, N-dimethyl-N-sulfopropylammonium sulfobetaine, preferably 10 or more, preferably 18 or less, more preferably 14 or less, preferably having 10 or more carbon atoms in the alkanoyl group, and Examples thereof include N-alkanoylaminopropyl-N, N-dimethyl-N- (2-hydroxysulfopropyl) ammonium sulfobetaine, preferably 18 or less, more preferably 14 or less.

As the carbobetaine, N-alkyl-N, N-dimethyl-N-carboxymethylammonium betaine having an alkyl group having a carbon number of preferably 10 or more, preferably 18 or less, and more preferably 14 or less, the following general formula ( Examples thereof include the compound represented by d2). From the viewpoint of detergency, the compound represented by the following general formula (d2) is preferable.

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

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

In the hard surface cleaning agent composition of the present invention, the component (d) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass, from the viewpoint of detergency. % Or more, preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 2% by mass or less.

When the cleaning agent composition for a hard surface of the present invention contains the component (d), the content of the component (c) and the content of the component (d) are different from the viewpoint of the cleaning power of soap scum and the cleaning power of water stains. The mass 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. Below, it is more preferably 15 or less.

The detergent composition for a hard surface of the present invention may contain (e) an anionic surfactant [hereinafter referred to as (e) component], but it may impair the effect of the (c) component. It is preferable that the content is small from the viewpoint of detergency. In the present invention, the content of the component (e) is preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less with respect to the content of the component (c). This ratio is 0% by mass, that is, the detergent composition for a hard surface of the present invention does not have to contain the component (e).

Here, the anionic surfactant of the component (e) is usually used by those skilled in the art, and for example, a hydrocarbon group having 7 or more and 22 or less carbon atoms, a sulfate ester group, a phosphoric acid ester group, and a phosphonic acid group. , Anionic surfactants having a sulfonic acid group or a carboxy group.

Specifically, alkylbenzene sulfonate, alkane sulfonate, alkyl sulfate ester salt, polyoxyethylene alkyl ether sulfate ester salt, α-olefin sulfonate, α-sulfo fatty acid methyl ester salt, polyoxyethylene alkyl (or polyoxyethylene alkyl). Alkenyl) ether carboxylate, polyoxyethylene amide alkyl (or alkenyl) ether carboxylate, fatty acid salt, alkyl phosphate ester salt, polyoxyethylene alkyl ether phosphate, etc., and the salts include sodium, potassium, etc. Examples thereof include inorganic salts such as alkali metal salts, ammonium salts and magnesium salts, and organic salts such as monoethanolammonium, diethanolammonium and triethanolammonium.

From the viewpoint of detergency, the content of the anionic surfactant in the hard surface cleaning composition of the present invention is preferably 3% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less. , More preferably 0.5% by mass or less, further preferably 0.1% by mass or less, and preferably 0% by mass or more, or 0% by mass. In the present invention, the acid type conversion value is used as the amount of the anionic surfactant.

The content of the surfactant in the hard surface cleaning composition of the present invention is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.5% by mass or more, and more. It is more preferably 1.0% by mass or more, preferably 8% by mass or less, more preferably 7% by mass or less, still more preferably 5% by mass or less, still more preferably 4.5% by mass or less. The content of the surfactant is the total content of the component (c), the component (d), the component (e) and other surfactants. Examples of the surfactant other than the component (c), the component (d) and the component (e) include a nonionic surfactant such as a polyoxyalkylene alkyl ether.

The hard surface cleaning agent composition of the present invention can further contain (f) a water-soluble solvent [hereinafter referred to as (f) component]. The water-soluble solvent is preferably a water-soluble organic solvent having 2 or more carbon atoms, more preferably 3 or more carbon atoms, and preferably 10 or less carbon atoms, more preferably 8 or less carbon atoms, and as a specific example, ethanol. , Isopropyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, isoprene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, 3-methyl-3-methoxybutanol, benzyl alcohol, phenoxyethanol, phenylglycol, phenoxy More preferably, one or more water-soluble organic solvents selected from isopropanol, butyl diglycol (diethylene glycol monobutyl ether), dibutyrene glycol, and benzyl alcohol. Among them, one or more water-soluble organic solvents selected from benzyl alcohol, butyl diglycol, ethanol, and propylene glycol are 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 detergent composition for a hard surface of the present invention contains the component (f), the composition contains the component (f) in an amount of preferably 0.2% by mass or more, more preferably 0.5% by mass or more. Then, it is preferably contained in an amount of 8% by mass or less, more preferably 5% by mass or less.

The detergent composition for a hard surface of the present invention may contain (g) a thickener [hereinafter referred to as (g) component] from the viewpoint of enhancing the cleaning power on a hard surface such as a vertical surface where it is difficult to stay. can.
As the thickener, one or more selected from smectite-type clay minerals, natural polymers and synthetic polymers are preferable, and one or more selected from nonionic polysaccharides, natural polymers and synthetic polymers are more preferable. Preferably, one or more selected from nonionic polysaccharides is more preferable.
Specifically, one or more selected from hydroxyethyl cellulose, xanthan gum, and polyvinylpyrrolidone are preferable, and hydroxyethyl cellulose is more preferable.

When the hard surface cleaning agent composition of the present invention contains the component (g), the composition contains the component (g) in an amount of preferably 0.05% by mass or more, more preferably 0.1% by mass or more. Then, it is preferably contained in an amount of 3% by mass or less, more preferably 2% by mass or less.

The detergent composition for a hard surface of the present invention has a pH at 25 ° C. of preferably 6 or more, more preferably 6.5 or more, still more preferably 6.8 or more, and preferably 9 from the viewpoint of detergency. It is 5.5 or less, more preferably 9 or less, still more preferably 8.5 or less.

The hard surface cleaning agent composition of the present invention contains water. The detergent composition for a hard surface of the present invention contains water in an amount of preferably 80% by mass or more, more preferably 85% by mass or more, and preferably 95% by mass or less, more preferably 93% by mass or less.

From the viewpoint of enhancing the detergency on a hard surface that does not easily stay, such as a vertical surface, a thickener can be contained as the component (g), and the detergent composition for a hard surface of the present invention has a viscosity of 25 ° C. It is preferably 10 mPa · s or more and 450 mPa · s or less. This viscosity was measured as a value after 1 minute at 60 rpm using a B-type rotational viscometer and an appropriate rotor.

In order to increase the added value of the product, a fragrance, a pigment, a preservative, an antioxidant and the like can be arbitrarily added to the hard surface detergent composition of the present invention.

The hard surface targeted by the hard surface cleaner composition of the present invention may be a hard surface of tile, glass, stainless steel, plastic or ceramic.
The cleaning agent composition for a hard surface of the present invention is suitably used for cleaning a hard surface such as a bathroom, a bathtub, a washbasin, a tile, a dressing room, a washbasin, a mirror, a sink around a kitchen, a countertop, and a water supply. .. It is suitably used for bathrooms. Here, the term "for bathroom" refers not only to bathrooms but also to articles having other hard surfaces existing in the bathroom, such as bathtubs and washbasins. The present invention preferably targets a hard surface to which water stains and soap scum stains are attached.

[How to clean the hard surface]
INDUSTRIAL APPLICABILITY The present invention provides a method for cleaning a hard surface, which comprises contacting the cleaning composition for a hard surface of the present invention with a hard surface for a predetermined time, and then rinsing the hard surface with water.
Further, the present invention provides a method for removing scale stains and soap scum stains, which comprises contacting the hard surface cleaning agent composition of the present invention with a hard surface for a predetermined time, and then rinsing the hard surface with water. To. That is, the cleaning agent composition for a hard surface of the present invention is brought into contact with a hard surface to which water stains and soap scum stains are attached for a predetermined time, and then the hard surface is rinsed with water. This is a method for removing soap scum stains.
The matters described in the detergent composition for a hard surface of the present invention can be appropriately applied to these methods. The preferred embodiment of the composition is also the same as the above-mentioned hard surface detergent composition of the present invention.

Specifically, the cleaning method of the present invention is to bring the hard surface cleaning agent composition into contact with a hard surface with a stock solution, or to make the hard surface cleaning agent composition hard without diluting with a stock solution. A cleaning method in which the cleaning agent composition for a hard surface is brought into contact with the surface, that is, the cleaning composition for a hard surface is brought into contact with the hard surface without being diluted is preferably mentioned. Further, there is a cleaning method in which the cleaning agent composition for a hard surface is brought into contact with a hard surface to which water stains and soap scum stains are attached without diluting. As a method of contacting with the hard surface, a method of applying to the hard surface is preferable.

Contacting the hard surface cleaning agent composition without diluting it means that the cleaning agent composition is intentionally diluted with water or the like and then not brought into contact with the hard surface. For example, when the cleaning agent composition for a hard surface is brought into contact with a hard surface to which water droplets or the like are attached, or when the cleaning agent composition for a hard surface is brought into contact with a hard surface and then water droplets are attached to the hard surface. Can be understood to be in contact with the hard surface without diluting the hard surface cleaner composition.

In the present invention, for example, the undiluted solution of the detergent composition for a hard surface is adhered to a hard surface as it is, that is, without changing the composition. For example, the cleaning agent composition for a hard surface is brought into contact with a hard surface to which water stains and soap scum stains are attached without adhering to the water-containing absorbent cotton. After contacting the hard surface, the composition of the cleaning agent composition for the hard surface may change. That is, after contacting the hard surface, the composition of the cleaning agent composition for the hard surface may be diluted or concentrated.

In the cleaning method of the present invention, the cleaning agent composition for a hard surface may be applied directly from a bottle in order to bring the composition into contact with a hard surface with a stock solution. Examples of the bottle include a squeeze bottle and the like.

In the present invention, a concentrated composition containing the component (a), the component (b), and the component (c) of the present invention is prepared, and the concentrated composition is diluted with water to form a cleaning agent for a hard surface of the present invention. The composition may be prepared and contacted with a hard surface. That is, the concentrated composition containing the component (a), the component (b), and the component (c) of the present invention is diluted with water to prepare the detergent composition for a hard surface of the present invention, and the cleaning for the hard surface is prepared. A method for cleaning a hard surface may be used in which the agent composition is brought into contact with the hard surface without being diluted.

From the viewpoint of detergency, the time for leaving the hard surface cleaning agent composition of the present invention in contact with the hard surface is preferably 1 minute or longer, preferably 2 minutes or longer, more preferably 3 minutes or longer, and further. It is preferably more than 3 minutes, more preferably 4 minutes or more, still more preferably 5 minutes or more, and from the viewpoint of efficient washing, preferably 60 minutes or less, more preferably 30 minutes or less, still more preferable. Is 15 minutes or less, more preferably 10 minutes or less. The temperature when left to stand may be room temperature, for example, 10 ° C. or higher and 30 ° C. or lower.

Further, in the present invention, the hard surface can be cleaned with a cleaning article in which the cleaning agent composition for a hard surface of the present invention is supported on a substrate.
As an example, there is provided a method for cleaning a hard surface, in which the composition for cleaning agent for a hard surface of the present invention is applied to a hard surface, left to stand for a predetermined time, and then wiped off. For wiping and cleaning, it is preferable to use a cloth, a rag, a non-woven fabric, or the like to remove the composition applied to the hard surface from the hard surface.

Further, the hard surface cleaning agent composition of the present invention can be impregnated into a substrate and used as a cleaning article. The cleaning article in which the substrate is impregnated with the cleaning agent composition for a hard surface of the present invention is preferable from the viewpoint of workability of cleaning work.

The substrate used for the cleaning article impregnated with the hard surface cleaning agent composition is flexible, can be impregnated with the hard surface cleaning agent composition, and has sufficient strength at the time of use. However, the one that does not generate waste is used. It is preferable to use a substrate that can be impregnated with the amount of the cleaning agent composition for a hard surface described below under no load.

Examples of such a substrate include a fibrous structure composed of a fibrous material, for example, various papers, non-woven fabrics, woven fabrics or knitted fabrics. Examples of the fibrous material constituting these fiber structures include cellulosic fibers, modified cellulosic fibers, synthetic fibers, and a mixture of two or more thereof.

Further, a porous structure (for example, a sponge-like structure) obtained by dispersing bubbles in a resin can also be used as the substrate.

Further, the cleaning method of wiping the hard surface using the cleaning article impregnated with the cleaning agent composition for hard surface of the present invention is preferable for light cleaning of the hard surface from the viewpoint of workability of cleaning work. Cleaning articles impregnated with the hard surface cleaning agent composition are those in which the substrate is pre-impregnated with the cleaning agent composition, or the dried substrate is impregnated with the hard surface cleaning agent composition immediately before use. Any of the things may be used. Further, the cleaning article impregnated with the cleaning agent composition for a hard surface may be attached to a mop-shaped cleaning tool and used, or may be directly held by hand and used for wiping.

When the hard surface cleaning agent composition is impregnated in advance, the impregnation rate of the hard surface cleaning agent composition is the mass of the substrate [that is, the mass standard of the substrate in the unimpregnated state (dry state)] from the viewpoint of cleanability. Per, it is preferably 100% by mass or more, more preferably 150% by mass or more, preferably 1000% by mass or less, more preferably 400% by mass or less, and 350% by mass or less. Is more preferable. When the impregnation rate is 100% by mass or more, sufficient detergency can be obtained. If it is 1000% by mass or less, the amount of the cleaning agent composition for a hard surface released to the surface to be cleaned is appropriate, no dirt or dirt dust remains on the surface to be cleaned, and various materials such as wood-based materials are used. Can be used without affecting the cleaning surface. From the viewpoint of further improvement of cleanability, when the substrate is a sheet, the basis weight before impregnation of the hard surface detergent composition is the retention of the hard surface detergent composition required for cleaning a certain area. From the viewpoint of sheet operability and cost, for example, 40 g / m ² or more is preferable, 50 g / m ² or more is more preferable, and 200 g / m ² or less is preferable, and 150 g. It is more preferably / m ^{2 or less.}

When using a cleaning article impregnated with a hard surface cleaning agent composition, the hard surface cleaning agent composition of the present invention may be separately used while being sprayed on the object to be cleaned or the cleaning article. Clean a larger area according to the method of use.

In the present invention, the cleaning agent composition for a hard surface of the present invention is brought into contact with the hard surface and left for a predetermined time, and after further cleaning if necessary, the hard surface is rinsed with water. When rinsing, an external force (physical force) such as hand washing may be applied, or simply rinsing with a stream of water.

[Aspects of the present invention]
Hereinafter, aspects of the present invention will be illustrated. The matters described in the cleaning agent composition for a hard surface and the method for cleaning a hard surface of the present invention can be appropriately applied to these aspects. In addition, the matters described in each aspect can be appropriately applied to each other. The present invention is not limited to these aspects.

<1>
A hard surface cleaning agent composition containing a metal sealant, a surfactant, and water.
As the metal sequestering agent, one or more metal sequestering agents selected from (a) a carboxylic acid type metal sequestering agent [hereinafter referred to as (a) component], and (b) a phosphonic acid type metal sequestering agent and a phosphoric acid type metal sequestering agent. [Hereinafter referred to as (b) component] and
(A) / (b), which is the mass ratio of the content of the component (a) to the content of the component (b), is 0.20 or more and 40 or less.
As a surfactant, (c) a cationic surfactant [hereinafter referred to as (c) component] is contained.
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.
Detergent composition for hard surfaces.

<2>
The hard surface cleaning agent composition according to <1>, wherein the component (a) is a polyvalent carboxylic acid type metal sequestering agent having 2 or more and 4 or less carboxy groups.

<3>
(A) The component is one or more selected from hydroxycarboxylic acids having 3 or more and 8 or less carbon atoms and salts thereof, and further one or more selected from citric acid, malic acid, and salts thereof. The hard surface cleaning agent composition according to <1> or <2>, which is an acid or a salt thereof.

<4>
<1> to <3> containing the component (a) preferably more than 0% by mass, more preferably 0.2% by mass or more, and preferably 8% by mass or less, more preferably 7% by mass or less. The cleaning agent composition for a hard surface according to any one of the above items.

<5>
The phosphonic acid type metal sequestering agent of the component (b) is ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid, ethanehydroxy-1. , 1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, aminopoly (methylenephosphonic acid), polyethylenepolyaminepoly (methylenephosphonic acid), and salts thereof The hard surface cleaning agent composition according to any one of <1> to <4>, which is one or more selected.

<6>
<1> to <5 containing the component (b) preferably 0.3% by mass or more, more preferably 0.4% by mass or more, and preferably 8% by mass or less, more preferably 6% by mass or less. > The cleaning agent composition for a hard surface according to any one of Items.

<7>
<1> to <6>, wherein the component (c) is one or more cationic surfactants selected from the compound represented by the following general formula (c1) and the compound represented by the general formula (c2). The cleaning agent composition for a hard surface according to any one of the above items.

[In the formula, R ^1c represents a long-chain alkyl group having 8 or more and 16 or less carbon atoms, a long-chain alkenyl group or a long-chain hydroxyalkyl group, and R ^2c , R ^3c and R ^4c are the same or different, respectively. 1 or 3 carbon atoms an alkyl group, a polyoxyethylene group having 1 to 3 hydroxyalkyl group or an average addition mole number of 10 or less carbon atoms, Y ^- is a halogen atom, or a number of 1 to 5 sulfonic carbon Anion residue of acid ester or sulfate ester is shown. ]

[In the formula, R ^5c represents a long-chain alkyl group having 8 or more and 16 or less carbon atoms, a long-chain alkenyl group or a long-chain hydroxyalkyl group, and R ^6c and R ^7c have the same or different carbon atoms, respectively. An alkyl group having 3 or more carbon atoms, a hydroxyalkyl group having 1 or more carbon atoms or 3 or less carbon atoms, or a polyoxyethylene group having an average addition molar number of 10 or less is shown, and R ^8c indicates an alkylene group having 1 or more carbon atoms and 3 or less carbon atoms. Z ⁻ indicates a halogen atom or an anion residue of a sulfonic acid ester or a sulfuric acid ester having 1 or more and 5 or less carbon atoms. ]

<8>
The hard surface detergent composition according to any one of <1> to <7>, which further contains (d) an amphoteric surfactant [hereinafter referred to as (d) component] as a surfactant.

<9>
The hard surface according to <8>, wherein the component (d) is one or more amphoteric surfactants selected from the compound of the following general formula (d1) and the compound represented by the following general formula (d2). Detergent composition.

<10>
(D) The component is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, and preferably 5% by mass or less, more preferably 3% by mass. The hard surface cleaning agent composition according to <8> or <9>, which is more preferably contained in an amount of 2% by mass or less.

<11>
(C) / (d), which is the mass ratio of the content of the component (c) to the content of the component (d), is preferably 0.2 or more, more preferably 0.4 or more, still more preferably 0. The hard surface cleaning agent composition according to any one of <8> to <10>, which is 6 or more, more preferably 1.0 or more, and preferably 20 or less, more preferably 15 or less.

<12>
As the surfactant, (e) anionic surfactant [hereinafter referred to as (e) component] is optionally contained, and the content of the (e) component is 50% by mass or less with respect to the content of the (c) component. The hard surface detergent composition according to any one of <1> to <11>.

<13>
The content of the component (e) is preferably 3% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less, still more preferably 0.5% by mass or less, still more preferably 0.1% by mass. Hereinafter, the hard surface cleaning agent composition according to <12>, which is preferably 0% by mass or more, or 0% by mass.

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

<15>
The hard surface cleaning agent composition according to any one of <1> to <14>, further containing (f) a water-soluble solvent [hereinafter referred to as (f) component].

<16>
(F) The component (f) is preferably a water-soluble organic solvent having 2 or more carbon atoms, more preferably 3 or more carbon atoms, and preferably 10 or less carbon atoms, more preferably 8 or less carbon atoms, according to <14>. Cleaning agent composition for hard surfaces.

<17>
<15> or <16> containing the component (f) preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and preferably 8% by mass or less, more preferably 5% by mass or less. > The hard surface cleaning agent composition according to.

<18>
The hard surface cleaning agent composition according to any one of <1> to <17>, further containing (g) a thickener [hereinafter referred to as (g) component]].

<19>
The component (g) is contained in an amount of preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and preferably 3% by mass or less, more preferably 2% by mass or less, according to <18>. Detergent composition for hard surfaces.

<20>
The cleaning agent composition for a hard surface according to any one of <1> to <19>, wherein the hard surface is tile, glass, stainless steel, plastic or ceramic.

<21>
(A) / (b), which is the mass ratio of the content of the component (a) to the content of the component (b), is 0.20 or more, preferably 0.30 or more, more preferably 0.50 or more, and more. 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, still more preferably 8 or less, even more preferably. The hard surface cleaning agent composition according to any one of <1> to <20>, which is 5 or less, more preferably 4 or less.

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

<23>
A method for cleaning a hard surface, wherein the cleaning agent composition for a hard surface according to any one of <1> to <22> is brought into contact with the hard surface for a predetermined time, and then the hard surface is rinsed with water.

<24>
The predetermined time is 1 minute or more, preferably 2 minutes or more, more preferably 3 minutes or more, further preferably more than 3 minutes, still more preferably 4 minutes or more, still more preferably 5 minutes or more, and preferably. The method for cleaning a hard surface according to <23>, wherein is 60 minutes or less, more preferably 30 minutes or less, still more preferably 15 minutes or less, still more preferably 10 minutes or less.

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

Examples The hard surface detergent compositions shown in Tables 1 to 5 were prepared and evaluated for the following items. The results are shown in Tables 1-5.

<Cleaning power>
(1) Evaluation method for cleaning power of soap scum stains (1-1) Preparation of model soap scum stains The detergency of model soap scum stains in which soap and sebum were combined was evaluated. The method for producing model soap scum stains is shown below. 90% by mass of bar soap (Kao White), 10% by mass of model sebum stains, mixed at 50-60 ° C, and kept warm is the solution A. The composition of the model sebum stain is 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. A solution obtained by incubating a calcium chloride solution having a German hardness of 10 ° C. at 20 to 30 ° C. is referred to as a B solution. Apply solution A as thinly and evenly as possible to a polypropylene plate (50 mm x 100 mm x 2 mm), let it air dry at 20 to 30 ° C for 5 minutes, then apply solution B as thinly and evenly as possible, and apply 5 at 20 to 30 ° C. Let it air dry for minutes. This operation of solution A application → natural drying → B solution application → natural drying was repeated 30 to 50 times to prepare a model soap scum stain.

(1-2) Soap scum cleaning power evaluation A
Place the plate with the model soap scum stains prepared in (1-1) horizontally so that the surface with the stains is on the top surface, and drop one drop of each hard surface cleaning agent composition on the model soap scum stains with a dropper. After dropping (about 0.3 mL) and leaving it for a predetermined time as shown in the table, it was sufficiently rinsed with ion-exchanged water, and the detergency was judged according to the following criteria. As a specific method, the uncoated plate, the pre-cleaning plate after the stain coating, and the post-cleaning plate are photographed under the same shooting conditions such as brightness, and the gray scale of each plate is obtained from the obtained image. It was measured. The cleaning rate of the plate before cleaning was set to 0%, the cleaning rate of the uncoated plate was set to 100%, and the cleaning rate of the plate after cleaning was calculated. ImageJ 1.47v, an image processing software, was used for grayscale measurement.

(1-3) Soap scum cleaning power evaluation B
Place the plate with the model soap scum stains prepared in (1-1) vertically, apply 1 mL of each hard surface cleaning agent composition to the model soap scum stains with a dropper, leave it for 10 minutes, and then ion-exchange water. Rinse thoroughly with, and the detergency was judged according to the following criteria.
The uncoated plate, the pre-cleaning plate after the stain coating, and the post-cleaning plate were photographed under the same imaging conditions such as brightness, and the gray scale of each plate was measured from the obtained images. The cleaning rate of the plate before cleaning was set to 0%, the cleaning rate of the uncoated plate was set to 100%, and the cleaning rate of the plate after cleaning was calculated. ImageJ 1.47v, an image processing software, was used for grayscale measurement.

(2) water scale stains detergency evaluation method (2-1) as possible CaCl ₂ aqueous solution 0.3mL of _SiO 2 / 300ppm models limescale stains manufacturing 300ppm at the bottom 25mm portion of the slide glass (76 mm × 26 mm) uniformly coated Then, it was dried on a hot plate heated to 140 ° C., and then rinsed with ion-exchanged water. The operation of applying the solution on the slide glass and drying it was repeated three times to prepare a model scale stain.

(2-2) Water stain cleaning power evaluation A
Place the slide glass with the model scale stains made in (2-1) horizontally so that the surface with the stains is on the top surface, and cut the slide glass to the size of the model scale stains (Curelet 4 cm). Place x 4 cm manufactured by Kawamoto Sangyo Co., Ltd., drop 1 mL of each hard surface cleaning agent composition, leave it for the specified time shown in the table, and then reciprocate the entire surface of the slide glass 5 times with a light force (about 200 g weight). ). Then, after the slide glass was sufficiently rinsed with ion-exchanged water, the detergency was judged according to the following criteria.
As a specific method of evaluation criteria, the uncoated slide glass, the pre-cleaned slide glass after the stain application, and the post-cleaning slide glass were photographed under the same shooting conditions such as brightness, and each of the obtained images was taken. The gray scale of the slide glass was measured. The cleaning rate of the pre-cleaning slide glass was 0%, the cleaning rate of the uncoated slide glass was 100%, and the cleaning rate of the post-cleaning plate was calculated. ImageJ 1.47v, an image processing software, was used for grayscale measurement.

(2-3) Water stain cleaning power evaluation B
A slide glass with model scale stains prepared in (2-1) is placed vertically against the model scale stains, 1 mL of each hard surface detergent composition is applied to the model scale stains with a dropper, and the mixture is left for 10 minutes, and then each detergent composition. The part in contact with the object was rubbed with a light force (about 200 g weight) 5 times back and forth using degreased cotton (Curelet 4 cm x 4 cm manufactured by Kawamoto Sangyo Co., Ltd.). Then, after sufficiently rinsing with ion-exchanged water, the detergency was judged according to the following criteria.
The uncoated slide glass, the pre-cleaned slide glass after the stain was applied, and the post-cleaned slide glass were photographed under the same shooting conditions such as brightness, and the gray scale of each slide glass was measured from the obtained images. The cleaning rate of the pre-cleaning slide glass was 0%, the cleaning rate of the uncoated slide glass was 100%, and the cleaning rate of the post-cleaning plate was calculated. ImageJ 1.47v, an image processing software, was used for grayscale measurement.

<Adhesiveness>
^{Apply 1 mL of each hard surface cleaning agent composition to the top of a 15 cm 2} porcelain tile that stands vertically, measure the mass of the cleaning liquid remaining on the tile after 5 seconds, and evaluate the adhesiveness on the vertical surface according to the following criteria. did.
〇: 0.80 g or more of cleaning liquid remains (80% or more remains)
Δ: 0.5 g to 0.79 g of cleaning liquid remains (50% to 79% remains)
X: Cleaning liquid of 0.49 g or less remains (49% or less remains)
The viscosity of the composition was measured (25 ° C.) at 60 rpm using a B-type rotational viscometer as a value after 1 minute, and is shown in the table. At low viscosities, the rotor No. No. 1 was used, and the rotor No. 1 was used so as to be within the measurement range of viscosity as needed. 2 or 3 was used.

The components in the table are as follows. For each component, the mass% in the table is shown based on the amount converted to the effective amount.
-Laurylamide propylbetaine: amphoteric surfactant, in the general formula (d2), R ^4d is an alkyl group having 11 carbon atoms, R ^5d and R ^6d are methyl group compounds, Anchtor 20AB, manufactured by Kao Co., Ltd., alkyl ether. Sodium sulfate: anionic surfactant, alkyl group with 12 to 16 carbon atoms, ethylene oxide average addition mole number 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 moles of oxyethylene group added. Natural polymer of anionic polysaccharide, KELZAN, manufactured by Sansho Co., Ltd. ・ Polyvinylpyrrolidone: synthetic polymer, PVP K-90 ISP TECHNOLOGIES, manufactured by INC

Claims

A hard surface cleaning agent composition containing a metal sealant, a surfactant, and water.
As the metal sequestering agent, one or more metal sequestering agents selected from (a) a carboxylic acid type metal sequestering agent [hereinafter referred to as (a) component], and (b) a phosphonic acid type metal sequestering agent and a phosphoric acid type metal sequestering agent. [Hereinafter referred to as (b) component] and
(A) / (b), which is the mass ratio of the content of the component (a) to the content of the component (b), is 0.20 or more and 40 or less.
As a surfactant, (c) a cationic surfactant [hereinafter referred to as (c) component] is contained.
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.
Detergent composition for hard surfaces.
The hard surface detergent composition according to claim 1, further comprising (d) an amphoteric surfactant as a surfactant.
Claimed, wherein (e) an anionic surfactant is optionally contained as the surfactant, and the content of (e) the anionic surfactant is 50% by mass or less with respect to the content of the component (c). The detergent composition for a hard surface according to 1 or 2.
The hard surface cleaning agent composition according to any one of claims 1 to 3, further containing (f) a water-soluble solvent.
The cleaning agent composition for a hard surface according to any one of claims 1 to 4, wherein the hard surface is tile, glass, stainless steel, plastic or ceramic.
A method for cleaning a hard surface, wherein the cleaning agent composition for a hard surface according to any one of claims 1 to 5 is brought into contact with the hard surface for a predetermined time, and then the hard surface is rinsed with water.
The method for cleaning a hard surface according to claim 6, wherein the predetermined time is 1 minute or more.
The method for cleaning a hard surface according to claim 6 or 7, wherein the hard surface is a hard surface to which water stains and soap scum stains are attached.