JP2022036907A - Liquid detergent composition for clothing - Google Patents

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

The present invention relates to a liquid detergent composition for clothing and a method for cleaning clothing.

High detergency has been pursued for laundry detergents. On the other hand, the progress of washing machines is remarkable, and models that automatically add detergents and fabric softeners are on the market. It is desired that the cleaning agent used for washing in which the amount of the cleaning agent added and the amount of water used is controlled can be maintained without changing the performance from the beginning to the end of the use. It is also desired to have excellent rinsing foam breaking property so that rinsing can be completed with as little water as possible.

Enzymes are generally used as cleaning agents for clothing from the viewpoint of detergency against various stains adhering to clothing. However, the enzyme is unstable in a liquid detergent containing water, and the cleaning power tends to decrease when the detergent containing the enzyme is stored for a long period of time. Conventionally, there have been various proposals for enhancing the stability of an enzyme in a liquid detergent containing an enzyme.

Patent Document 1 describes (A) a specific nonionic surfactant, (B) a polyoxyalkylene alkyl ether sulfuric acid or a salt thereof, (C) a linear alkylbenzene sulfonic acid or a salt thereof, (D) an enzyme, and (E). It contains water, and the mass ratio represented by the component (A) / [component (B) + component (C)] is 0.5 to 3.5, and is represented by the component (B) / component (C). Liquid detergents for clothing are disclosed having a mass ratio of 90/10 to 10/90.

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

Patent Document 3 describes (a) polyoxyethylene / polyoxypropylene alkyl ether and (b) at least one of the ethyleneoxide / propyleneoxide adduct of trimethylolpropane and the ethyleneoxide / propyleneoxide adduct of glycerin (a). ): (B) = nonionic surfactant (A), alkanolamine (B), enzyme (C), xylene sulfonate and cumene, which are blended in a mass ratio of 3: 1 to 20: 1. The nonionic surfactant (A) contains 1 of the solubilizer (D) composed of at least one of the sulfonates, the calcium additive, and water, and the nonionic surfactant (A) is 1 in the entire liquid cleaning composition for hard surfaces. It contains ~ 10% by mass, alkanolamine (B) 10 ~ 30% by mass, enzyme (C) 0.1 ~ 5% by mass, and the pH of the liquid detergent composition for hard surface at 25 ° C. is 8.0 ~. Liquid detergent compositions for hard surfaces set in the range of 10.0 are disclosed.

Patent Document 4 describes (A) polyoxyethylene polyoxypropylene alkyl ether 6% by mass to 40% by mass, (B) starch degrading enzyme, (C) enzyme stabilizer, (D) solubilizer, and (E). ) A pre-soaking cleaning agent composition containing a pH adjuster is disclosed.

Patent Document 5 describes a liquid detergent composition containing (a) a specific nonionic surfactant, (b) an enzyme, (c) an enzyme stabilizer, and (d) an organic polyvalent carboxylic acid and / or a salt thereof. The thing is disclosed.

International Publication No. 2017/038930 Japanese Unexamined Patent Publication No. 2018-115286 Japanese Unexamined Patent Publication No. 2016-172814 Japanese Unexamined Patent Publication No. 2016-11385 Japanese Unexamined Patent Publication No. 2002-69489

The present invention provides a liquid detergent composition for clothing containing an enzyme, which has excellent detergency and defoaming property after storage, particularly after storage at a high temperature.

The present invention contains the following components (a), (b), (c) and water, and is a mass ratio of the content of the component (a) to the content of the component (c) as an enzyme protein. (A) / (c) relates to a liquid detergent composition for clothing, which is 100 or more and 16000 or less.
(A) Component: Nonionic surfactant represented by the following general formula (1) RO-[(EO) _n / (PO) _m ] -H (1)
[R in the formula 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 the average number of added moles, and n is. The number is 8 or more and 40 or less, m is 1 or more and 6 or less, and EO and PO may be random addition or block addition. ]
(B) Component: Inorganic calcium salt (c) Component: Glycolytic enzyme

The present invention also relates to a method for washing clothes by washing the clothes with a washing liquid obtained by mixing the liquid detergent composition for clothes and water of the present invention, and then rinsing the clothes with water.

According to the present invention, there is provided a liquid detergent composition for clothes containing an enzyme, which has excellent detergency and defoaming property after storage, particularly after storage at a high temperature, and a method for cleaning clothes using the same. Will be done. The liquid detergent composition for clothing of the present invention has excellent detergency, and even after being stored at a high temperature of, for example, about 40 ° C., it can exhibit excellent detergency and has good defoaming property. The amount of water can be reduced.

<Liquid detergent composition for clothing>
The component (a) is a nonionic surfactant represented by the following general formula (1).
RO-[(EO) _n / (PO) _m ] -H (1)
[R in the formula 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 the average number of added moles, and n is. The number is 8 or more and 40 or less, m is 1 or more and 6 or less, and EO and PO may be random addition or block addition. ]

In the general formula (1), the carbon number of R is preferably 10 or more from the viewpoint of improving detergency, maintaining detergency after high-temperature storage (hereinafter referred to as "maintaining detergency after storage"), and improving foam breakage. Is 12 or more, and 24 or less, preferably 18 or less, and more preferably 14 or less.

In the general formula (1), examples of the aliphatic hydrocarbon group of R include an alkyl group and an alkenyl group, and an alkyl group is preferable. R is a linear or branched aliphatic hydrocarbon group, for example, a linear or branched alkyl group, a linear or branched alkenyl group, from the viewpoint of improving detergency, maintaining detergency after storage, and improving foam breakage. Is preferable, and a linear alkyl group is more preferable.

In the general formula (1), n is a number of 8 or more and 40 or less, and is preferably 10 or more, more preferably 12 or more, still more preferably, from the viewpoint of improving detergency, maintaining detergency after storage, and improving foam breakage. Is 14 or more, more preferably 16 or more, and preferably 35 or less, more preferably 30 or less, still more preferably 24 or less, still more preferably 20 or less.

In the general formula (1), m is a number of 1 or more and 6 or less, preferably 2 or more, and preferably 4 or less from the viewpoint of improving detergency, maintaining detergency after storage, and improving foam breakage. ..

The ratio of the number of PO-added moles to the number of EO-added moles in the general formula (1), that is, m / n, which is the ratio of m to n, is a viewpoint of improving cleanability, maintaining cleanability after storage, and improving foam breakage. Therefore, it is preferably 0.03 or more, more preferably 0.05 or more, further preferably 0.1 or more, and preferably 0.7 or less, more preferably 0.5 or less, still more preferably 0.25 or less. be.

The ratio of the number of PO added moles in the total number of added moles of EO and PO in the general formula (1), that is, m / (n + m), which is the ratio of m to the total number of n and m, is improved in detergency and after storage. From the viewpoint of maintaining cleanability and improving foam breakability, it is preferably 0.03 or more, more preferably 0.05 or more, still more preferably 0.08 or more, and preferably 0.4 or less, more preferably 0.3. Below, it is more preferably 0.2 or less.

As the component (a), a nonionic surfactant represented by the following general formula (2) is preferable.
RO- (EO) _n1- (PO) _m- (EO) _n2 -H (2)
[R in the formula 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, and EO and PO are block-bonded in this order. , N1, n2 and m are the average number of added moles, n1 is a number of 0 or more and 20 or less, m is a number of 1 or more and 6 or less, n2 is a number of 0 or more and 20 or less, and n1 and n2. The total of is 8 or more, and EO and PO are block additions. ]

In the general formula (2), specific examples and preferable examples of R and m are the same as the general formula (1).
In the general formula (2), n1 is a number of 0 or more and 20 or less, and when n1 is not 0, it is preferably 4 or more, more preferably from the viewpoint of improving detergency, maintaining detergency after storage, and improving foam breakage. It is preferably 5 or more, more preferably 7 or more, and preferably 18 or less, more preferably 16 or less, still more preferably 12 or less.

In the general formula (2), n2 is a number of 0 or more and 20 or less, and when n2 is not 0, it is preferably 4 or more, more preferably from the viewpoint of improving detergency, maintaining detergency after storage, and improving foam breakage. It is preferably 5 or more, more preferably 7 or more, and preferably 19 or less, more preferably 18 or less, still more preferably 17 or less.

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

The ratio of the number of moles of PO added to the number of moles of EO added in the general formula (2), that is, m / (n1 + n2), which is the ratio of m to the total of n1 and n2, is the nonionic surfactant of the general formula (1). It corresponds to m / n of, and the preferable range is also the same as m / n.

The ratio of the number of moles of PO added to the total number of moles of EO and PO added in the general formula (2), that is, m / (n1 + n2 + m), which is the ratio of m to the total of n1, n2, and m, is the general formula (1). It corresponds to m / (n + m) of the nonionic surfactant of the above, and the preferable range is also the same as m / (n + m).

The liquid detergent composition for clothing of the present invention contains the component (a) in the composition, preferably 3% by mass or more, more preferably, from the viewpoint of improving the detergency, maintaining the detergency after storage, and improving the foam breaking property. Is contained in an amount of 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, still more preferably 25% by mass or less.

(B) The component is an inorganic calcium salt.
Examples of the component (b) include calcium halide such as calcium chloride, calcium carbonate, calcium sulfate, calcium silicate and the like. (B) The component is calcium chloride from the viewpoint of easy availability and maintenance of cleanability after storage. Is preferable.

From the viewpoint of maintaining detergency after storage, the liquid cleaning agent composition for clothing of the present invention contains the component (b) in the composition in an amount of preferably 0.001% by mass or more, more preferably 0.005% by mass or more. It is further preferably contained in an amount of 0.008% by mass or more, preferably 1% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.2% by mass or less.

(C) The component is a glycolytic enzyme.
Examples of the component (c) include amylase, sucrase, maltase, lactase, pullulanase, fructofuranosidase and the like.
As the component (c), amylase is preferable, and α-amylase is more preferable from the viewpoint of improving detergency and maintaining detergency after storage. Specific commercially available enzymes that can be used include the brand name Rapidase (manufactured by Gist Brokers), the brand names Termamil, Duramil, Stainzyme, and Amplify Prime 100L (manufactured by Novozyme Japan Co., Ltd.), the brand names Plaster ST and Plaster OxAm. (Manufactured by Junenkoa International), trademark name, Preferred S210 (manufactured by DuPont Co., Ltd.) can be mentioned.

From the viewpoint of improving the detergency and maintaining the detergency after storage, the liquid cleaning agent composition for clothing of the present invention contains the component (c) as an enzyme protein, preferably 0.0005% by mass or more in the composition. It is preferably contained in an amount of 0.0008% by mass or more, more preferably 0.001% by mass or more, preferably 1% by mass or less, more preferably 0.1% by mass or less, still more preferably 0.05% by mass or less. In the present invention, the amount of the component (c) as an enzyme protein may be adopted as long as the component (c) is a commercially available product and the amount as an enzyme protein is known. Further, when the amount of the component (c) as an enzyme protein is measured, it may be measured based on the Lowry method. For the Lowry method, a commercially available measurement kit, for example, a DC protein assay kit (BIO-RAD) can be used. The specific measurement method when using the DC protein assay kit (BIO-RAD) is, for example, as follows. Add 20 μL of an appropriately diluted enzyme solution to 10 μL of A reagent of the DC protein assay kit, add 80 μL of B reagent of the DC protein assay kit, incubate at room temperature for 15 minutes, and then microplate reader (for example, Infinite®). Measure the absorbance at 750 nm with a 200PRO (manufactured by Tecan, etc.). A calibration curve is prepared from a sample having a known protein concentration (for example, BSA Standard Solution (Fuji Film Wako Reagent)), and the protein mass in the enzyme is quantified from the absorbance obtained above.

The liquid detergent composition for clothing of the present invention has the content of the component (a) and the content of the component (c) as an enzyme protein from the viewpoints of improving the detergency, maintaining the detergency after storage, and improving the foam breaking property. The mass ratio (a) / (c) of (a) / (c) is 100 or more, preferably 500 or more, more preferably 700 or more, and 16000 or less, more preferably 10000 or less, still more preferably 7000 or less, still more preferably. It is 5000 or less, more preferably 3000 or less, still more preferably 1500 or less, still more preferably 1000 or less.

The liquid detergent composition for clothing of the present invention has a mass ratio of the content of the component (a) to the content of the component (b) from the viewpoint of improving the detergency, maintaining the detergency after storage, and improving the foam breaking property. (A) / (b) is preferably 10 or more, more preferably 50 or more, still more preferably 100 or more, and preferably 10000 or less, more preferably 2000 or less, still more preferably 500 or less, still more preferable. Is 150 or less.

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

The liquid detergent composition for clothing of the present invention is further improved from the viewpoints of improving detergency, maintaining detergency after storage, improving foam breaking property, improving liquid stability of the composition, and improving workability at the time of producing the composition. , A nonionic surfactant in which ethylene oxide is added to a secondary alcohol [excluding the component (a)] [[hereinafter referred to as the component (d)] can be contained.
(D) The component is ethylene oxide in a secondary alcohol from the viewpoints of improving detergency, maintaining detergency after storage, improving foam breaking property, improving liquid stability of the composition, and improving workability during composition production. The nonionic surfactant added with the above, specifically, the nonionic surfactant of the following general formula (d1) is preferable.
RO- (EO) _s -H (d1)
[In the formula, R is a linear or branched secondary alkyl group having 8 or more and 24 or less carbon atoms, EO is an ethyleneoxy group, and s is the average number of added moles, which is 3 or more and 24 or less. Is. ]

R in the formula (d1) is a linear number from the viewpoint of improving detergency, maintaining detergency after storage, improving foam breaking property, improving liquid stability of the composition, and improving workability at the time of producing the composition. It is preferably a secondary alkyl group, and the carbon number of R is preferably 10 or more, more preferably 12 or more, and preferably 18 or less, more preferably 14 or less. The secondary alkyl group means an alkyl group in which the carbon atom bonded to —O— among the carbon atoms of R in the formula (d1) is a secondary carbon atom.

The s in the formula (d1) is preferably 4 or more from the viewpoints of improving detergency, maintaining detergency after storage, improving foam breakage, improving liquid stability of the composition, and improving workability during composition production. , More preferably 5 or more, and preferably 18 or less, more preferably 16 or less, still more preferably 12 or less.

In the liquid detergent composition for clothing of the present invention, the component (d) is preferably 1 in the composition from the viewpoint of improving the foam breakability, the liquid stability of the composition, and the workability at the time of producing the composition. It is contained in an amount of 20% 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, from the viewpoint of improving detergency, maintaining detergency after storage, and improving foam breakage.

The liquid detergent composition for clothing of the present invention may further contain a surfactant other than the component (a) and the component (d) as the component (e) within a range that does not affect the effect of the present invention. can.
As the component (e), one or more surfactants selected from nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants other than the components (a) and (d). Agents are mentioned. The surfactant of the component (e) preferably has a molecular weight of 5000 or less.

As the nonionic surfactant other than the component (a) and the component (d), an alcohol alkoxylate, an ester alkoxylate, a polyhydric alcohol fatty acid ester which may contain an alkyleneoxy group, an alkyl glycoside, a polyethylene glycol, and a polyoxy. Examples thereof include ethylene / polyoxypropylene / block copolymer and polyoxypropylene / polyoxyethylene / polyoxypropylene / block copolymer. Examples of the alcohol alkoxylate include polyoxyalkylene alkyl ether and polyoxyalkylene alkenyl ether. Examples of the polyhydric alcohol fatty acid ester that may contain an alkyleneoxy group include glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, polyethylene glycol fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, and polyoxyethylene sorbitan fatty acid. Esters and the like can be mentioned.

Examples of the cationic surfactant include a quaternary ammonium salt-type cationic surfactant. In the quaternary ammonium salt-type cationic surfactant, one or two of the four groups bonded to the nitrogen atom are hydrocarbon groups having 8 or more carbon atoms and 24 or less carbon atoms, and the rest have 1 or more carbon atoms and 3 or less carbon atoms. A quaternary ammonium salt which is a hydrocarbon group of the above can be mentioned. Examples of the cationic surfactant include compounds represented by the following general formula (e1).

[In the formula, R ^e1 is a chain hydrocarbon group having 8 or more carbon atoms and 24 or less carbon atoms, and ^{Re 2} is a chain hydrocarbon group having 8 or more carbon atoms and 24 or less carbon atoms, and an alkyl group having 1 or more carbon atoms and 3 or less carbon atoms. Alternatively, they are hydroxyalkyl groups having 1 or more and 3 or less carbon atoms, and R ^e3 and R ^e4 are independently alkyl groups having 1 or more and 3 or less carbon atoms, or hydroxyalkyl groups having 1 or more and 3 or less carbon atoms, and X. ^-Is an alkyl sulfate ion having 1 or more and 3 or less carbon atoms, or a halide ion. ]

In the general formula (e1), the number of carbon atoms of the chain hydrocarbon group of R ^e1 is preferably 9 or more, more preferably 10 or more, preferably 18 or less, more preferably 14 or less, still more preferably 12 or less. R ^e2 is a chain hydrocarbon group having 8 or more carbon atoms and 24 or less carbon atoms, an alkyl group having 1 or more carbon atoms and 3 or less carbon atoms, or a hydroxyalkyl group having 1 or more carbon atoms and 3 or less carbon atoms ^. The number of carbon atoms is preferably 9 or more, more preferably 10 or more, preferably 18 or less, more preferably 14 or less, still more preferably 12 or less. The chain hydrocarbon group of R ^e2 is preferably an alkyl group or an alkenyl group, and more preferably an alkyl group. R ^e3 and R ^e4 are each independently a methyl group, an ethyl group, or a hydroxyalkyl group having 1 or more and 3 or less carbon atoms. Specific examples of the chain hydrocarbon group of R ^e1 and R ^e2 are an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group and a hexadecyl group, preferably a nonyl group and a decyl group, and more preferably a decyl group. Specific examples of the hydroxyalkyl group having 1 or more and 3 or less carbon atoms include a hydroxymethyl group, a hydroxyethyl group and a hydroxypropyl group. X ^- is CH ₃ SO _4- ^, CH ₃ CH ₂ SO _4- ^, or a halide ion.

More specific compounds of the compound represented by the general formula (e1) are N-ethyl-N, N-dimethyltetradecylammonium salt, trimethylhexadecyl salt, N, N-dioctyl-N, N-dimethylammonium. Salt, N, N-dinonyl-N, N-dimethylammonium salt, N, N-didesyl-N, N-dimethylammonium salt, N, N-dioctyl-N-ethyl-N-methylammonium salt, N, N- Examples thereof include one or more compounds selected from dinonyl-N-ethyl-N-methylammonium salt and N, N-didecyl-N-ethyl-N-methylammonium salt, mono-long chain ammonium salt and dilong chain. A type ammonium salt can also be used in combination. The counterion serving as these salts is a halide ion such as CH ₃ SO _4- ^, CH ₃ CH ₂ SO _4- ^, or chlor ion.

Examples of anionic surfactants include sulfonates with aliphatic hydrocarbon groups of 8 to 18 carbon atoms, sulfate esters with aliphatic hydrocarbon groups of 10 to 24 carbon atoms, and 10 or more carbon atoms. Included is one or more anionic surfactants selected from 24 or less fatty acids or salts thereof.

For example, examples of the anionic surfactant include an internal olefin sulfonate having 10 or more and 18 or less carbon atoms, a sulfate ester salt having an alkyl group or alkenyl group having 10 or more and 24 carbon atoms or less, and an alkyl group having 10 or more and 24 carbon atoms or less. Alternatively, a polyoxyalkylene alkyl or an alkenyl ether sulfate ester salt having an alkenyl group, an alkylbenzene sulfonate having an alkyl group having 8 or more and 18 or less carbon atoms (an alkyl group having 8 or more and 18 or less carbon atoms is an alkyl substituted with a benzene ring). Means a group and does not include a benzene skeleton), sulfonates having an alkyl group or alkenyl group having 10 or more and 24 or less carbon atoms (excluding internal olefin sulfonates having 10 or more and 18 or less carbon atoms), and carbon. Examples thereof include one or more anionic surfactants selected from tens or more and 24 or less fatty acids or salts thereof. Examples of these salts include alkali metal salts, alkaline earth metal (1/2 atom) salts, ammonium salts and organic ammonium salts. Examples of the alkali metal salt include sodium salts and potassium salts. Examples of the organic ammonium salt include alkanolammonium salts having 1 or more and 6 or less carbon atoms.

Examples of the amphoteric tenside include an alkyl or alkenylamine oxide having 10 or more and 24 or less carbon atoms, an alkyl or alkenyl betaine having 10 or more and 24 or less carbon atoms, and an alkyl or alkenyl sulfobetaine having 10 or more and 24 or less carbon atoms.

The content of the component (e) is not particularly limited as long as it does not affect the effect of the present invention, but is 5% by mass or less, further 3% by mass or less, and 2% by mass or less in the composition. Further, it may be 1% by mass or less, further 0.5% by mass or less, further 0.1% by mass or less, and may be 0% by mass.
In the liquid detergent composition for clothing of the present invention, the content of the cationic surfactant in the composition may be 5% by mass or less, further 3% by mass or less, further 1% by mass or less, and 0. It may be 1% by mass or more, and further 0.5% by mass or more.
The liquid detergent composition for clothing of the present invention comprises an anionic surfactant (excluding fatty acids) in the composition from the viewpoint of improving detergency, maintaining detergency after storage, and improving foam breakage. The content is preferably 1% by mass or less, further 0.5% by mass or less, further 0.1% by mass, and the content of the anionic surfactant (however, excluding fatty acids) is 0% by mass. May be. That is, the liquid detergent composition for clothing of the present invention does not contain an anionic surfactant (however, excluding fatty acids), or the content of the anionic surfactant (however, excluding fatty acids) is contained in the composition. It is preferably 1% by mass or less.

The liquid detergent composition for clothing of the present invention has a surfactant content of preferably 8% by mass or more in the composition from the viewpoint of improving detergency, maintaining detergency after storage, and improving foam breakage. It is more preferably 10% by mass or more, preferably 50% by mass or less, and more preferably 30% by mass or less. The total amount of the surfactant may be the total content of the component (a), the component (d) and the component (e).

The liquid detergent composition for clothing of the present invention has a nonionic surfactant content of preferably 5% by mass from the viewpoint of improving detergency, maintaining detergency after storage, and improving foam breakage. As mentioned above, it is more preferably 8% by mass or more, preferably 50% by mass or less, and more preferably 30% by mass or less. The total amount of the nonionic surfactant is the total content of the nonionic surfactant other than the component (a), the component (d), and the component (a) and the component (d) among the components (e). It may be there.

In the liquid detergent composition for clothing of the present invention, the proportion of the component (a) in the total amount of the surfactant is preferably 20% by mass or more, more preferably 30 from the viewpoint of improving the cleaning property and the foam breaking property. By mass or more, more preferably 40% by mass or more, and from the viewpoint of maintaining detergency after storage and improving foam breaking property, preferably 100% by mass or less, more preferably 95% by mass or less, still more preferably 90% by mass. Below, it is even more preferably 85% by mass or less. The total amount of the surfactant may be the sum of the contents of the component (a), the component (d) and the component (e) in the composition.

In the liquid detergent composition for clothing of the present invention, from the viewpoint of improving detergency, maintaining detergency after storage, and improving foam breakage, the proportion of the component (a) in the total amount of the nonionic surfactant is preferable. It is 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 the nonionic surfactant contains the nonionic surfactant other than the component (a), the component (d), and the component (a) and the component (d) in the composition (e). It may be the total amount.

The liquid detergent composition for clothing of the present invention may contain the following components (1) to (11) as other optional components as long as the effects of the present invention are not affected.
(1) Alkaline agent The liquid detergent composition for clothing of the present invention preferably contains an alkaline agent from the viewpoint of improving the detergency. The alkaline agent is an inorganic alkaline agent such as an alkali metal hydroxide or an alkali metal carbonate, or an alkanol group having 1 or more and 3 or less carbon atoms having 2 or more and 4 or less carbon atoms among the groups bonded to a nitrogen atom. Examples thereof include alkanolamines in which the remainder is an alkyl group having 1 or more and 4 or less carbon atoms or a hydrogen atom. Of these, the alkanol group is preferably a hydroxyalkyl group and more preferably a hydroxyethyl group. Other than the alkanol group, a hydrogen atom or a methyl group is preferable, and a hydrogen atom is particularly preferable. 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, as the component (1), an alkanolamine selected from monoethanolamine and triethanolamine is preferable, and monoethanolamine is more preferable.
Further, the alkaline agent as 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 detergent composition for clothing of the present invention, the component (1) may be blended in an amount such that the pH will be described later. Specifically, it may be contained in the composition in an amount of 0.01% by mass or more, further 0.5% by mass or more, and 10% by mass or less, further 8% by mass or less. In the present invention, the amount of the alkaline agent of the component (1), especially the alkanolamine, includes the amount derived from other components such as the counterion of the anionic surfactant and blended in the composition. It shall be.

(2) Chelating agent As a specific example of the chelating agent, for example, aminopolyacetic acid such as ethylenediamine tetraacetic acid, diethylenetriaminepentacetic acid and hydroxyethyliminodiacetic acid or salts thereof, organic acids such as citric acid, lactic acid, tartaric acid and malic acid or Examples thereof include 1-hydroxyethylidene-1,1-diphosphonic acid, diethylenetriaminepenta (methylenephosphonic acid), alkali metals or lower amine salts thereof. (2) The content of the chelating agent of the component is 0.1% by mass or more and 5% by mass or less, preferably 0.1% by mass or more and 4% by mass, in the composition when regarded as an acid type. Hereinafter, it is more preferably 0.1% by mass or more and 3% by mass or less.

(3) Anti-contamination agent and / or polymer-based dispersant Examples of the anti-recontamination agent and / or polymer-based dispersant include polyacrylic acid, polymaleic acid, and carboxymethyl cellulose. The content of the anti-recontamination agent and / or the polymer-based dispersant is preferably 0.01% by mass or more and 10% by mass or less in the composition.

(4) Bleaching agent Examples of the bleaching agent include hydrogen peroxide, sodium percarbonate, sodium perborate and the like. The content of the bleaching agent is preferably 0.01% by mass or more and 10% by mass or less in the composition.

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

(6) Enzymes other than the component (c) Examples of the enzyme other than the component (c) include one or more enzymes selected from cellulase, protease and lipase. The content of the enzyme is preferably 0.001% by mass or more and 2% by mass or less in the composition. The enzyme (6) is preferably an enzyme containing a protease in that higher detergency can be obtained against stains such as meat sauce on which spilled food stains are attached on clothes with sebum stains. ..
In the liquid detergent composition for clothing of the present invention, the proportion of the component (c) in the total amount of the enzyme is preferably 5% by mass or more, more preferably 20% by mass, from the viewpoint of improving the cleaning property of spilled food. The above is more preferably 40% by mass or more, preferably 100% by mass or less, and may be 100% by mass.

(7) Fluorescent dyes Examples of fluorescent dyes include fluorescent dyes commercially available as Chinopearl CBS (trade name, manufactured by Chivas Specialty Chemicals) and Whitex SA (trade name, manufactured by Sumitomo Chemical Co., Ltd.). The content of the fluorescent dye is preferably 0.001% by mass or more and 1% by mass or less in the composition.

(8) Antioxidant Examples of the antioxidant include butylhydroxytoluene, cresol distyrene, sodium sulfite, sodium hydrogen sulfite and the like. The content of the antioxidant is preferably 0.01% by mass or more and 2% by mass or less in the composition.

(9) Appropriate amount of antifoaming agent such as pigments, fragrances, antibacterial preservatives, and silicones.

(10) Organic solvent having a hydroxyl group As the organic solvent having a hydroxyl group, one or more compounds selected from the following components (10-1) to (10-6) are used.
(10-1) Component: A monohydric alcohol having an aliphatic hydrocarbon group having 2 or more and 6 or less carbon atoms. The component (10-1) is selected from, for example, ethanol, 1-propanol, 2-propanol and 1-butanol. Examples include monohydric alcohol.

(10-2) Component: Alcohol with 2 or more and 6 or less carbon atoms and divalent or more and 6 or less valent (10-2) As a component, for example, ethylene glycol, propylene glycol, butylene glycol, 2-methyl-2,4-pentanediol. , 1,5-Pentanediol, 1,6-hexanediol and divalent or trivalent alcohols selected from glycerin. 2-Methyl-2,4-pentanediol is also referred to as hexylene glycol.

(10-3) Component: Polyalkylene glycol containing an alkylene glycol unit having 2 or more and 4 or less carbon atoms As a component of (10-3), for example, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, etc. Examples thereof include polyethylene glycol having a weight average molecular weight of 400 or more and 4000 or less, and polyalkylene glycol selected from polypropylene glycol having a weight average molecular weight of 400 or more and 4000 or less.

(10-4) Component: As a monoalkyl ether (10-4) component of (mono or poly) alkylene glycol having an alkylene glycol unit having 2 or more and 4 or less carbon atoms and an alkyl group having 1 or more and 4 or less carbon atoms. For example, 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-. Examples include compounds selected from ethoxy-2-propanol.

(10-5) Component: Alkyl glyceryl ether having an alkyl having 1 or more and 8 or less carbon atoms As the component of (10-5), for example, 1-methyl glyceryl ether, 2-methyl glyceryl ether, 1,3-dimethyl glyceryl ether, 1 Examples thereof include alkyl glyceryl ethers selected from 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.

(10-6) Component: Aromatic alkyl ether of (mono or poly) alkylene glycol having 2 or 3 carbon atoms of alkylene glycol As a component (10-6), for example, 2-phenoxyethanol, diethylene glycol monophenyl ether, triethylene. Examples thereof include compounds selected from glycol monophenyl ethers, polyethylene glycol monophenyl ethers having an average molecular weight of about 480, 2-benzyloxyethanol and diethylene glycol monobenzyl ethers.

The term "(mono or poly) alkylene glycol" in the components (10-4) and (10-6) means monoalkylene glycol or polyalkylene glycol. Further, the “polyalkylene glycol” means that the alkylene glycol unit is contained in an amount of 2 or more and 9 or less.

The component (10) is selected from the components (10-1), (10-2), (10-4), and (10-6) from the viewpoint of further improving the storage stability at low temperatures. One or more compounds are preferred.
More specifically, the liquid cleaning agent composition for clothing of the present invention is one or more compounds selected from ethanol, propylene glycol, diethylene glycol monobutyl ether, 2-phenoxyethanol, diethylene glycol monophenyl ether and triethylene glycol monophenyl ether. Is preferably contained. The liquid cleaning agent composition for clothing of the present invention may contain 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. preferable.
The content of the component (10) is preferably 1% by mass or more, more preferably 4% by mass or more, still more preferably 5% by mass or more, and preferably 40% by mass or less, more preferably 20% by mass or more in the composition. It is mass% or less, and even more preferably 10 mass% or less.

(11) Hydrotropic agent A hydrotropic agent can be blended for the stability of the liquid detergent composition for clothing. The hydrotropic agent of the present invention is an organic compound having an anionic group, further contains one or two alkyl groups selected from a methyl group, an ethyl group or a propyl group, and contains a sulfonic acid group or a carboxylic acid group. Examples thereof include one alkylbenzene carboxylic acid or alkylbenzene sulfonic acid or a salt thereof, and benzoic acid or a salt thereof. More specifically, it is paratoluene sulfonic acid, cumene sulfonic acid, metaxylene sulfonic acid, 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 preferable, and it may be blended as an acid and neutralized with an alkaline agent in the composition. In the liquid detergent composition for clothing of the present invention, the hydrotropic agent is converted into an acid type compound, preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and further more. It can be preferably contained in an amount of 1% by mass or more, preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less.

The liquid detergent composition for clothing 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 can be used. The liquid cleaning agent composition for clothing of the present invention contains water in the composition, preferably 50% by mass or more, more preferably 60% by mass, from the viewpoint of physical properties such as viscosity of the composition and workability at the time of washing clothing. % Or more, preferably 90% by mass or less, more preferably 85% by mass or less.

The liquid detergent composition for clothing of the present invention has a pH at 25 ° C. of preferably 6.5 or more, more preferably 7 or more, from the viewpoint of improving detergency, maintaining detergency after storage, and improving foam breakage. It is more preferably 8 or more, 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 was measured by the following method.
<pH measurement method>
HORIBA, Ltd. pH meter D-52 is calibrated with a pH electrode (model 6637) in advance with a phthalic acid buffer solution (pH 4.01), a phosphoric acid standard solution (pH 6.84), and a borate standard solution (pH 9.18). Rinse thoroughly with ion-exchanged water. A pH electrode calibrated and washed as described above is placed in a liquid detergent composition for clothing whose temperature has been adjusted to 25 ° C., and measurement is performed using the AUTO HOLD mode of a pH meter until the measured value becomes constant.

The liquid cleaning agent composition for clothing of the present invention is used for cleaning clothing such as clothing, towels, bedding, and textile products for bedding (sheets, pillowcases, etc.). Textile products other than these that can be washed can also be washed as clothing in the present invention.

Although the details of the mechanism of expression of the effect of the present invention have not been clarified, it is considered as follows. Among the stains adhering to clothing, spilled food stains, etc., have reduced detergency in combination with other stains because sugar components such as starch solidify or denature with the evaporation of water. it is conceivable that. In the present invention, since the detergency is improved by adding the saccharide-degrading enzyme to the liquid detergent composition for clothing, the saccharide-degrading enzyme firmly adheres by decomposing the carbs in the stain. It is considered that the detergency is improved by facilitating the permeation of the surfactant, which is a cleaning component, into the existing stains. Furthermore, it is presumed that the decrease in detergency compared to before storage when stored at high temperature assuming a place of living where the detergent composition is used is due to the decrease in the activity of the glycolytic enzyme due to storage. can. In the liquid cleaning agent composition for clothing of the present invention, the glycolytic enzyme of the present invention causes a change in the conformation of the enzyme active site and the decomposition and denaturation of the enzyme protein in the composition during storage. By using the relatively hydrophobic nonionic surfactant (component (a)) of the present invention and the glycolytic enzyme (component (c)) of the present invention in a specific ratio, (a) Inhibiting the active site of glycolysis reaction, including interaction with the inorganic calcium salt (component (b)), which is generally said to contribute to enzyme stabilization, by appropriately adsorbing the component on the surface of the enzyme protein. It is probable that it is stabilizing without any problems. On the other hand, in general washing, a detergent composition having extremely high effervescence causes inconveniences such as an increase in the load on rinsing and overflow of bubbles due to drainage. The nonionic surfactant that contributes to the stabilization of the glycolytic enzyme of the present invention has relatively high hydrophobicity and excellent foam breaking property, and the component (a) is also a dirt cleaning component, so that it can be regarded as a dirt component. Since the interaction between the components (a) and the glycolytic enzyme is strong, it is considered that the adsorbent of the component (a) and the glycolytic enzyme are more likely to exist in the vicinity of the dirt component, and the detergency is further improved. The present invention is not particularly limited to the above-mentioned mechanism of action.

<How to wash clothes>
The present invention provides a method for washing clothes by washing the clothes with a washing liquid obtained by mixing the liquid detergent composition for clothes of the present invention and water, and then rinsing the clothes with water.
The method for washing clothes of the present invention may be a method for washing clothes by washing the clothes with a washing liquid containing (a) component, (b) component, (c) component and water.
The matters described in the liquid detergent composition for clothes of the present invention can be appropriately applied to the method of washing clothes of the present invention.

The content of the component (a) in the cleaning liquid is preferably 0.0005% by mass or more, more preferably 0.0008% by mass or more, from the viewpoint of improving the cleaning property, maintaining the cleaning property after storage, and improving the foam breaking property. It is more preferably 0.001% by mass or more, preferably 0.5% by mass or less, more preferably 0.3% by mass or less, still more preferably 0.1% by mass or less.

Further, the content of the component (b) in the cleaning liquid is preferably 0.000005% by mass or more, more preferably 0.00001% by mass, from the viewpoint of improving the cleaning property, maintaining the cleaning property after storage, and improving the foam breaking property. % Or more, more preferably 0.00005% by mass or more, and preferably 0.01% by mass or less, more preferably 0.0075% by mass or less, still more preferably 0.005% by mass or less.

Further, the content of the component (c) in the cleaning liquid is preferably 0.0000005% by mass or more, more preferably 0.0000005% by mass or more, as an enzyme protein from the viewpoint of improving the cleaning property, maintaining the cleaning property after storage, and improving the foam breaking property. It is 0.000001% by mass or more, more preferably 0.000005% by mass or more, and preferably 0.001% by mass or less, more preferably 0.00075 mass% or less, still more preferably 0.0005% by mass or less.

The cleaning liquid is preferably prepared by diluting the liquid detergent composition for clothing of the present invention with water so that the content of each component is within this range. The specific dilution ratio is preferably 500 times or more, more preferably 800 times or more, and preferably from the viewpoint of the form such as the viscosity of the liquid detergent composition for clothes of the present invention and workability at the time of washing clothes. May be 5000 times or less, more preferably 3000 times or less.

The water used in the method for washing clothes of the present invention is preferably water having hardness. The hardness of water is German hardness, preferably 1 ° dH or higher, more preferably 2 ° dH or higher, still more preferably 3.5 °, from the viewpoint of improving cleanability, maintaining cleanability after storage, and improving foam breakage. It is dH or more, more preferably 5 ° dH or more, still more preferably 7 ° dH or more, and preferably 20 ° dH or less, more preferably 18 ° dH or less, still more preferably 15 ° dH or less. Here, the German hardness (° dH) as used herein means that the concentration of calcium and magnesium in water is 1 mg / L (ppm) = about 0.056 ° dH (1 ° dH = 17.) in terms of CaCO ₃ equivalent concentration. Refers to the one expressed in 8 ppm).
The calcium and magnesium concentrations for this German hardness are determined by chelatometric titration using ethylenediaminetetraacetic acid disodium salts.
The specific method for measuring the German hardness of water in the present specification is shown below.
<Measurement method of German hardness of water>
〔reagent〕
-0.01 mol / l EDTA-2Na solution: 0.01 mol / l aqueous solution of ethylenediaminetetraacetic acid disodium (titration solution, 0.01 M EDTA-Na2, manufactured by SIGMA-ALDRICH)
-Universal BT indicator (Product name: Universal BT, manufactured by Dojin Kagaku Kenkyusho Co., Ltd.)
-Ammonia buffer solution for hardness measurement (a solution in which 67.5 g of ammonium chloride is dissolved in 570 ml of 28 w / v% ammonia water and the total volume is 1000 ml with ion-exchanged water).
[Measurement of hardness]
(1) Collect 20 ml of water as a sample in a conical beaker with a whole pipette.
(2) Add 2 ml of ammonia buffer for hardness measurement.
(3) Add 0.5 ml of Universal BT indicator. Confirm that the solution after addition is purplish red.
(4) While shaking the conical beaker well, a 0.01 mol / l EDTA · 2Na solution is dropped from the burette, and the time when the sample water turns blue is defined as the end point of the titration. (5) The total hardness is calculated by the following formula.
Hardness (° dH) = T × 0.01 × F × 56.0774 × 100 / A
T: 0.01 mol / l EDTA.2Na solution titration (mL)
A: Sample capacity (20 mL, volume of sample water)
F: Factor of 0.01 mol / l EDTA ・ 2Na solution

The cleaning liquid used in the present invention has (a) component, (b) component, (c) component, and German hardness of 1 ° dH or more from the viewpoint of improving detergency, maintaining detergency after storage, and improving foam breakage. A cleaning solution obtained by mixing water of 20 ° dH or less is preferable. Further, the cleaning liquid may be a cleaning liquid 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.

In the method for cleaning clothing of the present invention, the value of the bath ratio expressed by the ratio of the mass of clothing (kg) and the amount of cleaning liquid (liter), that is, the amount of cleaning liquid (liter) / mass of clothing (kg) (hereinafter, The value of) is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, still more preferably 5 or more, and preferably 5 or more, from the viewpoint of ensuring cleanability. Is 400 or less, more preferably 300 or less.

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

In the method of washing clothes of the present invention, after washing the clothes, the clothes are rinsed with water. The water used for rinsing may also be water having the above hardness. In rinsing, rinse water can be used for clothing at a ratio similar to the bath ratio of the cleaning solution. Further, the rinsing time can be in the same range as the washing time.

The method for washing clothes of the present invention is also suitable for a rotary washing method. The rotary cleaning method means a cleaning method in which clothing that is not fixed to a rotating device rotates around a rotating shaft together with a cleaning liquid. The rotary washing method can be carried out by a rotary washing machine. Specific examples of the rotary washing machine include a drum type washing machine, a pulsator type washing machine, and an agitator type washing machine. As each of these rotary washing machines, those commercially available for home use can be used. In recent years, drum-type washing machines have rapidly become widespread in that the amount of water used for one washing can be further reduced. In particular, the drum-type washing machine can reduce the amount of water during washing.

Hereinafter, aspects of the present invention will be illustrated. The matters described in the liquid detergent composition for clothes and the method for washing clothes of the present invention can be modified and applied to these aspects as necessary. In addition, the description of each aspect can be modified as necessary and applied to other aspects.

<1>
It contains the following components (a), (b), (c) and water, and is the mass ratio of the content of the component (a) to the content of the component (c) as an enzyme protein (a) /. A liquid detergent composition for clothing, wherein (c) is 100 or more and 16000 or less.
(A) Component: Nonionic surfactant represented by the following general formula (1) RO-[(EO) _n / (PO) _m ] -H (1)
[R in the formula 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 the average number of added moles, and n is. The number is 8 or more and 40 or less, m is 1 or more and 6 or less, and EO and PO may be random addition or block addition. ]
(B) Component: Inorganic calcium salt (c) Component: Glycolytic enzyme

<2>
The liquid detergent for clothes according to <1>, wherein the carbon number of R in the general formula (1) is 10 or more, preferably 12 or more, and 24 or less, preferably 18 or less, more preferably 14 or less. Composition.

<3>
The liquid cleaning agent composition for clothing according to <1> or <2>, wherein the aliphatic hydrocarbon group of R in the general formula (1) is an alkyl group or an alkenyl group, preferably an alkyl group.

<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. The liquid cleaning agent composition for clothing according to any one of <1> to <3>.

<5>
In the general formula (1), n is 8 or more, preferably 10 or more, more preferably 12 or more, still more preferably 14 or more, still more preferably 16 or more, and 40 or less, preferably 35 or less, more preferably. The liquid detergent composition for clothing according to any one of <1> to <4>, wherein the number is 30 or less, more preferably 24 or less, still more preferably 20 or less.

<6>
The liquid detergent for clothing according to any one of <1> to <5>, wherein m is a number of 1 or more, preferably 2 or more, and 6 or less, preferably 4 or less in the general formula (1). Composition.

<7>
The ratio of m to n in the general formula (1), m / n, is preferably 0.03 or more, more preferably 0.05 or more, still more preferably 0.1 or more, and preferably 0.7 or less. The liquid detergent composition for clothing according to any one of <1> to <6>, more preferably 0.5 or less, still more preferably 0.25 or less.

<8>
M / (n + m), which is the ratio of m to the total of n and m in the general formula (1), is preferably 0.03 or more, more preferably 0.05 or more, still more preferably 0.08 or more, and. The liquid detergent composition for clothing according to any one of <1> to <7>, preferably 0.4 or less, more preferably 0.3 or less, still more preferably 0.2 or less.

<9>
(A) The liquid detergent composition for clothing according to any one of <1> to <8>, which contains a nonionic surfactant represented by the following general formula (2) as a component.
RO- (EO) _n1- (PO) _m- (EO) _n2 -H (2)
[R in the formula 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, and EO and PO are block-bonded in this order. , N1, n2 and m are the average number of added moles, n1 is a number of 0 or more and 20 or less, m is a number of 1 or more and 6 or less, n2 is a number of 0 or more and 20 or less, and n1 and n2. The total of is 8 or more, and EO and PO are block additions. ]

<10>
The liquid detergent for clothes according to <9>, wherein the carbon number of R in the general formula (2) is 10 or more, preferably 12 or more, and 24 or less, preferably 18 or less, more preferably 14 or less. Composition.

<11>
The liquid cleaning agent composition for clothing according to <9> or <10>, wherein the aliphatic hydrocarbon group of R in the general formula (2) is an alkyl group or an alkenyl group, preferably an alkyl group.

<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. The liquid cleaning agent composition for clothing according to any one of <9> to <11>.

<13>
In the general formula (2), n1 is preferably a number of 4 or more, more preferably 5 or more, still more preferably 7 or more, and preferably 18 or less, more preferably 16 or less, still more preferably 12 or less. The liquid detergent composition for clothing according to any one of <9> to <12>.

<14>
The liquid detergent for clothing according to any one of <9> to <13>, wherein m is a number of 1 or more, preferably 2 or more, and 6 or less, preferably 4 or less in the general formula (2). Composition.

<15>
In the general formula (2), n2 is preferably a number of 4 or more, more preferably 5 or more, further preferably 7 or more, and preferably 19 or less, more preferably 18 or less, still more preferably 17 or less. The liquid detergent composition for clothing according to any one of <9> to <14>.

<16>
In the general formula (2), the total of n1 and n2 is 8 or more, preferably 10 or more, more preferably 12 or more, still more preferably 14 or more, still more preferably 16 or more, and 40 or less, preferably 35 or less. The liquid detergent composition for clothing according to any one of <9> to <15>, more preferably 30 or less, still more preferably 24 or less, still more preferably 20 or less.

<17>
M / (n1 + n2), which is the ratio of m to the total of n1 and n2 in the general formula (2), is preferably 0.03 or more, more preferably 0.05 or more, still more preferably 0.1 or more, and The liquid detergent composition for clothing according to any one of <9> to <16>, preferably 0.7 or less, more preferably 0.5 or less, still more preferably 0.25 or less.

<18>
M / (n1 + n2 + m), which is the ratio of m to the total of n1, n2, and m in the general formula (2), is preferably 0.03 or more, more preferably 0.05 or more, still more preferably 0.08 or more. The liquid detergent composition for clothing according to any one of <9> to <17>, preferably 0.4 or less, more preferably 0.3 or less, still more preferably 0.2 or less.

<19>
(A) The component in the composition is preferably 3% by mass or more, more preferably 5% by mass or more, further preferably 8% by mass or more, and preferably 50% by mass or less, more preferably 30% by mass or less, further. The liquid detergent composition for clothing according to any one of <1> to <18>, preferably containing 25% by mass or less.

<20>
(B) Any of <1> to <19> containing one or more inorganic calcium salts selected from calcium halide (for example, calcium chloride), calcium carbonate, calcium sulfate, and calcium silicate as a component. The liquid cleaning agent composition for clothing described.

<21>
(B) The liquid detergent composition for clothing according to any one of <1> to <20>, which contains calcium chloride as a component.

<22>
The component (b) is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, still more preferably 0.008% by mass or more, and preferably 1% by mass or less in the composition, more preferably. The liquid cleaning agent composition for clothing according to any one of <1> to <21>, which contains 0.5% by mass or less, more preferably 0.2% by mass or less.

<23>
(C) The clothing according to any one of <1> to <22>, which contains one or more glycolytic enzymes selected from amylase, sucrase, maltase, lactase, pullulanase, and fructofuranosidase as a component. Liquid detergent composition.

<24>
(C) The liquid detergent composition for clothing according to any one of <1> to <23>, which contains amylase and α-amylase as components.

<25>
The component (c) as an enzyme protein is preferably 0.0005% by mass or more, more preferably 0.0008% by mass or more, still more preferably 0.001% by mass or more, and preferably 1% by mass in the composition as an enzyme protein. The liquid cleaning agent composition for clothing according to any one of <1> to <24>, which is more preferably 0.1% by mass or less, still more preferably 0.05% by mass or less.

<26>
(A) / (c), which is the mass ratio 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 <1> to <16000 or less, more preferably 10000 or less, still more preferably 7000 or less, still more preferably 5000 or less, still more preferably 3000 or less, still more preferably 1500 or less, still more preferably 1000 or less. 25> The liquid detergent composition for clothing according to any one of.

<27>
(A) / (b), which is the mass ratio of the content of the component (a) to the content of the component (b), is preferably 10 or more, more preferably 50 or more, still more preferably 100 or more, and preferably 100 or more. The liquid detergent composition for clothing according to any one of <1> to <26>, wherein is 10000 or less, more preferably 2000 or less, still more preferably 500 or less, still more preferably 150 or less.

<28>
(B) / (c), which is the mass ratio 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, still more preferably 0.5 or more. It is even more preferably 1 or more, still more preferably 3 or more, still 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. , The liquid detergent composition for clothing according to any one of <1> to <27>.

<29>
Further, for clothing according to any one of <1> to <28>, which contains, as the component (d), a nonionic surfactant [excluding the component (a)] in which ethylene oxide is added to a secondary alcohol. Liquid detergent composition.

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

<31>
The liquid detergent composition for clothing according to <30>, wherein the carbon number of R in the formula (d1) is preferably 10 or more, more preferably 12 or more, and preferably 18 or less, more preferably 14 or less. thing.

<32>
The s in the formula (d1) is preferably 4 or more, more preferably 5 or more, and preferably 18 or less, more preferably 16 or less, still more preferably 12 or less, <30> or <31>. The liquid detergent composition for clothing according to.

<33>
<29> to <32, which contain the component (d) in the composition, 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. > The liquid detergent composition for clothing according to any one of.

<34>
The liquid detergent composition for clothing according to any one of <1> to <33>, wherein the content of the anionic surfactant (excluding fatty acids) in the composition is 1% by mass or less.

<35>
The liquid detergent for clothing according to any one of <1> to <34>, wherein 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. Composition.

<36>
A method for cleaning clothes, wherein the clothes are washed with a washing liquid obtained by mixing the liquid detergent composition for clothes according to any one of <1> to <35> and water, and then the clothes are rinsed with water.

<Examples 1 to 13 and Comparative Examples 1 to 6>
The liquid detergent compositions for clothing shown in Tables 1 and 2 were prepared using the following components, and the obtained compositions were used to evaluate the detergency and defoaming property before and after storage by the following method.

<Ingredients>
(A) Component (a-1) In the general formula (2), R is a lauryl group, n1 is an average of 9, m is an average of 2, and n2 is an average of 9. Polyoxyalkylene alkyl ether. (A-2) A polyoxyalkylene alkyl ether (a-3) in which R is a lauryl group, n1 is an average of 9, m is an average of 4, and n2 is an average of 9 in the general formula (2). 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. Polyoxyalkylene alkyl ether (a-4) 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. Polyoxyalkylene alkyl ether (a-5) In the general formula (2), R is lauryl. Polyoxyalkylene alkyl ether which is a group, n1 is 10 on average, m is 2 on average, and n2 is 0 on average.

Component (a') [Comparative compound of component (a)]
(A'-1) 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'-1) -2) Polyoxyalkylene alkyl ether (a'-3) carbon in which R is a lauryl group, n1 is 21 on average, m is 0 on average, and n2 is 0 on average in the general formula (2). Sodium linear alkylbenzene sulfonic acid salt with 11 to 13 chains ・ (a'-4) Sodium alkyl sulfate with 12 carbon chains

(B) Ingredients ・ Calcium chloride

(C) Ingredients-Amylase: Amylase 100L, manufactured by Novozymes (The content of the enzyme protein in the product is 6% by mass, and the mass% of the component (c) in the table is the mass% as the enzyme protein).

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

Other Ingredients-Cationic Surfactant 1: N, N-didecil-N-ethyl-N-Methylammonium Sulfate Ethyl Salt (Cotamin D10-ES, manufactured by Kao Corporation)
-Cationic surfactant 2: N-ethyl-N, N-dimethyltetradecylammonium sulfate ethyl salt (Cotamin 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.)

<Evaluation method for detergency>
(1) Detergency before storage Five sheets of spilled contaminated cloth were placed in 600 mL of a cleaning solution containing 0.5 g of a liquid detergent composition for clothing immediately after preparation and water, and a targotometer (MS-8212 manufactured by UESHIMA) was added. , Inner diameter 12 cm, height 17.5 cm) for 10 minutes at 85 rpm / min. The concentration of the liquid detergent composition for clothing in the cleaning liquid was 0.0833% by mass. The cleaning solution was prepared using Wakayama City water. The water temperature of the washing liquid was 20 ° C., and this temperature was maintained even during washing. As the spilled food contaminated cloth, 0.2 mg of pork cutlet sauce (Bull-Dock Sauce Co., Ltd.) was applied to a cotton knitted cloth (6 cm × 6 cm) and dried overnight. After washing, it was rinsed with Wakayama City water for 30 seconds.

The reflectance of the uncontaminated raw cloth (cotton knitted cloth) and the contaminated cloth before and after washing at 460 nm was measured with a self-recording color meter (Shimadzu Corporation), and the washing rate (%) was calculated by the following formula. The table shows the average cleaning rate of 5 artificially contaminated cloths. The higher the cleaning rate, the better.

(2) Detergency after storage Similar to (1), however, the cleaning liquid was prepared using a liquid detergent composition for clothing after being stored at 40 ° C. for 4 weeks, and the cleaning rate was measured.

<Evaluation method for foam breakability>
Screw tube Nо. Add 50 ml of Wakayama City water and 166.8 μl of liquid detergent composition for each clothing to 8 (Maruem), and use a vertical shaker (TAITEC, SR-2 DW) for 5 minutes at 300 rpm.
I shook it. The foam height 10 minutes after the end of shaking was measured and evaluated according to the following evaluation criteria.
◯: The foam height after 10 minutes is 10 mm or less.
X: The foam height after 10 minutes exceeds 10 mm.

* 1 The ratio of (a') is a ratio determined by the amount of the surfactant corresponding to the nonionic surfactant in the component (a').

Claims (7)

It contains the following components (a), (b), (c) and water, and is the mass ratio of the content of the component (a) to the content of the component (c) as an enzyme protein (a) /. A liquid detergent composition for clothing, wherein (c) is 100 or more and 16000 or less.
(A) Component: Nonionic surfactant represented by the following general formula (1) RO-[(EO) _n / (PO) _m ] -H (1)
[R in the formula 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 the average number of added moles, and n is. The number is 8 or more and 40 or less, m is 1 or more and 6 or less, and EO and PO may be random addition or block addition. ]
(B) Component: Inorganic calcium salt (c) Component: Glycolytic enzyme Claim 1 that the component (a) is a nonionic surfactant having m / (n + m) of 0.03 or more and 0.4 or less, which is the ratio of m to the total of n and m in the general formula (1). The liquid detergent composition for clothing according to. The liquid detergent composition for clothing according to claim 1 or 2, which contains (a) a nonionic surfactant represented by the following general formula (2) as a component.
RO- (EO) _n1- (PO) _m- (EO) _n2 -H (2)
[R in the formula 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, and EO and PO are block-bonded in this order. , N1, n2 and m are the average number of added moles, n1 is a number of 0 or more and 20 or less, m is a number of 1 or more and 6 or less, n2 is a number of 0 or more and 20 or less, and n1 and n2. The total of is 8 or more, and EO and PO are block additions. ] Any of claims 1 to 3, wherein (b) / (c), which is the mass ratio of the content of the component (b) to the content of the component (c) as an enzyme protein, is 0.1 or more and 100 or less. The liquid detergent composition for clothing according to item 1. The clothing according to any one of claims 1 to 4, wherein (a) / (b), which is the mass ratio of the content of the component (a) to the content of the component (b), is 10 or more and 10,000 or less. Liquid detergent composition for. The liquid detergent composition for clothing according to any one of claims 1 to 5, wherein the content of the anionic surfactant (excluding fatty acids) in the composition is 1% by mass or less. A method for washing clothes by washing the clothes with a washing liquid obtained by mixing the liquid detergent composition for clothes according to any one of claims 1 to 6 and water, and then rinsing the clothes with water.