Liquid detergent composition for tableware

Abstract

To provide a liquid detergent composition for tableware, suppressing adhesion of stain such as oil stain and water scale to a washing object, and having high washing force to the stain.SOLUTION: A liquid detergent composition for tableware as a liquid detergent composition containing (A) component, (B) component, (C) component and (D) component is such that: the (A) component is an anionic surfactant; the (B) component is at least one kind selected from a semipolar surfactant and an ampholytic surfactant; the (C) component is an aminocarboxylic acid type chelate agent; the (D) component is polyethylenimine (excluding one containing an oxyalkylene group); the content of the (A) component is 4-12 mass%, and the content of the (D) component is 0.05-2.5 mass% based on the total mass of the liquid detergent composition for tableware; and a mass ratio represented by the (C) component / the (D) component is 0.8-100.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Due to changes in consumer lifestyles, emphasis is being placed on "time saving" and "cleanliness" when washing dishes. Important factors that contribute to "time saving" include "quick drainage of dishes (improved drainability)" and "easy removal of grease and limescale (improved ease of cleaning)" when air-drying washed dishes without wiping them. Important factors that contribute to "cleanliness" include "inhibiting adhesion of grease and limescale to washed dishes" as well as "improved ease of cleaning limescale adhering to sinks and the like." It is desirable for liquid dishwashing detergent compositions to satisfy these factors.

[0003] As examples of detergents that provide excellent water drainage from dish surfaces after washing, Patent Document 1 describes a liquid dishwashing detergent composition containing an anionic surfactant, at least one selected from semi-polar surfactants and amphoteric surfactants, cationized cellulose, and a specific polyoxyalkylene alkyl ether. Patent Document 2 describes a liquid dishwashing detergent composition containing 25 to 60 mass% of surfactants, the liquid dishwashing detergent composition containing an anionic surfactant, at least one selected from semi-polar surfactants and amphoteric surfactants, and cationized cellulose. Patent Document 3 describes a liquid dishwashing detergent composition containing an anionic surfactant, at least one selected from semi-polar surfactants and amphoteric surfactants, at least one selected from fatty acid monoalkanolamides and polyoxyethylene fatty acid monoalkanolamides, and cationized cellulose. Furthermore, as a detergent capable of reducing water spots, which are traces of water left behind after drying on stainless steel surfaces such as sinks, Patent Document 4, for example, describes a liquid dishwashing detergent composition containing an anionic surfactant (excluding soap (higher fatty acid salt)), at least one surfactant selected from semi-polar surfactants and amphoteric surfactants, cationized cellulose, and an aminocarboxylic acid-type chelating agent. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2018-035251 [Patent Document 2] Japanese Patent Application Laid-Open No. 2003-155499 [Patent Document 3] Japanese Patent Application Publication No. 2018-035252 [Patent Document 4] International Publication No. 2024 / 014555 Summary of the Invention [Problem to be solved by the invention]

[0005] In recent years, liquid dishwashing detergent compositions have been desired to inhibit adhesion of stains such as oil stains and limescale to the surfaces of tableware. Furthermore, liquid dishwashing detergent compositions are sometimes used to clean stainless steel sinks and the like, and it is therefore desired that they can easily remove limescale stains adhering to sinks and the like. However, conventional liquid dishwashing detergent compositions using cationized cellulose have had problems in that when dishes that have been washed with the detergent composition are reused or when the used dishes are washed, oil stains, water stains, and other stains tend to adhere to the surface of the dishes, and problems exist in the ease of cleaning water stains on stainless steel surfaces. Therefore, an object of the present invention is to provide a liquid dishwashing detergent composition that inhibits adhesion of dirt such as oily dirt and limescale dirt to objects to be cleaned and has high detergency against such dirt. [Means for solving the problem]

[0006] The present invention has the following aspects. [1] A liquid dishwashing detergent composition containing component (A), component (B), component (C), and component (D), The component (A) is an anionic surfactant, The component (B) is at least one selected from a semi-polar surfactant and an amphoteric surfactant, The component (C) is an aminocarboxylic acid type chelating agent, The component (D) is polyethyleneimine (excluding those containing an oxyalkylene group), the content of the component (A) is 4 to 12 mass% and the content of the component (D) is 0.05 to 2.5 mass% relative to the total mass of the liquid dishwashing detergent composition; A liquid dishwashing detergent composition in which the mass ratio of the component (C) to the component (D) is 0.08 to 100. [2] (E) further contains the component, The liquid dishwashing detergent composition according to [1] above, wherein the component (E) is a Guerbet-type nonionic surfactant. [3] The liquid dishwashing detergent composition according to [1] or [2], wherein the mass ratio represented by the component (A) / (the component (C)+the component (D)) is 0.5 to 12.5. [Effects of the Invention]

[0007] The liquid dishwashing detergent composition of the present invention can inhibit adhesion of stains such as oil stains and water stains to objects to be cleaned, and can also enhance the detergency against such stains. DETAILED DESCRIPTION OF THE INVENTION

[0008] 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 as "to" means a numerical range that includes the numbers before and after "to" as the lower and upper limits. For example, A to B is equivalent to A or more and B or less.

[0009] The liquid dishwashing detergent composition of the present invention (hereinafter also simply referred to as "liquid detergent composition") contains the following components (A) to (D). In addition to the components (A) to (D), the liquid detergent composition preferably further contains the following component (E). The liquid detergent composition may further contain components other than components (A) to (E) (hereinafter also referred to as "optional components") in addition to components (A) to (D), as needed, within the range that does not impair the effects of the present invention.

[0010] <Component (A)> Component (A) is an anionic surfactant. When the liquid detergent composition contains the component (A), it is possible to inhibit adhesion of dirt such as oily dirt and water stains to the object to be cleaned, and to enhance the detergency against such dirt.

[0011] Examples of component (A) include linear alkylbenzenesulfonic acid or a salt thereof, α-olefinsulfonic acid or a salt thereof, internal olefinsulfonic 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, alkylcarboxylic 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.

[0012] As component (A), from the viewpoint of further suppressing adhesion of dirt such as oily dirt and water stains to the object to be cleaned and further enhancing the cleaning power against such dirt, alkyl ether sulfate esters or salts thereof, alkanesulfonic acids or salts thereof, linear alkylbenzenesulfonic acids or salts thereof, and α-olefinsulfonic acids or salts thereof are preferred.

[0013] 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 1 is 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.)

[0014] 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.

[0015] 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.

[0016] 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. In the linear alkylbenzenesulfonic acid or a salt thereof, the linear alkyl bonded to the benzene ring preferably has 8 to 16 carbon atoms, and more preferably 10 to 14 carbon atoms. 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.

[0017] 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.

[0018] The content of component (A) is 4 to 12 mass %, preferably 6 to 10 mass %, based on the total mass of the liquid detergent composition. When the content of component (A) is equal to or greater than the above-mentioned lower limit, adhesion of oily stains, water stains, and other stains to 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, adhesion of oily stains, water stains, and other stains to the object to be cleaned can be suppressed and detergency against these stains can be enhanced. Furthermore, gelation of the liquid detergent composition can be suppressed, thereby improving the liquid stability of the liquid detergent composition.

[0019] <(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), the liquid detergent composition can suppress adhesion of dirt such as oily dirt and water stains to the object to be cleaned, and can enhance the detergency against such dirt. 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.

[0020] 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)

[0021] 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 5is an alkylene group having 1 to 4 carbon atoms, and p is an integer of 0 to 1.

[0022] 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, lauryl dimethylamine oxide is preferred from the viewpoint of further suppressing adhesion of dirt such as oily dirt and water stains to the object to be cleaned and further enhancing the cleaning power against such dirt.

[0023] 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.

[0024] The content of component (B) is preferably 2.5 to 15 mass% and more preferably 5 to 10 mass% based on the total mass of the liquid detergent composition. When the content of component (B) is equal to or greater than the above-mentioned lower limit, adhesion of dirt such as oily dirt and water stains to the object to be cleaned can be further suppressed, and detergency against such dirt can be further enhanced. When the content of component (B) is equal to or less than the above-mentioned upper limit, gelation of the liquid detergent composition can be suppressed, and the liquid stability of the liquid detergent composition can be improved.

[0025] 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 "A / B ratio"), is preferably 0.25 to 2, more preferably 0.8 to 1.7. When the A / B ratio is equal to or greater than the above lower limit, adhesion of dirt such as oily dirt and water stains to the object to be cleaned can be further suppressed. When the A / B ratio is equal to or less than the above upper limit, detergency against dirt such as oily dirt and water stains can be further improved.

[0026] <(C) component> Component (C) is an aminocarboxylic acid type chelating agent. When the liquid detergent composition contains the component (C), it is possible to inhibit adhesion of dirt such as oily dirt and water stains to the object to be cleaned, and to enhance the detergency against such dirt.

[0027] Examples of component (C) include ethylenediaminetetraacetic acid or a salt thereof, nitrilotriacetic acid or a salt thereof, diethylenetriaminepentaacetic acid or a salt thereof, β-alaninediacetic acid or a salt thereof, ethylenediaminedisuccinic acid or a salt thereof, L-aspartic acid-N,N-diacetic acid or a salt thereof, dihydroxyethylethylenediaminediacetic acid or a salt thereof, hydroxyethyliminodiacetic acid or a salt thereof, hydroxyethylethylenediaminetriacetic acid or a salt thereof, triethylenetetraminehexaacetic acid or a salt thereof, 1,3-diamino-2-hydroxypropanetetraacetic acid or a salt thereof, dihydroxyethylglycine or a salt thereof, glycoletherdiaminetetraacetic acid or a salt thereof, L-glutamic acid diacetic acid or a salt thereof, and methylglycine diacetic acid or a salt thereof. Examples of the salt form of component (C) include sodium salts and potassium salts. The component (C) may be used alone or in an appropriate combination of two or more types. As component (C), from the viewpoints of further suppressing adhesion of dirt such as oily dirt and water stains to the object to be cleaned and further enhancing the detergency against such dirt, L-glutamic acid diacetic acid or a salt thereof, methylglycine diacetic acid or a salt thereof, and ethylenediaminetetraacetic acid or a salt thereof are preferred. Of these, methylglycine diacetic acid or a salt thereof is more preferred.

[0028] The content of component (C) is preferably 0.2 to 5 mass% and more preferably 0.5 to 2.5 mass% based on the total mass of the liquid detergent composition. When the content of component (C) is within the above range, adhesion of oily stains, water stains, and other stains to the object to be cleaned can be further suppressed, and detergency against these stains can be further enhanced. In particular, when the content of component (C) is equal to or less than the above upper limit, adhesion of oily stains, water stains, and other stains to the object to be cleaned can be further suppressed, and detergency against these stains can be further enhanced.

[0029] <(D) component> Component (D) is polyethyleneimine (excluding those containing oxyalkylene groups). When the liquid detergent composition contains component (D), it is possible to inhibit adhesion of dirt such as oily dirt and water stains to the object to be cleaned, and to enhance the detergency against such dirt.

[0030] 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.

[0031] 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.

[0032] Examples of polyethyleneimine or its main chain include compounds represented by the following general formulas (d1) to (d3): In addition, the wavy lines in formulas (d1) and (d2) represent the bonding positions with adjacent groups.

[0033] [ka]

[0034] [ka]

[0035] [ka]

[0036] 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 component (D) has a weight-average molecular weight within the above range, adhesion of oily stains, water stains, and other dirt to the object to be cleaned can be further suppressed, and the cleaning power against such dirt can be further enhanced. Furthermore, the liquid stability of the liquid detergent composition can be further improved. 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.

[0037] 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 viewpoint of further suppressing adhesion of dirt such as oily dirt and water stains to the object to be cleaned and further enhancing the cleaning power against such dirt.

[0038] 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.

[0039] 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.

[0040] As component (D), from the viewpoint of suppressing adhesion of dirt such as oily dirt and water stains to the object to be cleaned and enhancing the detergency against such dirt, the products manufactured by BASF under the trade names "Lupasol G 100," "Lupasol HF," "Lupasol PS," and "Lupasol SK" are preferred, the products manufactured by BASF under the trade names "Lupasol PS" and "Lupasol SK" are more preferred, and the product manufactured by BASF under the trade name "Lupasol SK" is even more preferred.

[0041] The content of component (D) is 0.05 to 2.5% by mass, preferably 0.1 to 1% by mass, and more preferably 0.1 to 0.5% by mass, relative to the total mass of the liquid detergent composition. When the content of component (D) is at least the above-mentioned lower limit, adhesion of dirt such as oily dirt and water stains to the object to be cleaned can be suppressed. When the content of component (D) is at most the above-mentioned upper limit, the detergency against dirt such as oily dirt and water stains can be enhanced, and gelation of the liquid detergent composition can be suppressed, improving the liquid stability of the liquid detergent composition.

[0042] 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 0.08 to 100, preferably 0.5 to 25, and more preferably 2 to 15. When the C / D ratio is equal to or greater than the above-mentioned lower limit, the detergency against stains such as oil stains and water stains can be enhanced. When the C / D ratio is equal to or less than the above-mentioned upper limit, adhesion of stains such as oil stains and water stains to the object to be cleaned can be suppressed.

[0043] Furthermore, the mass ratio of component (A) to the total amount of components (C) and (D), expressed as component (A) / (component (C)+component (D)) (hereinafter also referred to as the "A / (C+D) ratio"), is preferably 0.05 to 12.5, more preferably 3.5 to 8.5. If the A / (C+D) ratio is within the above range, adhesion of dirt such as oily dirt and water stains to the object to be cleaned can be further suppressed, and the detergency against these dirt can be further improved.

[0044] 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.

[0045] <(E) component> Component (E) is a Guerbet-type nonionic surfactant. By including component (E), the liquid detergent composition can further inhibit adhesion of dirt such as oily dirt and water stains to the object to be cleaned, and can further enhance the cleaning power against such dirt.

[0046] The component (E) is preferably a Guerbet alcohol-type nonionic surfactant represented by the following general formula (e1) (hereinafter also referred to as "component (e1)"). R 5 -CH(R 6 )-CH2-O-(R 7 O) q -H (e1) However, R 5 and R 6 are each independently a chain monovalent hydrocarbon group, and R 5 and R 6 The total number of carbon atoms is 4 to 16, and R 7 is a hydrocarbon group having 1 to 3 carbon atoms, and q is R 7 A number between 1 and 20 indicating the average number of O repeats. The (e1) component is a hydrophobic part (R 5 -CH(R 6The )-CH2-) structure is bulky. This easily disrupts the arrangement of the surfactant, especially in concentrated liquid detergent compositions with little water, and makes the liquid detergent composition less likely to solidify when placed at low temperatures compared to common branched nonionic surfactants that are not Guerbet-type. Furthermore, the bulky structure of the hydrophobic portion of component (e1) reduces the total amount of surfactant aligned at the interface with the stain when component (e1) is adsorbed onto hydrophobic substances such as oily stains, while increasing the ability to reduce interfacial tension, thereby enhancing the detergency of oily stains.

[0047] Examples of the component (E) include 2-propylheptyl alcohol ethoxylate, etc. A preferred commercially available product of the component (E) is "Lutensol XP-100" manufactured by BASF.

[0048] The content of component (E) is preferably 1 to 6 mass %, more preferably 2 to 4.5 mass %, based on the total mass of the liquid detergent composition. When the content of component (E) is within the above range, adhesion of dirt such as oily dirt and water stains to the object to be cleaned can be further suppressed, and the detergency against such dirt can be further enhanced.

[0049] In the liquid detergent composition, the mass ratio of component (D) to component (E), expressed as component (D) / component (E) (hereinafter also referred to as the "D / E ratio"), is preferably 0.008 to 2.5, more preferably 0.01 to 1.0, even more preferably 0.02 to 0.65, and particularly preferably 0.045 to 0.25. If the D / E ratio is within the above range, adhesion of dirt such as oily dirt and water stains to the object to be cleaned can be further suppressed, and the detergency against such dirt can be further enhanced.

[0050] <Optional ingredients> The optional components may be any components that are used in liquid dishwashing detergent compositions, such as surfactants other than components (A), (B), and (E) (hereinafter also referred to as "optional surfactants"), preservatives, inorganic builders, hydrotropes, chelating agents other than component (C) (hereinafter also referred to as "optional chelating agents"), polymeric compounds other than component (D) (hereinafter also referred to as "other polymeric compounds"), pH adjusters, solvents, fragrances, colorants, thickeners, disinfectants, antibacterial agents, antioxidants, etc.

[0051] Examples of optional surfactants include cationic surfactants and nonionic surfactants other than component (E). 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.

[0052] Examples of nonionic surfactants other than component (E) include polyoxyalkylene alkyl ethers and alkyl polyglycosides. The nonionic surfactants other than the component (E) may be used singly or in appropriate combination of two or more.

[0053] 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.

[0054] 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.

[0055] 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.

[0056] 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 liquid detergent composition can fully exhibit its effect without reducing its detergency.

[0057] 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.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] 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. If 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.

[0062] 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.

[0063] Examples of other polymer compounds include polysaccharide polymer compounds such as carboxymethyl cellulose (CMC), and acrylic acid polymer compounds such as acrylic acid-maleic anhydride copolymer sodium salt (MA agent). Other polymer compounds that may be used include the water-soluble polymers described in JP 2009-16622 A (e.g., alkylene oxide adducts of polyalkyleneamines), polyester soil release polymers described in WO 2012 / 136427 A, and cleaning builders described in JP 2017-210748 A (e.g., sodium salts of copolymers of olefins and maleic acid). The other polymer compounds may be used singly or in combination of two or more. The amount of the other polymer compound is preferably 0.001 to 5% by mass, more preferably 0.01 to 1% by mass, based on the total mass of the liquid detergent composition.

[0064] 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.

[0065] Examples of the solvent include water and organic solvents other than hydrotropes (hereinafter also referred to as "other organic solvents"). Among these, water is preferred as the solvent. By using water as the solvent, the liquid detergent composition can be easily prepared. In addition, when the liquid detergent composition is used to clean an object to be cleaned, the solubility in water is improved. The solvent may be used alone or in combination of two or more.

[0066] 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.

[0067] 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 having a molecular weight of about 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 the other organic solvent is preferably from 0.01 to 10 mass %, more preferably from 0.1 to 5 mass %, based on the total mass of the liquid detergent composition.

[0068] The fragrance may be any fragrance used in ordinary liquid detergents, including, for example, blended fragrance compositions 1 to 4 listed in Tables 1 to 8 of JP 2020-132680 A. The fragrance may be used alone or in combination of two or more. The content of the fragrance is preferably 0.001 to 0.3 mass %, more preferably 0.01 to 0.1 mass %, based on the total mass of the liquid detergent composition.

[0069] The dye is not particularly limited, and examples thereof include dyes described in the "Legal Dyes Handbook" (Japan Cosmetic Industry Association) and dyes in which the end of the chromophore structure is chemically modified with a water-soluble polymer or the like. The dyes may be used alone or in combination of two or more. The content of the colorant is preferably from 0.00001 to 0.01% by mass, more preferably from 0.0001 to 0.001% by mass, relative to the total mass of the liquid detergent composition.

[0070] The thickener is not particularly limited, and examples thereof include xanthan gum (manufactured by Sansho Co., Ltd., product name "Kelzan T"), diutan gum (manufactured by Sansho Co., Ltd., product name "KELCO-VIS DG"), and cellulose nanofiber (manufactured by Mori Machinery Corporation, product name "C-100"), etc. The thickener may be used alone or in combination of two or more. The content of the thickener is preferably from 0.001 to 1 mass %, more preferably from 0.01 to 0.5 mass %, based on the total mass of the liquid detergent composition.

[0071] Examples of disinfectants include zinc sulfate, zinc chloride, and zinc oxide. The disinfectant may be used alone or in combination of two or more. The content of the disinfectant is preferably 0.001 to 5 mass %, more preferably 0.01 to 1 mass %, based on the total mass of the liquid detergent composition.

[0072] 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 disinfectants such as quaternary ammonium salts (benzalkonium chloride, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkylbenzyldimethylammonium salts, alkylpyridinium salts), bis-(2-pyridylthio-1-oxide) zinc, polyhexamethylene biguanidine hydrochloride, 8-oxyquinoline, and polylysine. The antibacterial agent may be used alone or in combination of two or more. The content of the antibacterial agent is preferably from 0.001 to 5 mass %, more preferably from 0.01 to 1 mass %, based on the total mass of the liquid detergent composition.

[0073] Examples of antioxidants include monophenol-based antioxidants such as dibutylhydroxytoluene and butylhydroxyanisole; bisphenol-based antioxidants such as 2,2'-methylenebis(4-methyl-6-t-butylphenol); and polymeric phenol-based antioxidants such as dl-α-tocopherol. The antioxidants may be used alone or in combination of two or more.

[0074] The total content of all components contained in the liquid detergent composition is 100% by mass.

[0075] <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.

[0076] <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.

[0077] <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.

[0078] 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."

[0079] <Action and effect> The liquid detergent composition of the present invention inhibits adhesion of stains such as oil stains and water stains to objects to be cleaned, has high detergency against such stains, and is excellent in ease of cleaning. In particular, glass tableware is prone to stains such as oil stains and water stains. However, once the tableware is cleaned using the liquid detergent composition of the present invention, stains such as oil stains and water stains are less likely to adhere to the tableware when the washed tableware is reused or when the used tableware is washed. Furthermore, even if such stains adhere to the tableware, they can be easily cleaned. Furthermore, stainless steel surfaces such as sinks are prone to the adhesion and accumulation of water stains. However, the liquid detergent composition of the present invention has excellent ease of cleaning against water stains, so that cleaning a stainless steel surface using the liquid detergent composition of the present invention makes it difficult for stains such as water stains to adhere, and even if they do adhere, they can be easily cleaned. Furthermore, water stains and other stains already adhering to the stainless steel surface can also be easily cleaned.

[0080] The effect of the present invention is not certain, but is presumed as follows. The (D) component in the liquid detergent modifies the surface of the dishwashing object, allowing water to drain faster and preventing the buildup of limescale and oily stains. In addition, the (D) component acts on stains such as limescale that have built up on stainless steel surfaces such as sinks, making it easy to remove them. Furthermore, the liquid detergent composition containing components (A), (B), and (C) enhances the above-mentioned effect of component (D). This is thought to be because component (D) forms a complex with component (A), which facilitates adsorption to the surface of the object to be cleaned. In addition, it is thought that a portion of component (B) forms a complex with a portion of component (A), which facilitates removal of oily stains during cleaning, which facilitates adsorption of component (D) and the complex composed of components (A) and (D) to the surface of the object to be cleaned. Furthermore, it is thought that component (C) acts on metal ions on the surface of the object to be cleaned (particularly on metal surfaces such as glass and stainless steel) and on scale (specifically, calcium carbonate, etc.) adhering to these surfaces, thereby removing the metal ions and scale during cleaning, which facilitates adsorption of component (D) and the complex composed of components (A) and (D) to the surface of the object to be cleaned.

[0081] By further containing component (E), the liquid detergent composition can further inhibit adhesion of oily stains, water stains, and other stains to dishware after washing and further enhance its detergency against such stains. This is thought to be due to the improved wettability of the liquid detergent to the objects to be washed and to stains such as oily stains and water stains adhering to their surfaces. [Example]

[0082] 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.

[0083] "Raw materials used" The following compounds were used as component (A). A-1 (AES(1)): Polyoxyethylene(1) linear alkyl (C12 / 14=75 / 25; derived from natural fats and oils) ether sulfate sodium salt (synthesized according to the synthesis method described below). A-2 (LAS): Sodium linear alkylbenzene sulfonate having 10 to 14 carbon atoms (manufactured by Teika Corporation, trade name "Teika Power (registered trademark) L121" neutralized with sodium hydroxide). A-3 (SAS): Sodium secondary alkanesulfonate having 14 to 17 carbon atoms (manufactured by Clariant Japan Co., Ltd., trade name "HOSTAPUR (registered trademark) SAS30A"). A-4 (AOS): Sodium α-olefin sulfonate having 14 carbon atoms (manufactured by Lion Specialty Chemicals Co., Ltd., trade name "Lipolan (registered trademark) LB-440").

[0084] (Method of synthesizing A-1) A 4-liter autoclave was charged with 400 g of Procter & Gamble's CO1270 alcohol (C12 / C14 = 75% / 25%, mass ratio) as the raw alcohol and 0.8 g of potassium hydroxide as the reaction catalyst. The autoclave was then purged with nitrogen and heated with stirring. Next, 91 g of ethylene oxide was introduced and reacted while maintaining the temperature at 180°C and the pressure at 0.3 MPa or less. The average number of moles of ethylene oxide added in the resulting polyoxyalkylene ether was 1. Next, 237 g of the resulting polyoxyalkylene ether ethylene oxide was placed in a 500 mL flask equipped with a stirrer, and after replacing the atmosphere with nitrogen, 96 g of liquid sulfuric anhydride (sulfan) was slowly added dropwise while maintaining the reaction temperature at 40°C. After the addition was completed, stirring was continued for 1 hour (sulfation reaction) to obtain polyoxyethylene alkyl ether sulfate. The resulting polyoxyethylene alkyl ether sulfate was then neutralized with aqueous sodium hydroxide solution to obtain A-1.

[0085] The following compounds were used as component (B). B-1(AX): Lauryl dimethylamine oxide (manufactured by Lion Specialty Chemicals Co., Ltd., product name "Cadenax DM12D-W").

[0086] The following compounds were used as component (C). C-1 (MGDA): Trisodium methylglycine diacetate (manufactured by BASF, trade name "TrilonMLiquid"). C-2 (GLDA): Tetrasodium L-glutamate diacetate (manufactured by Akzo Nobel, trade name "Dissolvine (registered trademark) GL-47-S"). C-3 (EDTA): Tetrasodium ethylenediaminetetraacetic acid (manufactured by BASF, trade name "Trilon BX Liquid").

[0087] The compound shown below was used as component (D). D-1: Polyethyleneimine (manufactured by BASF, trade name "Lupasol SK", weight average molecular weight 2,000,000). D-2: Polyethyleneimine (manufactured by BASF, trade name "Lupasol PS", weight average molecular weight 750,000). D-3: Polyethyleneimine (manufactured by BASF, trade name "Lupasol G 100", weight average molecular weight 5,000). D-4: Polyethyleneimine (manufactured by BASF, trade name "Lupasol FG", weight average molecular weight 800). The weight average molecular weight of the component (D) was measured under the above-mentioned measurement conditions.

[0088] The compound shown below was used as a comparative product (component (D')) for component (D). D'-5: Alkoxylated polyethyleneimine (EO adduct of polyethyleneimine, manufactured by BASF, trade name "Sokalan HP 20"). D'-6: Cationic cellulose (manufactured by The Dow Chemical Company, trade name "UCAREJR 125", a compound having a quaternary nitrogen content of 1.9% by mass and a viscosity of a 2.0% by mass aqueous solution at 25°C of 130 mPa·s).

[0089] The compound shown below was used as component (E). E-1: Guerbet-type nonionic surfactant (2-propylheptyl alcohol ethoxylate, manufactured by BASF, trade name "LutensolXP-100", a compound having a branched alkyl group with 10 carbon atoms and an average repeating number of oxyethylene groups of 10).

[0090] The following compound was used as a comparative product (component (E')) for component (E). E'-2: Linear nonionic surfactant (manufactured by Lion Specialty Chemicals Co., Ltd., trade name "LMAO-90", a compound having a linear alkyl group with 12 or 14 carbon atoms and an average repeating number of oxyethylene groups of 15).

[0091] As optional components, the compounds shown below were used. (hydrotropic agent) Paratoluenesulfonic acid (Kanto Chemical Co., Ltd.) In the table, this is referred to as p-TSH. Ethanol (manufactured by Japan Alcohol Sales Co., Ltd.) In the table, it is referred to as EtOH. Sodium benzoate (manufactured by Fushimi Pharmaceutical Co., Ltd.). In the table, this is listed as sodium benzoate. (Optional chelating agent) Citric acid (manufactured by Fuso Chemical Co., Ltd., product name "Citric Acid"). (pH adjuster) Sodium hydroxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product name "Sodium Hydroxide"). (solvent) Water: Ion-exchanged water.

[0092] "Examples 1 to 37, Comparative Examples 1 to 12" <Preparation of Liquid Detergent Composition> 1000 g of liquid detergent compositions having the formulations shown in Tables 1 to 6 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), (D), and (E), 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 adjust the pH at 25°C to the values ​​listed in Tables 1 to 6. 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") to directly immerse the glass electrode 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 their ability to inhibit adhesion of oil stains and water stains, and for their ease of cleaning water stains from stainless steel surfaces, as described below. The results are shown in Tables 1 to 6.

[0093] <Evaluation> (Evaluation of the inhibition of adhesion of complex stains such as oil stains and water stains on glass surfaces) A glass (manufactured by Toyo Sasaki Glass Co., Ltd., product name "Tumbler HS 210 ml") was used as the object to be cleaned. 38 g of tap water and 2 g of the liquid detergent composition were applied to a dishwashing sponge measuring 11.5 cm x 7.5 cm x 3 cm, and the sponge was rubbed by hand 10 times, followed by scrubbing the surface of the object to be cleaned 10 times. This was followed by rinsing with tap water for 10 seconds and drying, which constituted one set of operations. This operation was repeated three times. 5 mL of oily soil (olive oil) was then applied to the surface of the glass, and the glass was again rinsed with tap water (water temperature 25°C, 5 L / min) for 10 seconds. The glass was placed almost vertically against a commercially available screen, and the amount of complex soiling adhering to the glass after drying was visually observed. In this evaluation method, three glasses were evaluated based on the following evaluation criteria, and an average score was calculated. Separately, a glass was rinsed with tap water for 10 seconds and then dried, which constituted one set. This procedure was repeated three times. Five milliliters of oily soil (olive oil) was then applied to the surface of the glass, and it was again rinsed with tap water (25°C, 5 L / min) for 10 seconds. The glass was placed almost vertically against a commercially available partition, and the amount of composite soiling on the glass after drying was visually observed. This was used as a blank. (Evaluation criteria) 5 points: Complex soiling was reduced by 70% or more compared to the blank. 4 points: Complex soiling was reduced by 50-60% compared to the blank. 3 points: Complex soiling was reduced by 30 to 40 percent compared to the blank. 2 points: The amount of complex dirt was reduced by 10 to 20% compared to the blank. 1 point: No change from blank.

[0094] (Evaluation of the ease of cleaning water stains on stainless steel surfaces) A 10 cm × 10 cm stainless steel plate (numerous scratches were made in a 2 cm × 2 cm area in the center with the hard side (nonwoven fabric side) of a dishwashing sponge) was used as the evaluation subject. The surface of this stainless steel plate was rinsed with hard water (30°C hard water, water temperature 25°C, 5 L / min) for 10 seconds and then air-dried to form limescale stains. After dripping 1 g of liquid detergent composition, the plate was rinsed with tap water for 10 seconds, rinsed again with hard water (30°C hard water, water temperature 25°C, 5 L / min) for 10 seconds, and then air-dried. After dripping 1 g of liquid detergent composition, the plate was rinsed with tap water for 10 seconds and air-dried, and then the limescale removal was evaluated visually based on the following evaluation criteria. Separately, a similarly scratched 10cm x 10cm stainless steel plate surface was rinsed for 10 seconds with hard water (30°C hard water, water temperature 25°C, 5 L / min) and allowed to air dry to form limescale stains. It was then rinsed for 10 seconds with tap water, rinsed again for 10 seconds with hard water (30°C hard water, water temperature 25°C, 5 L / min), air dried, rinsed again for 10 seconds with tap water, air dried, and the removal of limescale stains after that was used as a blank. (Evaluation criteria) 5 points: All dirt has been removed. 4 points: Most of the dirt has been removed. 3 points: Some dirt has been removed. 2 points: Slight dirt has been removed. 1 point: No dirt was removed at all (same as blank).

[0095] [Table 1]

[0096] [Table 2]

[0097] [Table 3]

[0098] [Table 4]

[0099] [Table 5]

[0100] [Table 6]

[0101] The blending amounts in Tables 1 to 6 are pure content values. Component amounts without a blending amount 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, "C / D ratio" is the mass ratio expressed as component (C) / component (D). "A / B ratio" is the mass ratio expressed as component (A) / component (B). "A / (C+D) ratio" is the mass ratio expressed as component (A) / (component (C)+component (D)). "D / E ratio" is the mass ratio expressed as component (D) / component (E).

[0102] As is clear from Tables 1 to 4, the liquid detergent compositions of each Example were able to inhibit the adhesion of complex soils to glass surfaces, and also exhibited excellent ease of cleaning even against water stains on stainless steel surfaces. On the other hand, as is clear from Tables 5 and 6, the liquid detergent compositions of Comparative Example 1, in which the content of component (A) was 3 mass%, and Comparative Example 2, in which the content of component (A) was 13 mass%, were inferior in inhibiting the adhesion of complex soils on glass surfaces and in easily cleaning water stains on stainless steel surfaces. The liquid detergent compositions of Comparative Example 3, in which the content of component (D) was 0.01% by mass, and Comparative Example 4, in which the content of component (D) was 3% by mass, were inferior in inhibiting the adhesion of complex soils to glass surfaces and in easily cleaning water stains from stainless steel surfaces. The liquid detergent compositions of Comparative Examples 5 and 6, which contained component (D') instead of component (D), were inferior in inhibiting adhesion of complex soils to glass surfaces and in easily cleaning water stains from stainless steel surfaces. The liquid detergent compositions of Comparative Example 7, in which the C / D ratio was 160, and Comparative Example 8, in which the C / D ratio was 0.04, were inferior in inhibiting the adhesion of complex soils to glass surfaces and in easily cleaning water stains from stainless steel surfaces. The liquid detergent compositions of Comparative Examples 9 to 12, which lacked any of the components (A) to (D), were inferior in inhibiting adhesion of complex soils to glass surfaces and in easily cleaning water stains from stainless steel surfaces. From the above results, it was confirmed that application of the present invention can suppress adhesion of oil stains and water stains on glass surfaces and can also improve the ease of cleaning water stains on stainless steel surfaces.< / ph>

Claims

1. A liquid dishwashing detergent composition comprising component (A), component (B), component (C), and component (D), The component (A) is an anionic surfactant, The component (B) is at least one selected from a semi-polar surfactant and an amphoteric surfactant, The component (C) is an aminocarboxylic acid type chelating agent, The component (D) is polyethyleneimine (excluding those containing an oxyalkylene group), the content of the component (A) is 4 to 12 mass% and the content of the component (D) is 0.05 to 2.5 mass% based on the total mass of the liquid dishwashing detergent composition; A liquid dishwashing detergent composition, wherein the mass ratio of component (C) to component (D) is 0.08 to 100.

2. Further containing component (E), 2. The liquid dishwashing detergent composition according to claim 1, wherein the component (E) is a Guerbet-type nonionic surfactant.

3. 3. The liquid dishwashing detergent composition according to claim 1, wherein the mass ratio of the component (A) to the component (C) plus the component (D) is 0.5 to 12.5.

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