Liquid detergent composition for dishwashers

Abstract

To provide a liquid detergent composition for a dishwasher having both of low foaming property and re-adhesion preventing performance.SOLUTION: (A) at least one selected from the group consisting of sulfosuccinic acid and salts thereof, (B) an anionic surfactant excluding the following component (c1), (C) at least one selected from the group consisting of maleic monoesters (c1) and maleic diesters (c2), and (D) at least one selected from the group consisting of aromatic sulfonic acids, aromatic carboxylic acids and salts thereof.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] In general, a dedicated detergent (a dishwasher detergent composition) is used for cleaning with a dishwasher. Liquid dishwasher detergent compositions are required to have various functions such as low foaming (low foaming) and detergency. For example, Patent Document 1 proposes 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) in its working examples. According to the invention of Patent Document 1, the detergent composition has excellent detergency against oily stains, cloudy stains, tea stains, and proteinaceous stains, storage stability, and low foaming properties. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2015-10187 Summary of the Invention [Problem to be solved by the invention]

[0004] Washing dishes using a dishwasher is more likely to result in redeposition of dirt than washing dishes by hand. For example, solid matter such as spices may redeposit on dishes after washing. Under harsh conditions, such as when a dishwasher is used frequently or when stubborn complex soils such as solid grease and protein are repeatedly washed, a large amount of complex soil may redeposit and accumulate around the food residue filter inside the dishwasher. When complex soils accumulate inside the dishwasher, they may redeposit on dishes, causing psychological anxiety for consumers. For this reason, liquid dishwasher detergent compositions are required to prevent soils detached from the items being washed from adhering to the items being washed (anti-redeposition properties).

[0005] The present invention has been made in view of the above circumstances, and aims to provide a liquid detergent composition for dishwashers that has excellent low-foaming properties and excellent anti-redeposition properties. [Means for solving the problem]

[0006] The present invention has the following aspects. <1> Component (A): at least one selected from sulfosuccinic acid and its salts, Component (B): an anionic surfactant (excluding component (c1) below), Component (C): at least one selected from the following component (c1) and the following component (c2); A liquid dishwasher detergent composition comprising: (D) component: at least one selected from the group consisting of aromatic sulfonic acids, aromatic carboxylic acids, and salts thereof. Component (c1): A compound represented by the following formula (c1). [ka] (R 2c is a linear or branched alkyl or alkenyl group having 8 to 18 carbon atoms; A 2 O is an oxyalkylene group, n is a number from 0 to 10, and Mc is hydrogen. Component (c2): A compound represented by the following formula (c2). [ka] (R 2a and R 2b are each independently a linear or branched alkyl or alkenyl group having 8 to 18 carbon atoms. <2> The component (B) contains a sulfosuccinic acid monoalkyl ester salt. <1> The liquid dishwasher detergent composition according to claim 1. <3> The mass ratio of the component (D) to the component (A) is 0.1 to 2000. <1> or <2> The liquid dishwasher detergent composition according to claim 1. <4> The mass ratio of the component (A) to the component (C) is 0.01 to 100. <1> ~ <3> 1. The liquid dishwasher detergent composition according to claim 1, <5> the mass ratio represented by {the component (C) + the component (D)} / the component (A) is 0.1 to 2500; <1> ~ <4> 1. The liquid dishwasher detergent composition according to claim 1, <6> The total mass of the surfactants is 0.1 to 10 relative to the total mass of the liquid dishwasher detergent composition. <1> ~ <5> 1. The liquid dishwasher detergent composition according to claim 1, [Effects of the Invention]

[0007] The liquid detergent composition for dishwashers of the present invention has excellent low foaming properties and excellent anti-redeposition properties. DETAILED DESCRIPTION OF THE INVENTION

[0008] The liquid detergent composition for dishwashers of the present invention (hereinafter sometimes simply referred to as "liquid detergent composition") comprises component (A), component (B), component (C), and component (D).

[0009] <Component (A)> Component (A) is at least one selected from sulfosuccinic acid and its salts. By including component (A), the liquid detergent composition exhibits an anti-redeposition effect.

[0010] Examples of salts of component (A) include alkali metal salts, alkaline earth metal salts, and alkanolamine salts. Examples of the alkali metal salt include sodium salts and potassium salts. Examples of alkaline earth metal salts include calcium salts and magnesium salts. Examples of the alkanolamine salt include monoethanolamine salt and diethanolamine salt.

[0011] As component (A), sulfosuccinates are preferred, alkali metal salts of sulfosuccinic acid are more preferred, and sodium sulfosuccinate is even more preferred. The above-mentioned component (A) may be used alone or in combination of two or more.

[0012] The content of component (A) is preferably 0.01 to 1 mass %, more preferably 0.05 to 0.5 mass %, and even more preferably 0.065 to 0.1 mass %, relative to the total mass of the liquid detergent composition. When the content of component (A) is within the above range, the anti-redeposition properties can be further improved.

[0013] <(B) component> Component (B) is an anionic surface surfactant excluding component (c1) described below. By including component (B), the liquid detergent composition exhibits anti-redeposition properties and low foaming properties.

[0014] Examples of component (B) include sulfosuccinate esters or salts thereof, alkyl sulfates or salts thereof, secondary alkane sulfonic acids or salts thereof, alkyl ether sulfates or salts thereof, linear alkylbenzene sulfonic acids or salts thereof, and soaps. Examples of salts of component (B) include alkali metal salts, alkaline earth metal salts, and alkanolamine salts. Examples of the alkali metal salt include sodium salts and potassium salts. Examples of alkaline earth metal salts include calcium salts and magnesium salts. Examples of the alkanolamine salt include monoethanolamine salt and diethanolamine salt.

[0015] Examples of sulfosuccinate salts include compounds represented by the following formula (b1) (component (b1)). The component (b1) can be said to be at least one selected from the group consisting of monoalkylsulfosuccinic acids and salts thereof 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 (i.e., which may have an oxyalkylene group), and monoalkenylsulfosuccinic acids and salts thereof 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.

[0016] [ka]

[0017] In formula (b1), 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 from 0 to 10; and Ma and Mb each independently represent a counter ion.

[0018] In formula (b1), R 1 The number of carbon atoms in R is 8 to 18, preferably 10 to 16, and more preferably 12 to 16. 1 When the number of carbon atoms is within the above range, the low foaming property and the anti-redeposition property can be further improved.

[0019] In formula (b1), 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 (b1), m represents the average number of repetitions of AO and is a number from 0 to 10, preferably 0 to 5, and more preferably 4. When m is within the above range, low foaming properties and anti-redeposition properties can be further improved.

[0020] In formula (b1), Ma and Mb each independently represent 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, alkali metal ions are preferred from the viewpoint of preventing redeposition, with sodium ions and potassium ions being more preferred, and sodium ions being 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 ions. 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.

[0021] As the component (b1), a sulfosuccinic acid monoalkyl ester salt (monoalkyl sulfosuccinate) is preferred. When m is 0, for example, monolauryl disodium sulfosuccinate is preferred. When m is 1 or more, for example, polyoxyethylene monoalkyl sulfosuccinate is preferred. Specific examples of polyoxyethylene monoalkyl sulfosuccinates include polyoxyethylene (1) monoalkyl (carbon number 12 to 14) disodium sulfosuccinate, polyoxyethylene (2) monoalkyl (carbon number 12 to 14) disodium sulfosuccinate, polyoxyethylene (2) monolauryl disodium sulfosuccinate, polyoxyethylene (2) monoalkyl (carbon number 12 to 14) sulfosuccinate 2 triethanolamine, polyoxyethylene (3) monoalkyl (carbon number 12 to 14) disodium sulfosuccinate, polyoxyethylene (3) monolauryl disodium sulfosuccinate, polyoxyethylene (3) monolauryl magnesium sulfosuccinate, and polyoxyethylene (3) monococonut oil fatty acid (carbon number 8 to 1 8) Disodium sulfosuccinate, polyoxyethylene (5) monoalkyl (C12-14) disodium sulfosuccinate, polyoxyethylene (5) monococonut oil fatty acid (C8-18) disodium sulfosuccinate, polyoxyethylene (5) monolauryl sulfosuccinate diethanolamide, polyoxyethylene (5) lauryl magnesium sulfosuccinate, polyoxyethylene (5) monococonut oil fatty acid (C8-18) disodium sulfosuccinate, polyoxyethylene (5) lauroylethanolamide disodium sulfosuccinate, polyoxyethylene (7) monoalkyl (C12-14) disodium sulfosuccinate, and polyoxyethylene (7) monolauryl magnesium sulfosuccinate. The number in parentheses after polyoxyethylene indicates the average number of repeating oxyethylene groups. The component (b1) may be one type alone or a combination of two or more types.

[0022] Examples of alkyl sulfates or salts thereof include compounds having an alkyl group with a carbon number of 8 to 18. The alkyl group of the alkyl sulfates or salts thereof preferably has 10 to 14 carbon atoms, and more preferably 10 carbon atoms. The secondary alkanesulfonic acid or a salt thereof may be a secondary alkanesulfonic acid having 8 to 18 carbon atoms or a salt thereof. Examples of alkyl ether sulfates or salts thereof include compounds having an alkyl group having 8 to 18 carbon atoms. Examples of linear alkylbenzenesulfonic acids or salts thereof include compounds having an alkyl group having 8 to 18 carbon atoms. The above-mentioned component (B) may be one type alone or a combination of two or more types.

[0023] The component (B) preferably contains the component (b1). The content of component (b1) relative to the total mass of component (B) is preferably 50 mass% or more, more preferably 80 mass% or more, and may be 100 mass%. When the content of component (b1) is equal to or greater than the above lower limit, low foaming properties and anti-redeposition properties can be further improved.

[0024] The content of component (B) 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 component (B) is equal to or greater than the above-mentioned lower limit, the anti-redeposition properties can be further improved. When the content of component (B) is equal to or less than the above-mentioned upper limit, the low-foaming properties can be further improved.

[0025] <(C) component> Component (C) is at least one compound selected from the group consisting of a compound represented by formula (c1) (component (c1)) and a compound represented by formula (c2) (component (c2)). The liquid detergent composition exhibits anti-redeposition properties by including component (C).

[0026] The component (c1) is a compound (component (c1)) represented by the following formula (c1): The component (c1) is a so-called maleic acid monoester.

[0027] [ka]

[0028] (R 2c is a linear or branched alkyl or alkenyl group having 8 to 18 carbon atoms; A 2 O is an oxyalkylene group, n is a number from 0 to 10, and Mc is hydrogen.

[0029] In formula (c1), R 2c The number of carbon atoms is 8 to 18, preferably 10 to 16, and more preferably 12 to 16, from the viewpoint of low foaming and anti-redeposition properties. A 2 O is an oxyalkylene group, preferably an oxyalkylene group having 2 to 3 carbon atoms (i.e., an oxyethylene group or an oxypropylene group), and more preferably containing an oxyethylene group. 2 O may be one type alone or a combination of two or more types. n is a number of 0 to 10, preferably 0 to 5, and more preferably 4, from the viewpoint of low foaming and anti-redeposition properties.

[0030] The component (c2) is a compound (component (c2)) represented by the following formula (c2): The component (c2) is a so-called maleic acid diester. [ka]

[0031] (R 2a and R 2b are each independently a linear or branched alkyl or alkenyl group having 8 to 18 carbon atoms.

[0032] In formula (c2), R 2a and R 2b The number of carbon atoms is 8 to 18, preferably 8 to 14, and more preferably 8 to 12, from the viewpoint of low foaming and anti-redeposition properties. R 2a and R 2b are each independently preferably 2-propylheptyl or 3,5,5-trimethylhexyl.

[0033] Component (C) may contain at least one of components (c1) and (c2), but preferably contains at least component (c1). By including component (c1), the low-foaming properties and anti-redeposition properties can be further improved.

[0034] The content of component (C) is preferably 0.01 to 1 mass%, more preferably 0.01 to 0.1 mass%, and even more preferably 0.03 to 0.05 mass%, relative to the total mass of the liquid detergent composition. When the content of component (C) is at least the above lower limit, the anti-redeposition properties can be further improved. When the content of component (C) is not more than the above upper limit, the low-foaming properties can be further improved.

[0035] <(D) component> Component (D) is at least one selected from the group consisting of aromatic sulfonic acids, aromatic carboxylic acids, and salts thereof. The liquid detergent composition contains component (D), which provides excellent anti-redeposition properties. Component (D) does not contain anionic surfactants. The component (D) is preferably an aromatic sulfonic acid represented by the following formula (d1) or a salt thereof, or an aromatic carboxylic acid represented by the general formula (d2) or a salt thereof.

[0036] [ka]

[0037] In formulas (d1) and (d2), M 2 , M 3 R represents a hydrogen atom, an alkali metal ion, an ammonium ion, an alkylamine, or an alkanolamine. 2 ~R 5 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkenyl group, or a carbonyl group.

[0038] Examples of (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 anti-redeposition properties and low foaming properties, 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. These components (D) may be used alone or in combination of two or more.

[0039] The content of component (D) is preferably 0.1 to 10 mass%, more preferably 0.5 to 5 mass%, and particularly preferably 1 to 5 mass%, based on the total mass of the liquid detergent composition. When the content of component (D) is equal to or greater than the above-mentioned lower limit, the anti-redeposition properties can be further improved. When the content of component (D) is equal to or less than the above-mentioned upper limit, the low-foaming properties can be further improved.

[0040] <Mass ratio of each component> In the liquid detergent composition, the mass ratio of component (A) to component (C), expressed as component (A) / component (C), (A / C ratio) is preferably from 0.01 to 100, more preferably from 0.1 to 50, even more preferably from 1 to 10, and particularly preferably from 1 to 5. When the A / C ratio is within the above range, low foaming properties and anti-redeposition properties can be further improved.

[0041] In the liquid detergent composition, the mass ratio of component (D) to component (A), expressed as component (D) / component (A) (D / A ratio), is preferably from 0.1 to 2000, more preferably from 5 to 500, even more preferably from 10 to 100, and particularly preferably from 40 to 100. When the D / A ratio is within the above range, low foaming properties and anti-redeposition properties can be further improved.

[0042] In the liquid detergent composition, the mass ratio (CD / A ratio) of the total amount of components (C) and (D) to component (A), expressed as {component (C) + component (D)} / component (A), is preferably 0.1 to 2500, more preferably 2 to 500, even more preferably 8 to 100, and particularly preferably 30 to 70. When the CD / A ratio is within the above range, low foaming properties and anti-redeposition properties can be further improved.

[0043] In the liquid detergent composition, the total amount of components (C) and (D) (CD amount) is preferably 0.1 to 15 mass% relative to the total mass of the liquid detergent composition, more preferably 1 to 10 mass%, and even more preferably 2 to 5 mass%. When the CD amount is equal to or greater than the lower limit, the anti-redeposition properties can be further improved. When the CD amount is equal to or less than the upper limit, the low-foaming properties can be further improved.

[0044] <Optional ingredients> The liquid detergent composition of the present invention may contain any component typically contained in detergents for washing dishes, as long as it does not detract from the objectives of the present invention. For example, substances typically used in liquid detergent compositions for dishwashers, such as surfactants other than components (A) and (C) (optional surfactants), enzymes, chelating agents, silicone antifoaming agents, stabilizers, thickeners, solvents, plant extracts, oil absorbents, dish protectants, colorants, hydrotropes other than component (d) (excluding component (D)), antioxidants, pH adjusters, fragrances, and bleaches, may be used. The total amount of components (A), (B), (C), (D) and any optional components does not exceed 100% by mass.

[0045] Examples of optional surfactants include nonionic surfactants other than component (c2), cationic surfactants, amphoteric surfactants, and semi-polar surfactants. The total mass of the surfactants (including the components (A) and (C)) is preferably from 0.1 to 10 mass %, more preferably from 1 to 5 mass %, based on the total mass of the liquid detergent composition.

[0046] 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 more easily prepared.

[0047] 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.

[0048] Examples of hydrotropic agents (excluding component (D)) include polyols such as ethylene glycol and propylene glycol.

[0049] 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, N-methylpropanol, 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 and citric acid. Among inorganic bases, potassium hydroxide and sodium hydroxide are preferred in terms of storage stability and cost of the liquid detergent composition, with potassium hydroxide being particularly preferred in terms of storage stability, liquid fluidity, and the like. Among organic bases, monoethanolamine is preferred. One pH adjuster may be used alone, or two or more may be used in appropriate combination. The content of the pH adjuster may be appropriately determined so as to adjust the liquid detergent composition to a predetermined pH.

[0050] 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.

[0051] The viscosity of the liquid detergent composition at 25°C is preferably from 10 to 2000 mPa·s, more preferably from 100 to 1000 mPa·s. The viscosity of the liquid detergent composition at 25°C is a value measured in accordance with Viscosity Measurement Method 2, General Test Method, of 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.

[0052] The pH of the liquid detergent composition at 25°C is preferably 5-10, 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.

[0053] <Manufacturing method> The method for producing the liquid detergent composition of the present invention is not particularly limited, and it can be produced in accordance with a conventional method. For example, the liquid detergent composition can be produced by mixing components (A), (B), (C), and (D), a portion of water, and, if necessary, other optional components, adjusting the pH to a predetermined level using a pH adjuster if necessary, and then mixing with the remaining water.

[0054] <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 soiling of the dishes. A method for cleaning an object to be cleaned in a dishwasher using a liquid detergent composition includes a method having both a washing step and a rinsing step. Examples of washing methods include a step of washing objects while heating the washing liquid prepared by introducing tap water at room temperature (preferably about 5 to 30°C) into the dishwasher chamber to a predetermined washing temperature (the temperature of the washing liquid circulating during washing) (hereinafter referred to as the "washing step"), a step of rinsing the washed objects with tap water at room temperature (hereinafter referred to as the "rinsing (1) step"), and a step of further rinsing the objects after the rinsing (1) step while heating the tap water from room temperature to preferably 70 to 75°C at a rate of 2 to 3°C / minute (hereinafter referred to as the "rinsing (2) step"). The washing time in the washing step is preferably 10 to 40 minutes. In a typical standard wash cycle, the wash temperature is about 55 to 65°C and the temperature rise rate is about 2 to 3°C / min. In a low-temperature wash cycle, the wash 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 wash cycles, and exhibits excellent detergency even at a wash temperature of 35°C, for example. The amount of liquid detergent composition used per use is preferably 2 to 9 g per approximately 3 liters of tap water in any course.

[0055] <Action and effect> The liquid detergent composition described above uses the components (A), (B), (C), and (D) in combination, and therefore has excellent low foaming properties and anti-redeposition properties. [Example]

[0056] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following description.

[0057] (Raw materials used) <Component (A)> A-1: Sodium sulfosuccinate, manufactured by ALFA Chemistry, trade name "Trisodium sulfonatosuccinate."

[0058] <(B) component> B-1: Sodium monoalkyl sulfosuccinate (EO 3 mol) manufactured by Toho Chemical Co., Ltd., trade name "KOHACOOL L-300", AO in formula (b1) is an oxyethylene group, m is 3, R 1 A mixture of alkyl groups with 12, 14, and 16 carbon atoms. B-2: Sodium monoalkyl sulfosuccinate (EO 4 mol) manufactured by Toho Chemical Co., Ltd., trade name "KOHACOOL L-400", AO in formula (b1) is an oxyethylene group, m is 4, R 1 A mixture of alkyl groups with 12, 14, and 16 carbon atoms. B-3: Sodium monoalkyl sulfosuccinate (EO 0 mol), manufactured by Toho Chemical Co., Ltd., trade name "Kohakuru L-40", m in formula (b1) is 0, R 1 A mixture of alkyl groups with 12, 14, and 16 carbon atoms. ·B-4: Sodium di(2-propylheptyl) sulfosuccinate, synthetic product 1. ·B-5: Sodium di(3,5,5-trimethylhexyl) sulfosuccinate, synthetic product 2. B-6: Sodium di-2-ethylhexyl sulfosuccinate, manufactured by Lion Specialty Chemicals Co., Ltd., product name "Repearl 870P." B-7: Sodium decyl sulfate (C10AS), manufactured by Fluorochem LTD., trade name "n-Decyl sodium sulfate." B-8: Sodium dodecyl sulfate (C12AS), manufactured by Lion Specialty Chemicals Co., Ltd., product name "Sunol LM-1130." B-9: Sodium secondary alkane sulfonate (SAS, carbon number 14-17), manufactured by Clariant Japan Co., Ltd., trade name "HOSTAPUR SAS 30A". B-10: Sodium alkyl ether sulfate (AES, carbon 12-14, EO=2), manufactured by New Japan Chemical Co., Ltd., trade name "Shinoline SPE-1250." B-11: Linear alkylbenzene sulfonic acid (LAS, carbon number 10-14), manufactured by Lion Specialty Chemicals Co., Ltd., product name "Lipon LS-250".

[0059] Purified products were used for B-1, B-2, and B-3. Each component can be purified by recrystallization or standard liquid chromatography (reverse-phase or anion-exchange column). For example, anion-exchange column chromatography purification can be performed using Bio-Rad's Bio-Rex as the stationary phase and a mobile phase of methanol:water = 8:2 (volume ratio) with formic acid (100 mmol / L). The second peak detected, monoalkylsulfosuccinic acid (the first one to be separated is the ester) can be separated and purified.

[0060] <(C) component> · C-1: Alkyl maleic acid monoesters (EO 3 moles) with carbon numbers 12, 14, and 16, synthetic product 3. · C-2: Alkyl maleic acid monoesters with carbon numbers of 12, 14, and 16 (EO 4 moles), synthetic product 4. · C-3: Alkyl maleic acid monoesters with carbon numbers of 12, 14, and 16 (EO 0 moles), synthetic product 5. · C-4: 2-Propylheptyl maleic acid diester, synthetic product 6. · C-5: 3,5,5-trimethylhexyl maleic acid diester, synthetic product 7. ·C-6: Di-2-ethylhexyl maleate diester, synthetic product 8.

[0061] <(D) component> D-1: Sodium benzoate, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. D-2: Sodium cumene sulfonate, manufactured by Teika Co., Ltd., 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.

[0062] <Optional ingredients> Xanthan gum (Kelco brand name "KELZAN T"). Propylene glycol (Fujifilm Wako Pure Chemical Industries, Ltd., reagent). Sodium citrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). Fragrance: any one of the blended fragrance compositions 1 to 4 and the fragrance components listed in Table 1 of JP 2020-132680 A. pH adjuster: Sodium hydroxide (Kanto Chemical Co., Ltd., 48% sodium hydroxide), sulfuric acid (Fujifilm Wako Pure Chemical Industries, Ltd., special grade reagent). Water: Ion-exchanged water.

[0063] <Synthesis example> [Synthetic product 1] A 1-L autoclave was charged with 550 g of 2-propyl-1-heptanol, 170 g of maleic anhydride, and 1 g of paratoluenesulfonic acid, and the temperature was gradually increased to 180°C while bubbling with nitrogen at a stirring speed of 250 rpm. After reaching 180°C, the mixture was reacted for 4 hours. After cooling to 60°C, 170 g of anhydrous sodium bisulfite was charged, and the mixture was heated to 110°C while bubbling with nitrogen and reacted for 2 hours. After cooling to 60°C, the mixture was removed from the vessel to obtain B-4 (Synthetic Product 1).

[0064] [Synthetic product 2] B-5 (Synthetic Product 2) was obtained in the same synthetic method as for Synthetic Product 1, except that 3,5,5-trimethylhexanol (500 g) was used instead of 2-propyl-1-heptanol.

[0065] [Synthetic product 3] A 1-liter autoclave was charged with 320 g of triethylene glycol monolauryl ether, 100 g of maleic anhydride, and 0.25 g of sodium acetate, and the autoclave was thoroughly purged with nitrogen gas. The autoclave was heated to 70°C, and after reaching 70°C, the mixture was reacted for 5 hours. After cooling to 60°C, the mixture was removed from the autoclave and C-1 (synthetic product 3) was obtained.

[0066] [Synthetic product 4] C-2 (Synthetic Product 4) was obtained in the same synthesis method as for Synthetic Product 3, except that tetraethylene glycol monododecyl ether (360 g) was used instead of triethylene glycol monolauryl ether.

[0067] [Synthetic product 5] C-3 (Synthetic Product 5) was obtained in the same synthetic method as for Synthetic Product 3, except that ethylene glycol monododecyl ether (230 g) was used instead of triethylene glycol monolauryl ether.

[0068] [Synthetic product 6] C-4 (Synthetic Product 6) was obtained in the same synthetic method as for Synthetic Product 3, except that 2-propyl-1-heptanol (320 g) was used instead of triethylene glycol monolauryl ether.

[0069] [Synthetic product 7] C-5 (Synthetic Product 7) was obtained in the same synthetic method as for Synthetic Product 3, except that 3,5,5-trimethylhexanol (300 g) was used instead of triethylene glycol monolauryl ether.

[0070] [Synthetic product 8] C-6 (Synthetic Product 8) was obtained in the same synthetic method as for Synthetic Product 3, except that 2-ethylhexanol (260 g) was used instead of triethylene glycol monolauryl ether.

[0071] (Evaluation method) The evaluation of the anti-redeposition property and low foaming property described below was carried out by washing using a dishwasher with the following specifications. A dishwasher (model NP-45MD9SP, manufactured by Panasonic Corporation) was used as the dishwasher. In each evaluation, the dishwasher was operated with the automatic detergent dispenser turned off and in the soiling level L2 or L3 course. The details of the L2 and L3 courses are shown below. L2 Courses: Tap water at approximately 5°C is introduced into the cabinet, and the washing solution is prepared. The washing solution is heated to approximately 55°C at a rate of 2-3°C / min while washing for 30 minutes, and then the washing solution is drained. Fresh tap water is then introduced, and rinsing and draining are repeated twice. After draining, fresh tap water is introduced and the water is heated to approximately 65°C at a rate of 2-3°C / min while rinsing once (rinsing time: approximately 50 minutes). After draining, the dishes are dried by circulating warm air. L3 course: Tap water at approximately 5°C is introduced into the cabinet, and the washing solution is prepared. The temperature is raised to approximately 60°C at a rate of 2-3°C / min. The washing solution is then washed for 40 minutes, and then drained. Fresh tap water is then introduced, and the rinsing and draining process is repeated three times. After draining, fresh tap water is introduced, and the temperature is raised to approximately 70°C at a rate of 2-3°C / min. The rinsing is performed once (rinsing time: approximately 70 minutes). After draining, the dishes are dried by circulating warm air.

[0072] <Re-deposition prevention property> <Dirt used for evaluation> The stains used were a mixture of oil (beef tallow / lard / butter / salad oil = 3 / 3 / 3 / 1 (mass ratio)), tonkatsu sauce (KAGOME, Kagome Sauce Tonkatsu), tomato juice (Nippon Del Monte, Tomato Juice), eggs (large size), instant curry (Otsuka Foods, Bon Curry Gold Hot), and rice (equivalent to Koshihikari rice, type 1, which is independently distributed; the ratio of rice to water was the standard for the rice cooker, and rice used was cooked within 12 hours). 2g of the oil mixture and 5g of pork cutlet sauce were applied to a medium-sized bowl (radius 80mm, height 45mm). 5g of tomato juice was spread evenly over glass cups (radius 30mm, height 110mm). Curry stains were created by mixing 200g of the instant curry, 1 egg, and 150g of rice, and 30g of the mixture was placed on a large plate (radius 115mm, height 25mm) to evenly soil the surface of the plate. The mixture was then discarded, leaving about 10 grains of rice behind. The items to be washed (tableware to be cleaned) were six of the above medium-sized bowls, six glass cups, and six large plates. After creating the stains on each of the dishes, they were placed in the cabinet and left for one hour. According to the instruction manual of the automatic dishwasher, the dishwasher was loaded with the items to be washed in the designated area, and 8 g of each liquid detergent composition was added and operated on the L2 course. After washing was completed, new items were prepared and the washing process was repeated 10 times. After repeated washing, the degree of dirt around the food residue filter was observed and touched with fingers, and the anti-redeposition ability of complex dirt was evaluated based on the following evaluation criteria.

[0073] <Evaluation Criteria> ◎◎◎: No slimy residue at all, and no complex stains could be visually detected. ◎◎: There is a slight slimy feeling, but no complex dirt can be visually confirmed. ⊚: There is a slight slimy feeling, but no complex stains can be visually confirmed. ○: There is a slimy feeling, but no complex stains can be visually confirmed. ×: Slimy feeling and complex stains can be visually confirmed.

[0074] <Low foaming> 16 g of each liquid detergent composition and 6 g of well-beaten whole egg were added to a dishwasher and run on the L3 cycle. When the water temperature reached 50°C after the start of washing, the operation was stopped and the door was opened. 10 seconds later, foaming inside the dishwasher was observed and the low-foaming properties were evaluated based on the following evaluation criteria.

[0075] <Evaluation Criteria> ◎◎◎: No bubbles were observed. ⊚◎: Foam generation was observed, but it was at a level that could be seen with the naked eye at the bottom of the dishwasher. ⊚: Foam generation was observed, but it only slightly covered the liquid surface. ○: Foam generation was observed, but the foam height was lower than that of the water jet nozzle. ×: Foam generation was observed, the foam height exceeded the water jet nozzle, and air bubbles were observed. "Air entrapment" refers to a condition in which, when a large amount of foam is generated during cleaning, air gets into the circulation pump, weakening the spray power and causing abnormal noise. In this test, the presence or absence of air entrapment was determined by checking for abnormal noise.

[0076] <Examples 1 to 53 and Comparative Examples 1 to 4> According to the compositions shown in Tables 1 to 12, 0.8 kg of each liquid detergent composition was prepared by dissolving components (A), (B), (C), (D), and optional components in water as a solvent and adjusting the pH. Specifically, water was added to a 1-L beaker (12 cm diameter) so that the total amount of water constituted 80% by mass of the entire composition. A mixer (SHINTO SCIENCE CO., LTD., HEIDON FBL1200 Three-One Motor) was equipped with a four-blade paddle with a diameter of 7.5 cm, a width of 1.5 cm, and an angle of 45°. Then, xanthan gum and propylene glycol were added while stirring at 400 to 900 rpm to prevent the contents from scattering. Next, components (A), (B), (C), (D), and optional components (excluding the remaining fragrance and water) were added, and the pH was adjusted to 7.5. The fragrance was then added, and the mixture was stirred at 650 rpm for 5 minutes. The remaining water was added so that the total composition was 100% by mass, and the mixture was stirred at 650 rpm for 1 minute to obtain the liquid detergent composition for each example. The pH (25°C) of the liquid detergent composition was measured using a glass electrode pH meter (HM-30G, manufactured by DKK-TOA Corporation) after adjusting the liquid detergent to 25°C in accordance with JIS Z 8802:2011 "pH measurement method." The content of each component in the table is expressed in mass %, and all components are expressed as pure content amounts. A blank space in the table indicates that the ingredient is not included.

[0077] [Table 1]

[0078] [Table 2]

[0079] [Table 3]

[0080] [Table 4]

[0081] [Table 5]

[0082] [Table 6]

[0083] [Table 7]

[0084] [Table 8]

[0085] [Table 9]

[0086] [Table 10]

[0087] As shown in Tables 1 to 12, Examples 1 to 53 in which the present invention was applied had low foaming properties of "◯" to "◎◎◎" and anti-redeposition properties of "◯" to "◎◎◎". In Comparative Examples 1 to 4, which lacked any of the components (A) to (D), the anti-redeposition properties were all rated "poor."

Claims

1. Component (A): at least one selected from sulfosuccinic acid and its salts, Component (B): an anionic surfactant (excluding component (c1) below), Component (C): at least one selected from the following component (c1) and the following component (c2), Component (D): at least one selected from the group consisting of aromatic sulfonic acids, aromatic carboxylic acids, and salts thereof. Component (c1): A compound represented by the following formula (c1). 【Chemistry 1】 (R ２ｃ represents a linear or branched alkyl or alkenyl group having 8 to 18 carbon atoms; A ２ O is an oxyalkylene group, n is a number from 0 to 10, and Mc is hydrogen. Component (c2): A compound represented by the following formula (c2). 【Chemistry 2】 (R ２ａ and R ２ｂ are each independently a linear or branched alkyl or alkenyl group having 8 to 18 carbon atoms.

2. 2. The liquid dishwasher detergent composition according to claim 1, wherein the component (B) comprises a sulfosuccinic acid monoalkyl ester salt.

3. The liquid dishwasher detergent composition according to claim 1 or 2, wherein the mass ratio of the component (D) to the component (A) is 0.1 to 2000.

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