Liquid detergent composition for clothing

Abstract

To provide a liquid detergent composition for clothing blended with an enzyme which has excellent cleaning power and foam diminishing properties after storage, especially after storage at a high temperature.SOLUTION: There is provided a liquid detergent composition for clothing which comprises (a) a nonionic surfactant represented by the following general formula (1), (b) an inorganic calcium salt, (c) a glycolytic enzyme and water, wherein the mass ratio (a) / (c) of the content of (a) to the content of (c) as an enzyme protein is 100 or more and 16000 or less. R-O-[(EO)n / (PO)m]-H (1) [wherein, R is an aliphatic hydrocarbon group having 10 or more and 24 or less carbon atoms. EO is an ethyleneoxy group, PO is a propyleneoxy group, n and m are an average addition mole number, n is a number of 8 or more and 40 or less, m is a number of 1 or more and 6 or less and EO and PO may be random addition or block addition.]SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a liquid detergent composition for clothing and a method for cleaning clothing. [Background technology]

[0002] High cleaning performance has been pursued for laundry detergents. Meanwhile, remarkable advances have been made in washing machines, with models now appearing on the market that automatically add detergent and fabric softener. Detergents used in laundry where the amount of detergent added and the amount of water used are controlled are expected to maintain their performance from start to finish. They are also expected to have excellent rinse-off properties so that rinsing can be completed with as little water as possible.

[0003] Enzymes are generally used in laundry detergents in terms of their detergency against various stains adhering to clothing. However, enzymes are unstable in liquid detergents containing water, and detergents containing enzymes tend to lose their detergency when stored for a long period of time. Various proposals have been made to improve the stability of enzymes in liquid detergents containing enzymes.

[0004] Patent Document 1 discloses a liquid detergent for clothing that contains (A) a specific nonionic surfactant, (B) polyoxyalkylene alkyl ether sulfate or a salt thereof, (C) linear alkylbenzene sulfonic acid or a salt thereof, (D) an enzyme, and (E) water, in which the mass ratio represented by component (A) / [component (B)+component (C)] is 0.5 to 3.5, and the mass ratio represented by component (B) / component (C) is 90 / 10 to 10 / 90.

[0005] Patent Document 2 discloses a neutral detergent composition containing a nonionic surfactant as component (A), an aromatic sulfonic acid or a salt thereof as component (B), a polyhydric alcohol as component (C), an amylase as component (D), a protease as component (E), and water as component (F), wherein the mass ratio of (C) / (B) is 0.7 to 200.

[0006] Patent Document 3 discloses a liquid detergent composition for hard surfaces that contains a nonionic surfactant (A) prepared by blending (A) a polyoxyethylene-polyoxypropylene alkyl ether and (B) at least one of an ethylene oxide-propylene oxide adduct of trimethylolpropane and an ethylene oxide-propylene oxide adduct of glycerin in a mass ratio of (A):(B)=3:1 to 20:1, an alkanolamine (B), an enzyme (C), a solubilizer (D) composed of at least one of a xylene sulfonate and a cumene sulfonate, a calcium additive, and water, wherein the nonionic surfactant (A), the alkanolamine (B), and the enzyme (C) account for 1 to 10 mass% of the nonionic surfactant, 10 to 30 mass% of the alkanolamine, and 0.1 to 5 mass% of the enzyme, based on the total mass of the liquid detergent composition for hard surfaces, and the pH of the liquid detergent composition for hard surfaces at 25°C is set in the range of 8.0 to 10.0.

[0007] Patent Document 4 discloses a pre-soak detergent composition containing (A) 6% to 40% by mass of a polyoxyethylene polyoxypropylene alkyl ether, (B) an amylolytic enzyme, (C) an enzyme stabilizer, (D) a solubilizing agent, and (E) a pH adjuster.

[0008] Patent Document 5 discloses a liquid detergent composition containing (a) a specific nonionic surfactant, (b) an enzyme, (c) an enzyme stabilizer, and (d) an organic polycarboxylic acid and / or a salt thereof. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] International Publication No. 2017 / 038930 [Patent Document 2] Japanese Patent Application Publication No. 2018-115286 [Patent Document 3] Japanese Patent Application Laid-Open No. 2016-172814 [Patent Document 4] Japanese Patent Application Laid-Open No. 2016-11385 [Patent Document 5] Japanese Patent Application Laid-Open No. 2002-69489 Summary of the Invention [Problem to be solved by the invention]

[0010] The present invention provides a liquid detergent composition for clothing containing an enzyme, which has excellent detergency and foam-removing properties after storage, particularly after storage at high temperatures. [Means for solving the problem]

[0011] The present invention relates to a liquid detergent composition for clothing, which contains the following components (a), (b), and (c), and water, wherein the mass ratio (a) / (c) of the content of component (a) to the content of component (c) as an enzyme protein is 100 or more and 16,000 or less: Component (a): a nonionic surfactant represented by the following general formula (1): RO-〔(EO) n / (PO) m 〕-H (1) [In the formula, R is an aliphatic hydrocarbon group having 10 to 24 carbon atoms, EO is an ethyleneoxy group, PO is a propyleneoxy group, n and m are the average number of moles added, n is a number of 8 to 40, and m is a number of 1 to 6, and EO and PO may be added randomly or in blocks.] (b) Ingredient: inorganic calcium salt (c) Ingredient: Carbohydrate-degrading enzyme

[0012] The present invention also relates to a method for washing clothes, which comprises washing clothes with a cleaning liquid obtained by mixing the liquid detergent composition for clothes of the present invention with water, and then rinsing the clothes with water. [Effects of the Invention]

[0013] According to the present invention, there are provided a liquid detergent composition for clothing containing an enzyme, which has excellent detergency and foam-removal properties after storage, particularly after storage at high temperatures, and a method for cleaning clothing using the same. The liquid detergent composition for clothing of the present invention has excellent detergency and can still exhibit excellent detergency even after storage at high temperatures, for example, around 40°C, and its good foam-removal properties allow for a reduction in the number of rinsing times and the amount of water used. DETAILED DESCRIPTION OF THE INVENTION

[0014] <Liquid detergent composition for clothing> Component (a) is a nonionic surfactant represented by the following general formula (1): RO-〔(EO) n / (PO) m 〕-H (1) [In the formula, R is an aliphatic hydrocarbon group having 10 to 24 carbon atoms, EO is an ethyleneoxy group, PO is a propyleneoxy group, n and m are the average number of moles added, n is a number of 8 to 40, and m is a number of 1 to 6, and EO and PO may be added randomly or in blocks.]

[0015] In general formula (1), the number of carbon atoms in R is 10 or more, preferably 12 or more, and 24 or less, preferably 18 or less, more preferably 14 or less, from the viewpoints of improving detergency, maintaining detergency after storage at high temperatures (hereinafter referred to as "maintenance of detergency after storage"), and improving foam-removal properties.

[0016] In general formula (1), examples of the aliphatic hydrocarbon group for R include alkyl and alkenyl groups, with alkyl groups being preferred. From the viewpoints of improving cleaning performance, maintaining cleaning performance after storage, and improving foam-removal properties, R is preferably a linear or branched aliphatic hydrocarbon group, such as a linear or branched alkyl group or a linear or branched alkenyl group, with a linear alkyl group being more preferred.

[0017] In general formula (1), n ​​is a number from 8 to 40, and from the viewpoints of improving cleaning performance, maintaining cleaning performance after storage, and improving foam-removing properties, n is preferably 10 or more, more preferably 12 or more, even more preferably 14 or more, still more preferably 16 or more, and is preferably 35 or less, more preferably 30 or less, even more preferably 24 or less, and still more preferably 20 or less.

[0018] In general formula (1), m is a number of 1 or more and 6 or less, and is preferably 2 or more and preferably 4 or less from the viewpoints of improving cleaning performance, maintaining cleaning performance after storage, and improving foam-removing properties.

[0019] The ratio of the number of moles of PO added to the number of moles of EO added in general formula (1), i.e., the ratio of m to n, m / n, is preferably 0.03 or more, more preferably 0.05 or more, even more preferably 0.1 or more, and is preferably 0.7 or less, more preferably 0.5 or less, even more preferably 0.25 or less, from the viewpoints of improving detergency, maintaining detergency after storage, and improving foam-removal properties.

[0020] The ratio of the number of moles of PO added to the total number of moles of EO and PO added in general formula (1), i.e., m / (n+m), which is the ratio of m to the sum of n and m, is preferably 0.03 or more, more preferably 0.05 or more, even more preferably 0.08 or more, and preferably 0.4 or less, more preferably 0.3 or less, even more preferably 0.2 or less, from the viewpoints of improving detergency, maintaining detergency after storage, and improving foam-breaking properties.

[0021] The component (a) is preferably a nonionic surfactant represented by the following general formula (2). RO-(EO) n1 -(PO) m -(EO) n2 -H (2) [In the formula, R is an aliphatic hydrocarbon group having 10 to 24 carbon atoms, EO is an ethyleneoxy group, and PO is a propyleneoxy group, EO and PO are block-bonded in this order, n1, n2, and m are the average number of moles added, n1 is a number of 0 to 20, m is a number of 1 to 6, n2 is a number of 0 to 20, the sum of n1 and n2 is 8 or more, and EO and PO are block-bonded.]

[0022] In the general formula (2), specific examples and preferred examples of R and m are the same as those in the general formula (1). In general formula (2), n1 is a number from 0 to 20. When n1 is not 0, from the viewpoints of improving cleaning performance, maintaining cleaning performance after storage, and improving foam-removing properties, it is preferably 4 or more, more preferably 5 or more, even more preferably 7 or more, and is preferably 18 or less, more preferably 16 or less, even more preferably 12 or less.

[0023] In general formula (2), n2 is a number from 0 to 20. When n2 is not 0, from the viewpoints of improving cleaning performance, maintaining cleaning performance after storage, and improving foam-removing properties, it is preferably 4 or more, more preferably 5 or more, even more preferably 7 or more, and is preferably 19 or less, more preferably 18 or less, even more preferably 17 or less.

[0024] The sum of n1 and n2 in general formula (2) corresponds to n in general formula (1), and the preferred range is also the same as that of n.

[0025] The ratio of the number of moles of PO added to the number of moles of EO added in general formula (2), i.e., m / (n1+n2), which is the ratio of m to the sum of n1 and n2, corresponds to m / n of the nonionic surfactant in general formula (1), and the preferred range is also the same as m / n.

[0026] In general formula (2), the ratio of the number of moles of PO added to the total number of moles of EO and PO added, i.e., the ratio of m to the sum of n1, n2, and m, m / (n1+n2+m), corresponds to m / (n+m) of the nonionic surfactant in general formula (1), and the preferred range is also the same as m / (n+m).

[0027] From the viewpoints of improving detergency, maintaining detergency after storage, and improving foam-removal properties, the liquid detergent composition for clothing of the present invention contains component (a) in an amount of preferably 3% by mass or more, more preferably 5% by mass or more, even more preferably 8% by mass or more, and preferably 50% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less, of the composition.

[0028] Component (b) is an inorganic calcium salt. (b) Component includes calcium halides such as calcium chloride, calcium carbonate, calcium sulfate, calcium silicate, etc. Component (b) is preferably calcium chloride from the viewpoints of availability and maintenance of cleaning properties after storage.

[0029] From the viewpoint of maintaining cleaning performance after storage, the liquid detergent composition for clothing of the present invention contains component (b) in an amount of preferably 0.001% by mass or more, more preferably 0.005% by mass or more, even more preferably 0.008% by mass or more, and preferably 1% by mass or less, more preferably 0.5% by mass or less, even more preferably 0.2% by mass or less in the composition.

[0030] Component (c) is a carbohydrate-degrading enzyme. Examples of component (c) include amylase, sucrase, maltase, lactase, pullulanase, and fructofuranosidase. Component (c) is preferably an amylase, and more preferably α-amylase from the viewpoint of improving cleaning performance and maintaining cleaning performance after storage. Specific examples of commercially available enzymes that can be used include Rapidase (manufactured by Gist Brokers), Termamyl, Duramyl, Stainzyme, and Amplify Prime 100L (manufactured by Novozym Japan), Plaster ST and Plaster OxAm (manufactured by Genencor International), and Preferenz S210 (manufactured by DuPont).

[0031] From the viewpoint of improving detergency and maintaining detergency after storage, the liquid detergent composition for clothing of the present invention contains, as enzyme protein, preferably 0.0005% by mass or more, more preferably 0.0008% by mass or more, even more preferably 0.001% by mass or more, and preferably 1% by mass or less, more preferably 0.1% by mass or less, and even more preferably 0.05% by mass or less of the composition. In the present invention, the amount of the enzyme protein of the component (c) may be determined by using a commercially available product of which the amount of the enzyme protein is known. Furthermore, the amount of the enzyme protein of the component (c) may be determined by the Lowry method. For the Lowry method, a commercially available assay kit, such as the DC Protein Assay Kit (BIO-RAD), can be used. A specific assay method using the DC Protein Assay Kit (BIO-RAD) is, for example, as follows. To 10 μL of Reagent A from the DC Protein Assay Kit, add 20 μL of appropriately diluted enzyme solution, add 80 μL of Reagent B from the DC Protein Assay Kit, and incubate at room temperature for 15 minutes. After that, measure the absorbance at 750 nm using a microplate reader (e.g., Infinite® 200PRO (Tecan)). A calibration curve is created using a sample with a known protein concentration (e.g., BSA Standard Solution (Fujifilm Wako Reagents)), and the amount of protein in the enzyme is quantified from the absorbance obtained above.

[0032] In the liquid detergent composition for clothing of the present invention, from the viewpoints of improving detergency, maintaining detergency after storage, and improving foam-removal properties, the mass ratio (a) / (c) of the content of component (a) to the content of component (c) as an enzyme protein is 100 or more, preferably 500 or more, more preferably 700 or more, and 16,000 or less, more preferably 10,000 or less, even more preferably 7,000 or less, still more preferably 5,000 or less, still more preferably 3,000 or less, still more preferably 1,500 or less, and still more preferably 1,000 or less.

[0033] In the liquid detergent composition for clothing of the present invention, from the viewpoints of improving detergency, maintaining detergency after storage, and improving foam-removal properties, the mass ratio (a) / (b) of the content of component (a) to the content of component (b) is preferably 10 or more, more preferably 50 or more, even more preferably 100 or more, and preferably 10,000 or less, more preferably 2,000 or less, even more preferably 500 or less, and even more preferably 150 or less.

[0034] In the liquid detergent composition for clothing of the present invention, from the viewpoint of improving detergency and maintaining detergency after storage, the mass ratio (b) / (c) of the content of component (b) to the content of component (c) as an enzyme protein is more preferably 0.1 or more, even more preferably 0.5 or more, still more preferably 1 or more, still more preferably 3 or more, and more preferably 100 or less, still more preferably 50 or less, still more preferably 20 or less, still more preferably 10 or less, still more preferably 5 or less.

[0035] The liquid detergent composition for clothing of the present invention may further contain a nonionic surfactant in which ethylene oxide is added to a secondary alcohol [excluding component (a)] [hereinafter referred to as component (d)] from the viewpoints of improving detergency, maintaining detergency after storage, improving foam-removal properties, improving the liquid stability of the composition, and improving workability during production of the composition. From the viewpoints of improving cleaning performance, maintaining cleaning performance after storage, improving foam-removal properties, improving the liquid stability of the composition, and improving workability during production of the composition, component (d) is preferably a nonionic surfactant in which ethylene oxide is added to a secondary alcohol, specifically a nonionic surfactant represented by the following general formula (d1): RO-(EO) s -H (d1) [In the formula, R is a linear or branched secondary alkyl group having from 8 to 24 carbon atoms, EO is an ethyleneoxy group, and s is the average number of moles added, which is from 3 to 24.]

[0036] From the viewpoints of improving cleaning performance, maintaining cleaning performance after storage, improving foam-removal, improving the liquid stability of the composition, and improving workability during production of the composition, R in formula (d1) is preferably a linear secondary alkyl group, and the number of carbon atoms in R is preferably 10 or more, more preferably 12 or more, and preferably 18 or less, more preferably 14 or less. Note that a secondary alkyl group refers to an alkyl group in which the carbon atom bonded to —O— among the carbon atoms of R in formula (d1) is a secondary carbon atom.

[0037] In formula (d1), s is preferably 4 or more, more preferably 5 or more, from the viewpoints of improving cleaning performance, maintaining cleaning performance after storage, improving foam-removal property, improving the liquid stability of the composition, and improving workability during production of the composition, and is preferably 18 or less, more preferably 16 or less, and even more preferably 12 or less.

[0038] The liquid detergent composition for clothing of the present invention contains component (d) in an amount of preferably 1% by mass or more, more preferably 5% by mass or more, in terms of improving foam-removal properties, improving the liquid stability of the composition, and improving workability during production of the composition, and preferably 20% by mass or less, more preferably 15% by mass or less, in terms of improving detergency, maintaining detergency after storage, and improving foam-removal properties.

[0039] The liquid detergent composition for clothing of the present invention may further contain a surfactant other than the components (a) and (d) as component (e), within a range that does not affect the effects of the present invention. Component (e) may be one or more surfactants selected from nonionic surfactants other than components (a) and (d), cationic surfactants, anionic surfactants, and amphoteric surfactants. The surfactant for component (e) preferably has a molecular weight of 5,000 or less.

[0040] Nonionic surfactants other than components (a) and (d) include alcohol alkoxylates, ester alkoxylates, polyhydric alcohol fatty acid esters that may contain alkyleneoxy groups, alkyl glycosides, polyethylene glycols, polyoxyethylene-polyoxypropylene block copolymers, and polyoxypropylene-polyoxyethylene-polyoxypropylene block copolymers. Alcohol alkoxylates include polyoxyalkylene alkyl ethers and polyoxyalkylene alkenyl ethers. Polyhydric alcohol fatty acid esters that may contain alkyleneoxy groups include glycerin fatty acid esters, polyglycerin fatty acid esters, propylene glycol fatty acid esters, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, sucrose fatty acid esters, and polyoxyethylene sorbitan fatty acid esters.

[0041] Examples of cationic surfactants include quaternary ammonium salt cationic surfactants. Examples of quaternary ammonium salt cationic surfactants include quaternary ammonium salts in which, of the four groups bonded to the nitrogen atom, one or two are hydrocarbon groups having from 8 to 24 carbon atoms, and the remaining groups are hydrocarbon groups having from 1 to 3 carbon atoms. Examples of cationic surfactants include compounds represented by the following general formula (e1):

[0042] [ka]

[0043] [In the formula, R e1 is a chain hydrocarbon group having 8 to 24 carbon atoms, and R e2 is a chain hydrocarbon group having 8 to 24 carbon atoms, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms, and R e3 and R e4 are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, and X -is an alkyl sulfate ion having 1 to 3 carbon atoms, or a halide ion.

[0044] In general formula (e1), R e1 The number of carbon atoms in the chain hydrocarbon group R is preferably 9 or more, more preferably 10 or more, and is preferably 18 or less, more preferably 14 or less, and even more preferably 12 or less. e2 is a chain hydrocarbon group having 8 to 24 carbon atoms, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms, and R e2 The number of carbon atoms in the chain hydrocarbon group R is preferably 9 or more, more preferably 10 or more, and is preferably 18 or less, more preferably 14 or less, and even more preferably 12 or less. e2 The chain hydrocarbon group R is preferably an alkyl group or an alkenyl group, more preferably an alkyl group. e3 , R e4 are each independently a methyl group, an ethyl group, or a hydroxyalkyl group having 1 to 3 carbon atoms. e1 , R e2 Specific examples of the chain hydrocarbon group include an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, and a hexadecyl group, with a nonyl group and a decyl group being preferred, and a decyl group being more preferred.Specific examples of the hydroxyalkyl group having 1 to 3 carbon atoms include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.X - is CH3SO4 - , CH3CH2SO4 - , or a halide ion.

[0045] More specific examples of the compound represented by general formula (e1) include one or more compounds selected from N-ethyl-N,N-dimethyltetradecylammonium salt, trimethylhexadecyl salt, N,N-dioctyl-N,N-dimethylammonium salt, N,N-dinonyl-N,N-dimethylammonium salt, N,N-didecyl-N,N-dimethylammonium salt, N,N-dioctyl-N-ethyl-N-methylammonium salt, N,N-dinonyl-N-ethyl-N-methylammonium salt, and N,N-didecyl-N-ethyl-N-methylammonium salt. Mono-long chain ammonium salts and di-long chain ammonium salts can also be used in combination. The counter ion for these salts is CH3SO4 - , CH3CH2SO4 - , or a halide ion such as chloride ion.

[0046] Examples of the anionic surfactant include one or more anionic surfactants selected from sulfonates having an aliphatic hydrocarbon group having from 8 to 18 carbon atoms, sulfates having an aliphatic hydrocarbon group having from 10 to 24 carbon atoms, and fatty acids or salts thereof having from 10 to 24 carbon atoms.

[0047] Examples of anionic surfactants include one or more anionic surfactants selected from internal olefin sulfonates having 10 to 18 carbon atoms, sulfate salts having an alkyl or alkenyl group having 10 to 24 carbon atoms, polyoxyalkylene alkyl or alkenyl ether sulfate salts having an alkyl or alkenyl group having 10 to 24 carbon atoms, alkylbenzene sulfonates having an alkyl group having 8 to 18 carbon atoms (an alkyl group having 8 to 18 carbon atoms refers to an alkyl group substituted on a benzene ring, excluding the benzene skeleton), sulfonates having an alkyl or alkenyl group having 10 to 24 carbon atoms (excluding internal olefin sulfonates having 10 to 18 carbon atoms), and fatty acids having 10 to 24 carbon atoms or salts thereof. Examples of these salts include alkali metal salts, alkaline earth metal (half atom) salts, ammonium salts, and organic ammonium salts. Examples of alkali metal salts include sodium salts and potassium salts. Examples of organic ammonium salts include alkanolammonium salts having 1 to 6 carbon atoms.

[0048] Examples of amphoteric surfactants include alkyl or alkenyl amine oxides having 10 to 24 carbon atoms, alkyl or alkenyl betaines having 10 to 24 carbon atoms, and alkyl or alkenyl sulfobetaines having 10 to 24 carbon atoms.

[0049] The content of component (e) is not particularly limited as long as it is within a range that does not affect the effects of the present invention, but it may be 5% by mass or less, further 3% by mass or less, 2% by mass or less, further 1% by mass or less, further 0.5% by mass or less, further 0.1% by mass or less, or even 0% by mass in the composition. The content of cationic surfactant in the liquid laundry detergent composition of the present invention may be 5% by mass or less, further 3% by mass or less, or even 1% by mass or less, and may be 0.1% by mass or more, or even 0.5% by mass or more. From the viewpoints of improving detergency, maintaining detergency after storage, and improving foam-removal properties, the content of anionic surfactants (excluding fatty acids) in the liquid detergent composition for clothing of the present invention is preferably 1% by mass or less, more preferably 0.5% by mass or less, even more preferably 0.1% by mass, and the content of anionic surfactants (excluding fatty acids) may be 0% by mass. In other words, it is preferable that the liquid detergent composition for clothing of the present invention does not contain anionic surfactants (excluding fatty acids), or that the content of anionic surfactants (excluding fatty acids) in the composition is 1% by mass or less.

[0050] From the viewpoints of improving detergency, maintaining detergency after storage, and improving foam-removal properties, the content of surfactant in the liquid detergent composition for clothing of the present invention is preferably 8% by mass or more, more preferably 10% by mass or more, and preferably 50% by mass or less, more preferably 30% by mass or less. The total amount of surfactant may be the combined content of components (a), (d), and (e).

[0051] From the viewpoints of improving detergency, maintaining detergency after storage, and improving foam-removal properties, the content of nonionic surfactant in the liquid detergent composition for clothing of the present invention is preferably 5% by mass or more, more preferably 8% by mass or more, and preferably 50% by mass or less, more preferably 30% by mass or less. The total amount of nonionic surfactant may be the sum of the contents of component (a), component (d), and the nonionic surfactants in component (e) other than components (a) and (d).

[0052] In the liquid detergent composition for clothing of the present invention, from the viewpoint of improving detergency and foam-removal, the proportion of component (a) in the total amount of surfactants is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and from the viewpoint of maintaining detergency and improving foam-removal after storage, it is preferably 100% by mass or less, more preferably 95% by mass or less, even more preferably 90% by mass or less, and even more preferably 85% by mass or less. The total amount of surfactants may be the sum of the contents of components (a), (d), and (e) in the composition.

[0053] In the liquid detergent composition for clothing of the present invention, from the viewpoints of improving detergency, maintaining detergency after storage, and improving foam-removal properties, the proportion of component (a) in the total amount of nonionic surfactants is preferably 30% by mass or more, more preferably 40% by mass or more, and preferably 100% by mass or less, and may be 100% by mass. The total amount of nonionic surfactants may be the sum of the contents of component (a), component (d), and the nonionic surfactants in component (e) other than component (a) and component (d) in the composition.

[0054] The liquid detergent composition for clothing of the present invention may contain the following components (1) to (11) as other optional components to the extent that they do not affect the effects of the present invention. (1) Alkaline agent The liquid detergent composition for clothing of the present invention preferably contains an alkaline agent to improve detergency. Examples of alkaline agents include inorganic alkaline agents such as alkali metal hydroxides and alkali metal carbonates, and alkanolamines in which one to three of the groups bonded to the nitrogen atom are alkanol groups having from 2 to 4 carbon atoms, and the remaining groups are alkyl groups or hydrogen atoms having from 1 to 4 carbon atoms. Among these, the alkanol group is preferably a hydroxyalkyl group, and more preferably a hydroxyethyl group. A hydrogen atom or a methyl group is preferred, with a hydrogen atom being particularly preferred, other than the alkanol group. Examples of alkanolamines include alkanolamines such as 2-aminoethanol, N-methylethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, diethanolamine, N-methyldiethanolamine, and triethanolamine. In the present invention, component (1) is preferably an alkanolamine selected from monoethanolamine and triethanolamine, with monoethanolamine being more preferred. The alkaline agent, which is the component (1), can also be used to adjust the pH of the liquid detergent composition for clothing of the present invention to a predetermined value. In the liquid laundry detergent composition of the present invention, component (1) may be blended in an amount sufficient to achieve the pH described below. Specifically, the composition may contain 0.01% by mass or more, preferably 0.5% by mass or more, and 10% by mass or less, and even 8% by mass or less. In the present invention, the amount of the alkaline agent (1), particularly the alkanolamine, blended in the composition includes the amount derived from other components, such as counterions of anionic surfactants, blended in the composition.

[0055] (2) Chelating agents Specific examples of chelating agents include aminopolyacetic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and hydroxyethyliminodiacetic acid, or salts thereof; organic acids such as citric acid, lactic acid, tartaric acid, and malic acid, or salts thereof; 1-hydroxyethylidene-1,1-diphosphonic acid, diethylenetriaminepenta(methylenephosphonic acid), and alkali metal or lower amine salts thereof. The content of the chelating agent of component (2), considered as an acid type, in the composition is 0.1% by mass or more and 5% by mass or less, preferably 0.1% by mass or more and 4% by mass or less, and more preferably 0.1% by mass or more and 3% by mass or less.

[0056] (3) Anti-redeposition agents and / or polymeric dispersants Examples of the anti-redeposition agent and / or polymer-based dispersant include polyacrylic acid, polymaleic acid, carboxymethyl cellulose, etc. The content of the anti-redeposition agent and / or polymer-based dispersant in the composition is preferably 0.01% by mass or more and 10% by mass or less.

[0057] (4) Bleach Examples of bleaching agents include hydrogen peroxide, sodium percarbonate, sodium perborate, etc. The content of the bleaching agent in the composition is preferably 0.01% by mass or more and 10% by mass or less.

[0058] (5) Bleach activator Examples of bleach activators include tetraacetylethylenediamine and bleach activators represented by general formulas (I-2) to (I-7) of JP-A-6-316700. The content of the bleach activator in the composition is preferably 0.01% by mass or more and 10% by mass or less.

[0059] (6) Enzymes other than component (c) The enzyme other than component (c) may be one or more enzymes selected from cellulase, protease, and lipase. The content of the enzyme in the composition is preferably 0.001% by mass or more and 2% by mass or less. The enzyme (6) is preferably an enzyme containing protease, since it provides higher cleaning performance for stains on clothing with sebum stains and food stains such as meat sauce. In addition, from the viewpoint of improving cleaning properties for food spills, the proportion of component (c) in the total amount of enzyme in the liquid detergent composition for clothing of the present invention is preferably 5% by mass or more, more preferably 20% by mass or more, even more preferably 40% by mass or more, and preferably 100% by mass or less, and may even be 100% by mass.

[0060] (7) Fluorescent dyes Examples of the fluorescent dye include those commercially available under the trade names Tinopal CBS (manufactured by Ciba Specialty Chemicals) and Whitex SA (manufactured by Sumitomo Chemical Co., Ltd.) The content of the fluorescent dye in the composition is preferably 0.001% by mass or more and 1% by mass or less.

[0061] (8) Antioxidants Examples of the antioxidant include butylhydroxytoluene, distyrenated cresol, sodium sulfite, sodium hydrogen sulfite, etc. The content of the antioxidant in the composition is preferably 0.01% by mass or more and 2% by mass or less.

[0062] (9) Add appropriate amounts of coloring matter, fragrance, antibacterial preservatives, and antifoaming agents such as silicone.

[0063] (10) Organic solvents containing hydroxyl groups As the organic solvent having a hydroxyl group, one or more compounds selected from the following components (10-1) to (10-6) are used. Component (10-1): A monohydric alcohol having an aliphatic hydrocarbon group with 2 to 6 carbon atoms Examples of the component (10-1) include monohydric alcohols selected from ethanol, 1-propanol, 2-propanol, and 1-butanol.

[0064] (10-2) Component: Dihydric to hexahydric alcohol having 2 to 6 carbon atoms Examples of the component (10-2) include dihydric or trihydric alcohols selected from ethylene glycol, propylene glycol, butylene glycol, 2-methyl-2,4-pentanediol, 1,5-pentanediol, 1,6-hexanediol, and glycerin. 2-Methyl-2,4-pentanediol is also known as hexylene glycol.

[0065] Component (10-3): Polyalkylene glycol containing alkylene glycol units having 2 to 4 carbon atoms Examples of the component (10-3) include polyalkylene glycols selected from diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycols having a weight-average molecular weight of 400 or more and 4000 or less, and polypropylene glycols having a weight-average molecular weight of 400 or more and 4000 or less.

[0066] Component (10-4): a monoalkyl ether of (mono- or poly) alkylene glycol having an alkylene glycol unit having from 2 to 4 carbon atoms and an alkyl group having from 1 to 4 carbon atoms Examples of the component (10-4) include compounds selected from diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol.

[0067] Component (10-5): Alkyl glyceryl ether having an alkyl group with 1 to 8 carbon atoms Examples of the component (10-5) include alkyl glyceryl ethers selected from 1-methyl glyceryl ether, 2-methyl glyceryl ether, 1,3-dimethyl glyceryl ether, 1-ethyl glyceryl ether, 1,3-diethyl glyceryl ether, triethyl glyceryl ether, 1-pentyl glyceryl ether, 2-pentyl glyceryl ether, 1-octyl glyceryl ether, and 2-ethylhexyl glyceryl ether.

[0068] (10-6) Component: Aromatic alkyl ether of (mono- or poly-) alkylene glycol having an alkylene glycol unit having 2 or 3 carbon atoms Examples of the component (10-6) include compounds selected from 2-phenoxyethanol, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, polyethylene glycol monophenyl ether having an average molecular weight of about 480, 2-benzyloxyethanol, and diethylene glycol monobenzyl ether.

[0069] In the above components (10-4) and (10-6), the term "(mono- or poly)alkylene glycol" refers to a monoalkylene glycol or a polyalkylene glycol. Furthermore, "polyalkylene glycol" refers to a glycol containing 2 to 9 alkylene glycol units.

[0070] From the viewpoint of further improving storage stability at low temperatures, the component (10) is preferably one or more compounds selected from the components (10-1), (10-2), (10-4), and (10-6). More specifically, the liquid detergent composition for clothing of the present invention preferably contains one or more compounds selected from ethanol, propylene glycol, diethylene glycol monobutyl ether, 2-phenoxyethanol, diethylene glycol monophenyl ether, and triethylene glycol monophenyl ether. The liquid detergent composition for clothing of the present invention preferably contains one or more organic solvents selected from ethanol, propylene glycol, diethylene glycol monobutyl ether, 2-phenoxyethanol, and polyethylene glycol phenyl ether as the organic solvent having a hydroxyl group. The content of component (10) in the composition is preferably 1% by mass or more, more preferably 4% by mass or more, even more preferably 5% by mass or more, and preferably 40% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass or less.

[0071] (11) Hydrotropes A hydrotrope can be blended for the stability of the liquid detergent composition for fabrics. The hydrotrope of the present invention is an organic compound having an anionic group, further containing one or two alkyl groups selected from a methyl group, an ethyl group or a propyl group, and having one sulfonic acid group or carboxylic acid group, and examples thereof include alkylbenzenecarboxylic acid, alkylbenzenesulfonic acid or salts thereof, and benzoic acid or salts thereof. More specifically, they are p-toluenesulfonic acid, cumenesulfonic acid, metaxylenesulfonic acid, and benzoic acid, and the salt is preferably an alkali metal salt. In the present invention, p-toluenesulfonic acid or an alkali metal salt thereof is preferred, and it may be blended as an acid and neutralized with an alkaline agent in the composition. The liquid detergent composition for fabrics of the present invention can contain a hydrotrope, in terms of an acid-type compound, in the composition, preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and preferably 5% by mass or less, more preferably 4% by mass or less, still more preferably 3% by mass or less.

[0072] The liquid detergent composition for fabrics of the present invention contains water. As the water, ion-exchanged water, distilled water, tap water, water containing 1 mg / kg or more and 5 mg / kg or less of sodium hypochlorite, etc. can be used. From the viewpoints of physical properties such as the viscosity of the composition and the workability during fabric washing, the liquid detergent composition for fabrics of the present invention contains water in the composition, preferably 50% by mass or more, more preferably 60% by mass or more, and preferably 90% by mass or less, more preferably 85% by mass or less.

[0073] From the viewpoints of improving detergency, maintaining detergency after storage, and improving foam breakage property, the pH of the liquid detergent composition for fabrics of the present invention at 25°C is preferably 6.5 or more, more preferably 7 or more, still more preferably 8 or more, and preferably 11 or less, more preferably 10.5 or less, still more preferably 10 or less. The pH is a value measured at 25°C using a glass electrode. Specifically, it is measured by the following method. <Method for Measuring pH> A pH electrode (Model 6367) in a Horiba pH meter D-52 is calibrated in advance with phthalate buffer solution (pH 4.01), phosphate standard solution (pH 6.84), and borate standard solution (pH 9.18), and then thoroughly rinsed with ion-exchanged water. The pH electrode, calibrated and washed as described above, is placed in a liquid laundry detergent composition adjusted to 25°C, and the pH is measured using the AUTO HOLD mode of the pH meter until the measured value becomes constant.

[0074] The liquid detergent composition for clothing of the present invention is used for washing clothing such as clothes, towels, bedding, textile products for bedding (sheets, pillowcases, etc.), etc. Washable textile products other than these can also be used as clothing to be washed in the present invention.

[0075] Although the details of the mechanism by which the effects of the present invention are exerted have not been fully elucidated, it is believed that the following occurs: Among stains adhering to clothing, food spills and the like are thought to be caused by carbohydrate components such as starch solidifying or denaturing as water evaporates, which, together with other stains, reduces the detergency. In the present invention, the addition of a carbohydrate-splitting enzyme to a liquid detergent composition for clothing improves detergency. It is therefore believed that the carbohydrate-splitting enzyme breaks down carbohydrates in the stain, thereby allowing the surfactant, a detergent component, to more easily penetrate firmly adhered stains, thereby improving detergency. Furthermore, the decrease in detergency observed when the detergent composition is stored at high temperatures compared to before storage, simulating the daily life in which it is used, can be presumed to be due to a decrease in the activity of the carbohydrate-splitting enzyme caused by storage. In the liquid laundry detergent composition of the present invention, the carbohydrate-degrading enzyme of the present invention undergoes conformational changes in the enzyme active site and degradation or denaturation of the enzyme protein during storage. By using a specific ratio of the relatively hydrophobic nonionic surfactant (component (a)) with a specific structure and the carbohydrate-degrading enzyme of the present invention (component (c)), component (a) is appropriately adsorbed to the surface of the enzyme protein. This, along with interactions with inorganic calcium salts (component (b)), which are generally believed to contribute to enzyme stabilization, is believed to stabilize the carbohydrate-degrading reaction active site without inhibiting it. On the other hand, in typical laundry, detergent compositions with extremely high foaming properties can cause problems such as increased rinsing load and excessive foam in the drain. The nonionic surfactants that contribute to the stabilization of the carbohydrate-degrading enzyme of the present invention are relatively hydrophobic and have excellent foam-removal properties. Furthermore, since component (a) is also a soil-cleaning component, it strongly interacts with soiling components. This is believed to facilitate the presence of adsorbates of component (a) and the carbohydrate-degrading enzyme in the vicinity of the soiling components, further improving cleaning performance. However, the present invention is not particularly limited to the above-mentioned mechanism of action.

[0076] <How to wash clothes> The present invention provides a method for washing clothes, which comprises washing clothes with a cleaning liquid obtained by mixing the liquid detergent composition for clothes of the present invention with water, and then rinsing the clothes with water. The method for washing clothes of the present invention may be a method for washing clothes in which clothes are washed with a washing liquid containing component (a), component (b), component (c), and water. The items described for the liquid detergent composition for clothing of the present invention can be applied as appropriate to the method for washing clothing of the present invention.

[0077] From the viewpoints of improving cleaning performance, maintaining cleaning performance after storage, and improving foam-removing properties, the content of component (a) in the cleaning solution is preferably 0.0005% by mass or more, more preferably 0.0008% by mass or more, even more preferably 0.001% by mass or more, and preferably 0.5% by mass or less, more preferably 0.3% by mass or less, even more preferably 0.1% by mass or less.

[0078] From the viewpoints of improving cleaning performance, maintaining cleaning performance after storage, and improving foam-removing properties, the content of component (b) in the cleaning solution is preferably 0.000005% by mass or more, more preferably 0.00001% by mass or more, even more preferably 0.00005% by mass or more, and preferably 0.01% by mass or less, more preferably 0.0075% by mass or less, even more preferably 0.005% by mass or less.

[0079] Furthermore, from the viewpoints of improving cleaning performance, maintaining cleaning performance after storage, and improving foam-removing properties, the content of component (c) in the cleaning solution is preferably 0.0000005% by mass or more, more preferably 0.000001% by mass or more, even more preferably 0.000005% by mass or more, as enzyme protein, and preferably 0.001% by mass or less, more preferably 0.00075% by mass or less, even more preferably 0.0005% by mass or less.

[0080] The cleaning solution is preferably prepared by diluting the liquid detergent composition for clothing of the present invention with water so that the content of each component falls within the ranges described above. The specific dilution ratio may be preferably 500 times or more, more preferably 800 times or more, and preferably 5000 times or less, more preferably 3000 times or less, from the viewpoints of the viscosity and other properties of the liquid detergent composition for clothing of the present invention and workability during laundry washing.

[0081] The water used in the method for washing clothes of the present invention preferably has hardness. From the viewpoints of improving detergency, maintaining detergency after storage, and improving foam-removal, the water hardness is preferably 1°dH or more, more preferably 2°dH or more, even more preferably 3.5°dH or more, even more preferably 5°dH or more, even more preferably 7°dH or more, and preferably 20°dH or less, more preferably 18°dH or less, and even more preferably 15°dH or less, on the German hardness scale. Here, German hardness (°dH) in this specification refers to the concentration of calcium and magnesium in water, expressed as a CaCO3-equivalent concentration of 1 mg / L (ppm) = approximately 0.056°dH (1°dH = 17.8 ppm). The calcium and magnesium concentrations for this German hardness scale are determined by chelate titration using ethylenediaminetetraacetic acid disodium salt. A specific method for measuring the German hardness of water in this specification is shown below. <Method for measuring water hardness in Germany> 〔reagent〕 0.01 mol / l EDTA·2Na solution: 0.01 mol / l aqueous solution of disodium ethylenediaminetetraacetic acid (titration solution, 0.01 M EDTA-Na2, manufactured by Sigma-Aldrich) ·Universal BT indicator (product name: Universal BT, manufactured by Dojindo Kagaku Kenkyusho Co., Ltd.) Ammonia buffer solution for hardness measurement (67.5 g of ammonium chloride dissolved in 570 ml of 28 w / v% ammonia water, and then made up to 1000 ml with ion-exchanged water) [Measurement of hardness] (1) Use a volumetric pipette to collect 20 ml of sample water into a conical beaker. (2) Add 2 ml of ammonia buffer solution for hardness measurement. (3) Add 0.5 ml of Universal BT indicator. After addition, confirm that the solution is reddish purple. (4) While shaking the conical beaker well, add 0.01 mol / l EDTA·2Na solution dropwise from the buret until the sample water turns blue. The end point of the titration is reached. (5) The total hardness is calculated using the following formula. Hardness (°dH)=T×0.01×F×56.0774×100 / A T:0.01mol / l Titration amount of EDTA・2Na solution (mL) A: Sample volume (20 mL, volume of sample water) F: Factor of 0.01 mol / l EDTA·2Na solution

[0082] From the viewpoints of improving detergency, maintaining detergency after storage, and improving foam-removal properties, the detergent solution used in the present invention is preferably a detergent solution obtained by mixing component (a), component (b), component (c), and water having a German hardness of 1° dH or more and 20° dH or less. Alternatively, the detergent solution may be a detergent solution obtained by mixing the liquid detergent composition for clothing of the present invention with water having a German hardness of 1° dH or more and 20° dH or less.

[0083] In the method for washing clothes of the present invention, the liquor ratio, which is the ratio of the mass of clothes (kg) to the amount of washing liquid (liters), i.e., the amount of washing liquid (liters) / mass of clothes (kg) (hereinafter, this ratio may be referred to as the liquor ratio), is preferably 2 or more, more preferably 3 or more, even more preferably 4 or more, and even more preferably 5 or more, from the viewpoint of ensuring washing performance, and is preferably 400 or less, more preferably 300 or less.

[0084] In the method for washing clothing of the present invention, the time for washing clothing is preferably 1 minute or more, more preferably 2 minutes or more, even more preferably 3 minutes or more, from the viewpoint of ensuring washability and further improving the texture-imparting effect on clothing, and is preferably 12 hours or less, more preferably 8 hours or less, even more preferably 6 hours or less, still more preferably 3 hours or less, and still more preferably 1 hour or less.

[0085] In the method for washing clothes of the present invention, after washing the clothes, the clothes are rinsed with water. The water used for rinsing may also have the above-mentioned hardness. In rinsing, the rinsing water can be used to the clothes at the same ratio as the bath ratio of the cleaning solution. The rinsing time can also be in the same range as the washing time.

[0086] The method for washing clothes of the present invention is also suitable for a rotary washing method. A rotary washing method refers to a washing method in which clothes that are not fixed to a rotating device rotate around a rotating shaft together with the washing liquid. The rotary washing method can be performed using a rotary washing machine. Specific examples of rotary washing machines include drum washing machines, pulsator washing machines, and agitator washing machines. These rotary washing machines can be commercially available for home use. Drum washing machines have rapidly become popular in recent years because they can reduce the amount of water used per wash, and drum washing machines can particularly reduce the amount of water used during washing.

[0087] The following are examples of embodiments of the present invention. The details of the liquid detergent composition for clothing and the method for cleaning clothing of the present invention can be applied to these embodiments with modifications as necessary. Furthermore, the description of each embodiment can be applied to other embodiments with modifications as necessary.

[0088] <1> A liquid detergent composition for clothing comprising the following components (a), (b), and (c) and water, wherein the mass ratio (a) / (c) of the content of component (a) to the content of component (c) as an enzyme protein is 100 or more and 16,000 or less: Component (a): a nonionic surfactant represented by the following general formula (1): RO-〔(EO) n / (PO) m 〕-H (1) [In the formula, R is an aliphatic hydrocarbon group having 10 to 24 carbon atoms, EO is an ethyleneoxy group, PO is a propyleneoxy group, n and m are the average number of moles added, n is a number of 8 to 40, and m is a number of 1 to 6, and EO and PO may be added randomly or in blocks.] (b) Ingredient: inorganic calcium salt (c) Ingredient: Carbohydrate-degrading enzyme

[0089] <2> In the general formula (1), the number of carbon atoms in R is 10 or more, preferably 12 or more, and 24 or less, preferably 18 or less, more preferably 14 or less. <1> The liquid detergent composition for clothing according to claim 1.

[0090] <3> In the general formula (1), the aliphatic hydrocarbon group of R is an alkyl group or an alkenyl group, preferably an alkyl group. <1> or <2> The liquid detergent composition for clothing according to claim 1.

[0091] <4> In the general formula (1), R is a linear or branched aliphatic hydrocarbon group, further a linear or branched alkyl group, or a linear or branched alkenyl group, further a linear alkyl group. <1> ~ <3> 10. The liquid detergent composition for clothing according to claim 9, wherein the detergent is a liquid detergent for clothing containing 10 or more hydroxypropyl methylcellulose.

[0092] <5> In general formula (1), n ​​is a number of 8 or more, preferably 10 or more, more preferably 12 or more, even more preferably 14 or more, still more preferably 16 or more, and 40 or less, preferably 35 or less, more preferably 30 or less, even more preferably 24 or less, and still more preferably 20 or less. <1> ~ <4> 10. The liquid detergent composition for clothing according to claim 9, wherein the detergent is a liquid detergent for clothing containing 10 or more hydroxypropyl methylcellulose.

[0093] <6> In the general formula (1), m is a number of 1 or more, preferably 2 or more, and 6 or less, preferably 4 or less. <1> ~ <5> 10. The liquid detergent composition for clothing according to claim 9, wherein the detergent is a liquid detergent for clothing containing 10 or more hydroxypropyl methylcellulose.

[0094] <7> The ratio of m to n in general formula (1), m / n, is preferably 0.03 or more, more preferably 0.05 or more, even more preferably 0.1 or more, and preferably 0.7 or less, more preferably 0.5 or less, even more preferably 0.25 or less. <1> ~ <6> 10. The liquid detergent composition for clothing according to claim 9, wherein the detergent is a liquid detergent for clothing containing 10 or more hydroxypropyl methylcellulose.

[0095] <8> The ratio of m to the sum of n and m in general formula (1), m / (n+m), is preferably 0.03 or more, more preferably 0.05 or more, even more preferably 0.08 or more, and is preferably 0.4 or less, more preferably 0.3 or less, even more preferably 0.2 or less. <1> ~ <7> 10. The liquid detergent composition for clothing according to claim 9, wherein the detergent is a liquid detergent for clothing containing 10 or more hydroxypropyl methylcellulose.

[0096] <9> Contains a nonionic surfactant represented by the following general formula (2) as component (a), <1> ~ <8> 10. The liquid detergent composition for clothing according to claim 9, wherein the detergent is a liquid detergent for clothing containing 10 or more hydroxypropyl methylcellulose. RO-(EO) n1 -(PO) m -(EO) n2 -H (2) [In the formula, R is an aliphatic hydrocarbon group having 10 to 24 carbon atoms, EO is an ethyleneoxy group, and PO is a propyleneoxy group, EO and PO are block-bonded in this order, n1, n2, and m are the average number of moles added, n1 is a number of 0 to 20, m is a number of 1 to 6, n2 is a number of 0 to 20, the sum of n1 and n2 is 8 or more, and EO and PO are block-bonded.]

[0097] <10> In the general formula (2), the number of carbon atoms in R is 10 or more, preferably 12 or more, and 24 or less, preferably 18 or less, more preferably 14 or less. <9> The liquid detergent composition for clothing according to claim 1.

[0098] <11> In the general formula (2), the aliphatic hydrocarbon group of R is an alkyl group or an alkenyl group, preferably an alkyl group. <9> or <10> The liquid detergent composition for clothing according to claim 1.

[0099] <12> In the general formula (2), R is a linear or branched aliphatic hydrocarbon group, further a linear or branched alkyl group, or a linear or branched alkenyl group, further a linear alkyl group. <9> ~ <11> 10. The liquid detergent composition for clothing according to claim 9, wherein the detergent is a liquid detergent for clothing containing 10 or more hydroxypropyl methylcellulose.

[0100] <13> In general formula (2), n1 is preferably 4 or more, more preferably 5 or more, even more preferably 7 or more, and is preferably 18 or less, more preferably 16 or less, even more preferably 12 or less. <9> ~ <12> 10. The liquid detergent composition for clothing according to claim 9, wherein the detergent is a liquid detergent for clothing containing 10 or more hydroxypropyl methylcellulose.

[0101] <14> In the general formula (2), m is a number of 1 or more, preferably 2 or more, and 6 or less, preferably 4 or less. <9> ~ <13> 10. The liquid detergent composition for clothing according to claim 9, wherein the detergent is a liquid detergent for clothing containing 10 or more hydroxypropyl methylcellulose.

[0102] <15> In general formula (2), n2 is preferably 4 or more, more preferably 5 or more, even more preferably 7 or more, and is preferably 19 or less, more preferably 18 or less, even more preferably 17 or less. <9> ~ <14> 10. The liquid detergent composition for clothing according to claim 9, wherein the detergent is a liquid detergent for clothing containing 10 or more hydroxypropyl methylcellulose.

[0103] <16> In general formula (2), the sum of n1 and n2 is 8 or more, preferably 10 or more, more preferably 12 or more, even more preferably 14 or more, still more preferably 16 or more, and is 40 or less, preferably 35 or less, more preferably 30 or less, even more preferably 24 or less, still more preferably 20 or less. <9> ~ <15> 10. The liquid detergent composition for clothing according to claim 9, wherein the detergent is a liquid detergent for clothing containing 10 or more hydroxypropyl methylcellulose.

[0104] <17> The ratio of m to the sum of n1 and n2 in general formula (2), m / (n1+n2), is preferably 0.03 or more, more preferably 0.05 or more, even more preferably 0.1 or more, and is preferably 0.7 or less, more preferably 0.5 or less, even more preferably 0.25 or less. <9> ~ <16> 10. The liquid detergent composition for clothing according to claim 9, wherein the detergent is a liquid detergent for clothing containing 10 or more hydroxypropyl methylcellulose.

[0105] <18> In general formula (2), the ratio of m to the sum of n1, n2, and m, m / (n1+n2+m), is preferably 0.03 or more, more preferably 0.05 or more, even more preferably 0.08 or more, and is preferably 0.4 or less, more preferably 0.3 or less, even more preferably 0.2 or less. <9> ~ <17> 10. The liquid detergent composition for clothing according to claim 9, wherein the detergent is a liquid detergent for clothing containing 10 or more hydroxypropyl methylcellulose.

[0106] <19> The composition contains the component (a) in an amount of preferably 3% by mass or more, more preferably 5% by mass or more, even more preferably 8% by mass or more, and preferably 50% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less. <1> ~ <18> 10. The liquid detergent composition for clothing according to claim 9, wherein the detergent is a liquid detergent for clothing containing 10 or more hydroxypropyl methylcellulose.

[0107] <20> (b) contains one or more inorganic calcium salts selected from calcium halide (e.g., calcium chloride), calcium carbonate, calcium sulfate, and calcium silicate; <1> ~ <19> 10. The liquid detergent composition for clothing according to claim 9, wherein the detergent is a liquid detergent for clothing containing 10 or more hydroxypropyl methylcellulose.

[0108] <21> (b) contains calcium chloride as an ingredient; <1> ~ <20> 10. The liquid detergent composition for clothing according to claim 9, wherein the detergent is a liquid detergent for clothing containing 10 or more hydroxypropyl methylcellulose.

[0109] <22> The composition contains the component (b) in an amount of preferably 0.001% by mass or more, more preferably 0.005% by mass or more, even more preferably 0.008% by mass or more, and preferably 1% by mass or less, more preferably 0.5% by mass or less, even more preferably 0.2% by mass or less. <1> ~ <21> 10. The liquid detergent composition for clothing according to claim 9, wherein the detergent is a liquid detergent for clothing containing 10 or more hydroxypropyl methylcellulose.

[0110] <23> (c) containing one or more carbohydrate-degrading enzymes selected from amylase, sucrase, maltase, lactase, pullulanase, and fructofuranosidase; <1> ~ <22> 10. The liquid detergent composition for clothing according to claim 9, wherein the detergent is a liquid detergent for clothing containing 10 or more hydroxypropyl methylcellulose.

[0111] <24> (c) Contains amylase and further α-amylase as components; <1> ~ <23> 10. The liquid detergent composition for clothing according to claim 9, wherein the detergent is a liquid detergent for clothing containing 10 or more hydroxypropyl methylcellulose.

[0112] <25> The component (c) is contained in the composition as an enzyme protein in an amount of preferably 0.0005% by mass or more, more preferably 0.0008% by mass or more, even more preferably 0.001% by mass or more, and preferably 1% by mass or less, more preferably 0.1% by mass or less, even more preferably 0.05% by mass or less. <1> ~ <24> 10. The liquid detergent composition for clothing according to claim 9, wherein the detergent is a liquid detergent for clothing containing 10 or more hydroxypropyl methylcellulose.

[0113] <26> The mass ratio (a) / (c) of the content of the component (a) to the content of the component (c) as an enzyme protein is 100 or more, preferably 500 or more, more preferably 700 or more, and 16,000 or less, more preferably 10,000 or less, even more preferably 7,000 or less, still more preferably 5,000 or less, still more preferably 3,000 or less, still more preferably 1,500 or less, and still more preferably 1,000 or less. <1> ~ <25> 10. The liquid detergent composition for clothing according to claim 9, wherein the detergent is a liquid detergent for clothing containing 10 or more hydroxypropyl methylcellulose.

[0114] <27> The mass ratio (a) / (b) of the content of the component (a) to the content of the component (b) is preferably 10 or more, more preferably 50 or more, even more preferably 100 or more, and is preferably 10,000 or less, more preferably 2,000 or less, even more preferably 500 or less, and still more preferably 150 or less. <1> ~ <26> 10. The liquid detergent composition for clothing according to claim 9, wherein the detergent is a liquid detergent for clothing containing 10 or more hydroxypropyl methylcellulose.

[0115] <28> The mass ratio (b) / (c) of the content of the component (b) to the content of the component (c) as an enzyme protein is more preferably 0.1 or more, even more preferably 0.5 or more, still more preferably 1 or more, still more preferably 3 or more, and more preferably 100 or less, still more preferably 50 or less, still more preferably 20 or less, still more preferably 10 or less, still more preferably 5 or less. <1> ~ <27> 10. The liquid detergent composition for clothing according to claim 9, wherein the detergent is a liquid detergent for clothing containing 10 or more hydroxypropyl methylcellulose.

[0116] <29> Further, the composition contains, as component (d), a nonionic surfactant in which ethylene oxide is added to a secondary alcohol (excluding component (a)). <1> ~ <28> 10. The liquid detergent composition for clothing according to claim 9, wherein the detergent is a liquid detergent for clothing containing 10 or more hydroxypropyl methylcellulose.

[0117] <30> Contains a nonionic surfactant represented by the following general formula (d1) as component (d), <29> The liquid detergent composition for clothing according to claim 1. RO-(EO) s -H (d1) [In the formula, R is a linear or branched secondary alkyl group having from 8 to 24 carbon atoms, EO is an ethyleneoxy group, and s is the average number of moles added, which is from 3 to 24.]

[0118] <31> The number of carbon atoms in R in formula (d1) is preferably 10 or more, more preferably 12 or more, and preferably 18 or less, more preferably 14 or less. <30> The liquid detergent composition for clothing according to claim 1.

[0119] <32> In formula (d1), s is preferably 4 or more, more preferably 5 or more, and is preferably 18 or less, more preferably 16 or less, and even more preferably 12 or less. <30> or <31> The liquid detergent composition for clothing according to claim 1.

[0120] <33> The composition contains the component (d) in an amount of preferably 1% by mass or more, more preferably 5% by mass or more, and preferably 20% by mass or less, more preferably 15% by mass or less. <29> ~ <32> 10. The liquid detergent composition for clothing according to claim 9, wherein the detergent is a liquid detergent for clothing containing 10 or more hydroxypropyl methylcellulose.

[0121] <34> The content of anionic surfactants (excluding fatty acids) in the composition is 1% by mass or less. <1> ~ <33> 10. The liquid detergent composition for clothing according to claim 9, wherein the detergent is a liquid detergent for clothing containing 10 or more hydroxypropyl methylcellulose.

[0122] <35> The content of the cationic surfactant in the composition is 5% by mass or less, further 3% by mass or less, and further 1% by mass or less. <1> ~ <34> 10. The liquid detergent composition for clothing according to claim 9, wherein the detergent is a liquid detergent for clothing containing 10 or more hydroxypropyl methylcellulose.

[0123] <36> <1> ~ <35> 10. A method for washing clothes, comprising washing clothes with a cleaning liquid obtained by mixing the liquid detergent composition for clothes according to any one of 1 to 9 above with water, and then rinsing the clothes with water. [Example]

[0124] <Examples 1 to 13 and Comparative Examples 1 to 6> The following liquid detergent compositions for clothing shown in Tables 1 and 2 were prepared using the components listed below, and the resulting compositions were evaluated for detergency and foam removal before and after storage using the methods described below.

[0125] <Composition ingredients> (a) Ingredients (a-1) A polyoxyalkylene alkyl ether in which, in the general formula (2), R is a lauryl group, n1 is 9 on average, m is 2 on average, and n2 is 9 on average. (a-2) A polyoxyalkylene alkyl ether in which, in the general formula (2), R is a lauryl group, n1 is 9 on average, m is 4 on average, and n2 is 9 on average. (a-3) A polyoxyalkylene alkyl ether in which, in the general formula (2), R is a lauryl group, n1 is 0 on average, m is 4 on average, and n2 is 17 on average. (a-4) A polyoxyalkylene alkyl ether in which, in the general formula (2), R is a lauryl group, n1 is 0 on average, m is 2 on average, and n2 is 10 on average. (a-5) A polyoxyalkylene alkyl ether in which, in the general formula (2), R is a lauryl group, n1 is 10 on average, m is 2 on average, and n2 is 0 on average.

[0126] Component (a') [Comparative compound for component (a)] (a'-1) A polyoxyalkylene alkyl ether in which, in the general formula (2), R is a lauryl group, n1 is 6 on average, m is 0 on average, and n2 is 0 on average. (a'-2) A polyoxyalkylene alkyl ether in which, in the general formula (2), R is a lauryl group, n1 is 21 on average, m is 0 on average, and n2 is 0 on average. (a'-3) Sodium linear alkylbenzenesulfonate having 11 to 13 carbon chains (a'-4) Sodium alkyl sulfate with 12 carbon chains

[0127] (b) Component Calcium chloride

[0128] (c) Component Amylase: Amplify Prime 100L, manufactured by Novozymes (the enzyme protein content in the product is 6% by mass, and the mass % of component (c) in the table is the mass % of the enzyme protein.)

[0129] (d) Ingredients (d-1): Softanol 70H (manufactured by Nippon Shokubai Co., Ltd.), a polyoxyalkylene alkyl ether obtained by adding an average of 7 moles of ethylene oxide to a secondary alcohol having 12 to 14 carbon atoms.

[0130] Other ingredients Cationic surfactant 1: N,N-didecyl-N-ethyl-N-methylammonium ethyl sulfate (Cortamin D10-ES, manufactured by Kao Corporation) Cationic surfactant 2: N-ethyl-N,N-dimethyltetradecylammonium ethyl sulfate (Cortamin 40ES, manufactured by Kao Corporation) Coconut oil fatty acid (Lunac L55, manufactured by Kao Corporation) Acrylic acid polymer (Aqualic LK-165, manufactured by Nippon Shokubai Co., Ltd.)

[0131] <How to evaluate cleaning performance> (1) Cleanability before storage Five pieces of food-stained cloth were placed in 600 mL of cleaning solution prepared by mixing 0.5 g of a liquid laundry detergent composition and water, and washed for 10 minutes at 85 rpm / min using a tergotometer (UESHIMA MS-8212, inner diameter 12 cm, height 17.5 cm). The concentration of the liquid laundry detergent composition in the cleaning solution was 0.0833% by mass. The cleaning solution was prepared using water from Wakayama City. The temperature of the cleaning solution was 20°C, and this temperature was maintained throughout the wash. The food-stained cloth was prepared by applying 0.2 mg of tonkatsu sauce (Bulldog Sauce Co., Ltd.) to a cotton knitted cloth (6 cm x 6 cm) and drying overnight. After washing, the cloth was rinsed for 30 seconds using water from Wakayama City.

[0132] The reflectance at 460 nm of the original fabric (cotton knitted fabric) before soiling and the soiled fabric before and after washing was measured using a recording colorimeter (Shimadzu Corporation), and the cleaning rate (%) was calculated using the following formula. The table shows the average cleaning rate of five artificially soiled fabrics. A higher value is preferable for the cleaning rate.

[0133]

number

[0134] (2) Cleanability after storage The same procedure as in (1) was repeated except that the washing solution was prepared using a liquid detergent composition for clothing that had been stored at 40°C for 4 weeks, and the washing rate was measured.

[0135] <Evaluation method for foam-removal> 50 ml of Wakayama City water and 166.8 μl of each liquid laundry detergent composition were added to a screw tube No. 8 (Maruem), and the mixture was shaken at 300 rpm for 5 minutes in a vertical shaker (TAITEC, SR-2 DW). The foam height was measured 10 minutes after the end of shaking and evaluated according to the following criteria. ○: The foam height after 10 minutes is 10 mm or less. ×: Foam height after 10 minutes exceeds 10 mm.

[0136] [Table 1]

[0137] [Table 2]

[0138] *1 The proportion of (a') is the proportion calculated based on the amount of surfactant equivalent to the nonionic surfactant in component (a').

Claims

1. A liquid detergent composition for clothing comprising the following components (a), (b), and (c) and water, wherein the mass ratio (a) / (c) of the content of component (a) to the content of component (c) as an enzyme protein is 100 or more and 3,000 or less: Component (a): a nonionic surfactant represented by the following general formula (2): RO-(EO) n1 -(PO) m -(EO) n2 -H (2) [In the formula, R is an aliphatic hydrocarbon group having from 10 to 24 carbon atoms, EO is an ethyleneoxy group, PO is a propyleneoxy group, EO and PO are block bonded in this order, n1, n2 and m are the average number of moles added, n1 is a number of from 0 to 20, m is a number of from 1 to 6, n2 is a number of from 0 to 20, the sum of n1 and n2 is 8 or more, and EO and PO are block bonded.] (b) Component: inorganic calcium salt (c) Component: Carbohydrate-degrading enzyme

2. 2. The liquid laundry detergent composition according to claim 1, wherein component (a) is a nonionic surfactant in which the ratio of m to the sum of n1, n2, and m in general formula (2), m / (n1 + n2 + m), is 0.03 or more and 0.4 or less.

3. 3. A liquid detergent composition for clothing as described in claim 1 or claim 2, wherein (b) / (c), which is the mass ratio of the content of component (b) to the content of component (c) as an enzyme protein, is 0.1 or more and 100 or less.

4. 4. The liquid detergent composition for clothing according to claim 1, wherein the mass ratio (a) / (b) of the content of the component (a) to the content of the component (b) is 10 or more and 10,000 or less.

5. 5. The liquid detergent composition for clothing according to claim 1, wherein the content of anionic surfactants (excluding fatty acids) in the composition is 1% by mass or less.

6. A method for washing clothes, comprising washing clothes with a cleaning liquid obtained by mixing the liquid detergent composition for clothes according to any one of claims 1 to 5 and water, and then rinsing the clothes with water.

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