Dishwashing detergent composition

Abstract

To provide a detergent composition for tableware, which suppresses the remaining of an odor on a hydrophobic surface and shortens a tableware washing time.SOLUTION: The detergent composition for tableware contains a component (A), a component (B), a component (C) and a component (D), wherein the component (A) is an anionic surfactant (provided that a linear alkylbenzene sulfonic acid and its salt are excluded). (B) is at least one selected from the group consisting of a semi-polar surfactant and an amphoteric surfactant, the component (C) is an enzyme, and the component (D) is polyethyleneimine (excluding one containing an oxyalkylene group). A mass ratio represented by the component (C) / the component (D) is 0.07 to 10.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] In recent years, it has become important to improve the washing experience of dishes. Factors that can improve the washing experience include improved detergency, improved foam performance (such as foam persistence), reduced odor retention on hydrophobic surfaces (such as the surfaces of plastic tableware), and reduced dishwashing time. In this way, the washing experience can be improved in many situations.

[0003] Patent Document 1 discloses a dishwashing detergent composition with excellent detergency that combines various activators and enzymes. According to the invention described in Patent Document 1, the cleaning experience is improved by increasing the detergency. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2020-63358 Summary of the Invention [Problem to be solved by the invention]

[0005] However, dishwashing detergent compositions are required to not only improve detergency by incorporating enzymes, but also to improve the cleaning experience in many situations.

[0006] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a dishwashing detergent composition that can suppress the persistence of odors on hydrophobic surfaces and shorten the dishwashing time. [Means for solving the problem]

[0007] The present invention has the following aspects. [1] A dishwashing detergent composition containing component (A), component (B), component (C), and component (D), The component (A) is an anionic surfactant (excluding linear alkylbenzene sulfonic acid and its salts), The component (B) is at least one selected from a semi-polar surfactant and an amphoteric surfactant, The component (C) is an enzyme, The component (D) is polyethyleneimine (excluding those containing an oxyalkylene group), The dishwashing detergent composition has a mass ratio of the component (C) / the component (D) of 0.07 to 10. [2] The dishwashing detergent composition according to [1], wherein the mass ratio represented by the component (A) / (the component (B)+the component (D)) is 0.3 to 2.5. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a dishwashing detergent composition that can suppress odors from remaining on hydrophobic surfaces and shorten the time required to wash dishes. DETAILED DESCRIPTION OF THE INVENTION

[0009] The following describes in detail the embodiments of the present invention, but the present invention is not limited to the following embodiments and can be implemented with various modifications within the scope of the gist thereof. In this specification and claims, a numerical range expressed by "to" means a numerical range that includes the numbers before and after "to" as the lower and upper limits. For example, X to Y is synonymous with at least X and at most Y.

[0010] The dishwashing detergent composition of the present invention (hereinafter also simply referred to as "liquid detergent composition") contains the following components (A) to (D).

[0011] <Component (A)> Component (A) is an anionic surfactant (excluding linear alkylbenzene sulfonic acid and its salts (LAS)). By including component (A) in the liquid detergent composition, it is possible to suppress lingering odors on the object to be cleaned, and to shorten the time required to clean the object to be cleaned.

[0012] Examples of component (A) include α-olefin sulfonic acid or a salt thereof, internal olefin sulfonic acid or a salt thereof, linear or branched alkyl sulfate ester or a salt thereof, alkyl ether sulfate ester or a salt thereof, alkenyl ether sulfate ester or a salt thereof, alkanesulfonic acid or a salt thereof, α-sulfofatty acid ester or a salt thereof, alkyl carboxylic acid or a salt thereof, and alkyl ether carboxylic acid or a salt thereof. Examples of the salt form 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 salts (monoethanolammonium salts), diethanolamine salts (diethanolammonium salts), and triethanolamine salts (triethanolammonium salts). Among these, alkali metal salts are preferred, sodium salts and potassium salts are more preferred, and sodium salts are even more preferred. The component (A) may be used alone or in combination of two or more.

[0013] As component (A), from the viewpoint of suppressing lingering odors on the items to be washed and shortening the time required to wash the items to be washed, alkyl ether sulfate esters or salts thereof, alkanesulfonic acids or salts thereof, and α-olefinsulfonic acids or salts thereof are preferred.

[0014] The alkyl ether sulfate or a salt thereof is preferably a compound represented by the following general formula (a1) (polyoxyalkylene alkyl ether sulfate or a salt thereof). R 1 -O-(EO) n -SO3-M + (a1) (In formula (a1), R 1is a linear alkyl group having 8 to 18 carbon atoms, and the carbon atom bonded to the oxygen atom is the primary carbon atom; EO is an oxyethylene group; n is the average number of moles of EO added; 0 <n≦4であり、M + is a cation.)

[0015] R in formula (a1) 1 R has 8 to 18 carbon atoms, preferably 10 to 14, and more preferably 12 to 14. 1 is preferably an alkyl group derived from a fat or oil raw material. Suitable fat or oil raw materials include palm kernel oil, coconut oil, etc. M in formula (a1) + Examples of the cations include hydrogen ions; alkali metal ions such as sodium and potassium; alkaline earth metal ions such as magnesium and calcium; and alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine. Among these, alkali metal ions are preferred, and sodium ions are more preferred. + If is a divalent cation, M + The number is multiplied by 1 / valence to give SO3 - For example, M + If is a magnesium ion, M + The number is 1 / 2.

[0016] Examples of the compound represented by formula (a1) include polyoxyethylene (1) linear alkyl (C12) ether sulfate sodium salt, polyoxyethylene (2) linear alkyl (C12) ether sulfate sodium salt, polyoxyethylene (4) linear alkyl (C12) ether sulfate sodium salt, polyoxyethylene (1) linear alkyl (C12 / 14=75 / 25; derived from natural fats and oils) ether sulfate sodium salt, polyoxyethylene (2) linear alkyl (C12 / 14=75 / 25; derived from natural fats and oils) ether sulfate sodium salt, and polyoxyethylene (4) linear alkyl (C12 / 14=75 / 25; derived from natural fats and oils) ether sulfate sodium salt. In the present invention, the value in parentheses for polyoxyethylene (1) etc. indicates that 1 mole of oxyethylene has been added on average. The compound represented by formula (a1) is preferably polyoxyethylene (1) linear alkyl (C12 / 14=75 / 25; derived from natural fats and oils) ether sulfate sodium salt.

[0017] The alkanesulfonic acid or its salt is preferably an alkanesulfonic acid having 10 to 20 carbon atoms or its salt, more preferably an alkanesulfonic acid having 14 to 17 carbon atoms or its salt, and even more preferably a secondary alkanesulfonic acid (SAS) having 14 to 17 carbon atoms or its salt. The α-olefin sulfonic acid or a salt thereof is preferably an α-olefin sulfonic acid having 10 to 20 carbon atoms or a salt thereof, and more preferably an α-olefin sulfonic acid having 14 to 16 carbon atoms or a salt thereof.

[0018] Examples of alkylcarboxylic acids or salts thereof include higher fatty acids or salts thereof, etc. Higher fatty acids are saturated fatty acids having 8 to 24 carbon atoms and unsaturated fatty acids having 8 to 24 carbon atoms. Examples of higher fatty acids or salts thereof include single fatty acids or salts thereof such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, oleic acid, and behenic acid; mixed fatty acids or salts thereof such as coconut fatty acid and beef tallow fatty acid; and the like. Examples of salt forms of higher fatty acids 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 salts (monoethanolammonium salts), diethanolamine salts (diethanolammonium salts), and triethanolamine salts (triethanolammonium salts). Among these, alkali metal salts are preferred, sodium salts and potassium salts are more preferred, and sodium salts are even more preferred. The higher fatty acid or salt thereof may be used alone or in combination of two or more.

[0019] Linear alkylbenzenesulfonic acid is composed of benzenesulfonic acid and a linear alkyl bonded to the benzene ring of the benzenesulfonic acid. The linear alkyl has, for example, 8 to 16 carbon atoms. The salt of linear alkylbenzenesulfonic acid is a salt in which hydrogen atoms of the sulfo group of benzenesulfonic acid are substituted with an alkali metal such as sodium.

[0020] The content of component (A) is preferably 1 to 20 mass% relative to the total mass of the liquid detergent composition, more preferably 3 to 15 mass%, and even more preferably 5 to 10 mass%. When the content of component (A) is equal to or greater than the above-mentioned lower limit, the cleaning time for the object to be cleaned can be shortened and odor lingering on the object to be cleaned can be suppressed. When the content of component (A) is equal to or less than the above-mentioned upper limit, foaming is reduced, shortening the rinsing time and shortening the cleaning time for the object to be cleaned.

[0021] <(B) component> The component (B) is at least one selected from the group consisting of semi-polar surfactants (hereinafter also referred to as "component (b1)") and amphoteric surfactants (hereinafter also referred to as "component (b2)"). By including component (B) in the liquid detergent composition, it is possible to suppress lingering odors on the object to be cleaned, and to shorten the time required to clean the object to be cleaned. The term "semi-polar surfactant" refers to a surfactant that becomes cationic or nonionic depending on the pH of the solution in which it dissolves or the dispersion in which it disperses. The component (B) may be used alone or in appropriate combination of two or more types. As the component (B), only the component (b1) may be used, only the component (b2) may be used, or the components (b1) and (b2) may be used in combination. As the component (B), the component (b1) is preferred.

[0022] Examples of the component (b1) include amine oxide surfactants and amine alkylene oxide surfactants, among which amine oxide surfactants are preferred. Examples of amine oxide surfactants include alkylamine oxides, alkanoylamide alkylamine oxides, etc. Among these, compounds represented by the following general formula (b1) are preferred. R 2 -(A) p -N(-R 3 )(-R 4 ) → O (b1)

[0023] R in formula (b1) 2 is a linear or branched alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms, and R 3 and R 4 are each independently an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms, and A is -C=O(-NH-R 5 )-, and R 5 is an alkylene group having 1 to 4 carbon atoms, and p is an integer of 0 to 1.

[0024] R in formula (b1) 2 The number of carbon atoms in R is preferably 10 to 14, and more preferably 12 to 14. 2 is preferably an alkyl group derived from a fat or oil raw material. R 3 , R 4 are each independently preferably an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group; R 2 and R 3 It is particularly preferable that each of the groups is a methyl group. p is preferably 0. Among these, from the viewpoint of suppressing odor lingering on the object to be cleaned and shortening the time required to clean the object to be cleaned, lauryl dimethylamine oxide and amidopropyl dimethylamine oxide are more preferred, and lauryl dimethylamine oxide is even more preferred.

[0025] Examples of component (b2) include carboxylate-type amphoteric surfactants, sulfate-type amphoteric surfactants, sulfonate-type amphoteric surfactants, phosphate-type amphoteric surfactants, etc. Among these, carboxylate-type amphoteric surfactants and sulfonate-type amphoteric surfactants are preferred. Examples of carboxylate-type amphoteric surfactants include betaine-type amphoteric surfactants such as lauryl dimethylaminoacetic acid betaine, coconut alkyl dimethylaminoacetic acid betaine, coconut oil fatty acid amidopropyl betaine, lauric acid amidopropyl dimethylaminoacetic acid betaine, coconut alkyl amidopropyl dimethylaminoacetic acid betaine, coconut oil fatty acid amidopropyl dimethylaminoacetic acid betaine (cocamidopropyl betaine), and lauryl dimethyl sulfobetaine. Examples of sulfonate-type amphoteric surfactants include betaine-type amphoteric surfactants such as lauryl hydroxysulfobetaine. From the viewpoint of suppressing odor lingering on the object to be cleaned and shortening the time required to clean the object to be cleaned, lauric acid amidopropyl betaine is preferred.

[0026] The content of component (B) is preferably 1 to 20 mass% relative to the total mass of the liquid detergent composition, more preferably 3 to 15 mass%, and even more preferably 5 to 10 mass%. When the content of component (B) is equal to or greater than the above-mentioned lower limit, the cleaning time for the object to be cleaned can be shortened and odors remaining on the object to be cleaned can be suppressed. When the content of component (B) is equal to or less than the above-mentioned upper limit, odors remaining on the object to be cleaned can be suppressed.

[0027] In the liquid detergent composition, the mass ratio of component (A) to component (B), expressed as component (A) / component (B) (hereinafter also referred to as the "A / B ratio"), is preferably 0.5 to 2.5, more preferably 0.8 to 1.6, and even more preferably 1.0 to 1.2. When the A / B ratio is within the above range, the efficiency of removing starch and protein can be improved and odors remaining on the object to be cleaned can be suppressed.

[0028] <(C) component> Component (C) is an enzyme (excluding catalase). By including component (C), the liquid detergent composition can suppress lingering odors on the object to be cleaned and shorten the cleaning time for the object to be cleaned.

[0029] Examples of the component (C) include amylase, protease, mannanase, cellulase, and lipase. Among these, amylase and protease are preferred, and a combination of amylase and protease is more preferred. The component (C) may be used alone or in combination of two or more.

[0030] The content of component (C) 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, calculated as protein, relative to the total mass of the liquid detergent composition. When the content of component (C) is equal to or greater than the lower limit, the efficiency of starch and protein removal can be improved and odors remaining on the object to be cleaned can be suppressed. When the content of component (C) is equal to or less than the upper limit, sliminess can be further reduced and the cleaning time for the object to be cleaned can be shortened.

[0031] The content of the enzyme preparation (C) (preparation content) is preferably 0.35 to 1 mass % and more preferably 0.5 to 0.8 mass % of the total mass of the liquid detergent composition. When the preparation content of the (C) ingredient is equal to or greater than the lower limit, the starch and protein removal efficiency can be improved and odors can be suppressed from remaining on the object to be cleaned. When the preparation content of the (C) ingredient is equal to or less than the upper limit, sliminess can be further reduced and the cleaning time for the object to be cleaned can be shortened.

[0032] When component (C) contains amylase, the content of amylase is preferably an amount that results in an amylase activity of 0.44 to 1.25 U, more preferably 0.63 to 1.00 U, as measured by the measurement method described in the Examples. If the amylase activity is equal to or greater than the lower limit, the efficiency of starch and protein removal can be improved and odors remaining on the object to be washed can be suppressed. If the amylase activity is equal to or less than the upper limit, sliminess can be further reduced and the washing time for the object to be washed can be shortened.

[0033] When component (C) contains amylase, the ratio of the content of component (C) (converted to protein amount) to amylase activity (U) (C / amylase activity ratio) is preferably 0.15 to 0.21, more preferably 0.16 to 0.19. When the C / amylase activity ratio is equal to or greater than the lower limit, the efficiency of starch and protein removal can be improved and odors remaining on the object to be washed can be suppressed. When the C / amylase activity ratio is equal to or less than the upper limit, sliminess can be further reduced and the washing time for the object to be washed can be shortened.

[0034] When component (C) contains a protease, the content of the protease is preferably an amount that results in a protease activity of 0.18 to 0.45 U, more preferably 0.24 to 0.37 U, as measured by the measurement method described in the Examples. If the protease activity is equal to or greater than the lower limit, the efficiency of starch and protein removal can be improved and odors remaining on the object to be washed can be suppressed. If the protease activity is equal to or less than the upper limit, sliminess can be further reduced and the washing time for the object to be washed can be shortened.

[0035] When component (C) contains a protease, the ratio of the content of component (C) (converted to protein amount) to the protease activity (U) (C / protease activity ratio) is preferably 0.43 to 0.50, more preferably 0.44 to 0.47. When the D / protease activity ratio is equal to or greater than the lower limit, the efficiency of starch and protein removal can be improved and odors remaining on the object to be washed can be suppressed. When the C / protease activity ratio is equal to or less than the upper limit, sliminess can be further reduced and the washing time for the object to be washed can be shortened.

[0036] When component (C) contains lipase, the content of lipase is preferably an amount that results in lipase activity of 0.2 to 0.6 U, more preferably 0.25 to 0.55 U, as measured by the measurement method described in the Examples. If the lipase activity is equal to or greater than the above-mentioned lower limit, the cleaning power against dirt can be further improved and odors remaining on the object to be cleaned can be suppressed. If the lipase activity is equal to or less than the above-mentioned upper limit, sliminess can be further reduced and the cleaning time for the object to be cleaned can be shortened.

[0037] When component (C) contains lipase, the ratio of the content of component (C) (converted to protein amount) to lipase activity (U) (C / lipase activity ratio) is preferably 0.30 to 0.38, more preferably 0.32 to 0.36. When the D / lipase activity ratio is equal to or greater than the above lower limit, the cleaning power against dirt can be further improved and odors remaining on the object to be washed can be suppressed. When the C / lipase activity ratio is equal to or less than the above upper limit, sliminess can be further reduced and the washing time for the object to be washed can be shortened.

[0038] When component (C) contains mannanase, the content of mannanase is preferably an amount that results in 0.35 to 1.1 U of mannanase, and more preferably an amount that results in 0.45 to 0.80 U of mannanase, as measured by the measurement method described in the Examples. If the mannanase activity is equal to or greater than the above-mentioned lower limit, the cleaning power against stains can be further improved and odors remaining on the object to be cleaned can be suppressed. If the mannanase activity is equal to or less than the above-mentioned upper limit, sliminess can be further reduced and the cleaning time for the object to be cleaned can be shortened.

[0039] When the (C) component contains mannanase, the ratio of the content (protein amount) of the (C) component to the mannanase (U) (C / mannanase activity ratio) is preferably 0.16 to 0.24, more preferably 0.18 to 0.22. When the C / mannanase activity ratio is equal to or greater than the above-mentioned lower limit, the cleaning power against stains can be further improved and odors remaining on the object to be washed can be suppressed. When the C / mannanase activity ratio is equal to or less than the above-mentioned upper limit, sliminess can be further reduced and the washing time for the object to be washed can be shortened.

[0040] <(D) component> Component (D) is polyethyleneimine (excluding those containing oxyalkylene groups). By including component (D) in the liquid detergent composition, it is possible to suppress the lingering of odors on the object to be cleaned, and to shorten the time required to clean the object to be cleaned.

[0041] Polyethyleneimine is a polymer obtained by polymerizing ethyleneimine, and typically forms a branched or network structure because some of the nitrogen atoms in the main chain serve as branching points, and the structure contains one or more primary, secondary, or tertiary amino groups. The amine groups contained in the polyethyleneimine main chain can be primary, secondary, or tertiary. The polyethyleneimine main chain can have a linear, branched, dendritic, or comb-like structure and can have a weight average molecular weight of 100 to 2,000 g / mol, 200 to 1,500 g / mol, 300 to 1,000 g / mol, 400 to 800 g / mol, or 500 to 700 g / mol.

[0042] The amine groups in the main chain of component (D) can be primary, secondary, or tertiary, and can be a mixture containing one or more primary, secondary, and tertiary amine groups. The combination of primary, secondary, and tertiary amine substituents can be in any ratio, for example, from about 1:1:1 to about 2:2:1, with branches occurring every 3 to 3.5 nitrogen atoms along the main chain or branched chain segment. Alternatively, the amine groups in the main chain can be predominantly one of primary, secondary, or tertiary amine substituents.

[0043] Examples of polyethyleneimine or its main chain include compounds represented by the following general formulas (1) to (3): In addition, the wavy lines in formulas (1) and (2) represent the bonding positions with adjacent groups.

[0044] [ka]

[0045] [ka]

[0046] [ka]

[0047] The weight-average molecular weight of component (D) is preferably 100 to 5,000,000, more preferably 4,000 to 5,000,000, and even more preferably 500,000 to 3,000,000. When the weight-average molecular weight of component (D) is within the above range, lingering odors on the object to be cleaned can be suppressed and the time required to clean the object can be shortened. The weight average molecular weight in this specification refers to a value determined by gel permeation chromatography (GPC) using polyethylene glycol as a standard substance.

[0048] The component (D) may be a modified product of polyethyleneimine, that is, the component (D) may be a modified polyethyleneimine. The component (D) may be used alone or in appropriate combination of two or more types. As component (D), modified polyethyleneimine is preferred from the viewpoints of suppressing odors from remaining on the object to be cleaned and shortening the time required to clean the object to be cleaned.

[0049] Modified polyethyleneimine refers to a compound obtained by reacting some or all of the primary or secondary amino groups in polyethyleneimine with other compounds, or by reacting polyethyleneimine with other polymers. Examples of modified polyethyleneimine include amide derivatives of polyethyleneimine, alkyl polyethyleneimine, quaternized polyethyleneimine, and polyethyleneimine substituted with terminal hydroxyl groups. Examples of modified polyethyleneimine include those described in JP-A-60-221088, JP-A-59-198190, JP-A-62-271791, JP-A-58-120879, JP-A-60-135585, JP-A-60-78906, U.S. Pat. No. 3,642,572, U.S. Pat. No. 4,144,123, and U.S. Pat. No. 4,371,674.

[0050] Commercially available polyethyleneimine products can be used, including, for example, products manufactured by BASF under the trade names "Lupasol FG," "Lupasol G 20," "Lupasol G 35," "Lupasol G 100," "Lupasol HF," "Lupasol PS," "Lupasol SK," "Lupasol SKA," "Lupasol PN 50," and "Lupasol PN 60"; and products manufactured by Nippon Shokubai Co., Ltd. under the trade 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.

[0051] As component (D), from the viewpoint of suppressing odor lingering on the object to be cleaned and shortening the cleaning time of the object to be cleaned, BASF products under the trade names "Lupasol G 100," "Lupasol HF," "Lupasol PS," and "Lupasol SK" are preferred, BASF products under the trade names "Lupasol PS" and "Lupasol SK" are more preferred, and BASF product under the trade name "Lupasol SK" is even more preferred.

[0052] The content of component (D) is preferably 0.1 to 5 mass% relative to the total mass of the liquid detergent composition, more preferably 0.5 to 3 mass%, and even more preferably 0.1 to 0.5 mass%. When the content of component (D) is equal to or greater than the above-mentioned lower limit, the efficiency of starch and protein removal is improved, odor lingering on the object to be cleaned can be suppressed, and foaming is reduced, shortening rinsing time and the cleaning time for the object to be cleaned can be shortened. When the content of component (D) is equal to or less than the above-mentioned upper limit, the cleaning time for the object to be cleaned can be shortened.

[0053] In the liquid detergent composition, the mass ratio of component (C) to component (D), expressed as component (C) / component (D) (hereinafter also referred to as the "C / D ratio"), is 0.07 to 10, preferably 0.16 to 8, and more preferably 0.5 to 1.6. When the C / D ratio is equal to or greater than the above-mentioned lower limit, the efficiency of starch and protein removal can be improved and odors remaining on the object to be cleaned can be suppressed. When the C / D ratio is equal to or less than the above-mentioned upper limit, odors remaining on the object to be cleaned can be suppressed. The content of component (C) is calculated as the formulation.

[0054] Furthermore, the mass ratio of component (A) to the total amount of components (B) and (D), expressed as component (A) / (component (B)+component (D)) (hereinafter also referred to as the "A / (B+D) ratio"), is preferably 0.3 to 2.5, more preferably 0.8 to 1.6, and even more preferably 0.9 to 1.2. When the A / (B+D) ratio is within the above range, the efficiency of removing starch and protein can be improved and odors remaining on the object to be washed can be suppressed.

[0055] The total content of components (A) to (D) is preferably 5 to 25 mass %, more preferably 10 to 20 mass %, and even more preferably 13 to 18 mass %, based on the total mass of the liquid detergent composition.

[0056] <Optional ingredients> The optional components may be any components that are used in dishwashing detergent compositions, such as surfactants other than components (A) and (B) (hereinafter also referred to as "optional surfactants"), preservatives, inorganic builders, hydrotropes, solvents other than hydrotropes, chelating agents, polymeric compounds other than component (D), pH adjusters, solvents, fragrances, colorants, thickeners, disinfectants, antibacterial agents, and antioxidants.

[0057] The optional surfactants include cationic surfactants and nonionic surfactants. Examples of cationic surfactants include didecyl dimethyl ammonium chloride, didecyl dimethyl ammonium methosulfate, distearyl dimethyl ammonium chloride, dioctyl dimethyl ammonium chloride, distearyl dihydroxyethyl ammonium chloride, di-tallow alkyl dimethyl ammonium chloride, di(stearoyloxyethyl) dimethyl ammonium chloride, di(oleoyloxyethyl) dimethyl ammonium chloride, di(palmitoyloxyethyl) dimethyl ammonium methosulfate, di(stearoyloxyisopropyl) dimethyl ammonium chloride, di(oleoyloxyisopropyl) dimethyl ammonium chloride, di(oleoyloxybutyl) dimethyl ammonium chloride, di(stearoyloxyethyl) methyl hydroxyethyl ammonium methosulfate, and tri(stearoyloxyethyl) methyl methosulfate. The "tallow alkyl" group has 14 to 18 carbon atoms. The cationic surfactant may be used alone or in appropriate combination of two or more kinds.

[0058] Examples of nonionic surfactants include polyoxyalkylene alkyl ethers and alkyl polyglycosides. The nonionic surfactants may be used singly or in appropriate combination of two or more.

[0059] The content of optional surfactants is preferably 3% by mass or less, more preferably 1% by mass or less, based on the total mass of the liquid detergent composition, and even more preferably substantially free of optional surfactants. Here, "substantially free of optional surfactants" means less than 0.1% by mass based on the total mass of the liquid detergent composition. When linear alkylbenzenesulfonic acid and its salts are contained as optional surfactants, the effects of the present invention are not impaired as long as the content is 2% by mass or less.

[0060] The total content of all surfactants contained in the liquid detergent composition (hereinafter also referred to as "total surfactant amount") is preferably 10 to 30 mass % and more preferably 12 to 25 mass % relative to the total mass of the liquid detergent composition. When the total surfactant amount is equal to or greater than the above lower limit, the liquid detergent composition can have sufficient detergency. When the total surfactant amount is equal to or less than the above upper limit, the liquid detergent composition can have sufficient detergency and good foam-breakdown properties.

[0061] By including a preservative in the liquid detergent composition, even if the liquid detergent composition is contaminated with microorganisms, the growth of bacteria can be suppressed. Examples of preservatives include isothiazoline compounds, such as benzisothiazolinone (1,2-benzisothiazolin-3-one), methylisothiazolinone (2-methyl-4-isothiazolin-3-one), butylbenzisothiazolinone, chloromethylisothiazolinone, octylisothiazolinone, and dichlorooctylisothiazolinone. The preservatives may be used alone or in combination of two or more.

[0062] The content of the preservative is preferably 0.0002 to 0.01% by mass (2 to 100 ppm by mass), more preferably 0.0005 to 0.004% by mass (5 to 40 ppm by mass), relative to the total mass of the liquid detergent composition. When the content of the preservative is within the above range, the effect of adding the preservative can be sufficiently obtained without reducing the detergency of the liquid detergent composition.

[0063] Examples of inorganic builders include metal oxides, such as zinc oxide and magnesium oxide. The inorganic builders may be used alone or in appropriate combination of two or more. When the liquid detergent composition contains an inorganic builder, the content of the inorganic builder is preferably 0.01 to 5% by mass relative to the total mass of the liquid detergent composition.

[0064] By including a hydrotrope in the liquid detergent composition, the liquid stability (particularly low temperature stability) of the liquid detergent composition is improved, making it easier to ensure a transparent appearance more stably. Examples of hydrotropic agents include aromatic sulfonic acids having 6 to 9 carbon atoms or salts thereof, aromatic carboxylic acids having 7 to 10 carbon atoms or salts thereof, 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.

[0065] Examples of aromatic sulfonic acids having 6 to 9 carbon atoms or salts thereof include xylenesulfonic acids or salts thereof, such as o-xylenesulfonic acid and m-xylenesulfonic acid; toluenesulfonic acids or salts thereof, such as o-toluenesulfonic acid, m-toluenesulfonic acid and p-toluenesulfonic acid; cumenesulfonic acids or salts thereof, such as m-cumenesulfonic acid and p-cumenesulfonic acid; and mesitylenesulfonic acid or salts thereof. Examples of aromatic carboxylic acids having 7 to 10 carbon atoms or salts thereof include benzoic acid or salts thereof, salicylic acid or salts thereof, phthalic acid or salts thereof, isophthalic acid or salts thereof, terephthalic acid or salts thereof, methyl p-oxybenzoate, ethyl p-oxybenzoate, n-propyl p-oxybenzoate, isopropyl p-oxybenzoate, β-oxynaphthoic acid, and esters thereof. Examples of the 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 alkanolamine salts such as monoethanolamine salts (monoethanolammonium salts), diethanolamine salts (diethanolammonium salts), and triethanolamine salts (triethanolammonium salts). Among these, alkali metal salts are preferred, sodium salts and potassium salts are more preferred, and sodium salts are even more preferred.

[0066] Examples of the monohydric alcohol having 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 hexyl glyceryl ether. The hydrotropic agent may be used alone or in combination of two or more.

[0067] The content of the hydrotrope agent is preferably 2 to 30 mass %, more preferably 3 to 10 mass %, based on the total mass of the liquid detergent composition. When the content of the hydrotrope agent is within the above range, the liquid detergent composition can have a sufficient liquid stabilizing effect without reducing the detergency.

[0068] The optional chelating agent may include, for example, organic acids and salts thereof such as glycolic acid, diglycolic acid, lactic acid, tartaric acid, carboxymethyltartaric acid, citric acid, malic acid, gluconic acid, and salts thereof. Examples of the salts include sodium salts. Preferred optional chelating agents are citric acid and its salts. The optional chelating agent may be used alone or in appropriate combination of two or more.

[0069] Examples of pH adjusters include inorganic alkali agents, organic alkali agents, and inorganic acids. Examples of inorganic alkaline agents include sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate. Examples of organic alkaline agents include amine compounds such as monoethanolamine, diethanolamine, triethanolamine, N-methylpropanol, 2-amino-2-methyl-1-propanol, N-(β-aminoethyl)ethanolamine, diethylenetriamine, morpholine, and N-ethylmorpholine. Examples of inorganic acids include hydrochloric acid and sulfuric acid. The organic acid may be acetic acid or the like. The pH adjuster may be used alone or in appropriate combination of two or more.

[0070] The solvent is preferably water. The use of water as a solvent makes it easier to prepare the liquid detergent composition. In addition, when the liquid detergent composition is used to clean an object to be cleaned, the solubility in water is improved. As the water, ion-exchanged water, distilled water, tap water, etc. can be used. The water content is preferably 90% by mass or less, more preferably 40 to 85% by mass, and even more preferably 50 to 85% by mass, based on the total mass of the dishwashing detergent composition. When the water content is equal to or greater than the lower limit, gelation of the liquid detergent composition is suppressed and the liquid uniformity is improved. When the water content is equal to or less than the upper limit, the liquid stability of the liquid detergent composition can be improved.

[0071] The total content of all components contained in the liquid detergent composition is 100% by mass.

[0072] <ph> The liquid detergent composition of the present invention preferably has a pH of 6 to 8 at 25°C. The pH (25°C) of the liquid detergent composition is a value measured by a method in accordance with JIS Z 8802:2011 "pH measurement method." The pH of the liquid detergent composition may be adjusted using the pH adjuster described above.

[0073] <Manufacturing method> The liquid detergent composition of the present invention is produced by a conventionally known production method. The liquid detergent composition can be produced, for example, by adding ingredients other than the pH adjuster to a portion of the water solvent, mixing them, adjusting the pH to a desired level with the pH adjuster as needed, and then adding the remainder of the water.

[0074] <How to use> The method of using the liquid detergent composition, i.e., the method of washing dishes, is described below. Examples of methods for washing dishes include a method in which a desired amount of the liquid detergent composition or a diluted solution thereof is applied to a cleaning tool and the cleaning tool is used to scrub the object to be cleaned (scrubbing operation), a method in which the liquid detergent composition is dispersed in water to prepare a cleaning liquid and the object to be cleaned is immersed in the cleaning liquid for a desired time (immersion time) (soaking operation), and a method in which the cleaning liquid is applied to the object to be cleaned and left to stand (spraying operation). In the soaking operation and the spraying operation, the object to be cleaned may be scrubbed with the cleaning tool in the cleaning liquid, if necessary. Each washing method may be performed on tableware immediately after use, on tableware that has been left for a short time (e.g., less than 5 hours) after use, or on tableware that has been left for a long time (e.g., up to about 24 hours) after use. After the scrubbing and soaking operations, the object is rinsed with rinse water to wash away any dishwashing detergent adhering to the object (rinsing operation). After the rinsing operation, a cleaned object is obtained.

[0075] Cleaning tools include sponges, brushes, cloths, etc. Examples of objects to be washed include ceramics, plastic utensils, metal utensils, and glass utensils. Examples of ceramics include tableware such as plates, bowls, and rice bowls. Examples of plastic utensils include plates, bowls, rice bowls, forks, spoons, cups, water bottles, and mugs. Examples of metal utensils include tableware such as forks and spoons, stainless steel sinks, bowls, water bottles, and mugs. Examples of glass utensils include tableware such as plates and cups. In addition to the above-mentioned tableware, examples of objects to be washed include cooking utensils such as pots, knives, cutting boards, airtight containers for storing food, frying pans, and kitchen equipment such as ranges and stoves. In this specification, tableware, sinks, cooking utensils, kitchen equipment, etc. are collectively referred to as "kitchenware."

[0076] The liquid detergent composition of the present invention can suppress odors from remaining on hydrophobic surfaces and can shorten the time required for washing dishes. [Example]

[0077] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following descriptions. The amounts of components used in each example are pure amounts unless otherwise specified.

[0078] "Raw materials used" The compounds shown below were used as components (A) and (A'). a-1: Alkyl ether sulfate (AES), polyoxyethylene (1) linear alkyl (C12 / 14=75 / 25; derived from natural fats and oils) sulfate sodium salt, "BRES (1)" manufactured by Lion Corporation. a-2: Sodium α-olefin sulfonate (AOS) with 14 carbon atoms, "Lipolan LB-440" manufactured by Lion Specialty Chemicals Co., Ltd. a-3: Sodium secondary alkanesulfonate (SAS) having 14 to 17 carbon atoms, "HOSTAPUR (registered trademark) SAS30A" manufactured by Clariant Japan Co., Ltd. a'-1: Linear alkylbenzene sulfonate (LAS), "Lion LH-200" manufactured by Lion Specialty Chemicals Co., Ltd.

[0079] The following compounds were used as component (B). b-1: Alkylamine oxide (AAO) with a linear alkyl group having 12 carbon atoms, "Cadenax DM12D-W(C)" manufactured by Lion Specialty Chemicals Co., Ltd. b-2: Amidopropyldimethylamine oxide (APDMAO), "GENAMINOX AP" manufactured by Clariant Japan. b-3: Lauryl amidopropyl betaine (LPB), Energicol L-30B manufactured by Lion Specialty Chemicals Co., Ltd.

[0080] The following compounds were used as component (C). c-1: Amylase and protease mixture (amylase / protease), "MedleyCore 210L" manufactured by Novozymes. c-2: Amylase, Novozymes "Achieve Alpha 100L". c-3: Protease, Novozymes "Blaze Pro 100L".

[0081] The compounds shown below were used as components (D) and (D'). d-1: Polyethyleneimine (manufactured by BASF Ltd., trade name "Lupasol SK"). d-2: Polyethyleneimine (manufactured by BASF Ltd., trade name "Lupasol G100"). d-3: Polyethyleneimine (manufactured by BASF Ltd., trade name "Lupasol FG"). d'-1: Alkoxylated polyethyleneimine (EO adduct of polyethyleneimine, manufactured by BASF Ltd., trade name "Sokalan HP20").

[0082] <Optional ingredients> XP-100: 2-propylheptyl alcohol ethoxylate (alkyl group: branched chain with 10 carbon atoms, average number of oxyethylene group repeats: 10 (BASF, Lutensol XP-100) Catalase: Novozymes "Terminox Ultra 50L". ·ethanol. Citric acid. ·Sodium lactate (Na lactate). · Paratoluenesulfonic acid (pTS). · Sodium benzoate (Na benzoate). Zinc oxide. Sulfamic acid. BIT: 1,2-benzisothiazolin-3-one (manufactured by Clariant Japan Co., Ltd., trade name "NIPACIDE BIT 20"). ·Fragrance. ·Sodium hydroxide (NaOH). Water: Ion-exchanged water.

[0083] "Examples 1 to 23, Comparative Examples 1 to 8" <Preparation of Liquid Detergent Composition> 1000 g of liquid detergent compositions having the formulations shown in Tables 1 to 4 were prepared by the following procedure. Component (A) and water (80% of the total water) were placed in a 1-L beaker and thoroughly stirred using a magnetic stirrer (Fine Corporation, trade name "F-606N"). Subsequently, components (B), (C), and (D), along with any optional components other than water and the pH adjuster (NaOH), were added and mixed. After mixing, an appropriate amount of pH adjuster was added, if necessary, to achieve the pH at 25°C values ​​listed in Tables 1 to 4. The remaining water was then added to bring the total volume to 100% by mass, and the mixture was further stirred thoroughly to obtain a liquid detergent composition. The pH (25°C) of the liquid detergent composition was measured by adjusting the liquid detergent composition to 25°C and using a glass electrode pH meter (DKK-TOA Corporation, trade name "HM-30G"), immersing the glass electrode directly in the dishwashing detergent. The pH reading after 1 minute was measured. The measurement method was in accordance with JIS Z 8802:2011 "pH Measurement Method." The liquid detergent compositions obtained in each example were evaluated for odor lingering on hydrophobic tableware, dishwashing time, amylase activity, and protease activity as follows. The results are shown in Tables 1 to 5.

[0084] <Evaluation> (No odor remaining on hydrophobic tableware (evaluation of odor lingering)) "Evaluation Method" Bon Curry Gold® was heated in a microwave oven at 600W for 2 minutes, and the curry, excluding the toppings, was stirred with a spoon. 0.5g was then evenly applied to a hydrophobic container (Iwasaki Industries Co., Ltd., Lastro Neokeeper 870mL) while weighing it with an electronic balance. The container was then air-dried at room temperature (25°C) for half a day to form a stain. 3g of each sample was added to 100g of 40°C tap water and left to stand for 30 minutes. The container was then rinsed with water at 25°C with 100mL / s, and expert evaluation (N=2) was conducted on a 4-point scale, using the following criteria: "Evaluation Criteria" ◎: No residual odor at all ○: Slight odor △: The smell is clearly detectable ×: Strong odor

[0085] (Dishwashing time evaluation) "Evaluation Method" To improve visibility, Sudan IV was uniformly dissolved in extra virgin olive oil (Ajinomoto Co., Inc.) at 0.1% by weight to prepare the soil sample for evaluation. Five ceramic dishes with a diameter of 21 cm were prepared, and 1 g of olive oil and 5 g of water were placed on each dish. 38 g of tap water at 25°C and 2 g of the sample were applied to a dishwashing sponge (3M Japan Co., Ltd.) and rubbed 10 times to wash the five ceramic dishes. Each dish was then rinsed with a 100 mL / s water flow at 25°C. The time from the start of washing to the end of rinsing was measured and evaluated according to the following criteria. "Evaluation Criteria" ◎: Less than 35 seconds ○: 35 to less than 40 seconds △: 40 to less than 45 seconds ×: 45 seconds or more

[0086] (amylase activity) Amylase activity was evaluated by the following constant amylase activity measurement method. "Evaluation Method" PhaDebas tablets (Magle Corporation, Phadebas Amylase Test for Amylase Activity Measurement), a cross-linked starch polymer containing an insoluble blue pigment, are hydrolyzed with alpha amylase, and the absorbance (620 nm) of the water-soluble blue pigment is measured to determine alpha amylase activity. First, a buffer solution is prepared. 20.0 g of sodium sulfite (Junsei Chemical Co., Ltd., special reagent grade, etc.), 6.15 g of potassium dihydrogen phosphate (Hayashi Pure Chemical Industries, Ltd., special reagent grade, etc.), 10.86 g of disodium hydrogen phosphate dodecahydrate (Kanto Chemical Co., Ltd., special reagent grade, etc.), 0.015 g of calcium chloride dihydrate (Kanto Chemical Co., Ltd., first grade, etc.), and 0.75 mL of Brij35 (MERCK, 30% aqueous solution) are precisely weighed and dissolved in ion-exchanged water to a final volume of 1 L. 0.5 g of enzyme-containing detergent is precisely weighed and dissolved in the above buffer solution to a final volume of 100 mL to form the sample solution. Place 1 mL of sample solution into a test tube (18 mm x 180 mm). Add 5.0 mL of buffer solution preheated to 37°C to the sample test tube, taking care not to let the solution touch the walls of the tube. Next, add one Padebas tablet with tweezers, stir for 10 seconds with a flash mixer, and place in a 37°C water bath. Repeat this procedure for each sample at 30-second intervals. After exactly 15 minutes (using a stopwatch), add 1.0 mL of 1 mol / L NaOH solution with a dispenser to stop the reaction, stir for 10 seconds with a flash mixer, leave at room temperature for 15 minutes, and then immediately filter through filter paper. If turbid, continue filtration using a filtration kit. Measure the absorbance of the sample and blank (enzyme-free composition) filtrates obtained by the above procedure at a measurement wavelength of λ = 620 nm (1 cm quartz cell, slit width 0.5 mm). Enzyme activity (U) = (sample absorbance) - (blank absorbance)

[0087] (protease activity) The protease activity was evaluated by the following protease activity measurement method. "Evaluation Method" The enzyme was applied to milk casein, and undigested proteins were precipitated with trichloroacetic acid (TCA), followed by filtration. The absorbance (λ = 275 nm) of the filtrate was measured to determine the amount of phenyl-containing amino acids (e.g., tyrosine) eluted, and protease activity was calculated. 1.2 g of milk casein (manufactured by CALBIOCHEM Co., Ltd.) was accurately placed in a 200 mL beaker, and 6 mL of 1 mol / L NaOH was gradually added while quickly kneading with a glass rod to swell the solution. Next, 160 mL of 0.05 mol / L boric acid solution was added, and the solution was stirred and dispersed with a stirrer. The pH was adjusted to 10.5 with 1 mol / L NaOH, and the volume was adjusted to 200 mL. 1 g of enzyme-containing detergent was accurately weighed and dissolved in ion-exchanged water to a final volume of 100 mL, which was used as the sample solution. 1 mL of the sample solution was placed in a test tube (18 mm x 180 mm). Add 5.0 mL of casein solution preheated to 37°C to the sample test tube without allowing the solution to touch the test tube walls, stir for 10 seconds with a flash mixer, and place in a 37°C water bath. This procedure is repeated for each sample at 30-second intervals. After exactly 30 minutes (using a stopwatch), add 5.0 mL of 0.44 mol / L TCA solution with a dispenser to stop the reaction, stir for 10 seconds with a flash mixer, and leave in the water bath for 30 minutes. Immediately filter through filter paper, then filter with a filtration filter (Tomsic, NP-44525-ACF). The absorbance of the sample and blank (enzyme-free) filtrate obtained by the above procedure is measured at a wavelength λ of 275 nm (1 cm quartz cell, slit width 0.5 mm). Enzyme activity (U) = (sample absorbance) - (blank absorbance)

[0088] [Table 1]

[0089] [Table 2]

[0090] [Table 3]

[0091] [Table 4]

[0092] [Table 5]

[0093] The blending amounts in Tables 1 to 5 are pure content values. Component amounts not listed in the tables are not blended. The "appropriate amount" of pH adjuster in the tables is the amount required to achieve the pH shown in the tables. The "balance" of water in the tables is the amount required to make the liquid detergent composition 100% by mass. In Tables 1 to 5, "A / B ratio" is the mass ratio expressed as component (A) / component (B). "C / D ratio" is the mass ratio expressed as component (C) / component (D). "A / (B+D) ratio" is the mass ratio expressed as component (A) / (component (B)+component (D)).

[0094] As is clear from Tables 1 to 5, the liquid detergent compositions of the respective Examples were able to exhibit excellent effects in the evaluation of the lack of odor remaining on hydrophobic tableware and the dishwashing time. On the other hand, as is clear from Table 5, the liquid detergent composition of Comparative Example 1, which did not contain component (A) (anionic surfactant), was inferior in the evaluation of the lack of odor remaining on hydrophobic tableware and the dishwashing time. The liquid detergent composition of Comparative Example 2, which contained a'-1 (linear alkylbenzene sulfonic acid) as component (A), was inferior in terms of leaving no odor on hydrophobic tableware. The liquid detergent composition of Comparative Example 3, which did not contain component (B), was inferior in the evaluation of the lack of odor remaining on hydrophobic tableware and the dishwashing time. The liquid detergent composition of Comparative Example 4, which did not contain component (C), was inferior in terms of the ability to leave no odor on hydrophobic tableware. The liquid detergent composition of Comparative Example 5, which did not contain component (D), was inferior in terms of the ability to leave no odor on hydrophobic tableware. The liquid detergent composition of Comparative Example 6, which contained d'-1 (alkoxylated polyethyleneimine (EO adduct of polyethyleneimine)) as component (D), was inferior in terms of leaving no odor on hydrophobic tableware. The liquid detergent composition of Comparative Example 7, which had a C / D ratio of 0.06, was inferior in terms of the ability to prevent odors from remaining on hydrophobic tableware. The liquid detergent composition of Comparative Example 8, which had a C / D ratio of 15.00, was inferior in terms of the ability to prevent odors from remaining on hydrophobic tableware. From the above results, it was confirmed that application of the present invention can improve the evaluation of odor elimination on hydrophobic tableware and the dishwashing time.< / ph>

Claims

1. A dishwashing detergent composition comprising component (A), component (B), component (C), and component (D), The component (A) is an anionic surfactant (excluding linear alkylbenzene sulfonic acid and its salts), The component (B) is at least one selected from a semi-polar surfactant and an amphoteric surfactant, The component (C) is an enzyme, The component (D) is polyethyleneimine (excluding those containing an oxyalkylene group), The dishwashing detergent composition has a mass ratio of component (C) / component (D) of 0.07 to 10.

2. The dishwashing detergent composition according to claim 1, wherein the mass ratio represented by the component (A) / (the component (B)+the component (D)) is 0.3 to 2.5.

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