Liquid detergent composition for dishwasher

Abstract

To provide a liquid detergent composition for a dishwasher having excellent reattachment prevention properties and filter clogging prevention properties even after long-term storage in a dishwasher.SOLUTION: There is provided a liquid detergent composition for a dishwasher comprising a component (a): at least one selected from a group consisting of compounds represented by a following formula (a), a component (b): an enzyme, a component (c): a chelating agent and a component (d): at least one selected from a group consisting of an aromatic sulfonic acid, an aromatic carboxylic acid and a salt thereof. 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 are each independently a counter ion.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a liquid detergent composition for dishwashers. [Background technology]

[0002] For cleaning with a dishwasher, a dedicated detergent (a detergent composition for dishwashers) is generally used. For example, the examples in Patent Document 1 show that a liquid detergent composition for dishwashers containing an anionic surfactant (alkanesulfonate, alkylbenzenesulfonate, or polyoxyalkylene alkyl ether sulfate), a specific chelating agent, an enzyme, and a specific compound (alcohol or aromatic carboxylic acid) has excellent detergency against oil stains, cloudy stains, tea stains, and protein stains, and also has good storage stability and low foaming properties when stored in a glass bottle. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2015-10187 A Summary of the Invention [Problem to be solved by the invention]

[0004] Washing with a dishwasher is more likely to result in redeposition of dirt than washing by hand. For example, solid matter such as spices may be redeposited on dishes after washing, and it is desirable to prevent such redeposition.

[0005] In recent years, dishwashers equipped with an automatic detergent dispenser function that automatically dispenses a single dose of a liquid detergent composition into the washing chamber from a detergent tank have been put to practical use. Usually, a filter is installed in the flow path from the detergent tank to the washing chamber. According to the findings of the present inventors, even if the stability is good when stored for a long period in a sealed state, a deterioration in performance may be observed or the filter may become clogged (filter blockage) when stored for a long period in the detergent tank of a dishwasher. This is thought to be because the detergent tank for automatic dispensing is a semi-open container and is stored in harsh conditions, such as being exposed to high temperatures.

[0006] The present invention has been made in consideration of the above circumstances, and an object of the present invention is to provide a liquid detergent composition for dishwashers that has excellent anti-redeposition properties and excellent anti-clogging properties for filters even after long-term storage in the dishwasher. [Means for solving the problem]

[0007] 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) components: an enzyme; (c) component: a chelating agent; A liquid detergent composition for dishwashers, comprising: component (d): 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] Component (e): The liquid dishwasher detergent composition according to [1], further comprising at least one selected from the group consisting of isothiazolinones and their derivatives. [3] The liquid detergent composition for use in dishwashers according to [1] or [2], wherein the mass ratio of the component (c) to the component (d) is 0.8 to 35. Effect of the Invention

[0008] According to the present invention, it is possible to provide a liquid detergent composition for dishwashers which has excellent anti-redeposition properties and excellent anti-clogging properties for filters even after long-term storage in the dishwasher. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The liquid detergent composition for dishwashers of the present invention (hereinafter also simply referred to as "liquid detergent composition") contains component (a), component (b), component (c) and component (d). The liquid detergent composition may further comprise component (e). The liquid detergent composition may further contain other components in addition to the components (a), (b), (c), (d) and (e).

[0010] <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.

[0011] [ka]

[0012] 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.

[0013] In formula (a), R 1R 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 anti-redeposition property and the anti-filter clogging property. 1 The number of carbon atoms is preferably 10 to 16, and more preferably 12 to 16.

[0014] 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, it is easy to improve anti-redeposition properties and anti-filter clogging properties. m is preferably from 0 to 4, more preferably 3 or 4, and particularly preferably 4.

[0015] 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 preventing redeposition and preventing filter clogging, 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.

[0016] 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.

[0017] Component (a) contributes to improving the prevention of redeposition and filter clogging, but if the content of component (a) is too high, it will separate and precipitate during storage, which can easily cause filter clogging. The content of the (a) component is preferably 0.1 to 10 mass%, more preferably 1 to 4 mass%, and particularly preferably 1.5 to 3 mass%, based on the total mass of the liquid detergent composition. When the content of the (a) component is equal to or greater than the lower limit, the anti-redeposition property is easily improved. When the content of the (a) component is within the above range, the anti-clogging property of the filter is easily improved.

[0018] <(b) Component> The (b) component is an enzyme. As component (b), any of the general enzymes that have been used in liquid detergent compositions for dishwashers can be used, such as amylase, protease, mannanase, cellulase, lipase, glucanase, etc. The component (b) may be used alone or in combination of two or more types. From the standpoint of cleaning power for rice grain stains, prevention of redeposition, and prevention of filter clogging, component (b) preferably contains at least one enzyme selected from the group consisting of amylase, protease, mannanase, cellulase, and lipase, more preferably contains at least one enzyme selected from the group consisting of amylase and protease, and particularly preferably contains amylase and protease.

[0019] Component (b) contributes to improving the prevention of redeposition. On the other hand, if the content of component (b) is too high, it will separate and precipitate during storage, which can easily cause filter clogging. The content of the (b) component is preferably 0.01 to 2 mass%, more preferably 0.1 to 1 mass%, and particularly preferably 0.3 to 0.7 mass% as an enzyme preparation based on the total mass of the liquid detergent composition. When the content of the (b) component is equal to or more than the lower limit, the anti-redeposition property is easily improved. On the other hand, when the content of the (b) component is equal to or less than the upper limit, the anti-filter clogging property is easily improved.

[0020] When component (b) contains amylase, the content of amylase is preferably an amount such that the amylase activity measured by the measurement method described in the Examples is 0.01 to 2 U. The amylase activity is more preferably 0.1 to 2 U, and particularly preferably 0.5 to 2 U. When the amylase activity is equal to or higher than the lower limit, the anti-reattachment property is easily improved. On the other hand, when the amylase activity is equal to or lower than the upper limit, the anti-filter clogging property is easily improved.

[0021] When component (b) contains a protease, the content of the protease is preferably an amount such that the protease activity measured by the measurement method described in the Examples is 0.01 to 2 U. The protease activity is more preferably 0.1 to 2 U, and particularly preferably 0.5 to 2 U. When the protease activity is equal to or higher than the lower limit, the anti-reattachment property is easily improved. On the other hand, when the protease activity is equal to or lower than the upper limit, the anti-filter clogging property is easily improved.

[0022] <(c) component> Component (c) is a chelating agent. As component (c), any of the general chelating agents that have been used in liquid detergent compositions for dishwashers can be used, including, for example, polymeric chelating agents and low molecular weight chelating agents.

[0023] 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. Among these, the polymer chelating agent is preferably an acrylic acid-maleic acid copolymer or a salt thereof. The copolymerization ratio (molar ratio) of acrylic acid to maleic acid is preferably acrylic acid / maleic acid=75 / 25 to 50 / 50, and the weight average molecular weight is preferably 10,000 or more and 100,000 or less. 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.

[0024] From the viewpoint of improving the anti-redeposition property and the anti-clogging property of the filter, the low molecular weight chelating agent is preferably a chelating agent having a molecular weight of 800 or less. 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. Of these, the low molecular weight chelating agent is preferably at least one selected from the group consisting of citrate, ethylenediaminetetraacetate, glutamic acid diacetate, and methylglycine diacetate, and particularly preferably sodium citrate.

[0025] From the viewpoint of improving anti-redeposition properties, the component (c) is preferably a low molecular weight chelating agent. The component (c) may be used alone or in combination of two or more types.

[0026] Component (c) contributes to improving the prevention of redeposition. On the other hand, if the content is too high, it will separate and precipitate during storage, which can easily cause filter clogging. The content of component (c) is preferably 5 to 20 mass%, more preferably 10 to 20 mass%, and particularly preferably 12 to 18 mass%, based on the total mass of the liquid detergent composition. When the content of component (c) is equal to or more than the lower limit, the anti-redeposition property is easily improved. When the content of component (c) is equal to or less than the upper limit, the anti-filter clogging property is easily improved.

[0027] <(d) component> The component (d) is at least one selected from the group consisting of aromatic sulfonic acids, aromatic carboxylic acids, and salts thereof. The component (d) does not contain an anionic surfactant. The component (d) is preferably an aromatic sulfonic acid represented by the following general formula (d1) or a salt thereof, or an aromatic carboxylic acid represented by the following general formula (d2) or a salt thereof.

[0028] [ka]

[0029] 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.

[0030] Specific examples of component (d) 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 preventing redeposition and filter clogging, benzoic acid, cumenesulfonic acid, m-xylenesulfonic acid, p-toluenesulfonic acid and salts thereof are preferred, and benzoic acid or a salt thereof is more preferred.

[0031] The component (d) may be used alone or in appropriate combination of two or more types. Component (d) contributes to improving the prevention of redeposition and filter clogging, but if the content of component (d) is too high, the amount of water becomes relatively small, and the components in the liquid detergent composition tend to separate and precipitate, which may cause filter clogging. The content of component (d) is preferably 0.5 to 10 mass%, more preferably 1 to 10 mass%, and particularly preferably 2 to 4 mass%, based on the total mass of the liquid detergent composition. When the content of component (d) is equal to or greater than the lower limit, it is easy to improve the anti-redeposition properties. When the content of component (d) is within the above range, it is easy to improve the anti-clogging properties of the filter.

[0032] In the liquid detergent composition, the mass ratio of component (c) to component (d) (hereinafter also referred to as "c / d ratio") is preferably from 0.8 to 35, more preferably from 1.2 to 18, and particularly preferably from 2 to 6. When the c / d ratio is within the above range, it is easy to improve the anti-redeposition properties and anti-filter clogging properties.

[0033] <(e) component> The component (e) is at least one selected from the group consisting of isothiazolinone and its derivatives. The component (e) may be used alone or in appropriate combination of two or more. The component (e) is preferably at least one selected from the group consisting of compounds represented by the following formula (e1) and compounds represented by the following formula (e2).

[0034] [ka]

[0035] In formula (e2), R 6 is any one selected from a hydrogen atom and a hydrocarbon group having 1 to 8 carbon atoms; R 7 is any one selected from a hydrogen atom, -CH3, a chlorine atom, a bromine atom, and -NH2, and R 8is any one selected from a hydrogen atom, -CH3, a chlorine atom, and -CH2NH2, and R 6 ~R 8 may be identical to each other.

[0036] The compound represented by the formula (e1) is 1,2-benzisothiazol-3-one (BIT). Specific examples of the compound represented by the formula (e2) include methylisothiazolinone (MIT), chloromethylisothiazolinone (CMIT), octylisothiazolinone (OIT), and dichlorooctylisothiazolinone (DCOIT). As the component (e), from the viewpoints of preventing redeposition and filter clogging, one or both of 1,2-benzisothiazol-3-one (BIT) and methylisothiazolinone (MIT) are preferred, with 1,2-benzisothiazol-3-one (BIT) being particularly preferred.

[0037] The content of component (e) is preferably 0.0005 to 0.05 mass%, more preferably 0.005 to 0.04 mass%, and particularly preferably 0.01 to 0.03 mass%, based on the total mass of the liquid detergent composition. When the content of component (e) is equal to or more than the lower limit, the anti-redeposition property is easily improved. When the content of component (e) is equal to or less than the upper limit, the anti-filter clogging property is easily improved.

[0038] <Other ingredients> The liquid detergent composition for dishwashers of the present invention may contain any ingredient that is usually contained in detergents for washing dishes, so long as it does not go against the purpose of the present invention. For example, substances that are usually used in liquid detergent compositions for dishwashers, such as surfactants other than component (a), silicone-based defoamers, stabilizers, thickeners, solvents, plant extracts, oil absorbents, dish protectants, colorants, hydrotropes other than component (d), antioxidants, pH adjusters, fragrances, and bleaches, may be used.

[0039] 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.

[0040] 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.

[0041] Silicone-based defoaming agent is not particularly limited, and can be any of the general defoaming agents used in liquid detergent compositions for dishwashers. Silicone-based defoaming agent is not particularly limited to oil type, compound type, self-emulsifying compound type, powder type, etc., but can be, for example, polyorganosiloxane oil or resin dispersion or emulsion such as polydimethylsiloxane, and polyorganosiloxane chemically adsorbed or melted on silica and silica particle combination, and for example, FS Antifoam 1266 (manufactured by Dow Chemical Co.), FS Antifoam 93 (manufactured by Dow Chemical Co.), etc. are preferred.

[0042] Examples of thickeners include water-soluble polymers such as pectin, carboxymethylcellulose, methylcellulose, hydroxymethylcellulose, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, tragacanth gum, carrageenan, locust bean gum, dextrin, dextrin fatty acid esters, acrylic acid polymers, methacrylic acid polymers, xanthan gum, guar gum, gelatin, sodium alginate, gum arabic, and starch; and water-swellable clay minerals such as smectite. Either natural or synthetic smectite can be used.

[0043] Examples of hydrotropic agents include polyols such as ethylene glycol and propylene glycol.

[0044] 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.

[0045] Liquid cleaning compositions typically include 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.

[0046] The viscosity of the liquid detergent composition at 25° C. is preferably from 10 to 2000 mPa·s, and more preferably from 100 to 1000 mPa·s. The viscosity of the liquid detergent composition at 25°C is a value measured by a method conforming to Viscosity Measurement Method No. 2 of the General Test Methods in the Quasi-Drug Ingredients Standards 2006. Specifically, the value is measured using a Vismetron viscometer with rotors No. 2 to No. 4 at a rotation speed of 6 rpm for 120 seconds.

[0047] 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 conforming to "pH measurement method" of JIS Z 8802:2011.

[0048] <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), (c), (d), a portion of water, and, if necessary, component (e) and any optional components other than the pH adjuster, adjusting the pH to a predetermined value using a pH adjuster if necessary, and then mixing with the remaining water.

[0049] <How to use> The liquid detergent composition of the present invention can be used in a dishwasher, and may be used depending on the type of dishwasher and the degree of dirt on the dishes, etc. 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.

[0050] <Action and effect> The liquid detergent composition described above contains components (a), (b), (c), and (d), and therefore has excellent anti-redeposition and anti-clogging properties for the filter even after long-term storage in a dishwasher. According to the findings of the present inventors, although the combination of components (a), (b) and (c) can contribute to improving the anti-redeposition properties, when a liquid detergent composition containing these components is stored for a long period of time in the detergent tank of a dishwasher, the anti-redeposition properties tend to decrease and the filter tends to clog. This is thought to be because the components separate and precipitate during storage, which creates a concentration gradient of the components in the detergent tank, decreasing the anti-redeposition properties and causing filter clogging. It is believed that by including component (d) in addition to components (a), (b), and (c), separation and precipitation of the components during storage in a dishwasher can be suppressed, thereby improving the prevention of redeposition and filter clogging. EXAMPLES

[0051] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following description.

[0052] <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."

[0053] [(a) Comparative product of ingredients] a'-1: Sodium linear alkylbenzene sulfonate (C10-14) (LAS), manufactured by Lion Specialty Chemicals Co., Ltd., product name "Lipon LS-250" a'-2: Sodium secondary alkane sulfonate (C14-17) (SAS), manufactured by Clariant Japan Co., Ltd., product name "HOSTAPUR SAS 30A" a'-3: Sodium linear alkyl sulfate (C12) (AS), manufactured by Lion Specialty Chemicals Co., Ltd., product name "Sunol LM-1130" a'-4: Sodium polyoxyethylene alkyl ether sulfate (C12-14, EO=2) (AES), manufactured by New Japan Chemical Co., Ltd., product name "Shinoline SPE-1250" a'-5: α-Olefin sulfonate sodium (C14) (AOS), manufactured by Lion Specialty Chemicals Co., Ltd., product name "Liporan LB-440" a'-6: Di-2-ethylhexyl sodium sulfosuccinate (DSS), manufactured by Lion Specialty Chemicals Co., Ltd., product name "Repearl 870P"

[0054] [(b) component] b-1: Amylase, manufactured by Novozymes, product name "Achieve alpha 100L". b-2: Protease, manufactured by Novozymes, product name "Blaze pro 100L". b-3: Mannanase, manufactured by Novozymes, trade name "Mannaway 200L". b-4: Cellulase, manufactured by Novozymes, product name "Carezyme Premium 4500L". b-5: Lipase, manufactured by Novozymes, product name "Lipex Evity 200L". b-6: A mixed enzyme of amylase and protease, manufactured by Novozymes, product name "Intensa Core 200L".

[0055] [(c) component] c-1: Trisodium citrate (Na citrate), manufactured by Fuso Chemical Co., Ltd. c-2: Sodium ethylenediaminetetraacetate (EDTA-Na), Tokyo Chemical Industry Co., Ltd. c-3: Glutamic acid diacetate tetrasodium (GLDA-Na), manufactured by Chelest. c-4: Tetrasodium methylglycine diacetate (MGDA-Na), manufactured by BASF, trade name "Trilon M Compactate". c-5: Sodium salt of maleic acid-acrylic acid copolymer (MA), molar ratio of acrylic acid / maleic acid = 60 / 40, weight average molecular weight 50,000, active ingredient 40% by mass, manufactured by Nippon Shokubai Co., Ltd., product name "Aqualic TL400".

[0056] [(d) component] d-1: Sodium benzoate, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. d-2: Sodium cumene sulfonate, manufactured by Teika Corporation, trade name "Teikatox N5040". d-3: Sodium m-xylene-4-sulfonate, manufactured by Tokyo Chemical Industry Co., Ltd. d-4: Sodium p-toluenesulfonate, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

[0057] [(d) Comparative product of ingredients] d'-1: 2-phenoxyethanol, Fujifilm Wako Pure Chemical Industries, Ltd.

[0058] [(e) component] e-1: 1,2-Benzisothiazol-3-one (BIT), manufactured by Tokyo Chemical Industry Co., Ltd. e-2: Methylisothiazolinone (MIT), manufactured by Kanto Chemical Co., Ltd.

[0059] [Common ingredients] The following components were used as common components in the liquid detergent compositions of each example. The content (mass %) of each component is the ratio to the total mass of the liquid detergent composition. - 0.2% by mass of xanthan gum (manufactured by Kelco, trade name "KELZAN T"). Calcium chloride (Fujifilm Wako Pure Chemical Industries, Ltd., reagent) 0.3% by mass. Propylene glycol (Fujifilm Wako Pure Chemical Industries, Ltd., reagent) 5.0% by mass. Fragrance: 0.050 mass% of any one of the blended fragrance compositions 1 to 4 and the fragrance components listed in Table 1 of Tables 1 to 8 of JP2020-132680A.

[0060] [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.

[0061] <Examples 1 to 41 and Comparative Examples 1 to 11> According to the compositions shown in Tables 1 to 5, 0.8 kg of each liquid detergent composition was prepared by dissolving component (a), component (b), component (c), component (d), component (e), 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 of water 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, common components xanthan gum and propylene glycol were added, then component (c) was added, and then the pH was adjusted to about 7 with a pH adjuster (sodium hydroxide or sulfuric acid), and then components (a), (b), (d), (e), and the remaining common components were added, and the pH was adjusted to 7.5 with the pH adjuster. After the addition was completed, the mixture was 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."

[0062] Among the obtained liquid detergent compositions, those containing amylase were subjected to the measurement of amylase activity, and those containing protease were subjected to the measurement of protease activity. The results are shown in Tables 1 to 5. Each enzyme activity was measured by the following measurement method.

[0063] <Amylase activity measurement method> Phadebas tablets (Magle, Phadebas Amylase Test for measuring amylase activity), which are cross-linked starch polymers containing an insoluble blue pigment, are hydrolyzed with alpha amylase, and the absorbance (620 nm) of the water-soluble blue pigment is measured to determine alpha amylase activity. Specifically, first prepare a buffer solution by precisely weighing out 20.0 g of sodium sulfite (Junsei Chemical Co., Ltd., special grade reagent, etc.), 6.15 g of potassium dihydrogen phosphate (Hayashi Pure Chemical Industries, Ltd., special grade, etc.), 10.86 g of disodium hydrogen phosphate dodecahydrate (Kanto Chemical Co., Ltd., special grade, etc.), 0.015 g of calcium chloride dihydrate (Kanto Chemical Co., Ltd., first grade reagent, etc.), and 0.75 mL of Brij35 (MERCK, 30% aqueous solution), dissolving them in ion-exchanged water, and then diluting to a constant volume of 1 L. Next, 0.5 g of the liquid detergent composition is weighed out and dissolved in the above buffer solution to a constant volume of 100 mL to prepare a sample solution. 1 mL of the sample solution is placed in a test tube (18 mm x 180 mm). 5.0 mL of the buffer solution, which has been preheated to 37°C, is placed in the test tube containing the sample solution, so that the buffer does not touch the test tube wall, and then one Fadebas tablet is placed with tweezers, stirred with a flash mixer for 10 seconds, and placed in a water bath at 37°C. After exactly 15 minutes (using a stopwatch), 1.0 mL of 1 mol / L-NaOH aqueous solution is added with a dispenser to stop the reaction, stirred with a flash mixer for 10 seconds, left at room temperature for 15 minutes, and then immediately filtered with filter paper. If the solution is turbid, it is then filtered with a filtration kit. The absorbance of the filtrate obtained by the above procedure is measured at a wavelength λ of 620 nm and is regarded as the absorbance of the sample. Separately, as a blank, a liquid cleaning composition having the same composition as the sample except that no enzyme is added is prepared, and the same procedure as above is carried out, with the measured absorbance being the blank absorbance. From the measurement results, calculate amylase activity (U) using the following formula. Amylase activity (U) = (absorbance of sample) - (absorbance of blank)

[0064] <Protease activity measurement method> The enzyme is applied to milk casein, and the undigested protein is precipitated by adding trichloroacetic acid (hereafter abbreviated as "TCA"), followed by filtration. The absorbance (λ=275 nm) of the filtrate is measured to determine the amount of eluted amino acid with a phenyl group (e.g., tyrosine), and the protease activity is calculated. Specifically, 1.2 g of milk casein (CALBIOCHEM) was placed in a 200 mL beaker, and 6 mL of 1 mol / L NaOH solution was gradually added while kneading with a glass rod to make the casein swell. Next, 160 mL of 0.05 mol / L boric acid solution was added, and the casein solution was adjusted to pH 10.5 with 1 mol / L NaOH solution, and then the casein solution was made up to 200 mL by measuring. Next, 1 g of the liquid detergent composition is weighed out and dissolved in ion-exchanged water to a constant volume of 100 mL to prepare a sample solution. 1 mL of the sample solution is placed in a test tube (18 mm x 180 mm). 5.0 mL of casein solution, preheated to 37°C, is added to the test tube containing the sample solution, with the buffer solution not touching the test tube wall, and stirred for 10 seconds with a flash mixer, then placed in a water bath at 37°C. After exactly 30 minutes (using a stopwatch), 5.0 mL of 0.44 mol / L-TCA solution is added with a dispenser to stop the reaction, stirred for 10 seconds with a flash mixer, and left in a water bath for 30 minutes, and then immediately filtered with filter paper, followed by filtration with a filter (Tomsic, NP-44525-ACF). The absorbance of the filtrate obtained by the above procedure is measured at a measurement wavelength λ of 275 nm (1 cm quartz cell, slit width 0.5 mm). Separately, as a blank, a liquid cleaning composition having the same composition as the sample except that no enzyme is added is prepared, and the same procedure as above is carried out, with the measured absorbance being the blank absorbance. From the measurement results, the protease activity (U) is calculated using the following formula. Protease activity (U) = (absorbance of sample) - (absorbance of blank).

[0065] <Evaluation> The liquid detergent compositions of the Examples and Comparative Examples were evaluated as follows. The evaluation results are shown in Tables 1 to 5. In each evaluation, a Panasonic NP-45MD9SP dishwasher was used. In each evaluation, the dishwasher was operated with the automatic detergent dispenser turned off and in the dirt level L2 course. The details of the L2 course are shown below. L2 Courses: Tap water at about 5°C is introduced into the cabinet, and the washing solution is heated to about 55°C at 2-3°C / min while washing for 30 minutes, and the washing solution is drained. Next, new tap water is introduced, and rinsing and draining are repeated twice. After draining, new tap water is introduced and the water is heated to about 65°C at 2-3°C / min while rinsing once (rinsing time is about 50 minutes), and after draining, the dishes are dried while circulating hot air.

[0066] [Re-deposition prevention] The anti-reattachment property after harsh storage was evaluated by the following procedure.

[0067] "Prepare for filth" The soil used for the evaluation was prepared according to the following procedure. The stains used were tomato juice (tomato juice manufactured by Nippon Del Monte Co., Ltd.), eggs (large size), instant curry (Bon Curry Gold spicy manufactured by Otsuka Foods Co., Ltd.), and rice (equivalent to Koshihikari rice type 1, which is a self-distributed rice, the ratio of rice to water was the standard for rice cookers, and rice cooked within 12 hours). The tableware that was cleaned by attaching dirt to it was a ceramic plate (large plate: radius 115mm, height 25mm, small plate: radius 60mm, height 20mm) and a glass cup (radius 30mm, height 110mm).The tableware that was cleaned without attaching dirt to it was a medium-sized bowl (radius 80mm, height 45mm). Egg stains: Eggs were heated in a frying pan over low heat to prepare soft-boiled fried eggs. The fried eggs were stirred well and the entire surface of the small plates was coated with the egg stains to prepare a total of 12 dirty plates. Tomato juice stains: Tomato juice was poured into the glass cups and tilted to contaminate the entire cup, preparing a total of six dirty cups. Curry stains: 200g of instant curry, 1 egg, and 150g of rice were mixed. 30g of the mixture was placed on the large plate, and the surface of the plate was uniformly contaminated. After that, the mixture was discarded except for about 10 grains of rice, which were then crushed with a spoon and attached to the large plate. In this way, a total of 6 contaminated dirty plates were prepared.

[0068] "Evaluation Method" The liquid detergent composition was filled into the automatic detergent dispenser tank of a dishwasher, the automatic detergent dispenser was turned off, and the dishes were washed 30 times using the L2 cycle, followed by harsh storage (simulating storage in the tank for one month). Next, the prepared dirty plate and dirty cup and six uncontaminated bowls were loaded into the designated locations based on the dishwasher's instructions, 8 g of the liquid cleaning composition after harsh storage was added, and the dishwasher was operated on the L2 course. After the operation was completed, the inner bowls were visually observed, and the total amount of solid re-adhered matter, such as tomato juice, eggs, curry spices, etc., adhering to the six inner bowls was calculated. The same procedure was repeated three times, the total number of redeposited particles was averaged, and the anti-redeposition ability of solid matter was evaluated based on the following evaluation criteria. A rating of ○, ◎, ◎◎, ◎◎◎, and ◎◎◎◎ was deemed to be acceptable. (Evaluation Criteria) ◎◎◎◎: The total average of re-attached material on six medium-sized bowls was 0 points. ◎◎◎: The total average of re-attached material on six medium-sized bowls is greater than 0 points but less than 1 point. ◎◎: The total average of the re-attached material on six medium-sized bowls is 1 point or more but less than 2 points. ◎: The total average of the reattached material on six medium-sized bowls is between 2 and 3 points. ○: The total average of the reattached material on the six medium-sized bowls is between 3 and 4 points. ×: The total average of the reattached matter on the six medium-sized bowls was 4 points or more.

[0069] [Prevents filter clogging] The filter clogging prevention property after harsh storage was evaluated by the following procedure.

[0070] "Evaluation Method" The anti-clogging properties of the liquid detergent composition were evaluated using a test sieve, assuming a filter to be attached to the detergent tank of an automatic detergent dispenser type dishwasher. Specifically, the liquid detergent composition was filled into the automatic detergent dispenser tank of a dishwasher, the automatic detergent dispenser was turned off, and the dishes were washed 30 times using the L2 cycle, followed by harsh storage (simulating storage in the tank for one month). A 30 mesh filter (inner diameter 75 mm, depth 20 mm, manufactured by Tokyo Screen Co., Ltd.) was prepared, and 0.8 kg of the liquid detergent composition after harsh storage was passed through the filter 10 times for filtration. The amount of residue on the filter was then visually observed. In addition, the time required for the first filtration was compared with the time required for the tenth filtration. The clogging prevention property was evaluated based on the following evaluation criteria. Evaluations of ○, ◎, ◎◎, and ◎◎◎ were deemed to be acceptable. (Evaluation Criteria) ◎◎◎: No residue was found at all. A: A small amount of residue was observed. ◎: Residue can be seen, but no clogging such as changes in filtration time is observed. ○: A large amount of residue can be seen, but no clogging or changes in filtration time can be observed. ×: A large amount of residue was observed, the filtration time was long, and clogging was observed.

[0071] [Table 1]

[0072] [Table 2]

[0073] [Table 3]

[0074] [Table 4]

[0075] [Table 5]

[0076] The liquid detergent compositions of Examples 1 to 41 passed both the anti-redeposition property and the anti-filter clogging property after harsh storage. Comparative Example 1, which did not contain the component (a), failed both in terms of anti-redeposition property and anti-filter clogging property after harsh storage. Comparative Example 2, which did not contain the component (b), failed in preventing redeposition after harsh storage. Comparative Example 3, which did not contain the component (c), failed in preventing redeposition after harsh storage. Comparative Example 4, which did not contain the component (d), failed both in terms of anti-redeposition properties and anti-filter clogging properties after harsh storage. Comparative Examples 5 to 10, in which a comparative product (anionic surfactant) was used instead of component (a), failed both in anti-redeposition property and anti-filter clogging property after harsh storage. Comparative Example 11, in which a comparative product (aromatic alcohol) was used instead of component (d), failed both in anti-redeposition properties and anti-filter clogging properties after harsh storage.

Claims

1. (a) Components: At least one selected from the group consisting of compounds represented by the following formula (a), (b) Components: Enzymes and, (c) Ingredients: Chelating agent and (d) A liquid dishwasher detergent composition comprising: at least one selected from the group consisting of aromatic sulfonic acid, aromatic carboxylic acid, and salts thereof. 【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. (e) The liquid dishwasher detergent composition according to claim 1, further comprising at least one selected from the group consisting of isothiazolinone and its derivatives.

3. The liquid detergent composition for dishwashers according to claim 1 or 2, wherein the mass ratio represented by component (c) / component (d) is 0.8 to 35.

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