CN108138094B

CN108138094B - Liquid detergent composition for clothes

Info

Publication number: CN108138094B
Application number: CN201680057439.5A
Authority: CN
Inventors: 杉山阳一; 开麻衣
Original assignee: Kao Corp
Current assignee: Kao Corp
Priority date: 2015-10-05
Filing date: 2016-09-23
Publication date: 2021-03-09
Anticipated expiration: 2036-09-23
Also published as: WO2017061283A1; JP2017071664A; JP6732424B2; CN108138094A

Abstract

The present invention provides a liquid detergent composition for clothing, which contains (a) an alkyl sulfate salt having 10 to 18 carbon atoms, (b) an alkyl ether sulfate salt represented by the following general formula (1), (c) a nonionic surfactant, (d) 1 or more sulfates selected from organic ammonium sulfates and inorganic sulfates having 1 to 8 carbon atoms (excluding calcium sulfate), (e) a protease, and water, wherein the total content of the content of (a) and the content of (b) is 5 to 40% by mass, the content of (d) is 2 to 8% by mass, and the mass ratio of the content of (a)/((b)) is 0.5 to 10. R-O- (AO)_n－SO₃M (1) (wherein R is an aliphatic hydrocarbon group having 10 to 18 carbon atoms, AO is an alkylene oxide group selected from an alkylene oxide group having 2 carbon atoms and an alkylene oxide group having 3 carbon atoms, n is an integer of 1 to 20 inclusive, and M is a cation).

Description

Liquid detergent composition for clothes

Technical Field

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

Background

As an evaluation of the completion of washing, consumers pay particularly strong attention to the decontamination of the collar and sleeve. It is known that collar stains and sleeve stains contain proteins in addition to sebum. As a liquid detergent for improving the stain removal of collars and sleeves, a composition containing a protease which directly decomposes proteins is known.

For example, Japanese patent application laid-open No. 2001-524591 discloses a gel cleansing detergent composition containing a structuring agent characterized by a polyoxyalkylene alkyl ether sulfate, a protease, a fatty acid and sodium sulfate, and imparting excellent detergency and desired rheology.

Jp 2014-62231 a describes a liquid detergent containing a polyoxyethylene alkyl ether sulfate, 2 compounds having a specific hydrocarbon group and polyoxyalkylene group, and a water-soluble inorganic salt for increasing viscosity, and realizing an increase in viscosity and excellent in storage stability under low-temperature conditions. Among them, sodium sulfate and calcium chloride are disclosed as water-soluble inorganic salts.

JP-A-59-22998 discloses an enzyme-containing liquid detergent composition containing a polyoxyalkylene alkyl ether sulfate having 2 to 7 oxyethylene groups in the molecule, a protease, and an aminocarboxylic acid, and having excellent enzyme storage stability.

Japanese patent application laid-open No. 6-502197 discloses an enzyme-containing detergent containing an alkyl sulfate, a fatty acid, water as a solvent, ethanol, and glycerin, and having excellent enzyme stability.

Disclosure of Invention

JP-A-2001-524591, JP-A-2014-62231, JP-A-59-22998 and JP-A-6-502197 do not describe techniques for further improving the stability of protease in a liquid detergent composition and for achieving both the cleaning performance of protease against protein stains during washing.

The present invention provides a liquid detergent composition for clothes, which has excellent detergency on protein-containing stains and excellent stability of protease in the liquid detergent composition for clothes.

The present inventors have conducted extensive studies and found a technique for further improving the detergency of a protease against protein-containing stains during washing.

Among the various components constituting the liquid detergent composition for clothing, the following were confirmed as a result of focusing attention on the surfactant and the inorganic salt: when an alkyl sulfate salt and a polyoxyalkylene alkyl ether sulfate salt having a specific structure are used in a specific mass ratio and a specific sulfate salt is used in combination, the cleaning effect of the protease in the cleaning solution on protein-containing stains is increased.

It was also confirmed that: a certain amount of the specific sulfate salt makes it easy for proteins having a low molecular weight due to the decomposition by proteases to dissolve in a washing liquid, and thus exerts a remarkable effect in the decontamination of collars and sleeves containing proteins.

Further, alkyl sulfate salts are components contributing to improvement of detergency, but tend to affect enzyme stability. However, in the present invention, it was found that: even when such an alkyl sulfate salt is contained, the stability of the protease in the liquid detergent composition can be improved by blending specific amounts of a polyoxyalkylene alkyl ether sulfate salt, a nonionic surfactant and a specific sulfate salt.

The present invention has been completed based on the above findings.

The present invention relates to a liquid detergent composition for clothing, which comprises the following components (a), (b), (c), (d), (e) and water,

(a) the components: alkyl sulfate salts having 10 to 18 carbon atoms;

(b) the components: an alkyl ether sulfate represented by the following general formula (1),

R－O－(AO)_n－SO₃M (1)

wherein R is an aliphatic hydrocarbon group having 10 to 18 carbon atoms, AO is an alkylene oxide group selected from an alkylene oxide group having 2 carbon atoms and an alkylene oxide group having 3 carbon atoms, n is an integer of 1 to 20, and M is a cation. Angle (c);

(c) the components: a nonionic surfactant;

(d) the components: 1 or more sulfates selected from organic ammonium sulfates and inorganic sulfates (excluding calcium sulfate) having 1 or more and 8 or less carbon atoms;

(e) the components: a protease,

wherein the total content of the component (a) and the component (b) is 5 to 40 mass%,

(d) the content of the component (B) is 2-8 mass%,

(a) the mass ratio of the content of component (a) to the content of component (b) is 0.5 to 10 inclusive.

The present invention also relates to the use of the above-described liquid detergent composition for clothing of the present invention in immersion cleaning.

The invention also relates to a washing method of clothes, which comprises the following working procedures 1-3:

step 1: mixing a soaking liquid containing the liquid detergent composition for clothing of the present invention and water with clothing;

and a step 2: a step of immersing the clothes in the immersion liquid after the step 1; and

step 3: and a step of washing the clothes with agitation in a washing liquid containing the detergent composition for clothes and water after the step 2.

According to the present invention, a liquid detergent composition for clothing which is excellent in detergency on protein-containing stains and is excellent in stability of protease in a liquid detergent composition for clothing can be obtained. Further, by soaking the laundry in a washing liquid containing the liquid detergent composition for laundry and water, the amount of labor for washing the laundry with agitation after soaking the laundry can be reduced.

Detailed Description

< component (a) >

(a) The component (A) is alkyl sulfate with 10-18 carbon atoms. The alkyl sulfate salt having 10 or more and 18 or less carbon atoms is an alkyl sulfate salt having an alkyl group having 10 or more and 18 or less carbon atoms.

(a) The composition has a cleaning effect on stains by using surface activation energy. Further, by using the component (a) in combination with the component (d) of the present invention, the cleaning action of the protease as the component (e) on protein stains can be enhanced. In addition, it is also believed that: (a) the component improves the cleaning effect on protein-containing stains by improving the enzymatic activity of protease.

The carbon number of the alkyl group contained in the component (a) is preferably 10 or more and 16 or less in order to improve the enzymatic activity of the protease and to improve the cleaning performance against protein-containing stains. That is, the component (a) preferably has an alkyl group having 10 to 16 carbon atoms, and more preferably an alkylsulfate salt having a chain alkyl group.

Examples of the salt constituting the component (a) include alkali metal salts such as sodium and potassium, and alkanolamine salts having 2 to 6 total carbon atoms. From the viewpoint of improving the enzymatic activity of the protease, an alkali metal salt is preferred, and a sodium salt is more preferred.

< component (b) >

(b) The component (A) is alkyl ether sulfate represented by the following general formula (1).

R－O－(AO)_n－SO₃M (1)

Wherein R is an aliphatic hydrocarbon group having 10 to 18 carbon atoms, AO is an alkylene oxide group selected from an alkylene oxide group having 2 carbon atoms and an alkylene oxide group having 3 carbon atoms, n is an integer of 1 to 20 inclusive, and M is a cation. Angle (c)

In the general formula (1), R is preferably an alkyl group, and more preferably a chain alkyl group. In addition, from the viewpoint of improving the detergency, R preferably has 10 or more and 16 or less carbon atoms. R is preferably an alkyl group having 10 to 16 carbon atoms, and more preferably a chain alkyl group.

In the general formula (1), AO is an alkylene oxide group selected from an alkylene oxide group having 2 carbon atoms and an alkylene oxide group having 3 carbon atoms. As AO, for example, 1 or more kinds of groups selected from an ethyleneoxy group and a propyleneoxy group are listed. When n is an integer of 2 or more and 20 or less, AO may contain an ethyleneoxy group and a propyleneoxy group. When AO comprises an ethyleneoxy group and a propyleneoxy group, either one may be bonded to R-O-. When AO contains an ethyleneoxy group and a propyleneoxy group, the bonding mode of the ethyleneoxy group and the propyleneoxy group may be either a random type or a block type, or a combination mode in which the random type and the block type are mixed may be used. From the viewpoint of easy availability of the component (b), AO is preferably an ethyleneoxy group.

In the general formula (1), n is not particularly limited, but is preferably 3 or less, more preferably 2 or less, and still more preferably 1, from the viewpoint of improving the detergency. The liquid detergent composition for clothing of the present invention preferably contains, as component (b), a compound of formula (1) wherein n is 1 or more and 3 or less, more preferably 1 or more and 2 or less, and still more preferably 1.

In terms of improving the cleaning performance, the total mass of the compound in which n is 1 and the compound in which n is 2 in the general formula (1) in all the components (b) is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 55% by mass or more, further preferably 60% by mass or more, further preferably 65% by mass or more, and 100% by mass or less, preferably 90% by mass or less, more preferably 85% by mass or less.

In addition, in the component (b), the proportion of the compound having n of 6 to 20 in the general formula (1) is preferably 10% by mass or less, more preferably 9% by mass or less, further preferably 8% by mass or less, further preferably 7% by mass or less, further preferably 6% by mass or less, further preferably 5% by mass or less, further preferably 4% by mass or less, further preferably 3% by mass or less, in terms of further improving the cleaning effect of the protease as the component (d) of the present invention against protein-containing stains. The lower limit of the ratio is 0 mass% or more. Further, the lower limit of the proportion is 0 mass% or more than 0 mass%.

In the present invention, the constituent ratio of the compound of the component (b) having different n in the general formula (1) may be the same as that of the compound of the general formula (1)SO of (A)₃The constituent ratio of compounds in which n is different in the compound in which the M group is replaced with H. For example, SO in the general formula (1) can be analyzed by gas chromatography₃The area ratio obtained by the distribution of compounds in which the M group is replaced with H and n is different is regarded as the mass fraction, and is used as the composition ratio of compounds in which n is different in the general formula (1) as the component (b).

Even when the component (b) represented by the general formula (1) can be obtained, if it is difficult to directly measure the composition ratio, the component (b) may be decomposed with an acid to generate SO₃The compound in which the M group is replaced with H is used as the constituent ratio of the compound of the component (b) in which n is different in the general formula (1). In this case, specifically, the component (b) may be decomposed with an acid to produce SO₃The compound in which the M group is replaced with H is analyzed by gas chromatography for the distribution of n in the compound, and the obtained area ratio is regarded as the mass fraction, and used as the composition ratio of the compound of formula (1) in which n is different in component (b).

In the case of the above method, the analysis conditions of the gas chromatography and the above-mentioned conditions of the acid decomposition are exemplified as follows.

< analytical conditions for gas chromatography >

GC equipment: 7890A, manufactured by Agilent Technologies Inc

Column: DB-5 (30m, inner diameter 0.25mm, film thickness 0.25 μm), manufactured by Agilent Technologies Co., Ltd

A detector; FID

Carrier gas: helium, 1mL/min

Temperature rising conditions are as follows: the temperature was raised from 100 ℃ to 325 ℃ at 5 ℃/min. Thereafter, the mixture was held at 325 ℃ for 35 minutes.

Pretreatment of a sample: a sample (50 mg) was put into a 2mL glass vial, and 1mL of a trimethylsilylating agent (GL Sciences) was added thereto and mixed, followed by reaction at 30 ℃ for 5 minutes.

< Condition for acid decomposition of component (b) >

A300 mL glass ground Erlenmeyer flask was charged with 4g of sample. 200mL of 2N hydrochloric acid and zeolite were placed in an Erlenmeyer flask, and a ground air-cooling tube was placed. The Erlenmeyer flask was put in an oil bath at 140 ℃ and refluxed for 3 hours, and then cooled to 30 ℃.1 drop of 1% phenolphthalein solution was added to the Erlenmeyer flask using a Pasteur pipette. Subsequently, a 35% aqueous sodium hydroxide solution was added until the contents in the Erlenmeyer flask became pale pink.

The contents were transferred to a 1000mL separatory funnel, 200mL of petroleum ether was added, and extraction was performed 3 times. The petroleum ether layer was washed with 50mL of a 10% aqueous solution of sodium chloride for 3 times, and then dehydrated by adding 20g of anhydrous sodium sulfate. A500 mL Erlenmeyer flask was charged with a solution obtained by removing anhydrous sodium sulfate by filtration, and petroleum ether was distilled off.

In the general formula (1), M is a cation forming a salt. Examples of M include alkali metal ions such as sodium ion and potassium ion, and alkanolammonium ion. From the viewpoint of enhancing the activity of the protease, M is preferably an alkali metal ion, and more preferably a sodium ion. The alkanolammonium ion is preferably an alkanolammonium ion having 2 to 6 total carbon atoms.

< component (c) >

(c) The component is nonionic surfactant. It is thought that the component (c) has an effect of improving the storage stability of the protease in the liquid detergent composition for clothing.

The component (c) is preferably a nonionic surfactant having a polyoxyalkylene group, and more preferably a nonionic surfactant having a polyoxyalkylene group with an average number of moles of addition of 3 to 50 moles.

The component (c) is more preferably a nonionic surfactant represented by the following general formula (c 1).

R^1c－O－(A’O)_m－H (c1)

[ in the formula, R^1cIs an aliphatic hydrocarbon group having 8 to 18 carbon atoms, A 'O is an alkylene oxide group selected from an alkylene oxide group having 2 carbon atoms and an alkylene oxide group having 3 carbon atoms, m is the average molar number of addition of A' O, and m is a number of 3 to 50. Angle (c)

It is possible to further improve the stain containing protein stainIn terms of detergency, R in the general formula (c1)^1cThe number of carbon atoms of (a) is preferably 10 or more, more preferably 12 or more, and preferably 16 or less.

In addition, R in the general formula (c1), in order to make the viscosity of the liquid detergent composition for clothing of the present invention lower, R in the general formula (c1)^1cThe number of carbon atoms of (a) is preferably 10 or more, and preferably 16 or less, and more preferably 14 or less.

R in the general formula (c1)^1cThe aliphatic hydrocarbon group of (2) includes aliphatic hydrocarbon groups selected from alkyl groups and alkenyl groups, and preferably alkyl groups.

In the general formula (c1), m is the average molar number of addition of a' O, and m is preferably 4 or more, more preferably 5 or more, further preferably 6 or more, and further preferably 7 or more, from the viewpoint of further improving the storage stability of the protease in the liquid detergent composition for clothing. In terms of being able to further improve the effect of the component (d) on improving the cleaning performance of the protease against protein stains, m is preferably 45 or less, more preferably 40 or less, further preferably 35 or less, further preferably 30 or less, further preferably 25 or less, further preferably 20 or less, further preferably 18 or less, further preferably 16 or less, further preferably 14 or less, further preferably 12 or less.

A' O is an alkylene oxide group selected from alkylene oxide groups having 2 carbon atoms and alkylene oxide groups having 3 carbon atoms. Examples of A' O include 1 or more groups selected from an ethyleneoxy group and a propyleneoxy group. In terms of being able to further improve the storage stability of the protease in the liquid detergent composition for clothing, a' O is preferably an alkylene oxide group containing an ethyleneoxy group. A' O is preferably ethyleneoxy.

< ingredient (d) >

(d) The component (A) is at least 1 sulfate selected from organic ammonium sulfate and inorganic sulfate (excluding calcium sulfate) with carbon number of 1-8. With the component (d), the amount of the protease-decomposed low-molecular-weight protein on the clothes dispersed from the clothes into the washing liquid can be increased. In addition, the stability of protease in the liquid detergent composition for clothes can be improved by the component (d).

As the organic ammonium sulfate having 1 to 8 carbon atoms, a compound represented by the following general formula (d1) is preferable in terms of further improving the cleaning performance of the protease against protein stains.

〔(C_nH_2n+1)_xN(C₂H₄OH)_y〕²⁺·SO₄ ^2－ (d1)

In the formula, n is an integer of 0 to 2 inclusive, x and y are each a number of 0 to 4 inclusive, and x + y is 4, excluding the case where n is 0 and x is 4. C_nH_2n+1When there are more than one radical, more than one C_nH_2n+1The radicals are identical or different. Angle (c)

As the organic ammonium sulfate having 1 to 8 carbon atoms, 1 or more compounds selected from monoethanol ammonium sulfate, methyl monoethanol ammonium sulfate, ethyl monoethanol ammonium sulfate, methyl diethanol ammonium sulfate, ethyl diethanol ammonium sulfate, and triethanol ammonium sulfate are preferable, and 1 or more compounds selected from monoethanol ammonium sulfate and triethanol ammonium sulfate are more preferable, in terms of further improving the cleaning effect of the protease on protein stains.

As the inorganic sulfate (excluding calcium sulfate, among them), from the viewpoint of further improving the cleaning effect of the protease against protein stains, 1 or more kinds of inorganic sulfate selected from the group consisting of ammonium sulfate, alkali metal sulfate and alkaline earth metal sulfate other than calcium sulfate are preferable. Examples of the alkali metal sulfate include lithium sulfate, sodium sulfate, and potassium sulfate. As the alkaline earth metal sulfate other than calcium sulfate, magnesium sulfate is exemplified.

As the inorganic sulfate (excluding calcium sulfate), alkali metal sulfates are preferable in terms of high effect of dispersing protein stains decomposed on clothes in a washing liquid by protease.

As the component (d), 1 or more sulfate salts selected from acid anhydrides and hydrates can be used. Therefore, the component (d) may be 1 or more sulfate salts selected from organic ammonium sulfate salts having 1 to 8 carbon atoms, inorganic sulfate salts (excluding calcium sulfate), acid anhydrides of the above sulfate salts, and hydrates of the above sulfate salts.

The component (d) is preferably 1 or more sulfate selected from inorganic sulfates (excluding calcium sulfate), more preferably 1 or more inorganic sulfates selected from alkali metal sulfates and alkaline earth metal sulfates other than calcium sulfate, and still more preferably 1 or more inorganic sulfates selected from alkali metal sulfates.

< ingredient (e) >

(e) The component is protease.

Preferred proteases include those which function in neutral or alkaline aqueous solutions. Preferred proteases are alkaline proteases.

Specific examples of preferred proteases include (e1) the alkaline protease described in International publication No. 99/018218, preferably the alkaline protease in which 70% or more of the amino acid sequence shown in SEQ ID NO. 1 or SEQ ID NO. 2 of the publication is preserved; (e2) the alkaline protease described in Japanese unexamined patent publication No. 5-25492 is preferably alkaline protease K-16, alkaline protease K-14 or the like.

Further, examples of the protease include (e3) proteases produced by the genus Bacillus subtilisin manufactured by Novistin under the trade name Savinase (registered trademark), Kannase (registered trademark), Everlase (registered trademark), Alcalase (registered trademark), Porazyme (registered trademark), and Esperase (registered trademark); (e4) FN2 (registered trademark), FN3 (registered trademark), and FN4 (registered trademark), pure Prime (registered trademark) manufactured by dupont; (e5) alkali proteases manufactured by kao corporation, such as KAP4.3G (registered trademark) and KAP11.1G (registered trademark); (e6) proteases and variants thereof supplied under these trade names.

More preferred proteases are alcalases in which 80% or more of the amino acid sequence represented by sequence number 1 or sequence number 2 described in international publication No. 99/018218 is conserved, Savinase, everlast, Alcalase manufactured by noviko, Purafect Prime manufactured by dupont, and Alcalase manufactured by kao corporation.

From the viewpoint that the cleaning performance can be further improved by using a combination with the component (a) or the component (b), Savinase is more preferable.

From the viewpoint of detergency, the activity of the protease (e) component is preferably 5000mPU/g or more, more preferably 20000mPU/g or more per 1g of the amount of the enzyme protein, that is, the specific activity. The specific activity of the protease is a value obtained by converting the activity unit of the protease measured by the following method into an activity per 1g of the enzyme protein of the protease. The activity unit of protease can be measured by the method described in examples.

< ingredient (f) >

The laundry detergent composition of the present invention may contain a polyhydric alcohol of two or more and six or less as the component (f).

By using the component (f) in combination with the components (c) and (d), the storage stability of the protease in the liquid detergent composition for clothes can be further improved.

Preferred examples of the diol include 1 or more compounds selected from ethylene glycol, propylene glycol, diethylene glycol, and triethylene glycol. As a preferred compound of the trihydric alcohol, glycerol may be mentioned. The preferred compound of the tetrahydric alcohol may be exemplified by pentaerythritol. Preferred compounds of the alcohol having five or more and six or less include sugar alcohols having five or more and six or less. As the pentasaccharide alcohol, xylitol may be mentioned. Examples of the hexahydric sugar alcohol include sorbitol and mannitol. The component (f) is preferably a compound of 1 or more selected from propylene glycol, glycerin, diethylene glycol, triethylene glycol, and sorbitol, and preferably a compound of 1 or more selected from propylene glycol, glycerin, and sorbitol, in terms of further improving the storage stability of the protease.

< ingredient (g) >

The laundry detergent composition of the present invention may contain a calcium ion donor as the component (g).

(g) The component (A) is a compound having a property of being ionized in water, and is used as a stabilizer for protease. (g) The component (C) is preferably an inorganic compound, and specifically, calcium chloride is exemplified.

< composition of liquid detergent composition for clothes, etc. >

The liquid detergent composition for clothing of the present invention has an improved cleaning effect of protease on protein-containing stains, and thus has excellent cleaning ability on protein-containing stains adhered to clothing. In addition, in the washing liquid prepared from the liquid detergent composition for clothing of the present invention, the storage stability of protease is more excellent.

The content of the component (a) and the content of the component (b) in the liquid detergent composition for clothing of the present invention are each a value converted from a counter ion (i.e., a cation forming a salt) to sodium, that is, a value converted from a sodium salt.

In the liquid detergent composition for clothing of the present invention, the total content of the content of component (a) and the content of component (b) is 5 to 40% by mass.

In order to further improve the cleaning performance of protein-containing stains, the total content of the component (a) and the component (b) in the liquid detergent composition for clothing of the present invention is preferably 6% by mass or more, more preferably 7% by mass or more, even more preferably 8% by mass or more, and even more preferably 9% by mass or more. In addition, in terms of further improving the storage stability of the liquid detergent composition for clothing of the present invention, the total content of the component (a) and the content of the component (b) in the liquid detergent composition for clothing of the present invention is preferably 35% by mass or less, more preferably 30% by mass or less, further preferably 25% by mass or less, and further preferably 20% by mass or less.

In the liquid detergent composition for clothing of the present invention, the mass ratio of the content of component (a) to the content of component (b) is 0.5 to 10 inclusive, in terms of "(content of component (a)/(content of component (b)".

In order to further enhance the effect of a specific sulfate-enhanced protease as the component (d) on the cleaning effect of protein-containing stains, the mass ratio of the content of the component (a) to the content of the component (b) is 0.5 or more, preferably 0.55 or more, more preferably 0.6 or more, further preferably 0.65 or more, further preferably 0.7 or more, further preferably 0.75 or more, further preferably 0.8 or more, further preferably 0.85 or more, and further preferably 0.9 or more in terms of "(content of component (a)/(content of component (b)".

In addition, in order to further improve the storage stability of the protease in the laundry detergent composition of the present invention, the mass ratio of the content of the component (a) to the content of the component (b) is 10 or less, preferably 9 or less, more preferably 8 or less, further preferably 7 or less, further preferably 6 or less, further preferably 5 or less, further preferably 4 or less, further preferably 3 or less, further preferably 2 or less, in terms of "(content of component (a)/(content of component (b)".

In the present invention, in the production of the liquid detergent composition for clothing, a mixture containing the component (a) and the component (b) may be used as a supply source of the component (a) and the component (b). Examples of such a mixture include polyoxyalkylene alkyl ether sulfate salts having an alkyl group having 10 to 18 carbon atoms in which the structure and the proportion of the compound are known. Polyoxyalkylene alkyl ether sulfate ester salts are generally obtained by sulfating alkylene oxide adducts of alcohols, and are obtained as a mixture of compounds having different numbers of moles of alkylene oxide added. Thus, a mixture containing the component (a) and the component (b) of the present invention can be formed.

In the liquid detergent composition for clothing of the present invention, the mass ratio of the content of component (c) to the total content of the content of component (a) and the content of component (b) is preferably 0.02 to 2 "(content of component (c)/[ (content of component (a) + (content of component (b)") in terms of further improving the storage stability of protease in the liquid detergent composition for clothing and further improving the cleaning performance against protein-containing stains.

In order to further improve the storage stability of the protease, the mass ratio "(content of component (c))/[ (content of component (a) + (content of component (b)) ] is preferably 0.04 or more, more preferably 0.06 or more, still more preferably 0.08 or more, still more preferably 0.1 or more, and still more preferably 0.12 or more.

When the content of the component (c) in the liquid detergent composition for clothes is large, the storage stability of the protease is higher. However, if the storage stability is too high, the action of the protease in the washing liquid to decompose the protein contained in the stain may be weak, and it may be difficult to achieve the cleaning effect of the protease on the protein stain. In order to further improve the cleaning performance against protein-containing stains, the mass ratio "(content of component (c))/[ (content of component (a) + content of component (b)) ] is preferably 1.8 or less, more preferably 1.6 or less, still more preferably 1.4 or less, yet more preferably 1.2 or less, yet more preferably 1.0 or less, yet more preferably 0.8 or less, yet more preferably 0.6 or less, yet more preferably 0.4 or less.

The content of the component (d) in the liquid detergent composition for clothing of the present invention is 2 to 8% by mass.

The content of the component (d) in the liquid detergent composition for clothing of the present invention is preferably 2.2% by mass or more, more preferably 2.4% by mass or more, further preferably 2.6% by mass or more, further preferably 2.8% by mass or more, and further preferably 3% by mass or more, in terms of improving the cleaning rate of stains by increasing the solubility of proteins having low molecular weights in a cleaning liquid by the action of a protease. In order to further improve the storage stability of the protease in the liquid detergent composition for clothing, the storage stability is preferably 7% by mass or less, more preferably 6% by mass or less, and still more preferably 5% by mass or less.

The content of the component (d) in the liquid detergent composition for clothing of the present invention is preferably 1.4% by mass or more, more preferably 1.5% by mass or more, further preferably 1.6% by mass or more, further preferably 1.7% by mass or more, further preferably 1.8% by mass or more, further preferably 1.9% by mass or more, further preferably 2.0% by mass or more, and preferably 7% by mass or less, more preferably 6% by mass or less, further preferably 5.5% by mass or less, further preferably 4.0% by mass or less, further preferably 3.5% by mass or less in terms of sulfate ion.

The content of the component (e) in the liquid detergent composition for clothing of the present invention is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and preferably 1% by mass or less, more preferably 0.8% by mass or less, and further preferably 0.5% by mass or less, in terms of the amount of enzyme protein.

In the present invention, the amount of the enzyme protein of component (e) is a value expressed in terms of bovine serum Albumin (BovineSerum Albumin, manufactured by SIGMA corporation, product number A-7030) according to the method of Lowry et al (Lowry, O.H.et. al., J.biol.chem., 193, 265 (1951)).

When the liquid detergent composition for clothing of the present invention contains the component (f), the content of the component (f) in the composition is preferably 0.2 mass% or more and 10 mass% or less. The content of the component (f) in the laundry detergent composition is more preferably 0.4% by mass or more, still more preferably 0.6% by mass or more, and still more preferably 0.8% by mass or more, from the viewpoint of further improving the storage stability of the protease in the composition, and is more preferably 9% by mass or less, still more preferably 8% by mass or less, and still more preferably 7% by mass or less from the viewpoint of cost reduction.

When the liquid detergent composition for clothing of the present invention contains the component (g), the content of the component (g) in the composition is preferably 0.01 mass% or more and 0.15 mass% or less in terms of calcium ion. The content of the component (g) in the composition is more preferably 0.02 mass% or more, and still more preferably 0.03 mass% or more in terms of calcium ions, from the viewpoint of improving the stability of the protease. From the viewpoint of detergency, the content of the component (g) in the composition is more preferably 0.12% by mass or less, still more preferably 0.1% by mass or less, and still more preferably 0.08% by mass or less in terms of calcium ions.

The liquid detergent composition for clothing of the present invention has a pH of 4 to 10 at 25 ℃. In terms of excellent storage stability of the protease in the liquid detergent composition for clothing, the pH is preferably 4.5 or more, more preferably 5.0 or more, further preferably 5.5 or more, further preferably 6.0 or more, further preferably 6.5 or more, further preferably 7.0 or more, further preferably 7.5 or more, further preferably 8.0 or more, and preferably 9.8 or less, more preferably 9.5 or less. The pH can be measured using a pH meter using a glass electrode.

In the liquid detergent composition of the present invention, the following components (i) to (v) can be blended as other components in such an amount that the effects of the present invention are not impaired.

(i) Anti-redeposition agents and dispersants

As the component (i), polyacrylic acid, polymaleic acid, and a recontamination preventing agent and a dispersing agent such as a polymer described in claims 1 to 21 (page 1, column 3, line 5 to page 3, column 4, line 14) of Japanese patent laid-open No. Sho 59-62614 are exemplified. (i) The component (B) is preferably polyacrylic acid, polymaleic acid or a salt thereof, and more preferably polyacrylic acid or a salt thereof.

The content of the component (i) in the laundry detergent composition of the present invention is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, and is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less.

(ii) Fluorescent dyes

Examples of the component (ii) include fluorescent dyes sold as Tinopal CBS (trade name, manufactured by Ciba Specialty Chemicals) or Whitex SA (trade name, manufactured by Sumitomo chemical Co., Ltd.).

(iii) A monohydric, trihydric or higher alcohol having 1 to 6 carbon atoms

Examples of the component (iii) include 1 or more alcohols selected from ethanol, ethylene glycol, propylene glycol and glycerin.

The content of (iii) in the liquid detergent composition for clothing of the present invention is preferably 0.5% by mass or more, more preferably 1% by mass or more, and is preferably 15% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less, in terms of the effect of easily dispersing the composition in water, the effect of suppressing separation into two or more phases during storage of the composition, the appearance of cloudiness, and the like.

(iv) Coloring matter, perfume, antibacterial antiseptic, defoaming agent such as silicone, and pH regulator.

(v) A surfactant other than the component (a), the component (b) and the component (c).

The surfactant as component (v) may contain, for example, a surfactant selected from fatty acids having 10 to 18 carbon atoms or salts thereof. However, in terms of maintaining the high detergency of the present invention, the content of the fatty acid having 10 or more and 18 or less carbon atoms or a salt thereof is preferably 10% by mass or less, more preferably 8% by mass or less, and further preferably 5% by mass or less, relative to the total content of the component (a), the component (b), and the component (c). The lower limit is 0 mass% or more than 0 mass%.

The content of the fatty acid salt is a mass obtained by replacing a cation as a counter ion with a hydrogen ion, that is, a mass of a compound converted into an acid form.

The surfactant (v) may contain an amine oxide having one alkyl group having 10 to 16 carbon atoms. Specifically, an amine oxide having one alkyl group having 10 or more and 16 or less carbon atoms and two groups selected from an alkyl group having 1 or more and 3 or less carbon atoms and a hydroxyalkyl group having 1 or more and 3 or less carbon atoms is exemplified.

The above-mentioned liquid detergent composition for clothes is suitably used for a liquid detergent for clothes.

< method for washing clothes >

The liquid detergent composition for clothing of the present invention is suitable for immersion washing. The liquid detergent composition for clothing of the present invention can be mixed with water to form a washing liquid, and thus suitably used for immersion washing. In the present invention, "soaking washing" refers to a washing method having a period of time during which laundry is soaked in a washing liquid for a certain time. Preferably: in the immersion washing, after immersing in a washing liquid for a certain period of time, the clothes and the washing liquid are mixed by hand or by mechanical force of a washing machine or the like, and agitated and washed. In addition, after the laundry is soaked in the washing liquid for a certain period of time, the laundry is scrubbed using a tool such as a brush.

Specifically, the method for washing clothes includes the following steps 1 to 3.

Step 1 is a step of mixing the liquid composition for clothing of the present invention and water in an immersion liquid with clothing.

In step 1, the concentration of the liquid detergent composition for clothing in the immersion liquid obtained by mixing the liquid detergent composition for clothing of the present invention with water is preferably 2.5g/L or more, more preferably 3g/L or more, and still more preferably 3.5g/L or more, from the viewpoint of cleaning performance. On the other hand, the concentration of the liquid detergent composition for clothing in the immersion liquid is preferably 10g/L or less, more preferably 8g/L or less, and still more preferably 6g/L or less, from the viewpoint of rinsing properties.

As the water used in step 1, water having a hardness of 1 ° DH to 30 ° DH, as a german hardness, can be used. From the viewpoint of more reliably receiving the effect of excellent detergency against protein-containing stains, water having a german hardness of 1 ° DH or more, further 3 ° DH or more, further 5 ° DH or more, further 6 ° DH or more, further 8 ° DH or more, further 9 ° DH or more, and further 10 ° DH or more may be used. From the viewpoint of foaming properties during washing and foam persistence, water having a hardness of 30 ° DH or less, further 25 ° DH or less, and further 20 ° DH or less in terms of the german hardness can be used. "hardness" means the total hardness determined by chelate titration using ethylenediaminetetraacetic acid disodium salt.

In step 1, from the viewpoint of easiness of washing at the time of hand washing, the ratio of the volume (liter) of the soaking liquid obtained by mixing the liquid detergent composition for clothes of the present invention with water to the mass (kg) of clothes (hereinafter, this ratio will be referred to as "bath ratio") is preferably 1 or more, more preferably 2 or more, further preferably 3 or more, and further preferably 5 or more in terms of [ volume (liter) of washing liquid ]/[ mass (kg) of clothes ]. From the viewpoint of detergency, the bath ratio is preferably 100 or less, preferably 90 or less, preferably 20 or less, and more preferably 10 or less.

In step 1, a soaking solution obtained by mixing water and the liquid detergent composition for clothing of the present invention in advance may be mixed with clothing. In addition, water including laundry after mixing laundry with water may be mixed with the liquid detergent composition for laundry of the present invention. At this time, the impregnation liquid is formed by mixing water including laundry and the liquid detergent composition for laundry of the present invention. Further, laundry, water and the liquid detergent composition for laundry of the present invention may be mixed at the same time. At this time, the immersion liquid is formed by mixing water and the liquid detergent composition for clothing of the present invention.

Step 2 is a step of immersing the clothes in the immersion liquid after step 1.

In the washing method of the present invention, the time for soaking the laundry is preferably 10 minutes or longer, more preferably 20 minutes or longer, from the viewpoint of cleaning performance against protein-containing stains or from the viewpoint of reducing the amount of labor required in step 3 described later. In order to shorten the time required for washing, 120 minutes or less is preferable, and 60 minutes or less is more preferable. In the present invention, the "time for soaking laundry" refers to a time from a time point when the liquid detergent composition for laundry of the present invention, water and laundry are mixed in a mass necessary for 1 washing to a time point when the agitation washing in the step 3 is started.

Step 3 is a step of washing the clothes with agitation in a washing liquid containing the detergent composition for clothes and water after step 2. The term "agitation washing" refers to washing of laundry by agitating laundry and a washing liquid manually or by mechanical force such as a washing machine. The washing of the laundry and the washing liquid by stirring by hand means: rubbing the clothes in the washing liquid to rub the clothes containing the washing liquid against each other, thereby washing the clothes; scrubbing the laundry containing the washing liquid with a brush or the like to wash the laundry; agitating the laundry in the washing liquid by a hand through a rotating operation or a reciprocating operation, thereby washing the laundry; the laundry is washed by performing an operation of compressing the laundry in the washing liquid by hand a plurality of times.

The laundry detergent composition used in step 3 may be the liquid laundry detergent composition of the present invention. The laundry detergent composition used in step 3 may be a laundry detergent composition different from the liquid laundry detergent composition of the present invention. The laundry detergent composition used in step 3 is preferably the liquid laundry detergent composition of the present invention, in terms of further improving the cleaning effect of protease on stains including protein stains.

More specific embodiments of the present invention are shown below. In these embodiments, the above-mentioned matters concerning the liquid detergent composition for clothes and the method of washing clothes can be suitably applied.

＜1＞

A liquid detergent composition for clothing, which comprises the following components (a), (b), (c), (d), (e) and water,

(a) the components: alkyl sulfate salts having 10 to 18 carbon atoms;

R－O－(AO)_n－SO₃M (1)

wherein R is an aliphatic hydrocarbon group having 10 to 18 carbon atoms, AO is an alkylene oxide group selected from an alkylene oxide group having 2 carbon atoms and an alkylene oxide group having 3 carbon atoms, n is an integer of 1 to 20 inclusive, and M is a cation. Angle (c);

(c) the components: a nonionic surfactant;

(e) the components: a protease,

wherein the total content of the component (a) and the content of the component (b) is 5% by mass or more, preferably 6% by mass or more, more preferably 7% by mass or more, further preferably 8% by mass or more, further preferably 9% by mass or more, and 40% by mass or less, preferably 35% by mass or less, more preferably 30% by mass or less, further preferably 25% by mass or less, further preferably 20% by mass or less,

(d) the content of the component (B) is 2% by mass or more, preferably 2.2% by mass or more, more preferably 2.4% by mass or more, further preferably 2.6% by mass or more, further preferably 2.8% by mass or more, further preferably 3% by mass or more, and 8% by mass or less, preferably 7% by mass or less, more preferably 6% by mass or less, further preferably 5% by mass or less,

(a) the mass ratio of the content of component (a) to the content of component (b) is 0.5 or more, preferably 0.55 or more, more preferably 0.6 or more, further preferably 0.65 or more, further preferably 0.7 or more, further preferably 0.75 or more, further preferably 0.8 or more, further preferably 0.85 or more, further preferably 0.9 or more, and 10 or less, preferably 9 or less, more preferably 8 or less, further preferably 7 or less, further preferably 6 or less, further preferably 5 or less, further preferably 4 or less, further preferably 3 or less, further preferably 2 or less [ (the content of component (a) ]/[ (the content of component (b) ].

＜2＞

The liquid detergent composition for clothing described in < 1 > wherein AO in the alkyl ether sulfate salt represented by the general formula (1) is an ethyleneoxy group.

＜3＞

The liquid detergent composition for clothing of < 1 > or < 2 >, wherein the total mass of the compound in which n is 1 and the compound in which n is 2 in the general formula (1) is 40% by mass or more, preferably 50% by mass or more, more preferably 55% by mass or more, further preferably 60% by mass or more, further preferably 65% by mass or more, and 100% by mass or less, preferably 90% by mass or less, more preferably 85% by mass or less of the total of the components (b).

＜4＞

The liquid detergent composition for clothing according to any one of the claims < 1 > - < 3 >, wherein the proportion of the compound of the general formula (1) in which n is 6 to 20 inclusive is 10% by mass or less, preferably 9% by mass or less, more preferably 8% by mass or less, further preferably 7% by mass or less, further preferably 6% by mass or less, further preferably 5% by mass or less, further preferably 4% by mass or less, further preferably 3% by mass or less, and 0% by mass or more, or 0% by mass, based on the total amount of the component (b).

＜5＞

The liquid detergent composition for clothing according to any one of < 1 > - < 4 >, wherein the mass ratio of the content of the component (c) to the total content of the contents of the components (a) and (b) is 0.02 or more, preferably 0.04 or more, more preferably 0.06 or more, further preferably 0.08 or more, further preferably 0.1 or more, further preferably 0.12 or more, and 2 or less, preferably 1.8 or less, more preferably 1.6 or less, further preferably 1.4 or less, further preferably 1.2 or less, further preferably 1.0 or less, further preferably 0.8 or less, further preferably 0.6 or less, further preferably 0.4 or less, in terms of the content of the component (c)/(the content of the component (a) + (b).

＜6＞

The liquid detergent composition for clothing according to any one of claims < 1 > - < 5 >, wherein the component (c) is a nonionic surfactant having a polyoxyalkylene group, and further a nonionic surfactant having a polyoxyalkylene group with an average number of moles of addition of 3 to 50 moles.

＜7＞

The liquid detergent composition for clothing described in < 6 > wherein the component (c) is a nonionic surfactant represented by the following general formula (c 1).

R^1c－O－(A’O)_m－H (c1)

[ in the formula, R^1cIs an aliphatic hydrocarbon group having 8 or more and 18 or less carbon atoms, a 'O is an alkylene oxide group selected from an alkylene oxide group having 2 or more carbon atoms and an alkylene oxide group having 3 or more carbon atoms, m is an average addition mole number of a' O, and m is a number of 3 or more, preferably 4 or more, more preferably 5 or more, further preferably 6 or more, further preferably 7 or more, and 50 or less, preferably 45 or less, more preferably 40 or less, further preferably 35 or less, further preferably 30 or less, further preferably 25 or less, further preferably 20 or less, further preferably 18 or less, further preferably 16 or less, further preferably 14 or less, further preferably 12 or less. Angle (c)

＜8＞

The liquid detergent composition for clothing of < 7 > wherein, in the general formula (c1), A' O is an alkyleneoxy group containing an ethyleneoxy group.

＜9＞

The liquid detergent composition for clothing of < 8 > wherein, in the general formula (c1), A' O is an ethyleneoxy group containing an ethyleneoxy group.

＜10＞

The liquid detergent composition for clothing as claimed in any one of < 1 > -9 > wherein the organic ammonium sulfate having 1 to 8 carbon atoms as component (d) is a compound represented by the following general formula (d1),

〔(C_nH_2n+1)_xN(C₂H₄OH)_y〕²⁺·SO₄ ^2－ (d1)

wherein n is an integer of 0 to 2 inclusive, x and y are each a number of 0 to 4 inclusive, x + y is 4, excluding the case where n is 0 and x is 4, and C_nH_2n+1When there are more than one radical, more than one C_nH_2n+1The radicals are identical or different.

＜11＞

The liquid detergent composition for clothing described in < 10 > wherein the compound represented by the general formula (d1) is at least 1 compound selected from the group consisting of monoethanol ammonium sulfate, methyl monoethanol ammonium sulfate, ethyl monoethanol ammonium sulfate, methyl diethanol ammonium sulfate, ethyl diethanol ammonium sulfate, diethanol ammonium sulfate and triethanol ammonium sulfate.

＜12＞

The liquid detergent composition for clothing as claimed in any one of < 1 > - < 11 >, wherein the inorganic sulfate (excluding calcium sulfate) as the component (d) is at least 1 inorganic sulfate selected from the group consisting of ammonium sulfate, alkali metal sulfate and alkaline earth metal sulfate excluding calcium sulfate.

＜13＞

The liquid detergent composition for clothing of < 12 > wherein the alkali metal sulfate is 1 or more selected from the group consisting of lithium sulfate, sodium sulfate and potassium sulfate, and the alkaline earth metal sulfate other than calcium sulfate is 1 or more selected from the group consisting of inorganic sulfates selected from the group consisting of magnesium sulfate.

＜14＞

The liquid detergent composition for clothing according to any one of < 1 > - < 13 >, wherein the content of the component (d) is 1.4% by mass or more, preferably 1.5% by mass or more, more preferably 1.6% by mass or more, further preferably 1.7% by mass or more, further preferably 1.8% by mass or more, further preferably 1.9% by mass or more, further preferably 2.0% by mass or more, and 7% by mass or less, preferably 6% by mass or less, more preferably 5.5% by mass or less, further preferably 4.0% by mass or less, further preferably 3.5% by mass or less in terms of sulfate ion.

＜15＞

The liquid detergent composition for clothing according to any one of < 1 > - < 14 >, wherein a polyhydric alcohol having 2 to 8 carbon atoms and two or more and six or less atoms is further contained as component (f).

＜16＞

The liquid detergent composition for clothing described in < 15 > wherein the component (f) is at least 1 compound selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, glycerin, pentaerythritol, and sugar alcohols having six or more members selected from the group consisting of five members and six members, and further is at least 1 compound selected from the group consisting of propylene glycol, glycerin, diethylene glycol, triethylene glycol, and sorbitol.

＜17＞

The liquid detergent composition for clothing of < 15 > or < 16 >, wherein the content of the component (f) is 0.2% by mass or more, preferably 0.4% by mass or more, more preferably 0.6% by mass or more, further preferably 0.8% by mass or more, and 10% by mass or less, preferably 9% by mass or less, more preferably 8% by mass or less, further preferably 7% by mass or less.

＜18＞

The liquid detergent composition for clothing according to any one of < 1 > - < 17 >, which further comprises a calcium ion donor as the component (g), wherein the content of the component (g) is 0.01% by mass or more, preferably 0.02% by mass or more, more preferably 0.03% by mass or more, and 0.15% by mass or less, preferably 0.12% by mass or less, more preferably 0.1% by mass or less in terms of calcium ions.

＜19＞

The liquid detergent composition for clothing of < 18 > wherein the component (g) is calcium chloride.

＜20＞

The liquid detergent composition for clothing according to any one of < 1 > - < 19 >, wherein the liquid detergent composition for clothing has a pH at 25 ℃ of 4 or more, preferably 4.5 or more, more preferably 5.0 or more, further preferably 5.5 or more, further preferably 6.0 or more, further preferably 6.5 or more, further preferably 7.0 or more, further preferably 7.5 or more, further preferably 8.0 or more, and 10 or less, preferably 9.8 or less, more preferably 9.5 or less, as measured by a pH meter using a glass electrode.

＜21＞

Use of the liquid detergent composition for clothing described in any one of < 1 > -to < 20 > for immersion washing.

＜22＞

A method for washing clothes, comprising the following steps 1 to 3:

step 1: mixing a liquid immersion agent containing the liquid detergent composition for clothing of any one of < 1 > -20 > and water with clothing;

Examples

< examples 1 to 19, comparative examples 1 to 6 >

Liquid detergent compositions for clothes shown in table 2 were prepared using the following components, and the obtained compositions were evaluated for detergency and enzyme activity stability by the following methods. The results are shown in table 2. Wherein the pH of the composition is adjusted using monoethanolamine or citric acid. For the measurement of pH, a pH meter using a glass electrode was used.

< formulation >

(a) Component (a) and component (b)

Cndot (a-1): sodium lauryl sulfate corresponding to component (a).

(ab-1): a surfactant mixture containing the component (a) and the component (b) in the composition of table 1; the content of component (a) and the content of component (b) in component (ab-1) were 50.3% by mass and 49.7% by mass, respectively.

(ab-2): a surfactant mixture containing the component (a) and the component (b) in the composition of table 1; the content of component (a) and the content of component (b) in component (ab-2) were 30.5% by mass and 69.5% by mass, respectively.

(ab-3): a surfactant mixture containing the component (a) and the component (b) in the composition of table 1; the content of component (a) in component (ab-3) was 19.0% by mass, and the content of component (b) was 81% by mass.

(c) Composition (I)

(c-1): in the above general formula (c1), R^1cA polyoxyethylene alkyl ether which is a mixed alkyl group of dodecyl/tetradecyl (mass ratio) 90/10, in which a' O is an ethyleneoxy group, and m is a number of 10 on average.

(c-2): in the above general formula (c1), R^1cA polyoxyethylene alkyl ether which is a mixed alkyl group of dodecyl/tetradecyl (mass ratio) 90/10, in which a' O is an ethyleneoxy group, and m is a number of 3 on average.

(c-3): in the above general formula (c1), R^1cA polyoxyethylene alkyl ether which is a mixed alkyl group of dodecyl/tetradecyl (mass ratio) 90/10, in which a' O is an ethyleneoxy group, and m is a number of 20 on average.

(d) Composition (I)

(d-1): sodium sulfate, 1 mol of sodium sulfate in the sulfate ion content of 68 mass%.

(d-2): potassium sulfate, wherein the content of sulfate ions in 1 mol of potassium sulfate is 55% by mass.

(d-3): triethanol ammonium sulfate, the content of sulfate ion in 1 mol triethanol ammonium sulfate was 35 mass%.

(d ') component (d'): (d) comparative Compound of Components

(d' -1): sodium chloride

(d' -2): sodium carbonate

(e) Composition (I)

H (e-1); savinase Ultra 16L (manufactured by Novixin Co., Ltd.)

H (e-2); alkali protease (KAP, Kao corporation)

(f) Composition (I)

(f-1): propylene glycol

(f-2): glycerol

(f-3): diethylene glycol

(f-4): triethylene glycol

(g) Composition (I)

(g-1): calcium chloride. The content of calcium ions in 1 mol of calcium chloride was 36% by mass.

< evaluation of detergency >

4 pieces (12 g in total) of AS-10 artificially contaminated cloth (cloth cut to 10 cm. times.10 cm, manufactured by Testfabrics) were put into 1L of a washing liquid obtained by mixing a liquid detergent composition for clothes and water, immersed for 30 minutes, and then washed at 100r/min for 3 minutes by a Terbot Meter (MS-8212, manufactured by Ueshima, inner diameter 12cm, height 17.5 cm). The concentration of the liquid detergent composition in the washing liquid was 0.4 mass%. The water used for the preparation of the washing solution was adjusted to 10 ℃ DH (178 mgCaCO) by adding calcium chloride to ion-exchanged water to adjust the German hardness₃Water per liter). The temperature of the washing liquid is 30 ℃, and the temperature is also maintained during the soaking process of the artificial polluted cloth. After washing, rinsing was carried out for 30 seconds in water adjusted to the same 10 ° DH.

The cleaning ability was measured by an automatic recording colorimeter (shimadzu corporation) for the reflectance at 550nm of the original cloth before the contamination and the contaminated cloth before and after the washing, and the cleaning rate (%) was determined by the following equation. The average cleaning efficiency of 4 artificially contaminated cloths is shown in the table.

The cleaning efficiency is preferably higher. In this evaluation, it can be more clearly recognized that: when the average cleaning rate is 55% or more, the detergent composition is superior to a detergent composition having a general level of cleaning power.

< evaluation of enzyme Activity stability >

After 1.0mL of 50mM boric acid buffer (pH10.5) containing 1% (w/v) casein (Hammerstein; Merck) was held at 30 ℃ for 5 minutes, 0.1mL of an enzyme solution was added and the reaction was carried out at 30 ℃ for 15 minutes. Subsequently, 2.0mL of a TCA solution (0.11M trichloroacetic acid, 0.22M sodium acetate, 0.33M acetic acid) was added as a reaction termination solution, the mixture was left at room temperature for 10 minutes, and then acid-denatured protein was removed by filtration, and the amount of an acid-soluble protein degradation product contained in the filtrate was determined by the Lowry method. That is, to 0.5mL of the filtrate was added 2.5mL of an alkaline copper solution [ a solution prepared by mixing 1% (w/v) aqueous potassium tartrate solution, 1% (w/v) aqueous copper sulfate solution, and a 0.1M aqueous sodium hydroxide solution of sodium carbonate (sodium carbonate concentration: 2% (w/v)) at 1: 100(v/v) ], and the mixture was incubated at 30 ℃ for 10 minutes, then 0.25mL of a diluted phenol reagent (a reagent prepared by diluting a phenol reagent (Kanto Kagaku Co., Ltd.) 2 times with ion-exchanged water) was added, and the mixture was incubated at 30 ℃ for 30 minutes, followed by measuring the absorbance at 660nm and determining the enzyme activity from the absorbance value. In addition, the results obtained by adding the TCA solution and leaving at room temperature for 10 minutes and then adding the enzyme solution were used as blanks.

The enzyme activity before storage and the enzyme activity after storage at 40 ℃ for 14 days were measured for the liquid detergent compositions in Table 1 by the methods described above, and the enzyme activity stability was determined by the following equation. The enzyme activity stability is preferably one having a high value, and in this evaluation, 70% or more is a practically preferable level.

Enzyme activity stability (%) (enzyme activity after storage)/(enzyme activity before storage) × 100

[ Table 1]

In Table 2, (a)/(b) is a mass ratio of [ (content of component (a) ]/[ (content of component (b) ], and (c)/[ (a) + (b) ] is a mass ratio of (content of component (c) ]/[ (content of component (a) + (content of component (b) ].

The content of component (a) and the content of component (b) shown in table 2 are values obtained by rounding off the 2 nd position after the decimal point in the total of the content based on the composition shown in table 1 and the content of component (a-1) shown in table 2. Table 2 shows the mass ratios obtained from the values.

The parenthesized numerals of the component (d) are mass% based on sulfate ions.

The mass% of the component (e) is mass% based on the amount of the enzyme protein.

The parenthesized numerals of the component (g) are% by mass of calcium ions.

These are also the same in table 3.

< test examples 1 to 4 >

Liquid detergent compositions for clothes were prepared by changing the respective compositions as shown in table 3 based on the liquid detergent compositions for clothes of comparative example 1 and examples 1, 3 and 5, and the detergency thereof was evaluated in the same manner as in example 1. The results are shown in table 3. Wherein the pH of the composition is adjusted using monoethanolamine or citric acid.

[ Table 3]

Comparative example 7 is a composition which does not contain component (d), and in which the ratio of (a)/(b), expressed by mass, of the content of component (a) to the content of component (b) in the liquid detergent composition for clothing is outside the range of the present invention. (a) The difference between the cleaning rate of the composition of comparative example 7 containing no component (d) and the cleaning rate of comparative example 1 containing component (d) and (a)/(b) which are outside the range of the present invention was 2%, and the improvement in cleaning rate by the inclusion of component (d) was low.

On the other hand, it is known that: the cleaning efficiency of examples 1, 3 and 5 containing the component (d) in each comparative example was remarkably improved compared with the compositions of comparative examples 8, 9 and 10 in which (a)/(b) was within the range of the present invention but the component (d) was not contained.

Further, it is clear from test examples 2 to 4 that: (a) the greater the amount of component (d) contained, the greater the degree of improvement in cleaning efficiency.

< blend examples 1 to 7 >

Liquid detergent compositions for clothing of formulation examples 1 to 7 in table 4 were prepared by using the formulation components used in example 1 and the like. The pH of the composition is adjusted using monoethanolamine or citric acid. The compositions of blend examples 1 to 7 are all expected to have the effects of the present invention.

It is also conceivable: among formulation examples 5 to 7, formulation example 7 was the highest in enzyme activity stability, followed by formulation example 5 and then formulation example 6. In addition, it is conceivable that: in order to further improve the effect of the component (d) on improving the detergency performance of protease against protein stains, blending examples 5 and 6 were the highest, followed by blending example 7. The blending example 6 is preferable in that the balance of the above 2 effects can be achieved.

[ Table 4]

Claims

1. A liquid detergent composition for clothing characterized by:

comprises the following components (a), (b), (c), (d) and (e) and water,

(a) the components: alkyl sulfate salts having 10 to 18 carbon atoms;

R－O－(AO)_n－SO₃M (1)

wherein R is an aliphatic hydrocarbon group having 10 to 18 carbon atoms, AO is an alkylene oxide group selected from an alkylene oxide group having 2 carbon atoms and an alkylene oxide group having 3 carbon atoms, n is an integer of 1 to 20 inclusive, and M is a cation;

(c) the components: a nonionic surfactant;

(d) the components: 1 or more sulfates selected from organic ammonium sulfates having 1 or more and 8 or less carbon atoms and inorganic sulfates other than calcium sulfate;

(e) the components: a protease,

(d) the content of the component (B) is 2-8 mass%,

2. A liquid laundry detergent composition according to claim 1, wherein:

in the general formula (1), AO is an ethyleneoxy group.

3. A liquid laundry detergent composition according to claim 1, wherein:

the total mass of the compound in which n is 1 and the compound in which n is 2 in the general formula (1) is 40 to 100 mass% of the total component (b).

4. A liquid laundry detergent composition according to claim 3, wherein:

the total mass of the compound in which n is 1 and the compound in which n is 2 in the general formula (1) is 40 to 85 mass% of the total of the components (b).

5. A liquid detergent composition for clothing according to any one of claims 1 to 3, wherein:

the proportion of the compound of the general formula (1) in which n is 6 to 20 inclusive is 10 to 0 mass% inclusive in all the components (b).

6. A liquid detergent composition for clothing according to any one of claims 1 to 3, wherein:

in the general formula (1), R is an aliphatic hydrocarbon group having 10 to 16 carbon atoms.

7. A liquid laundry detergent composition according to claim 6, wherein:

in the general formula (1), R is an alkyl group having 10 to 16 carbon atoms.

8. A liquid detergent composition for clothing according to any one of claims 1 to 3, wherein:

(a) the total content of the component (b) and the content of the component (b) is 9 to 20 mass%.

9. A liquid detergent composition for clothing according to any one of claims 1 to 3, wherein:

(a) the mass ratio of the content of component (a) to the content of component (b) is 0.5 to 5 inclusive.

10. A liquid detergent composition for clothing according to any one of claims 1 to 3, wherein:

(c) the mass ratio of the content of component (c) to the total content of the content of component (a) and the content of component (b) is 0.02 to 2 inclusive.

11. A liquid laundry detergent composition according to claim 10, wherein:

(c) the mass ratio of the content of component (c) to the total content of the content of component (a) and the content of component (b) is 0.08 to 0.4 inclusive.

12. A liquid detergent composition for clothing according to any one of claims 1 to 3, wherein:

(c) the component is nonionic surfactant with polyoxyalkylene group.

13. A liquid laundry detergent composition according to claim 12, wherein:

(c) a nonionic surfactant represented by the following general formula (c1),

R^1c－O－(A’O)_m－H (c1)

in the formula, R^1cIs an aliphatic hydrocarbon group having 8 to 18 carbon atoms, A 'O is an alkylene oxide group selected from an alkylene oxide group having 2 carbon atoms and an alkylene oxide group having 3 carbon atoms, m is the average molar number of addition of A' O, and m is a number of 3 to 50.

14. A liquid laundry detergent composition according to claim 13, wherein:

in the general formula (c1), A' O is an alkyleneoxy group containing an ethyleneoxy group.

15. A liquid laundry detergent composition according to claim 14, wherein:

in the general formula (c1), A' O is an ethyleneoxy group.

16. A liquid laundry detergent composition according to claim 13, wherein:

in the general formula (c1), m is a number of 3 to 20 inclusive.

17. A liquid laundry detergent composition according to claim 13, wherein:

in the general formula (c1), R^1cIs an aliphatic hydrocarbon group having 12 to 16 carbon atoms.

18. A liquid laundry detergent composition according to claim 13, wherein:

in the general formula (c1), R^1cThe aliphatic hydrocarbon group of (b) is an alkyl group.

19. A liquid detergent composition for clothing according to any one of claims 1 to 3, wherein:

the organic ammonium sulfate having 1 to 8 carbon atoms as the component (d) is a compound represented by the following general formula (d1),

〔(C_nH_2n+1)_xN(C₂H₄OH)_y〕²⁺·SO₄ ^2－ (d1)

in the formula: n is an integer of 0 to 2 inclusive; x and y are each a number of 0 to 4, x + y is 4, excluding the case where n is 0 and x is 4; there are a plurality of C_nH_2n+1When it is basic, a plurality of C_nH_2n+1The radicals are identical or different from one another.

20. A liquid laundry detergent composition according to claim 19, wherein:

the compound represented by the general formula (d1) is at least 1 compound selected from monoethanol ammonium sulfate, methyl monoethanol ammonium sulfate, ethyl monoethanol ammonium sulfate, methyl diethanol ammonium sulfate, ethyl diethanol ammonium sulfate, and triethanol ammonium sulfate.

21. A liquid detergent composition for clothing according to any one of claims 1 to 3, wherein:

the inorganic sulfate other than calcium sulfate as the component (d) is 1 or more inorganic sulfates selected from the group consisting of ammonium sulfate, alkali metal sulfate and alkaline earth metal sulfate other than calcium sulfate.

22. A liquid laundry detergent composition according to claim 21, wherein:

the alkali metal sulfate is 1 or more selected from lithium sulfate, sodium sulfate and potassium sulfate, and the alkaline earth metal sulfate other than calcium sulfate is 1 or more selected from magnesium sulfate.

23. A liquid detergent composition for clothing according to any one of claims 1 to 3, wherein:

the content of the component (d) is 1.4 to 7 mass% in terms of sulfate ion.

24. A liquid detergent composition for clothing according to any one of claims 1 to 3, wherein:

and a polyhydric alcohol having 2 to 8 carbon atoms and two or more and six or less carbon atoms as component (f).

25. A liquid laundry detergent composition according to claim 24, wherein:

(f) the component (A) is at least 1 compound selected from ethylene glycol, propylene glycol, diethylene glycol, glycerol, pentaerythritol and sugar alcohol with more than five elements and less than six elements.

26. A liquid laundry detergent composition according to claim 24, wherein:

(f) the content of the component (B) is 0.2-10% by mass.

27. A liquid detergent composition for clothing according to any one of claims 1 to 3, wherein:

further contains a calcium ion donor as the component (g), and the content of the component (g) is 0.01 to 0.15 mass% in terms of calcium ions.

28. A liquid laundry detergent composition according to claim 27, wherein:

the component (g) is calcium chloride.

29. A liquid detergent composition for clothing according to any one of claims 1 to 3, wherein:

the liquid detergent composition for clothing has a pH of 4 to 10 at 25 ℃ as measured by a pH meter using a glass electrode.

30. Use of the liquid detergent composition for clothing according to any one of claims 1 to 29 in a soak wash.

31. A method for washing clothes, characterized in that,

the method comprises the following steps 1-3:

step 1: mixing a liquid immersion agent containing the liquid detergent composition for clothing according to any one of claims 1 to 29 and water with clothing;

and a step 2: a step of immersing the clothes in the immersion liquid after step 1; and