Dishwasher detergent composition

Abstract

To provide a dishwasher detergent composition which has excellent foam suppression properties and cleaning ability for protein-lipid composite stains under acidic stain coexistence and can prevent accumulation of stains or cleaning components on glass tableware during repeated washing under coexistence of stains.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 following formula (a1), a component (a2): at least one selected from a group consisting of an alkyl or alkenyl sulfate ester having an alkyl group having a carbon number of 8 to 18 or an alkenyl group having a carbon number of 8 to 18 and a salt thereof, a component (b): a chelating agent having molecular weight of 800 or less and a component (c): at least one selected from a group consisting of silica and a silicone compound.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 washing 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 α-sulfofatty acid alkyl ester salt and an amidoamine, and has excellent foam suppression and cleaning power for oily stains at low temperatures. Patent Document 2 discloses a liquid detergent composition for dishwashers that contains an anionic surfactant having an alkyl or alkenyl group with 10 carbon atoms, a copolymer of (meth)acrylic acid and a (meth)acrylic acid ester, and water, and has excellent foam suppression and cleaning power for complex stains. Patent Document 3 discloses a liquid detergent composition for dishwashers that contains a surfactant, a chelating agent, at least one selected from the group consisting of carbonates and hydrogen carbonates, and water, and has a pH of 7.5 to 10, and has excellent foam suppression and cleaning power for complex stains. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2018-184554 A [Patent Document 2] JP 2018-83862 A [Patent Document 3] Patent Publication No. 2021-91837 Summary of the Invention [Problem to be solved by the invention]

[0004] However, the dishwasher detergent compositions of Patent Documents 1 and 2 do not have sufficient cleaning power for lipid-protein complex stains (e.g., egg stains) firmly attached to dishes under harsh conditions where a large amount of acidic stains such as dressing stains and tomato juice stains coexist. When the dishwashing detergent composition of Patent Document 3 is used for repeated cleaning in the presence of dirt, dirt and cleaning components (e.g., silicone-based defoaming agents) may gradually accumulate on the surface of glass tableware. For example, when beer is poured into a glass after such cleaning, the accumulated dirt and cleaning components may cause the beer foam to disappear immediately.

[0005] The present invention has been made in consideration of the above circumstances, and has an object to provide a detergent composition for dishwashers which has excellent foam-inhibiting properties and excellent detergency for lipid / protein complex stains in the coexistence of acidic stains, and which can inhibit the accumulation of stains and detergent components on glass tableware during repeated washing in the coexistence of stains. [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 selected from the group consisting of alkyl or alkenyl sulfate esters having an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms and salts thereof, polyoxyalkylene alkyl or alkenyl ether sulfate esters having an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms and salts thereof, and internal olefin sulfonic acids having 16 to 24 carbon atoms and salts thereof; (b) component: a chelating agent having a molecular weight of 800 or less; Component (c): at least one selected from the group consisting of silica and silicone compounds; A dishwasher cleaning composition comprising: [ka] In the formula, R 1represents a linear or branched alkyl group having 8 to 18 carbon atoms or a linear or branched alkenyl group having 8 to 18 carbon atoms, AO represents an oxyalkylene group, m represents the average number of repetitions of AO and is a number of 0 to 10, and Ma and Mb each independently represent a counter ion. [2] Component (d): The dishwasher detergent composition according to [1], further comprising a polyol. [3] The dishwasher detergent composition according to [1] or [2], wherein the mass ratio of the sum of the (a1) component and the (a2) component to the (c) component is 1 to 1,000. Effect of the Invention

[0007] The present invention provides a detergent composition for dishwashers that has excellent foam-inhibiting properties and cleaning power for lipid-protein complex stains in the presence of acidic stains, and that can inhibit the accumulation of stains and cleaning components on glass tableware during repeated washing in the presence of stains. 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) and (c). The cleaning composition may further contain a component (d). The cleaning composition may further contain other components in addition to 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 of R is 8 to 18, it is easy to improve the foam suppression property and the cleaning power for lipid-protein complex stains in the presence of acidic stains, and it is easy to suppress the accumulation of stains and cleaning ingredients on glass tableware during repeated washing in the presence of stains. 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 is a number from 0 to 10 indicating the average number of repetitions of AO. When m is 0 to 10, it is easy to improve the foam-suppressing property and the cleaning power for lipid-protein complex stains in the presence of acidic stains, and it is easy to suppress the accumulation of stains and cleaning components on glass tableware during repeated cleaning in the presence of stains. m is preferably 0 to 4, more preferably 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, alkali metal ions are preferred, sodium ions and potassium ions are more preferred, and sodium ions are particularly preferred, from the viewpoints of foam suppression, improving the cleaning power for lipid-protein complex soils, and suppressing the accumulation of soils and cleaning components during repeated cleaning. 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.

[0015] The content of the (a1) component is preferably 0.1 to 10 mass%, more preferably 0.5 to 5 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, the cleaning power for lipid-protein complex stains in the presence of acidic stains is easily improved, and the accumulation of stains and cleaning components on glass tableware during repeated washing in the presence of stains is easily suppressed. When the content of the (a1) component is equal to or less than the above upper limit, the foam suppressing property is easily improved.

[0016] <(a2) component> The component (a2) is at least one member selected from the group consisting of alkyl or alkenyl sulfate esters having an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms and salts thereof (hereinafter also referred to as “component (a2-1)”), polyoxyalkylene alkyl or alkenyl ether sulfate esters having an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms and salts thereof (hereinafter also referred to as “component (a2-2)”), and internal olefin sulfonic acids having 16 to 24 carbon atoms and salts thereof (hereinafter also referred to as “component (a2-3)”).

[0017] The component (a2-1) is represented by the following formula (a2-1). R 2 -OS(=O)-OMc (a2-1) In the formula, R 1 represents an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms, and Mc is a counter ion.

[0018] In formula (a2-1), R 2 When the carbon number of R is 8 to 18, it is easy to improve the foam suppression property and the cleaning power for lipid and protein complex stains in the presence of acidic stains. 2 The number of carbon atoms is preferably 8 to 14, and more preferably 8 to 12. R 2 The alkyl group and the alkenyl group may each be straight-chain or branched.

[0019] In formula (a2-1), Mc is a counter ion. Examples of the counter ion include the same as Ma and Mb. Among them, from the viewpoint of the detergency for lipid-protein complex soil in the presence of acidic soil, an alkali metal ion is preferable, a sodium ion or a potassium ion is more preferable, and a sodium ion is particularly preferable. 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.

[0020] Examples of the component (a2-1) include sodium dodecyl sulfate and sodium decyl sulfate.

[0021] The component (a2-2) is represented, for example, by the following formula (a2-2). R 3 -O-(AO) n -S(=O)2-OMd (a2-2) In the formula, R 3 represents an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms, AO represents an oxyalkylene group, n represents the average number of repetitions of AO and is a number greater than 0 and not greater than 4, and Md represents a counter ion.

[0022] In formula (a2-2), R 3 When the carbon number of R is 8 to 18, it is easy to improve the cleaning power for lipid / protein complex stains in the presence of acidic stains while maintaining the foam suppressing property. 3 The number of carbon atoms is preferably 10 to 16, and more preferably 12 to 14. R 3 The alkyl group and the alkenyl group may each be straight-chain or branched.

[0023] In formula (a2-2), AO is an oxyalkylene group. Examples of the oxyalkylene group include the same as those mentioned above. In formula (a2-2), n represents the average number of repeats of AO and is a number greater than 0 and not greater than 4. When n is greater than 0 and not greater than 4, it is easy to improve the cleaning power for lipid / protein complex soils in the coexistence of acidic soils while maintaining the foam-suppressing property. n is preferably 1 to 4, and more preferably 2 to 4. (AO) n As for (PO) j / (EO) k PO is an oxypropylene group, j is a number of 0 or more and less than 4 indicating the average number of repetitions of PO, EO is an oxyethylene group, k is a number of 0 or more and 4 or less indicating the average number of repetitions of EO, and j+k is a number of 0 or more and 4 or less. [(PO) j / (PO) k ] indicates that there is no limitation on the order of PO and EO. If j is greater than 0, then (PO) j / (EO) k In the formula, PO and EO may be added randomly or in blocks, and the arrangement thereof is not important.

[0024] In formula (a2-2), Md is a counter ion. Examples of the counter ion include the same as Ma and Mb. Among them, from the viewpoints of foam suppression and detergency for lipid-protein complex soil in the presence of acidic soil, alkali metal ions are preferred, sodium ions and potassium ions are more preferred, and sodium ions are particularly preferred. When Md is a divalent or higher valent counter ion, Md is considered to be bonded to -O at a number obtained by multiplying Md by 1 / valence.

[0025] Examples of the (a2-2) component include polyoxyethylene (1) linear alkyl (C12) ether sulfate sodium salt, polyoxyethylene (2) linear alkyl (C12) ether sulfate sodium salt, polyoxyethylene (4) linear alkyl (C12) ether sulfate sodium salt, polyoxypropylene (0.4) polyoxyethylene (1.5) linear alkyl (C12) ether sulfate sodium salt, polyoxyethylene (1) linear alkyl (C12 / 14=7 Examples of such ether sulfate include polyoxyethylene (2) linear alkyl (C12 / 14=75 / 25; derived from natural fats and oils) ether sulfate sodium salt, polyoxyethylene (4) linear alkyl (C12 / 14=75 / 25; derived from natural fats and oils) ether sulfate sodium salt, and polyoxypropylene (0.4) polyoxyethylene (1.5) linear alkyl (C12 / 14=75 / 25; derived from natural fats and oils) ether sulfate sodium salt. Here, for example, "polyoxyethylene (1)" means that the average number of repeating oxyethylene groups is 1 (the average number of moles of ethylene oxide added is 1). "C12 / 14=75 / 25; derived from natural fats and oils" means a mixture of a compound having a linear alkyl group with 12 carbon atoms and a compound having a linear alkyl group with 14 carbon atoms (mixing ratio: 75 / 25 by mass), and the linear alkyl group is derived from natural fats and oils.

[0026] In the component (a2-3), an "internal olefin sulfonic acid" is an olefin sulfonic acid in which the carbon-carbon double bond is at the second or higher position (internal). Note that an olefin sulfonic acid in which the carbon-carbon double bond is at the first position (α-position) is called an α-olefin sulfonic acid. When the carbon number of the (a2-3) component is 16 to 24, it is easy to improve the cleaning power for lipid / protein complex stains in the coexistence of acidic stains while maintaining the foam-suppressing property. The carbon number of the (a2-3) component is preferably 16 to 20, and more preferably 16 to 18. Examples of the salt of internal olefin sulfonic acid include alkali metal salts (sodium salt, potassium salt, etc.), alkaline earth metal salts (calcium salt, magnesium salt, etc.), ammonium salts, and alkanolamine salts (monoethanolamine salt, diethanolamine salt, etc.). Examples of the component (a2-3) include the internal olefin sulfonate salts described in JP 2018-115329 A.

[0027] The component (a2) may be used alone or in combination of two or more types. Of the above, the component (a2) is preferably the component (a2-1) since it is more likely to improve the cleaning power for lipid-protein complex stains in the presence of acidic stains. The component (a2-1) may be used in combination with other components (a2).

[0028] The content of the (a2) component is preferably 0.1 to 10 mass%, more preferably 0.5 to 5 mass%, and even more preferably 3 to 5 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, the cleaning power for lipid-protein complex soils in the coexistence of acidic soils is easily improved. When the content of the (a2) component is equal to or less than the above upper limit, the foam suppressing property is easily improved.

[0029] The mass ratio of component (a1) / component (a2) is preferably 0.01 or more and 100 or less, more preferably 0.1 or more and 10 or less, from the viewpoint of the cleaning power for lipid-protein complex stains in the presence of acidic stains, and the accumulation of stains and cleaning components on glass tableware during repeated cleaning in the presence of stains.

[0030] <(b) Component> Component (b) is a chelating agent having a molecular weight of 800 or less. By using a chelating agent having a molecular weight of 800 or less, the cleaning power for lipid-protein complex stains in the presence of acidic stains is easily improved, and the accumulation of stains and cleaning components on glass tableware during repeated washing in the presence of stains is easily suppressed. The molecular weight of component (b) is preferably 100 to 800, more preferably 150 to 500.

[0031] Examples of the component (b) 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, 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 is preferred, with sodium citrate being particularly preferred. The component (b) may be used alone or in combination of two or more types.

[0032] The content of component (b) is preferably 1 to 20 mass%, more preferably 5 to 15 mass%, and even more preferably 10 to 15 mass%, based on the total mass of the detergent composition. When the content of component (b) is equal to or more than the lower limit, the cleaning power for lipid-protein complex stains in the presence of acidic stains is likely to be improved, and the accumulation of stains and cleaning components on glass tableware during repeated washing in the presence of stains is likely to be suppressed. When the content of component (b) is equal to or less than the upper limit, the foam suppressing property is likely to be improved.

[0033] <(c) component> The component (c) is at least one selected from the group consisting of silica and silicone compounds. By including the component (c), the detergent composition can maintain its foam-suppressing properties while improving its ability to inhibit the buildup of stains and cleaning components on glass tableware during repeated washing in the presence of stains. The (c) component may be made of silica, may be made of a silicone compound, or may be made of silica and a silicone compound. Examples of the (c) component 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 (c) 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 (c) component can be a commercially available product. For example, oil-type products include DOWSIL FS 1265 Fluid and DOWSIL SH200 Fluid 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 manufactured by Dow Chemical Co., Ltd.; self-emulsifying compound-type products include XIAMETER ACP-1266 Antifoam Compound and DOWSIL FS Antifoam 80 manufactured by Dow Chemical Co., Ltd.; and emulsion-type products include DOWSIL FS Antifoam 93 and XIAMETER AFE-1530 Antifoam Emulsion manufactured by Dow Chemical Co., Ltd.

[0035] From the viewpoint of foam-suppressing properties, component (c) is preferably a compound type, a self-emulsifying compound type, or an emulsion type. As component (c), those containing treated amorphous silica, dimethylsiloxane-treated silica, and 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 (c) may be used alone or in combination of two or more types.

[0036] The (c) component preferably contains 1 to 50% by mass of silica, more preferably 1 to 20% by mass, and even more preferably 1 to 10% by mass, based on the total mass of the (c) component. When the silica content is equal to or greater than the lower limit, the foam suppression property and cleaning power for rice grain stains are easily improved. When the silica content is equal to or less than the upper limit, the cleaning power for rice grain stains is easily improved.

[0037] The content of component (c) is preferably 0.01 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 component (c) is equal to or more than the lower limit, the foam suppression property is likely to be improved. When the content of component (c) is equal to or less than the upper limit, the accumulation of dirt and cleaning components on glass tableware during repeated washing in the presence of dirt is likely to be suppressed. The content of silica is preferably 0.0001 to 0.5 mass%, more preferably 0.0005 to 0.1 mass%, and particularly preferably 0.001 to 0.1 mass%, based on the total mass of the detergent composition. When the content of silica is equal to or more than the lower limit, the foam suppression property is likely to be improved. When the content of silica is equal to or less than the upper limit, the accumulation of dirt and cleaning components on glass tableware during repeated washing in the presence of dirt is likely to be suppressed.

[0038] In the detergent composition, the mass ratio represented by the sum of the components (a1) and (a2) to the component (c) (hereinafter also referred to as the "(a1+a2) / c ratio") is preferably 1 to 1000, more preferably 10 to 500, and particularly preferably 20 to 100. When the (a1+a2) / c ratio is equal to or greater than the above lower limit, accumulation of dirt and cleaning components on glass tableware during repeated washing in the presence of dirt is easily suppressed. When the (a1+a2) / c ratio is equal to or less than the above upper limit, foam suppression is easily improved.

[0039] <(d) component> Component (d) is a polyol.

[0040] The molecular weight of component (d) is preferably 4000 or less. When the molecular weight of component (d) is 4000 or less, it is easy to suppress the accumulation of dirt and cleaning components on glass tableware during repeated washing in the presence of dirt while maintaining the foam-suppressing properties. The molecular weight of component (d) is preferably 2000 or less, more preferably 1000 or less. The lower limit of the molecular weight of component (c) is not particularly limited, but is, for example, 60 or more.

[0041] Examples of the component (d) include propylene oxide adducts of trihydric to hexahydric alcohols, compounds represented by the following formula (d-2), compounds represented by the following formula (d-3), monosaccharides and derivatives thereof, and sugar alcohols. HO-(CH2CH2O) s -(CH2CH(CH3)O) t -H (d-2) R 6 -O-(CH2CH2O) p -(CH2CH(CH3)O) q -H (d-3) In the formula, s is 0 or more, t is 0 or more, s+t is 1 or more, and R 6 represents a linear or branched alkyl group having 1 to 4 carbon atoms or a linear or branched alkenyl group having 1 to 4 carbon atoms, p is 0 or more, q is 0 or more, and p+q is 1 or more.

[0042] Examples of the tri- to hexahydric alcohol in the propylene oxide adduct of a tri- to hexahydric alcohol include glycerin, polyglycerin, trimethylolpropane, pentaerythritol, and sorbitol. Examples of propylene oxide adducts of trihydric to hexahydric alcohols include triol-, tetraol-, pentaol-, or hexaol-type polypropylene glycols, etc. Among these, triol-type polypropylene glycols are preferred from the viewpoints of foam suppression and suppression of accumulation of stains and cleaning components on glass tableware during repeated washing in the presence of stains, and propylene oxide adducts of glycerin are more preferred, with the compound represented by the following formula (d-1) being particularly preferred.

[0043] [ka] In the formula, PO is an oxypropylene group, and a, b and c each independently represent the average repetition number of PO and are numbers from 10 to 350.

[0044] The weight average molecular weight of the propylene oxide adduct of a trihydric to hexahydric alcohol is preferably 200 or more, more preferably 250 or more, and is preferably 4000 or less, more preferably 2000 or less, and even more preferably 1000 or less. The above lower limit and the above upper limit can be appropriately combined. When the weight average molecular weight of the propylene oxide adduct is the above lower limit or more, it is easy to maintain the foam suppression property. When the weight average molecular weight of the propylene oxide adduct is the above upper limit or less, it is easy to suppress the accumulation of dirt and cleaning components on glass tableware during repeated washing in the presence of dirt. The weight average molecular weight of the propylene oxide adduct of trihydric to hexahydric alcohols is a value measured by gel permeation chromatography using polypropylene glycol (weight average molecular weights: 800, 1200, 2000, 4000) as a standard substance.

[0045] The propylene oxide adduct of the trihydric to hexahydric alcohol can be produced by addition polymerization of propylene oxide to the trihydric to hexahydric alcohol. In this case, the amount of propylene oxide to be added to the alcohol can be adjusted to produce a propylene oxide adduct having a desired weight average molecular weight.

[0046] In the formula (d-2), s is 0 or more, and preferably 0 to 3. t is 0 or more, and is preferably 1 to 3. s+t is 1 or more, and is preferably 1 to 6.

[0047] Examples of the compound represented by formula (d-2) include propylene glycol, dipropylene glycol, tripropylene glycol, ethylene glycol, diethylene glycol, and polyethylene glycol. The number average molecular weight of the polyethylene glycol is preferably 200 or more, more preferably 250 or more, and is preferably 4000 or less, more preferably 2000 or less, and even more preferably 1000 or less. The above lower limit and the above upper limit can be appropriately combined. When the number average molecular weight of the polyethylene glycol is the above lower limit or more, it is easy to maintain the foam suppression property. When the number average molecular weight of the polyethylene glycol is the above upper limit or less, it is easy to suppress the accumulation of dirt and cleaning components on glass tableware during repeated washing in the presence of dirt.

[0048] In formula (d-3), R 6 R is a linear or branched alkyl group having 1 to 4 carbon atoms or a linear or branched alkenyl group having 1 to 4 carbon atoms. 6 The number of carbon atoms is preferably 2 to 4, and more preferably 4. p is 0 or more, and preferably 0 to 3. q is 0 or more, and preferably 0 to 3. p+q is 1 or more, and preferably 1 to 5.

[0049] Examples of the compound represented by formula (d-3) include propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monopropyl ether, propylene glycol monopropyl ether, diethylene glycol monobutyl ether, and propylene glycol monobutyl ether.

[0050] Examples of monosaccharides include hexoses such as glucose and fructose; and pentoses such as ribose and xylulose. Examples of the derivatives of monosaccharides include ethers of the above-mentioned monosaccharides with alcohols having 1 to 5 carbon atoms. Examples of sugar alcohols include glycerin, sorbitol, erythritol, xylitol, and mannitol.

[0051] The component (d) may be used alone or in combination of two or more types. As component (d), from the viewpoints of foam-inhibiting properties and suppressing the accumulation of dirt and cleaning components on glass tableware during repeated washing in the presence of dirt, at least one selected from the group consisting of propylene oxide adducts of trihydric to hexahydric alcohols, propylene glycol, and polyethylene glycols having a number average molecular weight of 250 to 2000 is preferred, and propylene glycol is particularly preferred.

[0052] The content of component (d) is preferably 0.1 to 10 mass%, more preferably 0.5 to 7 mass%, based on the total mass of the detergent 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 cleaning power for lipid-protein complex soils in the coexistence of acidic soils is easily improved.

[0053] <Other ingredients> The dishwashing detergent composition of the present invention may contain any component that is usually contained in detergents for washing dishes, so long as it does not go against the purpose of the present invention. For example, substances that are usually used in dishwashing detergent compositions, such as surfactants other than the components (a1) and (a2), enzymes, stabilizers, thickeners, solvents, plant extracts, oil absorbents, dish protectants, colorants, hydrotropes (excluding the component (d)), antioxidants, pH adjusters, fragrances, and bleaches, may be used.

[0054] 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.

[0055] The enzyme is not particularly limited, and any of the enzymes generally used in dishwasher detergent compositions can be used. Examples include amylase, protease, lipase, cellulase, glucanase, etc. Among them, amylase and protease are preferred from the viewpoint of the cleaning power for complex soils. The content of the enzyme is preferably 0.001 to 2 mass%, more preferably 0.01 to 1 mass%, as an enzyme preparation, based on the total mass of the detergent composition. When the content of the enzyme is equal to or greater than the lower limit, the cleaning power against complex soils is easily improved. On the other hand, when the content of the enzyme exceeds the preferred upper limit, the effect of improving the cleaning power reaches a plateau and the cost becomes high.

[0056] 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.

[0057] Examples of hydrotropic agents include 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.

[0058] 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.

[0059] The detergent composition may be a liquid or a solid such as a powder or tablet. A liquid detergent composition is preferable because it is easy to suppress the accumulation of dirt and detergent components on glass tableware during repeated washing in the presence of dirt. Hereinafter, a liquid detergent composition is also referred to as a "liquid detergent composition".

[0060] 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.

[0061] 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.

[0062] 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.

[0063] <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), a portion of water, and, if necessary, one or more of the optional components other than the pH adjuster (such as component (d)), adjusting the pH to a predetermined value using a pH adjuster if necessary, and then mixing with the remaining water.

[0064] <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 the 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.

[0065] <Action and effect> The detergent composition described above contains components (a1), (a2), (b), (c) and (d), and therefore has excellent foam-suppressing properties and cleaning power for lipid-protein complex stains in the presence of acidic stains. In addition, it can suppress the accumulation of stains and cleaning components on glass tableware during repeated washing in the presence of stains. EXAMPLES

[0066] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following description.

[0067] <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 10, 12, and 14, "Kohacool L-40" manufactured by Toho Chemical Co., Ltd. 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), "Kohacool L-300" manufactured by Toho Chemical Co., Ltd. a1-3: In the formula (a1), AO is EO, m is 4, Ma and Mb are sodium ions, R 1is a mixture of sodium monoalkyl sulfosuccinate EO4 with carbon numbers 12, 14, and 16, "Kohacool L-400" manufactured by Toho Chemical Co., Ltd. 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, "Softanol MES-9" manufactured by Nippon Shokubai Co., Ltd.

[0068] [(a2) component] a2-1: Linear alkyl (C10) sulfate sodium salt (C10AS), "n-Decyl sodium sulfate" manufactured by Fluorochem Ltd. a2-2: Sodium polyoxyethylene alkyl ether sulfate (C12-14, EO=2) (AES), "Shinoline SPE-1250" manufactured by New Japan Chemical Co., Ltd. a2-3: Sodium internal olefin sulfonate (sodium internal olefin sulfonate synthesized by the method described in Production Example 1 of JP 2018-115329 A) (IOS).

[0069] [Component (a'): other surfactant] a'-1: Sodium linear alkylbenzene sulfonate (C10-14) (LAS), "Lipon LS-250" manufactured by Lion Specialty Chemicals Co., Ltd. a'-2: Sodium secondary alkane sulfonate (C14-17) (SAS), "HOSTAPUR SAS 30A" manufactured by Clariant Japan Co., Ltd. a'-3: Di-2-ethylhexyl sodium sulfosuccinate (DSS), "Repearl 870P" manufactured by Lion Specialty Chemicals Co., Ltd.

[0070] [(b) component] b-1: Trisodium citrate (Na citrate), manufactured by Fuso Chemical Co., Ltd. b-2: Trisodium methylglycine diacetate (MGDA), manufactured by BASF. b-3: Tetrasodium glutamic diacetate (GLDA), manufactured by Chelest. b-4: Sodium ethylenediaminetetraacetate (EDTA), manufactured by Tokyo Chemical Industry Co., Ltd.

[0071] [(c) component] c-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), "DOWSIL FS Antifoam 93" manufactured by Dow Chemical Japan Co., Ltd. c-2: Self-emulsifying compound type silicone composition (containing treated amorphous silica), "XIAMETER AFE-1266 Antifoam Compound" manufactured by Dow Chemical Japan, Ltd. c-3: Compound type silicone composition (containing dimethylsiloxane-treated silica), "XIAMETER AFE-1500 Antifoam Compound" manufactured by Dow Chemical Japan Co., Ltd. c-4: Self-emulsifying compound type silicone composition (reaction product of dimethylsiloxane / silica (content: 1.0-10.0%), containing octamethylcyclotetrasiloxane), "DOWSIL FS Antifoam 80" manufactured by Dow Chemical Japan Co., Ltd.

[0072] [(d) component] d-1: Propylene glycol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. d-2: Polyethylene glycol, number average molecular weight 1000, "PEG-1000" manufactured by Sanyo Chemical Industries, Ltd. d-3: Propylene oxide adduct of glycerin (PPG), triol type, weight average molecular weight 4000, "Sannyx GP-4000" manufactured by Sanyo Chemical Industries, Ltd.

[0073] [Optional ingredients] pH adjuster: Sodium hydroxide (48% Sodium Hydroxide, Kanto Chemical Co., Ltd.). pH adjuster: sulfuric acid (special reagent grade, Fujifilm Wako Pure Chemical Industries, Ltd.).

[0074] <Examples 1 to 34 and Comparative Examples 1 to 8> According to the compositions shown in Tables 1 to 5, 0.8 kg of each of the liquid detergent compositions of Examples 1 to 34 and Comparative Examples 1 to 8 was prepared by dissolving component (a1), component (a2), component (b), component (c), component (d), and a pH adjuster in water as a solvent. Specifically, water was added to a 1L beaker (diameter 12 cm) so that the total amount of water was 40% by mass of the entire composition. A stirrer (HEIDON FBL1200 Three-One Motor, manufactured by Shinto Scientific Co., Ltd.) was equipped with a four-blade paddle with a diameter of 7.5 cm, width of 1.5 cm, and angle of 45 degrees, and then, while stirring at a rotation speed of 400 to 900 rpm so as not to scatter the contents, components (b) and (c) were added while mixing, and then a pH adjuster (sodium hydroxide or sulfuric acid) was added to adjust the pH to 7. Then, components (a1), (a2), and (d) were added while stirring at a rotation speed of 650 rpm of the stirrer. After the addition was completed, the mixture was stirred for 5 minutes, and the remaining water was added so that the entire composition was 100% by mass, and the mixture was stirred for 1 minute at a rotation speed of 650 rpm of the stirrer 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) after adjusting the liquid detergent composition to 25° C. The measurement method was in accordance with JIS Z 8802:2011 "pH measurement method."

[0075] <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 and L3 courses 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.

[0076] [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.

[0077] [Cleaning power for complex stains] The detergency of lipid-protein complex soils in the presence of acidic soils was evaluated using the following procedure.

[0078] "Prepare for filth" The soil used for the evaluation was prepared according to the following procedure. Tomato juice stains: Tomato juice (Tomato juice, manufactured by Nippon Del Monte Co., Ltd.) was poured into each of six cups (manufactured by Toyo Sasaki Glass Co., Ltd.) and the entire cup was contaminated by tilting it. Dressing stains: Dressing (olive oil & onion dressing, manufactured by Kewpie Corporation) was applied to the entire surface of each of six medium-sized bowls (made of ceramic, radius 80 mm, height 45 mm). Egg stains: A large egg was heated in a frying pan over low heat to prepare a soft-boiled fried egg. The yolk of the fried egg was spread onto six spoons (stainless steel, length: 180 mm), six forks (stainless steel, length: 180 mm), and six small plates (ceramic, radius 60 mm, height 20 mm), and left for one hour. Complex soiling: 200g of instant curry (Otsuka Foods Co., Ltd., Bon Curry Gold Hot), one large egg, and 150g of rice (equivalent to Koshihikari rice, the rice to water ratio was the standard for the rice cooker, and cooked within 12 hours) were mixed. 30g of the resulting mixture was placed on six large plates (ceramic, radius 115mm, height 25mm) and the surfaces of the plates were uniformly contaminated. After that, the mixture was discarded leaving about 10 grains of rice, and the rice grains were crushed with a spoon and attached to the large plates.

[0079] "Evaluation of cleaning power" The prepared soiled dishes (6 cups, 6 spoons, 6 forks, 6 medium bowls, 6 small plates, and 6 large plates) were placed in the designated locations according to the instructions of the dishwasher, 8 g of the liquid detergent composition was added, and a cleaning treatment was performed using the L2 cycle. After the cleaning treatment, the spoons and forks were observed, and the cleaning power for lipid-protein complex soils in the presence of acidic soils was evaluated based on the following evaluation criteria. A rating of ○, ◎, ◎◎, or ◎◎◎ was deemed to be acceptable. (Evaluation Criteria) ◎◎◎◎: No dirt remaining on any of the spoons and forks. ◎◎◎: Of the total 12 spoons and forks, one or less spoons or forks had visible remaining dirt. ◎◎: Of the total of 12 spoons and forks, 2 or fewer spoons and forks were found to be dirty. ◎: Of a total of 12 spoons and forks, 3 or fewer spoons and forks were found to be dirty. Good: Of the total of 12 spoons and forks, 4 or fewer spoons and forks had visible residual dirt. ×: Of the total of 12 spoons and forks, 5 or more spoons and forks had visible residual dirt.

[0080] [Beer foam stability] A glass (upper diameter 63 mm, lower diameter 53 mm, height 100 mm) was loaded into the dishwasher at a designated location based on the instruction manual, and 6 g of a mixture of beef tallow / lard / butter / salad oil = 3 / 3 / 3 / 1 (mass ratio) and 8 g of a liquid detergent composition were added, and the process of performing a cleaning treatment using 3° dH hard water with the L2 course was repeated 10 times. Thereafter, beer was poured into the glass removed from the dishwasher so that it would foam to a thickness of 3 cm, and the disappearance of the foam was observed, and the stability of the beer foam was evaluated based on the following evaluation criteria. A rating of ○, ◎, ◎◎, or ◎◎◎ was deemed to be acceptable. It can be judged that the better the stability of the beer foam, the more the accumulation of dirt and cleaning components on the glass surface during repeated cleaning processes is suppressed. (Evaluation Criteria) ◎◎◎◎: The thickness of the foam did not change even after more than 7 minutes. ◎◎◎: The thickness of the foam after 5 minutes did not change, but the thickness of the foam after 7 minutes was reduced to half. ◎◎: The thickness of the foam after 3 minutes remained unchanged, but the thickness of the foam after 5 minutes was reduced to half. ◎: The thickness of the foam after 1 minute remained unchanged, but the thickness of the foam after 3 minutes was reduced to half. ○: The thickness of the foam was reduced to half after 1 minute. ×: All bubbles disappeared within 1 minute.

[0081] [Table 1]

[0082] [Table 2]

[0083] [Table 3]

[0084] [Table 4]

[0085] [Table 5]

[0086] The liquid detergent compositions of Examples 1 to 34 passed all the tests for foam suppression, cleaning power for lipid / protein complex soil in the coexistence of acidic soil, and beer foam stability. Comparative Examples 1 and 2 not containing the component (a1), and Comparative Example 3 not containing the component (a2) failed in the detergency for lipid / protein complex soiling in the coexistence of acidic soiling. Comparative Example 4, which did not contain the component (b), failed in terms of beer foam stability. Comparative Example 5, which did not contain the component (c), failed in terms of foam suppression. Comparative Examples 6 to 8, in which other surfactants were used instead of the component (a1), were unsatisfactory in terms of foam suppression and cleaning power for lipid / protein complex soils in the coexistence of acidic soils.

Claims

1. (a1) Components: At least one selected from the group consisting of compounds represented by the following formula (a1), (a2) Components: At least one selected from the group consisting of alkyl or alkenyl sulfate esters and salts thereof having an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms, polyoxyalkylene alkyl or alkenyl ether sulfate esters and salts thereof having an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms, and internal olefin sulfonic acid and salts thereof having 16 to 24 carbon atoms, (b) Components: Chelating agent with a molecular weight of 800 or less, (c) 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-.

2. (d) Component: The dishwasher detergent composition according to claim 1, further comprising a polyol.

3. The dishwasher detergent composition according to claim 1 or 2, wherein the mass ratio expressed as the sum of component (a1) and component (a2) / component (c) is 1 to 1000.

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