JP7170528B2 - Liquid cleaning composition for toilet - Google Patents

Description

The present invention relates to a liquid cleaning composition for toilets.

A toilet bowl is generally cleaned by applying a toilet liquid detergent composition to an object to be cleaned and then rubbing (scrubbing) it with a cleaning brush. When rubbing the object to be cleaned with the cleaning brush, the user bends forward or bends over, which is troublesome and places a heavy physical burden on the user.
Also, areas such as the underside of the rim of the toilet bowl are hard to reach areas for the cleaning brush and are difficult to clean.

To address these problems, an antifouling detergent composition containing a specific polysiloxane, a specific surfactant, a metal chelating agent, and water has been proposed (Patent Document 1). According to the invention of Patent Document 1, an improvement in detergency and an improvement in durability of the antifouling effect are achieved.

Japanese Patent Application Laid-Open No. 2004-162041

However, accumulation of stains on the toilet bowl causes strong urinary stone stains. Therefore, liquid detergent compositions for toilets are required to have improved detergency. In addition, simply increasing the content of cleaning ingredients (surfactants, chelating agents, etc.) in order to enhance the cleaning power will make it possible to clean objects other than toilet bowls (for example, toilet seats, floors, etc.). When a cleaning method (wiping cleaning) in which an agent composition is applied and then wiped off is applied, the surface tends to be sticky or slimy (low wiping ability).
Accordingly, an object of the present invention is to provide a liquid detergent composition for toilets that has excellent detergency and good wiping properties.

［式（ｂ１）中、Ｒ^１：炭素数２又は３のアルキレン基であり、ｍは（Ｒ^１Ｏ）の平均繰り返し数を表す１～６の数である。］
［２］前記（Ｂ）成分の含有量が、０．２～５質量％である、［１］に記載のトイレ用の液体洗浄剤組成物。
［３］前記（Ｂ）成分／｛前記（Ｃ）成分＋前記（Ｄ）成分｝で表される質量比が、０．１～０．８である、［１］又は［２］に記載のトイレ用の液体洗浄剤組成物。
［４］前記（Ａ）成分が、両性界面活性剤を含有する、［１］～［３］のいずれか一項に記載のトイレ用の液体洗浄剤組成物。 The present invention has the following aspects.
[1] (A) component: 0.5 to 5% by mass of surfactant,
(B) component: a compound represented by the following formula (b1);
(C) component: an aminocarboxylic acid-based chelating agent;
(D) component: a polyvalent carboxylic acid-based chelating agent;
(E) component: water and
contains
The mass ratio represented by the component (C)/component (D) is 1.5 to 10,
A liquid detergent composition for toilets, wherein the total amount of the component (C) and the component (D) is 0.5 to 3% by mass.

[In formula (b1), R ¹ is an alkylene group having 2 or 3 carbon atoms, and m is a number of 1 to 6 representing the average number of repetitions of (R ¹ O). ]
[2] The liquid detergent composition for toilets according to [1], wherein the content of component (B) is 0.2 to 5% by mass.
[3] According to [1] or [2], the mass ratio represented by (B) component/{(C) component + (D) component} is 0.1 to 0.8. A liquid cleaning composition for toilets.
[4] The liquid detergent composition for toilets according to any one of [1] to [3], wherein the component (A) contains an amphoteric surfactant.

[5] The component (A) contains an amphoteric surfactant (a1), and the content of the component (a1) is 50% by mass or more relative to the total mass of the component (A). The liquid detergent composition for toilets according to any one of [1] to [4].
[6] The liquid detergent for toilets according to any one of [1] to [5], wherein the mass ratio represented by component (A)/component (B) is 0.2 to 10.

According to the liquid detergent for textile products of the present invention, excellent detergency and good wiping properties can be achieved.

(Liquid detergent composition for toilet)
The liquid detergent composition for toilets of the present invention (hereinafter sometimes simply referred to as liquid detergent composition) contains components (A) to (E).

<(A) Component>
(A) Component is a surfactant. A liquid detergent composition exhibits detergency by containing (A) component.
Component (A) may be any surfactant that is commonly used in liquid detergent compositions, such as an amphoteric surfactant (component (a1)), an anionic surfactant (component (a2)), and a nonionic surfactant. (component (a3)), amine oxide surfactants (component (a4)), cationic surfactants, and the like. Among these, the (a1) component is preferable as the (A) component. By using component (a1) in combination with component (B), component (C) and component (D), excellent detergency can be exhibited without rubbing the object to be cleaned after applying the liquid detergent composition. In addition, the liquid detergent composition contains the (a1) component, thereby enhancing wiping properties.

The content of component (A) is 0.5 to 5% by mass, preferably 0.8 to 4% by mass, more preferably 1 to 2.5% by mass, relative to the total mass of the liquid detergent composition. preferable. By setting the content of component (A) within the above range, excellent detergency can be exhibited without rubbing the object to be cleaned, and wiping properties can be enhanced.

<<(a1) component>>
The component (a1) is an amphoteric surfactant. The component (a1) is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include betaine-based amphoteric surfactants and amino acid-based amphoteric surfactants. Among these, betaine-based amphoteric surfactants are preferred.
Examples of betaine-based amphoteric surfactants include carbobetaine-based amphoteric surfactants, amidobetaine-based amphoteric surfactants, sulfobetaine-based (hydroxysulfobetaine-based, amidosulfobetaine-based) amphoteric surfactants, and imidazolinium betaine. amphoteric surfactants, phosphobetaine amphoteric surfactants, aminopropionic acid amphoteric surfactants, and the like. Carbobetaine-based amphoteric surfactants and amidobetaine-based amphoteric surfactants are preferred, and amidobetaine-based amphoteric surfactants are more preferred.

(1) Carbobetaine-based amphoteric surfactants include betaine laurate dimethylaminoacetate, betaine myristyldimethylaminoacetate, betaine stearyldimethylaminoacetate, and the like.
(2) Amphoteric surfactants based on amidobetaine include coconut oil fatty acid amidopropylbetaine (cocamidopropylbetaine), lauramidopropylbetaine, isostearamidopropylbetaine and the like.
(3) Examples of sulfobetaine-based amphoteric surfactants include, for example, coconut oil fatty acid dimethylaminohydroxysulfobetaine, lauryldimethylaminohydroxysulfobetaine, laurylhydroxysulfobetaine, coconut oil fatty acid dimethylsulfopropylbetaine, laurylsulfobetaine, stearylsulfo betaine, myristylsulfobetaine and the like.
(4) Examples of imidazolinium betaine amphoteric surfactants include coconut oil alkyl-N-hydroxyethylimidazolinium betaine, coconut oil alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine, 2- Alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine and the like can be mentioned.
(5) Phosphobetaine-based amphoteric surfactants include, for example, lauryl hydroxyphosphobetaine.
(6) Examples of aminopropionic acid-based amphoteric surfactants include sodium laurylaminodipropionate and triethanolamine laurylaminodipropionate.
(7) Amphoteric amino acid surfactants include laurylamino fatty acid salts, stearylamino fatty acid salts, myristylamino fatty acid salts, and the like.

As the component (a1), among the above, lauramidopropyl betaine, lauryldimethylaminoacetic acid betaine, and stearyldimethylaminoacetic acid betaine are preferable, and from the viewpoint of wiping properties, lauramidopropyl betaine and lauryldimethylaminoacetic acid betaine are particularly preferable. .
Examples of the counter ion of the salt include alkali metal salt ions, ammonium salt ions, and alkanolamine salt ions. Among these, ions of alkali metal salts are preferred, and sodium ions and potassium ions are more preferred.

(a1) Component is commercially available. Examples of commercially available component (a1) include lauramidopropyl betaine “Enagicol L-30B (manufactured by Ipposha Yushi Kogyo Co., Ltd.)” and coconut oil fatty acid amidopropyl betaine “CAB-30 (manufactured by Ipposha Yushi Kogyo Co., Ltd.)”, “TEGO BETAIN CK-OK (manufactured by Degussa)” as coconut oil fatty acid amidopropyl betaine, and “ANHOLEX PB-1 (Miyoshi Oil)” as palm kernel oil fatty acid amidopropyl betaine. Co., Ltd.)”, “Lebon LD-36 (manufactured by Sanyo Chemical Industries Co., Ltd.)” and “Ovazoline LB-SF (manufactured by Toho Chemical Industry Co., Ltd.)”, which are lauryldimethylaminoacetic acid betaine, stearyldimethylaminoacetic acid There is "Amphitol 86B" manufactured by Kao Corporation, which is betaine.

The amphoteric surfactant in the surfactant is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 100% by mass.

<<(a2) component>>
Component (a2) is an anionic surfactant. As component (a2), conventionally known anionic surfactants can be used, for example, surfactants (1) to (11) below.
(1) A linear or branched alkylbenzenesulfonate (LAS or ABS) having an alkyl group of 8 to 18 carbon atoms.
(2) alkanesulfonates having 10 to 20 carbon atoms;
(3) α-olefin sulfonate (AOS) having 10 to 20 carbon atoms.
(4) Alkyl sulfates or alkenyl sulfates (AS) having 10 to 20 carbon atoms.
(5) an alkylene oxide having 2 to 4 carbon atoms, or an average of 0.5 to 10 of ethylene oxide and propylene oxide (molar ratio EO/PO = 0.1/9.9 to 9.9/0.1) Alkyl (or alkenyl) ether sulfate (AES) having a straight or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms attached by moles.
(6) an average of 3 to 30 moles of either an alkylene oxide having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO/PO = 0.1/9.9 to 9.9/0.1); Alkyl (or alkenyl) phenyl ether sulfate having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added.
(7) any alkylene oxide having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO/PO = 0.1/9.9 to 9.9/0.1), an average of 0.5 to An alkyl (or alkenyl) ether carboxylate having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added by 10 moles.
(8) Alkyl polyhydric alcohol ether sulfates such as alkyl glyceryl ether sulfonic acid having 10 to 20 carbon atoms.
(9) Long chain monoalkyl, dialkyl or sesquialkyl phosphates.
(10) Polyoxyethylene monoalkyl, dialkyl or sesquialkyl phosphates.
(11) Higher fatty acid salts (soaps) having 10 to 20 carbon atoms.
Salts constituting the salt include alkali metal salts such as sodium salts and potassium salts; alkaline earth metal salts such as magnesium salts and calcium salts; monoethanolamine salts (monoethanolammonium), diethanolamine salts (diethanolammonium), and triethanolamine. Alkanolamine salts such as salts (triethanolammonium); ammonium salts, etc., among which sodium salts and potassium salts are preferred.

<<(a3) component>>
The (a3) component is a nonionic surfactant. Component (a3) includes, for example, the following surfactants (1) to (8).
(1) an average of 3 to 30 mol of either an alkylene oxide having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO/PO = 0.1/9.9 to 9.9/0.1); A polyoxyalkylene alkyl ether having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added.
(2) an average of 3 to 30 moles of either an alkylene oxide having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO/PO = 0.1/9.9 to 9.9/0.1); A polyoxyalkylene alkyl (or alkenyl) phenyl ether having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added.
(3) C1-2 alkyl esters of long-chain fatty acids with 10-20 carbon atoms and alkylene oxides with 2-4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO/PO = 0.1/9) .9 to 9.9/0.1) added with an average of 3 to 30 moles of fatty acid alkyl ester alkoxylate.
(4) A sorbitan ester of a long-chain fatty acid with 10 to 20 carbon atoms and an alkylene oxide with 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO/PO = 0.1/9.9 to 9.9. 9/0.1) added with an average of 3 to 30 moles of polyoxyalkylene sorbitan fatty acid ester.
(5) A long-chain fatty acid with 10 to 20 carbon atoms and an alkylene oxide with 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO/PO = 0.1/9.9 to 9.9/0) A polyoxyalkylene fatty acid ester having an average of 3 to 30 moles of .1) added thereto.
(6) Either an alkylene oxide having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO/PO = 0.1/9.9 to 9.9/0.1) is added to hydrogenated castor oil, average 3 to 30 mol added.
(7) Esters of long-chain fatty acids having 10 to 20 carbon atoms and glycerin.
(8) Linear or branched alkyl polyglycosides having 10 to 20 carbon atoms.

<<(a4) component>>
Component (a4) is an amine oxide surfactant (semipolar surfactant). Examples of component (a4) include alkylamine oxides such as dodecyldimethylamine oxide, myristyldimethylamine oxide and coconut alkyldimethylamine oxide; amidoamine oxides such as coconut oil fatty acid amidopropylamine oxide and lauramidopropylamine oxide; mentioned. Among them, dodecyldimethylamine oxide (AX) is preferred.

The component (A) may be used singly or in combination of two or more.

<(B) Component>
Component (B) is a compound represented by formula (b1). Component (B) is a so-called glycol-type solvent.

In formula (b1), R ¹ is an alkylene group having 2 or 3 carbon atoms. R ¹ is an ethylene group or a propylene group, preferably ethylene. That is, R ¹ O is an alkyleneoxy group.
m is a number of 1 to 6, preferably 1 to 3, more preferably 1, representing the average number of repeating (R ¹ O) (ie, the average number of added moles of ethylene oxide or propylene oxide).

Component (B) includes, for example, monoethylene glycol monophenyl ether, triethylene glycol monophenyl ether, monopropylene glycol monophenyl ether, tripropylene glycol monophenyl ether, and the like. Among them, monoethylene glycol monophenyl ether is particularly preferable as the component (B) in terms of detergency.
These (B) components may be used singly or in combination of two or more.

The content of component (B) is preferably 0.2 to 5% by mass, more preferably 0.5 to 3% by mass, relative to the total mass of the liquid detergent composition. (B) If content of a component is in the said range, wiping off property will be improved more.

The mass ratio represented by component (A)/component (B) (A/B ratio) is preferably 0.2 to 10, more preferably 0.3 to 10, and even more preferably 0.5 to 2.5. . If A/B ratio is more than the said lower limit, wiping off property will be improved more. If the A/B ratio is equal to or less than the above upper limit, the detergency can be further enhanced.

<(C) Component)>
Component (C) is an aminocarboxylic acid-based chelating agent. Component (C) is a chelating agent having a nitrogen atom and a carboxy group. Component (C) includes, for example, DEG (dihydroxyethylglycine: N-(2-hydroxylethyl)glycine), HEIDA (N-(2-hydroxyethyl)iminodiacetic acid: N-(2-hydroxyethyl) iminodiacetic acid), HEDTA (hydroxyethylethylenediamine tetraacetic acid: N-(hydroxyethyl)ethylenediamine tetraacetic acid), NTA (nitrilotriacetic acid: Nitrilo Triacetic Acid), DTPA (diethylenetriamine pentaacetic acid: Diethylene Triamine Pentaacetic Acid), ethylenediethyl ethyl HEDTA Ｅｔｈｙｌｅｎｅ Ｄｉａｍｉｎｅ Ｔｒｉａｃｅｔｉｃ Ａｃｉｄ）、ＥＤＴＡ（エチレンジアミン四酢酸：Ｅｔｈｙｌｅｎｅ Ｄｉａｍｉｎｅ Ｔｅｔｒａａｃｅｔｉｃ Ａｃｉｄ）、ＭＧＤＡ（メチルグリシン二酢酸：ＭｅｔｈｙｌＧｌｙｃｉｎｅＤｉａｃｅｔｉｃ Ａｃｉｄ）、ＧＬＤＡ（Ｌグルタミン酸二酢酸：Ｄｉｃａｒｂｏｘｙｍｅｔｈｙｌｅ Ｇｌｕｔａｍｉｃ Ａｃｉｄ）、ＡＳＤＡ（アスパラギン酸二酢酸：Ａｓｐａｒｔａｔｅ Ｄｉａｃｅｔｉｃ Acid), EDDS (Ethylenediamine Discuccinic Acid), HIDS (Hydroxye Iminodisuccinic Acid), IDS (Iminodisuccinic Acid), and salts of the above compounds (e.g., alkali metal salts) and water Japanese foods, etc. are mentioned. Among them, MGDA, GLDA, EDTA and alkali metal salts thereof are preferred. These (C) components can further enhance detergency.
These (C) components may be used singly or in combination of two or more.

The content of component (C) is preferably 0.3 to 2.5% by mass, more preferably 0.5 to 2% by mass, more preferably 0.7 to 1.0% by mass, relative to the total mass of the liquid detergent composition. 8% by mass is more preferred. (C) If content of a component is more than the said lower limit, detergency will be improved more. (C) If content of a component is below the said upper limit, wiping off property will be improved more.

<(D) Component>
Component (D) is a polyvalent carboxylic acid-based chelating agent (non-nitrogen-containing). Component (D) is a chelating agent having a carboxy group, and this carboxy group may form a salt. The component (D) may have only a carboxy group as a functional group, or may have a functional group other than the carboxy group. Examples of the component (D) having functional groups other than carboxyl include hydroxycarboxylic acids (salts).
Component (D) includes, for example, acetic acid, adipic acid, monochloroacetic acid, oxalic acid, succinic acid, oxydisuccinic acid, carboxymethylsuccinic acid, carboxymethyloxysuccinic acid, glycolic acid, diglycolic acid, lactic acid, tartaric acid, carboxymethyl Tartaric acid, citric acid, malic acid, gluconic acid, salts thereof, and the like. Among them, citric acid, malic acid, and lactic acid are particularly preferable as component (D). If it is these (D) components, detergency will be improved more.
These (D) components may be used singly or in combination of two or more.

The content of component (D) is preferably 0.1 to 0.8% by mass, more preferably 0.2 to 0.7% by mass, relative to the total mass of the liquid detergent composition. (D) If content of a component is more than the said lower limit, detergency will be improved more. (D) If content of a component is below the said upper limit, wiping off property will be improved more.

The total amount of components (C) and (D) (CD total amount) is 0.5 to 3% by mass, and 0.5 to 2.8% by mass, relative to the total mass of the liquid detergent composition. %, more preferably 0.8 to 2.5% by mass. If the total amount of CD is equal to or more than the above lower limit, the detergency can be further enhanced. If the CD total amount is equal to or less than the above upper limit, the wiping property can be further enhanced.

The mass ratio (C/D ratio) represented by component (C)/component (D) is 1.5 to 10, preferably 1.6 to 6, more preferably 2 to 4. If the C/D ratio is at least the above lower limit, the detergency can be further enhanced. If the C/D ratio is equal to or less than the above upper limit, the detergency can be further enhanced.

The mass ratio (B/(C+D) ratio) represented by (B) component/{(C) component + (D) component} is preferably 0.1 to 0.8, and 0.4 to 0.7. more preferred. When the B/(C+D) ratio is at least the above lower limit, the detergency and wiping properties can be further enhanced. If the B/(C+D) ratio is equal to or less than the above upper limit, the wiping property can be further enhanced.

<(E) component>
The (E) component is water.
The content of component (E) is preferably 80 to 95% by mass, more preferably 88 to 94% by mass, relative to the total mass of the liquid detergent composition.

<Optional component>
The liquid cleansing composition of the present invention can contain, if necessary, components that are usually used in cleansing compositions for toilets, in addition to the components described above. Such optional ingredients include, for example, bactericides, preservatives, antifungal agents, pigments, antioxidants, thickeners, ultraviolet absorbers, solubilizers (excluding component (B)), fragrances, A pH adjuster etc. are mentioned.

The pH adjuster is not particularly limited, but it is preferable to use an alkaline agent selected from sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and its derivatives, monoethanolamine, diethanolamine, triethanolamine, etc. It is more preferable to use an alkaline agent selected from sodium, potassium hydroxide, monoethanolamine, and triethanolamine, and potassium hydroxide is even more preferable.
One type of pH adjuster may be used, or two or more types may be used in combination.

(Production method)
A liquid detergent composition is manufactured by a conventionally well-known manufacturing method. For example, a method of adding the components (A) to (D) to component (E), which is a solvent, optionally adding optional components, and mixing them.

(how to use)
As a method of using the liquid detergent composition, for example, the liquid detergent composition is contained in a discharge container, an appropriate amount of the liquid detergent composition is applied to the toilet bowl from the discharge container, and after a certain period of time has passed, flushing or the like is performed. Rinsing and "rinsing" are examples of usage methods.
Another method of using the liquid detergent composition includes a method of applying an appropriate amount of the liquid detergent composition to the toilet bowl and rubbing it with a cleaning brush for "scrubbing".
Alternatively, there is a method of use in which the liquid detergent composition is applied to the toilet seat or toilet floor and then wiped off with a cloth or paper for "wiping off".

A spray container, a squeeze container, etc. are mentioned as a discharge container which accommodates a liquid detergent composition. Among them, a spray container is preferable as the discharge container for containing the liquid detergent composition because of its excellent applicability to the object to be cleaned.
Spray containers include aerosol spray containers, trigger spray containers (direct pressure type or pressure accumulation type), dispenser spray containers, and the like. These containers may be manually operated or electrically operated. Examples of the aerosol spray container include those described in JP-A-9-3441 and JP-A-9-58765. When filling an aerosol spray container, LPG (liquefied propane gas), DME (dimethyl ether), carbon dioxide gas, nitrogen gas, nitrous oxide gas, etc. can be used as the propellant. These propellants may be used alone or in combination of two or more.
Examples of trigger spray containers include those described in JP-A-9-268473 and JP-A-10-76196.
Examples of dispenser spray containers include those described in, for example, JP-A-9-256272.
Examples of the pressure accumulation type trigger spray container include those described in JP-A-2013-154276.

[EXAMPLES] Hereafter, although an Example is shown and this invention is demonstrated in detail, this invention is not limited by the following description.

(Raw materials used)
<(A) Component: Surfactant>
· A-1: Lauramidopropyl Betaine, "Enagicol L-30B" manufactured by Lion Corporation.
· A-2: Betaine lauryldimethylaminoacetate, "Lebon LD-36" manufactured by Sanyo Chemical Industries, Ltd.
· A-3: Betaine stearyldimethylaminoacetate, Kao Corporation "Amphitol 86B".
· A-4: 12-16 alkyl polyglucoside (APG), manufactured by Cognis, "PLANTACARE 1200up").
· A-5: Polyoxyethylene (average 5 mol) isostearyl ether, Emalex 1805 (Nippon Emulsion Co., Ltd.).
A-6: SAS, sodium secondary alkanesulfonate, manufactured by Clariant Japan Co., Ltd., "HOSTAPUR SAS 30A").
· A-7: AX, n-dodecyldimethylamine oxide, manufactured by Lion Specialty Chemicals Co., Ltd., "Cadenax DM12D-W".
A-8: Dodecyltrimethylammonium chloride, Lipocard 12-37w (Lion Specialty Chemicals Co., Ltd.).
A-9: Stearyltrimethylammonium chloride, Lipocard T-833 (Lion Specialty Chemicals Co., Ltd.).

<(B) Component: Compound Represented by Formula (b1)>
· B-1: Ethylene glycol monophenyl ether (phenoxyethanol), manufactured by Nippon Nyukazai Co., Ltd., "phenyl glycol".
· B-2: Diethylene glycol monophenyl ether, manufactured by Nippon Nyukazai Co., Ltd., "Phenyl glycol (2 mol)".
· B-3: Hexaethylene glycol monophenyl ether, Nippon Nyukazai Co., Ltd., "Phenyl glycol (5.5 mol)".
<Component (B'): Comparative product of component (B)>
· B'-1: diethylene glycol monobutyl ether, manufactured by Nippon Nyukazai Co., Ltd., "butyl diglycol".

<(C) component: Aminocarboxylic acid-based chelating agent>
· C-1: Ethylenediaminetetraacetic acid, manufactured by Akzo Nobel, "Disolvin NA2".
· C-2: trisodium methylglycine diacetate (alkali metal salt of MGDA), manufactured by BASF, "Trilon M".
· C-3: Tetrasodium glutamate diacetate (GLDA-Na), manufactured by Akzo Nobel.
<(D) Component: Polyvalent carboxylic acid-based chelating agent>
· D-1: Citric acid, Fuso Chemical Industry Co., Ltd., "purified citric acid (anhydrous)".
· D-2: Lactic acid, manufactured by Wako Pure Chemical Industries, Ltd. (reagent).
· D-3: Malic acid, manufactured by Wako Pure Chemical Industries, Ltd. (reagent).

<Optional component>
- pH adjuster: sulfuric acid (Kanto Kagaku Co., Ltd.), potassium hydroxide, "liquid caustic potash" manufactured by AGC Corporation.
· Polyvinyl alcohol (PVA): "PVA-217" manufactured by Kuraray Co., Ltd.
- Ethanol: "Synthetic 95" manufactured by Nippon Alcohol Sales Co., Ltd.
· 2-methyl-4-isothiazolin-3-one (MIT): "ACTICIDE (registered trademark) M20" manufactured by So Japan Co., Ltd.
Perfume: Perfume composition A of JP-A-2003-183697.

(Evaluation method)
<Wipeability>
100 μL of the liquid detergent composition of each example was placed on a slide glass, and lightly wiped with eight-folded toilet paper. After drying, a professional panelist evaluated the remaining wiping marks by visual inspection and finger touch according to the following evaluation criteria.

≪Evaluation Criteria≫
I: Absolutely no wiping marks remain, and no stickiness is felt.
II: A very slight fine linear wiping mark remains, but it is not sticky and does not bother me.
III: Slightly fine linear wiping marks remain, but stickiness is not noticeable.
IV: A wiping mark remains partially, and stickiness is also felt.
V: A wiping mark remains on the entire surface, and stickiness is also felt.

<Detergency>
100 μL of urine from five adult males was placed on a PP (polypropylene) plate of 25 mm×100 mm, left at room temperature (25° C.) for 24 hours, and dried. After drying, the PP plate was immersed in 20 mL of the liquid detergent composition of each example for 30 seconds in a 50 mL vial bottle and taken out. After washing the removed PP plate twice with water, five expert panelists evaluated the degree of residual dirt according to the following evaluation criteria. The average value of the evaluation results of the expert panelists was calculated, and 3 to 5 points were regarded as passing.

≪Evaluation Criteria≫
5 points: The dirt is completely removed.
4 points: Almost all stains are removed.
3 points: About half of the dirt is removed.
2 points: Slightly soiled.
1 point: The dirt is not removed at all.

(Examples 1 to 44, Comparative Examples 1 to 8)
500 g of the liquid detergent composition of each example was prepared by the following procedure.
According to the formulations in Tables 1 to 7, components (A) to (D) and common components are mixed with component (E), and if necessary, a pH adjuster (sulfuric acid or potassium hydroxide) is newly added to pH 7. 0 to obtain the liquid detergent composition of each example.
The compounding amount in the table is a pure content conversion value. Ingredients whose blending amounts are not listed in the table are not blended. In the table, the "balance" of component (E) is the amount required to bring the total amount of the liquid detergent composition to 100% by mass. In the table, the "appropriate amount" of sulfuric acid is the amount required to adjust the pH of the liquid detergent composition to 7.0.
The obtained liquid detergent composition of each example was evaluated for wiping property and detergency, and the results are shown in the table.
However, Examples 39 and 40 are reference examples.

As shown in Tables 1 to 7, Examples 1 to 44 to which the present invention was applied had a wiping property of "I" to "III" and a detergency of "3.0" or more.
Comparative Example 2 in which the content of component (A) is 0.10% by mass, Comparative Example 3 in which component (B) is used as a comparative product, Comparative Example 4 in which the C/D ratio is 1.25, C/D ratio Comparative Example 6 with a CD of 12.33 and Comparative Example 8 with a CD total amount of 0.42% by mass gave an evaluation of "I" or "II" in the wiping property, but the evaluation of the detergency was 1.0%. 0 to 2.0.
Comparative Example 1 in which the content of the component (A) was 7% by mass and Comparative Example 7 in which the total amount of CD was 3.6 had a detergency evaluation of 3.0 to 4.0, but the wiping property was was "IV" or "V".
From these results, it was confirmed that the liquid detergent composition to which the present invention is applied has excellent detergency and wiping properties.

Claims (4)

(A) component: a surfactant ;
(B) component: monoethylene glycol monophenyl ether ;
(C) component: an aminocarboxylic acid-based chelating agent;
(D) component: a polyvalent carboxylic acid-based chelating agent;
(E) component: water and
contains
The mass ratio represented by the component (C)/component (D) is 1.5 to 10,
The content of the component (A) is 0.5 to 5% by mass with respect to the total mass of the liquid detergent composition,
The content of the component (C) is 0.3 to 2.0% by mass with respect to the total mass of the liquid detergent composition,
A liquid detergent composition for toilets, wherein the total amount of the component (C) and the component (D) is 0.5 to 3% by mass relative to the total mass of the liquid detergent composition. The liquid detergent composition for toilets according to claim 1, wherein the content of component (B) is 0.2 to 5% by mass with respect to the total mass of the liquid detergent composition. The liquid cleanser for toilets according to claim 1 or 2, wherein the mass ratio represented by component (B)/component (C) + component (D) is 0.1 to 0.8. agent composition. The liquid detergent composition for toilets according to any one of claims 1 to 3, wherein the component (A) contains an amphoteric surfactant.