JP6990071B2 - Liquid detergent composition for hard surfaces - Google Patents

Description

The present invention relates to a liquid detergent composition for a hard surface and a method for removing water stains on a hard surface.

The living environment equipment that surrounds us has various hard surfaces made of tiles, plastics, metals, etc., 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.

For example, Patent Document 1 describes (a) 0.5% by mass or more of a betaine-type amphoteric surfactant and 3% by mass or less, and (b) 0.5% by mass or more and 10% by mass or less of a specific aromatic alcohol. , (C) 1% by mass or more and 8% by mass or less of the chelating agent, and (d) water, and the ratio of the component (a) in the total surfactant is 65% by mass or more and at 25 ° C. Disclosed are sterilizing and cleaning agent compositions for hard surfaces having a pH of 2 or more and 6 or less.
Further, Patent Document 2 discloses a cleaning composition for a bathroom, which comprises at least a surfactant, a chelating agent, a polymer compound, a solvent and a fragrance.

Japanese Unexamined Patent Publication No. 2015-11345 Special Table 2003-183698 Gazette

In Patent Documents 1 and 2, it is an object to remove the calcium salt of fatty acid, but it cannot be said that it is sufficient for water stains.
In the present invention, the scale stain refers to a stain in which a scaly pattern is deposited by polymerizing and accumulating silicic acid contained in water on a hard surface.

The present invention relates to a liquid detergent composition for a hard surface, which is excellent in detergency against water stains adhering to a hard surface (hereinafter, also simply referred to as detergency), and a method for removing scale stains using the same.

In the present invention, one or more selected from (a) a phosphonic acid-based chelating agent and a phosphoric acid-based chelating agent (hereinafter referred to as (a) component) are contained in an amount of 0.2% by mass or more and 10% by mass or less, (b) (a). ) A chelating agent other than the component (hereinafter referred to as the component (b)) is contained in an amount of 0% by mass or more and 10% by mass or less, (c) a surfactant (hereinafter referred to as the component (c)), and a liquid cleaning for a hard surface containing water. It is an agent composition
The viscosity at 25 ° C. is more than 6 mPa · s and 1000 mPa · s or less.
Used for cleaning, which is in contact with a hard surface and left for 1 minute or longer.
The present invention relates to a liquid detergent composition for a hard surface.

Further, in the present invention, the component (a) is 0.2% by mass or more and 10% by mass or less, and (b) (b-1) a carboxylic acid-based chelating agent (however, the component (a) is excluded) (hereinafter, (b-). A liquid detergent composition for a hard surface containing 1) component) of 0.2% by mass or more and 10% by mass or less, (c) component and water.
The viscosity at 25 ° C. is more than 6 mPa · s and 1000 mPa · s or less.
The present invention relates to a liquid detergent composition for a hard surface.

Further, the present invention contains the component (a) of 0.2% by mass or more and 10% by mass or less, the component (b) of 0% by mass or more and 10% by mass or less, the component (c) and water, and has a viscosity of 25 ° C. The present invention relates to a method for removing water stains, wherein a liquid detergent composition for a hard surface having a mass of more than 6 mPa · s and 1000 mPa · s or less is brought into contact with a hard surface and left for 1 minute or more.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a liquid detergent composition for a hard surface, which is excellent in detergency against water stains adhering to a hard surface, and a method for removing water stains using the same.

Surface photograph of a stainless steel faucet with water stains before cleaning Surface photograph of the faucet of FIG. 1 after cleaning with the liquid detergent composition for a hard surface of Example 2.

<Liquid detergent composition for hard surfaces>
The present inventor has found that the cause of water stain is that silicic acid contained in tap water is polymerized and the polymer is accumulated on a hard surface in a scale shape.
In addition, the present inventor uses the component (a) of the present invention in order to remove the scale stain, and combines the component (c) and, if necessary, the component (b) in a specific viscosity region and pH region. It has been found that contacting a liquid detergent composition for a hard surface with a hard surface is effective in removing water stains.
Although such an effect is not always clear, the liquid detergent composition for a hard surface of the present invention sequentially removes silicic acid molecules from the vicinity of the surface of the silicic acid polymer, which causes water stains. It is presumed that this is because it can be removed.

<(A) component>
The component (a) of the present invention is one or more selected from a phosphonic acid-based chelating agent and a phosphoric acid-based chelating agent.
Examples of the phosphonic acid-based chelating 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- 1 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 thereof1 More than seeds 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.
Examples of the phosphoric acid-based chelating agent include orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid, hexametaphosphoric acid, and one or more selected from salts thereof.
From the viewpoint of detergency, the component (a) is preferably a phosphonic acid-based chelating agent, more preferably one or more selected from hydroxyphosphonic acid and salts thereof, and ethane-1-hydroxy-1,1-diphosphonic acid or a component thereof. Salt is more preferred.

The liquid cleaning agent composition for a hard surface of the present invention contains the component (a) in an amount of 0.2% by mass or more, preferably 0.3% by mass or more, and more preferably 0.4% by mass or more from the viewpoint of detergency. More preferably 0.5% by mass or more, further preferably 1% by mass or more, still more preferably 1.5% by mass or more, and from the viewpoint of economic efficiency, 10% by mass or less, preferably 8% by mass or less. , More preferably 6% by mass or less, further preferably 4% by mass or less, still more preferably 3% by mass or less. In the present invention, the acid type conversion value is used for the content of the component (a).

<(B) component>
The component (b) of the present invention is a chelating agent other than the component (a).
As the component (b), a carboxylic acid-based chelating agent (however, excluding the component (a)) (hereinafter, also referred to as the component (b-1)) is preferably mentioned. As the carboxylic acid-based chelating agent, one or more chelating agents selected from hydroxycarboxylic acid and its salt, and aminocarboxylic acid and its salt are more preferable.

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 selected from hydroxycarboxylic acids having 1 or more carbon atoms, preferably 3 or more carbon atoms, and 10 or less carbon atoms, preferably 8 or less carbon atoms and salts thereof. More than one kind is preferable, and one or more kinds selected from citric acid, malic acid and salts thereof are more preferable.

Aminocarboxylic acids and salts thereof include nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, hydroxyethylenediamineacetic acid, diethylenetriaminetetraacetic acid, glycoletherdiaminetetraacetic acid, hydroxyethyliminodiacetic acid, triethylenetetraminehexacetic acid, gencoric acid and One or more selected from these salts can be mentioned. Specific examples of the salt include alkali metal salts, ammonium salts and alkanolamine salts.

From the viewpoint of detergency, the component (b-1) 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 thereof. One or more are more preferable, and citric acid or a salt thereof is further preferable.

The liquid cleaning agent composition for a hard surface of the present invention contains the component (b) in an amount of 0% by mass or more, preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and further, from the viewpoint of detergency. It is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, and from the viewpoint of economic efficiency, 10% by mass or less, preferably 8% by mass or less, more preferably 7% by mass. %, More preferably 6% by mass or less. In the present invention, the acid type conversion value is used for the content of the component (b).

Further, in the liquid cleaning agent composition for a hard surface of the present invention, the component (b-1) is contained in an amount of 0% by mass or more, preferably 0.2% by mass or more, more preferably 0.5% by mass, from the viewpoint of detergency. % Or more, more preferably 1% by mass or more, still more preferably 2% by mass or more, still more preferably 3% by mass or more, and from the viewpoint of economic efficiency, 10% by mass or less, preferably 8% by mass or less. It is preferably contained in an amount of 7% by mass or less, more preferably 6% by mass or less. In the present invention, the acid type conversion value is used for the content of the component (b-1).

In the liquid detergent composition for a hard surface of the present invention, the ratio of the component (b-1) to the component (b) is preferably 50% by mass or more, more preferably 70% by mass or more, from the viewpoint of detergency. It is more preferably 80% by mass or more, still more preferably 90% by mass or more, and preferably 100% by mass or less, and may be substantially 100% by mass or even 100% by mass.

The liquid detergent composition for a hard surface of the present invention contains a component (a) and a component (b), preferably a component (a) and a component (b-1), so that the cost is low. It is excellent in economy and can obtain high detergency.

When the component (a) and the component (b) are contained in the liquid detergent composition for a hard surface of the present invention, the mass ratio of the content of the component (a) to the content of the component (b) (a). / (B) is preferably 0.02 or more, more preferably 0.05 or more, still more preferably 0.1 or more, still more preferably 0.15 or more, still more preferably 0. 2 or more, and from the viewpoint of economic efficiency, preferably 10 or less, more preferably 8 or less, still more preferably 5 or less, still more preferably 3 or less, still more preferably 1 or less, still more preferably 0.8 or less. , More preferably 0.6 or less, still more preferably 0.5 or less.

When the component (a) and the component (b-1) are contained in the liquid detergent composition for a hard surface of the present invention, the mass of the content of the component (a) and the content of the component (b-1) The ratio (a) / (b-1) is preferably 0.02 or more, more preferably 0.05 or more, still more preferably 0.1 or more, still more preferably 0.15 or more, from the viewpoint of detergency. More preferably 0.2 or more, and from the viewpoint of economic efficiency, preferably 10 or less, more preferably 8 or less, still more preferably 5 or less, still more preferably 3 or less, still more preferably 1 or less, still more. It is preferably 0.8 or less, more preferably 0.6 or less, and even more preferably 0.5 or less.

<(C) component>
The component (c) of the present invention is a surfactant.
From the viewpoint of detergency, the component (c) is preferably one or more selected from amphoteric surfactants and nonionic surfactants, and more preferably one or more selected from amphoteric surfactants.

Examples of the amphoteric tenside include one or more amphoteric surfactants selected from carbobetaine, sulfobetaine, and amine oxide.
The liquid detergent composition for hard surfaces of the present invention preferably contains at least one selected from carbobetaine as the component (c).

As the carbobetaine, N-alkyl-N, N-dimethyl-N-carboxymethylammonium betaine or N-alkyl-N, N-dimethyl-N-carboxymethylammonium betaine having an alkyl group or an alkenyl group having a carbon number of preferably 10 or more, preferably 18 or less, and more preferably 14 or less. Examples thereof include N-alkenyl-N, N-dimethyl-N-carboxymethylammonium betaine, and compounds represented by the following general formula (c1). From the viewpoint of detergency, the compound represented by the following general formula (c1) is preferable.

[In the formula, R ^1c represents an alkyl group or an alkenyl group having 7 or more and 21 or less carbon atoms, and R ^2c and R ^3c independently represent an alkyl group having 1 or more and 3 or less carbon atoms. ]

In the general formula (c1), R ^1c is an alkyl group or alkenyl group having a carbon number of 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, an undecyl group, a dodecyl group, or a tridecylic group is preferable.
In the general formula (c1), R ^2c and R ^3c are preferably methyl groups.

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

As the amine oxide, the compound of the following general formula (c2) is suitable.

[In the formula, R ^4c represents a hydrocarbon group having 8 or more and 22 or less carbon atoms, preferably an alkyl group or an alkenyl group, more preferably an alkyl group, and R ^5c and R ^6c are the same or different 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 (c2), R ^4c is preferably an alkyl group having 10 or more and 18 or less carbon atoms, more preferably an alkyl group having 12 or more and 16 or less carbon atoms, and further preferably. It is 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.
R ^5c and R ^6c are each preferably a methyl group having 1 carbon atom from the viewpoint of detergency.

Nonionic surfactants include alkyl monoglyceryl ethers, polyoxyalkylene monoalkyl or alkenyl ethers, alkyl polyglycosides (glycoside-type nonionic surfactants), sorbitan nonionic surfactants, aliphatic alkanolamides, fatty acids. One or more selected from the group consisting of monoglyceride and citrus fatty acid ester is preferable, and two or more of these may be used.

As the alkyl monoglyceryl ether, a compound represented by the following general formula (c3) is suitable.
R ^7c- O- (Gly) _r -H (c3)
[In the formula, R ^7c indicates a hydrocarbon group having 6 to 18 carbon atoms, Gly indicates a structural unit derived from glycerin, and preferably indicates a residue obtained by removing one hydroxyl group and one hydrogen atom from glycerin. r indicates a number of 1 or more and 4 or less. ]

In the general formula (c3), from the viewpoint of detergency, R ^7c preferably has 6 or more carbon atoms, more preferably 7 or more carbon atoms, still more preferably 8 or more carbon atoms, and preferably 18 or less carbon atoms. It is preferably a hydrocarbon group having 12 or less carbon atoms, and more preferably 10 or less carbon atoms.

In the general formula (c3), r is preferably 1 or more, and preferably 2 or less. The compound of 1 is more preferable for r.
The structure represented by Gly is the structure represented by —CH ₂ CH (OH) CH ₂ − in which the hydroxyl groups at the 1- and 3-positions of glycerin are bonded, or the structure in which the hydroxyl groups at the 1-position and the 2-position of glycerin are bonded. It has a structure represented by -CH (CH ₂ OH) CH _2- , and differs depending on the catalyst and reaction conditions.

To obtain the compound of the general formula (c3), for example, an alkyl alcohol represented by R ^7c -OH is used as an alcohol having 6 to 10 carbon atoms, and an epoxy compound such as epihalohydrin or glycidol is used as an acid catalyst such as BF ₃ . Alternatively, a method of reacting with an aluminum catalyst to produce the product can be used. For example, when 2-ethylhexanol is used, the resulting 2-ethylhexyl monoglyceryl ether is a mixture that may contain a plurality of products as described in Japanese Patent Application Laid-Open No. 2001-49291.

In the polyoxyalkylene monoalkyl or alkenyl ether, the carbon number of the alkyl group or the alkenyl group is preferably 6 or more, more preferably 8 or more, still more preferably 10 or more, still more preferably 12 or more, from the viewpoint of detergency. From the same viewpoint, it is preferably 22 or less, more preferably 18 or less, still more preferably 16 or less, still more preferably 14 or less.

In the polyoxyalkylene monoalkyl or alkenyl ether, the average number of moles of alkylene oxide added is preferably more than 0, more preferably 1 or more, still more preferably 3 or more, and preferably from the same viewpoint, from the viewpoint of detergency. Is 50 or less, more preferably 30 or less, still more preferably 20 or less, still more preferably 10 or less.
From the viewpoint of detergency, the alkylene oxide is preferably one or more selected from ethylene oxide, propylene oxide, and butylene oxide, more preferably one or more selected from ethylene oxide and propylene oxide, and further preferably. Is ethylene oxide.

Preferred examples of the polyoxyalkylene monoalkyl or alkenyl ether include a nonionic surfactant represented by the following general formula (c4).
R ^8c O [(C ₂ H ₄ O) _l / (C ₃ H ₆ O) _j ] H (c4)
[In the formula, R ^8c represents a hydrocarbon group having 6 or more and 22 or less carbon atoms. l and j indicate the average number of added moles, l indicates a number of 0 or more and 30 or less, j indicates a number of 0 or more and 30 or less, and l and j do not become 0 at the same time. "/" Indicates that the oxyethylene group and the oxypropylene group may be added to either random or block regardless of the order. ]

In the above general formula (c4), the carbon number of R ^8c is preferably 8 or more, more preferably 10 or more, still more preferably 12 or more from the viewpoint of detergency, and preferably 18 or more from the same viewpoint. Below, it is more preferably 16 or less, still more preferably 14 or less.
From the viewpoint of detergency, R ^8c is preferably an alkyl group or an alkenyl group, and more preferably an alkyl group.
Specific examples of the alkyl group include various octyl groups (including 2-ethylhexyl groups), various nonyl groups, various decyl groups, various undecylic groups, various dodecyl groups (lauryl groups), various tridecylic groups, and various tetradecyl groups. Examples thereof include various pentadecyl groups, various hexadecyl groups, various heptadecyl groups, and various octadecyl groups.
Examples of the alkenyl group include various octanyl groups, various nonanyl groups, various decanyl groups, various undecanyl groups, various dodecanyl groups, various tridecanyl groups, various tetradecanyl groups, various pentadecanyl groups, various hexadecanyl groups, various heptadecanyl groups, and various octadecanyl groups (for example). , Oleyl group, linoleic group). In addition, "various" means various isomers including n-, sec-, tert-, and iso-.

The total of l and j in the general formula (c4) is preferably 1 or more, more preferably 2 or more, and preferably 20 or less, more preferably 20 or less, from the viewpoint of storage stability. It is 10 or less, more preferably 8 or less.

The HLB value of the polyoxyalkylene monoalkyl or alkenyl ether as the component (c4) and the nonionic surfactant represented by the general formula (c4) is preferably 5 or more, more preferably 7 or more from the viewpoint of detergency. And, from the same viewpoint, it is preferably 19 or less, more preferably 15 or less, still more preferably 13 or less.
Here, the HLB value is defined by the Griffin formula shown below.
HLB value = 20 x Mw / M
(In the formula, M is the molecular weight of the nonionic surfactant, and Mw is the molecular weight of the hydrophilic portion of the nonionic surfactant.)
In the general formula (c4), the hydrophilic portion is the total portion of the oxyethylene group and the oxypropylene group.

As the alkylpolyglycoside (glycoside-type nonionic surfactant), a nonionic surfactant represented by the following general formula (c5) is preferable.
R ^9c (OR ^10c ) _s G _t (c5)
[In the formula, R ^9c represents an alkyl group having 8 or more and 18 or less carbon atoms, preferably 12 or more and 14 or less carbon atoms, an alkenyl group or an alkylphenyl group, preferably an alkyl group, and R ^10c has carbon atoms. It represents an alkylene group of 2 or more and 4 or less, and G represents a residue derived from a reducing sugar having 5 or 6 carbon atoms. s indicates the average number of added moles, which is a number of 0 or more and 5 or less. t indicates a number whose average value is 1 or more and 5 or less. ]

In the general formula (c5), R ^9c is a linear or branched alkyl group having 8 or more carbon atoms, preferably 10 or more carbon atoms, and 18 or less, preferably 14 or less carbon atoms from the viewpoint of detergency.
In the general formula (c5), s is preferably 0 or more and 2 or less, and more preferably 0, from the viewpoint of storage stability. From the viewpoint of storage stability, t is preferably 1.1 or more, preferably 1.5 or less, and more preferably 1.4 or less. In addition, t is a measured value by the proton NMR method.
In the general formula (c5), G includes residues derived from one or more monosaccharides selected from glucose and fructose in terms of their availability and cost. Further, G includes residues derived from one or more polysaccharides selected from maltose and sucrose. G is preferably a residue derived from the monosaccharide of glucose.

The sorbitan-based nonionic surfactant, aliphatic alkanolamide, fatty acid monoglyceride, and fatty acid fatty acid ester are preferably linear or branched alkyl groups having 8 to 18 carbon atoms, more preferably 12 to 14 carbon atoms. It is preferable to have.

The component (c) is preferably one or more selected from carbobetaine and polyoxyalkylene monoalkyl or alkenyl ether from the viewpoint of detergency and rinsability, and is a compound represented by the general formula (c1) and a general formula. One or more selected from the compounds represented by (c4) is more preferable, and the compound represented by the general formula (c1) is further preferable.

In the liquid detergent composition for a hard surface of the present invention, the surfactant which is the component (c) is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and further, from the viewpoint of detergency. It is preferably 0.2% by mass or more, and from the viewpoint of rinsability, it is preferably 2% by mass or less, more preferably 1.5% by mass or less, still more preferably 1% by mass or less, still more preferably 0.5% by mass. % Or less.

Further, the liquid detergent composition for a hard surface of the present invention may contain an anionic surfactant from the viewpoint of improving foaming property, but it is preferable to limit the content from the viewpoint of rinsing property. ..

Here, the anionic surfactant is usually used by those skilled in the art, and is, for example, a hydrocarbon group having 7 or more and 22 or less carbon atoms, a sulfate ester group, a phosphoric acid ester group, a phosphonic acid group, a sulfonic acid group, or the like. Examples thereof include an anionic surfactant having 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.

In the liquid detergent composition for hard surfaces of the present invention, the mass ratio (anionic surfactant) between the content of the anionic surfactant and the content of the total chelating agent containing the components (a) and (b). / Chelating agent) is preferably 0.30 or less, more preferably 0.28 or less, still more preferably 0.25 or less, still more preferably 0.2 or less, still more preferably 0. It is 1 or less, more preferably 0.05 or less, even more preferably 0.02 or less, and preferably 0 or more, and may be 0.

In the liquid cleaning agent composition for hard surfaces of the present invention, the mass ratio of the content of the anionic surfactant to the total content of the component (a) and the component (b) [anionic surfactant / ((a). ) + (B))] is preferably 0.30 or less, more preferably 0.28 or less, still more preferably 0.25 or less, still more preferably 0.2 or less, still more preferably, from the viewpoint of rinsability. Is 0.1 or less, more preferably 0.05 or less, even more preferably 0.01 or less, and preferably 0 or more, and may be 0.

In the liquid cleaning composition for hard surfaces of the present invention, the mass ratio of the content of the anionic surfactant to the total content of the component (a) and the component (b-1) [anionic surfactant / ( (A) + (b-1))] is preferably 0.30 or less, more preferably 0.28 or less, still more preferably 0.25 or less, still more preferably 0.2 or less, from the viewpoint of rinsability. , More preferably 0.1 or less, even more preferably 0.05 or less, even more preferably 0.01 or less, and preferably 0 or more, and may be 0.
In the present invention, the acid type conversion value is used for the content of the anionic surfactant.

<(D) component>
The liquid detergent composition for hard surfaces of the present invention preferably contains a thickener as the component (d).
The thickener of the component (d) is used from the viewpoint of adjusting the viscosity of the composition described later and enhancing the detergency.

(D) The components are smectite-type clay minerals mainly composed of montmorillonite, hectrite, permiculite, attapargite, sepiolite, and mixtures thereof; methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, guar gum and locust. Natural polymers such as nonionic polysaccharides such as bean gum, anionic polysaccharides such as xanthan gum, carrageenan and gellan gum; synthetic polymers such as polyvinyl alcohol, polyvinylpyrrolidone and polyethylene glycol can be mentioned.

The component (d) is preferably one or more selected from smectite-type clay minerals, natural polymers and synthetic polymers from the viewpoint of detergency, and is selected from nonionic polysaccharides, natural polymers and synthetic polymers. One or more of them are more preferable, and one or more selected from nonionic polysaccharides are further preferable.
Specifically, the component (d) is preferably one or more selected from hydroxyethyl cellulose, xanthan gum, and polyvinylpyrrolidone, and more preferably hydroxyethyl cellulose, from the viewpoint of detergency.

The liquid cleaning agent composition for a hard surface of the present invention preferably contains the component (d) in an amount of 0.01% by mass or more, more preferably 0.05% by mass, from the viewpoint of improving the cleaning power by improving the viscosity. Above, more preferably 0.1% by mass or more, still more preferably 0.2% by mass or more, and from the viewpoint of detergency and rinsability, preferably 3% by mass or less, more preferably 2% by mass or less, further. It is preferably 1% by mass or less, more preferably 0.9% by mass or less, still more preferably 0.8% by mass or less, and further preferably 0.5% by mass or less from the viewpoint of low cost and excellent economic efficiency. contains.

<(E) component>
The liquid detergent composition for hard surfaces of the present invention preferably contains a glycol-based solvent as the component (e).
The glycol-based solvent of the component (e) is used from the viewpoint of detergency of soap scum and sebum stains.
In the present invention, the glycol system means that it belongs to any of a compound having two hydroxyl groups and an ether compound in which one or both hydrogen atoms of the hydroxyl groups are substituted with other groups. The ether compound is preferably an aliphatic ether compound. Further, an ether compound in which one hydrogen atom of the hydroxyl group of the glycol compound is substituted with another group is preferable.

The component (e) is preferably a glycol-based water-soluble solvent having 2 or more and 12 or less carbon atoms. In the present invention, water solubility means dissolving 50 g or more in 100 g of water at 20 ° C.
From the viewpoint of detergency, the total carbon number of the component (e) is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, still more preferably 5 or more, still more preferably 6 or more, and cleaning. From the viewpoint of force, it is preferably 12 or less, more preferably 10 or less, still more preferably 8 or less.

The components (e) include ethylene glycol (2 carbon atoms), propylene glycol (3 carbon atoms), diethylene glycol (4 carbon atoms), propylene glycol monomethyl ether (4 carbon atoms), and isoprene glycol (carbon number 4) from the viewpoint of detergency. Number 5), Propylene Glycol Monoethyl Ether (5 Carbons), 3-Methyl-3-methoxybutanol (6 Carbons), Ethylene Glycol Monobutyl Ether (6 Carbons), Dipropylene Glycol (6 Carbons), Diethylene Glycol Mono One or more selected from butyl ether (8 carbon atoms), dibutylene diglycol (8 carbon atoms) and dipropylene glycol monobutyl ether (10 carbon atoms) can be mentioned.

As the component (e), glycols having 2 or 3 carbon atoms such as ethylene glycol, polyethylene glycol, propylene glycol and polypropylene glycol, their polyethers or their monoalkyl ethers are preferable. The alkyl group of this monoalkyl ether is preferably 1 or more and 4 or less carbon atoms, and is a methyl group, an ethyl group, various propyl groups, and various butyl groups. The variety includes normal, iso, and tertiary.

As the component (e), more preferably, from the viewpoint of detergency, propylene glycol (3 carbon atoms), ethylene glycol monobutyl ether (6 carbon atoms), propylene glycol monobutyl ether (7 carbon atoms), diethylene glycol monobutyl ether (carbon number of carbon atoms). 8), and one or more selected from the group consisting of dipropylene glycol monobutyl ether (10 carbon atoms). It is particularly preferable to contain diethylene glycol monobutyl ether (8 carbon atoms) as the component (e).

In the liquid detergent composition for hard surface of the present invention, the component (e) is preferably 1% by mass or more, more preferably 1.5% by mass or more, still more preferably, from the viewpoint of detergency of soap scum and sebum stains. Is contained in an amount of 2% by mass or more, preferably 10% by mass or less, more preferably 8% by mass or less, still more preferably 6% by mass or less, still more preferably 5% by mass or less.

<(F) component>
From the viewpoint of the detergency of soap scum stains, the liquid detergent composition for hard surfaces of the present invention preferably contains an aromatic alcohol [hereinafter referred to as component (f)].
The component (f) is preferably one or more selected from benzyl alcohol, 2-phenoxyethanol, and 2-benzyloxyethanol.

The liquid detergent composition for a hard surface of the present invention contains the component (f) in an amount of preferably 0.3% by mass or more, more preferably 0.5% by mass or more, and high temperature stability from the viewpoint of detergency. From the viewpoint, it is preferably contained in an amount of 10% by mass or less, more preferably 5% by mass or less, further preferably 3% by mass or less, still more preferably 2% by mass or less, still more preferably 1.5% by mass or less.

In order to increase the added value of the product, a fragrance, a dye, a preservative, an antioxidant and the like can be arbitrarily added to the liquid detergent composition for a hard surface of the present invention (however, the above (a)). ~ (F) component excluded).

The liquid detergent composition for hard surfaces of the present invention contains water. That is, the balance other than the components (a) to (c) and the optional components is water. The liquid detergent composition for a hard surface of the present invention contains water, preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 85% by mass or more, and. It is preferably contained in an amount of 95% by mass or less, more preferably 93% by mass or less. As the water, it is preferable to use ion-exchanged water, sterile ion-exchanged water, or the like.

In the liquid detergent composition for a hard surface of the present invention, the pH at 25 ° C. is preferably more than 6, more preferably 6.3 or more, still more preferably 6.5 or more, still more preferable, from the viewpoint of detergency. Is 6.8 or more, and from the viewpoint of hypoallergenicity to the skin, it is preferably 9.5 or less, more preferably 9 or less, still more preferably 8.5 or less.

The viscosity of the liquid detergent composition for a hard surface of the present invention at 25 ° C. exceeds 6 mPa · s, preferably 10 mPa · s or more, more preferably 15 mPa · s or more, and the detergency and detergency and From the viewpoint of rinsability, 1000 mPa · s or less, preferably 800 mPa · s or less, and further preferably 600 mPa · s or less, more preferably 600 mPa · s or less, from the viewpoint of reducing the blending amount of the component (d) and being excellent in cost and economy. It is 400 mPa · s or less, more preferably 200 mPa · s or less, still more preferably 100 mPa · s or less. The viscosity can be adjusted by the component (d), the component (e), and the like.
The viscosity of the liquid detergent composition for a hard surface of the present invention was measured as a value after 1 minute at 60 rpm using a B-type rotational viscometer. No. 1 was used, and if necessary, the rotor No. 1 was used so as to be within the measurement range of viscosity. Use 2 or 3.

The liquid 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 the kitchen, a countertop, and a water supply. Further, 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 hard surface is suitable for cleaning tiles, glass, stainless steel, plastics or ceramics.

<How to clean the hard surface and how to remove scale stains>
The present invention contains (a) a component (a) of 0.2% by mass or more and 10% by mass or less, (b) a component of 0% by mass or more and 10% by mass or less, (c) a component and water, and has a viscosity of 6 mPa at 25 ° C. A method for cleaning a hard surface, in which a liquid detergent composition for a hard surface having a mass of more than s and a mass of 1000 mPa · s or less is brought into contact with the hard surface and left for 1 minute or more.
In the method for cleaning a hard surface of the present invention, the liquid detergent composition for a hard surface of the present invention is used. A preferred embodiment of the composition is the same as the above-mentioned liquid detergent composition for hard surface of the present invention.
That is, the liquid detergent composition for a hard surface of the present invention is a hard surface liquid detergent composition used for cleaning by contacting it with a hard surface and leaving it to stand for 1 minute or more.

Further, the present invention contains the component (a) of 0.2% by mass or more and 10% by mass or less, the component (b) of 0% by mass or more and 10% by mass or less, the component (c) and water, and has a viscosity of 25 ° C. It is also a method for removing water stains by bringing a liquid detergent composition for a hard surface, which is more than 6 mPa · s and 1000 mPa · s or less, into contact with a hard surface and leaving it for 1 minute or more.
By the method of the present invention, water stains can be removed by cleaning the hard surface.

Specifically, the cleaning method of the present invention is such that the liquid detergent composition for a hard surface is brought into contact with a hard surface with a stock solution, or the liquid detergent composition for a hard surface is not diluted with a stock solution. A cleaning method in which the liquid detergent composition for a hard surface is brought into contact with the hard surface without diluting the liquid detergent composition for the hard surface is preferably brought into contact with the hard surface. Further, there is a cleaning method in which the liquid detergent composition for a hard surface is brought into contact with a hard surface to which water stains are attached without diluting. As a method of contacting with the hard surface, a method of applying to the hard surface is preferable.
The term "contacting the liquid cleaning agent composition for a hard surface with a hard surface without diluting" 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, the liquid detergent composition for a hard surface may be brought into contact with a hard surface to which water droplets or the like are attached, or the liquid detergent composition for a hard surface may be brought into contact with a hard surface and then water droplets may be attached to the hard surface. In this case, it can be understood that the liquid detergent composition for a hard surface is brought into contact with the hard surface without being diluted.
In the present invention, the undiluted solution of the liquid detergent composition for a hard surface is adhered to a hard surface as it is, that is, without changing the composition. For example, the liquid detergent composition for a hard surface is brought into contact with a hard surface to which scale stains are attached without adhering to the water-containing absorbent cotton. After contacting the hard surface, the composition of the liquid detergent composition for the hard surface may vary. That is, after contacting the hard surface, the composition of the liquid detergent composition for the hard surface may be diluted or concentrated.
In the cleaning method of the present invention, the liquid detergent composition for a hard surface may be applied directly from a bottle in order to bring the liquid detergent composition for a hard surface into contact with the hard surface with an undiluted solution, and examples of the bottle include a squeeze bottle and the like. ..

However, 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 liquid detergent for a hard surface of the present invention. An object may be prepared and brought into contact 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 a liquid detergent composition for a hard surface of the present invention, and is used for the hard surface. A method for cleaning a hard surface may be used in which the liquid detergent composition is brought into contact with the hard surface without being diluted.

From the viewpoint of detergency, the time to leave after applying to a hard surface is preferably 1 minute or longer, preferably 2 minutes or longer, more preferably 3 minutes or longer, still more preferably more than 3 minutes, still more preferably 4 minutes. 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 15 minutes or less, still more preferably 10 minutes or less. Is.
After leaving it, it is usually rinsed with water. When rinsing, mechanical force (physical force) may be applied by hand or simply rinsing with a stream of water.
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 liquid 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 liquid cleaning agent composition for a hard surface of the present invention is applied to a hard surface 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 liquid detergent composition for a hard surface 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 liquid detergent 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 liquid detergent composition for hard surface has flexibility and can be impregnated with the liquid detergent composition for hard surface, and has sufficient strength at the time of use. The one that has the above and does not generate waste etc. is used. It is preferable to use a substrate that can be impregnated with the amount of the liquid detergent composition for hard surfaces 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 mixtures 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 with the cleaning article impregnated with the liquid 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 liquid detergent composition for hard surface are those in which the substrate is pre-impregnated with the detergent composition, or the dried substrate is impregnated with the liquid detergent composition for hard surface immediately before use. It may be any of the above. Further, the cleaning article impregnated with the liquid detergent 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 liquid detergent composition for hard surface is impregnated in advance, the impregnation rate of the liquid detergent composition for hard surface is the mass of the substrate [that is, the mass of the substrate in the unimpregnated state (dry state) from the viewpoint of cleanability. Criteria], 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. It is more preferably% or less. When the impregnation rate is 100% by mass or more, sufficient cleaning performance against stains and dirt can be obtained. If it is 1000% by mass or less, the amount of the liquid detergent composition for a hard surface released to the surface to be cleaned is appropriate, no dirt or dirt or dust remains on the surface to be cleaned, and from various materials such as wood-based materials. It can be used without affecting the cleaning surface. From the viewpoint of further improving the cleaning property, when the substrate is a sheet, the basis weight before impregnation of the liquid detergent composition for hard surface is the retention of the liquid detergent composition for hard surface required for cleaning a certain area. From the viewpoint of properties, operability of the sheet, and cost, 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 liquid detergent composition for a hard surface, the liquid detergent composition for a hard surface 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.

Regarding the above-described embodiment, the present invention further discloses the following liquid detergent composition for a hard surface, a method for cleaning a hard surface, and a method for removing water stains. To these aspects, the matters described in the liquid detergent composition for a hard surface of the present invention, the method for cleaning a hard surface, and the method for removing water stains can be appropriately applied to each other.

<1>
(A) One or more selected from phosphonic acid-based chelating agents and phosphoric acid-based chelating agents (hereinafter referred to as component (a)) is 0.2% by mass or more and 10% by mass or less, other than (b) and (a) components. A liquid detergent composition for a hard surface containing 0% by mass or more and 10% by mass or less of a chelating agent (hereinafter referred to as component (b)), (c) a surfactant (hereinafter referred to as component (c)), and water. There,
The viscosity at 25 ° C. is more than 6 mPa · s and 1000 mPa · s or less.
Used for cleaning, which is in contact with a hard surface, preferably applied and left for 1 minute or longer.
Liquid detergent composition for hard surfaces.

<2>
(B) The component is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, still more preferably 2% by mass or more, still more preferably 3% by mass or more. The hard surface liquid detergent composition according to <1>, preferably containing 8% by mass or less, more preferably 7% by mass or less, still more preferably 6% by mass or less.

<3>
The mass ratio (a) / (b) of the content of the component (a) to the content of the component (b) is preferably 0.02 or more, more preferably 0.05 or more, still more preferably 0.1 or more. , More preferably 0.15 or more, even more preferably 0.2 or more, and preferably 10 or less, more preferably 8 or less, still more preferably 5 or less, even more preferably 3 or less, still more preferably 1. Hereinafter, the liquid cleaning agent composition for a hard surface according to the above <1> or <2>, which is more preferably 0.8 or less, still more preferably 0.6 or less, still more preferably 0.5 or less. ..

<4>
The mass ratio of the content of the anionic surfactant to the total content of the component (a) and the component (b) [anionic surfactant / ((a) + (b))] is preferably 0. 30 or less, more preferably 0.28 or less, still more preferably 0.25 or less, still more preferably 0.2 or less, still more preferably 0.1 or less, still more preferably 0.05 or less, still more preferably. The liquid detergent composition for a hard surface according to any one of <1> to <3> above, which is 0.01 or less, and preferably 0 or more.

<5>
The mass ratio [anionic surfactant / ((a) + (b))] between the content of the anionic surfactant and the total content of the component (a) and the component (b) is 0. The liquid detergent composition for a hard surface according to any one of <1> to <3>.

<6>
(A) One or more selected from phosphonic acid-based chelating agents and phosphoric acid-based chelating agents (hereinafter referred to as (a) component) are 0.2% by mass or more and 10% by mass or less, (b) (b-1) carboxylic acid. Acid-based chelating agent (excluding component (a)) (hereinafter referred to as component (b-1)) is 0.2% by mass or more and 10% by mass or less, (c) surfactant (hereinafter, component (c)). ) And a liquid detergent composition for hard surfaces containing water.
The viscosity at 25 ° C. is more than 6 mPa · s and 1000 mPa · s or less.
Liquid detergent composition for hard surfaces.

<7>
The component (b-1) is a hydroxycarboxylic acid and a salt thereof, and one or more chelating agents selected from an aminocarboxylic acid and a salt thereof, preferably a hydroxycarboxylic acid having 3 or more and 8 or less carbon atoms and a salt thereof. The hard according to the above <6>, which is one or more selected from, more preferably one or more selected from citric acid, malic acid, and salts thereof, and further preferably citric acid or a salt thereof. Liquid cleaning agent composition for surface.

<8>
The component (b-1) is preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, still more preferably 3% by mass or more, and preferably 8% by mass or less. The liquid detergent composition for a hard surface according to the above <6> or <7>, more preferably 7% by mass or less, still more preferably 6% by mass or less.

<9>
Mass ratio of (a) component content to (b-1) component content The mass ratio of (a) / (b-1) is preferably 0.02 or more, more preferably 0.05 or more. More preferably 0.1 or more, still more preferably 0.15 or more, still more preferably 0.2 or more, and preferably 10 or less, more preferably 8 or less, still more preferably 5 or less, still more preferably 3 Hereinafter, any of the above <6> to <8>, more preferably 1 or less, still more preferably 0.8 or less, still more preferably 0.6 or less, still more preferably 0.5 or less. The liquid cleaning agent composition for a hard surface according to the above.

<10>
The mass ratio of the content of the anionic surfactant to the total content of the component (a) and the component (b-1) [anionic surfactant / ((a) + (b-1))] is It is preferably 0.30 or less, more preferably 0.28 or less, still more preferably 0.25 or less, still more preferably 0.2 or less, still more preferably 0.1 or less, still more preferably 0.05 or less. The liquid detergent composition for a hard surface according to any one of <6> to <9>, more preferably 0.01 or less, and preferably 0 or more.

<11>
The mass ratio of the content of the anionic surfactant to the total content of the component (a) and the component (b-1) [anionic surfactant / ((a) + (b-1))] is 0. The liquid detergent composition for a hard surface according to any one of <6> to <9>.

<12>
(A) The component is preferably 0.3% by mass or more, more preferably 0.4% by mass or more, still more preferably 0.5% by mass or more, still more preferably 1% by mass or more, still more preferably 1. 5% by mass or more, preferably 8% by mass or less, more preferably 6% by mass or less, still more preferably 4% by mass or less, still more preferably 3% by mass or less. The liquid cleaning agent composition for a hard surface according to any one.

<13>
The component (c) is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, further preferably 0.2% by mass or more, and preferably 2% by mass or less, more preferably 1.5% by mass. The liquid cleaning agent composition for a hard surface according to any one of <1> to <12> above, which contains by mass or less, more preferably 1% by mass or less, still more preferably 0.5% by mass or less.

<14>
The mass ratio (anionic surfactant / chelating agent) of the content of the anionic surfactant to the content of the component (a) and the total chelating agent containing the component (b) is preferably 0.30 or less. More preferably 0.28 or less, still more preferably 0.25 or less, still more preferably 0.2 or less, still more preferably 0.1 or less, still more preferably 0.05 or less, still more preferably 0.02. The liquid detergent composition for a hard surface according to any one of <1> to <13> above, which is preferably 0 or more.

<15>
The mass ratio (anionic surfactant / chelating agent) between the content of the anionic surfactant and the content of the components (a) and the total chelating agent containing the component (b) is 0, the above <1>. The liquid detergent composition for a hard surface according to any one of <13>.

<16>
The liquid detergent composition for a hard surface according to any one of <1> to <15>, which further contains (d) a thickener (hereinafter referred to as a component (d)).

<17>
The liquid detergent composition for a hard surface according to <16>, wherein the component (d) is a thickener selected from the following (1) to (3).
(1) Smectite-type clay minerals mainly composed of montmorillonite, hectrite, permiculite, attapargite, sepiolite, and mixtures thereof (2) Methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, guar gum and locust bean gum. Natural polymer selected from nonionic polysaccharides selected from, and anionic polysaccharides selected from xanthan gum, carrageenan and gellan gum (3) Synthetic polymer selected from polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol.

<18>
(D) The component is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, still more preferably 0.2% by mass or more, and preferably. 3% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less, still more preferably 0.9% by mass or less, still more preferably 0.8% by mass or less, still more preferably 0.5. The liquid cleaning agent composition for a hard surface according to the above <16> or <17>, which contains by mass or less.

<19>
The liquid detergent composition for a hard surface according to any one of <1> to <18>, which further contains (f) an aromatic alcohol [hereinafter referred to as (f) component].

<20>
The liquid detergent composition for a hard surface according to <19> above, wherein the component (f) is one or more selected from benzyl alcohol, 2-phenoxyethanol, and 2-benzyloxyethanol.

<21>
The component (f) is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less. The liquid detergent composition for a hard surface according to <19> or <20>, which further preferably contains 2% by mass or less, more preferably 1.5% by mass or less.

<22>
Water is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 85% by mass or more, and preferably 95% by mass or less, more preferably 93% by mass or more. The liquid detergent composition for a hard surface according to any one of <1> to <21>, which is contained below.

<23>
The pH at 25 ° C. is preferably greater than 6, more preferably 6.3 or higher, still more preferably 6.5 or higher, even more preferably 6.8 or higher, and preferably 9.5 or lower, more preferably 9 or higher. Hereinafter, the liquid detergent composition for a hard surface according to any one of <1> to <22>, which is more preferably 8.5 or less.

<24>
The viscosity at 25 ° C. is preferably 10 mPa · s or more, more preferably 15 mPa · s or more, and preferably 800 mPa · s or less, more preferably 600 mPa · s or less, still more preferably 400 mPa · s or less, still more preferably. Is 200 mPa · s or less, more preferably 100 mPa · s or less, the liquid detergent composition for a hard surface according to any one of <1> to <23>.

<25>
The liquid detergent composition for a hard surface according to any one of <1> to <24>, wherein the hard surface is tile, glass, stainless steel, plastic or ceramic.

<26>
A method for cleaning a hard surface using the liquid detergent composition for a hard surface according to any one of <1> to <25>.

<27>
(A) 0.2% by mass or more and 10% by mass or less of one or more selected from phosphonic acid-based chelating agents and phosphoric acid-based chelating agents, and (b) 0% by mass or more and 10% by mass of chelating agents other than the components (a). % Or less, (c) a liquid detergent composition for a hard surface containing a surfactant and water and having a viscosity at 25 ° C. of more than 6 mPa · s and 1000 mPa · s or less is preferably brought into contact with the hard surface. A method of cleaning a hard surface that is applied and left for 1 minute or longer.

<28>
The time of contact with a hard surface, preferably after coating, and then left to stand is preferably 2 minutes or longer, more preferably 3 minutes or longer, still more preferably more than 3 minutes, still more preferably 4 minutes or longer, still more preferably. The method for cleaning a hard surface according to the above <27>, which is 5 minutes or more, preferably 60 minutes or less, more preferably 30 minutes or less, still more preferably 15 minutes or less, still more preferably 10 minutes or less. ..

<29>
(A) 0.2% by mass or more and 10% by mass or less of one or more selected from phosphonic acid-based chelating agents and phosphoric acid-based chelating agents, and (b) 0% by mass or more and 10% by mass of chelating agents other than the components (a). % Or less, (c) a liquid detergent composition for a hard surface containing a surfactant and water and having a viscosity at 25 ° C. of more than 6 mPa · s and 1000 mPa · s or less is preferably brought into contact with the hard surface. A method of removing water stains by applying and leaving for 1 minute or more.

<30>
The time of contact with a hard surface, preferably after application, and then left to stand is preferably 2 minutes or longer, more preferably 3 minutes or longer, still more preferably more than 3 minutes, still more preferably 4 minutes or longer, still more preferably. The method for removing scale stains according to the above <29>, which is 5 minutes or more, preferably 60 minutes or less, more preferably 30 minutes or less, still more preferably 15 minutes or less, still more preferably 10 minutes or less. ..

The liquid detergent composition for hard surface shown in Table 1 was prepared using the following compounding ingredients, and the following items were evaluated. The results are shown in Table 1. The liquid detergent composition for a hard surface shown in Table 1 was prepared by a conventional method. That is, after adding the components (a) to (f) to an appropriate amount of ion-exchanged water and dissolving them at room temperature (25 ° C), sodium hydroxide is added to adjust the pH (25 ° C) to add a fragrance. Added. The mass% of the compounding components in Table 1 are all numerical values based on the effective amount. Further, the component (a) and the component (b) indicate the mass% based on the amount in terms of acid. Further, the sodium alkyl ether sulfate ester of the component (c) shows a mass% based on the amount in terms of acid.
Table 1 shows the viscosities of the liquid detergent composition for hard surfaces measured (25 ° C.) at 60 rpm using a B-type rotational viscometer as a value after 1 minute. At low viscosities, the rotor No. No. 1 was used, and if necessary, the rotor No. 1 was used so as to be within the measurement range of viscosity. 2 or 3 was used.

<Ingredients>
(A) Ingredients-Etan-1-hydroxy-1,1-diphosphonic acid: Phosphonic acid-based chelating agent, Italmatch Japan Co., Ltd., Diquest 2010CS, 60% by mass aqueous solution-Aminotrimethylenephosphonic acid: Phosphonic acid-based Chelating agent, Italmatch Japan Co., Ltd., Diquest 2006, 39% by mass aqueous solution ・ Tripolyphosphate: Phosphonic acid-based chelating agent, Aditya Birla Chemicals (Thailand) Limited (b) component ・ Citrate: Carboxylic acid-based chelating Agent ((b-1) component), manufactured by Wako Pure Chemical Industries, Ltd., Wako special grade

(C) Ingredients-Lauric acid amidopropylbetaine: an amphoteric surfactant, in the general formula (c1), R ^1c is an alkyl group having 11 carbon atoms, R ^2c and R ^3c are compounds having a methyl group, Anchtor 20AB, Kao Co., Ltd. ) Polyoxyethylene (7) Alkyl ether: Nonionic surfactant, in general formula (c4), R ^8c is an alkyl group having 12 carbon atoms, l is 7 and j is 0, a compound, sophthalol 70H, Kao ( () Is the average number of moles of oxyethylene group added. ・ Alkyl ether sulfate sodium: anionic surfactant, alkyl group has 12 to 16 carbon atoms, ethylene oxide average number of moles of 4.0, ES-4K. , Made by Kao Co., Ltd.

(D) Ingredients-Hydroxyethyl cellulose ether: Natural polymer of nonionic polysaccharide, HEC Daicel SE850K, Daicel FineChem Co., Ltd.-Xanthan gum: Natural polymer of anionic polysaccharide, KELZAN, Sansho Co., Ltd.-Polyvinylpyrrolin Don: Synthetic polymer, PVP K-90 ISP TECHNOLOGIES, INC (e) component-Diethylene glycol monobutyl ether: Glycol solvent, BDG (butyl diglycol), Nippon Emulsor Co., Ltd. (f) component-benzyl alcohol: Wako Pure Chemical Industry Co., Ltd., benzyl alcohol, Wako special grade

(1) Detergency evaluation 0.3 mL of 300 ppm SiO _{2/300 ppm CaCl 2 aqueous} solution was applied as evenly as possible to the lower 25 mm portion of the slide glass (76 mm × 26 mm), and dried on a hot plate heated to 140 ° C. After that, it was 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 stain of scale stain.
Put cotton wool (Curelet 4 x 4 cm ² manufactured by Kawamoto Corporation) cut to the size of the model stain on the slide glass with the model stain, and drop 1 mL of the liquid detergent composition for each hard surface. After being left for a predetermined time as shown in Table 1, the entire surface of the slide glass was rubbed with a light force (about 200 g weight) 5 times back and forth. 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) Evaluation of rinsability after washing 24 mL of each washing liquid is sprinkled on the bathroom floor of 100 x 120 cm ² , rubbed 70 times with a sponge, then rinsed with tap water shower, and the time until the bubbles disappear completely is the standard below. Evaluated in. The temperature of tap water during rinsing was 30 ° C., and the flow rate was constant at about 143 mL / sec.
The bubbles disappear within 1:25 seconds and the rinse is complete.
Bubbles do not disappear even after 2:25 seconds.
3: It takes more than 30 seconds for the bubbles to disappear.

(3) Practical evaluation of detergency A stainless steel plate was installed in a kitchen sink at home for one month, and degreased cotton (curelet 4 x 4 cm) cut into 2 x 2 cm ² was placed on the surface of the stainless steel plate with water stains on it. ² Place Kawamoto Sangyo Co., Ltd., drop 1 mL of the liquid detergent composition for hard surface of Example 2, leave it for 20 minutes, and then reciprocate the entire surface of the faucet 5 times with a light force (about 200 g weight). Rubbed with. After that, the surface of the plate was thoroughly rinsed with ion-exchanged water. The hard surface of the stainless steel plate before and after cleaning was photographed under the same imaging conditions such as brightness. The photograph before cleaning is shown in FIG. 1, and the photograph after cleaning is shown in FIG.

Comparing FIGS. 1 and 2, the scaly scale stains that had adhered before cleaning were mostly scaly scale stains after cleaning with the liquid detergent composition for hard surface of Example 2. It can be seen that it has been removed.

Claims (8)

(A) One or more selected from phosphonic acid-based chelating agents and phosphoric acid-based chelating agents (hereinafter referred to as (a) component) are 0.3 % by mass or more and 6 % by mass or less, (b) (b-1) carboxylic acid. Acid-based chelating agent (excluding component (a)) (hereinafter referred to as component (b-1)) is 0.2% by mass or more and 10% by mass or less, (c) surfactant (hereinafter, component (c)). ) And a liquid detergent composition for hard surfaces containing water.
The viscosity at 25 ° C. is more than 6 mPa · s and 1000 mPa · s or less .
The mass ratio (a) / (b-1) between the content of the component (a) and the content of the component (b-1) is 0.02 or more and 10 or less.
Liquid detergent composition for hard surfaces. The liquid detergent composition for a hard surface according to claim 1 , wherein the pH at 25 ° C. exceeds 6. (C) The liquid detergent composition for a hard surface according to claim 1 or 2 , wherein the content of the component is 2% by mass or less. (C) Any of claims 1 to 3 , wherein the mass ratio (anionic surfactant / chelating agent) between the content of the anionic surfactant and the content of the total chelating agent in the component is 0.3 or less. The liquid detergent composition for a hard surface according to Item 1. The liquid detergent composition for a hard surface according to any one of claims 1 to 4 , further comprising (d) a thickener. The liquid detergent composition for a hard surface according to any one of claims 1 to 5 , wherein the hard surface is tile, glass, stainless steel, plastic or ceramic. A method for cleaning a hard surface using the liquid detergent composition for a hard surface according to any one of claims 1 to 6 . A method for removing water stains by contacting the liquid detergent composition for a hard surface according to any one of claims 1 to 6 with a hard surface.

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