Dishwasher detergent composition

Abstract

To provide a dishwasher detergent composition which has excellent foam suppression properties and oil stains reattachment prevention properties.SOLUTION: There is provided a dishwasher detergent composition comprising a component (a1): at least one selected from a group consisting of compounds represented by a formula (a1), a component (a2): at least one selected from a group consisting of compounds represented by a formula (a2), a component (b): a chelating agent, a component (c): an enzyme and a component (d): at least one selected from silica and a silicone compound. R1 represents 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, R2 and R3 represent a linear or branched chain alkyl group having a carbon number of 5 to 18 or a linear or branched-chain alkenyl group having a carbon number of 5 to 18, AO represents an oxyalkylene group, m, p and r represent a number of 0 to 10 representing an average repeating number of AO and Ma, M and, Mc represent a counter ion.SELECTED DRAWING: None

Description

[Technical field]

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

[0002] In general, a dedicated detergent (a detergent composition for dishwashers) is used for cleaning with a dishwasher. A detergent composition for dishwashers is required to have both low foaming (foam suppression) and cleaning power. Patent Document 1 discloses a detergent composition for dishwashers that contains an amidoamine and an anionic surfactant and has excellent foam suppression and cleaning power for oily stains. Patent Document 2 discloses a detergent composition for dishwashers that contains an amidoamine, an alkylbenzenesulfonic acid, a chelating agent, and a silicone compound and has excellent foam suppression and cleaning power for protein stains. Patent Document 3 discloses a detergent composition for dishwashers that contains a branched alkyl sulfosuccinate ester in which the branched alkyl group has 9 to 11 carbon atoms and an inorganic alkali agent and has excellent foam suppression and cleaning power for complex stains containing proteins and lipids. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2015-10186 A [Patent Document 2] Patent Publication No. 2021-4333 [Patent Document 3] JP 2022-100664 A Summary of the Invention [Problem to be solved by the invention]

[0004] However, the dishwasher detergent compositions of Patent Documents 1 to 3 do not have sufficient properties for preventing oily stains from re-adhering to the interior walls of a dishwasher, and when a large amount of dishes and oily stains are brought into the dishwasher, oily stains tend to re-adhere to the interior walls.

[0005] The present invention has been made in consideration of the above circumstances, and an object of the present invention is to provide a detergent composition for dishwashers that is excellent in foam-suppressing properties and in preventing the re-adhesion of oily stains to the inner wall surfaces of the dishwasher. [Means for solving the problem]

[0006] The present invention has the following aspects. [1] Component (a1): at least one compound selected from the group consisting of compounds represented by the following formula (a1): Component (a2): at least one compound selected from the group consisting of compounds represented by the following formula (a2): (b) component: a chelating agent; (c) components: an enzyme; Component (d): at least one selected from the group consisting of silica and silicone compounds; A dishwasher cleaning composition comprising: [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. [ka] In the formula, R 2 and R 3 each independently represents a linear or branched alkyl group having 5 to 18 carbon atoms or a linear or branched alkenyl group having 5 to 18 carbon atoms, AO is an oxyalkylene group, p and r each independently represent the average number of repetitions of AO and are numbers of 0 to 10, and Mc is a counter ion. [2] The dishwasher detergent composition according to [1], wherein the mass ratio of the component (a1) / the component (a2) is 0.25 to 50. Effect of the Invention

[0007] According to the present invention, it is possible to provide a detergent composition for a dishwasher which is excellent in foam suppression property and in preventing re-adhesion of oily stains to the inner wall surface of the dishwasher. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] The dishwasher detergent composition of the present invention (hereinafter also simply referred to as "detergent composition") contains the components (a1), (a2), (b), (c) and (d). The cleaning composition may further contain other components (hereinafter also referred to as "optional components") other than the components (a1), (a2), (b), (c) and (d).

[0009] <Component (a1)> The component (a1) is at least one selected from the group consisting of compounds represented by the following formula (a1): The component (a1) 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] 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.

[0011] In formula (a1), 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 is 8 to 18, it is easy to improve the foam suppression property and the prevention of oil stains from re-adhering to the inner wall surface.1 The number of carbon atoms is preferably 10 to 16, and more preferably 12 to 16.

[0012] In formula (a1), 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 (a1), 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 the foam suppression property and the property of preventing oil stains from re-adhering to the inner wall surface of the cabinet. m is preferably from 0 to 4, more preferably from 3 to 4, and particularly preferably 4.

[0013] In formula (a1), 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 foam suppression and prevention of reattachment of oil stains to the inner wall surface, 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.

[0014] As the component (a1), 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 (a1) may be used alone or in combination of two or more types.

[0015] The content of the (a1) component is preferably 0.1 to 10 mass%, more preferably 1 to 4 mass%, and even more preferably 1.5 to 3 mass%, based on the total mass of the detergent composition. When the content of the (a1) component is equal to or more than the above lower limit, it is easy to improve the prevention of oily stains from re-adhering to the interior wall surface. When the content of the (a1) component is equal to or less than the above upper limit, it is easy to improve the foam suppression property.

[0016] <(a2) component> The component (a2) is at least one selected from the group consisting of compounds represented by the following formula (a2): The component (a2) can also be said to be at least one selected from the group consisting of dialkylsulfosuccinic acids and salts thereof having a linear or branched alkyl group having 8 to 18 carbon atoms, which may have 20 moles or less of alkylene oxide added thereto, and dialkenylsulfosuccinic acids and salts thereof having a linear or branched alkenyl group having 5 to 18 carbon atoms, which may have 20 moles or less of alkylene oxide added thereto.

[0017] [ka] In the formula, R 2 and R 3 each independently represents a linear or branched alkyl group having 5 to 18 carbon atoms or a linear or branched alkenyl group having 5 to 18 carbon atoms, AO is an oxyalkylene group, p and r each independently represent the average number of repetitions of AO and are numbers of 0 to 10, and Mc is a counter ion.

[0018] In formula (a2), R 2 and R 3 R is independently a linear or branched alkyl group having 5 to 18 carbon atoms or a linear or branched alkenyl group having 5 to 18 carbon atoms. 2 , R 3 When the carbon number is 5 to 18, it is easy to improve the foam suppression property and the prevention of oil stains from re-adhering to the inner wall surface. 2 The number of carbon atoms in 3 Each of the groups independently has preferably 8 to 16 carbon atoms, and more preferably 8 to 12 carbon atoms. R2 and R 3 Examples of the alkyl group include a hexyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tridecyl group, a 2-ethylhexyl group, a n-octyl group, a sec-octyl group, an isopentyl group, an isononyl group, a 3,5,5-trimethylhexyl group, an isodecyl group, and a 2-propylheptyl group.

[0019] In formula (a2), AO is an oxyalkylene group. Examples of the oxyalkylene group include the same as those mentioned above. In formula (a2), p and r each independently represent the average number of repetitions of AO and are numbers from 0 to 10. When p and r are from 0 to 10, it is easy to improve the foam suppression property and the prevention of oil stain reattachment to the inner wall surface. p and r each independently are preferably from 0 to 6, and particularly preferably 0.

[0020] In formula (a2), Mc is a counter ion. Examples of the counter ion include the same as Ma and Mb. Among them, from the viewpoint of foam suppression and prevention of oil stain reattachment to the inner wall surface, alkali metal ions are preferred, sodium ions and potassium ions are more preferred, and sodium ions are particularly preferred. When Mc is a counter ion with a valency of 2 or more, Mc is considered to be bonded to -O at a number obtained by multiplying Mc by 1 / valency.

[0021] As the component (a2), a dialkyl sulfosuccinate is preferable. Examples of the dialkyl sulfosuccinate include sodium di(2-ethylhexyl)sulfosuccinate, sodium di(3,5,5-trimethylhexyl)sulfosuccinate, sodium di(2-isodecyl)sulfosuccinate, sodium di(2-propylheptyl)sulfosuccinate, and sodium ditridecylsulfosuccinate. The component (a2) may be used alone or in combination of two or more types.

[0022] The content of the (a2) component is preferably 0.05 to 5 mass%, more preferably 0.05 to 1 mass%, and even more preferably 0.1 to 1 mass%, based on the total mass of the detergent composition. When the content of the (a2) component is equal to or more than the above lower limit, it is easy to improve the prevention of oil stains from re-adhering to the interior wall surface. When the content of the (a2) component is equal to or less than the above upper limit, it is easy to improve the foam suppression property.

[0023] In the detergent composition, the mass ratio of component (a1) to component (a2) (hereinafter also referred to as "a1 / a2 ratio") is preferably 0.25 to 50, more preferably 0.5 to 25, and particularly preferably 1 to 10. When the a1 / a2 ratio is equal to or more than the above lower limit, the foam suppression property is easily improved. When the a1 / a2 ratio is equal to or less than the above upper limit, the prevention of oil stain redeposition on the interior wall surface is easily improved.

[0024] <(b) Component> Component (b) is a chelating agent. As the component (b), any of the general chelating agents that have been used in dishwasher detergent compositions can be used, including, for example, polymeric chelating agents and low molecular weight chelating agents.

[0025] 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.

[0026] From the viewpoint of improving foam suppression and prevention of oil stains from re-adhering to the interior walls of the container, 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. Among these, the low molecular weight chelating agent is preferably at least one selected from the group consisting of citric acid and its salts, ethylenediaminetetraacetic acid and its salts, glutamic acid diacetic acid and its salts, and methylglycine diacetic acid and its salts, and particularly preferably sodium citrate.

[0027] As component (b), from the viewpoint of improving foam suppression properties and preventing re-adhesion of oil stains to the interior walls of the container, a low molecular weight chelating agent is preferred. The component (b) may be used alone or in combination of two or more types.

[0028] The content of the (b) component is preferably 5 to 20 mass%, more preferably 10 to 20 mass%, and even more preferably 12 to 18 mass%, based on the total mass of the detergent composition. When the content of the (b) component is equal to or more than the above lower limit, it is easy to improve the prevention of oil stains from re-adhering to the interior wall surface. When the content of the (b) component is equal to or less than the above upper limit, it is easy to improve the foam suppression property.

[0029] <(c) component> The (c) component is an enzyme. As component (c), any of the general enzymes that have been used in dishwasher detergent compositions can be used, such as amylase, protease, mannanase, cellulase, lipase, and glucanase. The component (c) may be used alone or in combination of two or more types. From the viewpoint of improving foaming inhibitory properties and preventing the re-adhesion of oily stains to the interior walls of the oven, component (c) 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.

[0030] The content of the (c) component is preferably 0.01 to 2 mass % as an enzyme preparation, more preferably 0.1 to 1 mass %, particularly preferably 0.3 to 0.7 mass %, based on the total mass of the detergent composition. If the content of the (b) component is equal to or greater than the lower limit, it is easy to improve the prevention of oil stains from reattaching to the inner wall surface of the cabinet. On the other hand, if the content of the (c) component exceeds the preferred upper limit, the effect of improving performance will plateau and the cost will increase.

[0031] When the component (c) 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. If the amylase activity is equal to or higher than the lower limit, it is easy to improve the prevention of oil stains from re-adhering to the inner wall surface. On the other hand, if the amylase activity exceeds the preferred upper limit, the effect of improving performance will plateau and the cost will increase.

[0032] When the component (c) 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, it is easy to improve the prevention of reattachment of oil stains to the inner wall surface. On the other hand, even if the protease activity exceeds the preferred upper limit, the effect of improving performance reaches a plateau and the cost becomes high.

[0033] <(d) component> The component (d) is at least one selected from the group consisting of silica and silicone compounds. By including the component (d), the detergent composition can improve the ability to prevent oily stains from re-adhering to the interior walls of the container while maintaining the foam-suppressing properties. The component (d) may be made of silica, may be made of a silicone compound, or may be made of silica and a silicone compound. In terms of foam suppression, it is preferable that the component (d) is made of silica and a silicone compound. Examples of the component (d) made of silica and a silicone compound include a mixture of silica and a silicone compound, silica surface-treated with a silicone compound, and a reaction product of silica and a silicone compound. Examples of the silicone compound include various silicone oils. Examples of the (d) component include oil type, compound type, self-emulsifying compound type, emulsion type, etc. The oil type contains silicone oil. The compound type contains silicone oil, silica, and a dispersant (nonionic surfactant, acrylic acid polymer, etc.). The compound type may contain silica treated with silicone oil. The self-emulsifying compound type is a compound type to which an emulsifier has been added, and when mixed with water, it self-emulsifies to form an emulsion. The emulsion type is an oil-in-water emulsion in which the compound type is emulsified with an emulsifier.

[0034] The (d) component can be a commercially available product. For example, oil-type products include DOWSIL FS 1265 Fluid and DOWSIL SH200 Fluid, which are manufactured by Dow Chemical Co., Ltd.; compound-type products include XIAMETER ACP-1500 Antifoam Compound, DOWSIL ACP-3073 Antifoam Compound, and DOWSIL ACP-3258 Antifoam Compound, which are manufactured by Dow Chemical Co., Ltd.; self-emulsifying compound-type products include DOWSIL FS Antifoam 80 and XIAMETER ACP-1266 Antifoam Compound, which are manufactured by Dow Chemical Co., Ltd.; and emulsion-type products include DOWSIL FS Antifoam 93 and XIAMETER AFE-1530 Antifoam Emulsion, which are manufactured by Dow Chemical Co., Ltd.

[0035] From the viewpoints of maintaining the foam-suppressing properties and improving the ability to prevent oil stains from re-adhering to the interior walls of the cabinet, component (d) is preferably a compound type, a self-emulsifying compound type, or an emulsion type. As component (d), those containing treated amorphous silica, dimethylsiloxane-treated silica, or a reaction product of dimethylsiloxane and silica are preferred, those containing treated amorphous silica are more preferred, and DOWSIL FS Antifoam 93 is particularly preferred. The component (d) may be used alone or in combination of two or more types.

[0036] The (d) component preferably contains 1 to 50 mass % of silica, more preferably 1 to 20 mass %, and even more preferably 1 to 10 mass %, based on the total mass of the (d) component. When the silica content is equal to or greater than the lower limit, it is easy to improve the foam suppression property. When the silica content is equal to or less than the upper limit, it is easy to improve the prevention of re-adhesion of oil stains to the interior wall surface.

[0037] The content of component (d) is preferably 0.01 to 1 mass%, more preferably 0.05 to 1 mass%, and particularly preferably 0.1 to 0.5 mass%, based on the total mass of the cleaning composition. When the content of component (d) is equal to or more than the above lower limit, the foam suppression property is easily improved. When the content of component (d) is equal to or less than the above upper limit, the prevention of re-adhesion of oily stains to the interior wall surface is easily improved. The content of silica is preferably 0.0001 to 0.1 mass%, more preferably 0.0005 to 0.1 mass%, and particularly preferably 0.001 to 0.05 mass%, based on the total mass of the cleaning composition. When the content of silica is equal to or more than the lower limit, the foam suppression property is easily improved. When the content of silica is equal to or less than the upper limit, the prevention of re-adhesion of oily stains to the interior wall surface is easily improved.

[0038] <Optional ingredients> The dishwashing detergent composition of the present invention may contain any component that is generally contained in detergents for washing dishes, so long as it does not go against the object of the present invention. For example, substances that are generally used in dishwashing detergent compositions, such as surfactants other than the components (a1) and (a2), stabilizers, thickeners, solvents, plant extracts, oil absorbents, dish protectants, colorants, hydrotropes, antioxidants, pH adjusters, fragrances, and bleaches, may be used.

[0039] 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.

[0040] 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.

[0041] Examples of hydrotropic agents include polyols such as ethylene glycol and propylene glycol; aromatic sulfonic acids such as sodium cumene sulfonate, potassium cumene sulfonate, ammonium cumene sulfonate, sodium xylene sulfonate, potassium xylene sulfonate, ammonium xylene sulfonate, sodium toluene sulfonate, potassium toluene sulfonate, and ammonium toluene sulfonate; and aromatic carboxylic acids such as sodium benzoate.

[0042] 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 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 appropriate combination of two or more. The content of the pH adjuster may be appropriately set so as to adjust the cleaning composition to a predetermined pH.

[0043] The detergent composition may be a liquid or a solid such as a powder or a tablet. From the viewpoint of usability, compatibility with an automatic dishwasher, etc., a liquid detergent composition is preferable. Hereinafter, a liquid detergent composition is also particularly referred to as a "liquid detergent composition".

[0044] 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.

[0045] 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.

[0046] 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.

[0047] <Manufacturing method> The method for producing the cleaning 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 (a1), (a2), (b), (c), (d), a portion of water, and, if necessary, one or more of the 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.

[0048] <How to use> The 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 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 detergent composition for dishwashers 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. When the detergent composition is a liquid, the amount of detergent composition used at one time is preferably 2 to 9 g per about 3 liters of tap water in any course.

[0049] <Action and effect> The above-described detergent composition contains components (a1), (a2), (b), (c) and (d), and therefore has excellent foam-suppressing properties. It also has excellent properties for preventing re-adhesion of oily stains to the interior walls of the cabinet, and can prevent re-adhesion of oily stains to the interior walls of the cabinet even if a large amount of dishes and oily stains are brought into the cabinet. EXAMPLES

[0050] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following description.

[0051] <Raw materials used> [Component (a1)] a1-1: In the formula (a1), 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." a1-2: In the formula (a1), 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." a1-3: In the formula (a1), 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." a1-4: In the formula (a1), 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."

[0052] [(a1) Comparative product of component] 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., trade name "Sunol LM-1130". a'-4: Sodium polyoxyethylene alkyl ether sulfate (C12-14, EO=2) (AES), manufactured by New Japan Chemical Co., Ltd., trade name "Shinoline SPE-1250." a'-5: Sodium α-olefin sulfonate (C14) (AOS), manufactured by Lion Specialty Chemicals Co., Ltd., product name "Liporan LB-440".

[0053] [(a2) component] a2-1: In the formula (a2), p and r are 0, Mc is a sodium ion, R 2 and R 3 is 2-ethylhexyl group (sodium dialkyl sulfosuccinate C8), manufactured by Lion Specialty Chemicals Co., Ltd., product name "Repearl 870P".

[0054] [(b) Component] b-1: Trisodium citrate (Na citrate), manufactured by Fuso Chemical Co., Ltd. b-2: Sodium ethylenediaminetetraacetate (EDTA), manufactured by Tokyo Chemical Industry Co., Ltd. b-3: Tetrasodium glutamic diacetate (GLDA), manufactured by Chelest. b-4: Tetrasodium methylglycine diacetate (MGDA), manufactured by BASF, trade name "Trilon M Compactate". b-5: Sodium salt of maleic acid-acrylic acid copolymer (MA), acrylic acid / maleic acid molar ratio = 60 / 40, weight average molecular weight 50,000, active ingredient 40% by mass, manufactured by Nippon Shokubai Co., Ltd., product name "Aqualic TL400".

[0055] [(c) component] c-1: Amylase, manufactured by Novozymes, product name "Achieve alpha 100L". c-2: Protease, manufactured by Novozymes, product name "Blaze pro 100L". c-3: Mannanase, manufactured by Novozymes, trade name "Mannaway 200L". c-4: Cellulase, manufactured by Novozymes, product name "Carezyme Premium 4500L". c-5: Lipase, manufactured by Novozymes, product name "Lipex Evity 200L". c-6: A mixed enzyme of amylase and protease, manufactured by Novozymes, product name "Intensa Core 200L".

[0056] [(d) component] d-1: Emulsion type silicone composition (containing treated amorphous silica (content: 1.0 to 10.0%), α-(C12-C14 alkyl)ω-hydroxypolyethylene-polypropylene glycol, propanediol, and sodium salt of acrylic acid polymer), manufactured by Dow Chemical, product name "DOWSIL FS Antifoam 93". d-2: Self-emulsifying compound type silicone composition (reaction product of dimethylsiloxane / silica (content: 1.0 to 10.0%), containing octamethylcyclotetrasiloxane), manufactured by Dow Chemical, product name "DOWSIL FS Antifoam 80". d-3: Emulsion type silicone composition (containing dimethylsiloxane-treated silica (content: 1.0 to 10.0%), methylcellulose, and propanediol), manufactured by Dow Chemical, product name "XIAMETER AFE-1530 Antifoam Emulsion".

[0057] [(d) Comparative product of ingredients] d'-1: BASF, product name "Plurafac LF 403", aliphatic alcohol alkoxylate. d'-2: BASF product name "Pluronic RPE1740", PO·EO·PO block polymer.

[0058] [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. Sodium cumene sulfonate (manufactured by Teika Corporation, product name "Teikatox N5040") 2.0% by mass. Sodium benzoate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., reagent) 4.0% 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.

[0059] [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.

[0060] <Examples 1 to 36 and Comparative Examples 1 to 12> According to the compositions shown in Tables 1 to 5, components (a1), (a2), (b), (c), (d) and optional components were dissolved in water as a solvent and the pH was adjusted to prepare 0.8 kg of each of the liquid detergents of Examples 1 to 36 and Comparative Examples 1 to 5. Specifically, water was added to a 1 L beaker (diameter 12 cm) so that the total amount of water was 40 mass % of the entire composition. A mixer (SHINTO Scientific Co., Ltd., HEIDON FBL1200 Three-One Motor) 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 to prevent the contents from scattering, the common components xanthan gum and propylene glycol were added, then component (d) was added, and then the pH was adjusted to about 7 with a pH adjuster (sodium hydroxide or sulfuric acid), and then components (a1), (a2), (b), (c), 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."

[0061] 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.

[0062] <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 cleaning composition is weighed out and dissolved in the above buffer solution to a constant volume of 100 mL to prepare the 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, pre-warmed to 37°C, is added to the test tube containing the sample solution, being careful not to let the buffer touch the test tube wall, and then one Padebas tablet is added 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 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, a cleaning composition having the same composition as the sample except that no enzyme is blended is prepared as a blank, and the same procedure as above is carried out, and the measured absorbance is regarded as the absorbance of the blank. From the measurement results, calculate amylase activity (U) using the following formula. Amylase activity (U) = (absorbance of sample) - (absorbance of blank)

[0063] <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 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, a cleaning composition having the same composition as the sample except that no enzyme is blended is prepared as a blank, and the same procedure as above is carried out, and the measured absorbance is regarded as the absorbance of the blank. From the measurement results, the protease activity (U) is calculated using the following formula. Protease activity (U) = (absorbance of sample) - (absorbance of blank).

[0064] <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 or L3 course. The details of the L2 course and L3 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. L3 Course: Tap water at about 5°C is introduced into the cabinet, and the washing liquid is heated to about 60°C at 2-3°C / min while washing for 40 minutes, and the washing liquid is drained. Next, new tap water is introduced, and rinsing and draining are repeated three times. After draining, new tap water is introduced and the water is heated to about 70°C at 2-3°C / min while rinsing once (rinsing time is about 70 minutes), and after draining, the dishes are dried while circulating hot air.

[0065] [Foam control] 16 g of the liquid detergent composition and 6 g of well-beaten whole egg were added to the dishwasher, and the dishwasher was operated on the L3 course. When the water temperature reached 50°C after the start of washing, the operation was stopped and the door was opened at the same time. 10 seconds later, foaming in the cabinet was observed, and the foam suppression ability was evaluated based on the following evaluation criteria. A rating of ○, ◎, ◎◎, or ◎◎◎ was deemed to be acceptable. (Evaluation Criteria) : No bubbles were observed. ⊚: Generation of bubbles was observed, but the level was such that bubbles could be seen visually 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 bubbles" refers to a state in which, when a large amount of foam is generated during cleaning, air gets into the circulation pump, weakening the water spray power and generating abnormal noise. In this test, the presence or absence of air bubbles was evaluated by checking for abnormal noise.

[0066] [Oil stains re-adhering inside the cabinet] A large amount of dishes and oily stains were brought into the oven and washed, and the ability to prevent oily stains from re-adhering to the interior walls was evaluated using the following procedure. As the oil stain, a mixture of beef tallow / lard / butter / salad oil = 3 / 3 / 3 / 1 (mass ratio) was used. As the stained dishes, three ceramic large dishes (radius 115 mm, height 25 mm) with 6 g of oil stains attached thereto, and three ceramic large dishes with 6 g of retort curry (Otsuka Foods Co., Ltd., Bon Curry Gold Hot) attached thereto were prepared. These stained dishes were loaded in the designated locations based on the instruction manual of the dishwasher. In addition, 12 small dishes (radius 60 mm, height 20 mm), 6 medium bowls (radius 80 mm, height 45 mm), 6 tea bowls, 6 soup bowls, and 6 glasses were all loaded in the designated locations based on the instruction manual of the dishwasher. Then, 8 g of the liquid detergent composition was added, and washing was repeated 10 times using the L2 course. After repeated cleaning, the state of the area around the food residue filter on the bottom of the chamber was visually observed, and the ability to prevent re-adhesion of oil stains to the chamber wall was evaluated based on the following evaluation criteria. A rating of ○, ◎, ◎◎, or ◎◎◎ was deemed to be acceptable. (Evaluation Criteria) ◎◎◎: No oil film is visible around the food residue filter, and no oil film can be felt even when rubbing it with a finger. ◎◎: No oil film is visible around the food waste filter, but a slight oil film can be felt when rubbing with a finger. ◎: No oil film is visible around the food waste filter, but an oil film can be felt when rubbing with a finger. ○: A slight oil film is visible around the food waste filter. ×: An oil film is clearly visible around the food waste filter.

[0067] [Table 1]

[0068] [Table 2]

[0069] [Table 3]

[0070] [Table 4]

[0071] [Table 5]

[0072] The liquid detergent compositions of Examples 1 to 36 all passed the test for foam suppression and prevention of oil stain redeposition onto the interior walls of the cabinet. Comparative Example 1, which did not contain the component (a1), Comparative Example 2, which did not contain the component (a2), Comparative Example 3, which did not contain the component (b), and Comparative Example 4, which did not contain the component (c), each failed to prevent oil stains from re-adhering to the interior walls of the container. Comparative Example 5, which did not contain the component (d), failed in terms of foam suppression. Comparative Examples 6 to 10, which used a comparative product instead of the (a1) component, failed in terms of foam suppression. In particular, Comparative Examples 7 to 12 failed in terms of preventing re-adhesion of oil stains to the interior walls of the container. Comparative Examples 11 and 12, in which a comparative product was used instead of component (d), failed in terms of foam suppression.

Claims

1. (a1) Components: At least one selected from the group consisting of compounds represented by the following formula (a1), (a2) Component: At least one selected from the group consisting of compounds represented by the following formula (a2), (b) Ingredients: Chelating agent and (c) Ingredients: Enzymes and, (d) Components: At least one selected from the group consisting of silica and silicone compounds, A dishwasher detergent composition containing the following: 【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-. 【Chemistry 2】 In the formula, R ２ and R ３ Each of the following is independently a linear or branched alkyl group having 5 to 18 carbon atoms or a linear or branched alkenyl group having 5 to 18 carbon atoms, AO is an oxyalkylene group, p and r are independently numbers from 0 to 10 indicating the average repeating number of AO, and Mc is a counterion.

2. The dishwasher detergent composition according to claim 1, wherein the mass ratio represented by component (a1) / component (a2) is 0.25 to 50.

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