Liquid detergent composition for hard surfaces

Abstract

To provide a liquid detergent composition for hard surfaces capable of suppressing adhesion of stains including water scale and oily soil to hard surfaces and capable of exhibiting excellent cleaning performance without applying mechanical force.SOLUTION: A liquid detergent composition for hard surfaces comprises following components: (A) a non-soap anionic surfactant, (B) a cationized polysaccharide, (C) a chelating agent, and (D) a compound represented by the following general formula (d1), wherein a content of the component (B) is 0.01 mass% to 5 mass% with respect to a total mass of the liquid detergent composition for hard surfaces. Ph-X-OH (d1) (in the formula (d1), Ph is a phenyl group, X is R6 or (OR7)m, R6 is an alkylene group having 1 or 2 carbon atoms, R7 is an alkylene group having 2 or 3 carbon atoms, and m is a number of 1 to 6).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a liquid cleaning composition for hard surfaces. [Background technology]

[0002] BACKGROUND ART As a detergent composition for mainly washing (cleaning target) items such as tableware and cooking utensils, there is a liquid detergent composition for hard surfaces (hereinafter, also simply referred to as "liquid detergent composition"). As a liquid detergent composition capable of suppressing the adhesion of water stains to hard surfaces, for example, Patent Document 1 discloses a liquid detergent composition containing a nonionic surfactant, a polymer such as a vinylpyrrolidone homopolymer, and a specific amphoteric surfactant. As a liquid detergent composition with excellent drainage properties, for example, Patent Document 2 discloses a dishwashing detergent containing an anionic surfactant, at least one surfactant selected from an amine oxide surfactant and an amphoteric surfactant, a cationic polymer compound, and a chelating agent.

[0003] In general households, for example, a method has been used in which a liquid detergent composition is applied to a cleaning tool such as a sponge soaked in water, the tool is rubbed to create a lather, and the liquid detergent composition is then spread over the hard surfaces of dishes and the like, followed by scrubbing. Alternatively, a method has been used in which water is collected in a tub, sink, or the like, a liquid detergent composition is diluted in the water, and dishes and the like are scrubbed in the water. In these cleaning methods, the strong mechanical force required for scrubbing results in poor cleaning efficiency and is tiring.

[0004] In contrast to this, there are liquid detergent products for hard surfaces (hereinafter also simply referred to as "liquid detergent products") in which a liquid detergent composition is contained in a trigger-type spray container. When using such a liquid detergent product, the liquid detergent composition is sprayed onto an object to be cleaned, such as tableware, and left for a desired period of time. Thereafter, the object to be cleaned is rinsed with water or lightly scrubbed, and cleaning effects equal to or better than those of ordinary scrubbing can be obtained. Patent Document 3, for example, discloses a liquid detergent composition for hard surfaces that contains alkylbenzenesulfonic acid or a salt thereof, a specific solvent, a specific nonionic surfactant, and one or more surfactants selected from amphoteric surfactants and / or amine oxide surfactants, and water, and that can be used in a trigger-type spray container to exhibit excellent detergency against solid grease adhering to vertical surfaces. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Special Publication No. 2001-510231 [Patent Document 2] Japanese Patent Publication No. 2022-63462 [Patent Document 3] Japanese Patent Publication No. 2023-82823 Summary of the Invention [Problem to be solved by the invention]

[0006] Liquid detergent compositions are also sometimes used to clean sinks, and conventional methods for cleaning sinks have involved scrubbing with a cleaning tool (such as a sponge) impregnated with the liquid detergent composition. As a result of extensive investigations, the present inventors have obtained the following findings. When the sink is repeatedly scrubbed, water spreads unevenly when it is poured into the sink. This is thought to be because the surface of the sink is scratched or otherwise changed due to friction with the cleaning tools that occurs when the sink is cleaned, the effect of the liquid detergent composition, etc. When water poured into the sink spreads unevenly, dirt (e.g., limescale, oil stains, etc.) is more likely to adhere to the sink surface. Furthermore, even when dishes are washed with running water, dirt on the sink surface cannot be sufficiently removed. Therefore, the present invention aims to provide a liquid detergent composition for hard surfaces that can suppress the adhesion of dirt such as water stains and oil stains to hard surfaces and can exert an excellent cleaning effect without the application of mechanical force. [Means for solving the problem]

[0007] The present invention has the following aspects. [1] Component (A): a non-soap anionic surfactant, (B) component: a cationized polysaccharide; (C) component: a chelating agent; Component (D): a compound represented by the following general formula (d1), A liquid cleaning composition for hard surfaces comprising: A liquid detergent composition for hard surfaces, wherein the content of the component (B) is 0.01 to 5% by mass relative to the total mass of the liquid detergent composition for hard surfaces. Ph-X-OH (d1) (In formula (d1), Ph is a phenyl group, and X is R 6 OR 7 ) m R 6 is an alkylene group having 1 or 2 carbon atoms, and R 7 is an alkylene group having 2 or 3 carbon atoms, and m is a number from 1 to 6. [2] The liquid detergent composition for hard surfaces according to [1] above, wherein the mass ratio of the component (B) to the component (D) is 0.001 to 50. [3] The liquid cleaning composition for hard surfaces according to [1] or [2] above, which is for use as a trigger spray. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a liquid detergent composition for hard surfaces that can inhibit adhesion of stains such as water stains and oil stains to hard surfaces and that can exert an excellent cleaning effect without applying mechanical force. 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 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. Furthermore, the term "hard surface" refers to the surface of an article made of a hard material. Examples of materials for hard surfaces include plastics, ceramics, glass, and metals (such as stainless steel and aluminum).

[0010] [Liquid cleaning composition for hard surfaces] The liquid detergent composition for hard surfaces of the present invention (hereinafter also simply referred to as "liquid detergent composition") contains the following components (A), (B), (C), and (D). The liquid detergent composition may further contain, in addition to the components (A), (B), (C), and (D), components other than the components (A), (B), (C), and (D) (hereinafter also referred to as "optional components"), as necessary, within a range that does not impair the effects of the present invention.

[0011] <Component (A)> Component (A) is a non-soap anionic surfactant. Non-soap anionic surfactants are anionic surfactants excluding higher fatty acids and their salts (so-called soaps). "Higher fatty acids" are saturated fatty acids having 8 to 24 carbon atoms and unsaturated fatty acids having 8 to 24 carbon atoms. In other words, component (A) is an anionic surfactant excluding saturated fatty acids having 8 to 24 carbon atoms, unsaturated fatty acids having 8 to 24 carbon atoms, and salts thereof. By including component (A), the liquid detergent composition can inhibit adhesion of stains such as water stains and oil stains to hard surfaces, and can exert an excellent cleaning effect even if such stains are attached without the need for mechanical force.

[0012] 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, and α-sulfofatty acid ester or a salt thereof. Examples of salt forms of non-soap 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 adhesion of stains such as water stains and oil stains to hard surfaces and further enhancing the cleaning effect against such stains, alkyl ether sulfates or salts thereof, alkanesulfonic acids or salts thereof, linear alkylbenzenesulfonic 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 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.)

[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 this specification, the number 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. 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.

[0018] The content of component (A) is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, and even more preferably 1 to 10% by 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, the cleaning effect on stains such as water stains and oil stains is further enhanced. When the content of component (A) is equal to or less than the above-mentioned upper limit, adhesion of stains such as water stains and oil stains to hard surfaces can be further suppressed. In addition, gelation of the liquid detergent composition can be suppressed, improving liquid stability.

[0019] <(B) component> Component (B) is a cationized polysaccharide. The liquid detergent composition containing component (B) enhances the water spreadability (wettability) of hard surfaces, making the hard surfaces hydrophilic and allowing water to flow uniformly, suppressing the adhesion of stains such as water stains and oil stains, and providing excellent cleaning effects even when such stains are attached without the application of mechanical force.

[0020] The cationic functional group of the cationized polysaccharide may be a quaternary ammonium group having three radical groups. The three radical groups may be the same or different, and examples thereof include a hydrogen atom, an alkyl group, a hydroxyalkyl group, an epoxyalkyl group, an alkenyl group, and an aryl group. The number of carbon atoms in each of the alkyl group, hydroxyalkyl group, and alkenyl group is preferably 1 to 22, more preferably 1 to 14, and even more preferably 1 to 3. Counterions of cationized polysaccharides include, but are not limited to, halides such as chloride, fluoride, bromide, iodide, sulfate, methyl sulfate, and mixtures thereof.

[0021] Examples of quaternary ammonium salts include 3-chloro-2-hydroxypropyltrimethylammonium chloride, 2,3-epoxypropyltrimethylammonium chloride, diallyldimethylammonium chloride, vinylbenzenetrimethylammonium chloride, trimethylammonium ethyl methacrylate chloride, methacrylamidepropyltrimethylammonium chloride, and tetraalkylammonium chloride.

[0022] An example of a cationic functional group in a cationic polysaccharide is trimethylamino(2-hydroxyl)propyl, which has a counterion.

[0023] Examples of the cationic polysaccharides include cationic guar gum, cationic cellulose, and cationic starch. Alternatively, component (B) may be a reaction product obtained by alkylating hydroxyethyl cellulose with an alkyl (preferably lauryl) glycidyl ether and then cationizing the alkyl ether with a glycidyl trialkyl ammonium halide such as glycidyl trimethyl ammonium chloride, glycidyl triethyl ammonium chloride, glycidyl trimethyl ammonium bromide, or glycidyl triethyl ammonium bromide. The degree of substitution of the alkyl group in this reaction product is preferably 0.01 to 0.5, and the degree of substitution of the cationic group is preferably 0.001 to 0.4. Among these, from the viewpoints of further increasing the wettability of hard surfaces, particularly stainless steel surfaces, making the hard surfaces more uniformly hydrophilic, and further enhancing the effect of inhibiting adhesion of stains such as water stains and oil stains, preferred are cationized guar gum and cationized cellulose, with cationized guar gum being more preferred. The component (B) may be used alone or in combination of two or more.

[0024] Cationized guar gum is a cationic derivative of guar gum. Guar gum is a polysaccharide composed of the sugars galactose and mannose. Its backbone is a linear chain of β-1,4-linked mannose residues to which galactose residues are 1,6-linked at every second mannose to form short branches.

[0025] The degree of cationization of the cationized guar gum is preferably 0.1 to 3 mass %, more preferably 0.9 to 3 mass %. If the degree of cationization is within the above range, the wettability of hard surfaces, particularly stainless steel surfaces, is further improved. The degree of cationization of cationized guar gum is the content (mass %) of nitrogen atoms derived from a cationizing agent in the molecules of the cationized guar gum, i.e., the degree of cationization of cationized guar gum is the content of nitrogen atoms relative to the total mass of the cationized guar gum. The degree of cationization of the cationized guar gum is calculated based on the specified chemical structure. When the ratio of any monomer in the cationized guar gum is unknown, or when the chemical structure of the cationized guar gum is not specified, the degree of cationization of the cationized guar gum is calculated from the nitrogen content determined experimentally. The nitrogen content in the cationized guar gum can be measured by, for example, the Kjeldahl method.

[0026] The weight-average molecular weight of the cationized guar gum is preferably 100,000 Da to 3,500,000 Da, more preferably 500,000 Da to 3,500,000 Da, and even more preferably 1,500,000 Da to 3,500,000 Da. If the weight-average molecular weight is within the above range, the wettability of hard surfaces, particularly stainless steel surfaces, is further improved. The weight average molecular weight of the cationized guar gum is a value determined from the molecular weight distribution obtained by GPC (gel permeation chromatography) using polyethylene glycol of known molecular weight as the standard.

[0027] The viscosity of a 0.5% by mass aqueous solution of cationized guar gum at 25° C. is preferably 30 to 1000 mPa·s, more preferably 50 to 500 mPa·s, and even more preferably 50 to 300 mPa·s. When the viscosity of a 0.5% by mass aqueous solution of cationized guar gum is within the above range, an excellent balance is achieved between improved wettability of hard surfaces, particularly stainless steel surfaces, and the stability of the liquid detergent composition.

[0028] The viscosity of a 0.5% by mass aqueous solution of cationized guar gum is a value measured using a B-type viscometer at a measurement temperature of 25° C. The viscosity measurement conditions are as follows. <<Rotor and rotation speed>> The rotor numbers and rotation speeds corresponding to the viscosities to be measured are as follows: When the viscosity of the object to be measured is less than 500 mPa·s: Rotor No. 2, rotation speed 60 rpm. When the viscosity of the object to be measured is 500 mPa·s or more but less than 2000 mPa·s: Rotor No. 3, rotation speed 60 rpm. When the viscosity of the object to be measured is 2000 mPa·s or more but less than 10000 mPa·s: Rotor No. 4, rotation speed 60 rpm. When the viscosity of the object to be measured is 10,000 mPa·s or more but less than 50,000 mPa·s: Rotor No. 4, rotation speed 12 rpm. <<Reading the numbers>> 60 seconds after the rotor starts spinning.

[0029] Examples of the cationized guar gum include cationized hydroxyalkyl guar gums such as cationized hydroxyethyl guar gum, cationized hydroxypropyl guar gum, and cationized hydroxybutyl guar gum; and cationized carboxyalkyl guar gums such as cationized carboxymethyl guar gum, cationized carboxylpropyl guar gum, cationized carboxybutyl guar gum, and carboxymethyl hydroxypropyl guar gum. Among these, cationized hydroxypropyl guar gum is preferred, and specifically, guar hydroxypropyltrimonium chloride and hydroxypropyl guar hydroxypropyltrimonium chloride are more preferred. The cationized guar gum may be used alone or in combination of two or more kinds.

[0030] An example of guar hydroxypropyltrimonium chloride is shown in the following general formula (b1), and an example of hydroxypropyl guar hydroxypropyltrimonium chloride is shown in the following general formula (b2).

[0031] [ka]

[0032] In formula (b1), R 2 and R 3 are each independently a hydrogen atom or a group represented by the following formula (b11), and j is a number representing the number of repetitions. Note that the wavy line in formula (b11) represents the bonding position to the adjacent group.

[0033] [ka]

[0034] [ka]

[0035] In formula (b2), R 4 and R 5 are each independently a hydrogen atom, a group represented by the following formula (b21) or a group represented by the following formula (b22), and k is a number representing the number of repetitions. Note that the wavy lines in formula (b21) and formula (b22) represent the bonding positions to adjacent groups.

[0036] [ka]

[0037] Commercially available cationized guar gum products include those shown below. Commercially available products of guar hydroxypropyltrimonium chloride (INCI name) include, for example, trade names "Jaguar (registered trademark) C14S" and "Jaguar (registered trademark) C17K" manufactured by Solvay. An example of a commercially available product of hydroxypropyl guar hydroxypropyltrimonium chloride (INCI name) is "Jaguar (registered trademark) C162" manufactured by Solvay.

[0038] Examples of cationized cellulose include a compound represented by the following general formula (b3) (hereinafter also referred to as "compound (b3)"), a compound represented by the following general formula (b4) (hereinafter also referred to as "compound (b4)"), a compound represented by the following general formula (b5) (hereinafter also referred to as "compound (b5)"), and a compound represented by the following general formula (b6) (hereinafter also referred to as "compound (b6)"). Specific examples of the cationized cellulose include cation-modified hydroxyethyl cellulose such as hydroxytrimethylammoniopropyl hydroxyethyl cellulose chloride and hydroxyethyl cellulose dimethyl diallyl ammonium chloride polymer. Among these, compound (b3) is preferred from the viewpoint of further increasing the wettability of hard surfaces, particularly stainless steel surfaces.

[0039] [ka]

[0040] In formula (b3), s, t, and u are numbers each representing the number of repetitions.

[0041] [ka]

[0042] In formula (b4), x, y, v, and w are numbers each representing the number of repetitions.

[0043] [ka]

[0044] In formula (b5), q and r are numbers each representing the number of repetitions.

[0045] [ka]

[0046] The weight-average molecular weight of the compound (b3) is 10,000 to several million. The weight-average molecular weight of the compound (b4) is 10,000 to several million. The weight-average molecular weight of the compound (b5) is 10,000 to several hundred thousand. The weight-average molecular weight of the compound (b6) is 10,000 to several hundred thousand. These weight average molecular weights are values ​​determined from the molecular weight distribution obtained by GPC (gel permeation chromatography) using polyethylene glycol of known molecular weight as the standard.

[0047] The degree of cationization of the cationized cellulose is preferably 0.5 to 3.5 mass%, more preferably 1.5 to 2.5 mass%. When the degree of cationization of the cationized cellulose is within the above range, the wettability of hard surfaces, particularly stainless steel surfaces, is further improved. Here, the "degree of cationization" refers to the content (mass %) of nitrogen atoms derived from the cationizing agent in the molecules of the cationized cellulose, that is, the content of nitrogen atoms relative to the total mass of the cationized cellulose. The degree of cationization of the cationized cellulose is calculated based on the specified chemical structure. When the chemical structure of the cationized cellulose is not specified, such as when the ratio of any monomer in the cationized cellulose is unknown, the degree of cationization of the cationized cellulose is calculated from the experimentally determined nitrogen content. Examples of methods for measuring the nitrogen content in cationized cellulose include the Kjeldahl method.

[0048] The viscosity of a 2% by mass aqueous solution of cationized cellulose at 25°C is preferably 50 to 35,000 Pa·s, more preferably 70 to 500 mPa·s, and even more preferably 70 to 200 Pa·s. When the viscosity of a 2% by mass aqueous solution of cationized cellulose is within the above range, an excellent balance is achieved between improved wettability of hard surfaces, particularly stainless steel surfaces, and the stability of the liquid detergent composition. The viscosity of a 2% by mass aqueous solution of cationized cellulose is a value measured using a B-type viscometer at a measurement temperature of 25° C. The viscosity measurement conditions are the same as those for measuring the viscosity of a 0.5% by mass aqueous solution of cationized guar gum.

[0049] Commercially available cationized cellulose products include, for example, "Leoguard GP (quaternary nitrogen content 1.8% by mass)," "Leoguard MGP (quaternary nitrogen content 1.8% by mass)," and "Leoguard MLP (quaternary nitrogen content 0.6% by mass)" manufactured by Lion Specialty Chemicals Co., Ltd.; and "UCARE JR125 (quaternary nitrogen content 1.9% by mass)," "UCARE JR400 (quaternary nitrogen content 1.9% by mass)," and "UCARE LR30M (quaternary nitrogen content 1.0% by mass)" manufactured by The Dow Chemical Company. Among these, "UCARE JR125" and "UCARE JR400" are preferred, with "UCARE JR125" being more preferred, from the viewpoint of enhancing the wettability of hard surfaces, particularly stainless steel surfaces. The cationized cellulose may be used alone or in combination of two or more kinds.

[0050] The content of component (B) is 0.01 to 5 mass%, preferably 0.05 to 2 mass%, based on the total mass of the liquid detergent composition. When the content of component (B) is within the above range, adhesion of stains such as water stains and oil stains to hard surfaces can be suppressed, and excellent cleaning effects can be achieved without the need for mechanical force. In particular, when the content of component (B) is equal to or greater than the above lower limit, adhesion of stains such as water stains and oil stains to hard surfaces can be suppressed, and when it is equal to or less than the above upper limit, cleaning effects against stains such as water stains and oil stains are enhanced.

[0051] <(C) component> Component (C) is a chelating agent. By including component (C), the liquid detergent composition can inhibit adhesion of stains such as water stains and oil stains to hard surfaces, and even if such stains do adhere, it can exert an excellent cleaning effect without requiring mechanical force.

[0052] Examples of the component (C) include hydroxycarboxylic acid type chelating agents and aminocarboxylic acid type chelating agents. The component (C) may be used alone or in combination of two or more.

[0053] Examples of hydroxycarboxylic acid-type chelating agents include organic acids and salts thereof, such as glycolic acid, diglycolic acid, lactic acid, tartaric acid, carboxymethyltartaric acid, citric acid, malic acid, and gluconic acid. Examples of salt forms include sodium salts and potassium salts. Among these, citric acid, malic acid, lactic acid, tartaric acid, and salts thereof are preferred, and citric acid and salts thereof are more preferred. The hydroxycarboxylic acid type chelating agent may be used alone or in combination of two or more.

[0054] Examples of aminocarboxylic acid type chelating agents include ethylenediaminetetraacetic acid (EDTA), hydroxyethylenediaminetriacetic acid (HEDTA), dihydroxyethylglycine (DHEG), hydroxyethyleneiminodiacetic acid (HIDA), diethylenetriaminepentaacetic acid (DTPA), methylglycine diacetic acid (MGDA), aspartic acid diacetic acid (ASDA), isoserine diacetic acid (ISDA), β-alanine diacetic acid (ADAA), serine diacetic acid (SDA), L-glutamic acid diacetic acid (GLDA), imino Examples of suitable hydroxyiminodisuccinic acids include disuccinic acid (IDS), hydroxyiminodisuccinic acid (HIDS), N-lauroylethylenediaminetriacetic acid, nitrilotriacetic acid (NTA), triethylenetetraaminehexaacetic acid (TTHA), 1,3-propanediaminetetraacetic acid (PDTA), 1,3-diamino-2-hydroxypropanetetraacetic acid (DPTA-OH), glycoletherdiaminetetraacetic acid (GEDTA), dicarboxymethylglutamic acid (CMGA), (S,S)-ethylenediaminedisuccinic acid (EDDS), and salts thereof. Examples of suitable salts include sodium salts and potassium salts. Among these, MGDA, GLDA, EDTA, HEDTA, DHEG, HIDA, DTPA, and salts thereof are preferred, MGDA, GLDA, EDTA, and salts thereof are more preferred, and MGDA and salts thereof are even more preferred. The aminocarboxylic acid type chelating agent may be used alone or in combination of two or more.

[0055] The content of component (C) is preferably 0.05 to 5 mass% and more preferably 0.1 to 4 mass% based on the total mass of the liquid detergent composition. When the content of component (C) is equal to or greater than the above-mentioned lower limit, the cleaning effect on stains such as water stains and oil stains is further enhanced. When the content of component (C) is equal to or less than the above-mentioned upper limit, the adhesion of stains such as water stains and oil stains to hard surfaces can be further suppressed.

[0056] The mass ratio of the total content of components (A) and (C) to the content of component (B), expressed as (component (A) + component (C)) / component (B), (hereinafter also referred to as "(A+C) / B ratio"), is preferably 0.5 to 500, more preferably 1 to 300, even more preferably 2 to 150, and particularly preferably 4.5 to 100. When the (A+C) / B ratio is within the above range, adhesion of stains such as water stains and oil stains to hard surfaces can be further suppressed. In particular, when the (A+C) / B ratio is equal to or less than the above upper limit, the cleaning effect against stains such as water stains and oil stains is further enhanced.

[0057] <(D) component> The component (D) is a compound represented by the following general formula (d1). By including component (D), the liquid detergent composition can inhibit adhesion of stains such as water stains and oil stains to hard surfaces, and even if such stains are attached, it can exert an excellent cleaning effect without requiring mechanical force. Ph-X-OH (d1) (In formula (d1), Ph is a phenyl group, and X is R 6 OR 7 ) m R 6 is an alkylene group having 1 or 2 carbon atoms, and R 7 is an alkylene group having 2 or 3 carbon atoms, and m is a number from 1 to 6.

[0058] X in formula (d1) is R from the viewpoint of being able to further suppress adhesion of stains such as water stains and oil stains to hard surfaces and further enhancing the cleaning effect against these stains. 6 is an alkylene group with one carbon atom, R 7 is preferably an alkylene group having 2 carbon atoms, and m is preferably 1 to 2.

[0059] Examples of the component (D) include benzyl alcohol (X is an alkylene group having one carbon atom), phenyl glycol (X is (OR 7 ) m , R 7 is an alkylene group having 2 carbon atoms, m is 1), phenyl diglycol (X is (OR 7 ) m , R 7 is an alkylene group having 2 carbon atoms, and m is 2. From the viewpoint of being able to further inhibit adhesion of stains such as water stains and oil stains to hard surfaces and further enhancing the cleaning effect against such stains, benzyl alcohol and phenyl glycol are more preferred, and phenyl glycol is even more preferred. The component (D) may be used alone or in combination of two or more.

[0060] The content of component (D) is preferably 0.1 to 20% by mass, more preferably 0.5 to 12% by mass, and even more preferably 1 to 8% by mass, based on the total mass of the liquid detergent composition. When the content of component (D) is within the above range, adhesion of stains such as water stains and oil stains to hard surfaces can be further suppressed. In particular, when the content of component (D) is equal to or greater than the above lower limit, the cleaning effect against stains such as water stains and oil stains is further enhanced.

[0061] The mass ratio of the content of component (B) to the content of component (D), expressed as (B) component / (D) component (hereinafter also referred to as "B / D ratio"), is preferably 0.001 to 50, more preferably 0.002 to 30, even more preferably 0.005 to 10, and particularly preferably 0.01 to 3. When the B / D ratio is within the above range, adhesion of stains such as water stains and oil stains to hard surfaces can be further suppressed. In particular, when the B / D ratio is equal to or less than the above upper limit, the cleaning effect against stains such as water stains and oil stains is further enhanced.

[0062] The total content of components (A), (B), (C), and (D) is preferably 3 to 30% by mass, more preferably 5 to 15% by mass, based on the total mass of the liquid detergent composition. When the total content of components (A) to (D) is equal to or greater than the above-mentioned lower limit, the effects of the present invention become more pronounced. When the total content of components (A) to (D) is equal to or less than the above-mentioned upper limit, the liquid stability of the liquid detergent composition is further improved.

[0063] <Optional ingredients> Examples of optional components include surfactants other than component (A) (hereinafter also referred to as "optional surfactants"), polymeric compounds other than component (B) (hereinafter also referred to as "other polymeric compounds"), preservatives, inorganic builders, hydrotropes, pH adjusters, solvents, fragrances, colorants, disinfectants, antibacterial agents, and antioxidants. The total content of all components contained in the liquid detergent composition is 100% by mass.

[0064] (Optional surfactant) Examples of the optional surfactant include nonionic surfactants, amphoteric surfactants, amine oxide type surfactants, cationic surfactants, higher fatty acids or salts thereof, and the like. The optional surfactants may be used alone or in combination of two or more.

[0065] Examples of nonionic surfactants include polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl (or alkenyl) phenyl ethers, fatty acid alkyl ester alkoxylates in which alkylene oxide is added between the ester bonds of long-chain fatty acid alkyl esters, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene fatty acid esters, polyoxyalkylene hydrogenated castor oil, glycerin fatty acid esters, and alkyl polyglycosides. The nonionic surfactants may be used alone or in combination of two or more.

[0066] Examples of amphoteric surfactants 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 laurylhydroxysulfobetaine. The amphoteric surfactants may be used alone or in combination of two or more.

[0067] Examples of the amine oxide surfactant include lauryl dimethylamine oxide (n-dodecyl dimethylamine oxide), coconut alkyl dimethylamine oxide, lauryl diethylamine oxide, and lauric acid amide propyl dimethylamine oxide. The amine oxide surfactants may be used alone or in combination of two or more.

[0068] 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 surfactants may be used alone or in combination of two or more.

[0069] 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; and mixed fatty acids or salts thereof such as coconut fatty acid and beef tallow fatty acid. Examples of the salt form 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), triethanolamine salts (triethanolammonium salts), etc. 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.

[0070] The content of the optional surfactant is preferably 0.1 to 10 mass %, more preferably 0.1 to 5 mass %, based on the total mass of the liquid detergent composition. The total content of all surfactants contained in the liquid detergent composition (total surfactant amount) is preferably 0.1 to 25 mass% and more preferably 1 to 20 mass% based on 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 exhibit sufficient detergency. When the total surfactant amount is equal to or less than the above upper limit, gelation of the liquid detergent composition can be suppressed.

[0071] (Other polymer compounds) 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.

[0072] (preservatives) 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.

[0073] 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.

[0074] (inorganic builder) Examples of inorganic builders include metal oxides, such as zinc oxide and magnesium oxide. The inorganic builders may be used alone or in combination of two or more. The content of the inorganic builder is preferably 0.01 to 5% by mass relative to the total mass of the liquid detergent composition.

[0075] (hydrotropic agent) 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.

[0076] 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), triethanolamine salts (triethanolammonium salts), etc. Among these, alkali metal salts are preferred, sodium salts and potassium salts are more preferred, and sodium salts are even more preferred.

[0077] 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.

[0078] The content of the hydrotrope agent is preferably 0.1 to 10 mass %, more preferably 0.5 to 5 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.

[0079] (pH adjuster) Examples of pH adjusters include inorganic alkaline agents, organic alkaline agents, inorganic acids, and organic 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, for example, be acetic acid. The pH adjusters may be used alone or in combination of two or more.

[0080] (solvent) Examples of the solvent include water and organic solvents other than component (D) (hereinafter also referred to as "other organic solvents"). Among these, water is preferred as the solvent. Using water as the solvent makes it easier to prepare the liquid detergent composition. In addition, when using the liquid detergent composition for cleaning, the solubility in water is improved. The solvent may be used alone or in combination of two or more.

[0081] Examples of water include ion-exchanged water, distilled water, and tap water. The water content is preferably 60 to 90% by mass, more preferably 80 to 90% by mass, based on the total mass of the liquid 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.

[0082] 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% by mass, more preferably from 0.1 to 5% by mass, based on the total mass of the liquid detergent composition.

[0083] (fragrance) 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 %, relative to the total mass of the liquid detergent composition.

[0084] (coloring agent) The colorant 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 colorant 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, and more preferably from 0.0001 to 0.001% by mass, relative to the total mass of the liquid detergent composition.

[0085] (disinfectant) 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.

[0086] (Antibacterial agent) Examples of antibacterial agents include diphenyl ether antibacterial agents such as diclosan (4,4'-dichloro-2-hydroxydiphenyl ether) and triclosan (5-chloro-2-(2,4-dichlorophenoxy)phenol), cationic 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.

[0087] (antioxidant) 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.

[0088] <ph> The pH of the liquid detergent composition at 25°C is preferably 5-10, more preferably 6-8. The pH of the liquid detergent composition at 25°C is a value measured by a method in accordance with JIS Z 8802:2011 "pH measurement method."

[0089] <Manufacturing method> The liquid detergent composition 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.

[0090] <Discharge container> The liquid detergent composition may be in the form of a product contained in a dispensing container. Hereinafter, a product having the liquid detergent composition of the present invention and a dispensing container containing the liquid detergent composition of the present invention will also be referred to as a "liquid detergent product for hard surfaces" or simply as a "liquid detergent product." Examples of the discharge container include a spray container, a squeeze container, etc. Among these, a spray container is preferred because of its excellent applicability to the object to be cleaned. Examples of the spray container include a trigger-type spray container, an aerosol-type spray container, and a dispenser-type spray container. Among these, a trigger-type spray container is preferred. That is, the liquid detergent composition of the present invention is suitable for use as a trigger-type spray, and is preferably contained in a trigger-type spray container for use.

[0091] There are no particular limitations on the trigger-type spray container, and containers (sprayers) used for general cleaning agent products (cleaning agents contained in trigger-type spray containers) can be used. Specifically, the trigger-type spray container may be one that can spray the liquid detergent composition in a mist. It may also be one that can spray either a mist or a foam, and can switch between these forms. Furthermore, it may be one that can switch between a wide pattern that sprays the liquid detergent composition over a wide area and a narrow pattern that sprays the liquid detergent composition over a narrow area. The trigger-type spray container can have a known mechanism and may be of either a direct pressure type or a pressure accumulation type. Examples of trigger-type spray containers include those described in JP-A-10-146546 and JP-A-2000-24561.

[0092] <How to use> The method of using the liquid detergent composition is to bring the liquid detergent composition into contact with an object to be cleaned to clean it. Specifically, the liquid detergent composition is stored in a discharge container such as a trigger-type spray container, and an appropriate amount of the liquid detergent composition is applied from the discharge container to the object to be cleaned to bring it into contact with the object, and if necessary, after a certain period of time has passed, the liquid detergent composition is rinsed with running water, which is called "rinsing." Another method of use is "scrubbing," in which an appropriate amount of the liquid detergent composition is applied to the object to be cleaned, and then rubbed with a cleaning tool such as a sponge, brush, or cloth. Alternatively, a method of use may be "wiping and washing" in which an appropriate amount of the liquid detergent composition is applied to the object to be cleaned, brought into contact with the object, and then wiped off with a cloth or paper.

[0093] The object to be cleaned may be any hard surface such as an article, for example, kitchenware, bathroom utensils, toilet utensils, etc. The liquid detergent composition of the present embodiment is suitable as a liquid detergent composition for kitchen utensils, particularly as a liquid detergent composition for sinks, because it can inhibit adhesion of stains such as water stains and oil stains and can exert an excellent cleaning effect without requiring mechanical force. In this specification, sinks; tableware such as plates, chopsticks, and spoons; cooking utensils such as pots, knives, and cutting boards; and kitchen equipment such as ranges, extractor fans, and stoves are collectively referred to as "kitchenware."

[0094] <Action and effect> The liquid detergent composition of the present invention can inhibit adhesion of stains such as water stains and oil stains to hard surfaces. Moreover, because it has excellent detergency against stains such as water stains and oil stains, it can easily clean objects having stains such as water stains and oil stains without applying mechanical force such as scrubbing the object with hands or a cleaning tool such as a sponge, i.e., it has excellent cleanability. Here, "without applying mechanical force" means that no intentional cleaning operation is performed other than contact with the liquid detergent composition. Note that cases where the liquid detergent composition contacted with the object to be cleaned flows down naturally, vibrations not intended for cleaning are transmitted to the object to be cleaned, and the liquid detergent composition contacted with the object to be cleaned is rinsed with water correspond to cases where the object to be cleaned is cleaned without applying mechanical force.

[0095] The reason why the liquid detergent composition of the present invention can inhibit adhesion of stains such as water stains and oil stains to hard surfaces and has excellent detergency against these stains is not clear, but is presumed to be as follows. When the liquid detergent composition of the present invention comes into contact with a hard surface to be cleaned, the wettability of the hard surface, particularly a stainless steel surface, is increased, and the liquid detergent composition, particularly component (B), adheres more easily to the hard surface, making the hard surface hydrophilic. As a result, water spreads evenly when rinsing with running water, making it difficult for stains such as water stains and oil stains to adhere to the hard surface, and even if they do adhere, they can be easily cleaned. Furthermore, component (C) acts on limescale (specifically, calcium carbonate, etc.) adhering to hard surfaces, thereby removing the limescale during cleaning and inhibiting its accumulation.

[0096] Furthermore, as described above, repeated scrubbing of the sink tends to make the surface of the sink more susceptible to damage due to friction with the cleaning implements that occurs when the sink is cleaned, the effects of the liquid detergent composition, etc. This makes it easier for stains such as water stains and oil stains to adhere to the sink surface, and even rinsing with running water when washing dishes, etc., makes it difficult to sufficiently remove stains from the sink surface. However, the liquid detergent composition of the present invention can inhibit adhesion of stains such as water stains and oil stains to hard surfaces and exhibits excellent cleaning effects without the application of mechanical force. Therefore, even if the object to be cleaned is, for example, a scratched sink, by applying the liquid detergent composition of the present invention to the object and bringing it into contact with the object, the object can be cleaned without the application of mechanical force. Furthermore, once the object to be cleaned is cleaned with the liquid detergent composition of the present invention, stains such as oil stains and water stains are less likely to adhere to the object to be cleaned, and even if stains adhere to the object to be cleaned, they can be easily cleaned. Furthermore, the vertical surfaces of sinks are particularly prone to limescale buildup, and limescale tends to be difficult to remove. However, with the liquid detergent composition of the present invention, the liquid detergent composition, particularly component (B), can easily adhere to not only horizontal surfaces but also vertical surfaces, making it easy to remove limescale. In addition, the liquid detergent composition of the present invention can exert excellent cleaning effects without the application of mechanical force, so even if the liquid detergent composition of the present invention is used to clean a sink, for example, it has little effect on the condition of the sink surface and is less likely to scratch the sink surface. [Example]

[0097] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following description.

[0098] "Raw materials used" The following compounds were used as component (A). A-1 (LAS): Sodium linear alkylbenzene sulfonate having 10 to 14 carbon atoms (trade name "Teika Power (registered trademark) L121" manufactured by Teika Corporation, neutralized with sodium hydroxide). A-2 (AES(1)): Polyoxyethylene(1) linear alkyl (C12 / 14=75 / 25; derived from natural fats and oils) ether sulfate sodium salt (synthesized by the following method). 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 with 14 to 16 carbon atoms (manufactured by Lion Specialty Chemicals Co., Ltd., trade name "Lipolan (registered trademark) LB-440"). · A-5: Di-2-ethylhexyl sodium sulfosuccinate (manufactured by Toho Chemical Industry Co., Ltd., trade name "Aerol CT-1L").

[0099] <Synthesis method of A-2> In a 4L autoclave, 400 g of "CO1270 alcohol (C12 / C14 = 75% / 25%, mass ratio)", a product of Procter & Gamble Co., as the raw material alcohol and 0.8 g of potassium hydroxide as the reaction catalyst were charged respectively. After replacing the inside of the autoclave with nitrogen, the temperature was raised while stirring. Subsequently, while maintaining the temperature at 180 °C and the pressure at 0.3 MPa or less, 91 g of ethylene oxide was introduced and reacted. The average number of moles of ethylene oxide added to the obtained polyoxyalkylene ether was 1. Next, 237 g of ethylene oxide of the obtained polyoxyalkylene ether was taken into a 500 mL flask equipped with a stirrer, and after nitrogen substitution, 96 g of liquid anhydrous sulfuric acid (sulfan) was slowly dropped while maintaining the reaction temperature at 40 °C. After the dropping was completed, stirring was continued for 1 hour (sulfation reaction) to obtain polyoxyethylene alkyl ether sulfuric acid. Next, the obtained polyoxyethylene alkyl ether sulfuric acid was neutralized with an aqueous sodium hydroxide solution to obtain A-2.

[0100] (B) component or its comparative product used the following compounds. · B-1: Cationized guar gum (manufactured by Solvay, trade name "Jaguar (registered trademark) C17K", guar hydroxypropyltrimonium chloride, viscosity of 0.5 mass% aqueous solution at 25 °C is 230 mPa·s). · B-2: Cationized guar gum (manufactured by Solvay, trade name "Jaguar (registered trademark) C14S", guar hydroxypropyltrimonium chloride, viscosity of 0.5 mass% aqueous solution at 25 °C is 180 mPa·s). B-3: Cationic guar gum (manufactured by Solvay, trade name "Jaguar (registered trademark) C162", hydroxypropyl guar hydroxypropyltrimonium chloride, viscosity of 0.5% by mass aqueous solution at 25°C: 60 mPa·s). B-4: Cationic cellulose (manufactured by The Dow Chemical Company, trade name "UCARE JR125", quaternary nitrogen content 1.9% by mass, viscosity of a 2% by mass aqueous solution at 25°C 130 mPa·s). B-5: Guar gum (unmodified) (manufactured by Sansho Corporation, product name "SUPERGEL CSA 200 / 50", viscosity of 0.5% by mass aqueous solution at 25°C 70 mPa·s, comparison product for component (B)).

[0101] The following compounds were used as component (C). C-1: Citric acid (manufactured by Fuso Chemical Co., Ltd., product name "Citric Acid"). C-2: Lactic acid (manufactured by Musashino Chemical Laboratory Co., Ltd., product name "Sodium Lactate"). C-3: Trisodium methylglycine diacetate (manufactured by BASF, trade name "TrilonMLiquid"). C-4: Tetrasodium L-glutamate diacetate (manufactured by Akzo Nobel, trade name "Dissolvine (registered trademark) GL-47-S"). C-5: Tetrasodium ethylenediaminetetraacetate (manufactured by BASF, trade name "Trilon BX Liquid").

[0102] The compounds shown below were used as component (D) or comparative products. D-1: Phenyl glycol (manufactured by Sanyo Chemical Industries, Ltd., trade name "Newpol EFP"). D-2: Benzyl alcohol (manufactured by Junsei Chemical Co., Ltd., trade name "Benzyl Alcohol"). D-3: Phenyldiglycol (manufactured by Tokyo Chemical Industry Co., Ltd., trade name "Phenyldiglycol"). D-4: Butyl carbitol (manufactured by Tokyo Chemical Industry Co., Ltd., product name "Diethylene glycol monobutyl ether", comparison product for component (D)).

[0103] As optional components, the compounds shown below were used. pTS-H: p-toluenesulfonic acid (Kanto Chemical Co., Ltd.). TEA: Triethanolamine (manufactured by Nippon Shokubai Co., Ltd., product name "Triethanolamine S-80"). NaOH: Sodium hydroxide (AGC Corporation, trade name "48% Sodium Hydroxide"). AX: Lauryl dimethylamine oxide (manufactured by Lion Specialty Chemicals Co., Ltd., product name "Cadenax DM12D-W"). Water: Ion-exchanged water.

[0104] "Measurement and Evaluation" <Evaluation of adhesion inhibition of complex soiling caused by water stains and oil stains> The liquid detergent composition was placed in a commercially available Magica one-shot cleaning spray container (trigger-type spray container) to prepare a liquid detergent product. The subject of evaluation was a 10cm x 10cm stainless steel plate (with numerous scratches made in a 2cm x 2cm area in the center using the hard side (non-woven fabric side) of a dishwashing sponge). A liquid detergent composition was sprayed from a liquid detergent product onto the scratched surface of a stainless steel plate, left for 1 minute, and then rinsed with hard water (30°C hard water, water temperature 25°C, 5 L / min) for 10 seconds. After rinsing, 5 mL of olive oil (oil stains) was applied to the scratched surface of the stainless steel plate, and the stainless steel plate was again rinsed with hard water (30°C hard water, water temperature 25°C, 5 L / min) for 10 seconds. After rinsing, the scratched surface of the stainless steel plate was visually observed, and the inhibition of adhesion of complex soils was evaluated based on the following evaluation criteria. This test was performed three times and the average score was used for evaluation. Separately, a blank was prepared by carrying out the same procedure except that tap water was sprayed instead of the liquid detergent composition. (Evaluation criteria) 5 points: The amount of compound dirt generated was reduced by 70% or more compared to the blank. 4 points: The amount of compound dirt generated was reduced by about 50 to 60% compared to the blank. 3 points: The amount of compound dirt generated was reduced by about 30 to 40% compared to the blank. 2 points: The amount of compound dirt generated was reduced by about 10 to 20% compared to the blank. 1 point: Equivalent to the state of composite stains formed on the stainless steel plate in its initial surface state (blank).

[0105] <Evaluation of water stain cleanability> The liquid detergent composition was placed in a commercially available Magica one-shot cleaning spray container (trigger-type spray container) to prepare a liquid detergent product. The subject of evaluation was a 10cm x 10cm stainless steel plate (with numerous scratches made in a 2cm x 2cm area in the center using the hard side (non-woven fabric side) of a dishwashing sponge). 5 mL of 30°C hard water was dropped onto the scratched surface of the stainless steel plate, and the operation of air-drying was repeated five times to form limescale stains. With the limescale stained stainless steel plate leaning against a vertical surface, a liquid detergent composition from a liquid detergent product was sprayed onto the scratched surface of the stainless steel plate and left for 1 minute. The plate was then rinsed with tap water (water temperature 25°C, 5 L / min) for 10 seconds and dried. The number of limescale stains remaining on the surface of the stainless steel plate after drying was counted, and the limescale removal rate was calculated using the following formula. Removal rate [%] = (1 - number of limescale stains on the stainless steel plate after cleaning / number of limescale stains on the stainless steel plate before cleaning) x 100

[0106] The ease of cleaning limescale adhering to a vertical surface was evaluated based on the following criteria. (Evaluation criteria) 5 points: Removal rate is 80% or more (almost all limescale stains are removed). 4 points: Removal rate is between 60% and 80% (the majority of limescale stains are removed). 3 points: Removal rate is between 40% and 60% (about half of the limescale stains are removed). 2 points: Removal rate is between 20% and 40% (a small amount of dirt is removed). 1 point: Removal rate is less than 20% (almost no dirt is removed).

[0107] "Examples 1 to 39, Comparative Examples 1 to 7" According to the formulations shown in Tables 1 to 6, components (A) to (D) and optional components were mixed to prepare the liquid detergent compositions of each example. The pH (25°C) of the liquid detergent composition was measured by adjusting the temperature of the liquid detergent composition to 25°C, and using a glass electrode pH meter (manufactured by DKK-TOA Corporation, product name "HM-30G"), immersing the glass electrode directly in the dishwashing detergent and measuring the pH after 1 minute. The measurement was performed 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 complex soils and their ease of cleaning water stains. The results are shown in Tables 1 to 6.

[0108] [Table 1]

[0109] [Table 2]

[0110] [Table 3]

[0111] [Table 4]

[0112] [Table 5]

[0113] [Table 6]

[0114] The blending amounts in Tables 1 to 6 are calculated as pure components. Components without a blending amount listed in the tables are not blended. The "appropriate amount" of TEA (triethanolamine) and NaOH (sodium hydroxide) in the tables is the amount required to achieve the pH shown in the table. The "balance" amount of water in the tables is the amount required to make the liquid detergent composition 100% by mass. In Tables 1 to 6, "(A+C) / B ratio" is the mass ratio expressed as ((A) component + (C) component) / (B component). "B / D ratio" is the mass ratio expressed as (B) component / (D component).

[0115] As is clear from Tables 1 to 5, the liquid detergent compositions of each example were able to inhibit the adhesion of complex soiling, including water stains and oil stains, to scratched stainless steel surfaces (hard surfaces). Furthermore, water stains on vertical surfaces could be easily removed by simply rinsing with running water, without the need for mechanical force. On the other hand, as is clear from Table 6, the liquid detergent compositions of Comparative Examples 1 to 4, which did not contain any of the components (A) to (D), were inferior in inhibiting the adhesion of complex soils and in the ease of cleaning water stains. The liquid detergent compositions of Comparative Examples 5 and 6, in which the content of component (B) was 0.003% by mass or 6% by mass, were inferior in inhibiting adhesion of complex soils and in easy cleaning of water stains. The liquid detergent composition of Comparative Example 7, which used guar gum (unmodified) instead of component (B), was inferior in inhibiting adhesion of complex soils and in easy cleaning of water stains. From the above results, it was confirmed that by applying the present invention, it is possible to suppress the adhesion of dirt even on scratched hard surfaces, to improve the cleaning effect without applying mechanical force, and that water stains can be easily removed even on vertical surfaces by simply rinsing with running water.< / ph>

Claims

1. Component (A): a non-soap anionic surfactant; (B) component: a cationized polysaccharide; (C) component: a chelating agent; Component (D): a compound represented by the following general formula (d1), A liquid cleaning composition for hard surfaces comprising: A liquid detergent composition for hard surfaces, wherein the content of the component (B) is 0.01 to 5 mass % relative to the total mass of the liquid detergent composition for hard surfaces. Ph-X-OH...(d1) (In formula (d1), Ph is a phenyl group, and X is R ６ OR ７ ) ｍ It is. ６ is an alkylene group having 1 or 2 carbon atoms, and R ７ is an alkylene group having 2 or 3 carbon atoms, and m is a number from 1 to 6.

2. 2. The liquid cleaning composition for hard surfaces according to claim 1, wherein the mass ratio of the component (B) to the component (D) is 0.001 to 50.

3. The liquid cleaning composition for hard surfaces according to claim 1 or 2, which is for use as a trigger spray.

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