Dishwasher detergent composition

Abstract

To provide a dishwasher detergent composition that can achieve both low foaming and cleaning performance, which are in a trade-off relationship, regardless of the size of the dishwasher, and that can also suppress the adhesion and accumulation of tea stains on glass tableware and the glass surface of the dishwasher. [Solution] A dishwasher detergent composition comprising (A) component: an anionic surfactant and (B) component: polyethyleneimine (excluding those containing an oxyalkylene group), wherein the content of component (A) is 0.1 to 10% by mass of the total mass of the dishwasher detergent composition, and the content of component (B) is 0.01 to 1% by mass of the total mass of the dishwasher detergent composition.

Description

Technical Field

[0001] The present invention relates to a detergent composition for a dishwasher.

Background Art

[0002] In recent years, the number of single-person households has been increasing and is expected to reach about 40% in 2040. The movement to meet such needs has also been heating up in the dishwasher market, and dishwashers for a small number of people and single-person use have been launched by various companies. Dishwashers for a small number of people have many differences from conventional dishwashers for a large number of people, and new problems have arisen.

[0003] Major differences from conventional dishwashers include (1) reduction of water consumption, (2) increase in the range of detergent usage amounts, and (3) improvement in design by installing a glass surface. Regarding (1) above, from the perspective of water conservation, dishwashers with reduced water consumption have emerged. Regarding (2) above, a detergent composition for a dishwasher corresponding to the detergent usage amounts applicable to dishwashers of various sizes is desired. Regarding (3) above, most conventional dishwashers, both built-in type and tabletop type, do not have a glass window for viewing the washing process from the outside. However, in recent years, the number of dishwashers with a glass window has been increasing.

[0004] Regarding (1) and (2) above, when the detergent usage amount is large, there is a risk of an increase in the foam height inside the dishwasher cabinet, and when the detergent usage amount is small, there is a risk of a decrease in the dirt removal performance. Regarding (3) above, since the glass surface of the glass window of a dishwasher is usually not wiped inside after use, the accumulation of tea-colored stains due to repeated washing can be significantly visually recognized, which may damage the aesthetics. In addition, such accumulation is not good in terms of hygiene. The same applies to glass tableware.

[0005] Patent Document 1 discloses a dishwasher detergent excellent in low foaming property and oil detergency, which is a combination of an alkylamide amine and an anionic surfactant. Patent Document 2 discloses a dishwasher detergent that combines a surfactant, a chelating agent, and polylysine, and is excellent at preventing the accumulation of complex stains. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2015-10186 [Patent Document 2] Japanese Patent Publication No. 2020-97658 [Overview of the project] [Problems that the invention aims to solve]

[0007] However, these technologies do not sufficiently reduce foaming. Furthermore, none of them consider maintaining the aesthetic appearance of the dishwasher's glass surface. Furthermore, using cationic polymers to improve low-foaming properties can lead to problems such as the cationic polymer itself adhering to the glass surface, and then tannins, which are polyphenols, adhering to it, making it easier for tea stains to adhere and accumulate on the glass surface. Therefore, the present invention aims to provide a dishwasher detergent composition that can achieve both low foaming and cleaning performance, which are in a trade-off relationship, regardless of the size of the dishwasher, and furthermore, can suppress the adhesion and accumulation of tea stains on glass tableware and the glass surface of the dishwasher. [Means for solving the problem]

[0008] The present invention has the following aspects. <1> (A) Ingredients: Anionic surfactant and (B) A dishwasher detergent composition comprising: polyethyleneimine (excluding those containing oxyalkylene groups), The content of component (A) is 0.1 to 10% by mass relative to the total mass of the dishwasher detergent composition. The content of the component (B) is 0.01 to 1% by mass based on the total mass of the dishwasher detergent composition, the dishwasher detergent composition. <2> The dishwasher detergent composition according to <1>, wherein the component (A) contains at least one selected from the group consisting of an anionic surfactant represented by the following formula (a-1) and an anionic surfactant represented by the following formula (a-2).

Chemical formula

Chemical formula

[0009] The dishwasher detergent composition of the present invention provides a dishwasher detergent composition that can achieve both low foaming and cleaning performance, which are in a trade-off relationship, regardless of the size of the dishwasher, and can also suppress the adhesion and accumulation of tea stains on glass tableware and the glass surface of the dishwasher. [Modes for carrying out the invention]

[0010] ≪Dishwasher detergent composition≫ The dishwasher detergent composition of the present invention (hereinafter sometimes simply referred to as "detergent composition") is a composition containing components (A) and (B).

[0011] <(A) component> (A) Component is an anionic surfactant. By including component (A), cleaning power can be enhanced and the adhesion and accumulation of tea stains can be suppressed.

[0012] (A) Examples of components include N-acyl amino acids or their salts, monoalkyl sulfosuccinic acid or its salts, dialkyl sulfosuccinic acid or its salts, linear alkylbenzene sulfonic acid or its salts (LAS), secondary alkane sulfonic acid or its salts (SAS), α-olefin sulfonic acid or its salts (AOS), linear or branched alkyl sulfate esters or their salts (AS), polyoxyalkylene alkyl (or alkenyl) ether sulfate esters or their salts (AES), α-sulfo fatty acid esters or their salts (α-SFE), internal olefin sulfonic acid or its salts (IOS), hydroxyalkane sulfonic acid or its salts (HAS), higher fatty acids or their salts (soap), alkyl phosphate esters or their salts, polyoxyalkylene alkyl phosphate esters or their salts, polyoxyalkylene alkylphenyl phosphate esters or their salts, etc. Among these, N-acyl amino acids or their salts, monoalkyl sulfosuccinic acid or its salts, dialkyl sulfosuccinic acid or its salts, linear alkylbenzene sulfonic acid or its salts (LAS), and secondary alkane sulfonic acid or its salts (SAS) are preferred, and N-acyl amino acids or their salts, monoalkyl sulfosuccinic acid or its salts, and dialkyl sulfosuccinic acid or its salts are more preferred. Examples of salt forms of anionic surfactants include alkali metal salts such as sodium salts and potassium salts; alkaline earth metal salts such as magnesium salts and calcium salts; and alkanolamine salts such as monoethanolamine salt (monoethanolammonium salt), diethanolamine salt (diethanolammonium salt), and triethanolamine salt (triethanolammonium salt). Among these, alkali metal salts are preferred, sodium salts and potassium salts are more preferred, and sodium salts are even more preferred.

[0013] N-acyl amino acid surfactants are anionic surfactants in which the nitrogen atom of an amino acid forms an amide bond with a fatty acid. Here, the group derived from the fatty acid is also called the "acyl group." Examples of amino acids include α-amino acids and β-amino acids. Examples of N-acyl amino acids or their salts include those represented by the following formula (a-1).

[0014] [ka]

[0015] In formula (a-1), R a1 R is a linear or branched alkyl group having 6 to 20 carbon atoms. a2 R is a hydrogen atom, or a linear or branched alkyl group having 1 to 6 carbon atoms. a3 is a linear or branched alkyl group having 1 to 6 carbon atoms, which may have a hydrogen atom or a carboxyl group, and the carboxyl group is -CO2M a2 It may also form a salt represented by M a2 is a counterion, a is a number that is either 0 or 1, and M a1 This is a hydrogen atom or a counterion.

[0016] As the anionic surfactant represented by formula (a-1), it is more preferable to select one or more from the group consisting of N-acyl-α-amino acid anionic surfactants represented by the following formula (a-1-1) and N-acyl-β-amino acid anionic surfactants represented by formula (a-1-2).

[0017] [ka]

[0018] In formula (a-1-1), R a1 , R a2 , R a3 M a2 and M a1 The same applies as described above.

[0019] [ka]

[0020] (a-1-2) Medium, R a1 , R a2 , R a3 M a2 and Ma1 The same applies as described above.

[0021] Examples of monoalkyl sulfosuccinic acid or its salts, and dialkyl sulfosuccinic acid or its salts include those represented by the following formula (a-2).

[0022] [ka]

[0023] In formula (a-2), R c11 is a linear or branched alkyl group having 6 to 18 carbon atoms, or a linear or branched alkenyl group having 6 to 18 carbon atoms, and X is a single bond or -O-(AO) t - is an alkylene oxy group with 2 to 4 carbon atoms, t is an integer from 0 to 10 indicating the average number of repeats, and M c1 is a hydrogen atom or counterion, and Y is -OM c11 or -(OA) r -OR c12 It is a group represented by M c11 is a hydrogen atom or counterion, OA is an oxyalkylene group having 2 to 4 carbon atoms, r is an integer from 0 to 10 indicating the average number of repeats of OA, and R c12 This is a linear or branched alkyl group having 6 to 18 carbon atoms, or a linear or branched alkenyl group having 6 to 18 carbon atoms.

[0024] As an anionic surfactant represented by formula (a-2), sulfosuccinic acid or a salt thereof represented by the following formula (a-2-1) or formula (a-2-2) is more preferred.

[0025] [ka]

[0026] In formula (a-2-1), R c11 , AO, t, M c1 and M c11 The same applies as described above.

[0027] [ka]

[0028] In formula (a-2-2), R c11 , AO, t, OA, r, R c12 and M c1 The same applies as described above.

[0029] In formula (a-1), R a1 A linear alkyl group having 6 to 18 carbon atoms is preferred, and a linear alkyl group having 7 to 17 carbon atoms is more preferred. R a2 Preferably, the group is a hydrogen atom or a linear alkyl group having 1 to 6 carbon atoms; more preferably, a hydrogen atom, a methyl group, an ethyl group, or a propyl group; and even more preferably, a hydrogen atom or a methyl group. R a3 The preferred group is a linear alkyl group having 1 to 6 carbon atoms, which may have a hydrogen atom or a carboxyl group; more preferably a hydrogen atom, a carboxymethyl group, or a 2-carboxyethyl group; and even more preferably a hydrogen atom or a 2-carboxyethyl group. The carboxyl group is -CO2M a2 It may form a salt represented by . M a1 and M a2 Examples of suitable materials include hydrogen ions and materials that can form water-soluble salts. Among these, materials that can form water-soluble salts are preferred. Examples of materials that can form water-soluble salts include alkali metal ions such as sodium ions and potassium ions; alkaline earth metal ions such as magnesium ions and calcium ions; ammonium ions; and alkanol ammonium ions such as monoethanolammonium ions (monoethanolammonium salt), diethanolammonium ions (diethanolammonium salt), and triethanolammonium ions (triethanolammonium salt). Among these, alkali metal ions are preferred from the viewpoint of preventing re-adhesion, sodium ions and potassium ions are more preferred, and sodium ions are particularly preferred. Ma1 and M a2 The counterions may be of the same type or different types, but counterions of the same type are preferred. Note M a1 and M a2 If the counterion is divalent or greater, M a1 and M a2 This is the number obtained by multiplying 1 by the valency, and represents a monovalent anion (-CO2). - It is assumed to be connected to ). For example, M a1 If it is a magnesium ion, M a1 The number is 1 / 2.

[0030] From the viewpoint of cleansing power, fatty acids that form an amide bond with the amino group of an amino acid are preferably derived from saturated or unsaturated linear or branched fatty acids having 4 to 30 carbon atoms, more preferably from saturated or unsaturated linear or branched fatty acids having 6 to 26 carbon atoms, and even more preferably from saturated or unsaturated linear or branched fatty acids having 8 to 24 carbon atoms. Examples of such fatty acids include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and oleic acid. Among these, from the viewpoint of low foaming and storage stability, one or more selected from lauric acid, myristic acid, palmitic acid, and oleic acid are preferred, with lauric acid being more preferred. Furthermore, the fatty acid-derived group (acyl group) in the N-acyl amino acid may be derived from a mixture of the above fatty acids, for example, obtained from coconut oil, palm kernel oil, etc. Among these, those obtained from coconut oil fatty acids or palm kernel fatty acids are preferred, and those obtained from coconut oil fatty acids are more preferred.

[0031] The amino acid portion of the N-acyl amino acid or its salt is preferably a neutral amino acid selected from glycine, alanine, and methylalanine, and an acidic amino acid selected from glutamic acid and aspartic acid, from the viewpoint of low foaming properties and cleaning power, with glycine, methylalanine, and glutamic acid being more preferred. Component (A) is preferably N-acylglycine, N-acylmethylalanine, or N-acylglutamic acid, with N-acylglutamic acid being more preferred. In these components (A), the carboxyl group is counterion M a1 and M a2 It is even more preferable that a salt is formed with it.

[0032] The above N-acyl amino acids or their salts may be used individually or in combination of two or more. Among these, from the viewpoint of low foaming and cleaning power, one or more selected from N-lauroyl glutamic acid, N-myristoyl glutamic acid, N-cocoyl glutamic acid, N-palm fatty acid glutamic acid, N-lauroyl aspartic acid, N-cocoyl glycine, N-cocoyl alanine, N-lauroyl alanine, N-lauroyl methyl alanine and their salts are preferred, one or more selected from N-cocoyl glutamic acid, N-cocoyl glycine, N-lauroyl methyl alanine and their salts are more preferred, and one or more selected from N-cocoyl glutamic acid and its salts are even more preferred.

[0033] Examples of salts of the above N-acyl amino acids or their salts include, from the viewpoint of low foaming properties, alkali metal salts such as sodium and potassium; alkaline earth metal salts such as calcium and magnesium; other inorganic salts such as aluminum and zinc; ammonium salts; quaternary ammonium salts derived from organic amines such as monoethanolamine, diethanolamine, triethanolamine, AMP (2-amino-2-methyl-1-propanol), and 2-amino-2-hydroxymethyl-1,3-propanediol; and other organic salts such as quaternary ammonium salts derived from basic amino acids such as arginine, lysine, histidine, and ornithine. From the viewpoint of availability, the salt of the N-acyl amino acid or its salt is preferably one or more salts selected from alkali metal salts, triethanolammonium salt (quaternary ammonium salt of protonated triethanolamine), and quaternary ammonium salt of protonated arginine (hereinafter also referred to as arginine salt), more preferably one or more salts selected from sodium salt, potassium salt, and triethanolammonium salt, even more preferably one or more salts selected from sodium salt and potassium salt, and even more preferably sodium salt.

[0034] Furthermore, when N-acyl amino acids are included, they are neutralized with a base before use. Examples of bases for neutralization include sodium hydroxide, potassium hydroxide, monoethanolamine, triethanolamine, diethanolamine, ammonia, AMP (2-amino-2-methyl-1-propanol), 2-amino-2-hydroxymethyl-1,3-propanediol, lysine, arginine, histidine, sodium acetate, potassium acetate, etc. From the viewpoint of low foaming properties and ease of availability, bases selected from sodium hydroxide, potassium hydroxide, arginine, and triethanolamine are preferred to form sodium salts, potassium salts, arginine salts, and triethanolammonium salts, and one or two bases selected from sodium hydroxide and potassium hydroxide are more preferred. In addition, various general bases such as sodium hydroxide, potassium hydroxide, triethanolamine, ammonia, lysine, arginine, and histidine may be used as needed to ensure that the pH of the detergent composition ultimately reaches the desired value. Furthermore, in any case, various common acids such as hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, citric acid, malic acid, lactic acid, fumaric acid, and succinic acid may be added to adjust the pH of the detergent composition. These (A) components may be a single type or a combination of two or more types.

[0035] In formula (a-2), R c11 Preferably, the alkyl group is a linear or branched alkyl group having 6 to 18 carbon atoms, more preferably a cocoyl group, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, or octyldecyl group, and even more preferably an octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, or octyldecyl group. The alkylene group of the alkylene oxy group is preferably an alkylene group having 2 or 3 carbon atoms, more preferably an ethylene group or a propylene group, and even more preferably an ethylene group. For t, values ​​from 1 to 9 are preferred, values ​​from 2 to 9 are more preferred from the viewpoint of low foaming, and values ​​from 3 to 8 are even more preferred from the viewpoint of balancing low foaming and cleaning power. M c1 As for M a1Examples similar to the counterions mentioned earlier can be cited. M c11 As for M a1 Examples similar to the counterions mentioned earlier can be cited. Examples of alkylene groups in oxyalkylene groups are the same as those listed for alkylene oxy groups. For r, values ​​from 1 to 9 are preferred, values ​​from 2 to 9 are more preferred from the viewpoint of low foaming, and values ​​from 3 to 8 are even more preferred from the viewpoint of balancing low foaming and cleaning power. R c12 For example, R c11 The same items mentioned above can be cited. These (A) components may be a single type or a combination of two or more types.

[0036] (A) The content of component (A) is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, and even more preferably 0.5 to 2% by mass, based on the total mass of the detergent composition. If the content of component (A) is above the lower limit, sufficient cleaning power can be obtained from component (A), making it easier to suppress the adhesion and accumulation of tea stains. If the content of component (A) is below the upper limit, foaming by component (A) can be easily suppressed, making it easier to improve low foaming properties.

[0037] <(B) component> Component (B) is polyethyleneimine (excluding those containing oxyalkylene groups). By containing component (B), the detergent composition can enhance low foaming properties and suppress the adhesion and accumulation of tea stains.

[0038] Polyethyleneimines are polymers obtained by polymerizing ethyleneimine. Typically, some of the nitrogen atoms in the main chain act as branching points, forming a branched or network structure, and containing one or more primary, secondary, or tertiary amino groups within that structure. The amino groups in the polyethyleneimine backbone are primary, secondary, or tertiary. The polyethyleneimine backbone can have a linear, branched, dendritic, or comb-like structure. The weight-average molecular weight of polyethyleneimine is preferably 200 to 3,000,000 g / mol, more preferably 250 to 2,500,000 g / mol, and even more preferably 300 to 2,000,000 g / mol. If the weight-average molecular weight of polyethyleneimine is above the lower limit, it is easier to neutralize the anionic properties of component (A) and improve low foaming properties. If the weight-average molecular weight of polyethyleneimine is below the upper limit, it is easier to maintain high cleaning power without excessively reducing the cleaning power of component (A). In addition, it is easier to prevent the adhesion and accumulation of dirt due to component (B) adhering to the glass surface alone.

[0039] (B) The amino groups in the main chain of component (B) are either primary, secondary, or tertiary, and the mixture contains one or more primary, secondary, or tertiary amino groups. The combination of primary, secondary, and tertiary amine substituents can be in any ratio, for example, about 1:1:1 to about 2:2:1, and branched along the main chain or branched chain segments every 3 to 3.5 nitrogen atoms. The main chain and branched chains consist of multiple ethylene groups and multiple primary, secondary, or tertiary amino groups bonded to them.

[0040] Examples of polyethyleneimines include compounds represented by the following formula (b). NH2-CH2CH2-〔N(R b1 )-CH2CH2〕 n1 -NH2···(b) In equation (b), n1 is a number that is 0 or greater than or equal to 1 on average. b1 is a hydrogen atom or -CH2CH2-[N(R b1 )-CH2CH2〕 n1 It is -NH2. The multiple n1s in equation (b) may be the same or different. The polyethyleneimines of the present invention also include modified polyethyleneimines in which the hydrogen atoms of the primary, secondary, and tertiary amino groups in formula (b) are substituted with modifying groups. The modifying groups do not contain oxyalkylene groups and include, for example, alkyl groups, hydroxyalkyl groups, alkylcarbonyl groups, alkylaminocarbonyl groups, alkyloxycarbonyl groups, and the like. In formula (b), n1 is a number of 0 or more on average, and is preferably 1 or more from the viewpoint of increasing the reaction sites with component (A) and improving low foaming properties. The average value of the total number of n1s is preferably 4 to 70,000 on average, more preferably 5 to 60,000, and even more preferably 6 to 50,000. If the average value of the total number of n1s is above the lower limit, it is easier to neutralize the anionic properties of component (A) and improve low foaming properties. If the average value of the total number of n1s is below the upper limit, it is easier to maintain high cleaning power without excessively reducing the cleaning power of component (A). In addition, it is easier to prevent the adhesion and accumulation of dirt due to component (B) adhering to the glass surface alone.

[0041] Examples of polyethyleneimines or their main chains include compounds represented by the following formulas (b1) to (b3). In formulas (b1) and (b2), the wavy lines indicate the bonding position with adjacent groups. In formula (b3), the terminal primary amino group may bond with an adjacent group to form a tertiary amino group. The main chain of polyethyleneimine, represented by formula (b1), is linear and consists of multiple primary amino groups, multiple secondary amino groups, and multiple ethylene groups. The main chain of polyethyleneimine represented by formula (b2) is branched and consists of multiple primary amino groups, multiple secondary amino groups, multiple tertiary amino groups, and multiple ethylene groups. The main chain of polyethyleneimine, represented by formula (b3), is dendritic and consists of multiple primary amino groups, multiple tertiary amino groups, and multiple ethylene groups.

[0042] [ka]

[0043] [ka]

[0044] [ka]

[0045] The weight-average molecular weight of component (B) is preferably 200 to 3,000,000, more preferably 250 to 2,500,000, and even more preferably 300 to 2,000,000. If the weight-average molecular weight of polyethyleneimine is above the lower limit, it is easier to neutralize the anionic properties of component (A) and improve low foaming properties. If the weight-average molecular weight of polyethyleneimine is below the upper limit, it is easier to maintain high cleaning power without excessively reducing the cleaning power of component (A). In addition, it is easier to prevent dirt from adhering to and accumulating on the glass surface by component (B) alone. (B) The weight-average molecular weight of component (B) was determined by gel permeation chromatography (GPC) using polyethylene glycol as the standard substance.

[0046] Component (B) may be a modified polyethyleneimine. That is, component (B) may be a modified polyethyleneimine. (B) Modified polyethyleneimine is preferred as component (B) from the viewpoint of further suppressing the adhesion of oil stains, tea stains, and limescale stains to the object to be cleaned, and further enhancing the cleaning power against these stains.

[0047] Modified polyethyleneimines are those obtained by the reaction of at least some of the primary or secondary amino groups in polyethyleneimine with reactive groups of other compounds or other polymers. Examples of reactive groups include isocyanate groups, anhydride groups, alkyl halides, and alkylcarbonyl halides. Examples of modified polyethyleneimines include amide derivatives of polyethyleneimine, alkyl polyethyleneimines, quaternary polyethyleneimines, and polyethyleneimines with hydroxyl groups substituted at the ends. Furthermore, as modified polyethyleneimines, for example, those described in Japanese Patent Publication No. 60-221088, Japanese Patent Publication No. 59-198190, Japanese Patent Publication No. 62-271791, Japanese Patent Publication No. 58-120879, Japanese Patent Publication No. 60-135585, Japanese Patent Publication No. 60-78906, U.S. Patent No. 3,642,572, U.S. Patent No. 4,144,123, U.S. Patent No. 4,371,674, etc., can be used.

[0048] Commercially available polyethyleneimines can be used. Examples of commercially available polyethyleneimines include BASF's product names "Lupasol FG," "Lupasol G20," "Lupasol G35," "Lupasol G100," "Lupasol HF," "Lupasol PS," "Lupasol SK," "Lupasol SKA," "Lupasol PN 50," and "Lupasol PN 60"; and Nippon Shokubai Co., Ltd.'s product names "Epomin SP-003," "Epomin SP-006," "Epomin SP-012," "Epomin SP-018," "Epomin SP-200," and "Epomin HM-2000." Of these, "Lupasol SK," "Lupasol SKA," "Lupasol PN 50," and "Lupasol PN 60" are commercially available modified polyethyleneimine products.

[0049] (B) As for component (B), from the viewpoint of suppressing the adhesion of oil stains, tea stains, and limescale stains to the object to be cleaned, and enhancing the cleaning power against these stains, BASF products named "Lupasol G100", "Lupasol HF", "Lupasol PS", and "Lupasol SK" are preferred, BASF products named "Lupasol PS" and "Lupasol SK" are more preferred, and BASF product named "Lupasol SK" is even more preferred. (B) Component may be used alone or in combination of two or more as appropriate.

[0050] The content of component (B) is preferably 0.01 to 1% by mass, more preferably 0.05 to 0.5% by mass, and even more preferably 0.1 to 0.3% by mass, relative to the total mass of the detergent composition. If the content of component (B) is above the lower limit, the cationic nature of component (B) easily cancels out the anionic nature of component (A), thus making it easier to improve low foaming properties. If the content of component (B) is below the upper limit, the cationic component (B) forms a complex with the anionic component (A), which adheres to the glass surface, thus making it easier to suppress the adhesion and accumulation of tea stains.

[0051] The mass ratio of component (B) to component (A) (hereinafter also referred to as the B / A ratio) is 0.001 to 10, preferably 0.01 to 2.5, and more preferably 0.05 to 0.6. If the B / A ratio is above the lower limit, the effect of component (B) in counteracting the anionic properties of component (A) can be sufficiently obtained, making it easier to improve low foaming properties. In addition, a sufficient complex of component (A) and component (B) can be formed, making it easier to suppress the adhesion and accumulation of tea stains due to only component (B) adhering to the glass surface. If the B / A ratio is below the upper limit, the solubility of component (A) can be increased, making it easier to improve the cleaning power of component (A). The high cleaning power of component (A) makes it easier to remove tea stains, making it easier to suppress the adhesion and accumulation of tea stains on the glass surface.

[0052] <Other ingredients> The cleaning agent composition may contain other components (optional components) besides components (A) and (B). Any optional component can be used in a detergent composition. Examples include chelating agents (hereinafter also referred to as component (C)), other surfactants (hereinafter also referred to as "optional surfactants"), enzymes, preservatives, inorganic builders, hydrotropes, polymer compounds, pH adjusters, solvents, fragrances, dyes, thickeners, disinfectants, antibacterial agents, antioxidants, etc.

[0053] The cleaning agent composition may contain a chelating agent as component (C). By including component (C), metal ions in tap water are chelated, suppressing the adhesion and accumulation of tea stains derived from tannins, which are polyphenols. Component (C) may be either a low molecular weight chelating agent with a molecular weight of 800 or less, or a high molecular weight chelating agent with a weight-average molecular weight of 800 or more. In this specification, the molecular weight of low molecular weight chelating agents can be measured by mass spectrometry, and the weight-average molecular weight of high molecular weight chelating agents can be calculated by a standard polystyrene equivalent method using gel permeation chromatography (GPC).

[0054] Examples of low molecular weight chelating agents include one or more selected from the group consisting of aminocarboxylic acid-based chelating agents and hydroxycarboxylic acid-based chelating agents.

[0055] Examples of aminocarboxylic acid-based chelating agents include aminocarboxylic acids or their salts, such as methylglycine diacetic acid or its salt, glutamate diacetic acid or its salt, nitrilotriacetic acid or its salt, ethylenediaminetetraacetic acid or its salt, diethylenetriaminepentaacetic acid or its salt, β-alanine diacetic acid or its salt, L-aspartate diacetic acid or its salt, iminodisuccinic acid or its salt, ethylenediaminedisuccinic acid or its salt (however, those having a hydroxyl group, an amino group, and a carboxyl group are classified as hydroxyaminocarboxylic acids); and hydroxyaminocarboxylic acids or their salts, such as serine diacetic acid or its salt, hydroxyiminodisuccinic acid or its salt, hydroxyethylethylenediaminetriacetic acid or its salt, and dihydroxyethylglycine or its salt.

[0056] Examples of hydroxycarboxylic acid chelating agents (excluding those that fall under the category of aminocarboxylic acid chelating agents) include lactic acid or its salts, malic acid or its salts, citric acid or its salts, tartaric acid or its salts, glycol or its salts, gluconic acid or its salts, etc.

[0057] Among these (C) components, citric acid or its salt, methylglycine diacetic acid or its salt, glutamate diacetic acid or its salt, ethylenediaminetetraacetic acid or its salt, hydroxyiminodisuccinic acid or its salt are preferred from the viewpoint of improving liquid stability at low temperatures.

[0058] Examples of polymer chelating agents include those having a carboxyl group or a salt thereof, a sulfo group or a salt thereof, or a phosphate group or a salt thereof as an anionic group. Among these, polycarboxylic acid polymers or salts thereof having a carboxyl group or a salt thereof are preferred. Examples of polycarboxylic acid polymers or salts thereof include polyacrylic acid or salts thereof, copolymers of acrylic acid and sulfonic acid monomers or salts thereof, and copolymers of maleic acid and acrylic acid or salts thereof. Graft polymers of these polymers with polyalkylene glycol or salts thereof can also be suitably used.

[0059] The acid value of the polymer chelating agent is preferably 300 to 1000 mg KOH / g, more preferably 450 to 900 mg KOH / g, and even more preferably 650 to 800 mg KOH / g. If the acid value of the polymer chelating agent is above the lower limit, it is easier to improve low foaming properties. If the acid value of the polymer chelating agent is below the upper limit, it is easier to maintain the pH near neutral and improve the stability of the solution. In this specification, the acid value can be measured in accordance with the neutralization titration method described in JIS K0070-1992.

[0060] (C) Examples of salts constituting component (C) include alkali metal salts such as sodium salts and potassium salts; alkanolamine salts such as monoethanolammonium salt (quaternary ammonium salt derived from monoethanolamine), diethanolammonium salt (quaternary ammonium salt derived from diethanolamine), and triethanolammonium salt (quaternary ammonium salt derived from triethanolamine); and ammonium salts. (C) Component may be used alone or in combination of two or more types.

[0061] The content of component (C) is preferably 1 to 60% by mass, more preferably 5 to 50% by mass, and even more preferably 8 to 30% by mass, based on the total mass of the detergent composition. If the content of component (C) is above the lower limit, it is easier to chelate metal ions in tap water, thus increasing the cleaning power of component (A). If the content of component (C) is below the upper limit, component (C) is easier to dissolve, thus increasing the low-foaming properties.

[0062] The mass ratio of component (C) to component (A) (hereinafter also referred to as the C / A ratio) is 0.5 to 35, preferably 1 to 30, and more preferably 3 to 26. If the C / A ratio is above the lower limit, it is easier to increase the cleaning power of component (A). If the C / A ratio is below the upper limit, it is easier to increase the low-foaming properties.

[0063] The detergent composition may contain, as an optional surfactant, cationic surfactants, nonionic surfactants, etc. Examples of optional surfactants include cationic surfactants and nonionic surfactants. Examples of cationic surfactants include didecyldimethylammonium chloride, didecyldimethylammonium methosulfate, dimethyldistearylammonium chloride, dimethyldioctylammonium chloride, di(2-hydroxyethyl)distearylammonium chloride, ditallow alkyldimethylammonium chloride, dimethyldi(2-stearoyloxyethyl)ammonium chloride, di(2-oleoyloxyethyl)dimethylammonium chloride, dimethyldi(2-palmitoyloxyethyl)ammonium methosulfate, dimethyldi(3-stearoyloxyisopropyl)ammonium chloride, dimethyldi(2-oleoyloxyisopropyl)ammonium chloride, dimethyldi(4-oleoyloxybutyl)ammonium chloride, N-(2-hydroxyethyl)-N-methyl-N,N-di(2-stearoyloxyethyl)ammonium methosulfate, and N-methyl-N,N,N-tri(2-stearoyloxyethyl)methosulfate. The number of carbon atoms in the "tallow alkyl" group is 14 to 18. Cationic surfactants may be used individually or in appropriate combinations of two or more types.

[0064] Examples of nonionic surfactants include polyoxyalkylene-type nonionic surfactants, Garbet alcohol-type nonionic surfactants, alkylphenols, alkylene oxide adducts of fatty acids having 8 to 22 carbon atoms or amines having 8 to 22 carbon atoms, polyoxyethylene polyoxypropylene block copolymers, fatty acid alkanolamides, polyhydric alcohol fatty acid esters or their alkylene oxide adducts, alkylene oxide adducts of hydrogenated castor oil, sugar fatty acid esters, N-alkyl polyhydroxy fatty acid amides, alkyl glycosides, and the like. Nonionic surfactants may be used individually or in combination of two or more types as appropriate.

[0065] The content of optional surfactants is preferably 3% by mass or less, more preferably 1% by mass or less, and even more preferably substantially absent, based on the total mass of the detergent composition. "Substantially absent" means less than 0.1% by mass, based on the total mass of the detergent composition.

[0066] The total amount of all surfactants contained in the detergent composition (hereinafter also referred to as "total surfactant amount") is preferably 0.3 to 15% by mass, more preferably 0.5 to 10% by mass, and even more preferably 1 to 5% by mass, relative to the total mass of the detergent composition. If the total surfactant amount is above the lower limit, the detergent composition can obtain sufficient cleaning power. If the total surfactant amount is below the upper limit, foaming inside the dishwasher can be suppressed without reducing the cleaning power.

[0067] The detergent composition contains an enzyme (component (D)), which enhances its cleaning power against complex stains including protein and oil stains, suppresses the mixing of complex stains and tea stains and prevents them from adhering to and accumulating on the glass surface of the dishwasher, and shortens the washing time.

[0068] (D) Examples of components include amylase, protease, mannanase, cellulase, and lipase. Among these, protease and lipase are preferred from the viewpoint of suppressing the adhesion and accumulation of protein and oil stains on the glass surface of the dishwasher, and a combination of protease and lipase is more preferred because they contribute to both protein and oil stains. Component (D) may be used alone or in combination of two or more types.

[0069] The content of component (D) is preferably 720 to 3000 ppm by mass, more preferably 850 to 2400 ppm by mass, and even more preferably 1110 to 1650 ppm by mass, based on the total mass of the detergent composition in terms of protein content. If the content of component (D) is above the lower limit above, the cleaning power against complex stains including protein and oil stains is enhanced, preventing complex stains and tea stains from mixing and adhering to and accumulating on the glass surface of the dishwasher, and shortening the washing time. If the content of component (D) is below the upper limit above, the amount of enzyme added does not need to be increased, thus reducing manufacturing costs, and preventing component (D) from remaining undissolved and precipitation, thus preventing a decrease in cleaning power.

[0070] ≪Method for quantifying enzymes (protein equivalent)≫ Using the Bio-Rad DC Protein Assay Kit, ovalbumin (the protein that forms egg white) is used as the standard protein. The buffer is 0.1N NaOH. Prepare solution A' by adding 20 μL of reagent S (surfactant solution) to 1 mL of reagent A (alkaline copper tartaric acid). Weigh 200 μL of the cleaning agent composition into a 2.0 mL microtube. Add 100 μL of solution A' and 800 μL of reagent B (forin reagent diluent) and mix well. After standing at room temperature, measure the absorbance at a measurement wavelength of 750 nm within 1 hour (1 cm quartz cell, slit width 0.5 mm). Perform the same procedure for ovalbumin solutions of known concentration and create a calibration curve. Use the absorbance of the measured samples to determine the protein amount from the calibration curve, and use this as the protein equivalent value of the enzyme. Furthermore, determine the concentration in the cleaning agent composition using the following formula. Protein equivalent value (mass %) = Protein amount (g) / 2.0 × 100

[0071] The content of component (D) as an enzyme preparation (preparation content) is preferably 0 to 1% by mass, more preferably 0.1 to 0.7% by mass, and even more preferably 0.2 to 0.5% by mass, relative to the total mass of the detergent composition. If the preparation content of component (D) is above the lower limit, the cleaning power against complex stains including protein and oil stains is enhanced, preventing complex stains and tea stains from mixing and adhering to and accumulating on the glass surface of the dishwasher, and shortening the washing time. If the preparation content of component (D) is below the upper limit, the amount of enzyme not added is not increased, thus reducing manufacturing costs, and preventing component (D) from remaining undissolved and precipitation, thus preventing a decrease in cleaning power.

[0072] If component (D) contains amylase, the amount of amylase is preferably such that the amylase activity measured by the measurement method described below is 0.44 to 1.25 U, and more preferably 0.63 to 1.00 U. If the amylase activity is above the lower limit, it enhances the cleaning power against complex stains including starch, protein, and oil stains, suppresses the mixing of complex stains and tea stains and their adhesion and accumulation on the glass surface of the dishwasher, and shortens the washing time. If the amylase activity is below the upper limit, it is not necessary to add more enzyme than required, which reduces manufacturing costs and prevents component (D) from remaining undissolved and precipitating, thus preventing a decrease in cleaning power.

[0073] If component (D) contains amylase, the ratio of the content of component (D) (calculated in terms of protein amount) to the amylase activity (U) (D / amylase activity ratio) is preferably 0.15 to 0.21, and more preferably 0.16 to 0.19. If the D / amylase activity ratio is above the lower limit, there is no need to add more enzyme than necessary, which reduces manufacturing costs and prevents component (D) from remaining undissolved and precipitation, thus preventing a decrease in cleaning power. If the D / amylase activity ratio is below the upper limit, it enhances cleaning power against complex stains including starch, protein, and oil stains, suppresses the mixing of complex stains and tea stains and prevents them from adhering to and accumulating on the glass surface of the dishwasher, and shortens the washing time.

[0074] If component (D) contains protease, the amount of protease is preferably such that the protease activity measured by the measurement method described later is 0.18 to 0.45 U, and more preferably 0.24 to 0.37 U. If the protease activity is above the lower limit, the cleaning power against complex stains including protein and oil stains is further enhanced, preventing the complex stains and tea stains from mixing and adhering to and accumulating on the glass surface of the dishwasher, and shortening the washing time. If the protease activity is below the upper limit, the amount of enzyme added does not need to be increased, thus reducing manufacturing costs, and preventing component (D) from remaining undissolved and precipitation, thus preventing a decrease in cleaning power.

[0075] If component (D) contains protease, the ratio of the content of component (D) (calculated in terms of protein amount) to the protease activity (U) (D / protease activity ratio) is preferably 0.43 to 0.50, and more preferably 0.44 to 0.47. If the D / protease activity ratio is above the lower limit, there is no need to add more enzyme than necessary, which reduces manufacturing costs and prevents component (D) from remaining undissolved and precipitation, thus preventing a decrease in cleaning power. If the D / protease activity ratio is below the upper limit, the cleaning power against complex stains including protein and oil stains is further enhanced, preventing complex stains and tea stains from mixing and adhering to and accumulating on the glass surface of the dishwasher, and shortening the washing time.

[0076] If component (D) contains lipase, the amount of lipase is preferably such that the lipase activity measured by the measurement method described below is 0.2 to 0.6 U, and more preferably 0.25 to 0.55 U. If the lipase activity is above the lower limit, the cleaning power against complex stains including protein and oil stains is further enhanced, the adhesion and accumulation of dirt on the glass surface of the dishwasher can be suppressed, and the cleaning time can be shortened. If the lipase activity is below the upper limit, the enzyme does not need to be added in excess, so manufacturing costs can be reduced, and component (D) can be prevented from remaining undissolved and precipitating, thus preventing a decrease in cleaning power.

[0077] If component (D) contains lipase, the ratio of the content of component (D) (calculated in terms of protein amount) to the lipase activity (U) (D / lipase activity ratio) is preferably 0.30 to 0.38, and more preferably 0.32 to 0.36. If the D / lipase activity ratio is above the lower limit, there is no need to add more enzyme than necessary, which reduces manufacturing costs and prevents component (D) from remaining undissolved and precipitation, thus preventing a decrease in cleaning power. If the D / lipase activity ratio is below the upper limit, the cleaning power against complex stains including protein and oil stains is further enhanced, the adhesion and accumulation of dirt on the glass surface of the dishwasher is suppressed, and the washing time can be shortened.

[0078] If component (D) contains mannanase, the amount of mannanase is preferably such that the mannanase activity measured by the measurement method described below is 0.35 to 1.1 U, and more preferably 0.45 to 0.80 U. If the mannanase activity is above the lower limit, the cleaning power against complex stains including polysaccharides other than starch, proteins, and oil stains is further enhanced, the adhesion and accumulation of dirt on the glass surface of the dishwasher can be suppressed, and the cleaning time can be shortened. If the mannanase activity is below the upper limit, the enzyme does not need to be added in excess, so manufacturing costs can be reduced, and component (D) can be prevented from remaining undissolved and precipitating, thus preventing a decrease in cleaning power.

[0079] If component (D) contains mannanase, the ratio of the content of component (D) to mannanase (U) (in terms of protein amount) (D / mannanase activity ratio) is preferably 0.16 to 0.24, and more preferably 0.18 to 0.22. If the D / mannanase activity ratio is above the lower limit, the enzyme does not need to be added more than necessary, thus reducing manufacturing costs and preventing component (D) from remaining undissolved and precipitation, thus preventing a decrease in cleaning power. If the D / mannanase activity ratio is below the upper limit, the cleaning power against complex stains including polysaccharides other than starch, proteins, and oil stains is further enhanced, suppressing the adhesion and accumulation of dirt on the glass surface of the dishwasher, and shortening the washing time.

[0080] (Measurement method) <Amylase activity> Amylase activity can be measured using the following method. The Phadebas tablet (manufactured by Magle, Phadebas Amylase Test for amylase activity measurement), which is a cross-linked starch polymer containing an insoluble blue pigment, is hydrolyzed with alpha-amylase, and the absorbance (620 nm) of the water-soluble blue pigment is measured to determine the alpha-amylase activity. 20.0 g of sodium sulfite (manufactured by Junsei Chemical Co., Ltd., reagent grade, etc.), 6.15 g of potassium dihydrogen phosphate (manufactured by Hayashi Pure Chemical Industries, Ltd., special grade, etc.), 10.86 g of disodium hydrogen phosphate dodecahydrate (manufactured by Kanto Chemical Co., Ltd., special grade, etc.), 0.015 g of calcium chloride dihydrate (manufactured by Kanto Chemical Co., Ltd., first grade, etc.), and 0.75 mL of Brij 35 (manufactured by MERCK, 30% aqueous solution) are accurately weighed, dissolved in deionized water, and diluted to 1000 mL to obtain a buffer solution. 0.5 g of the detergent composition as a sample is accurately weighed, dissolved in the above buffer solution, and diluted to 100 mL to obtain the sample solution. For each sample, two glass test tubes (18 mm × 180 mm) are prepared, one for the sample (A) and the other for the blank (B). 1 mL of the sample solution is placed only in test tube A. Add 5.0 mL of buffer solution, preheated to 37°C, to both test tubes, then add one Fadebath tablet. Mix with a flash mixer for 10 seconds, then place the test tubes in a 37°C water bath. Repeat this procedure at 30-second intervals. Exactly 15 minutes later, add 1.0 mL of 1 mol / L NaOH solution to both test tubes, mix with a flash mixer for 10 seconds, let stand at room temperature for 15 minutes, and then immediately filter through filter paper. If turbidity is present, filter using a filtration kit. Measure the absorbance of the filtrates of sample (A) and blank (B) (a washing agent composition with the enzyme replaced by water) obtained from the above procedure at a measurement wavelength λ=620 nm (1 cm quartz cell, slit width 0.5 mm). Calculate the enzyme activity value of amylase using the following formula. Enzyme activity value (U) = (Absorbance of sample) - (Absorbance of blank)

[0081] <Protease activity> Protease activity can be measured using the following method. Milk casein is treated with an enzyme, and the undegraded protein is precipitated by adding trichloroacetic acid (TCA), followed by filtration. By measuring the absorbance (λ=275nm) of this filtrate, the amount of amino acids containing a phenyl group (e.g., tyrosine) eluted is determined, and the protease activity is calculated. Precisely place 1.2 g of milk casein (CALBIOCHEM) into a 200 mL beaker and quickly knead it with a glass rod while gradually adding 6 mL of 1 mol / L NaOH to swell it. Next, add 160 mL of 0.05 mol / L boric acid solution, stir with a stirrer to disperse, adjust the pH to 10.5 with 1 mol / L NaOH, and then bring to a final volume of 200 mL. Accurately weigh 1 g of the detergent composition, dissolve it in deionized water, and bring to a final volume of 100 mL to prepare the sample solution. For each sample, prepare two glass test tubes (18 mm × 180 mm), one for the sample (A) and the other for the blank (B). Add 1 mL of the sample solution to both test tubes. Add 5.0 mL of the casein solution, which has been preheated to 37°C, to only test tube A of the sample, stir with a flash mixer for 10 seconds, and then place both test tubes in a 37°C water bath. Repeat this procedure at 30-second intervals. Exactly 30 minutes later, add 5.0 mL of 0.44 mol / L TCA solution to both test tubes, mix with a flash mixer for 10 seconds, leave in a water bath for 30 minutes, and immediately filter through filter paper. Then filter through a filtration filter (Tomsic, NP-44525-ACF). The absorbance of the filtrates of sample (A) and blank (B) (composition without casein) obtained by the above procedure was measured at a measurement wavelength λ=275nm (1cm quartz cell, slit width 0.5mm). The enzyme activity value of the protease was calculated using the following formula. Enzyme activity value (U) = (Absorbance of sample) - (Absorbance of blank)

[0082] <Lipase activity> Lipase activity can be measured using the following method. The measurement is performed using Lipase Kit S (Sumitomo Bakelite Co., Ltd., product number: BS-92101). The substrate (BALB, dimercaprol tributyrate), SDS (sodium dodecyl sulfate), and esterase inhibitor (PMSF, phenylmethylsulfonyl fluoride) are added to the sample washing composition. PMSF and SDS inactivate esterases other than lipase in the sample, while SDS activates the lipase in the sample. The activated lipase hydrolyzes BALB to produce dimercaprol (BAL). The resulting BAL quantitatively reacts with DTNB (5,5'-dithiobis(2-nitrobenzoic acid)) to produce a yellow 2-nitro-5-thiobenzoic acid (TNB) anion. The reaction of the lipase is stopped by adding a reaction stop solution. The lipase activity is calculated by measuring the absorbance (λ=412nm). Add 2.4 mL of buffer solution, which is a pH 8.6, 15% by mass aqueous solution of 2-amino-2-hydroxymethyl-1,3-propanediol, to a container containing the color developer (DTNB) to completely dissolve the color developer, and then add 22 mL of purified water to prepare the color developer stock solution. Next, transfer the entire volume to a 500 mL graduated cylinder, mix 1 volume of the color developer stock solution with 1 volume of the buffer solution, and then add 8 volumes of purified water to prepare the color developer solution. The reaction stop solution solidifies when stored in a cool place, so it is melted by heating (30°C, 5-10 minutes). Then, the entire volume is poured into a 500 mL graduated cylinder while washing with purified water, and the final volume is adjusted to 500 mL with purified water to prepare the reaction stop solution, which is then transferred to an Erlenmeyer flask. For each sample, prepare two glass test tubes: one for the sample (A) and the other for the blank (B). Add 1 mL of the color-developing solution and 50 μL of the sample to both test tubes and mix. Then add 20 μL of esterase inhibitor solution with a concentration of 0.1–1% by mass. After mixing, place both test tubes in a thermostat and incubate at 30±1°C for 5 minutes. After 5 minutes, while still in the thermostat, add 100 μL of substrate solution with a concentration of 0.1–1% by mass to test tube A only, mix, and immediately incubate at 30±1°C. After incubation is complete, while still in the thermostat, immediately add 2 mL of reaction stop solution to both test tubes. Remove both test tubes from the thermostat and mix. Then add 100 μL of substrate solution to test tube B only and mix again. The absorbance of the sample (A) and blank (B) (unreacted enzyme composition) was measured at a wavelength of 412 nm using purified water as a control (1 cm quartz cell, slit width 0.5 mm). The enzyme activity value of lipase was calculated using the following formula. Enzyme activity value (U) = (Absorbance of sample) - (Absorbance of blank)

[0083] <Mannanase activity> The mannanase activity is measured using the following method. By reacting a polysaccharide (galactomannan) with an enzyme (mannanase) in liquid detergent, and by using a p-hydroxybenzhydrazide (PAHBAH) chromogenic reagent to color the reducing end of galactomenan, the degree of galactomannan degradation is detected by measuring the absorbance (λ=275nm), and the mannanase activity is calculated. Dissolve 0.15 g of galactomannan (Megazyme) in 100 mL of deionized water and stir in a 50°C water bath until clear and homogeneous. After stirring, allow to stand in a 50°C water bath. Dissolve 46.85 g of anhydrous disodium hydrogen phosphate (special grade reagent, Kanto Chemical Co., Ltd.) and 9.4 g of sodium dihydrogen phosphate dihydrate (special grade reagent, Kanto Chemical Co., Ltd.) in 1000 mL of deionized water. For the PAHBAH colorimetric reagent, dissolve 0.552 g of Bismuth(3)acetate, 99% (Alfa Aesar, etc.), 2 g of p-hydroxybenzhydrazide (Wako Pure Chemical Industries, Ltd., etc.), and 5 g of (+)-potassium sodium tartrate tetrahydrate (special grade reagent, Junsei Chemical Co., Ltd., etc.) in 0.5 mol / L-NaOH to a total volume of 100 mL. Cover the entire mixture with aluminum foil to protect it from light and stir until the reagent dissolves. Weigh 0.07 g of the washing agent composition accurately, dissolve it in phosphate buffer (concentration 0.4 mol / L), and dilute to 100 mL to prepare the sample solution. For each sample, prepare two glass test tubes (18 mm × 180 mm), one for the sample (A) and the other for the blank (B). Add 2 mL of the sample solution and 5 mL of the galacton mannan substrate solution to each test tube. Add 2 mL of the washing agent composition as the sample to test tube A only, stir with a flash mixer for 10 seconds, and place in a 50°C water bath. Repeat this procedure at 30-second intervals. Dissolve 0.552 g of Bismuth(III)acetate, 99% (e.g., Alfa Aesar), 2 g of p-hydroxybenzhydrazide (e.g., Wako Pure Chemical Industries), and 5 g of (+)-potassium sodium tartrate tetrahydrate (special grade reagent, e.g., Junsei Chemicals) in 0.5 mol / L NaOH in a total volume of 100 mL. Cover the entire mixture with aluminum foil and stir until the reagents dissolve, protecting it from light, to prepare the PAHBAH color reagent. (Note that this reagent should not be stored for more than one day, but prepared and used daily.) Exactly 30 minutes later (using a stopwatch), add 4 mL of the PAHBAH color reagent, stir with a flash mixer for 10 seconds, and leave on ice for 10 minutes. At the same time, add 4 mL of the PAHBAH color reagent to the blank (composition without the washing agent composition) and stir with a flash mixer for 10 seconds to inactivate the enzyme.Next, add 5 mL of a 0.15% by mass galactomannan substrate solution, mix again with a flash mixer for 10 seconds, and then let stand on ice for 10 minutes. Then proceed to the color development procedure. Place each test tube containing the PAHBAH reagent into a 70°C water bath at 10-second intervals, remove after exactly 10 minutes, and let stand in an ice bath. Then immediately filter through filter paper. The absorbance of the filtrates of sample (A) and blank (B) (composition without detergent composition) obtained by the above procedure is measured using a spectrophotometer at a measurement wavelength λ=405nm (1cm quartz cell, slit width 0.5mm). The enzyme activity value of mannanase is calculated using the following formula. Enzyme activity value (U) = (Absorbance of sample) - (Absorbance of blank)

[0084] By containing a preservative in the cleaning agent composition, the growth of microorganisms can be suppressed even if they become contaminated with the cleaning agent composition. Examples of preservatives include isothiazoline compounds, specifically benzisothiazolinone (1,2-benzisothiazolinone-3-one), methylisothiazolinone (2-methyl-4-isothiazolinone-3-one), butylbenzisothiazolinone, chloromethylisothiazolinone, octylisothiazolinone, and dichlorooctylisothiazolinone. Preservatives may be used individually or in combination of two or more as appropriate.

[0085] The preservative content is preferably 0.0002 to 0.01% by mass (2 to 100 ppm by mass) relative to the total mass of the detergent composition, and more preferably 0.0005 to 0.004% by mass (5 to 40 ppm by mass). If the preservative content is within the above range, the effect of the formulation can be fully obtained without reducing the detergent power of the detergent composition.

[0086] Examples of inorganic builders include metal oxides. Examples of metal oxides include zinc oxide and magnesium oxide. Inorganic builders may be used individually or in combination of two or more types as appropriate. If the detergent composition contains an inorganic builder, the inorganic builder content is preferably 0.01 to 5% by mass relative to the total mass of the detergent composition.

[0087] The inclusion of a hydrotrope agent in the detergent composition improves its liquid stability (especially its low-temperature stability), making it easier to ensure a more stable transparent appearance. Examples of hydrotropes include aromatic sulfonic acids having 6 to 9 carbon atoms or their salts, aromatic carboxylic acids having 7 to 10 carbon atoms or their salts.

[0088] Examples of aromatic sulfonic acids having 6 to 9 carbon atoms or their salts include xylene sulfonic acid or its salts, such as o-xylene sulfonic acid and m-xylene sulfonic acid; toluene sulfonic acid or its salts, such as o-toluene sulfonic acid, m-toluene sulfonic acid, and p-toluene sulfonic acid; cumene sulfonic acid or its salts, such as m-cumene sulfonic acid and p-cumene sulfonic acid; and mesitylene sulfonic acid or its salts. Examples of aromatic carboxylic acids having 7 to 10 carbon atoms or their salts include benzoic acid or its salts, salicylic acid or its salts, phthalic acid or its salts, isophthalic acid or its salts, terephthalic acid or its salts, p-oxybenzoic acid, β-oxynaphthoic acid, and the like. Examples of salt forms of aromatic sulfonic acids and aromatic carboxylic acids include alkali metal salts such as sodium salts and potassium salts; alkaline earth metal salts such as magnesium salts and calcium salts; and alkanol ammonium salts such as monoethanolammonium salt, diethanolammonium salt, and triethanolammonium salt. Among these, alkali metal salts are preferred, sodium salts and potassium salts are more preferred, and sodium salts are even more preferred. Hydrotropes may be used individually or in combination of two or more types.

[0089] The hydrotrope content is preferably 2 to 30% by mass, and more preferably 3 to 10% by mass, relative to the total mass of the detergent composition. Within this range, sufficient liquid stabilization can be achieved without reducing the detergent power of the detergent composition.

[0090] Examples of polymer compounds (excluding those corresponding to component (B)) include polysaccharide polymer compounds such as carboxymethylcellulose (CMC). Alternatively, water-soluble polymers described in Japanese Patent Publication No. 2009-16622 (e.g., alkylene oxide adducts of polyalkyleneamines) and polyester soil-release polymers described in International Publication No. 2012 / 136427 may be used as polymer compounds. Polymer compounds may be used individually or in combination of two or more types. The polymer compound is preferably present in an amount of 0.001 to 5% by mass, and more preferably 0.01 to 1% by mass, relative to the total mass of the detergent composition.

[0091] Examples of pH adjusting agents include inorganic alkaline agents, organic alkaline agents, and inorganic acids. Examples of inorganic alkaline agents include sodium hydroxide, potassium hydroxide, sodium carbonate, and calcium carbonate. Examples of organic alkaline agents include amine compounds such as monoethanolamine, diethanolamine, triethanolamine, 3-(N-methylamino)-1-propanol, 2-amino-2-methyl-1-propanol, N-(2-aminoethyl)ethanolamine, diethylenetriamine, morpholine, and N-ethylmorpholine. Examples of inorganic acids include hydrochloric acid and sulfuric acid. Examples of organic acids include acetic acid. pH adjusters may be used individually or in combination of two or more types as appropriate.

[0092] Examples of solvents include water and organic solvents other than hydrotropes (hereinafter also referred to as "other organic solvents"). Among these, water is preferred as the solvent. Using water as the solvent makes it easier to prepare the cleaning agent composition. In addition, when cleaning objects with the cleaning agent composition, the solubility in water is improved. The solvent may be used alone or in combination of two or more types.

[0093] For the water source, deionized water, distilled water, tap water, etc., can be used. The water content is preferably 90% by mass or less, more preferably 40-85% by mass, and even more preferably 50-85% by mass, relative to the total mass of the detergent composition. If the water content is above the lower limit, gelation of the detergent composition is suppressed and the uniformity of the liquid is improved. If the water content is below the upper limit, the liquid stability of the detergent composition can be improved.

[0094] Other organic solvents include, for example, alcohols such as ethanol, glycerin, 1-propanol, 2-propanol, 1-butanol, and 3-methoxy-3-methyl-1-butanol (Solfit, trade name); glycols such as ethylene glycol, propylene glycol (PG), butylene glycol, and hexylene glycol; polyglycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol with a molecular weight of approximately 200 to 1000, and dipropylene glycol; and alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether (butyl carbitol), and diethylene glycol dimethyl ether. The content of other organic solvents is preferably 0.01 to 10% by mass, and more preferably 0.1 to 5% by mass, relative to the total mass of the detergent composition.

[0095] As for the fragrance, those commonly used in detergent compositions can be applied. Examples of fragrances include the blended fragrance compositions 1 to 4 described in Tables 1 to 8 of Japanese Patent Publication No. 2020-132680. Fragrances may be used individually or in combination of two or more. The fragrance content is preferably 0.001 to 0.3% by mass, and more preferably 0.01 to 0.1% by mass, relative to the total mass of the detergent composition.

[0096] The pigments are not particularly limited and include, for example, pigments listed in the "Handbook of Legal Pigments" (Japan Cosmetic Industry Association) or those in which water-soluble polymers, etc., are chemically modified at the ends of the chromophore structure. The pigments may be used individually or in combination of two or more types. The pigment content is preferably 0.00001 to 0.01% by mass, and more preferably 0.0001 to 0.001% by mass, relative to the total mass of the detergent composition.

[0097] The thickening agent is not particularly limited and examples include xanthan gum (manufactured by Sansho Co., Ltd., product name "KELZAN T"), dieutan gum (manufactured by Sansho Co., Ltd., product name "KELCO-VIS DG"), and cellulose nanofiber (manufactured by Mori Machinery Co., Ltd., product name "C-100"). The thickening agent may be used alone or in combination of two or more types. The amount of thickener is preferably 0.001 to 1% by mass, and more preferably 0.01 to 0.5% by mass, relative to the total mass of the detergent composition.

[0098] Examples of disinfectants include zinc sulfate, zinc chloride, and zinc oxide. Disinfectants may be used individually or in combination of two or more types. The disinfectant content is preferably 0.001 to 5% by mass, and more preferably 0.01 to 1% by mass, relative to the total mass of the cleaning agent composition.

[0099] Examples of antibacterial agents include diphenyl ether antibacterial agents such as diclosan (4,4'-dichloro-2-hydroxydiphenyl ether) and triclosan (5-chloro-2-(2,4-dichlorophenoxy)phenol), cationic bactericides such as quaternary ammonium salts (benzalkonium chloride, alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkylbenzyldimethylammonium salt, alkylpyridinium salt), bis-(2-pyridylthio-1-oxide)zinc, polyhexamethylene biguanidine hydrochloride, 8-oxyquinoline, and polylysine. Antimicrobial agents may be used individually or in combination of two or more types. The antibacterial agent content is preferably 0.001 to 5% by mass, and more preferably 0.01 to 1% by mass, relative to the total mass of the cleaning agent composition.

[0100] Examples of antioxidants include monophenol antioxidants such as dibutylhydroxytoluene and butylhydroxyanisole; bisphenol antioxidants such as 2,2'-methylenebis(4-methyl-6-t-butylphenol); and high molecular weight phenol antioxidants such as dl-α-tocopherol. Antioxidants may be used individually or in combination of two or more types.

[0101] Furthermore, the total content of all components contained in the detergent composition shall be 100% by mass.

[0102] The dosage form of the detergent composition of the present invention is not particularly limited and can be appropriately selected depending on the purpose, for example, liquid, cream, granular, tablet, etc.

[0103] <ph> The pH of the detergent composition of the present invention at 25°C is preferably 5 to 10, and more preferably 6 to 9. The pH (25°C) of the detergent composition is a value measured according to the method specified in JIS Z 8802:2011 "Method for Measuring pH". The pH of the detergent composition can be adjusted using the pH adjusting agent described above.

[0104] <Manufacturing method> The detergent composition of the present invention is manufactured by conventionally known manufacturing methods. One method for producing a detergent composition is to add components other than the pH adjuster to a portion of the water used as a solvent, mix them, adjust the pH to a desired level with the pH adjuster as needed, and then add the remaining water.

[0105] <How to use> The detergent composition of the present invention can be used for dishwashers, and should be used according to the model of the dishwasher and the degree of soiling of the dishes, etc. A method for cleaning objects using a dishwasher with a detergent composition includes a method that includes both washing and rinsing steps. As a washing method, for example, there is a method that includes the steps of: washing the objects to be washed while raising the temperature of a washing solution prepared by introducing tap water at room temperature (preferably around 5 to 30°C) into the dishwasher chamber to a predetermined washing temperature (temperature of the washing solution circulating during washing) (hereinafter referred to as the "washing step"); rinsing the washed objects with tap water at room temperature after washing (hereinafter referred to as the "rinsing (1) step"); and further rinsing the objects after the rinsing (1) step while raising the temperature of tap water at room temperature to preferably 70 to 75°C at a rate of 2 to 3°C / minute (hereinafter referred to as the "rinsing (2) step"). The washing time in the washing step is preferably 10 to 40 minutes. In a typical standard cycle, the washing temperature during the washing process is approximately 55-65°C, and the heating rate is approximately 2-3°C / minute. In a low-temperature cycle, for example, the washing temperature is approximately 35-45°C, and the heating rate is approximately 1°C / minute. The detergent composition of the present invention exhibits excellent cleaning power against protein and oil stains even in low-temperature washing, and for example, it exhibits excellent cleaning power even at a washing temperature of 35°C. The amount of the cleaning agent composition used per cycle is preferably 1 to 10 g per approximately 1 liter of tap water.

[0106] <Effects and Effects> As described above, although the mechanism is not clear, it is believed that the detergent composition of the present invention suppresses excessive foaming by component (A) by forming a complex between the anionic component (A) and the cationic component (B), thereby achieving both cleaning power and low foaming properties. Furthermore, it is thought that the complex adheres to the surface of glass tableware and the glass surface of dishwashers, thereby suppressing the adhesion and accumulation of tannin-derived tea stains. (A) Component makes it easier to remove protein and oil stains that adhere to tableware and the glass surface of dishwashers, thereby suppressing accumulation during repeated washing. This is thought to be because component (A) is an anionic surfactant with a polar group, and therefore can efficiently remove dirt through intermolecular forces such as hydrogen bonding. In particular, anionic surfactants with a carboxyl group tend to have excellent protein cleaning power, and it is thought that this also has an effect on oil stains that adhere and accumulate along with proteins. By making it easier to neutralize the anionic properties of component (A) with component (B), excessive foaming of (A) can be suppressed, thereby improving low-foaming properties. In particular, component (B) is highly cationic, having more reaction sites with anions (primary to tertiary amino groups) than other known cationic polymers. Therefore, it has a stronger effect of neutralizing the anionic properties of component (A) compared to other amine compounds. As a result, in this invention, component (B) is considered to be more effective in improving low-foaming properties than other amine compounds with lower cationic properties. Conventionally, component (B) has been used as a quick-drying component to improve water drainage and achieve a crisp finish. However, when only component (B) adheres to the glass surface, polyphenols such as tannins are adsorbed onto the cationic component (B), making it easier for tea stains to adhere and accumulate. In the present invention, by using components (A) and (B) in combination, it is possible to achieve both low foaming and cleaning performance through the above mechanism of action, and to suppress the adhesion and accumulation of not only oil stains but also tannin-derived tea stains and calcium carbonate-derived limescale. [Examples]

[0107] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following description.

[0108] (Raw materials used) <(A) component> a-1: Linear alkyl (12-14 carbon atoms) sodium benzenesulfonate (Lion Specialty Chemicals Co., Ltd. "Lypon LS-250"), the number of carbon atoms in the linear alkyl group is 12-14. a-2: Sodium secondary alkanesulfonate (Clariant Japan Co., Ltd. "HOSTAPUR SAS 30A"), the number of carbon atoms in the secondary alkyl group is 14 to 17. a-3: Sodium monoalkyl sulfosuccinate (Toho Chemical Industry Co., Ltd. "Kohacool L-400"), in formula (a-2-1), R c11 is a linear or branched alkyl group, or a linear or branched alkenyl group having 12, 14, and 16 carbon atoms, AO is an ethylene oxy group, t is 4, M c1 and M c11 This is a mixture of sodium ions. a-4: Sodium cocoyl glutamate (Asahi Kasei Chemicals Corporation "AminoSurfact ACDS-L"), in formula (a-1-1), R a1 R is a linear alkyl group having 7 to 17 carbon atoms. a2 R is a hydrogen atom, a3 This is a group represented by -CH2CH2CO2Na, M a1 This is a sodium ion.

[0109] <(B) component> b-1: Polyethyleneimine (Nippon Shokubai Co., Ltd. "Epomin SP-003", branched-chain polyethyleneimine, Mw: 300). b-2: Polyethyleneimine (BASF "Lupasol FG", branched-chain polyethyleneimine, Mw: 800). b-3: Polyethyleneimine (BASF "Lupasol G20", branched-chain polyethyleneimine, Mw: 1,300). b-4: Polyethyleneimine (BASF "Lupasol G100", branched-chain polyethyleneimine, Mw: 5,000). b-5: Polyethyleneimine (BASF "Lupasol SK", modified branched polyethyleneimine, Mw: 2,000,000). ·b'-1: Alkoxylated polyethyleneimine EO=10 (BASF's "Sokalan HP10", an EO adduct of polyethyleneimine, number of EO added moles: 10). ·b'-2: Alkoxylated polyethyleneimine EO=20 (EO adduct of polyethyleneimine "Sokalan HP20" from BASF, number of EO adduct moles: 20). ·b'-3: Alkoxylated polyethyleneimine EO=30 (EO adduct of polyethyleneimine "Sokalan HP30" from BASF, number of EO adduct moles: 30). ·b'-4:C18 Dimethylaminopropylamide (Toho Chemical Co., Ltd. "Catinal MPAS", Dimethylaminopropyl stearate).

[0110] <Optional ingredients> (C) Component • c-1: Citric acid (Fuso Chemical Co., Ltd. "Purified Citric Acid (Anhydrous)"). • c-2: Trisodium methylglycine diacetate (BASF "Trisodium methylglycine diacetate (MGDA)"). • c-3: Tetrasodium glutamate diacetate (Kirest Co., Ltd. "Tetrasodium glutamate diacetate (GLDA)"). • c-4: Ethylenediaminetetraacetate sodium (Tokyo Chemical Industries, Ltd. "Ethylenediaminetetraacetate sodium (EDTA)"). (Common components) (powder) • Enzymes (Novozymes Japan Co., Ltd. "Achieve Advance 150T")... appropriate amount. • Enzyme (Novozymes Japan Co., Ltd. "Stainzyme Plus Evity 24T")... appropriate amount. • Enzymes (Novozymes Japan Co., Ltd. "Blaze Evity 150T")... appropriate amount. • Enzymes (Novozymes Japan Co., Ltd. "Intensa Evity 200T")... appropriate amount. Sodium carbonate (Wako Pure Chemical Industries, Ltd., reagent)... appropriate amount. Nonionic surfactant (Dow's "Bright 1 Surfactant")... appropriate amount. (liquid) • Enzymes (Novozymes Japan Co., Ltd. "Achieve alpha 100L")... appropriate amount. • Enzymes (Novozymes Japan Co., Ltd. "Blaze pro 100L")... appropriate amount. • Enzymes (Novozymes Japan Co., Ltd. "Intensa Core 200L")... appropriate amount. Xanthan gum (Kelco "KELZAN T")... appropriate amount. • Silicone (Shin-Etsu Chemical Co., Ltd. "KM 98")... appropriate amount. • Fragrance: 0.050% by mass of any one of the fragrance compositions 1 to 4 listed in Tables 1 to 8 of Japanese Patent Publication No. 2020-132680, or any one of the fragrance components listed in Table 1. • Ion-exchanged water... Balance (the amount required to make the total mass of the detergent composition 100% by mass).

[0111] ≪Evaluation Method≫ <Low foaming> A small-sized automatic dishwasher (Panasonic Corporation, NP-TML1) was used, with 6g, 10g, and 25g of detergent, along with 6g of well-beaten whole egg, added. The tank was filled with 25°C tap water up to the FULL line, and the machine was operated (washing water volume: 1.4L). Ten minutes after the start of washing, the machine was stopped and the door was opened. Ten seconds later, the foaming inside the machine was observed, and the low-foaming properties were evaluated based on the evaluation criteria below. The evaluations for the examples and comparisons are based on the average of three tests conducted with each detergent amount, with ○, ◎, ◎◎, and ◎◎◎ being considered passing grades. (Evaluation Criteria) ◎◎◎: The foam height was lower than that of the water spray nozzle. ◎◎: The foam height was just barely reaching the water spray nozzle. ◎: The foam height reached the water spray nozzle, but the entire nozzle was still visible. ○: The foam height reached the water spray nozzle and covered a portion of the nozzle. ×: The foam height exceeded that of the water spray nozzle, indicating air entrapment. Air intrusion refers to the phenomenon where, during cleaning, a large amount of foam is generated, causing air to enter the circulation pump, weakening the spray force and producing abnormal noises. In this test, the presence or absence of abnormal noises was used for evaluation.

[0112] <Inhibits tea stain buildup> Three glasses were placed inside the automatic dishwasher, and 6g, 10g, and 25g of detergent and 100g of Healthia Green Tea α (Kirin Beverage Co., Ltd.) were added. The dishwasher was then operated. After repeating this operation 10 times, the glasses were observed, and the ability to suppress tea stain adhesion was evaluated based on the evaluation criteria below. The evaluations for the Examples and Comparative Examples are based on the average value of three glasses from 10 tests conducted with each detergent amount, with ○, ◎, ◎◎, and ◎◎◎ being considered passing grades. (Evaluation Criteria) ◎◎◎: No tea stains were found at all. ◎◎: Almost no tea stains were observed. ◎: Less severe tea stain adhesion was observed compared to the blank sample. ○: Tea stains similar to those on a blank surface were observed. ×: More tea stains were found than on the blank surface. A "blank" is defined as a glass placed inside an automatic dishwasher, into which only 200g of Healthia Green Tea α is added, and the glass is washed 10 times before being designated as a "blank".

[0113] (Examples 1-31, Comparative Examples 1-10) According to the compositions shown in Tables 1-7, each component was added to water and mixed to prepare a detergent composition for each example at pH 7. Note that the ingredient amounts in the table are calculated on a net basis. Also, a "-" in the ingredient amount in the table indicates that the ingredient is not included. For each example of a detergent composition, its low foaming properties and inhibition of tea stain adhesion were evaluated, and the results are shown in the table.

[0114] [Table 1]

[0115] [Table 2]

[0116] [Table 3]

[0117] [Table 4]

[0118] [Table 5]

[0119] [Table 6]

[0120] [Table 7]

[0121] As shown in Tables 1-7, Examples 1-31 showed low foaming properties ranging from "○" to "◎◎◎" and tea stain adhesion suppression ranging from "○" to "◎◎◎". Comparative Example 1, which did not contain component (A), showed a "fail" in inhibiting tea stain adhesion. Comparative Example 2, which contained 0.005% by mass of component (A), showed "failure" in inhibiting tea stain adhesion. Comparative Example 3, which contained 12% by mass of component (A), showed a low foaming property of "×". Comparative Examples 4-6, which used an EO adduct of polyethyleneimine instead of component (B), all showed a "×" rating for low foaming properties. Comparative Example 7, in which an amidoamine was used instead of component (B), showed no success in suppressing tea stain adhesion. Comparative Example 8, which did not contain component (B), showed a low foaming property of "×". Comparative Example 9, in which the content of component (B) was 0.001% by mass, showed a low foaming property of "×". Comparative Example 10, which contained 1.2% by mass of component (B), showed "×" in its ability to suppress tea stain adhesion. From the results above, it was found that by applying the present invention, it is possible to achieve both low foaming and cleaning performance, which are in a trade-off relationship, regardless of the size of the dishwasher (i.e., the concentration of the cleaning solution), and furthermore, it is possible to suppress the adhesion and accumulation of tea stains on glass tableware and the glass surface of the dishwasher.< / ph>

Claims

1. (A) Ingredients: Anionic surfactant and (B) Component: Polyethyleneimine (excluding those containing oxyalkylene groups), a dishwasher detergent composition comprising, The content of component (A) is 0.1 to 10% by mass relative to the total mass of the dishwasher detergent composition. A dishwasher detergent composition wherein the content of component (B) is 0.01 to 1% by mass relative to the total mass of the dishwasher detergent composition.

2. The dishwasher detergent composition according to claim 1, wherein the component (A) comprises one or more selected from the group consisting of anionic surfactants represented by the following formula (a-1) and anionic surfactants represented by the following formula (a-2). 【Chemistry 1】 In formula (a-1), R ａ１ R is a linear or branched alkyl group having 6 to 20 carbon atoms. ａ２ R is a hydrogen atom, or a linear or branched alkyl group having 1 to 6 carbon atoms. ａ３ is a linear or branched alkyl group having 1 to 6 carbon atoms, which may have a hydrogen atom or a carboxyl group, and the carboxyl group is -CO ２ M ａ２ It may form a salt represented by M ａ２ is a counterion, a is a number of 0s or 1s, M ａ１ This is a hydrogen atom or a counterion. 【Chemistry 2】 In formula (a-2), R ｃ１１ is a linear or branched alkyl group having 6 to 18 carbon atoms, or a linear or branched alkenyl group having 6 to 18 carbon atoms, X is a single bond or -O-(AO) ｔ -, AO is an alkyleneoxy group having 2 to 4 carbon atoms, t is an integer of 0 to 10 indicating the average number of repetitions, M ｃ１ is a hydrogen atom or a counter ion, Y is -OM ｃ１１ or -(OA) ｒ -OR ｃ１２ is a group represented by, M ｃ１１ is a hydrogen atom or a counter ion, OA is an oxyalkylene group having 2 to 4 carbon atoms, r is an integer of 0 to 10 indicating the average number of repetitions of OA, R ｃ１２ is a linear or branched alkyl group having 6 to 18 carbon atoms, or a linear or branched alkenyl group having 6 to 18 carbon atoms.

3. The dishwasher detergent composition according to claim 1, wherein component (A) comprises one or more selected from the group consisting of cocoyl glutamate and monoalkyl sulfosuccinate.

4. A dishwasher detergent composition according to any one of claims 1 to 3, wherein the mass ratio (B / A) of component (B) to component (A) is 0.001 to 10.

5. The dishwasher detergent composition according to any one of claims 1 to 3, wherein the weight-average molecular weight of component (B) is 200 to 3,000,000.

6. Furthermore, it contains component (C), The dishwasher detergent composition according to any one of claims 1 to 3, wherein the (C) component comprises one or more selected from the group consisting of aminocarboxylic acid-based chelating agents and hydroxycarboxylic acid-based chelating agents.

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