JP2019048963A - Liquid detergent composition for hard surface - Google Patents

Abstract

To provide a liquid detergent composition for hard surface which is excellent in detergency to water stain attached to a hard surface, and to provide a method for removing a water stain using the same.SOLUTION: A liquid detergent composition for hard surface contains 0.2 mass% or more and 10 mass% or less of (a) one or more selected from a phosphonic acid chelate agent and a phosphoric acid chelate agent (hereinafter referred to as component (a)), 0 mass% or more and 10 mass% or less of (b) a chelate agent other than the component (a), (c) a surface active agent and water, where viscosity at 25°C is more than 6 mPa s and 1,000 mPa s or less, and the composition is used for cleaning that is brought into contact with the hard surface and is left for 1 or more minutes.SELECTED DRAWING: None

Description

  The present invention relates to a liquid cleaner composition for hard surfaces, and a method of removing water stains on hard surfaces.

  In the living environment facilities that surround us, there are various hard surfaces made of tiles, plastics, metals, etc., and these hard surfaces are exposed to an environment where various dirt adheres in daily life situations. Above all, the hard surface used as a bathroom, a kitchen, etc. is a surface which people touch on a daily basis, so a lot of dirt remains and tends to be accumulated, and furthermore it has a property that it is difficult to remove by washing. There is. As a cleaning agent for a bathroom generally used for a bath, a wall and a floor of a bathroom, a cleaning agent containing a surfactant, a solvent, a sequestering agent, etc. in order to remove stains of metal soaps, particularly calcium salts of fatty acids. Is used.

For example, in Patent Document 1, (a) 0.5% by mass or more and 3% by mass or less of a betaine type amphoteric surfactant, 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 proportion of the component (a) in all surfactants is 65% by mass or more, at 25 ° C. A germicidal detergent composition for hard surfaces having a pH of 2 or more and 6 or less is disclosed.
Further, Patent Document 2 discloses a bathroom cleaning composition characterized by containing at least a surfactant, a chelating agent, a polymer compound, a solvent and a perfume.

JP, 2015-113455, A Japanese Patent Publication No. 2003-183698

In Patent Documents 1 and 2, the problem is to remove the calcium salt of fatty acid, but it can not be said that it is sufficient for water stains.
In the present invention, "water-based stain" refers to a stain in which a scaly pattern is deposited by the polymerization and accumulation of silicic acid contained in water on a hard surface.

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

The present invention comprises 0.2% by mass or more and 10% by mass or less of one or more selected from (a) phosphonic acid type chelating agents and phosphoric acid type chelating agents (hereinafter referred to as component (a)), (b) (a) Liquid cleaning for hard surfaces containing 0% by mass or more and 10% by mass or less of a chelating agent other than the component (hereinafter referred to as component (b)), (c) surfactant (hereinafter referred to as component (c)) and water. Agent composition,
The viscosity at 25 ° C exceeds 6 mPa · s and is 1000 mPa · s or less,
Used for cleaning in contact with a hard surface and left for 1 minute or longer
The present invention relates to a liquid detergent composition for hard surfaces.

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 chelating agent (excluding the component (a)) (hereinafter referred to as (b-) A liquid detergent composition for hard surfaces comprising 0.2 mass% or more and 10 mass% or less of component 1), component (c) and water;
The viscosity at 25 ° C. is more than 6 mPa · s and not more than 1000 mPa · s,
The present invention relates to a liquid detergent composition for hard surfaces.

  Further, the present invention contains 0.2% by mass to 10% by mass of the component (a), 0% by mass to 10% by mass of the component (b), the component (c) and water, and has a viscosity of 25 ° C. The liquid detergent composition for hard surfaces which is more than 6 mPa * s and 1000 mPa * s or less is made to contact with a hard surface, and it is related with the removal method of a water-borne stain which leaves for 1 minute or more.

  According to the present invention, it is possible to provide a liquid cleaner composition for hard surfaces, which is excellent in the detergency against water stains attached to hard surfaces, and a method of removing water stains using the same.

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

Liquid Cleaner Composition for Hard Surface
The present inventors have found that the cause of the water stain is that silicic acid contained in tap water is polymerized, and the polymer is accumulated on the hard surface in a bowl-like manner.
The present inventor also uses the component (a) of the present invention to remove the water stains, and combines the component (c) with the component (b) if necessary to obtain a specific viscosity range and pH range. It has been found that contacting the hard surface liquid detergent composition with the hard surface is effective for removing water stains.
Although such an effect is not necessarily clear, the liquid detergent composition for hard surface according to the present invention causes the silicic acid molecules to be sequentially released from the vicinity of the surface of the silicic acid polymer which is the cause of the water stain. It is guessed that it is because it can be removed.

<(A) component>
The component (a) of the present invention is at least one selected from phosphonic acid type chelating agents and phosphoric acid type chelating agents.
Examples of phosphonic acid chelating agents include ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid, ethanehydroxy-1,1,2- 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 1 There are more species. Examples of the salt include alkali metal salts such as sodium and potassium, ammonium salts or alkanolamine salts such as monoethanolamine and triethanolamine.
The phosphoric acid chelating agent includes one or more selected from orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid, hexametaphosphoric acid and salts thereof.
From the viewpoint of detergency, component (a) is preferably a phosphonic acid chelating agent, more preferably one or more selected from hydroxyphosphonic acid and a salt thereof, ethane-1-hydroxy-1,1-diphosphonic acid or its Salt is more preferred.

  The liquid detergent composition for a hard surface according to the present invention contains 0.2% by mass or more, preferably 0.3% by mass or more, more preferably 0.4% by mass or more of the component (a) from the viewpoint of detergency. , 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, and from the viewpoint of economy, 10% by mass or less, preferably 8% by mass or less The content is more preferably 6% by mass or less, still more preferably 4% by mass or less, still more preferably 3% by mass or less. In the present invention, the content of the component (a) is an acid-type conversion value.

<(B) component>
The component (b) of the present invention is a chelating agent other than the component (a).
Preferred examples of the component (b) include carboxylic acid chelating agents (except for the component (a)) (hereinafter also referred to as the component (b-1)). As a carboxylic acid chelating agent, one or more chelating agents selected from hydroxycarboxylic acids and salts thereof and aminocarboxylic acids and salts thereof are more preferably mentioned.

Examples of hydroxycarboxylic acids and salts thereof include citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, gluconic acid, diglycolic acid, oxydisuccinic acid, carboxymethyl succinic acid, carboxymethyl oxysuccinic acid, carboxymethyl tartaric acid, and the like One or more selected from salts can be mentioned. The salts specifically include alkali metal salts or ammonium salts and alkanolamine salts.
The hydroxycarboxylic acid and the salt thereof 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 from the viewpoint of detergency. More than one kind is preferable, and one or more kinds selected from citric acid, malic acid and salts thereof are more preferable.

  Examples of aminocarboxylic acids and salts thereof include nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, hydroxyethylenediamineacetic acid, diethylenetriaminepentaacetic acid, glycol ether diamine tetraacetic acid, hydroxyethyl iminodiacetic acid, triethylenetetramine hexaacetic acid, jincolic acid and One or more selected from these salts may be mentioned. Specific examples of the salt include alkali metal salts, ammonium salts and alkanolamine salts.

  From the viewpoint of detergency, component (b-1) is preferably one or more selected from hydroxycarboxylic acids having 3 to 8 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 more preferable.

  The liquid detergent composition for a hard surface according to the present invention contains 0% by mass or more, preferably 0.2% by mass or more, more preferably 0.5% by mass or more of the component (b) from the viewpoint of detergency. It is preferably at least 1% by mass, more preferably at least 2% by mass, still more preferably at least 3% by mass, and from the viewpoint of economy, 10% by mass or less, preferably 8% by mass or less, more preferably 7% by mass % Or less, more preferably 6% by mass or less. In the present invention, the content of the component (b) is converted to an acid type.

  From the viewpoint of detergency, the liquid detergent composition for a hard surface according to the present invention contains 0% by mass or more, preferably 0.2% by mass or more, and more preferably 0.5% by mass. % 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 economy, 10% by mass or less, preferably 8% by mass or less Preferably it is 7 mass% or less, More preferably, it is 6 mass% or less. In the present invention, as the content of the component (b-1), an acid type equivalent value is used.

  In the liquid detergent composition for a hard surface according to the present invention, the proportion of the component (b-1) in the component (b) is preferably 50% by mass or more, more preferably 70% by mass or more from the viewpoint of detergency. More preferably, it is 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 according to the present invention contains (a) component and (b) component, preferably contains (a) component and (b-1) component, thereby reducing the cost. It is excellent in economical efficiency and can obtain high washability.

  In the liquid detergent composition for hard surfaces of the present invention, when the component (a) and the component (b) are contained, 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. From the viewpoint of economy, 2 or more, 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, it is 0.6 or less, and still more preferably 0.5 or less.

  In the liquid detergent composition for hard surfaces of the present invention, when the component (a) and the component (b-1) are contained, 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. Still more preferably 0.2 or more, and from the viewpoint of economy, 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, more Preferably it is 0.8 or less, more preferably 0.6 or less, and still 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.

The amphoteric surfactant includes one or more amphoteric surfactants selected from carbobetaine, sulfobetaine, and amine oxide.
The liquid detergent composition for a hard surface according to the present invention preferably contains one or more selected from carbobetaine as the component (c).

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

[Wherein, R ^1c represents an alkyl group having 7 to 21 carbon atoms or an alkenyl group, and R ^2c and R ^3c each independently represent an alkyl group having 1 to 3 carbon atoms. ]

In the general formula (c1), R ^1c is preferably an alkyl 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. Preferred are decyl, undecyl, dodecyl and tridecyl.
In the general formula (c1), R ^2c and R ^3c are preferably methyl groups.

  The sulfobetaine is preferably an N-alkyl-N, N-dimethyl-N-sulfopropylammonium sulfobetaine or an alkyl or alkenyl group having a carbon number of preferably 10 or more, and preferably 18 or less, more preferably 14 or less. N-Alkenyl-N, N-dimethyl-N-sulfopropylammonium sulfobetaine, the alkyl or alkenyl group preferably has a carbon number of 10 or more, and preferably 18 or less, more preferably 14 or less. , N-dimethyl-N- (2-hydroxysulfopropyl) ammonium sulfobetaine or N-alkenyl-N, N-dimethyl-N- (2-hydroxysulfopropyl) ammonium sulfobetaine, carbon number of alkanoyl group is preferably 10 Above, and preferably below 18 More preferably, 14 or less N-alkanoylaminopropyl-N, N-dimethyl-N-sulfopropylammonium sulfobetaine, the carbon number of the alkanoyl group is preferably 10 or more, and preferably 18 or less, more preferably 14 or less. N-alkanoylaminopropyl-N, N-dimethyl-N- (2-hydroxysulfopropyl) ammonium sulfobetaine is mentioned.

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

[Wherein, R ^4c represents a hydrocarbon group having 8 to 22 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] 3 or less alkyl group is shown. D shows -NHC (= O)-group or -C (= O) NH- group, E shows a C1-C5 alkylene group. 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 to 18 carbon atoms, more preferably an alkyl group having 12 to 16 carbon atoms, from the viewpoint of detergency. It is an alkyl group having 12 to 14 carbon atoms, and more preferably an alkyl group having 12 carbon atoms.
Each of R ^5c and R ^6c is preferably a methyl group having 1 carbon atom from the viewpoint of detergency.

  Examples of nonionic surfactants include alkyl monoglyceryl ether, polyoxyalkylene monoalkyl or alkenyl ether, alkyl polyglycoside (glycoside type nonionic surfactant), sorbitan nonionic surfactant, aliphatic alkanolamide, fatty acid One or more selected from the group consisting of monoglycerides and sucrose fatty acid esters are preferred, and two or more may be used.

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

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

In the general formula (c3), r is preferably 1 or more and preferably 2 or less. r is more preferably a compound of 1;
The structure represented by Gly is a structure represented by -CH ₂ CH (OH) CH _2- in which the 1-position and 3-position hydroxyl groups of glycerin are bonded, or the 1- and 2-position hydroxyl groups of glycerin are combined The structure is represented by -CH (CH ₂ OH) CH _2- , which varies depending on the catalyst and reaction conditions.

In order to obtain the compound of the general formula (c3), for example, an alkyl alcohol represented by R ^7c -OH is used as the alcohol having 6 to 10 carbon atoms, an epoxy compound such as epihalohydrin or glycidol, an acid catalyst such as BF ₃ , Alternatively, a method of reaction by using an aluminum catalyst can be used. For example, when 2-ethylhexanol is used, the 2-ethylhexyl monoglyceryl ether obtained is a mixture which may contain a plurality of products as described in JP-A-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. And from the same viewpoint, it is preferably 22 or less, more preferably 18 or less, further preferably 16 or less, and still more preferably 14 or less.

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

As a preferable example of polyoxyalkylene monoalkyl or alkenyl ether, nonionic surfactant represented by the following general formula (c4) can be mentioned.
R ^8c O [(C ₂ H ₄ O) ₁ / (C ₃ H ₆ O) _j ] H (c 4)
[Wherein, R ^8c represents a hydrocarbon group having 6 to 22 carbon atoms. l and j indicate the average addition mole number, l indicates a number that is 0 or more and 30 or less, j indicates a number that is 0 or more and 30 or less, and l and j do not simultaneously become 0. "/" 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 from the same viewpoint, preferably 18 More preferably, it is 16 or less, more preferably 14 or less.
R ^8c is preferably an alkyl group or an alkenyl group, more preferably an alkyl group, from the viewpoint of detergency.
Specific examples of the alkyl group include various octyl groups (including 2-ethylhexyl group), various nonyl groups, various decyl groups, various undecyl groups, various dodecyl groups (lauryl groups), various tridecyl groups, various tetradecyl groups, Examples include various pentadecyl groups, various hexadecyl groups, various heptadecyl groups, and various octadecyl groups.
As an alkenyl group, 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, various octadecanyl groups (for example, , Oleyl group, linole group) can be mentioned. "Various" means various isomers including n-, sec-, tert- and iso-.

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

The HLB value of the polyoxyalkylene monoalkyl or alkenyl ether which is 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, and still more preferably 13 or less.
Here, the HLB value is defined by the Griffin equation shown below.
HLB value = 20 × Mw / M
(Wherein, 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 a total portion of an oxyethylene group and an oxypropylene group.

As an alkyl polyglycoside (glycoside type nonionic surfactant), the nonionic surfactant represented by the following general formula (c5) is preferable.
R 9 ^c (OR ^{10 c} ) _s G _t (c 5)
[Wherein, R ^9c represents a linear or branched alkyl group having 8 to 18 carbon atoms, preferably 12 to 14 carbon atoms, an alkenyl group or an alkylphenyl group, preferably an alkyl group, and R ^10c represents a carbon number 2 or more and 4 or less alkylene groups are shown, and G shows the residue derived from a C5- or 6-carbon reducing sugar. s represents an average added mole number and is a number of 0 or more and 5 or less. t shows the number whose average value becomes 1 or more and 5 or less. ]

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

  The sorbitan nonionic surfactant, aliphatic alkanolamide, fatty acid monoglyceride and sucrose fatty acid ester preferably have a carbon number of 8 to 18 and more preferably a carbon number of 12 to 14 and a linear or branched alkyl group. What has is preferable.

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

  The liquid detergent composition for a hard surface according to the present invention preferably contains 0.05% by mass or more, more preferably 0.1% by mass or more, of the surfactant which is the component (c), from the viewpoint of detergency. The content is preferably 0.2% by mass or more, and 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 from the viewpoint of rinseability. It contains less than%.

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

Here, the anionic surfactant is generally used by those skilled in the art, and for example, a hydrocarbon group having 7 to 22 carbon atoms, a sulfuric acid ester group, a phosphoric acid ester group, a phosphonic acid group, a sulfonic acid group or Anionic surfactants having a carboxy group can be mentioned.
Specifically, alkyl benzene sulfonate, alkane sulfonate, alkyl sulfate, polyoxyethylene alkyl ether sulfate, α-olefin sulfonate, α-sulfo fatty acid methyl ester, polyoxyethylene alkyl (or Alkenyl) ether carboxylates, polyoxyethylene amidoalkyl (or alkenyl) ether carboxylates, fatty acid salts, alkyl phosphate ester salts, polyoxyethylene alkyl ether phosphates, etc. And inorganic salts such as ammonium salts and magnesium salts, and organic salts such as monoethanol ammonium, diethanol ammonium and triethanol ammonium.

  In the liquid detergent composition for a hard surface according to the present invention, the mass ratio of the content of the anionic surfactant to the content of all the chelating agents including the (a) component and the (b) component (anionic surfactant (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, still more preferably 0.02 or less, and preferably 0 or more, and may be 0.

  In the liquid detergent composition for a hard surface according to the present invention, the mass ratio of the content of the anionic surfactant to the total content of the components (a) and (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, more preferably from the viewpoint of rinseability Is 0.1 or less, more preferably 0.05 or less, still more preferably 0.01 or less, and preferably 0 or more, and may be 0.

In the liquid detergent composition for a hard surface according to the present invention, the mass ratio of the content of the anionic surfactant to the total content of the components (a) and (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 rinseability Still more preferably 0.1 or less, still more preferably 0.05 or less, still more preferably 0.01 or less, and preferably 0 or more, and may be 0.
In addition, in this invention, content of an anionic surfactant uses an acid type conversion value.

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

  Smectite clay minerals containing montmorillonite, hectorite, permiculite, attapulgite, sepiolite and mixtures thereof as the component (d); 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, polyvinyl pyrrolidone and polyethylene glycol.

From the viewpoint of detergency, component (d) is preferably at least one selected from smectite clay minerals, natural polymers and synthetic polymers, and is selected from nonionic polysaccharides, natural polymers and synthetic polymers. 1 or more types are more preferable, and 1 or more types selected from nonionic polysaccharides are still more preferable.
Specifically, from the viewpoint of detergency, the component (d) is preferably at least one selected from hydroxyethyl cellulose, xanthan gum and polyvinyl pyrrolidone, with hydroxyethyl cellulose being more preferred.

  The liquid detergent composition for a hard surface according to the present invention is preferably 0.01% by mass or more, more preferably 0.05% by mass from the viewpoint of improving the detergency by improving the viscosity of the component (d). Or more, 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 from the viewpoint of detergency and rinseability. The content is preferably 1% by mass or less, more preferably 0.9% by mass or less, still more preferably 0.8% by mass or less, still more preferably 0.5% by mass or less from the viewpoint of low cost and excellent economy. contains.

<(E) component>
The hard surface liquid detergent composition of the present invention preferably contains a glycol solvent as the component (e).
The glycol solvent of the component (e) is used from the viewpoint of the cleaning property of soap scum and sebum dirt.
In the present invention, glycol-based means that the compound 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 by another group. The ether compound is preferably an aliphatic ether compound. Moreover, the ether compound by which one hydrogen atom of the hydroxyl group which a glycol compound has was substituted by the other group is preferable.

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

  As component (e), from the viewpoint of detergency, ethylene glycol (carbon number 2), propylene glycol (carbon number 3), diethylene glycol (carbon number 4), propylene glycol monomethyl ether (carbon number 4), isoprene glycol (carbon) Number 5), propylene glycol monoethyl ether (carbon number 5), 3-methyl-3-methoxybutanol (carbon number 6), ethylene glycol monobutyl ether (carbon number 6), dipropylene glycol (carbon number 6), diethylene glycol mono One or more selected from butyl ether (carbon number 8), dibutylene diglycol (carbon number 8) and dipropylene glycol monobutyl ether (carbon number 10) can be mentioned.

  The component (e) is preferably a glycol having 2 or 3 carbon atoms such as ethylene glycol, polyethylene glycol, propylene glycol or polypropylene glycol, polyethers thereof or monoalkyl ethers thereof. The alkyl group of this monoalkyl ether preferably has 1 to 4 carbon atoms, and is methyl, ethyl, various propyl groups, or various butyl groups. The variety includes normal, iso and tertiary.

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

  The liquid detergent composition for a hard surface according to the present invention is preferably 1% by mass or more, more preferably 1.5% by mass or more, and still more preferably the component (e) from the viewpoint of the cleaning properties of soap scum and sebum stains. Is preferably 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>
The liquid detergent composition for a hard surface according to the present invention preferably contains an aromatic alcohol [hereinafter referred to as component (f)] from the viewpoint of detergency of soap scum.
Component (f) is preferably at least one selected from benzyl alcohol, 2-phenoxyethanol and 2-benzyloxyethanol.

  The liquid detergent composition for a hard surface according to the present invention preferably has a component (f) of at least 0.3% by mass, more preferably at least 0.5% by mass, and high temperature stability from the viewpoint of detergency. From the viewpoint, the content is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, still more preferably 2% by mass or less, still more preferably 1.5% by mass or less.

  In the liquid detergent composition for hard surface according to the present invention, a flavor, a pigment, an antiseptic, an antioxidant and the like can be optionally blended in order to increase the added value of the product (however, the above (a)) ~ (F) excluding components).

  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 according to the present invention preferably contains 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 of water. Preferably it is 95 mass% or less, More preferably, it contains 93 mass% or less. As water, it is preferable to use ion exchange water, sterile ion exchange water or the like.

  The liquid detergent composition for a hard surface according to the present invention preferably has a pH at 25 ° C. of more than 6, more preferably 6.3 or more, still more preferably 6.5 or more, still more preferably from the viewpoint of detergency Is preferably not more than 9.5, more preferably not more than 9, and still more preferably not more than 8.5, from the viewpoint of mildness to the skin.

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

The liquid detergent composition for hard surfaces according to the present invention is suitably used for cleaning hard surfaces such as baths, bathtubs, washbasins, tiles, restrooms, washbasins, mirrors, sinks around kitchens, countertops, water tops, etc. And further preferably used for a bathroom. Here, for the bathroom is intended not only for the bathroom but also for articles having other hard surfaces present in the bathroom, such as a bathtub and a basin.
The hard surface is suitable for cleaning tiles, glass, stainless steel, plastic or ceramic.

<Method of cleaning hard surface and method of removing water stains>
The present invention contains 0.2% by mass or more and 10% by mass or less of the component (a), 0% by mass or more and 10% by mass or less of the component (b), the component (c) and water, and has a viscosity of 25 mPas at 25 ° C. A method for cleaning a hard surface, wherein the hard surface liquid detergent composition having a viscosity exceeding s and not more than 1000 mPa · s is brought into contact with the hard surface and left for 1 minute or more.
In the hard surface cleaning method of the present invention, the hard surface liquid detergent composition of the present invention is used. The preferred embodiment of the composition is the same as the hard surface liquid detergent composition of the present invention described above.
That is, the hard surface liquid detergent composition of the present invention is a hard surface liquid detergent composition which is used for contact with a hard surface, leaving it for one minute or longer for cleaning.

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

Specifically, in the cleaning method of the present invention, the hard surface liquid detergent composition is brought into contact with a hard surface with a stock solution, or the hard surface liquid detergent composition is not diluted with a stock solution. And the like. That is, a cleaning method in which the hard surface liquid detergent composition is brought into contact with the hard surface without dilution is preferably mentioned. Furthermore, there is a cleaning method in which the hard surface liquid detergent composition is brought into contact with a hard surface to which a water stain is attached without dilution. In addition, as a method of making it contact with a hard surface, the method of apply | coating to a hard surface is preferable.
To contact the hard surface without diluting the hard surface liquid detergent composition means not to contact the hard surface after the detergent composition is intentionally diluted with water or the like. For example, after the liquid detergent composition for hard surface is brought into contact with a hard surface to which water droplets or the like adhere, or after the liquid detergent composition for hard surface is brought into contact with a hard surface, the water droplets adhere to the hard surface It can be understood that the hard surface liquid cleaning composition is brought into contact with the hard surface without being diluted.
In the present invention, the stock solution of the hard surface liquid detergent composition is adhered to the 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 a water stain is attached, without being attached to a wet absorbent cotton. After contacting the hard surface, the composition of the hard surface liquid detergent composition may vary. That is, after being in contact with a hard surface, the composition of the hard surface liquid detergent composition may be diluted or concentrated.
In the cleaning method of the present invention, in order to bring the liquid detergent composition for hard surface into contact with the hard surface with a stock solution, it may be applied directly from a bottle, and examples of the bottle include squeeze bottles etc. .

  However, a concentrated composition containing the components (a), (b) and (c) of the present invention is prepared, and the concentrated composition is diluted with water to prepare the liquid detergent composition for hard surfaces of the present invention. An article 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 a liquid detergent composition for hard surfaces of the present invention, It may be a method of cleaning a hard surface where the liquid detergent composition is contacted with the hard surface without dilution.

After application to a hard surface, the time for leaving is preferably 1 minute or more, preferably 2 minutes or more, more preferably 3 minutes or more, still more preferably 3 minutes or more, still more preferably 4 minutes, from the viewpoint of detergency. Minutes or more, 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 preferably 15 minutes or less, still more preferably 10 minutes or less It is.
After leaving, usually rinse with water. When rinsing, mechanical force (physical force) may be applied by hand or the like, or it may be simply rinsed with water.
In addition, the temperature at the time of leaving may be room temperature, for example, 10 degreeC or more and 30 degrees C or less.
Further, in the present invention, the hard surface can be cleaned with a cleaning article in which the liquid surface cleaning composition for hard surface according to the present invention is carried on a substrate.

  As an example, there is provided a method of cleaning a hard surface, wherein the hard surface liquid cleaning composition of the present invention is applied to the hard surface and then wiped off. In the wiping and cleaning, it is preferable to remove the composition applied to the hard surface from the hard surface using a cloth, a rag, a non-woven fabric or the like.

  The hard surface liquid detergent composition of the present invention can also be used as a cleaning article by impregnating the substrate. An article for cleaning in which the substrate is impregnated with the hard surface liquid detergent composition of the present invention is preferable from the viewpoint of workability of the cleaning operation.

  The substrate used for the cleaning article impregnated with the hard surface liquid detergent composition is flexible, can be impregnated with the hard surface liquid detergent composition, and has sufficient strength when used Are used without the generation of waste and the like. It is preferable to use a substrate that can be impregnated with the amount of the liquid surface cleaning composition for hard surfaces described below under no load.

  Such substrates include fibrous structures comprised of fibrous materials, such as various papers, nonwovens, woven or knitted fabrics. As a fibrous material which comprises these fiber structures, a cellulose fiber, a modified cellulose fiber, a synthetic fiber, and the mixture of 2 or more types of these etc. are mentioned, for example.

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

  Further, a cleaning method of wiping a hard surface using a cleaning article impregnated with the liquid cleaner composition for hard surface according to the present invention is preferable for light cleaning of the hard surface from the viewpoint of workability of the cleaning operation. The cleaning article impregnated with the hard surface liquid detergent composition is obtained by pre-impregnating the substrate with the detergent composition, or the dried substrate is impregnated with the hard surface liquid detergent composition immediately before use. Any of the following can be used. The cleaning article impregnated with the hard surface liquid cleaning composition may be used by being attached to a mop-like cleaning tool, or may be used for direct cleaning by hand.

When the hard surface liquid detergent composition is previously impregnated, the impregnation rate of the hard surface liquid detergent composition is determined by the weight of the substrate [i.e., the non-impregnated state (dry state) of the substrate] from the viewpoint of cleanability. 100% by mass or more is preferable, 150% by mass or more is more preferable, and 1000% by mass or less is preferable, and 400% by mass or less is more preferable, and 350% by mass. It is further more preferable that the content is% or less. If the impregnation rate is 100% by mass or more, sufficient cleaning performance against stains and dirt can be obtained. If it is 1000 mass% or less, the amount of the liquid surface cleaning agent composition for hard surface to be cleaned to the surface to be cleaned is appropriate, and dirt and dirt do not remain on the surface to be cleaned, and various materials such as wood-based materials Can be used without affecting the cleaning surface. From the point of further improvement of the cleaning property, when the substrate is a sheet, the basis weight before impregnation of the hard surface liquid detergent composition is the retention of the hard surface liquid detergent composition necessary for cleaning a certain area. It is preferable that it is 40 g / m ² or more, more preferably 50 g / m ² or more, and preferably 200 g / m ² or less, from the viewpoints of elasticity and sheet operability and cost, and 150 g It is more preferable that it is / m < ² > or less.

  At the time of use of the cleaning article impregnated with the hard surface liquid cleaning composition, the hard surface liquid cleaning composition of the present invention may be separately used while being sprayed on the object to be cleaned or the cleaning article. . Clean the larger area by the method of use.

  With regard to the embodiments described above, the present invention further discloses the following hard surface liquid cleaning composition, a method of cleaning hard surfaces, and a method of removing water stains. In these embodiments, the matters described in the liquid surface cleaning composition for hard surfaces of the present invention, the method for cleaning hard surfaces, and the method for removing water stains can be appropriately applied to each other.

<1>
(A) 0.2% by mass or more and 10% by mass or less of one or more selected from phosphonic acid type chelating agents and phosphoric acid type chelating agents (hereinafter referred to as component (a)), other than component (b) (a) A liquid detergent composition for a hard surface comprising 0% by mass to 10% by mass 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 exceeds 6 mPa · s and is 1000 mPa · s or less,
Used for cleaning in contact with hard surface, preferably applied and left for 1 minute or more
Liquid surface cleaning composition for hard surfaces.

<2>
Component (b) 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 liquid detergent composition for a hard surface according to <1>, which contains preferably 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 , 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 or less, still more preferably 1 The liquid detergent composition for a hard surface according to the above <1> or <2>, having the following, still 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 (a) component and the (b) component [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 hard surfaces in any one of said <1>-<3> which is 0.01 or less, and preferably 0 or more.

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

<6>
(A) 0.2% by mass or more and 10% by mass or less of one or more selected from phosphonic acid chelating agents and phosphoric acid chelating agents (hereinafter referred to as component (a)), (b) (b-1) carbonic acid 0.2 wt% or more and 10 wt% or less of an acid-based chelating agent (but excluding component (a)) (hereinafter referred to as component (b-1)), surfactant (c) (component (c)) A liquid detergent composition for hard surfaces comprising water) and
The viscosity at 25 ° C. is more than 6 mPa · s and not more than 1000 mPa · s,
Liquid surface cleaning composition for hard surfaces.

<7>
Component (b-1) is at least one chelating agent selected from hydroxycarboxylic acids and salts thereof, and aminocarboxylic acids and salts thereof, preferably hydroxycarboxylic acids having 3 to 8 carbon atoms and salts thereof The hard as described in the above <6>, which is one or more selected from the following, more preferably one or more selected from citric acid, malic acid, and salts thereof, still more preferably citric acid or a salt thereof Liquid cleaning composition for surfaces.

<8>
The component (b-1) is preferably 0.5% by mass 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 preferably 8% by mass or less The liquid detergent composition for hard surfaces as described in said <6> or <7> which contains 7 mass% or less more preferably still more preferably 6 mass% or less.

<9>
The mass ratio of the mass ratio (a) / (b-1) of the content of the component (a) to the content of the component (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 Or less, still 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, in any of the above <6> to <8> Hard surface liquid detergent composition as described.

<10>
The mass ratio [anionic surfactant / ((a) + (b-1))] of the content of the anionic surfactant and the total content of the components (a) and (b-1) is Preferably it is 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 hard surfaces in any one of said <6>-<9> which is still more preferably 0.01 or less, and preferably 0 or more.

<11>
Mass ratio [anionic surfactant / ((a) + (b-1))] of the content of the anionic surfactant and the total content of the (a) component and the (b-1) component is 0 The liquid detergent composition for hard surfaces in any one of said <6>-<9> which is it.

<12>
The component (a) 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 of <1> to <11> Hard surface liquid detergent composition according to any of the foregoing.

<13>
The component (c) is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.2% by mass or more, and preferably 2% by mass or less, more preferably 1.5 The liquid cleaning agent composition for hard surfaces in any one of said <1>-<12> which contains the mass% or less, more preferably 1 mass% or less, still more preferably 0.5 mass% or less.

<14>
The mass ratio of the content of the anionic surfactant to the content of all the chelating agents including the components (a) and (b) (anionic surfactant / chelating agent) is preferably 0.30 or less, More preferably, it is 0.28 or less, 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 cleaning agent composition for hard surfaces in any one of said <1>-<13> which is the following, And preferably 0 or more.

<15>
Said <1> whose mass ratio (anionic surfactant / chelating agent) of content of anionic surfactant and content of all the chelating agents containing (a) component and (b) component is 0. The liquid detergent composition for hard surfaces in any one of-<13>.

<16>
Furthermore, the liquid detergent composition for hard surfaces in any one of said <1>-<15> which contains (d) thickener (Hereinafter, it is called (d) component.).

<17>
The liquid detergent composition for hard surfaces as described in said <16> which is a thickener in which (d) component is chosen from following (1)-(3).
(1) Smectite clay minerals containing montmorillonite, hectorite, permiculite, attapulgite, sepiolite, and mixtures thereof as a main component (2) methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxyethyl methylcellulose, hydroxypropyl methylcellulose, guar gum and locust bean gum And non-ionic polysaccharides selected from the following, and natural polymers selected from anionic polysaccharides selected from xanthan gum, carrageenan and gellan gum (3) synthetic polymers selected from polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol

<18>
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 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 detergent composition for hard surfaces as described in said <16> or <17> which contains mass% or less.

<19>
Furthermore, the liquid detergent composition for hard surfaces in any one of said <1>-<18> which contains (f) aromatic alcohol [Hereafter, it is called (f) component].

<20>
The liquid detergent composition for hard surfaces as described in said <19> whose component (f) is 1 or more types chosen from a benzyl alcohol, 2-phenoxy ethanol, and 2-benzyloxy ethanol.

<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 hard surfaces as described in said <19> or <20> which contains further 2 mass% or less still more preferably 1.5 mass% or less more preferably.

<22>
The content of 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 The liquid detergent composition for hard surfaces in any one of said <1>-<21> which is contained below.

<23>
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 preferably 6.8 or more, and preferably 9.5 or less, more preferably 9 The liquid cleaning agent composition for hard surfaces in any one of said <1>-<22> which is the following, Still 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 The liquid cleaning agent composition for hard surfaces in any one of said <1>-<23> which is 200 mPa * s or less, More preferably, it is 100 mPa * s or less.

<25>
The liquid detergent composition for hard surfaces in any one of said <1>-<24> whose hard surfaces are a tile, glass, stainless steel, a plastics, or a ceramic.

<26>
The method to wash | clean a hard surface using the liquid detergent composition for hard surfaces in any one of said <1>-<25>.

<27>
(A) 0.2% by mass or more and 10% by mass or less, and 0% by mass or more and 10% by mass of a chelating agent other than the component (b) (a): one or more selected from phosphonic acid chelating agents and phosphoric acid chelating agents % Or less, (c) a surfactant and water, and having a viscosity at 25 ° C. of more than 6 mPa · s and not more than 1000 mPa · s, the liquid detergent composition for hard surfaces is brought into contact with hard surfaces, preferably A method of cleaning hard surfaces which is applied and left for 1 minute or more.

<28>
The contact time with the hard surface, preferably after application, is preferably 2 minutes or more, more preferably 3 minutes or more, still more preferably 3 minutes or more, still more preferably 4 minutes or more, still more preferably The method for cleaning a hard surface according to <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, and 0% by mass or more and 10% by mass of a chelating agent other than the component (b) (a): one or more selected from phosphonic acid chelating agents and phosphoric acid chelating agents % Or less, (c) a surfactant and water, and having a viscosity at 25 ° C. of more than 6 mPa · s and not more than 1000 mPa · s, the liquid detergent composition for hard surfaces is brought into contact with hard surfaces, preferably Apply and leave for 1 minute or more.

<30>
The contact time with the hard surface, preferably after application, is preferably 2 minutes or more, more preferably 3 minutes or more, still more preferably 3 minutes or more, still more preferably 4 minutes or more, still more preferably The method for removing the varicella soil 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 surfaces shown in Table 1 was prepared using the following blending components, and the following items were evaluated. The results are shown in Table 1. The hard surface liquid detergent composition of Table 1 was prepared by a conventional method. That is, components (a) to (f) are added to an appropriate amount of ion-exchanged water and dissolved at room temperature (25 ° C.), and then sodium hydroxide is added to adjust pH (25 ° C.) to obtain a perfume. Added. In addition, the mass% of the compounding component in Table 1 is a numerical value based on all the effective components. Moreover, the (a) component and the (b) component have shown the mass% based on the quantity as acid conversion. Moreover, the alkylether sulfate sodium ester of (c) component has shown the mass% based on the quantity as acid conversion.
Further, the viscosity of the hard surface liquid detergent composition was measured (at 25 ° C.) as a value after one minute using a B-type rotational viscometer at 60 rpm, and the results are shown in Table 1. For low viscosity, rotor No. 1 and, if necessary, rotor No. 1 so as to fall within the viscosity measurement range. Two or three were used.

Ingredients
(A) Component · Ethan-1-hydroxy-1, 1-diphosphonic acid: Phosphonic acid type chelating agent, Italmatch Japan Ltd., Diquest 2010CS, 60 mass% aqueous solution · Aminotrimethylenephosphonic acid: Phosphonic acid type Chelating agent, Italmatch Japan Co., Ltd. product, Diquest 2006, 39% by mass aqueous solution tripolyphosphate: phosphoric acid type chelating agent, Aditya Birla Chemicals (Thailand) Limited manufactured company (b) component Citric acid: carboxylic acid type chelate Agent ((b-1) component), Wako Pure Chemical Industries, Ltd., Wako special grade

Component (c) lauric acid amidopropyl betaine: amphoteric surfactant, in the general formula (c1), a compound wherein R ^1c is an alkyl group having 11 carbon atoms, R ^2c and R ^3c are methyl groups, anthracite 20 AB, Kao (strain Polyoxyethylene (7) alkyl ether: nonionic surfactant, in the general formula (c4), R ^8c is an alkyl group having 12 carbon atoms, 1 is 7 and j is 0, softanol 70H, Kao ( Co., Ltd., (): average addition mole number of oxyethylene group · alkyl ether sulfate sodium ester: anionic surfactant, carbon number of alkyl group 12-16, ethylene oxide average addition mole number 4.0, ES-4 K , Made by Kao Corporation

(D) Component · Hydroxyethyl cellulose ether: Natural polymer of nonionic polysaccharide, HEC Daicel SE 850 K, Daicel Fine Chem Co., Ltd. · Xanthan gum: Natural polymer of anionic polysaccharide, KELZAN, manufactured by Tri Crystal Co., Ltd. · Polyvinylpyrroline Don: Synthetic polymer, PVP K-90 ISP TECHNOLOGIES, manufactured by INC (e) Component · Diethylene glycol monobutyl ether: Glycol based solvent, BDG (butyl diglycol), Nippon Emulsifier Co., Ltd. manufactured by (f) Component · Benzyl alcohol: Wako Pure Chemical Industries, Ltd., benzyl alcohol, Wako special grade

(1) only it was uniformly applied can in the lower 25mm of detergency evaluation 300ppm _{SiO 2} / 300ppm CaCl 2 aqueous solution 0.3mL slides in (76 mm × 26 mm), dried on a hot plate heated to 140 ° C. Then, it was rinsed with ion exchange water. The solution application on the slide glass and the operation of drying were repeated three times to produce a model stain of a water stain.
Place the absorbent cotton (Curelet 4 x 4 cm ² made by Kawamoto Sangyo Co., Ltd.) cut to the size of the model soil on the slide glass to which this model soil is attached, and drop 1 mL of each hard surface liquid detergent composition After leaving for a predetermined time described in Table 1, the entire surface of the slide glass was rubbed with a light force (about 200 g weight) for 5 times back and forth. After that, the slide glass was thoroughly rinsed with ion-exchanged water, and then the detergency was judged based on the following criteria.
As a specific method of evaluation criteria, slide glass without stain application, slide glass before cleaning after cleaning, slide glass after cleaning are photographed under the same shooting conditions such as brightness, and each image is obtained from the obtained images. The gray scale of the slide glass was measured. The pre-wash slide glass had a wash rate of 0%, and the non-stained slide glass had a wash rate of 100%. The image processing software ImageJ 1.47v was used for gray scale measurement.

(2) Evaluation of rinseability after washing 24mL of each cleaning solution on a 100 x 120 cm ² bathroom floor, after rubbing 70 times with a sponge, rinse with a tap water shower, and the time until foam disappears completely, the following criteria It evaluated by. The temperature of tap water at the time of rinsing was 30 ° C., and the flow rate was constant at about 143 mL / sec.
Foam disappears within 1:25 seconds and rinse is complete.
2: The bubbles do not disappear even after 25 seconds.
3: The bubble disappears for more than 30 seconds.

(3) Practical evaluation of detergency The absorbent cotton was cut into 2 × 2 cm ² on the surface of a stainless steel plate with stainless steel plate attached for 1 month in a kitchen sink of a real household, and then cured (curelet 4 × 4 cm ² Place the Kawamoto Sangyo Co., Ltd.), was added dropwise a hard surface liquid cleaning compositions 1mL of example 2 and allowed to stand for 20 minutes, reciprocating the entire surface of the faucet surface 5 times small force (approximately 200g weight) I rubbed it. Thereafter, the plate surface was rinsed thoroughly with deionized water. The hard surfaces of the stainless steel plate before and after cleaning were photographed under the same imaging conditions such as brightness. The photograph before washing is shown in FIG. 1, and the photograph after washing is shown in FIG.

Comparing FIG. 1 and FIG. 2, after scaly-like blister stains adhering before cleaning are washed using the liquid surface cleaning agent composition for hard surface of Example 2, scaly-like blister stains are mostly It can be seen that it has been removed.

Claims (10)

(A) 0.2% by mass or more and 10% by mass or less of one or more selected from phosphonic acid type chelating agents and phosphoric acid type chelating agents (hereinafter referred to as component (a)), other than component (b) (a) A liquid detergent composition for a hard surface comprising 0% by mass to 10% by mass 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 exceeds 6 mPa · s and is 1000 mPa · s or less,
Used for cleaning in contact with a hard surface and left for 1 minute or longer
Liquid surface cleaning composition for hard surfaces. (A) 0.2% by mass or more and 10% by mass or less of one or more selected from phosphonic acid chelating agents and phosphoric acid chelating agents (hereinafter referred to as component (a)), (b) (b-1) carbonic acid 0.2 wt% or more and 10 wt% or less of an acid-based chelating agent (but excluding component (a)) (hereinafter referred to as component (b-1)), surfactant (c) (component (c)) A liquid detergent composition for hard surfaces comprising water) and
The viscosity at 25 ° C. is more than 6 mPa · s and not more than 1000 mPa · s,
Liquid surface cleaning composition for hard surfaces.   The liquid for hard surfaces according to claim 2, wherein the mass ratio (a) / (b-1) of the content of the component (a) to the content of the component (b-1) is 0.02 or more and 10 or less. Cleaning composition.   The liquid detergent composition for hard surfaces in any one of Claims 1-3 whose pH in 25 degreeC exceeds six.   The liquid detergent composition for hard surfaces in any one of Claims 1-4 whose content of (c) component is 2 mass% or less.   The mass ratio (anionic surfactant / chelating agent) of the content of the anionic surfactant to the content of all the chelating agents in the component (c) is 0.3 or less. Liquid surface cleaning composition for hard surfaces according to any one of the preceding claims.   The liquid detergent composition for hard surfaces according to any one of claims 1 to 6, further comprising (d) a thickener.   The hard surface liquid cleaning composition according to any one of claims 1 to 7, wherein the hard surface is a tile, glass, stainless steel, plastic or ceramic.   A method of cleaning a hard surface using the hard surface liquid detergent composition according to any one of claims 1 to 8. (A) 0.2% by mass or more and 10% by mass or less of one or more selected from phosphonic acid type chelating agents and phosphoric acid type chelating agents (hereinafter referred to as component (a)), other than component (b) (a) A liquid detergent composition for hard surfaces comprising 0% by mass or more and 10% by mass or less of a chelating agent, (c) a surfactant and water, and having a viscosity of 25 ° C. and more than 6 mPa · s and 1000 mPa · s or less , A method of removing water stains which is left in contact with a hard surface and left for 1 minute or more.