Liquid detergent composition and detergent article in squeeze container

Abstract

To provide a liquid detergent composition which has good liquid blocking properties and stringiness prevention properties at high temperatures and good constant volume discharging property when used in a constant-volume discharging squeeze container.SOLUTION: There is provided a liquid detergent composition which comprises a component (a): at least one selected from a group consisting of compounds represented by a following formula (a), a component (b): a thickener, a component (c): at least one selected from a group consisting of an aromatic sulfonic acid, an aromatic carboxylic acid and a salt thereof and water. In the formula, R1 is a linear or branched-chain alkyl group having a carbon number of 8 to 18 or a linear or branched-chain alkenyl group having a carbon number of 8 to 18, AO is an oxyalkylene group, m is a number of 0 to 10 representing an average repeating number of AO and, Ma and Mb each independently are a counter ion.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to liquid detergent compositions and squeeze-packaged detergent articles. [Background technology]

[0002] 2. Description of the Related Art As a container for storing a liquid detergent composition, there is a squeeze container, which ejects the content liquid from a discharge port when the container body is squeezed to deform it. There are also squeeze containers for fixed-volume dispensing, which are designed so that the deformation amount when the container body is pressed is constant, thereby dispensing a fixed amount of the liquid content. Fixed-volume dispensing squeeze containers are suitable as containers for liquid detergent compositions for which a recommended amount to be used is set, such as detergents for dishwashers.

[0003] In a squeeze-container-packaged detergent article in which a liquid detergent composition is contained in a squeeze container for dispensing a fixed amount, it is desirable that there be little fluctuation in the amount dispensed when the dispensing operation is repeated. The examples of Patent Document 1 show that a liquid detergent article in which a liquid detergent composition containing a nonionic surfactant, a metal blocking agent, a thickener (a (meth)acrylic acid-based polymer), and water is contained in a fixed-volume dispenser squeeze container has good physical properties in terms of fixed-volume dispenseability with little fluctuation in the dispensed amount due to temperature changes, and liquid drainage (20°C) with no dripping after dispense at 20°C. The examples of Patent Document 2 show that a liquid detergent article in which a liquid detergent composition containing an anionic surfactant (alkyl sulfate), a cationic surfactant, a polysaccharide polymer (xanthan gum), a specific metal sequestering agent, and water is contained in a squeeze container for dispensing a fixed amount has good physical properties in terms of the fixed amount dispensing ability and the liquid drainage ability (20°C). The examples of Patent Document 3 show that a liquid detergent article in which a liquid detergent composition containing an anionic surfactant (alkyl sulfate, polyoxyalkylene alkyl ether sulfate), an aromatic sulfonic acid or aromatic carboxylic acid, a thickener (crosslinked polyacrylic acid, xanthan gum), and water is contained in a squeeze container for dispensing a fixed amount has good physical properties in terms of the ability to dispense a fixed amount, and also has good high-temperature stability with little change in appearance when stored in an environment of 50°C. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2016-60798 A [Patent Document 2] JP 2016-160279 A [Patent Document 3] JP 2017-110058 A Summary of the Invention [Problem to be solved by the invention]

[0005] The inventors have noted that when a containerized cleaning agent article is stored in a high-temperature location, such as on or near a dishwasher, the liquid temperature may become high when the article is used. According to the findings of the inventors, the liquid cleaning agent articles described in Patent Documents 1 to 3 have insufficient liquid drainage properties when the liquid temperature is high, and when the liquid temperature is high, they are prone to stringing after being discharged, posing problems in terms of usability. The present invention has been made in consideration of the above circumstances, and provides a liquid detergent composition that has good liquid cutting properties and anti-stringing properties at high temperatures, and also has good fixed-volume dispensing properties when contained in a fixed-volume squeeze container for use. [Means for solving the problem]

[0006] The present invention has the following aspects. [1] Component (a): at least one compound selected from the group consisting of compounds represented by the following formula (a): (b) component: a thickener; Component (c): A liquid detergent composition comprising water and at least one member selected from the group consisting of aromatic sulfonic acids, aromatic carboxylic acids, and salts thereof. [ka] In the formula, R 1 represents a linear or branched alkyl group having 8 to 18 carbon atoms or a linear or branched alkenyl group having 8 to 18 carbon atoms, AO represents an oxyalkylene group, m represents the average number of repetitions of AO and is a number of 0 to 10, and Ma and Mb each independently represent a counter ion. [2] The liquid detergent composition according to [1], wherein the mass ratio of the component (a) / the component (b) is 0.1 to 1,000. [3] The liquid detergent composition according to [1] or [2], wherein the mass ratio of the component (b) to the component (c) is 0.001 to 10. [4] A detergent article in a squeeze container, in which the liquid detergent composition according to any one of the above [1] to [3] is contained in a squeeze container. Effect of the Invention

[0007] According to the present invention, there is provided a liquid detergent composition which exhibits good liquid cutting properties and anti-stringing properties at high temperatures, and also exhibits good constant-volume dispensing properties when contained in a constant-volume squeeze container for use. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] The liquid detergent composition of the present invention comprises component (a), component (b), component (c), and water. The liquid detergent composition may further contain other components other than the components (a), (b), (c) and water.

[0009] <Component (a)> The component (a) is at least one selected from the group consisting of compounds represented by the following formula (a): The component (a) can also be said to be at least one selected from the group consisting of monoalkylsulfosuccinic acids having a linear or branched alkyl group having 8 to 18 carbon atoms, which may have 10 moles or less of alkylene oxide added thereto, and salts thereof, and monoalkenylsulfosuccinic acids having a linear or branched alkenyl group having 8 to 18 carbon atoms, which may have 10 moles or less of alkylene oxide added thereto, and salts thereof.

[0010] [ka]

[0011] In the formula, R 1 represents a linear or branched alkyl group having 8 to 18 carbon atoms or a linear or branched alkenyl group having 8 to 18 carbon atoms, AO represents an oxyalkylene group, m represents the average number of repetitions of AO and is a number of 0 to 10, and Ma and Mb each independently represent a counter ion.

[0012] In formula (a), R 1 R is a linear or branched alkyl group having 8 to 18 carbon atoms or a linear or branched alkenyl group having 8 to 18 carbon atoms. 1 When the carbon number of R is 8 to 18, it is easy to improve the liquid cut-off property at high temperatures and the prevention of stringiness at high temperatures. 1 The number of carbon atoms is preferably 10 to 16, and more preferably 12 to 16.

[0013] In formula (a), AO is an oxyalkylene group. Examples of the oxyalkylene group include an oxyethylene group, an oxypropylene group, and an oxybutylene group. Among these, an oxyethylene group is preferred. In formula (a), m represents the average number of repetitions of AO and is a number from 0 to 10. When m is from 0 to 10, liquid cut-off at high temperatures and prevention of stringiness at high temperatures are easily improved. m is preferably from 0 to 4, more preferably from 3 to 4, and particularly preferably 4.

[0014] In formula (a), Ma and Mb are each independently a counter ion. Examples of counter ions include hydrogen ions and ions capable of forming water-soluble salts. Among these, ions capable of forming water-soluble salts are preferred. Examples of ions capable of forming water-soluble salts include alkali metal ions such as sodium ions and potassium ions, alkaline earth metal ions such as calcium ions and magnesium ions, ammonium ions, and protonated ethanolamines. Among these, from the viewpoints of liquid drainage at high temperatures and prevention of stringing at high temperatures, alkali metal ions are preferred, sodium ions and potassium ions are more preferred, and sodium ions are particularly preferred. Ma and Mb may be the same type of counter ion or different types of counter ions, but are preferably the same type of counter ion. In addition, when Ma is a counter ion with a valence of 2 or more, Ma is considered to be bonded to -O with a number multiplied by 1 / valence. For example, when Ma is a magnesium ion, the number of Ma is 1 / 2. Similarly, when Mb is a counter ion with a valence of 2 or more, Mb is considered to be bonded to -SO3 with a number multiplied by 1 / valence.

[0015] As the component (a), monoalkyl sulfosuccinate is preferred. When m is 0, for example, disodium monolauryl sulfosuccinate is preferred. When m is 1 or more, for example, polyoxyethylene monoalkyl sulfosuccinate is preferred. Specific examples of polyoxyethylene monoalkyl sulfosuccinate are polyoxyethylene (1) monoalkyl (C12-14) disodium sulfosuccinate, polyoxyethylene (2) monoalkyl (C12-14) disodium sulfosuccinate, polyoxyethylene (2) monolauryl disodium sulfosuccinate, polyoxyethylene (2) monoalkyl (C12-14) sulfosuccinate di-triethanolamine, polyoxyethylene (3) monoalkyl (C12-14) disodium sulfosuccinate, polyoxyethylene (3) monolauryl disodium sulfosuccinate, polyoxyethylene (3) magnesium monolauryl sulfosuccinate, polyoxyethylene (3) monococonut oil fatty acid (C8-1 8) Disodium sulfosuccinate, polyoxyethylene (5) monoalkyl (carbon number 12-14) disodium sulfosuccinate, polyoxyethylene (5) monococonut oil fatty acid (carbon number 8-18) disodium sulfosuccinate, polyoxyethylene (5) monolauryl sulfosuccinate diethanolamide, polyoxyethylene (5) lauryl sulfosuccinate magnesium, polyoxyethylene (5) monococonut oil fatty acid (carbon number 8-18) disodium sulfosuccinate, polyoxyethylene (5) lauroylethanolamide disodium sulfosuccinate, polyoxyethylene (7) monoalkyl (carbon number 12-14) disodium sulfosuccinate, polyoxyethylene (7) monolauryl sulfosuccinate magnesium. The number in parentheses after polyoxyethylene indicates the average number of repeats of the oxyethylene group. The component (a) may be used alone or in combination of two or more types.

[0016] Component (a) contributes to improving liquid drainage at high temperatures and preventing stringiness at high temperatures. The content of component (a) is preferably 0.1 to 20 mass%, more preferably 0.5 to 5 mass%, and particularly preferably 1.5 to 3 mass%, based on the total mass of the liquid detergent composition. When the content of component (a) is equal to or greater than the lower limit, the anti-stringing property at high temperatures is easily improved. When the content of component (a) is within the above range, the liquid drainage property at high temperatures is easily improved.

[0017] <(b) Component> Component (b) is a thickener. The thickener preferably contains an acidic polysaccharide. Furthermore, the thickener may contain a thickener other than the acidic polysaccharide. The term "acidic polysaccharide" refers to a saccharide that is composed of two or more monosaccharides and has an acidic functional group that can form a salt with an inorganic cation when dissolved in water. Preferably, the polysaccharide is a water-soluble polymer that dissolves in water, and is a thickening polysaccharide that exhibits viscosity or gelation, particularly in the acidic pH range.

[0018] The monosaccharides that serve as the constituent units of acidic polysaccharides are not particularly limited, but include, for example, neutral sugars such as glucose, galactose (D-form and L-form), xylose, mannose, rhamnose, fucose, and arabinose; uronic acids such as guluronic acid, iduronic acid, mannuronic acid, glucuronic acid, and galacturonic acid; and amino sugars such as glucosamine and galactosamine. The acidic functional group is not particularly limited, but examples thereof include -COOH (carboxy group), -SO3H (sulfo group), -OSO3H, and -CH2OSO3H. Examples of acidic polysaccharides include xanthan gum, gellan gum, carrageenan, pectin, soybean polysaccharides, alginic acid, gum arabic, karaya gum, tragacanth gum, hyaluronic acid, agaropectin, porphyran, fucoidan (sulfated fucan), and ascophyllan. Among these, xanthan gum and gellan gum are preferred, and xanthan gum is more preferred. The acidic polysaccharides may be used alone or in combination of two or more.

[0019] As a thickener other than the acidic polysaccharide, any thickener known in the art for liquid detergents can be used, such as water-soluble polymers such as polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, acrylic acid-based polymers, and methacrylic acid-based polymers. The other thickening agents may be used alone or in combination of two or more.

[0020] Component (b) contributes to improving the liquid cut-off property and constant quantity discharge property at high temperatures. The content of component (b) is preferably 0.01 to 1 mass %, more preferably 0.1 to 0.5 mass %, and even more preferably 0.1 to 0.3 mass %, based on the total mass of the liquid detergent composition. When the content of component (b) is equal to or more than the lower limit, liquid drainage at high temperatures is easily improved, and when it is equal to or less than the upper limit, stringiness prevention at high temperatures is easily improved. Furthermore, when the content of component (b) is within the above range, constant-quantity discharge is easily improved. The proportion of the acidic polysaccharide in the total mass of component (b) is preferably from 50 to 100 mass %, more preferably from 90 to 100 mass %.

[0021] The mass ratio of component (a) / component (b) (hereinafter also referred to as "a / b ratio") is preferably 0.1 to 1000, more preferably 1 to 300, and particularly preferably 1 to 100. When the a / b ratio is equal to or greater than the lower limit, the prevention of stringiness at high temperatures is easily improved. When the a / b ratio is within the above range, the liquid drainage at high temperatures is easily improved.

[0022] <(c) component> The component (c) is at least one selected from the group consisting of aromatic sulfonic acids, aromatic carboxylic acids, and salts thereof. The component (c) does not contain an anionic surfactant. The component (c) is preferably an aromatic sulfonic acid represented by the following general formula (c1) or a salt thereof, or an aromatic carboxylic acid represented by the following general formula (c2) or a salt thereof.

[0023] [ka]

[0024] In formulas (c1) and (c2), M 2 , M 3 R represents a hydrogen atom, an alkali metal ion, an ammonium ion, an alkylamine, or an alkanolamine. 2 ~R 5 respectively represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkenyl group, or a carbonyl group.

[0025] Specific examples of component (c) include toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid, benzoic acid, phthalic acid, benzenesulfonic acid, sulfobenzoic acid, and salts thereof. Examples of the salts include alkali metal salts such as sodium and potassium, ammonium salts, and monoethanolamine salts. Among these, from the viewpoint of quantitative dischargeability, benzoic acid, cumenesulfonic acid, m-xylenesulfonic acid, p-toluenesulfonic acid and salts thereof are preferred, and m-xylenesulfonic acid or a salt thereof is more preferred. The component (c) may be used alone or in appropriate combination of two or more types.

[0026] The component (c) contributes to improving the ability to dispense a fixed amount of the mixture. The content of component (c) is preferably 0.1 to 10 mass %, more preferably 1 to 5 mass %, and particularly preferably 2 to 4 mass %, based on the total mass of the liquid detergent composition. When the content of component (c) is within the above range, it is easy to improve the constant-volume discharge property.

[0027] In the liquid detergent composition, the mass ratio of component (b) to component (c) (hereinafter also referred to as "b / c ratio") is preferably from 0.001 to 10, more preferably from 0.01 to 1, and particularly preferably from 0.01 to 0.5. When the b / c ratio is within the above range, the constant-volume discharge property is easily improved.

[0028] <Water> The liquid cleaning composition comprises water. The water content of the liquid detergent composition is preferably 70 to 99 mass %, more preferably 80 to 95 mass %, based on the total mass of the liquid detergent composition. When the water content is within the above range, the liquid detergent composition can be easily prepared.

[0029] <Other ingredients (optional ingredients)> The liquid detergent composition of the present invention may contain any component that is usually contained in a liquid detergent, so long as it does not go against the object of the present invention. For example, substances that are usually used in liquid detergent compositions, such as surfactants other than component (a), silicone-based antifoaming agents, enzymes, chelating agents, stabilizers, solvents, plant extracts, oil absorbents, tableware protectants, colorants, hydrotropes other than component (c), antioxidants, pH adjusters, fragrances, and bleaches, may be used.

[0030] Examples of the anionic surfactant include sulfonic acids, sulfates, carboxylic acids, and phosphates each having an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms, and salts thereof.

[0031] Examples of amidoamine surfactants include compounds represented by formula (a-1) described in JP 2021-4333 A. Specific examples of amidoamine surfactants include dimethylaminoethyl myristate, diethylaminoethyl myristate, dipropylaminoethyl myristate, dimethylaminopropyl myristate, diethylaminopropyl myristate, dipropylaminopropyl myristate, dimethylaminoethyl palmitate, diethylaminoethyl palmitate, dipropylaminoethyl palmitate, dimethylaminopropyl palmitate, diethylaminopropyl palmitate, dipropylaminopropyl palmitate, dimethylaminoethyl stearate, diethylaminoethyl stearate, dipropylaminoethyl stearate, dimethylaminopropyl stearate, diethylaminopropyl stearate, dipropylaminopropyl stearate, dimethylaminoethyl arachidate, diethylaminoethyl arachidate, dipropylaminoethyl arachidate, dimethylaminopropyl arachidate, dipropylaminoethyl arachidate, dimethylaminopropyl arachidate, diethylaminoethyl arachidate, dimethylaminopropyl arachidate, dipropylaminopropyl arachidate, dimethylaminoethyl arachidate, diethylaminoethyl arachidate, dimethylaminopropyl arachidate, dipropylaminoethyl arachidate, dimethylaminopropyl ... amide, arachidic acid diethylaminopropylamide, arachidic acid dipropylaminopropylamide, behenic acid dimethylaminoethylamide, behenic acid diethylaminoethylamide, behenic acid dipropylaminoethylamide, behenic acid dimethylaminopropylamide, behenic acid diethylaminopropylamide, behenic acid dipropylaminopropylamide, myristic acid dimethylaminoethylmethylamide, palmitic acid dimethylaminoethylmethylamide, stearic acid dimethylaminoethylmethylamide, arachidic acid dimethylaminoethylmethylamide, behenic acid dimethylaminoethylmethylamide, myristic acid dimethylaminopropylmethylamide, palmitic acid dimethylaminopropylmethylamide, stearic acid dimethylaminopropylmethylamide, arachidic acid dimethylaminopropylmethylamide, behenic acid dimethylaminopropylmethylamide, myristic acid amidopropyltrimethylammonium salt, palmitic acid amidopropyltrimethylammonium salt, stearic acid amidopropyltrimethylammonium salt, and the like.

[0032] In terms of appearance stability of the liquid detergent composition, it is preferable that the surfactant other than component (a) includes one or more selected from the group consisting of palmitic acid dimethylaminopropylamide, stearic acid dimethylaminopropylamide, and behenic acid dimethylaminopropylamide. The proportion of the component (a) relative to the total mass of the component (a) and other surfactants is preferably 50 to 100 mass %, more preferably 70 to 100 mass %, and particularly preferably 80 to 100 mass %.

[0033] Silicone-based defoaming agents are not particularly limited, and can be any of the general defoaming agents used in liquid detergent compositions. Silicone-based defoaming agents are not particularly limited to oil type, compound type, self-emulsifying compound type, powder type, etc., but can include, for example, polyorganosiloxane oil or resin dispersion or emulsion such as polydimethylsiloxane, and combination of polyorganosiloxane and silica particles in which polyorganosiloxane is chemically adsorbed or melted on silica, and for example, FS Antifoam 1266 (manufactured by Dow Chemical Co.), FS Antifoam 93 (manufactured by Dow Chemical Co.), etc. are preferred.

[0034] As the enzyme, any of the general enzymes that have been used in liquid detergent compositions so far can be used, such as amylase, protease, mannanase, cellulase, lipase, glucanase, etc.

[0035] As the chelating agent, any of the general chelating agents that have been used in liquid detergent compositions so far can be used, such as polymeric chelating agents and low molecular weight chelating agents. The polymer chelating agent is preferably one having a weight average molecular weight of 1,000 or more. Examples of the polymeric chelating agent include polyacrylic acid, polymethacrylic acid, acrylic acid-maleic acid copolymer, methacrylic acid-maleic acid copolymer, ethylene-maleic acid copolymer, and salts thereof. The salt constituting the polymeric chelating agent is preferably an alkali metal salt, and more preferably a sodium salt or a potassium salt. The weight average molecular weight of the polymer chelating agent is a value measured by gel permeation chromatography using sodium polyacrylate as a standard substance.

[0036] The low molecular weight chelating agent is preferably a chelating agent having a molecular weight of not more than 800. The molecular weight of the low molecular weight chelating agent is preferably 100 or more and 800 or less, and more preferably 150 or more and 500 or less. Examples of low molecular weight chelating agents include ethylenediaminetetraacetic acid, nitrilotriacetic acid, β-alanine diacetic acid, ethylenediamine disuccinic acid, L-aspartic acid-N,N-diacetic acid, dihydroxyethylethylenediaminediacetic acid, hydroxyethyliminodiacetic acid, citric acid, hydroxyethylethylenediaminetriacetic acid, glycol ether diamine tetraacetic acid, L-glutamic acid diacetic acid, 1,3-diamino-2-hydroxypropanetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, dihydroxyethylglycine, 3-hydroxy-2,2'-iminodisuccinic acid, serine diacetic acid, asparagine diacetic acid, methylglycine diacetic acid, hydroxyethanediphosphonic acid, aminotrimethylenephosphonic acid, tripolyphosphoric acid, and salts thereof. As the salt constituting the low molecular weight chelating agent, an alkali metal salt is preferable, and a sodium salt or a potassium salt is more preferable.

[0037] Examples of hydrotropic agents include polyols such as ethylene glycol and propylene glycol.

[0038] Examples of pH adjusters include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate; organic bases such as monoethanolamine, diethanolamine, triethanolamine, 2-amino-2-methyl-1-propanol, N-(β-aminoethyl)ethanolamine, diethylenetriamine, morpholine, and N-ethylmorpholine; inorganic acids such as hydrochloric acid and sulfuric acid; and organic acids such as oxalic acid. In terms of storage stability and cost of the liquid detergent composition, potassium hydroxide and sodium hydroxide are preferred among inorganic bases, and potassium hydroxide is particularly preferred from the viewpoints of storage stability, liquid fluidity, and the like. Among organic bases, monoethanolamine is preferred. The pH adjusters may be used alone or in combination of two or more. The content of the pH adjuster may be appropriately set so as to adjust the liquid detergent composition to a predetermined pH.

[0039] The pH of the liquid detergent composition at 25°C is preferably 5-10, and more preferably 6-9. The pH of the liquid detergent composition at 25°C is a value measured by a method in accordance with "pH measurement method" of JIS Z 8802:2011.

[0040] <Manufacturing method> The method for producing the liquid detergent composition of the present invention is not particularly limited, and the composition can be produced in accordance with a conventional method. For example, the liquid detergent composition can be produced by mixing components (a), (b), and (c), a portion of water, and, if necessary, any components other than the pH adjuster, adjusting the pH to a predetermined value using the pH adjuster if necessary, and then mixing the remaining water. If necessary, a step of cooling to room temperature may be provided, for example, when the reaction liquid is heated by heat of neutralization in the step of adding the pH adjuster.

[0041] <How to use> Methods for cleaning an object to be cleaned using the liquid cleaning agent composition of the present invention include a method in which the liquid cleaning agent is brought into contact with the object to be cleaned in its undiluted form and cleaned, and then rinsing with water, a method in which the liquid cleaning agent is brought into contact with the object to be cleaned in its undiluted form and cleaned, and then wiping it off, a method in which the liquid cleaning agent is brought into contact with a diluted solution of the liquid cleaning agent mixed with water and cleaned, and then rinsing with water, a method in which the liquid cleaning agent is brought into contact with a diluted solution of the liquid cleaning agent mixed with water and cleaned, and then wiping it off, etc. The cleaning may be a cleaning method that applies mechanical force. For example, the object to be cleaned may be scrubbed with a sponge or the like soaked in the undiluted solution or the diluted solution. The object to be cleaned may be applied to the object to be cleaned and then scrubbed with a sponge or the like. The object to be cleaned may be immersed in the diluted cleaning solution and then scrubbed with a sponge or the like. The undiluted solution may be discharged into a dishwasher and the dishwasher may be operated to clean the object. The object to be cleaned is preferably a hard surface of an article, etc. Examples include hard surfaces in a bathroom, bathroom supplies, hard surfaces in a toilet, toilet supplies, hard surfaces in a kitchen, and kitchen supplies (tableware, cooking utensils, etc.). By hard surface is meant a surface made of a hard material such as plastics, ceramics, glass, stainless steel, or the like.

[0042] The liquid detergent composition of the present invention can be suitably used in dishwashers, and may be used depending on the type of dishwasher and the degree of dirt on the dishes and the like. As a method for cleaning an object to be cleaned in a dishwasher using a liquid detergent composition, a method having both a cleaning step and a rinsing step can be mentioned. Examples of the washing method include a process of washing an object to be washed while heating a washing liquid prepared by introducing tap water at room temperature (preferably about 5 to 30°C) into a dishwashing machine chamber to a predetermined washing temperature (the temperature of the washing liquid circulating during washing) (hereinafter referred to as the "washing process"); a process of rinsing the object to be washed with tap water at room temperature (hereinafter referred to as the "rinsing (1) process"); and a process of further rinsing the object to be washed after the rinsing (1) process while heating the tap water at room temperature, preferably to 70 to 75°C at a rate of 2 to 3°C / min (hereinafter referred to as the "rinsing (2) process"). The washing time in the washing process is preferably 10 to 40 minutes. In the case of a general standard course, the washing temperature in the washing step is about 55 to 65°C, and the temperature rise rate is about 2 to 3°C / min. In the low temperature course, for example, the washing temperature is about 35 to 45°C, and the temperature rise rate is about 1°C / min. The liquid detergent composition of the present invention has excellent detergency against oily stains even in low temperature washing, and exhibits excellent detergency even at a washing temperature of, for example, 35°C. The amount of the liquid detergent composition used at one time is preferably 2 to 9 g per about 3 liters of tap water in any course.

[0043] <Cleaning product in a squeeze container> The squeeze-container-containing detergent article of the present invention is an article in which a liquid detergent composition is contained in a squeeze container. The squeeze container is not particularly limited, and a known squeeze container can be used depending on the application. The capacity of the squeeze container is preferably, for example, 100 to 1000 mL. The squeeze container is preferably a fixed-volume dispenser squeeze container, for example, a fixed-volume dispenser squeeze container having a container body made of squeezable plastic and configured so that it can be squeezed to a predetermined deformation amount when a predetermined position of the container body is pressed. A specific example is a squeeze container for dispensing a fixed amount, as described in JP 2016-160279 A. The amount of the liquid detergent composition discharged by one squeeze deformation is preferably, for example, 2 to 9 g.

[0044] <Action and effect> The liquid detergent composition described above contains components (a), (b), (c) and water, and therefore has good liquid drainage and anti-stringing properties at high temperatures, making it suitable for detergent articles in squeeze containers that are discharged from a discharge port. In addition, the composition has good constant-amount dispensing properties when used in a constant-amount dispensing squeeze container, and is therefore suitable for use as a cleaning agent article in a constant-amount dispensing squeeze container. In particular, it is believed that such an effect can be obtained by using a specific component (a) as a surfactant to be combined with components (b) and (c). EXAMPLES

[0045] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following description.

[0046] <Raw materials used> [Component (a)] a-1: In the formula (a), m is 0, Ma and Mb are sodium ions, R 1 is a mixture of sodium monoalkyl sulfosuccinate EO0 with carbon numbers of 10, 12, and 14, manufactured by Toho Chemical Co., Ltd. under the product name "Kohacool L-40." a-2: In the formula (a), AO is an oxyethylene group (EO), m is 3, Ma and Mb are sodium ions, R 1 is a mixture of carbon atoms of 10 and 12 (sodium monoalkyl sulfosuccinate EO3), manufactured by Toho Chemical Co., Ltd., under the product name "Kohacool L-300." a-3: In the formula (a), AO is EO, m is 4, Ma and Mb are sodium ions, R 1 is a mixture of sodium monoalkyl sulfosuccinate EO4 with carbon numbers 12, 14, and 16, manufactured by Toho Chemical Co., Ltd. under the product name "Kohacool L-400." a-4: In the formula (a), AO is EO, m is 9, Ma and Mb are sodium ions, R 1 is a mixture of sodium monoalkyl sulfosuccinate EO9 with carbon numbers 12, 13, and 14, manufactured by Nippon Shokubai Co., Ltd. under the trade name "Softanol MES-9."

[0047] [Component (a'): Comparative component] a'-1: SAS (secondary alkane sulfonic acid, trade name "SAS30", manufactured by Clariant Japan). a'-2: C10AS (sodium linear alkyl (carbon number 10) sulfate, manufactured by Fluorochem Ltd., trade name "n-Decyl sodium sulfate"). a'-3: LAS (sodium linear alkylbenzene sulfonate (C10-14), manufactured by Lion Specialty Chemicals Co., Ltd., product name "Lipon LS-250"). a'-4: AES (sodium polyoxyethylene alkyl ether sulfate (C12-14, EO=2), manufactured by New Japan Chemical Co., Ltd., "Shinoline SPE-1250"). a'-5: AOS (sodium α-olefin sulfonate (C14), manufactured by Lion Specialty Chemicals Co., Ltd., "Liporan LB-440"). a'-6: DSS (di-2-ethylhexyl sodium sulfosuccinate, (manufactured by Lion Specialty Chemicals Co., Ltd., product name "Repearl 870P").

[0048] [(b) component] b-1: Xanthan gum, manufactured by Kelco, product name "KELZAN T". b-2: Gellan gum, manufactured by Sansho Co., Ltd., product name "KELCO-CRETE DG".

[0049] [(c) component] c-1: m-Xylene sulfonic acid, manufactured by Itochu Chemical Frontier Corporation, product name "SXA". c-2: p-Toluenesulfonic acid, manufactured by Meiyu Sangyo Co., Ltd. c-3: Sodium benzoate, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. c-4: Sodium cumene sulfonate, manufactured by Teika Corporation, trade name "Teikatox N5040".

[0050] [Optional ingredients] Propylene glycol: Reagent manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Silicone compound: Manufactured by Dow Chemical Japan, product name "DOWSIL FS Antifoam 93".

[0051] [pH adjuster] Sodium hydroxide: 48% sodium hydroxide manufactured by Kanto Chemical Co., Ltd. Sulfuric acid: Manufactured by Fujifilm Wako Pure Chemical Industries, special reagent grade.

[0052] <Examples 1 to 15 and Comparative Examples 1 to 9> According to the compositions shown in Tables 1 to 3, 0.8 kg of each liquid detergent composition was prepared by dissolving component (a), component (b), component (c), and optional components in water as a solvent and adjusting the pH. Specifically, water was added to a 1L beaker (diameter 12 cm) so that the total amount was 40% by mass of the entire composition. A stirrer (HEIDON FBL1200 Three-One Motor, manufactured by Shinto Scientific Co., Ltd.) was equipped with a four-blade paddle with a diameter of 7.5 cm, width of 1.5 cm, and angle of 45 degrees, and then, while stirring at a rotation speed of 400 to 900 rpm so as not to scatter the contents, component (a) or component (a'), component (b), optional propylene glycol, and component (c) were added, and then the pH was adjusted to 7.5 with a pH adjuster (sodium hydroxide or sulfuric acid). Thereafter, the mixture was cooled to room temperature, and the remaining optional components were added while stirring at a rotation speed of 650 rpm of the stirrer, and the pH was adjusted to 7 with the pH adjuster. After the addition was completed, the mixture was further stirred at a rotation speed of 650 rpm for 5 minutes, and the remaining water was added so that the entire composition was 100% by mass, and the mixture was stirred at a rotation speed of 650 rpm for 1 minute to obtain a liquid detergent composition. The content of each component in the table is expressed in mass %, and the amount of each component is expressed as a pure content. A blank space in the table indicates that the ingredient is not included. The pH (25° C.) of the liquid detergent composition was measured using a glass electrode pH meter (HM-30G, manufactured by DKK-TOA Corporation) for the liquid detergent composition adjusted to 25° C. The measurement method was in accordance with JIS Z 8802:2011 "pH measurement method."

[0053] <Evaluation> The liquid detergent compositions of the Examples and Comparative Examples were evaluated as follows. The evaluation results are shown in Tables 1 to 3. [Quantitative dispensing performance] A fixed-volume squeeze container (Kao Corporation's "CuCute Ultra Clean" container) was used. With the nozzle facing downwards, this squeeze container is deformed by pressing a specific position on the side of the container with a finger until it is slightly depressed, causing a single dose of the liquid detergent composition to be forcefully dispensed from the nozzle. The squeeze container was filled with 400 g of the liquid detergent composition to obtain a detergent article. With the discharge port open, the container was held by hand and inverted so that the discharge port was facing downward, and the side of the container was pressed with a finger to discharge the liquid detergent composition. The amount (unit: g) of the liquid detergent composition vigorously discharged from the discharge port in one go was measured. This discharge operation was performed five times to obtain the average discharge amount. The liquid temperature was changed to 5°C, 20°C, and 40°C, and the average discharge amount was measured in the same manner at each temperature. Using the average discharge amount, the discharge amount difference was calculated using the following calculation formula. Three people measured in the same way to obtain the respective discharge amount differences, and the average value of the discharge amount differences of the three people was obtained. As an example, the measurement results of three people (measurers A, B, and C) in Example 3 and Comparative Example 9 are shown in Table 4. Based on the average value of the difference in the discharge amount, the quantitative discharge property was evaluated according to the following evaluation criteria. Discharge amount difference = Discharge amount at 5℃ / Discharge amount at 40℃ (Evaluation Criteria) ◎◎: Discharge volume difference is 0.9 or more and 1 or less. ◎: The difference in discharge volume is 0.7 or more and less than 0.9. ○: The difference in discharge amount is 0.5 or more and less than 0.7. ×: The difference in discharge amount is less than 0.5.

[0054] [Liquid cutting ability at high temperatures] In the evaluation of the above-mentioned constant-quantity discharge property, the above-mentioned discharge operation was performed at a liquid temperature of 40°C, and the amount of liquid dripping from the discharge port after one dose of the liquid detergent composition had been vigorously discharged was measured. Three examiners performed the discharge operation five times each, and the average value of 15 measured values ​​was taken as the amount of dripping. The liquid drainage property was evaluated according to the following evaluation criteria. ◎ and ○ were considered to be acceptable. (Evaluation Criteria) ◎: Dripping amount is less than 0.5g. ○: The amount of dripping is 0.5g or more but less than 1g. ×: Dripping amount is 1g or more.

[0055] [Prevents stringiness at high temperatures] In the evaluation of the above-mentioned constant-quantity discharge property, the side of the container was pressed with a finger to vigorously discharge one dose of the liquid detergent composition, and then the finger was returned to its original position while keeping the discharge port facing downward, and the stringiness of the liquid detergent composition from the discharge port was evaluated. Specifically, when the above-mentioned discharge operation was performed at a liquid temperature of 40°C, the liquid detergent composition that was still discharged from the discharge port even after the finger was returned to its original position was evaluated for stringiness prevention property according to the following evaluation criteria. ⊚ and ◯ were evaluated as pass. (Evaluation Criteria) ◎: There is absolutely no stringiness after the finger is returned to its original position. ○: There was a slight stringiness after the finger was returned to its original position, but it broke immediately. ×: After the finger is returned to its original position, the string is visible and does not break for a while.

[0056] [Table 1]

[0057] [Table 2]

[0058] [Table 3]

[0059] [Table 4]

[0060] The liquid detergent compositions of Examples 1 to 14 had liquid physical properties that were acceptable in terms of the ability to discharge a fixed amount, the ability to break at high temperatures, and the ability to prevent stringiness. Comparative Example 1, which did not contain component (a), failed to pass the cutability and stringiness prevention tests at high temperatures. Comparative Examples 2 to 7, in which anionic surfactants (a'-1) to (a'-6) were used instead of the component (a), also failed to pass the cutability and stringiness prevention tests at high temperatures. Comparative Example 8, which did not contain component (b), was unsatisfactory in terms of both the ability to dispense a fixed amount and the ability to cut at high temperatures. Comparative Example 9, which did not contain the component (c), failed in terms of the ability to dispense a fixed amount of fluid.

Claims

1. (a) Components: At least one selected from the group consisting of compounds represented by the following formula (a), (b) Ingredients: Thickener and (c) Components: At least one selected from the group consisting of aromatic sulfonic acids, aromatic carboxylic acids and their salts, A liquid detergent composition containing water. 【Chemistry 1】 In the formula, R １ is a linear or branched alkyl group having 8 to 18 carbon atoms or a linear or branched alkenyl group having 8 to 18 carbon atoms, AO is an oxyalkylene group, m is a number from 0 to 10 indicating the average repeating number of AO, Ma and Mb are independently counterions, and -C2H3(SO3Mb)- is -CH2-CH(SO3Mb)- or -CH(SO3Mb)-CH2-.

2. The liquid detergent composition according to claim 1, wherein the mass ratio represented by component (a) / component (b) is 0.1 to 1000.

3. The liquid detergent composition according to claim 1, wherein the mass ratio represented by component (b) / component (c) is 0.001 to 10.

4. A cleaning agent article in a squeeze container, wherein the liquid cleaning agent composition according to any one of claims 1 to 3 is contained in a squeeze container.

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