Dishwasher detergent composition

Abstract

To provide a dishwasher detergent composition that achieves a balance between cleaning power and decomposition power, which are in a trade-off relationship, resulting in excellent liquid stability even after long-term storage, superior cleaning power against starch stains that cause odors and mold, and prevention of odors and mold from leftover food when washing after long-term storage using a dishwasher for a small number of people. [Solution] A dishwasher detergent composition comprising (A) an anionic surfactant represented by formula (a) and (B) an enzyme containing amylase, wherein the content of component (A) is 0.3 to 10% by mass relative to the total mass of the dishwasher detergent composition, and the content of component (B) is 700 to 4500 ppm by mass in terms of protein content relative to the total mass of the dishwasher detergent composition.

Description

[Technical Field]

[0001] This invention relates to a dishwasher detergent composition. [Background technology]

[0002] In recent years, the number of single-person households has been increasing, and it is projected to reach approximately 40% by 2040. The market for dishwashers is heating up in response to this growing need, with various companies releasing dishwashers designed for smaller households. However, these smaller models differ significantly from conventional larger models, creating new challenges.

[0003] The main differences from conventional dishwashers are (1) the drying method is air-only, and (2) the amount of detergent used is reduced due to its smaller size. Regarding (1) above, conventional dishwashers use heaters for powerful drying, but dishwashers for small households do not have heaters in order to reduce size, and drying is set to air only. With air only, food residue accumulated in the food residue filter does not dry easily, and bacteria multiply in the moisture, creating a risk of odor and mold growth originating from the food residue. Furthermore, as a result of (2) above, the frequency of repurchasing detergent decreases and the use of long-stored products increases, raising concerns about a decrease in cleaning power, and also increasing the risk of reduced decomposition of dirt (complex stains of starch, protein, and oil) that causes odor and mold.

[0004] Patent Document 1 discloses a dishwasher detergent that combines an anionic surfactant, a chelating agent, an enzyme, an aromatic sulfonic acid, and a carboxylic acid, which has excellent cleaning power against various types of stains and good storage stability. Patent Document 2 discloses a dishwasher detergent that combines amidoamine and alkylbenzenesulfonic acid and is excellent at removing protein stains. Patent Document 3 discloses a detergent composition that contains an N-acyl amino acid surfactant, exhibiting excellent resistance to hard water and good foaming properties. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2015-10187 [Patent Document 2] Japanese Patent Publication No. 2021-4333 [Patent Document 3] Japanese Patent Application Publication No. 11-322688 [Overview of the project] [Problems that the invention aims to solve]

[0006] However, in (1) and (2) above, the performance in preventing odors from food residue during washing after long-term storage using a dishwasher designed for small numbers of people is insufficient, and mold may grow, and this risk is not mentioned. Furthermore, long-term storage can easily lead to the deterioration and deactivation of enzymes due to anionic surfactants, making it difficult to achieve both the cleaning power of anionic surfactants and the decomposition power (hydrolysis power) of enzymes. The present invention aims to provide a dishwasher detergent composition that achieves both cleaning power and decomposition power, which are in a trade-off relationship, thereby exhibiting excellent liquid stability even after long-term storage, superior cleaning power against starch stains that cause odors and mold, and preventing odors and mold from food residue when washing after long-term storage using a dishwasher for a small number of people. [Means for solving the problem]

[0007] The present invention has the following aspects. <1> (A) Components: An anionic surfactant represented by the following formula (a), (B) Components: Contains an enzyme including amylase, The content of component (A) is 0.3 to 10% by mass relative to the total mass of the dishwasher detergent composition. A dishwasher detergent composition in which the content of component (B) is 700 to 4500 ppm by mass in terms of protein content relative to the total mass of the dishwasher detergent composition. [ka] In formula (a), R a1 is a linear or branched alkyl group having 6 to 20 carbon atoms, X is -N(-R a2 )- or -O-, and R a2 is a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, R a3 is a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms which may have a carboxy group, and the carboxy group may form a salt represented by -CO2M a3 , M a3 is a counter ion, p is a number of 0 or 1, R a4 is a hydrogen atom or a methyl group, Y is a group represented by -CO2M a1 or -SO3M a2 , and M a1 and M a2 are each independently a hydrogen atom or a counter ion. <2> Furthermore, it contains a component (C), The dishwashing detergent composition according to <1>, wherein the component (C) is a polar group-containing aromatic compound or a salt thereof. <3> The dishwashing detergent composition according to <1> or <2>, wherein the mass ratio represented by [(mass of component (A))] / [(mass of component (B))] is 0.2 to 30. <4> The dishwashing detergent composition according to any one of <1> to <3>, wherein the mass ratio represented by [(mass of component (A)) + (mass of component (B))] / [(mass of component (C))] is 0.1 to 6.0.

Advantages of the Invention

[0008] According to the dishwashing detergent composition of the present invention, by achieving both detergency and decomposability that are in a trade-off relationship, it has excellent liquid stability even after long-term storage, excellent detergency for starch stains that cause odors and mold, and can also prevent odors and mold derived from leftover foods in cleaning after long-term storage using a dishwashing machine for a small number of people. A dishwashing detergent composition can be provided.

Embodiments for Carrying Out the Invention

[0009] The embodiments of the present invention will be described in detail below, but the present invention is not limited to the embodiments described below and can be implemented with various modifications within the scope of its gist. In this specification and in the claims, a numerical range represented by "~" means a numerical range that includes the numbers before and after "~" as the lower and upper limits, respectively. For example, A~B is synonymous with A or greater and B or less.

[0010] ≪Dishwasher detergent composition≫ The dishwasher detergent composition of the present invention (hereinafter also simply referred to as "detergent composition") contains the following components (A) and (B). The detergent composition may, if necessary, further contain components other than components (A) and (B) (hereinafter also referred to as "optional components") in addition to components (A) and (B), as long as it does not impair the effects of the present invention.

[0011] <(A) component> It is an anionic surfactant represented by the following formula (a).

[0012] [ka]

[0013] In formula (a), R a1 is a linear or branched alkyl group having 6 to 20 carbon atoms, and X is -N(-R a2 )- or -O-, R 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 a3 It may also form a salt represented by M a3 is the counterion, p is a number of 0s or 1s, and R a4 is a hydrogen atom or a methyl group, and Y is -CO2M a1 or -SO3Ma2 It is a group represented by M a1 and M a2 Each of these is independently a hydrogen atom or a counterion. The inclusion of component (A) in the detergent composition enhances low foaming properties and improves cleaning power against protein and oil stains compared to other anionic surfactants. Furthermore, it minimizes the impact on component (B), as described later, preventing enzyme degradation and precipitation, and improving liquid stability. Improved enzyme stability also helps prevent odors and mold growth from food residue.

[0014] In formula (a), R a1 As such, linear alkyl groups having 6 to 20 carbon atoms are preferred, and linear alkyl groups having 7 to 17 carbon atoms are more preferred. R a2 Preferably, the element is a hydrogen atom or a linear alkyl group having 1 to 6 carbon atoms, with a hydrogen atom being preferred. R a3 Preferably, the group is a linear alkyl group having 1 to 6 carbon atoms, which may have a hydrogen atom or a carboxyl group. A carboxymethyl group or a 2-carboxyethyl group is more preferred, and a 2-carboxyethyl group is even more preferred, as the increased number of anionic groups enhances the cleaning power. The carboxyl group is -CO2M a3 It may form a salt represented by . M a3Preferably, the salt can form a water-soluble salt. Examples of salts that can form a water-soluble salt 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, triethanolammonium ions, sodium ions, and potassium ions are preferred, and triethanolammonium ions are more preferred because they moderately chelate the metal ions of component (B) described later, increasing the stability of the enzyme and improving enzyme activity, thereby enhancing the odor and mold prevention performance from food residues. M a1 and M a2 As a counterion, M a3 Examples similar to those exemplified earlier can be given. M a1 ~M a3 The counterions may be of the same type or different types, but counterions of the same type are preferred. Note M a1 ~M a3 If the counterion is divalent or greater, M a1 ~M a3 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 ~M a3 If it is a magnesium ion, M a1 ~M a3 The number is 1 / 2.

[0015] Examples of component (A) include acyl amino acid-based anionic surfactants (hereinafter also referred to as "component (A1)") and sulfo fatty acid ester-based anionic surfactants (hereinafter also referred to as "component (A2)"). In this specification, acyl amino acid surfactants refer to N-acyl amino acid 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. In this specification, sulfo fatty acid ester-based anionic surfactant means an anionic surfactant having an ester bond derived from a fatty acid and a sulfo group or a salt thereof.

[0016] (A1) Component is preferably one represented by the following formula (a1).

[0017] [ka]

[0018] In formula (a1), R a1 , R a2 , R a3 M a1 and M a3 The same as above, and a is a number that is either 0 or 1.

[0019] (A2) A sulfo fatty acid ester-based anionic surfactant represented by the following formula (a2) is preferred as component (A2).

[0020] [ka]

[0021] In formula (a2), R a1 , R a3 , R a4 and M a2 This is the same as above.

[0022] (Component A1) (A1) Component is more preferably one or more selected from the group consisting of an N-acyl-α-amino acid anionic surfactant represented by the following formula (a1-1) and an N-acyl-β-amino acid anionic surfactant represented by the following formula (a1-2).

[0023] [ka]

[0024] In formula (a1-1), R a1 , R a2 , R a3 M a3 and M a1 The same applies as described above.

[0025] [ka]

[0026] (a1-2) Medium, R a1 , R a2 , R a3 M a3 and M a1 The same applies as described above.

[0027] From the viewpoint of cleaning 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 improving foam quality 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.

[0028] 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 foam quality, cleaning power, and rinsability, with glycine, alanine, methylalanine, and glutamic acid being more preferred. Component (A) is preferably N-acylglycine, N-acylalanine, N-acylmethylalanine, or N-acylglutamic acid, with N-acylglutamic acid being more preferred. From the viewpoint of cleaning power, the carboxyl group is counterion M a1 and M a3 It is even more preferable that a salt is formed.

[0029] 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 obtaining foam quality, cleaning power, and rinsability, 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-cocoyl alanine, N-lauroyl methyl alanine, and their salts are more preferred, and from the viewpoint of cleaning power, one or more selected from N-cocoyl glutamic acid and its salts are even more preferred.

[0030] Examples of salts of the above-mentioned N-acyl amino acids or their salts include, from the viewpoint of improving foaming and foam quality, 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 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, and from the viewpoint of enzyme stability, triethanolammonium salt is even more preferred.

[0031] 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 improving foaming and foam quality, and from the viewpoint of availability, a base selected from sodium hydroxide, potassium hydroxide, arginine, and triethanolamine is preferred to form sodium salts, potassium salts, arginine salts, and triethanolammonium salts, and one or more 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.

[0032] ((A2) component) The above sulfo fatty acid esters or their salts may be used individually or in combination of two or more. Among these, from the viewpoint of obtaining foam quality, cleaning power and rinsability, examples include lauroyl methyl isethionic acid or its salt, myristoyl methyl isethionic acid or its salt, oleoyl methyl isethionic acid or its salt, cocoyl methyl isethionic acid or its salt, lauroyl isethionic acid or its salt, myristoyl isethionic acid or its salt, oleoyl isethionic acid or its salt, cocoyl isethionic acid or its salt, etc. Among these, lauroyl methyl isethionic acid or its salt is preferred.

[0033] As salts of the above sulfo fatty acid esters, from the viewpoint of improving foaming and foam quality, examples include 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. As salts of sulfo fatty acid esters, from the viewpoint of availability, it is preferable that one or more salts are selected from alkali metal salts, triethanolammonium salts (quaternary ammonium salts of protonated triethanolamine), and quaternary ammonium salts of protonated arginine (hereinafter also referred to as arginine salts), and it is more preferable that one or more salts are selected from sodium salts, potassium salts, and triethanolammonium salts, and from the viewpoint of enzyme stability, triethanolammonium salt is even more preferable.

[0034] Furthermore, when incorporating sulfo fatty acid esters, they should be neutralized with a base, similar to N-acyl amino acids. From the viewpoint of enzyme stability, component (A1) is more preferable. These (A) components may be a single type or a combination of two or more types.

[0035] (A) The content of component (A) is preferably 0.3 to 10% by mass, more preferably 0.5 to 5.0% by mass, and even more preferably 1.0 to 3.0% by mass, relative to the total mass of the detergent composition. If the content of component (A) is above the lower limit, the cleaning power against starch, protein, and oil stains on the objects being cleaned and inside the dishwasher can be increased, thereby suppressing the adhesion and accumulation of dirt on the objects being cleaned and inside the dishwasher, and thereby improving the odor and mold prevention performance from food residue. If the content of component (A) is below the upper limit, the foaming of component (A) can be suppressed, thereby improving low foaming properties. In addition, by suppressing the decrease in cleaning power and liquid stability due to the decrease in solubility of component (A), the cleaning power against starch, protein, and oil stains on the objects being cleaned and inside the dishwasher can be improved, and thereby improving the odor and mold prevention performance from food residue.

[0036] <(B) component> (B) Component is an enzyme containing amylase. The inclusion of component (B) in the detergent composition promotes the decomposition of complex stains, including starch stains, thereby enhancing its cleaning power against starch stains. Furthermore, by using it in combination with component (A), which has high cleaning power but minimal impact on enzymes, it prevents enzyme degradation and precipitation, thereby improving liquid stability. By improving enzyme stability, it is also possible to prevent odors and mold originating from food residues.

[0037] (B) Component may include amylase, as well as protease, mannanase, cellulase, lipase, etc. Among these, protease is preferred from the viewpoint of suppressing the adhesion and accumulation of protein stains, and the combined use of amylase and protease is more preferable as it contributes to both starch and protein stains. (B) Component may be used alone or in combination of two or more types.

[0038] (B) The content of component (B) is 700 to 4500 ppm by mass in terms of protein content relative to the total mass of the detergent composition, preferably 700 to 4200 ppm by mass, more preferably 900 to 3000 ppm by mass, and even more preferably 1000 to 2000 ppm by mass. If the content of component (B) is above the lower limit, the cleaning time can be shortened by promoting the decomposition of complex stains including protein and oil stains. If the content of component (B) is below the upper limit, manufacturing costs can be reduced without adding more enzymes than necessary, and the decrease in liquid stability due to deterioration and precipitation of component (B) can be suppressed.

[0039] ≪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

[0040] The content of component (B) as an enzyme preparation (preparation content) is preferably 0.01 to 3.0% by mass, more preferably 0.1 to 2.0% by mass, and even more preferably 0.2 to 1.0% by mass, relative to the total mass of the detergent composition. If the preparation content of component (B) is above the lower limit, it is possible to promote the decomposition of complex stains including starch, protein, and oil stains, thereby suppressing the accumulation of stains on the objects to be cleaned and inside the dishwasher, thereby improving the odor and mold prevention performance from food residue. If the preparation content of component (B) is below the upper limit, it is possible to reduce manufacturing costs by not adding more enzyme than necessary, and it is possible to suppress the decrease in liquid stability due to the deterioration and precipitation of component (B) and improve the decomposition power by enzymes, thereby improving the odor and mold prevention performance from food residue.

[0041] The amylase content is preferably 0.10 to 15.0 U, and more preferably 0.20 to 9.00 U, relative to the total mass of the detergent composition, as measured by the amylase activity described in the examples. If the amylase activity is above the lower limit, the cleaning time can be shortened by promoting the decomposition of complex stains including starch stains and protein / oil stains. If the amylase activity is below the upper limit, manufacturing costs can be reduced by not adding more enzyme than necessary, and the decrease in liquid stability due to alteration and precipitation of component (B) can be suppressed.

[0042] The ratio of the content of component (B) (calculated in terms of protein amount) to the amylase activity (U) (B / amylase activity ratio) is preferably 0.1 to 0.8, and more preferably 0.3 to 0.6. If the B / amylase activity ratio is above the lower limit, manufacturing costs can be reduced by not adding more enzyme than necessary, and the decrease in liquid stability due to the deterioration and precipitation of component (B) can be suppressed. If the B / amylase activity ratio is below the upper limit, the cleaning time can be shortened by promoting the decomposition of complex stains including starch stains and protein and oil stains.

[0043] If component (B) contains a protease, the amount of protease is preferably 0.01 to 3.00 U, and more preferably 0.10 to 2.50 U, relative to the total mass of the detergent composition, as measured by the measurement method described in the examples. If the protease activity is above the lower limit, the cleaning time can be shortened by promoting the decomposition of complex stains including protein stains and starch / oil stains. If the protease activity is below the upper limit, manufacturing costs can be reduced without adding more enzyme than necessary, and a decrease in liquid stability due to alteration and precipitation of component (B) can be suppressed.

[0044] If component (B) contains a protease, the ratio of the content of component (B) (calculated in terms of protein amount) to the protease activity (U) (B / protease activity ratio) is preferably 0.1 to 10.0, and more preferably 1.0 to 5.0. If the B / protease activity ratio is above the lower limit, manufacturing costs can be reduced by not adding more enzyme than necessary, and the decrease in liquid stability due to the deterioration and precipitation of component (B) can be suppressed. If the B / protease activity ratio is below the upper limit, the cleaning time can be shortened by promoting the decomposition of protein stains and complex stains containing protein and oil stains.

[0045] If component (B) contains lipase, the amount of lipase is preferably 0.2 to 0.6 U, and more preferably 0.25 to 0.55 U, relative to the total mass of the cleaning agent composition, as measured by the lipase activity described below. If the lipase activity is above the lower limit, the cleaning power against oil stains can be further enhanced and the cleaning time can be shortened. If the lipase activity is below the upper limit, whitening of the inside of the cabinet can be prevented, manufacturing costs can be reduced without adding more enzyme than necessary, and a decrease in liquid stability due to deterioration and precipitation of component (B) can be suppressed.

[0046] If component (B) contains lipase, the ratio of the content of component (B) to the lipase activity (U) (calculated in terms of protein amount) (B / lipase activity ratio) is preferably 0.30 to 0.38, and more preferably 0.32 to 0.36. If the B / lipase activity ratio is above the lower limit, whitening inside the chamber can be prevented, manufacturing costs can be reduced without adding more enzyme than necessary, and a decrease in liquid stability due to deterioration and precipitation of component (B) can be suppressed. If the B / lipase activity ratio is below the upper limit, the cleaning power against oil stains can be further enhanced and the cleaning time can be shortened.

[0047] If component (B) contains mannanase, the amount of mannanase measured by the measurement method described below is preferably 0.35 to 1.1 U, and more preferably 0.45 to 0.80 U, relative to the total mass of the detergent composition. If the mannanase activity is above the lower limit, the cleaning power against polysaccharides other than starch and complex stains including starch, protein, and oil stains can be further enhanced, and the cleaning time can be shortened. If the mannanase activity is below the upper limit, the amount of enzyme added can be kept below the upper limit, reducing manufacturing costs, and the deterioration and precipitation of component (B) can be suppressed, preventing a decrease in liquid stability.

[0048] If component (B) contains mannanase, the ratio of the content of component (B) to mannanase (U) (calculated in terms of protein amount) (B / mannanase activity ratio) is preferably 0.16 to 0.24, and more preferably 0.18 to 0.22. If the B / mannanase activity ratio is above the lower limit, manufacturing costs can be reduced by not adding more enzyme than necessary, and the decrease in liquid stability due to the deterioration and precipitation of component (B) can be suppressed. If the B / mannanase activity ratio is below the upper limit, the cleaning power against polysaccharides other than starch and complex stains including starch, protein, and oil stains can be further enhanced, and the cleaning time can be shortened.

[0049] (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)

[0050] <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)

[0051] <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)

[0052] <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)

[0053] The mass ratio expressed as [(A) mass] / [(B) mass (protein amount equivalent)] (hereinafter also referred to as the "A / B ratio (protein amount equivalent)") is preferably 0.1 to 30.0, more preferably 1.0 to 20.0, and even more preferably 2.0 to 10.0. If the A / B ratio (protein amount equivalent) is above the lower limit, the proportion of component (A) increases, preventing the effect of (A) to alter and deactivate enzymes in the same way as protein stains from becoming stronger than its effect of moderately chelating and protecting metal ions, thereby suppressing alteration and precipitation of component (B) and improving liquid stability. If the A / B ratio (protein amount equivalent) is below the upper limit, it suppresses the decrease in cleaning power due to a lower proportion of component (A) and improves cleaning power against starch, protein, and oil stains.

[0054] The mass ratio expressed as [(A) component mass] / [(B) component mass (formulation content)] (hereinafter also referred to as the "A / B ratio") is preferably 0.2 to 30, more preferably 1.0 to 10, and even more preferably 2.0 to 5.0. If the A / B ratio is above the lower limit, it becomes easier to suppress the deterioration and precipitation of component (B), thereby improving liquid stability. If the A / B ratio is below the upper limit, it becomes easier to suppress the decrease in cleaning power, thereby improving the cleaning power against starch, protein, and oil stains.

[0055] <Optional ingredients> The cleaning agent composition may contain other components (optional components) besides components (A) and (B). Any optional component may be used in a detergent composition. Examples include polar group-containing aromatic compounds or their salts (hereinafter also referred to as component (C)), anionic surfactants other than component (A), other surfactants (hereinafter also referred to as "optional surfactants"), chelating agents, enzyme stabilizers, preservatives, inorganic builders, hydrotropes, polymer compounds, pH adjusters, solvents, fragrances, dyes, thickeners, disinfectants, antibacterial agents, antioxidants, etc.

[0056] (Aromatic compounds containing polar groups or their salts) The detergent composition contains a polar group-containing aromatic compound or a salt thereof (component (C)), which improves water drainage by allowing the aromatic ring to trap water and facilitate drying, thereby enhancing odor and mold prevention performance derived from food residues. In addition, the polar group appropriately chelates the metal ions of enzymes, thereby increasing the stability of the enzymes. In this specification, "polar group-containing aromatic compound" means a compound having an aromatic ring which may have substituents and one or more polar groups or a salt thereof. Examples of polar groups include hydroxyl groups, carboxyl groups, sulfol groups, primary amino groups, secondary amino groups, and tertiary amino groups. Among these, carboxyl groups are preferred. Examples of aromatic rings include benzene rings, naphthyl rings, and pyridine rings. Among these, benzene rings are preferred. Examples of substituents on the aromatic ring include C1-C6 alkyl groups, C1-C6 alkoxy groups, and halogen atoms. Among these, C1-C6 alkyl groups are preferred, methyl groups and ethyl groups are more preferred, and methyl groups are even more preferred. (C) Examples of components include benzoic acid, p-toluic acid, phthalic acid, isophthalic acid, and terephthalic acid. Among these, benzoic acid and phthalic acid are preferred because they have a low molecular weight, improve drainage, and enhance odor and mold prevention performance from food residue.

[0057] Examples of salt forms of 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 among these, sodium salts are even more preferred from the viewpoint of solubility. These (C) components may be a single type or a combination of two or more types.

[0058] (C) The content of component (C) is preferably 0.1 to 7.0% by mass, more preferably 1.0 to 5.0% by mass, and even more preferably 2.0 to 4.0% by mass, relative to the total mass of the detergent composition. If the content of component (C) is above the lower limit above, the accumulation of starch, protein, and oil stains on the objects to be washed and inside the dishwasher can be suppressed by increasing enzyme stability and enzyme activity, thereby improving odor and mold prevention performance from food residue. If the content of component (C) is below the upper limit above, manufacturing costs can be reduced by not adding more component (C) than necessary, and liquid stability can be improved by preventing the chelating effect from becoming too strong and altering or deactivating the enzyme.

[0059] The mass ratio expressed as [(A) mass + (B) mass (in protein amount)] / [(C) mass] (hereinafter also referred to as "(A+B) / C ratio (in protein amount)") is preferably 100 to 2000, more preferably 200 to 1500, and even more preferably 200 to 1000. If the (A+B) / C ratio (in protein amount) is above the lower limit, it becomes easier to suppress the decrease in cleaning power due to a lower proportion of components (A) and (B), thereby increasing the cleaning power against starch, protein, and oil stains. If the (A+B) / C ratio (in protein amount) is below the upper limit, the enzyme is stabilized, making it easier to suppress the alteration and precipitation of component (B), thereby increasing the stability of the solution.

[0060] The mass ratio expressed as [(A) component mass + (B) component mass (formulation content)] / [(C) component mass] (hereinafter also referred to as the "(A+B) / C ratio") is preferably 0.1 to 6.0, more preferably 0.3 to 3.0, and even more preferably 0.5 to 2.0. If the (A+B) / C ratio is above the lower limit, it becomes easier to suppress the decrease in cleaning power due to a lower proportion of components (A) and (B), thereby increasing the cleaning power against starch, protein, and oil stains. If the (A+B) / C ratio is below the upper limit, the enzyme is stabilized, making it easier to suppress the alteration and precipitation of component (B), thereby increasing the liquid stability.

[0061] (Anionic surfactants other than component (A)) Examples of anionic surfactants other than component (A) include linear alkylbenzene sulfonic acid or its salt, α-olefin sulfonic acid or its salt, internal olefin sulfonic acid or its salt, linear or branched alkyl sulfate ester or its salt, alkyl ether sulfate ester or its salt, alkenyl ether sulfate ester or its salt, alkane sulfonic acid or its salt, α-sulfo fatty acid ester or its salt, alkyl carboxylic acid or its salt, alkyl ether carboxylic acid or its salt. Among these, linear or branched alkyl sulfate ester or its salt, α-sulfo fatty acid ester or its salt, etc. are 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 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 among these, sodium salts are even more preferred from the viewpoint of solubility.

[0062] As an anionic surfactant other than component (A), for example, an anionic surfactant represented by the following formula (d) (hereinafter also referred to as "component (D)") is preferred.

[0063] [ka]

[0064] In formula (d), R d1 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, s is a number of 0s or 1s, Z is a hydrogen atom, -CO2M d2 A group represented by -C(=O)-(OA) r -OR d2 It is a group represented by M d2 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, and R d2 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, Y is a single bond or -O-, and M d1 This is a hydrogen atom or a counterion.

[0065] R d1 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, or hexadecyl group, and even more preferably an octyl group, decyl group, dodecyl group, tetradecyl group, or hexadecyl group. The alkylene group of the alkylene oxy group is preferably an alkylene group having 2 to 4 carbon atoms, more preferably an ethylene group or a propylene group, and even more preferably an ethylene group. When an alkylene oxy group is present, t is preferably 1 to 9, more preferably 2 to 9 from the viewpoint of low foaming, and even more preferably 3 to 8 from the viewpoint of balancing low foaming and cleaning power. Examples of alkylene groups in oxyalkylene groups are the same as those listed for alkylene oxy groups. When an oxyalkylene group is present, r is preferably 0 to 8, more preferably 0 to 5, and even more preferably 0. R d2 For example, R d1 The same items mentioned above can be cited. M d1 As for M a1 Examples similar to the counterions mentioned earlier can be cited. M d2 As for M a1 Examples similar to the counterions mentioned earlier can be cited.

[0066] (D) Component is more preferably one or more selected from the group consisting of sulfosuccinic acid or a salt thereof represented by the following formula (d-1), sulfosuccinic acid or a salt thereof represented by the following formula (d-2), and a sulfate ester or salt thereof having an alkyl or alkenyl group having 6 to 18 carbon atoms represented by the following formula (d-3).

[0067] [ka]

[0068] In formula (d-1), R d1 , AO, t, M d1 and M d2 This is the same as above.

[0069] [ka]

[0070] In formula (d-2), R d1 , AO, t, M d1 OA, r and R d2 This is the same as above.

[0071] [ka]

[0072] In formula (d-3), R d3M is a linear alkyl group having 8 to 20 carbon atoms, or a linear alkenyl group having 8 to 20 carbon atoms. d1 This is the same as above.

[0073] In formula (d-3), R d3 More preferably, the group is a cocoyl group, heptyl group, octyl group, decyl group, dodecyl group, tetradecyl group, or hexadecyl group; even more preferably, an octyl group, decyl group, dodecyl group, tetradecyl group, or hexadecyl group; and even more preferably, a decyl group. These (D) components may be a single type or a combination of two or more types.

[0074] The content of component (D) is preferably 0 to 5.0% by mass, and more preferably 0.5 to 2.0% by mass, relative to the total mass of the detergent composition. If the content of component (D) is above the lower limit, the accumulation of protein, oil, limescale, and other dirt on the glass surface of the dishwasher can be suppressed. If the content of component (D) is below the upper limit, foaming inside the dishwasher can be suppressed without reducing the cleaning power, making it easier to improve low-foaming properties.

[0075] (Other surfactants) Other types of surfactants include cationic surfactants and nonionic surfactants. Examples of cationic surfactants include didecyldimethylammonium chloride, didecyldimethylammonium methosulfate, distearyldimethylammonium chloride, dioctyldimethylammonium chloride, distearyldihydroxyethylammonium chloride, ditallow alkyldimethylammonium chloride, di(stearoyloxyethyl)dimethylammonium chloride, di(oleoyloxyethyl)dimethylammonium chloride, di(palmitoyloxyethyl)dimethylammonium methosulfate, di(stearoyloxyisopropyl)dimethylammonium chloride, di(oleoyloxyisopropyl)dimethylammonium chloride, di(oleoyloxybutyl)dimethylammonium chloride, di(stearoyloxyethyl)methylhydroxyethylammonium methosulfate, and tri(stearoyloxyethyl)methylmethosulfate. 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.

[0076] 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.

[0077] The content of other 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.

[0078] The total amount of all surfactants contained in the detergent composition (hereinafter also referred to as "total surfactant amount") is preferably 0.3 to 10% by mass, and more preferably 0.5 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, the solubility of the surfactant is not reduced, so foaming in the dishwasher is suppressed without reducing cleaning power, making it easier to improve low-foaming properties.

[0079] (Chelating agent) The detergent composition contains a chelating agent, which chelates metal ions (e.g., calcium ions) in tap water, thereby enhancing the cleaning power of component (A) and reducing its usage, contributing to low foaming, while also suppressing the adhesion and accumulation of limescale on the glass surface of dishwashers.

[0080] The chelating agent is not particularly limited, and any common chelating agent that has been used in dishwasher detergents can be used. The chelating agent 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).

[0081] 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.

[0082] 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. 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, glycolic acid or its salts, gluconic acid or its salts, etc. Among these, citric acid, methylglycine diacetic acid, glutamic acid diacetic acid, ethylenediaminetetraacetic acid, or salts thereof are preferred, and citric acid, methylglycine diacetic acid, or salts thereof are more preferred because they easily suppress the adhesion and accumulation of protein and oil stains on the glass surface of dishwashers at a pH near neutral, and a combination of citric acid or a salt thereof with methylglycine diacetic acid or a salt thereof is even more preferred.

[0083] When citric acid or its salt is used in combination with methylglycine diacetic acid or its salt, the mass ratio expressed as citric acid or its salt / methylglycine diacetic acid or its salt is preferably 0.2 to 1.0, and more preferably 0.3 to 0.8, from the viewpoint of balancing low foaming and cleaning power.

[0084] 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.

[0085] 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.

[0086] Examples of salts that make up chelating agents include alkali metal salts, alkaline earth metal salts, alkanolammonium salts, and ammonium salts. Examples of alkali metal salts include sodium salts and potassium salts. Examples of alkaline earth metal salts include magnesium salts and calcium salts. Examples of alkanol ammonium salts include monoethanolammonium salt, diethanolammonium salt, and triethanolammonium salt. These chelating agents may be used individually or in combination of two or more.

[0087] The chelating agent content is preferably 0 to 25% by mass, more preferably 2 to 20% by mass, and even more preferably 6 to 15% by mass, relative to the total mass of the detergent composition. If the chelating agent content is above the lower limit, the chelating agent chelates metal ions in tap water, thereby improving the activity of component (A) to enhance cleaning power and suppressing the adhesion and accumulation of starch, protein, and oil stains. It also suppresses the adhesion of limescale to the glass surface of dishwashers and the accumulation of starch, protein, and oil stains that adhere to limescale. Furthermore, by chelating metal ions derived from protein stains, the protein stains become easier to remove, thereby enhancing cleaning power and improving odor and mold prevention performance from food residue. If the chelating agent content is below the upper limit, the solubility of the chelating agent in water is increased, improving liquid stability. Furthermore, it prevents the chelation of metal ions that contribute to the stabilization of component (B) (enzyme), thereby preventing a decrease in liquid stability and decomposition power due to enzyme inactivation, and thereby improving the odor and mold prevention performance derived from food residue.

[0088] (Enzyme stabilizer) By including an enzyme stabilizer in the detergent composition, the decrease in liquid stability due to the alteration and precipitation of component (B) is suppressed, and the cleaning power of (B) is enhanced. Examples of enzyme stabilizers include boric acid, formic acid, lactic acid, borax, salts of formic acid, salts of lactic acid, and salts of inorganic acids. Among these, salts of inorganic acids are preferred, calcium salts of inorganic acids are more preferred, and calcium chloride and calcium sulfate are even more preferred. Enzyme stabilizers may be used individually or in combination of two or more as appropriate.

[0089] The enzyme stabilizer content is preferably 0.05 to 2.0% by mass, more preferably 0.1 to 1.0% by mass, and even more preferably 0.2 to 0.5% by mass, relative to the total mass of the detergent composition. If the enzyme stabilizer content is above the lower limit, component (B) will be more easily stabilized, improving liquid stability and enhancing odor and mold prevention performance from food residue. If the enzyme stabilizer content is below the upper limit, a decrease in cleaning power due to a decrease in the solubility of component (A) will be prevented, and its blending effect can be fully obtained.

[0090] (Preservative) 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.

[0091] 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.

[0092] (Inorganic Builder) 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.

[0093] (Hydrotrope agent) 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, monohydric alcohols having 2 to 4 carbon atoms, dihydric alcohols having 2 to 4 carbon atoms, and glyceryl ethers having 4 to 10 carbon atoms.

[0094] 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.

[0095] Examples of monohydric alcohols with 2 to 4 carbon atoms include ethanol, n-propanol, and isopropanol. Examples of dihydric alcohols having 2 to 4 carbon atoms include ethylene glycol, propylene glycol, and diethylene glycol. Examples of glyceryl ethers having 4 to 10 carbon atoms include glycerin and hexylglyceryl ether. Hydrotropes may be used individually or in combination of two or more types.

[0096] 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's cleaning power.

[0097] (polymer compound) Examples of polymer compounds (excluding those that fall under the category of chelating agents) 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.

[0098] (pH adjuster) 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.

[0099] (solvent) 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.

[0100] For the water used, 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.

[0101] 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 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.

[0102] (fragrance) 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.

[0103] (dye) 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.

[0104] (Thickening agent) 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.

[0105] (Disinfectant) 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.

[0106] (Antibacterial agent) 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.

[0107] (Antioxidant) 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.

[0108] Furthermore, the total content of all components contained in the detergent composition shall be 100% by mass.

[0109] <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.

[0110] <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 a pH adjuster as needed, and then add the remaining water.

[0111] <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, one may include a method comprising: a step 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 compartment to a predetermined washing temperature (temperature of the washing solution circulating during washing) (hereinafter referred to as the "washing step"); a step of rinsing the objects after washing with tap water at room temperature (hereinafter referred to as the "rinsing (1) step"); and a step of further rinsing the objects after the rinsing (1) step while 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 0.5 to 5 g per liter of tap water.

[0112] <Effects and Effects> The mechanism by which the effects of this invention are obtained is not clear, but it is presumed to be as follows. The detergent composition of the present invention exhibits a good balance between the cleaning power against protein and oil stains provided by a specific anionic surfactant and the decomposition power (hydrolysis power) against starch stains provided by amylase, thereby achieving the effects of the present invention. Generally, anionic surfactants cause denaturation and deactivation of enzymes, resulting in a trade-off between cleaning power and decomposition power. In this invention, by setting the blending amounts of component (A) and component (B) within a specific range, both cleaning power and decomposition power can be achieved, thereby improving liquid stability and odor / mold prevention performance. Furthermore, by breaking down food residue attached to dishes and other items to a degree that allows it to pass through the filter, and preventing it from remaining in the filter between the dishwasher interior and the drain, mold growth inside the interior is suppressed, and odor and mold prevention performance can be achieved. Although the size of food residue is larger than the particles of starch, protein, and oil stains, the detergent composition of the present invention has excellent penetration power for food residue, so it is thought that it can be broken down into monomer units by enzymes (hydrolysis), thereby reducing the amount remaining in the filter. In addition, mold growth inside the interior also depends on the amount of moisture, but since the detergent composition of the present invention has high cleaning power against starch, protein, and oil stains, it is thought that the adhesion and accumulation of these inside the interior will be suppressed, the inner surface of the interior will be smoothed and water will drain better, and odor and mold prevention performance will be further enhanced. In particular, the anionic surfactant used in the present invention has a good balance of hydrophobic and hydrophilic groups, so even after forming hydrogen bonds with water molecules, it does not remain inside the interior but can be discharged outside the interior. This is because dishwashers are made of composite materials such as plastic, glass, and stainless steel, and it is thought that the good balance between hydrophobicity and hydrophilicity contributes to how easily dishes dry. Furthermore, because the proportions of component (A) and component (B) are within a specific range, the detergent composition is considered to have a balanced proportion in which component (A) improves the stability of the solution by suppressing the alteration and deactivation of component (B) by component (A), and the polar groups of component (A) contribute to the appropriate chelation of metal ions that contribute to the stabilization of component (B). [Examples]

[0113] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following description. Unless otherwise specified, the amounts of components used in each example are calculated on a pure content basis.

[0114] "Raw materials used" The following compounds were used as component (A). ·A1-1: Sodium cocoyl glutamate (manufactured by Asahi Kasei Chemicals, product name "AminoSurfact ACDS-L"), in formula (a1-1), R a1 is a linear alkyl group having 7 to 17 carbon atoms, and R a2 is a hydrogen atom, and R a3 is a group represented by -CH2CH2CO2Na, and M a1 is a compound which is a sodium ion. ·A1-2: Sodium / potassium cocoamphoacetate mixture (manufactured by Asahi Kasei Chemicals Corporation, trade name "Aminosurfact ACDP-L"), in formula (a1-1), R a1 is a linear alkyl group having 7 to 17 carbon atoms, and R a2 is a hydrogen atom, and R a3 is a group represented by -CH2CH2CO2Na and -CH2CH2CO2K, and M a1 is a compound which is a mixture of sodium ions and potassium ions, and the ratio of sodium ions to potassium ions is 1:1. ·A1-3: Triethanolamine cocoamphoacetate (manufactured by Asahi Kasei Chemicals Corporation, trade name "Aminosurfact ACDT-L"), in formula (a1-1), R a1 is a linear alkyl group having 7 to 17 carbon atoms, and R a2 is a hydrogen atom, and R a3 is -CH2CH2CO2 - [N(CH2CH2OH)3] + is a group represented by, and M a1 is [N(CH2CH2OH)3] + is a compound which is. ·A1-4: Sodium cocoyl alaninate (manufactured by Ajinomoto Co., Inc., trade name "Amilite ACS-12"), in formula (a1-1), R a1 is a linear alkyl group having 7 to 17 carbon atoms, and R a2 is a hydrogen atom, and R a3 is a methyl group, and M a1 is a compound which is a sodium ion. ·A1-5: Sodium lauroyl methyl alaninate (manufactured by Lion Specialty Chemicals Co., Ltd., trade name "Enacol L-30"), in formula (a1-2), R a1 is a linear alkyl group having 11 carbon atoms, and R a2 is a hydrogen atom, and R a3 is a hydrogen atom, and M a1 It is a compound that contains sodium ions. ·A2-6: Sodium lauroyl methyl isethionate (manufactured by Ina Trading Co., Ltd., trade name "ISELUX"), in formula (a2), R a1 R is a linear alkyl group with 11 carbon atoms. a3 If R is a hydrogen atom a4 R is a methyl group, a4 If R is a hydrogen atom a3 It is a methyl group, M a2 It is a compound that contains sodium ions. · A'-7: Sodium secondary alkanesulfonate (manufactured by Clariant Japan, product name "HOSTAPUR SAS 30A"), a comparative product of component (A).

[0115] The following compounds were used as component (B). • B-1: Alpha-amylase (manufactured by Novozymes, product name "Achieve alpha 100L"). • B-2: Alpha-amylase (manufactured by Novozymes, product name "Termamyl Ultra 300L"). B-3: Protease (Subtilisin) and Alpha-Amylase (Novozymes, product name "Intensa Core 200L", p / a=60 / 40). • B-4: Protease (Subtilisin) and Alpha-Amylase (Novozymes, product name "Medley Core 210L", p / a=80 / 20).

[0116] <Optional ingredients> The following compounds were used as component (C). C-1: Sodium benzoate (manufactured by Fushimi Pharmaceutical Co., Ltd., product name "Sodium Benzoate"). • C-2: Sodium phthalate (manufactured by Tokyo Chemical Industry Co., Ltd., product name "Disodium Phthalate"). • C-3: Sodium terephthalate (manufactured by Tokyo Chemical Industry Co., Ltd., product name "Disodium Terephthalate").

[0117] • Enzyme stabilizer: Calcium chloride. • Fragrance: Any one of the blended fragrance compositions 1 to 4 described in Tables 1 to 8 of Japanese Patent Publication No. 2020-132680, or any one of the fragrance components described in Table 1. • pH adjuster: appropriate amount. • Water: Ion-exchanged water. The amount is such that the total mass is 100% by mass.

[0118] Examples 1-32, Comparative Examples 1-5 <Preparation of detergent composition> 1000g of a detergent composition with the composition shown in the table was prepared using the following procedure. Component (B) was placed in a 1L beaker and thoroughly stirred with a magnetic stirrer (product name: F-606N, manufactured by Fine). Subsequently, an appropriate amount of pH adjuster was added as needed to ensure the pH at 25°C was in the range of 6-8. Then, components (A), (C), and any optional components were added. After mixing was complete, an appropriate amount of pH adjuster was added again as needed. Finally, component (D) and the amount of water necessary to bring the total volume to 100% by mass were added, and the mixture was stirred thoroughly to obtain the detergent composition. Note that the units for the amounts in the table are in mass percent, and all components are shown in terms of their pure content. The pH (25°C) of the composition was measured using a glass electrode pH meter (HM-30G, manufactured by Toa DKK Co., Ltd.) after adjusting the detergent composition to 25°C. The measurement method was carried out in accordance with JIS Z 8802:2011 "Method for measuring pH". The protein equivalent and activity values ​​of the enzymes were measured by the method described herein.

[0119] <Evaluation of dishwasher detergents> Each of the cleaning agents in the examples and comparative examples was evaluated using the evaluation method described below. The evaluation results are shown in Tables 1 to 7. A dishwasher (Panasonic Corporation, model NP-TML1) was used as the dishwasher.

[0120] <Liquid stability> (Evaluation method) Two vials of detergent, each containing 50 mL, were left standing at -5°C for one week and at 40°C for three months. The appearance was visually observed after the specified time had elapsed. A score of ○ or higher was considered acceptable for both the examples and comparative examples. (Evaluation Criteria) ◎: The appearance remains unchanged even after standing at both -5℃ and 40℃. ○: At -5°C, it solidifies or separates and returns to its original liquid state with RT, or at 40°C, the liquid color changes to pale yellow. ×: After standing, the liquid color changes to dark yellow, or it separates and settles and does not return to its original state.

[0121] <Starch-based cleaning power> (Evaluation method) Three grams of rice porridge were applied to a bowl, heated in a 700W microwave for two minutes, and air-dried for one hour to create grime. Three grams of detergent (an average standard amount for single-person use) that had been stored for a long time was added to the dishwasher and the machine was run. After washing, the bowl was colored with iodine solution, and the starch cleaning power was evaluated based on the evaluation criteria below. The washing test was performed three times with each detergent, and the average of the colored area was evaluated. For the examples and comparative examples, a score of ○ or higher was considered a pass. (Evaluation Criteria) ◎: Colored area 0~15%. ○: Colored area 15-30%. △: Colored area 30-60%. ×: Colored area 60% or more.

[0122] <Odor and mold prevention performance from food waste> (Evaluation method) The following three types of grime were created and air-dried for one hour. I spread 3g of rice porridge onto a bowl and heated it in a 700W microwave for 2 minutes. The contents of the heated "Vegetable-Rich Chinese Rice Bowl Topping (Ajinomoto Frozen Foods Co., Ltd.)" were strained through a sieve, 6g of the strained sauce was spread onto a large plate (23cm in diameter or less), and heated in a 700W microwave for 2 minutes. I spread 6g of plain yogurt on a medium-sized plate. The aforementioned dishwasher was loaded with the three types of grime mentioned above, along with 3g of detergent (average standard usage for a single person) that had been stored for a long period (storage conditions: left standing in a 40°C constant temperature bath for 3 months), and the machine was operated. Twelve hours after the completion of the drying process, the food residue, along with the residue filter, was removed and its weight was measured. The weight of the residue filter alone, which had been measured beforehand, was subtracted from this value to obtain the "original food residue weight." The residue filter was then left in an 80°C constant temperature bath for 1 hour, removed, and its weight was measured to obtain the "dried food residue weight," and the "food residue moisture content" was calculated using the following formula. (Original leftover weight - Leftover weight after drying) / (Original leftover weight) × 100 = Leftover moisture percentage (by weight) Based on the evaluation criteria below, the odor and mold prevention performance derived from food residue were evaluated. A score of ○ or higher was considered a passing grade for both the examples and comparative examples. (Evaluation Criteria) ◎: The moisture content of leftover food is 10% by weight or less. ○: The moisture content of leftover food is 20% by weight or less. △: Moisture content of leftover food is less than 20-50% by weight. ×: The moisture content of the leftover food is 50% by weight or more. (Relationship between leftover food moisture content and odor / mold prevention performance) By combining amino acid-based surfactants with enzymes, the cleaning efficiency of the enzymes is improved, allowing for the fine breakdown of individual starch and protein stains, as well as complex stains of starch or protein and oil, thus reducing the amount of food residue. With less food residue, it becomes possible to reduce the moisture content of the residue by "air drying" alone. Reducing the amount of moisture in leftover food, which is one of the causes of odors and mold inside the dishwasher, contributes to "odor and mold prevention performance."

[0123] [Table 1]

[0124] [Table 2]

[0125] [Table 3]

[0126] [Table 4]

[0127] [Table 5]

[0128] [Table 6]

[0129] [Table 7]

[0130] The amounts listed in Tables 1-7 are calculated on a pure content basis. Ingredients not listed in the table are not included. In the table, "appropriate amount" for pH adjuster content refers to the amount required to achieve the pH shown in the table. In the table, "balance" for water content refers to the amount required to make the detergent composition 100% by mass.

[0131] As is clear from Tables 1 to 7, the detergent compositions of each example had liquid stability of "〇" or "◎", starch cleaning power of "〇" or "◎", and odor and mold prevention performance from food residue of "〇" or "◎".

[0132] Comparative Example 1, in which a secondary alkane sulfonate sodium salt was used instead of component (A), showed a "×" rating for both starch cleaning power and odor and mold prevention performance derived from food residue. Comparative Example 2, in which a secondary alkanesulfonate sodium salt was used instead of component (A), and an enzyme stabilizer was also used, showed improvement in both starch cleaning power and odor and mold prevention performance derived from food residue to "△", but was still insufficient. Comparative Example 3, which used a content of component (B) at 5% by mass (4887 ppm by mass in terms of protein content), showed a liquid stability of "×", and both the starch cleaning power and the odor and mold prevention performance from food residues were "△". Comparative Example 4, which did not contain component (B), showed a "×" rating for both starch cleaning power and odor and mold prevention performance derived from food residue. Comparative Example 5, which contained 20% by mass of component (A), had a liquid stability of "×", and both its starch cleaning power and its performance in preventing odors and mold from food residue were "△".< / ph>

Claims

1. (A) Component: An anionic surfactant represented by the following formula (a), (B) Components: Contains an enzyme including amylase, The content of component (A) is 0.3 to 10% by mass relative to the total mass of the dishwasher detergent composition. A dishwasher detergent composition in which the content of component (B) is 700 to 4500 ppm by mass in terms of protein content relative to the total mass of the dishwasher detergent composition. 【Chemistry 1】 In formula (a), R ａ１ is a linear or branched alkyl group having 6 to 20 carbon atoms, X is -N(-R ａ２ )- or -O-, R ａ２ is a hydrogen atom, or a linear or branched alkyl group having 1 to 6 carbon atoms, R ａ３ is a hydrogen atom, or a linear or branched alkyl group having 1 to 6 carbon atoms which may have a carboxy group, and the carboxy group may form a salt represented by -CO ２ M ａ３ , M ａ３ is a counter ion, p is a number of 0 or 1, R ａ４ is a hydrogen atom or a methyl group, Y is -CO ２ M ａ１ or -SO ３ M ａ２ , and M ａ１ and M ａ２ are each independently a hydrogen atom or a counter ion.

2. Furthermore, it contains component (C), The dishwasher detergent composition according to claim 1, wherein component (C) is a polar group-containing aromatic compound or a salt thereof.

3. A dishwasher detergent composition according to claim 1 or 2, wherein the mass ratio expressed as [mass of component (A)] / [mass of component (B)] is 0.2 to 30.

4. A dishwasher detergent composition according to claim 1 or 2, wherein the mass ratio expressed as [mass of component (A) + mass of component (B)] / [mass of component (C)] is 0.1 to 6.0.

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