Liquid toilet cleaning agent composition

Abstract

To provide a liquid detergent composition for toilets heightened in foamability at a low temperature, and reduced in temperature dependence of foamability.SOLUTION: A liquid detergent composition for toilets includes: at least one surfactant (constituent A) selected from amphoteric surfactants, and semi-polar surfactants; polyoxyalkylene alkyl ether (constituent B) represented by the following formula (1); and one or more polymer(s) (constituent C) selected from polyvinyl alcohol-based polymers and cellulose-based polymers, where the mass ratio expressed by constituent A / constituent(B) is 0.4-8. R-(OC2H4)n-OH (1). In the formula (1), R is a 8-18C aliphatic hydrocarbon group, n is a number expressing an average repeating number of (OC2H4), and n is 31-70.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a liquid detergent composition for toilets.

Background Art

[0002] For cleaning a toilet bowl, it is common to apply a liquid detergent composition for toilets to the object to be cleaned and then rub it with a cleaning brush (scrubbing). When scrubbing the object to be cleaned with a cleaning brush, one has to bend forward or assume a semi - crouched position, which is time - consuming and places a heavy physical burden. Also, the back of the rim of the toilet bowl and the like are areas where it is difficult for the cleaning brush to reach, making it difficult to clean.

[0003] Conventionally, a liquid detergent composition for toilets that combines an amphoteric surfactant and a polyvinyl alcohol - based polymer, has excellent detergency, good retention, and good discharge properties has been disclosed (see, for example, Patent Document 1).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, conventional liquid toilet cleaner compositions have a problem: in winter, when the temperature of the toilet space drops (low temperature environment), the liquid temperature of the toilet cleaner composition also drops, resulting in insufficient foaming (low foaming ability) when sprayed. To address this problem, simply increasing the amount of surfactant leaves streaks even when the toilet seat is sprayed and wiped. In addition, simply increasing the amount of surfactant results in an excessive amount of foam in summer when the temperature rises (high temperature environment), making the foam difficult to dissipate (poor usability). In other words, liquid toilet cleaner compositions are required to exhibit appropriate foaming ability in both low and high temperature environments (low temperature dependence).

[0006] The present invention has been made in view of the above circumstances, and aims to provide a liquid toilet cleaner composition that enhances foaming ability at low temperatures and reduces the temperature dependence of foaming ability. [Means for solving the problem]

[0007] The inventors, after diligent research, obtained the following findings. By using at least one type of amphoteric surfactant and a semipolar surfactant in combination with a nonionic surfactant of a specific number of ethylene oxide addition moles in a specific ratio, and by combining it with one or more polymers selected from specific polyvinyl alcohol-based polymers and cellulose-based polymers, it is possible to reduce the amount of foam produced by a liquid detergent composition at low temperatures without reducing its temperature dependence. The present invention has the following aspects. [1](A)Component: at least one selected from amphoteric surfactants and semipolar surfactants, (B) Component: A polyoxyalkylene alkyl ether represented by the following formula (1), (C) Components: One or more polymers selected from polyvinyl alcohol-based polymers and cellulose-based polymers, It contains, A liquid toilet cleaning agent composition wherein the mass ratio of component (A) to component (B) is 0.4 to 8. R-(OC2H4) n -OH···(1) (In formula (1), R is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, and n is a number representing the average number of repeats of (OC2H4), where n is between 31 and 70.) [2] The liquid toilet cleaning composition according to [1], wherein the content of component (A) is 0.15 to 5% by mass and the content of component (B) is 0.15 to 5% by mass with respect to the total mass of the liquid cleaning composition. [3] The liquid toilet cleaning composition according to [1] or [2], wherein component (C) is a polymer selected from polyvinyl alcohol-based polymers with a degree of saponification of 80% or more, carboxymethylcellulose, and hydroxyethylcellulose. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a liquid toilet cleaner composition that enhances foaming ability at low temperatures and reduces the temperature dependence of foaming ability. [Modes for carrying out the invention]

[0009] (Liquid cleaning agent composition for toilets) The liquid toilet cleaning agent composition of the present invention (hereinafter sometimes simply referred to as "liquid cleaning agent composition") contains components (A) to (C).

[0010] <(A) component> Component (A) is at least one selected from amphoteric surfactants and semipolar surfactants. The liquid detergent composition exhibits cleaning power by containing component (A). The liquid detergent composition, by containing component (A), has improved foaming properties when sprayed at room temperature, resulting in a larger amount of foam and improved wiping properties. Examples of component (A) include amphoteric surfactants (component (a1)) and semipolar surfactants (component (a2)). Among these, component (a1) is preferred as component (A).

[0011] (A) The content of component (A) is preferably 0.15 to 5% by mass, more preferably 0.25 to 4% by mass, and even more preferably 0.3 to 4% by mass, based on the total mass of the liquid detergent composition. (A) If the content of component (A) is above the lower limit, the foaming ability at room temperature is further enhanced and the amount of foam is increased. (A) If the content of component (A) is below the upper limit, the wiping ability is enhanced.

[0012] (a1) Ingredients (a1) Component is an amphoteric surfactant. Component (a1) is not particularly limited and can be appropriately selected depending on the purpose, for example, betaine-based amphoteric surfactants, amino acid-based amphoteric surfactants, etc. Among these, betaine-based amphoteric surfactants are preferred. Examples of betaine-based amphoteric surfactants include carbobetaine-based amphoteric surfactants, amidebetaine-based amphoteric surfactants, sulfobetaine-based (hydroxysulfobetaine-based, amidesulfobetaine-based) amphoteric surfactants, imidazolinium betaine-based amphoteric surfactants, phosphobetaine-based amphoteric surfactants, and aminopropionic acid-based amphoteric surfactants. Carbobetaine-based amphoteric surfactants and amidebetaine-based amphoteric surfactants are preferred, and amidebetaine-based amphoteric surfactants are more preferred.

[0013] (1) Examples of carbobetaine-based amphoteric surfactants include dimethylaminoacetic acid betaine laurate, myristyldimethylaminoacetic acid betaine, and stearyldimethylaminoacetic acid betaine. (2) Examples of amidobetaine-based amphoteric surfactants include coconut oil fatty acid amidopropyl betaine (cocamidopropyl betaine), lauric acid amidopropyl betaine, and isostearamidopropyl betaine. (3) Examples of sulfobetaine-based amphoteric surfactants include coconut oil fatty acid dimethylamino hydroxysulfobetaine, lauryl dimethylamino hydroxysulfobetaine, lauryl hydroxysulfobetaine, coconut oil fatty acid dimethyl sulfopropyl betaine, lauryl sulfobetaine, stearyl sulfobetaine, myristyl sulfobetaine, 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. (5) Examples of phosphobetaine amphoteric surfactants include lauryl hydroxyphosphobetaine and the like. (6) Examples of aminopropionic acid amphoteric surfactants include sodium lauryldiaminopropionate, triethanolamine lauryldiaminopropionate, and the like. (7) Examples of amino acid amphoteric surfactants include lauryl amino fatty acid salts, stearyl amino fatty acid salts, myristyl amino fatty acid salts, and the like.

[0014] Among the above, as the component (a1), lauric acid amidopropyl betaine, lauryl dimethylaminoacetic acid betaine, and stearyl dimethylaminoacetic acid betaine are preferable, and lauric acid amidopropyl betaine and lauryl dimethylaminoacetic acid betaine are particularly preferable from the aspect of wiping property. Examples of the counter ion of the salt include ions of alkali metal salts, ions of ammonium salts, ions of alkanolamine salts, and the like. Among these, ions of alkali metal salts are preferable, and sodium ions and potassium ions are more preferable.

[0015] (a1) component is commercially available. Commercially available (a1) components include, for example, "Enajicol L-30B (manufactured by Ichifunka Oil Industry Co., Ltd.)" which is lauramidopropyl betaine, "CAB-30 (manufactured by Ichifunka Oil Industry Co., Ltd.)" which is coconut oil fatty acid amide propyl betaine, "TEGO BETAIN CK-OK (manufactured by Degussa)" as coconut oil fatty acid amide propyl betaine, "Ampholex PB-1 (manufactured by Miyoshi Oil & Fat Co., Ltd.)" which is palm kernel oil fatty acid amide propyl betaine, "Levon LD-36 (manufactured by Sanyo Chemical Industries, Ltd.)" and "Obazoline LB-SF (manufactured by Toho Chemical Industry Co., Ltd.)" which are lauryldimethylaminoacetic acid betaine, and "Anhitol 86B" manufactured by Kao Corporation which is stearyldimethylaminoacetic acid betaine.

[0016] ≪(a2) component≫ (a2) component is an amine oxide type surfactant (semipolar surfactant). Examples of (a2) components include alkylamine oxides such as dodecyldimethylamine oxide, myristyldimethylamine oxide, and coconut alkyl dimethylamine oxide; and amidoamine oxides such as coconut oil fatty acid amide propylamine oxide and lauramide propylamine oxide. Among them, dodecyldimethylamine oxide (AX) is preferred.

[0017] (A) component may be used alone or in combination of two or more. As (A) component, it is preferably to contain (a1) component, and (a1) component is preferred.

[0018] <(B) component> (B) component is a polyoxyalkylene alkyl ether represented by the following formula (1). By containing (B) component in the liquid detergent composition of the present invention, the foaming property during spraying at normal temperature and low temperature is further enhanced, the amount of foam increases, and the wiping property is enhanced.

[0019] R-(OC2H4) n -OH···(1)

[0020] In formula (1), R is an aliphatic hydrocarbon group having 8 to 18 carbon atoms. R may be a straight chain or a branched chain. R may be a saturated hydrocarbon or an unsaturated hydrocarbon. The number of carbon atoms in R is preferably 12 to 18.

[0021] In formula (1), n ​​is a number between 31 and 70 that represents the average number of repeating oxyethylene groups (OC2H4). A value between 31 and 60 is preferred for n. If n is greater than or equal to the lower limit, foaming ability increases, resulting in a larger amount of foam and improved wipeability. If n is less than or equal to the upper limit, the amount of foam increases, resulting in improved wipeability.

[0022] (B) The content of component (B) is preferably 0.15 to 5% by mass, more preferably 1 to 4.75% by mass, and even more preferably 1 to 4.7% by mass, relative to the total mass of the liquid detergent composition. If the content of component (B) is above the lower limit, the foaming ability at room temperature and low temperature is further enhanced, resulting in a larger amount of foam. If the content of component (B) is below the upper limit, the wiping ability can be enhanced.

[0023] The mass ratio (A / B ratio) of component (A) / component (B) is between 0.4 and 8, preferably between 1 and 7.1, and more preferably between 1.4 and 5. If the A / B ratio is above the lower limit, the foaming ability at low temperatures is further enhanced, resulting in a larger volume of foam. If the A / B ratio is below the upper limit, the foaming ability at low temperatures is further enhanced, resulting in a larger volume of foam.

[0024] The total amount of component (A) and component (B) (AB total amount) is equal to the total mass of the liquid detergent composition. Preferably, the amount is 0.3 to 7% by mass, and more preferably 1 to 6% by mass. If the total amount of A and B is above the lower limit, the foaming ability at low temperatures will be further enhanced, resulting in a larger amount of foam. If the total amount of A and B is below the upper limit, the wipeability will be enhanced.

[0025] <(C) component)> Component (C) is one or more polymers selected from polyvinyl alcohol-based polymers (component (c1)) and cellulose-based polymers (component (c2)). By containing component (C), the liquid detergent composition can achieve higher foaming properties when sprayed at room temperature and low temperature, resulting in a larger amount of foam, and reducing the temperature dependence of the foam amount. In this paper, "polymer" refers to a compound with a molecular weight of 1,000 or more. The molecular weight of component (C) is the weight-average molecular weight measured by gel permeation chromatography using polyethylene glycol (PEG) as the standard substance.

[0026] (c1) Component refers to a "homopolymer type" obtained by preparing vinyl acetate from ethylene, polymerizing them individually, and saponifying them with alkali, and a "copolymer type" obtained by preparing vinyl acetate, copolymerizing it with other monomers, and saponifying it with alkali.

[0027] (c1) Examples of components include polyvinyl alcohol (PVA), cation-modified polyvinyl alcohol (cation-modified PVA), anionic-modified polyvinyl alcohol (anionic-modified PVA), etc. PVA is an unmodified homopolymer type. Commercially available PVA products include the Gosenol series (GL-03, EG-05, EG-30, EG-40, etc.) from Nippon Synthetic Chemical Co., Ltd., and the Poval (PVA) series (403, 405, 420, 420H, 424H, 203, 205, 210, 217, 220, 224, 235, 217E, 220E, 224E, etc.) from Kuraray Co., Ltd. The saponification value of PVA is preferably 70% or higher, more preferably 80% to 98%, and even more preferably 80% to 90%. If the saponification value is above the lower limit, the temperature dependence of the foam can be reduced. As copolymer types with PVA, anionic modified PVA such as carboxylic acid-modified PVA, undecylenic acid-modified PVA, and sulfonic acid-modified PVA, and cationic modified PVA such as ammonium-modified PVA, sulfonium-modified PVA, and amino group-modified PVA can be used. Examples of commercially available copolymer polymers include the Gosenex T series (T-350, T-330H, etc.), Gosenex L series (L-3266, etc.), and Gosenex K series (K-434, etc.) from Nippon Synthetic Chemical Co., Ltd., and the K polymer series (KL-506, KL-318, KL-118, KM-618, KM-118, etc.) and C polymer series (C-506, CM-318, etc.) from Kuraray Co., Ltd., but other polymers can also be used. The saponification value of the copolymerized polymer type is preferably 70% or higher, more preferably 75% to 99%, and even more preferably 80% to 99%, from the viewpoint of the temperature dependence of the foam. If the saponification value is above the lower limit, the temperature dependence of the foam can be further reduced. Among the copolymerized polymer types, anionically modified polyvinyl alcohol is preferred.

[0028] The average degree of polymerization of component (c1) is preferably 500 to 2,400. If the average degree of polymerization is above the lower limit, the temperature dependence of the foam can be further reduced. If the average degree of polymerization is below the upper limit, the temperature dependence of the foam can be further reduced.

[0029] The molecular weight of component (c1) is 1,000 or more, preferably 10,000 to 200,000, and more preferably 20,000 to 120,000.

[0030] The viscosity of component (c1) is preferably 5 to 95 Pa, and more preferably 5 to 30 Pa. If the viscosity of component (c1) is above the lower limit, foaming ability at low temperatures can be increased and the temperature dependence of the foam can be reduced. If the viscosity of component (c1) is below the upper limit, foaming ability at low temperatures can be increased and the temperature dependence of the foam can be reduced.

[0031] The viscosity of component (c1) can be measured by preparing a 4% aqueous solution, adjusting the temperature to 20°C, and reading the result after 60 seconds using a B-type (Brookfield type) viscometer at 60 rpm.

[0032] (c2) The component is a high-molecular-weight compound derived from polysaccharides obtained from dietary fiber or cellulose obtained by hydrolyzing cellulose acetate. (c2) Examples of components include methylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, ethylcellulose, and carboxymethylcellulose. Among these, carboxymethylcellulose and hydroxyethylcellulose are preferred from the viewpoint of further reducing the temperature dependence of the foam.

[0033] The average degree of polymerization of component (c2) is preferably 400 to 6,000. If the average degree of polymerization is above the lower limit, foaming ability at low temperatures can be improved and the temperature dependence of the foam can be further reduced. If the average degree of polymerization is below the upper limit, the temperature dependence of the foam can be reduced.

[0034] The molecular weight of component (c2) is 1,000 or more, preferably 10,000 to 1,500,000, and more preferably 500,000 to 1,200,000.

[0035] (C) The content of component (C) is preferably 0.01 to 1% by mass, more preferably 0.05 to 0.5% by mass, and even more preferably 0.05 to 0.3% by mass, relative to the total mass of the liquid detergent composition. If the content of component (C) is above the lower limit, the foaming ability when sprayed at low temperatures will be further enhanced, the amount of foam will increase, and the temperature dependence of the amount of foam will be reduced. If the content of component (C) is below the upper limit, the temperature dependence of the amount of foam will be reduced, and the wiping ability will be improved.

[0036] The mass ratio (A / BC ratio) expressed as (Component A) / (Component B + Component C) is preferably 0.3 to 7, and more preferably 0.3 to 3.5. If the A / BC ratio is above the lower limit, the temperature dependence of the foam quantity can be reduced. If the A / BC ratio is below the upper limit, the temperature dependence of the foam quantity can be reduced.

[0037] <(D) component> (D) Component is water. The liquid detergent composition of the present invention may optionally contain water as a solvent in addition to the above components. The content of component (D) is preferably 80 to 95% by mass, and more preferably 88 to 94% by mass, based on the total mass of the liquid detergent composition.

[0038] <Optional ingredients> The liquid cleaning agent composition of the present invention may optionally contain, in addition to the above-mentioned components, components that are commonly used in toilet cleaning agent compositions. Examples of such optional components include surfactants other than component (A) (optional surfactants), organic solvents, preservatives, chelating agents, disinfectants, antifungal agents, dyes, antioxidants, thickeners, ultraviolet absorbers, solubilizers, fragrances, pH adjusters, and the like.

[0039] Examples of optional surfactants include anionic surfactants, nonionic surfactants (excluding component (B)), and cationic surfactants.

[0040] Examples of organic solvents include monohydric alcohols and glycol ethers. Examples of monohydric alcohols include ethanol and isopropanol. Examples of glycol ethers include ethylene glycol ethers such as ethylene glycol monomethyl ether, propylene glycol ethers such as propylene glycol monoethyl ether, dialkyl glycol ether solvents, monoethylene glycol monophenyl ether, and others.

[0041] Examples of preservatives include isothiazolinone-based preservatives such as benzisothiazolinone, methylisothiazolinone, butylbenzisothiazolinone, chloromethylisothiazolinone, octylisothiazolinone, and dichlorooctylisothiazolinone. Among these, 1,2-benzisothiazolin-3-one and 2-methyl-4-isothiazolin-3-one are preferred as preservatives.

[0042] As chelating agents, aminocarboxylic acid-based chelating agents include DEG (dihydroxyethylglycine), HEIDA (N-(2-hydroxyethyl)iminodiacetic acid), HEDTA (hydroxyethylethylenediaminetetraacetic acid), NTA (nitrilotriacetic acid), DTPA (diethylenetriaminepentaacetic acid), HEDTA (hydroxyethylethylenediaminetriacetic acid), EDTA (ethylenediaminetetraacetic acid), MGDA (methylglycinediacetic acid), GLDA (L-glutamic acid diacetic acid), ASDA (aspartic acid diacetic acid), and EDDS. Examples of polycarboxylic acid chelating agents (non-nitrogen-containing) include ethylenediamine succinic acid, HIDS (hydroxyiminodisuccinic acid), IDS (iminodisuccinic acid), and salts (e.g., alkali metal salts) or hydrates of the above compounds, as well as acetic acid, adipic acid, monochloroacetic acid, oxalic acid, succinic acid, oxydisuccinic acid, carboxymethylsuccinic acid, carboxymethyloxysuccinic acid, glycolic acid, diglycolic acid, lactic acid, tartaric acid, carboxymethyltartaric acid, citric acid, malic acid, or gluconic acid, or salts thereof.

[0043] While not particularly limited, it is preferable to use an alkaline agent selected from sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and its derivatives, monoethanolamine, diethanolamine, triethanolamine, etc., and more preferably an alkaline agent selected from sodium hydroxide, potassium hydroxide, monoethanolamine, and triethanolamine, with sodium hydroxide and potassium hydroxide being even more preferable. pH adjusters may be used individually or in combination of two or more types.

[0044] (Manufacturing method) Liquid detergent compositions are manufactured by conventionally known manufacturing methods. For example, one method involves adding components (A) to (C) to a solvent component (D), adding optional components as needed, and mixing them together.

[0045] (How to use) One method of using the liquid cleaning agent composition is to place the liquid cleaning agent composition in a dispensing container, apply an appropriate amount of the liquid cleaning agent composition to the toilet bowl from the dispensing container, and then rinse it off with a flush or the like after a certain period of time. Another method of using the liquid cleaning agent composition involves applying an appropriate amount of the liquid cleaning agent composition to the toilet bowl and then scrubbing it with a cleaning brush. Alternatively, one method of use involves applying the liquid cleaning agent composition to the toilet seat or bathroom floor and then wiping it off with a cloth or paper towel.

[0046] Examples of dispensing containers for liquid detergent compositions include spray containers and squeeze containers. Among these, spray containers are preferred as dispensing containers for liquid detergent compositions because they offer excellent coating properties for the object to be cleaned. Examples of spray containers include aerosol spray containers, trigger spray containers (direct pressure type or pressurized type), and dispenser spray containers. These containers may be manually operated or electrically operated. Examples of aerosol spray containers include those described in Japanese Patent Publication No. 9-3441 and Japanese Patent Publication No. 9-58765. When filling aerosol spray containers, LPG (liquefied propane gas), DME (dimethyl ether), carbon dioxide, nitrogen gas, nitrous oxide gas, etc., can be used as propellants. These propellants may be used individually or in mixtures of two or more. Examples of trigger spray containers include those described in Japanese Patent Publication No. 9-268473 and Japanese Patent Publication No. 10-76196, among others. Examples of dispenser spray containers include those described in Japanese Patent Publication No. 9-256272, for example. Examples of pressurized trigger spray containers include those described in Japanese Patent Publication No. 2013-154276, etc. [Examples]

[0047] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following description.

[0048] (Raw materials used) <(A) Ingredient: Amphoteric surfactant> A-1: Lauric acid amidopropyl betaine: "Energicol L-30B" manufactured by Lion Corporation. A-2: Lauryldimethylaminoacetic acid betaine: "Rebon LD-36" manufactured by Sanyo Chemical Industries, Ltd. A-3: Stearyldimethylaminoacetic acid betaine: Kao Corporation "Anhitol 86B". A-4: C12AX, n-dodecyldimethylamine oxide: Manufactured by Lion Specialty Chemicals Co., Ltd., "KadenaX DM12D-W".

[0049] <(B) Component: Polyoxyalkylene alkyl ether> B-1: POE stearyl ether (EO40): Emarex 640 (Nippon Emulsion Co., Ltd.). B-2: POE lauryl ether (EO50): Emarex 750 (Nippon Emulsion Co., Ltd.). B-3: POE isotridecyl ether (EO60): TA600-75 (Lion Chemical Co., Ltd.). <(B') component: Comparison product of (B) component> B-4: POE stearyl ether (EO5): Emarex 605 (Nippon Emulsion Co., Ltd.). B-5: POE stearyl ether (EO20): Emarex 620 (Nippon Emulsion Co., Ltd.).

[0050] <(C) Components: Polyvinyl alcohol-based polymer or cellulose-based polymer> C-1: Polyvinyl alcohol: "POVAL 22-88" manufactured by Kuraray Co., Ltd. C-2: Polyvinyl alcohol: "Poval 26-80" manufactured by Kuraray Co., Ltd. C-3: Polyvinyl alcohol: "Poval 5-88" manufactured by Kuraray Co., Ltd. • C-4: Polyvinyl alcohol: "Poval 28-98" manufactured by Kuraray Co., Ltd. C-5: Polyvinyl alcohol: "Poval 95-88" manufactured by Kuraray Co., Ltd. • C-6: Carboxymethylcellulose: Daicel Finechem Co., Ltd. "CMC1290". • C-7: Cetyl hydroxyethylcellulose: "Polysurf67" manufactured by Ashland.

[0051] <Optional ingredients> pH adjuster: sulfuric acid (Kanto Chemical Industry Co., Ltd.), sodium hydroxide: liquid caustic sodium (AGC Inc.). • Ethanol: "Synthetic 95" manufactured by Nippon Alcohol Sales Co., Ltd. • Fragrance: Fragrance composition A as specified in Japanese Patent Publication No. 2003-183697. ·water

[0052] (Evaluation method) <Evaluation of foam volume> Each example of the liquid detergent composition was heated to 5°C (low temperature) or 25°C (room temperature) and placed in a dispensing container (Yoshino Kogyosho Co., Ltd. "TA-FA", foam trigger spray container, pressurized type, 1 stroke (approx. 0.8g / stroke)). Using this dispensing container, the liquid detergent composition was dispensed into a 200mL tall beaker in 5 strokes. After measuring the foam height with a ruler, the foam height per unit weight was calculated, and the foaming ability was evaluated based on the evaluation criteria below. ◎◎, ◎, and ○ were deemed to be passing grades. ≪Evaluation Criteria≫ ◎◎: Foam height is 1.0 cm / g or more. ◎: Foam height is 0.75 cm / g or more and less than 1.0 cm / g. ○: The foam height is 0.6 cm / g or more and less than 0.75 cm / g. △: Foam height is 0.3 cm / g or more but less than 0.6 cm / g. ×: Less than 0.3 cm / g.

[0053] <Evaluation of wipeability> 100 μL of each liquid cleaning agent composition was placed on a glass slide, and lightly wiped with toilet paper folded into eight. After drying, the degree of residue was evaluated by expert panelists visually and by touch according to the evaluation criteria below. ≪Evaluation Criteria≫ ◎◎: Leaves absolutely no streaks and feels completely non-sticky. ◎: Very slight, fine, linear streaks remain, but there is no stickiness and it is not noticeable. ○: A few thin, linear streaks remain, but the stickiness is not noticeable. △: Some streaks remain, and a sticky feeling can be felt. ×: Wipe marks remain all over, and a sticky feeling is also present.

[0054] <Evaluation of the temperature dependence of foam volume> Each example of the liquid detergent composition was heated to 5°C, 25°C, and 35°C and placed in a dispensing container (Yoshino Kogyosho Co., Ltd. "TA-FA", foam trigger spray container, pressurized type, 1 stroke (approx. 0.8g / stroke)). Using this dispensing container, the liquid detergent composition was dispensed into a 200mL tall beaker in 5 strokes. After measuring the foam height with a ruler, the foam height per unit weight was calculated, and the slope when plotted against liquid temperature was evaluated based on the evaluation criteria below. ≪Evaluation Criteria≫ ◎◎: The slope is 0.025 or less. ◎: The slope is greater than 0.025 and less than or equal to 0.035. ○: Greater than 0.035 and less than or equal to 0.045. △: Greater than 0.045 and less than or equal to 0.05. ×: Greater than 0.05.

[0055] (Examples 1-46, Comparative Examples 1-8) 500 g of each example liquid detergent composition was prepared according to the following procedure. According to the formulations in Tables 1-7, components (A)-(C) and the common component were mixed with water, and if necessary, a pH adjuster (sulfuric acid or potassium hydroxide) was added to adjust the pH to 7.0 to obtain the liquid detergent compositions for each example. The amounts listed in the table are calculated on a pure content basis. Ingredients not listed in the table are not included. In the table, the "balance" for the amount of water is the amount required to bring the total volume of the liquid detergent composition to 100% by mass. In the table, the "appropriate amount" for the amount of sulfuric acid is the amount required to adjust the pH of the liquid detergent composition to 7.0. For each example of the obtained liquid detergent composition, the amount of foam at room temperature (25°C), the amount of foam at low temperature (5°C), the wiping ability, and the temperature dependence of the foam amount were evaluated, and the results are shown in the table.

[0056] [Table 1]

[0057] [Table 2]

[0058] [Table 3]

[0059] [Table 4]

[0060] [Table 5]

[0061] [Table 6]

[0062] [Table 7]

[0063] As shown in Tables 1 to 7, in Examples 1 to 46 to which the present invention was applied, the amount of foam at room temperature (25°C) was "○" to "◎◎", the amount of foam at low temperature (5°C) was "○" to "◎◎", the wipeability was "○" to "◎◎", and the temperature dependence of the amount of foam was "○" to "◎◎". Examples 38 and 43 showed that the amount of foam at low temperatures (5°C) was greater when C-3 and C-4 were used together than when C-3 was used alone. Examples 40 and 44 showed that the temperature dependence of foam volume was reduced when C-2 and C-5 were used in combination compared to when C-5 was used alone. Examples 41 and 45 showed that when C-1 and C-6 were used together, the amount of foam at room temperature (25°C) was greater than when C-6 was used alone, the amount of foam at low temperature (5°C) was greater, and the temperature dependence of the foam amount was reduced. Examples 42 and 46 showed that when C-1 and C-7 were used together, the amount of foam at room temperature (25°C) was greater than when C-7 was used alone, the amount of foam at low temperature (5°C) was greater, and the temperature dependence of the foam amount was reduced. Comparative Example 1, which used component (B) as the comparison product, showed a "○" for foam volume at room temperature (25°C), a "×" for foam volume at low temperature (5°C), a "○" for wipeability, and a "×" for temperature dependence of foam volume. Comparative Example 2, which used component (B) as the comparison product, showed a "○" for foam volume at room temperature (25°C), a "△" for foam volume at low temperature (5°C), a "○" for wipeability, and a "△" for temperature dependence of foam volume. Comparative Example 3, with an A / B ratio of 0.27, had a foam volume of "◎" at room temperature (25°C), a foam volume of "×" at low temperature (5°C), excellent wipeability, and a temperature dependence of foam volume of "◎". Comparative Example 4, with an A / B ratio of 9.00, had a foam volume of "◎◎" at room temperature (25°C), a foam volume of "△" at low temperature (5°C), wipeability of "◎◎", and a temperature dependence of foam volume of "△". Comparative Example 5, with an A / B ratio of 16.00, had a foam volume of "◎◎" at room temperature (25°C), a foam volume of "×" at low temperature (5°C), wipeability of "◎◎", and a temperature dependence of foam volume of "×". Comparative Example 6, which did not contain component (A), had a foam volume of "◎" at room temperature (25°C), a foam volume of "△" at low temperature (5°C), a wipeability of "○", and a temperature dependence of foam volume of "×". Comparative Example 7, which did not contain component (B), had a foam volume of "◎" at room temperature (25°C), a foam volume of "×" at low temperature (5°C), wipeability of "◎◎", and a temperature dependence of foam volume of "×". Comparative Example 8, which did not contain component (C), had a foam volume of "◎◎" at room temperature (25°C), a foam volume of "○" at low temperature (5°C), wipeability of "◎◎", and a temperature dependence of foam volume of "×". These results confirm that the liquid detergent composition to which the present invention is applied exhibits excellent foam volume at room temperature (25°C), foam volume at low temperature (5°C), wipeability, and temperature dependence of foam volume.

Claims

1. (A) Components: At least one selected from amphoteric surfactants and semipolar surfactants, (B) Component: A polyoxyalkylene alkyl ether represented by the following formula (1), (C) Component: One or more polymers selected from polyvinyl alcohol-based polymers and cellulose-based polymers, It contains, The aforementioned component (A) is at least one selected from betaine-based amphoteric surfactants and amine oxide-type surfactants. The aforementioned component (C) is at least one selected from homopolymer-type polyvinyl alcohol, carboxymethylcellulose, hydroxyethylcellulose, and cetylhydroxyethylcellulose. The content of component (A) is 0.1 to 6% by mass, The content of component (B) is 0.1 to 5% by mass, The content of component (C) is 0.01 to 1% by mass, The mass ratio expressed as component (A) / component (B) is 0.4 to 8. A liquid toilet cleaning agent composition wherein the mass ratio of component (A) / (component (B) + component (C)) is 0.3 to 7. R-(OC ２ H ４ ) ｎ -OH・・・(1) (In formula (1), R is an aliphatic hydrocarbon group having 12 to 18 carbon atoms, and n is (OC ２ H ４ This number represents the average number of repetitions, where n is between 31 and 60.

2. The liquid toilet cleaning agent composition according to claim 1, wherein the content of component (A) is 0.15 to 5% by mass and the content of component (B) is 0.15 to 5% by mass, based on the total mass of the liquid cleaning agent composition.

3. The liquid toilet cleaning agent composition according to claim 1 or 2, wherein component (C) is a polymer selected from homopolymer type polyvinyl alcohol, carboxymethylcellulose, and hydroxyethylcellulose with a degree of saponification of 80% or more.

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