JP2017071664A - Liquid detergent composition for clothing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid detergent composition for clothing excellent in detergency to stains containing proteins and excellent in stability of protease in the liquid detergent composition for clothing.SOLUTION: There is provided a liquid detergent composition for clothing containing (a) alkyl sulfate ester salt having 10 to 18 carbon atoms, (b) alkylether sulfate ester salt represented by the following general formula (1), (c) a nonionic surfactant, (d) one or more kind of sulfate selected from organic ammonium sulfate having 1 to 8 carbon atoms and inorganic sulfate, excluding calcium sulfate, (e) protease and water with total content of (a) content and (b) content of 5 mass% to 40 mass%, (d) content of 2 mass% to 8 mass% and mass ratio of [(a) content]/[(b) content] of 0.5 to 10. R-O-(AO)-SOM (1), where R is an aliphatic hydrocarbon having 10 to 18, AO is an alkylene oxy group selected from an alkylene oxy group having 2 carbon atoms and an alkylene oxy group having 3 carbon atoms, n is an integer of 1 to 20 and M is a cation.SELECTED DRAWING: None

Description

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

Consumers are particularly conscious of removing dirt on their collars and sleeves as an evaluation of their finished laundry. It is known that collar stains and sleeve stains contain protein as well as sebum. A composition containing a protease that directly degrades proteins is known as a liquid cleaning agent that improves the removal of stains on collars and sleeves.
For example, Patent Document 1 discloses a gel laundry detergent composition containing a structuring agent characterized by polyoxyalkylene alkyl ether sulfates, proteases, fatty acids, and sodium sulfate that provides excellent cleaning and desirable rheology. Has been.
Patent Document 2 contains a polyoxyethylene alkyl ether sulfate, two compounds having a specific hydrocarbon group and a polyoxyalkylene group, a water-soluble inorganic salt for increasing the viscosity, and can increase the viscosity. Liquid detergents having excellent storage stability under low temperature conditions are described. Sodium sulfate and calcium chloride are disclosed as water-soluble inorganic salts.
Patent Document 3 discloses an enzyme-containing liquid detergent that contains a polyoxyalkylene alkyl ether sulfate having 2 to 7 oxyethylene groups in the molecule, a protease, and an aminocarboxylic acid, and has excellent enzyme storage stability. A composition is disclosed.
Patent Document 4 discloses an enzyme-containing detergent containing an alkyl sulfate ester salt, a fatty acid, water, ethanol, and glycerol as solvents and having excellent enzyme stability.

Japanese Patent Laid-Open No. 2001-524591 JP 2014-62231 A JP 59-22998 JP-A-6-502197

  None of Patent Documents 1 to 4 describes a technique for further improving the stability of protease in a liquid detergent composition and the ability to clean protein soil by protease during washing.

  The present invention provides a liquid detergent composition for clothing that is excellent in detergency against soil containing protein and that is excellent in protease stability in the liquid detergent composition for clothes.

As a result of repeated studies, the present inventors have found a technique for further improving the cleaning performance of soil containing proteins by protease during cleaning.
Focusing on surfactants and inorganic salts among a wide variety of ingredients that make up liquid detergent compositions for clothing, alkyl sulfate salts and polyoxyalkylene alkyl ether sulfate salts having a specific structure are identified. It was found that when used in a mass ratio and in combination with a specific sulfate, the cleaning effect of soil containing proteins by proteases in the cleaning liquid increases.
In addition, a certain amount of a specific sulfate salt can easily dissolve in a washing solution a protein whose molecular weight has been reduced by protease degradation, so that a remarkable effect can be exhibited in removing dirt from collars and sleeves containing protein. There was found.
Further, the alkyl sulfate ester salt as the component (a) is a component that contributes to the improvement of the detergency, but has a tendency to affect the stability of the enzyme. However, in the present invention, even when such a component (a) is contained, a liquid detergent composition can be prepared by blending a specific amount of polyoxyalkylene alkyl ether sulfate ester salt, nonionic surfactant and specific sulfate salt. It was found that the stability of proteases in the product can be improved.
The present invention has been completed based on these findings.

The present invention comprises the following component (a), component (b), component (c), component (d), component (e) and water:
The total content of the content of the component (a) and the content of the component (b) is 5% by mass or more and 40% by mass or less,
(D) The content of the component is 2% by mass or more and 8% by mass or less,
The mass ratio of the content of the component (a) and the content of the component (b) is 0.5 or more and 10 or less in [(a) component content] / [(b) component content].
The present invention relates to a liquid cleaning composition for clothing.
(A) Component: Alkyl sulfate ester salt having 10 to 18 carbon atoms (b) Component: Alkyl ether sulfate salt represented by the following general formula (1) R—O— (AO) _n —SO ₃ M (1 )
[In the formula, R is an aliphatic hydrocarbon group having 10 to 18 carbon atoms, AO is an alkyleneoxy group selected from an alkyleneoxy group having 2 carbon atoms and an alkyleneoxy group having 3 carbon atoms, and n is 1 It is an integer of 20 or more and M is a cation. ]
(C) Component: Nonionic surfactant (d) Component: One or more sulfates (e) selected from organic ammonium sulfates having 1 to 8 carbon atoms and inorganic sulfates (excluding calcium sulfate) Ingredient: Protease

  The present invention also relates to the use of the liquid cleaning composition for clothing of the present invention for pickling laundry.

Moreover, this invention relates to the washing | cleaning method of the clothing containing the following processes 1-3.
Step 1: Step of mixing the above-mentioned liquid cleaning composition for clothes of the present invention and water and clothing Step 2: Step of submerging clothing in the immersion liquid after Step 1: Step 3: Step After 2, the process of stirring and washing clothes in a cleaning liquid containing a cleaning composition for clothes and water

  ADVANTAGE OF THE INVENTION According to this invention, the liquid detergent composition for clothing excellent in the detergency with respect to the soil containing a protein and excellent in the stability of protease in the liquid detergent composition for clothing can be obtained. Furthermore, the labor for stirring and washing the clothes after the clothes are immersed can be reduced by immersing the clothes in the cleaning liquid containing the liquid cleaning composition for clothes and water.

<(A) component>
The component (a) is an alkyl sulfate salt having 10 to 18 carbon atoms. The alkyl sulfate ester salt having 10 to 18 carbon atoms means an alkyl sulfate salt having an alkyl group having 10 to 18 carbon atoms.

  The component (a) has a dirt cleaning action due to its surface activity. In addition, when the component (a) is used in combination with the component (d) of the present invention, it is possible to enhance the protein soil cleaning action by the protease (e) component. In addition, it is considered that the component (a) enhances the cleaning activity of the soil containing protein by increasing the enzyme activity of the protease.

  The number of carbon atoms of the alkyl group of the component (a) is preferably 10 or more and 16 or less from the viewpoint of enhancing the enzyme activity of the protease and enhancing the cleanability of soil containing protein. That is, the component (a) is preferably an alkyl sulfate ester salt having an alkyl group having 10 to 16 carbon atoms and 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 carbon atoms in total. From the viewpoint of increasing the enzyme activity of the protease, an alkali metal salt is preferable, and a sodium salt is more preferable.

<(B) component>
The component (b) is an alkyl ether sulfate salt represented by the following general formula (1).
R—O— (AO) _n —SO ₃ M (1)
[In the formula, R is an aliphatic hydrocarbon group having 10 to 18 carbon atoms, AO is an alkyleneoxy group selected from an alkyleneoxy group having 2 carbon atoms and an alkyleneoxy group having 3 carbon atoms, and n is 1 It is an integer of 20 or more and M is a cation. ]

  In general formula (1), R is preferably a chain alkyl group. Further, R is preferably from 10 to 16 carbon atoms from the viewpoint of improving detergency. R is preferably a chain alkyl group having 10 to 16 carbon atoms.

  In General Formula (1), AO is an alkyleneoxy group selected from an alkyleneoxy group having 2 carbon atoms and an alkyleneoxy group having 3 carbon atoms. Examples of AO include one or more groups selected from an ethyleneoxy group and a propyleneoxy group. When n is an integer of 2 or more and 20 or less, AO can contain an ethyleneoxy group and a propyleneoxy group. When AO contains an ethyleneoxy group and a propyleneoxy group, either 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 is bonded to either the random type or the block type, or the random type and the block type are mixed and bonded. It may be a thing. In view of easy availability of 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 even more preferably 1 from the viewpoint of improving detergency. The liquid detergent composition for clothing of the present invention preferably contains a compound in which n in the general formula (1) is 1 or more, 3 or less, 1 or more, 2 or less, and 1 as the component (b).

  From the viewpoint of improving detergency, 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 preferably 40% by mass or more, more preferably 50% by mass in all the components (b). % Or more, more preferably 55% by weight or more, further preferably 60% by weight or more, more preferably 65% by weight or more, and 100% by weight or less, preferably 90% by weight or less, more preferably 85% by weight. It is as follows.

  In addition, in the component (b), in the general formula (1), the specific sulfate of the component (d) further improves the cleaning effect of the soil containing protein by the protease which is the component (e) of the present invention. The ratio of the compound having n of 6 to 20 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, and further 6% by mass or less. Preferably, 5% by mass or less is more preferable, 4% by mass or less is more preferable, and 3% by mass or less is more preferable. The lower limit of this ratio is 0% by mass or more. Furthermore, the lower limit of this ratio is 0 mass% or more than 0 mass%.

In the present invention, the component ratio of the compound having different n in the general formula (1) in the component (b) is different from that of the compound having different n in the compound in which the SO ₃ M group in the general formula (1) is replaced with H. A composition ratio can be adopted. For example, the area ratio obtained by analyzing the distribution of compounds with different n in the compound in which the SO ₃ M group in the general formula (1) is replaced with H is regarded as a mass fraction. Can be used as the constituent ratio of the different compounds of n in the general formula (1) in the component (b).
In addition, even when the component (b) represented by the general formula (1) is available, when it is difficult to measure the composition ratio as it is, the component (b) is acid-decomposed to form a SO ₃ M group. A compound in which is replaced with H can be generated, and the constituent ratio of the different compounds in the compound can be used as the constituent ratio of the different compounds in the general formula (1) in the component (b). In this case, specifically, the component (b) was obtained by acid decomposition to generate a compound in which the SO ₃ M group was replaced with H, and then the distribution of n in the compound was analyzed by gas chromatography. The area ratio is regarded as a mass fraction, and this can be used as a constituent ratio of the different compounds of n in the general formula (1) in the component (b).

In the case of employing the above method, an example of analysis conditions by gas chromatography and the above-mentioned acid decomposition conditions are shown below.
<Analysis conditions for gas chromatography>
GC equipment; Agilent Technologies, 7890A
Column; manufactured by Agilent Technologies, DB-5 (30 m, inner diameter 0.25 mm, film thickness 0.25 μm)
Detector; FID
Carrier; helium gas, 1 mL / min
Temperature raising condition: The temperature is raised from 100 ° C. to 325 ° C. at 5 ° C./min. Thereafter, hold at 325 ° C. for 35 minutes.
Sample pretreatment: 50 mg of a sample is placed in a 2 mL vial, 1 mL of a trimethylsilylating agent (manufactured by GL Sciences) is added and mixed, and reacted at 30 ° C. for 5 minutes.

<Conditions for acid decomposition of component (b)>
Place 4 g of sample into a 300 mL glass Erlenmeyer flask with a slit. 200 mL of 2N hydrochloric acid and zeolite were put into an Erlenmeyer flask, and an air-cooled tube with a thread was set. The Erlenmeyer flask is placed in a 140 ° C. oil bath and refluxed for 3 hours, and then cooled to 30 ° C. One drop of 1% phenolphthalein solution was added to the Erlenmeyer flask using a Pasteur pipette. Next, 35% aqueous sodium hydroxide solution is added until the contents in the Erlenmeyer flask become a light pink color.
Transfer the contents to a 1000 mL separatory funnel, add 200 mL petroleum ether and extract 3 times. The petroleum ether layer is washed with 50 mL of a 10% aqueous sodium chloride solution three times, and then 20 g of anhydrous sodium sulfate is added for dehydration. A solution obtained by removing anhydrous sodium sulfate by filtration is placed in a 500 mL triangle, and topped with petroleum ether.

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

<(C) component>
The component (c) is a nonionic surfactant. (C) It is thought that a component has the effect which improves the storage stability of the protease in the liquid cleaning composition for clothes.

As the component (c), a nonionic surfactant having a polyoxyalkylene group and a nonionic surfactant having a polyoxyalkylene group having an average addition mole number of 3 mol to 50 mol are preferable.
As the component (c), a nonionic surfactant represented by the following general formula (c1) is more preferable.
R ^1c —O— (A′O) _m —H (c1)
[In the formula, R ^1c is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, and A′O is an alkyleneoxy group selected from an alkyleneoxy group having 2 carbon atoms and an alkyleneoxy group having 3 carbon atoms. , M is the average added mole number of A′O, and is a number of 3 or more and 50 or less. ]

The number of carbon atoms of R ^{1c in} the general formula (c1) is preferably 10 or more, more preferably 12 or more, and preferably 16 or less, from the viewpoint of further improving the cleaning performance of soil including protein soil.
In addition, the carbon number of R ^{1c in} the general formula (c1) is preferably 10 or more, preferably 16 or less, and more preferably 14 or less in that the viscosity of the liquid cleaning composition for clothing of the present invention can be further reduced. preferable.
In addition, examples of the aliphatic hydrocarbon group represented by R ^{1c in} the general formula (c1) include an aliphatic hydrocarbon group selected from an alkyl group and an alkenyl group, and an alkyl group is preferable.

M in the general formula (c1) is the average number of moles added of A′O, and is preferably 4 or more, and more preferably 5 or more in that the storage stability of the protease in the liquid detergent composition for clothing can be further improved. More preferably, 6 or more is still more preferable, and 7 or more is still more preferable. M is preferably 45 or less, more preferably 40 or less, still more preferably 35 or less, still more preferably 30 or less, and even more preferably 25 or less, in view of further improving the effect of the component (d) improving the protein stain detergency with protease. Is more preferable, 20 or less is more preferable, 18 or less is more preferable, 16 or less is more preferable, 14 or less is more preferable, and 12 or less is more preferable.
A′O is an alkyleneoxy group selected from an alkyleneoxy group having 2 carbon atoms and an alkyleneoxy group having 3 carbon atoms. A′O includes, for example, one or more groups selected from an ethyleneoxy group and a propyleneoxy group. A′O is preferably an alkyleneoxy group containing an ethyleneoxy group from the viewpoint that the storage stability of the protease in the liquid detergent composition for clothing can be further improved. A′O is preferably an ethyleneoxy group.

<(D) component>
The component (d) is one or more sulfates selected from organic ammonium sulfates having 1 to 8 carbon atoms and inorganic sulfates (excluding calcium sulfate). The amount of the low molecular weight protein decomposed by the protease on the clothing and dispersed in the washing liquid from the clothing can be improved by the component (d). Moreover, 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 from the viewpoint of further improving the cleanability of protein stains by protease.
[(C _n H _{2n + 1} ) _x N (C ₂ H ₄ OH) _y ] ^{2 +} · SO ₄ ²⁻ (d1)
[In the formula, n is an integer of 0 or more and 2 or less, x and y are each a number of 0 or more and 4 or less, and x + y is 4, except when n is 0 and x is 4. When there are a plurality of C _n H _{2n + 1} groups, they may be the same or different. ]

  The organic ammonium sulfate having 1 to 8 carbon atoms is monoethanolammonium sulfate, methylmonoethanolammonium sulfate, ethylmonoethanolammonium sulfate, methyldiethanolammonium, in order to further improve the effect of cleaning protein stains by protease. One or more compounds selected from sulfate, ethyl diethanolammonium sulfate, diethanolammonium sulfate and triethanolammonium sulfate are preferred, and one or more compounds selected from monoethanolammonium sulfate and triethanolammonium sulfate are preferred. More preferred.

Inorganic sulfate (excluding calcium sulfate) is one selected from ammonium sulfate, alkali metal sulfate, and alkaline earth metal sulfate excluding calcium sulfate in order to further enhance the effect of washing protein stains by protease. The above inorganic sulfates are preferred. Examples of the alkali metal sulfate include lithium sulfate, sodium sulfate, and potassium sulfate. Examples of the alkaline earth metal sulfate excluding calcium sulfate include magnesium sulfate.
As the inorganic sulfate (excluding calcium sulfate), an alkali metal sulfate is preferred because it has a high effect of dispersing protein stains decomposed on the clothing by the protease in the washing liquid.

  As the component (d), one or more sulfates selected from anhydrides and hydrates can be used. Accordingly, the component (d) is selected from organic ammonium sulfates having 1 to 8 carbon atoms, inorganic sulfates (excluding calcium sulfate), anhydrous sulfates, and sulfate hydrates. It can be one or more sulfates.

  The component (d) is preferably one or more sulfates selected from inorganic sulfates (excluding calcium sulfate), and one selected from alkali metal sulfates and alkaline earth metal sulfates excluding calcium sulfate. The above inorganic sulfates are more preferable, and one or more inorganic sulfates selected from alkali metal sulfates are more preferable.

<(E) component>
The component (e) is a protease.
Preferred proteases include proteases that can act in neutral or alkaline aqueous solutions. A preferred protease is an alkaline protease.

Specific examples of preferable protease include (e1) alkaline protease described in WO 99/018218, preferably 70% or more of the amino acid sequence represented by SEQ ID NO: 1 or 2 of the publication is conserved. (E2) Alkaline protease described in JP-A-5-25492, preferably alkaline protease K-16 or alkaline protease K-14.
As proteases, (e3) products of Sabinase (registered trademark), Cannase (registered trademark), Everase (registered trademark), Alcalase (registered trademark), Polarzyme (registered trademark), and Esperase (registered trademark) manufactured by Novozymes (E4) FN2 (registered trademark), FN3 (registered trademark) and FN4 (registered trademark), Duplex (registered trademark), Perfect Prime (produced by DuPont) (Registered Trademark), (e5) Alkaline protease manufactured by Kao Corporation, for example, KAP4.3G (Registered Trademark), KAP11.1G (Registered Trademark), (e6) Proteases or their variants supplied under these trade names Is mentioned.
Examples of the protease include alkaline protease in which 80% or more of the amino acid sequence represented by SEQ ID NO: 1 or 2 described in International Publication No. 99/018218 is conserved, sabinase, everase, alcalase, dupon from Novozymes. More preferred are Pfect, Practical Prime, and alkaline protease manufactured by Kao Corporation.
The protease is more preferably sabinase from the viewpoint that the detergency can be further improved by combination with the component (a) or the component (b).

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

<Component (f)>
The detergent composition for clothing of the present invention can contain a polyhydric alcohol having a valence of 2 to 6 as the component (f).
Component (f) can be further combined with component (c) and component (d) to further enhance the storage stability of protease in the liquid detergent composition for clothing.

  As a preferable compound of a divalent alcohol, one or more compounds selected from ethylene glycol, propylene glycol, diethylene glycol, and triethylene glycol can be given. A preferred compound of a trivalent alcohol is glycerin. A preferred compound of a tetravalent alcohol is pentaerythritol. Preferable compounds of 5 to 6 valent alcohols include 5 to 6 valent sugar alcohols. An example of the pentavalent sugar alcohol is xylitol. Examples of the hexavalent sugar alcohol include sorbitol and mannitol. One or more compounds selected from propylene glycol, glycerin, diethylene glycol, triethylene glycol and sorbitol are preferable, and one or more compounds selected from propylene glycol, glycerin and sorbitol are preferable in that the storage stability of protease can be further improved. .

<(G) component>
The detergent composition for clothing of the present invention can contain a calcium ion donor as the component (g).
The component (g) is a compound having a property of ion dissociation in water, and is used as a protease stabilizer. The component (g) is preferably composed of an inorganic compound, and specific examples include calcium chloride.

<Composition etc. of liquid detergent composition for clothing>
The liquid detergent composition for clothes of the present invention is excellent in the cleaning power of dirt containing protein adhering to clothes by enhancing the cleaning effect of dirt containing protein due to protease. Furthermore, in the cleaning liquid prepared from the liquid cleaning composition for clothing of the present invention, the storage stability of protease is excellent.

  The content of the component (a) and the component (b) in the liquid detergent composition for clothing of the present invention is a value obtained by converting a counter ion, that is, a cation forming a salt, into sodium, that is, converted into a sodium salt. Shall be used.

In the liquid detergent composition for clothing of the present invention, the total content of the content of the component (a) and the content of the component (b) is 5% by mass or more and 40% by mass or less.
The total content of the component (a) component and the component (b) content in the liquid detergent composition for clothing of the present invention is preferably from the standpoint of further enhancing the cleanability of soil containing protein. It is 6 mass% or more, More preferably, it is 7 mass% or more, More preferably, it is 8 mass% or more, More preferably, it is 9 mass% or more. Moreover, the total content of the content of the component (a) and the content of the component (b) in the liquid detergent composition for clothing of the present invention is more stable in storage stability of the liquid detergent composition for clothing. In terms of improvement, it is preferably 35% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, and still more preferably 20% by mass or less.

Moreover, as for the liquid cleaning composition for clothes of this invention, mass ratio of content of (a) component and content of (b) component is content of (a) component / content of (b) component Thus, it is 0.5 to 10.
The mass ratio between the content of the component (a) and the content of the component (b) is such that the effect of enhancing the specific sulfate salt as the component (d) enhances the cleaning effect of the soil containing proteins by protease. The content of the component (a) / the content of the component (b) is 0.5 or more, preferably 0.55 or more, more preferably 0.6 or more, still more preferably 0.65 or more, still more preferably 0. 0.7 or more, more preferably 0.75 or more, further preferably 0.8 or more, more preferably 0.85 or more, and further preferably 0.9 or more.
The mass ratio of the content of the component (a) to the content of the component (b) is such that the storage stability of the protease in the detergent composition for clothing of the present invention is further increased. Content / (b) component content of 10 or less, preferably 9 or less, more preferably 8 or less, still more preferably 7 or less, still more preferably 6 or less, still more preferably 5 or less, still more preferably 4 or less. More preferably, it is 3 or less, more preferably 2 or less.

  In the present invention, in the preparation of the liquid detergent composition for clothing, a mixture containing the component (a) and the component (b) can be used as a supply source for the component (a) and the component (b). As such a mixture, for example, a polyoxyalkylene alkyl ether sulfate ester salt having an alkyl group having 10 to 18 carbon atoms and having a known structure and ratio of the compound can be mentioned. The polyoxyalkylene alkyl ether sulfate ester salt is generally obtained by subjecting an alkylene oxide adduct of alcohol to sulfate esterification, and is obtained as a mixture of compounds having different addition mole numbers of alkylene oxide. Therefore, it can be a mixture containing the components (a) and (b) of the present invention.

The liquid detergent composition for clothing of the present invention is characterized in that the storage stability of the protease in the liquid detergent composition for clothing is further improved and the washing property of soil containing protein is further improved. The mass ratio of the content and the total content of the component (a) and the component (b) is (c) component content / [(a) component content + (b) Component content] is preferably 0.02 or more and 2 or less.
In terms of further improving the storage stability of the protease, the mass ratio (c) component content / [(a) component content + (b) component content] is preferably 0.04 or more, and 0.06 The above is more preferable, 0.08 or more is further preferable, 0.1 or more is further preferable, and 0.12 or more is further preferable.
When the content of the component (c) in the liquid detergent composition for clothing increases, the storage stability of the protease becomes higher. However, if the storage stability becomes too high, the protease in the cleaning solution weakens the action of degrading the protein contained in the soil, and it may be difficult to obtain a protein soil cleaning effect by the protease. The mass ratio (c) component content / [(a) component content + (b) component content] is preferably 1.8 or less in view of further improving the cleaning performance of soil containing protein. .6 or less is more preferable, 1.4 or less is further preferable, 1.2 or less is further preferable, 1.0 or less is further preferable, 0.8 or less is further preferable, 0.6 or less is further preferable, 0.4 The following is more preferable.

In the liquid detergent composition for clothing of the present invention, the content of the component (d) is 2% by mass or more and 8% by mass or less.
The content of the component (d) in the liquid detergent composition for clothing of the present invention is to increase the washing rate of dirt by increasing the solubility of the protein, which has been reduced in molecular weight by the action of protease, in the washing solution. Preferably, it is 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. . It is preferably 7% by mass or less, more preferably 6% by mass or less, and still more preferably 5% by mass or less from the viewpoint of further enhancing the storage stability of the protease in the liquid detergent composition for clothing.

  In addition, 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, and still more preferably 1 as sulfate ions. .6% by weight or more, more preferably 1.7% by weight or more, more preferably 1.8% by weight or more, more preferably 1.9% by weight or more, more preferably 2.0% by weight or more, and Preferably it is 7 mass% or less, More preferably, it is 6 mass% or less, More preferably, it is 5.5 mass% or less, More preferably, it is 4.0 mass% or less, More preferably, it is 3.5 mass% or less.

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 as the amount of enzyme protein. It is at most mass%, more preferably at most 0.8 mass%, still more preferably at most 0.5 mass%.
In the present invention, the amount of enzyme protein of component (e) is determined according to the method of Lowry et al. (Lowry, OH et al., J. Biol. Chem., 193, 265 (1951)). It is expressed in terms of serum albumin (Bovine Serum Albumin, manufactured by SIGMA, product number A-7030).

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

  When the liquid cleaning composition for clothing of the present invention contains the component (g), the content of the component (g) is 0.01 mass% or more and 0.15 mass% or less in the composition as calcium ions. preferable. In terms of improving the stability of the protease, the content of the component (g) is preferably 0.02% by mass or more, more preferably 0.03% by mass or more in the composition as calcium ions. From the viewpoint of detergency, the content of the component (g) is preferably 0.12% by mass or less, more preferably 0.1% by mass or less, and still more preferably 0.1% by mass or less in the composition as calcium ions. It is 08 mass% or less.

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

In the liquid cleaning composition of the present invention, as other components, the components shown in the following (i) to (vi) can be blended in an amount that does not impair the effects of the present invention.
(I) Anti-staining agent and dispersant (i) As the component, polyacrylic acid, polymaleic acid, and claims 1-21 of JP-A-59-62614 (page 1, column 3, line 5 to page 3, 4) Column 14 line) and a recontamination preventive agent and a dispersant such as a polymer. The component (i) is preferably polyacrylic acid, polymaleic acid or a salt thereof, more preferably polyacrylic acid or a salt thereof.
The content of the component (i) in the garment cleaning composition of the present invention is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and preferably Is 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less.

(Ii) Fluorescent dye (ii) Examples of the component (ii) include fluorescent dyes commercially available as Chino Pearl CBS (trade name, manufactured by Ciba Specialty Chemicals) and Whitetex SA (trade name, manufactured by Sumitomo Chemical Co., Ltd.).

(Iii) Monovalent to trivalent alcohol having 1 to 6 carbon atoms (iii) Examples of the component include one or more alcohols selected from ethanol, ethylene glycol, propylene glycol and glycerin.
In terms of the effect of easily dispersing the liquid detergent composition for clothing of the present invention in water, the effect of suppressing the composition from separating into two or more phases during storage or the appearance becoming cloudy, etc. The content of (iii) in the composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, and preferably 15% by mass or less, more preferably 10% by mass or less, Preferably it is 5 mass% or less.

(Iv) Dyes, fragrances, antibacterial preservatives, antifoaming agents such as silicone, and pH adjusters.

(V) Surfactants other than the components (a), (b) and (c).
As the surfactant (v), for example, a surfactant selected from fatty acids having 10 to 18 carbon atoms or salts thereof can be contained. However, in order to maintain the high detergency of the present invention, the content of the fatty acid having 10 to 18 carbon atoms or a salt thereof is the total content of the component (a), the component (b) and the component (c). On the other hand, it is preferably 10% by mass or less, more preferably 8% by mass or less, and still more preferably 5% by mass or less. A lower limit is 0 mass% or more than 0 mass%.
The content of the fatty acid salt is calculated by the mass obtained by replacing the cation as a counter ion with a hydrogen ion, that is, the mass converted to an acid type compound.
Further, as the surfactant (v), an amine oxide having one alkyl group having 10 to 16 carbon atoms can be contained. Specifically, an amine oxide having one alkyl group having 10 to 16 carbon atoms and two groups selected from an alkyl group having 1 to 3 carbon atoms and a hydroxyalkyl group having 1 to 3 carbon atoms is given. It is done.

  The liquid detergent composition for clothing described above is suitable for use in a liquid detergent for clothing.

<How to wash clothes>
The liquid detergent composition for clothing of the present invention is suitable for use in pickling laundry. The liquid detergent composition for clothes of the present invention is suitably used for soaking and washing as a washing liquid mixed with water. In the present invention, the soaking and laundering means a washing method in which clothes are soaked in a washing solution for a certain period of time. Preferably, in pickling washing, after being soaked in the cleaning liquid for a certain period of time, the clothes and the cleaning liquid are mixed and washed by stirring manually or by mechanical force such as a washing machine. In addition, after being immersed in a cleaning solution for a certain period of time, an operation of rubbing clothing using a tool such as a brush is performed.
Specifically, the washing | cleaning method of clothing including the following processes 1-3 is mentioned.
Step 1: A liquid cleaning composition for clothing of the present invention and a dipping solution containing water and a clothing are mixed Step 2: A step after Step 1 in which clothing is immersed in the dipping solution Step 3: Step 2 After, the step of stirring and washing the clothes in a cleaning solution containing a cleaning composition for clothes and water

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

  The water used in step 1 can be water having a German hardness of 1 ° DH to 30 ° DH. German hardness is 1 ° DH or higher, 3 ° DH or higher, 5 ° DH or higher, 6 ° DH or higher, 8 ° or higher due to the fact that it can realize the effect of excellent cleaning performance of soil containing protein. Water of DH or higher, further 9 ° DH or higher, and further 10 ° DH or higher can be used. From the viewpoints of foaming properties during washing and foam persistence, water having a German hardness of 30 ° DH or less, further 25 ° DH or less, and further 20 ° DH or less can be used. Hardness represents the total hardness determined by chelate titration method using ethylenediaminetetraacetic acid disodium salt.

  In step 1, the ratio (hereinafter referred to as bath ratio) of the volume (liter) of the immersion liquid obtained by mixing the liquid cleaning composition for clothing of the present invention and water and the mass (kg) of the clothing is as follows. From the viewpoint of ease of washing at the time of hand washing, [capacity of washing liquid (liter)] / [mass of clothing (kg)] is preferably 1 or more, more preferably 2 or more, and further preferably 3 or more, 5 or more is more preferable. 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, an immersion liquid obtained by previously mixing water and the liquid cleaning composition for clothing of the present invention may be mixed with clothing. Moreover, you may mix the water containing the clothing which mixed clothing and water, and the liquid cleaning composition for clothing of this invention. At this time, the immersion liquid is formed by mixing water containing clothing and the liquid cleaning composition for clothing of the present invention. Moreover, you may mix clothing, water, and the liquid cleaning composition for clothing of this invention simultaneously. At this time, an immersion liquid is formed by mixing water and the liquid cleaning composition for clothing of the present invention.

Step 2 is a step of immersing clothing in the immersion liquid after Step 1 described above.
In the cleaning method of the present invention, the time for immersing the clothes is preferably 10 minutes or more, more preferably 20 minutes or more, from the viewpoint of the ability to clean the soil containing protein, or from the viewpoint of reducing the labor required for Step 3 described later. . 120 minutes or less are preferable and 60 minutes or less are more preferable in terms of shortening the time required for washing. In the present invention, the time for immersing the clothes is the time when the liquid cleaning composition for clothes of the present invention, water, and clothes are mixed in a mass necessary for one washing, and stirring and washing in step 3 is started. Say time to.

Step 3 is a step of stirring and washing the garment after the step 2 in a washing liquid containing a garment cleaning composition and water. The stirring cleaning means that the clothes and the cleaning liquid are stirred manually or mechanically such as a washing machine to wash the clothes. Washing and washing clothes and cleaning solution manually is to wash the clothing in the cleaning solution, wash the clothing by rubbing the clothing containing the cleaning solution together, and rub the clothing containing the cleaning solution with a tool such as a brush. It means washing the clothes by washing the clothes and the clothes by manually rotating and reciprocating the clothes to wash the clothes, and manually compressing the clothes in the washing liquid a plurality of times.
The garment cleaning composition used in step 3 may be the garment liquid cleaning composition of the present invention. Moreover, the cleaning composition for clothing used in Step 3 may be a cleaning composition for clothing that is different from the liquid cleaning composition for clothing of the present invention. The liquid cleaning composition for clothing of the present invention is preferable as the clothing cleaning composition used in Step 3 in that it further enhances the cleaning action of the soil including protein soil caused by protease.

More specific embodiments of the present invention are shown below. The matters regarding the liquid cleaning composition for clothing and the method for washing the clothing described above can be appropriately applied to these embodiments.
<1>
Contains the following (a) component, (b) component, (c) component, (d) component, (e) component and water,
The total content of component (a) and component (b) is 5% by mass or more, preferably 6% by mass or more, more preferably 7% by mass or more, and still more preferably 8% by mass or more. More preferably, it is 9% by mass or more and 40% by mass or less, preferably 35% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, and further preferably 20% by mass or less.
The content of the component (d) is 2% by mass or more, preferably 2.2% by mass or more, more preferably 2.4% by mass or more, still more preferably 2.6% by mass or more, and further preferably 2.8% by mass. Or more, more 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, still more preferably 5% by mass or less,
The mass ratio of the content of the component (a) and the content of the component (b) is 0.5 or more, preferably 0.00 in terms of the content of the component (a) / the content of the component (b). 55 or more, more preferably 0.6 or more, still more preferably 0.65 or more, still more preferably 0.7 or more, still more preferably 0.75 or more, still more preferably 0.8 or more, still more preferably 0.85 or more. More preferably, it is 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, still more preferably 4 or less, further Preferably it is 3 or less, more preferably 2 or less,
Liquid detergent composition for clothing.
(A) Component: Alkyl sulfate ester salt having 10 to 18 carbon atoms (b) Component: Alkyl ether sulfate salt represented by the following general formula (1) R—O— (AO) _n —SO ₃ M (1 )
[In the formula, R is an aliphatic hydrocarbon group having 10 to 18 carbon atoms, AO is an alkyleneoxy group selected from an alkyleneoxy group having 2 carbon atoms and an alkyleneoxy group having 3 carbon atoms, and n is 1 It is an integer of 20 or more and M is a cation. ]
(C) Component: Nonionic surfactant (d) Component: One or more sulfates (e) selected from organic ammonium sulfates having 1 to 8 carbon atoms and inorganic sulfates (excluding calcium sulfate) Ingredient: Protease

<2>
The liquid detergent composition for clothes according to <1>, wherein in the alkyl ether sulfate salt represented by the general formula (1), AO is an ethyleneoxy group.

<3>
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 in all the components (b). More preferably, it is 60% by mass or more, more 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, described in <1> or <2>. Liquid detergent composition for clothing.

<4>
In the general formula (1), the ratio of the compound in which n is 6 or more and 20 or less is 10% by mass or less, preferably 9% by mass or less, more preferably 8% by mass or less, and still more preferably in all the components (b). 7% by mass or less, more preferably 6% by mass or less, further preferably 5% by mass or less, more preferably 4% by mass or less, still more preferably 3% by mass or less, and 0% by mass or more or more than 0% by mass. Or the liquid detergent composition for clothes of any one of <1>-<3> which is 0 mass%.

<5>
The mass ratio of the content of (c) component and the total content of (a) component and (b) component is (c) component content / [(a) component content Amount + content of component (b)] is 0.02 or more, 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, and 2 or less, preferably 1.8 or less, more preferably 1.6 or less, further preferably 1.4 or less, still more preferably 1.2 or less, still more preferably 1.0 or less, The liquid detergent composition for clothing according to any one of <1> to <4>, preferably 0.8 or less, more preferably 0.6 or less, and still more preferably 0.4 or less.

<6>
<1> to <5, wherein the component (c) is a nonionic surfactant having a polyoxyalkylene group, and further a nonionic surfactant having a polyoxyalkylene group having an average addition mole number of 3 to 50 mol. > The liquid cleaning composition for clothes of any one of>.

<7>
(C) The liquid cleaning composition for clothes according to <6>, wherein the component is a nonionic surfactant represented by the following general formula (c1).
R ^1c —O— (A′O) _m —H (c1)
[In the formula, R ^1c is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, and A′O is an alkyleneoxy group selected from an alkyleneoxy group having 2 carbon atoms and an alkyleneoxy group having 3 carbon atoms. , M is the average added mole number of A′O, 3 or more, preferably 4 or more, more preferably 5 or more, still more preferably 6 or more, still more preferably 7 or more, and 50 or less, preferably 45 or less. More preferably, it is 40 or less, More preferably, it is 35 or less, More preferably, it is 30 or less, More preferably, it is 25 or less, More preferably, it is 20 or less, More preferably, it is 18 or less, More preferably, it is 16 or less. The number is preferably 12 or less. ]

<8>
The liquid detergent composition for clothing according to <7>, wherein in the general formula (c1), A′O is an alkyleneoxy group containing an ethyleneoxy group.

<9>
The liquid detergent composition for clothing according to <8>, wherein in the general formula (c1), A′O is an ethyleneoxy group containing an ethyleneoxy group.

<10>
(D) The organic ammonium sulfate having 1 to 8 carbon atoms, which is a component, is a compound represented by the following general formula (d1), for clothing according to any one of <1> to <9> Liquid detergent composition.
[(C _n H _{2n + 1} ) _x N (C ₂ H ₄ OH) _y ] ^{2 +} · SO ₄ ²⁻ (d1)
[In the formula, n is an integer of 0 or more and 2 or less, x and y are each a number of 0 or more and 4 or less, and x + y is 4, except when n is 0 and x is 4. When there are a plurality of C _n H _{2n + 1} groups, they may be the same or different. ]

<11>
The compound represented by the general formula (d1) is monoethanol ammonium sulfate, methyl monoethanol ammonium sulfate, ethyl monoethanol ammonium sulfate, methyl diethanol ammonium sulfate, ethyl diethanol ammonium sulfate, diethanol ammonium sulfate, and The liquid detergent composition for clothes according to <10>, which is one or more compounds selected from triethanolammonium sulfate.

<12>
(D) The component inorganic sulfate (excluding calcium sulfate) is one or more inorganic sulfates selected from ammonium sulfate, alkali metal sulfate, and alkaline earth metal sulfate excluding calcium sulfate. The liquid cleaning composition for clothing according to any one of <1> to <11>.

<13>
The alkali metal sulfate is at least one selected from lithium sulfate, sodium sulfate and potassium sulfate, and the alkaline earth metal sulfate excluding calcium sulfate is at least one inorganic sulfate selected from magnesium sulfate. <12> The liquid cleaning composition for clothes according to <12>.

<14>
The content of the component (d) as sulfate ions is 1.4% by mass or more, preferably 1.5% by mass or more, more preferably 1.6% by mass or more, still more preferably 1.7% by mass or more, Preferably 1.8% by mass or more, more 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, more preferably 4.0% by mass or less, and further preferably 3.5% by mass or less, the liquid detergent composition for clothes according to any one of <1> to <13>.

<15>
The liquid detergent composition for clothing according to any one of <1> to <14>, further comprising, as component (f), a polyhydric alcohol having 2 to 8 carbon atoms and having 2 to 8 carbon atoms. .

<16>
(F) The component is one or more compounds selected from ethylene glycol, propylene glycol, diethylene glycol, glycerin, pentaerythritol, and sugar alcohols having a valence of 5 to 6. In addition, propylene glycol, glycerin, diethylene glycol, triethylene glycol And a liquid detergent composition for clothes according to <15>, which is at least one compound selected from sorbitol and sorbitol.

<17>
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, still more preferably 0.8% by mass or more, and 10% by mass. The liquid detergent composition for clothing according to <15> or <16>, preferably 9% by mass or less, more preferably 8% by mass or less, and still more preferably 7% by mass or less.

<18>
Further, as component (g), a calcium ion donor is contained, and the content of component (g) is 0.01% by mass or more, preferably 0.02% by mass or more, more preferably 0.03% as calcium ions. The clothing according to any one of <1> to <17>, which is not less than mass% and not more than 0.15 mass%, preferably not more than 0.12 mass%, more preferably not more than 0.1 mass%. Liquid detergent composition.

<19>
The liquid cleaning composition for clothes according to <18>, wherein the component (g) is calcium chloride.

<20>
The pH of the liquid detergent composition for use at 25 ° C. measured with a pH meter using a glass electrode is 4 or more, preferably 4.5 or more, more preferably 5.0 or more, and still more preferably 5 0.5 or more, more preferably 6.0 or more, more preferably 6.5 or more, more preferably 7.0 or more, more preferably 7.5 or more, more preferably 8.0 or more, and 10 or less, preferably Is a liquid detergent composition for clothing according to any one of <1> to <19>, which is 9.8 or less, more preferably 9.5 or less.

<21>
Use of the liquid cleaning composition for clothing according to any one of <1> to <20> for pickling and washing.

<22>
The washing | cleaning method of the clothing containing the following processes 1-3.
Step 1: Mixing the liquid cleaning composition for clothing according to any one of <1> to <20> and an immersion liquid containing water, and Step 2: Step 1 after the immersion Step 3 of immersing clothing in liquid Step 3: Step of stirring and washing clothing in a cleaning solution containing a cleaning composition for clothing and water after Step 2

<Examples 1-19, Comparative Examples 1-6>
A liquid detergent composition for clothing shown in Table 2 was prepared using the following components, and the cleaning power and enzyme activity stability were evaluated by the following methods using the obtained composition. The results are shown in Table 2. The pH of the composition was adjusted with monoethanolamine or citric acid. A pH meter using a glass electrode was used for pH measurement.

<Blending ingredients>
(A) component and (b) component. (A-1): Sodium lauryl sulfate ester, corresponding to component (a).
(Ab-1): A surfactant mixture containing the components (a) and (b) in the composition shown in Table 1, and the content of the component (a) in (ab-1) is 50.3% by mass. Yes, the content of component (b) is 49.7% by mass
(Ab-2): A surfactant mixture containing the components (a) and (b) in the composition shown in Table 1, and the content of the component (a) in (ab-2) is 30.5% by mass. Yes, the content of component (b) is 69.5% by mass
(Ab-3): Surfactant mixture containing the components (a) and (b) in the composition shown in Table 1, and the content of the component (a) in (ab-3) is 19.0% by mass. Yes, content of component (b) is 81% by mass

(C) Component / (c-1): In the general formula (c1), R ^1c is a mixed alkyl group of lauryl group / myristyl group = 90/10 (mass ratio), and A′O is an ethyleneoxy group. And m is an average number of 10, polyoxyethylene alkyl ether. (C-2): In the general formula (c1), R ^1c is lauryl group / myristyl group = 90/10 (mass ratio). A mixed alkyl group, A′O is an ethyleneoxy group, and m is an average number of 3. Polyoxyethylene alkyl ether (c-3): In the general formula (c1), R ^1c is Polyoxyethylene alkyl ether in which lauryl group / myristyl group = 90/10 (mass ratio), mixed alkyl group, A′O is ethyleneoxy group, and m is an average of 20

(D) Component / (d-1): Sodium sulfate. The content of sulfate ions in 1 mol of sodium sulfate is 68% by mass.
-(D-2): Potassium sulfate. The content of sulfate ions in 1 mol of potassium sulfate is 55% by mass.
(D-3): The content of sulfate ion in 1 mol of triethanolammonium sulfate and triethanolammonium sulfate is 35% by mass.

(D ′) component: Comparative compound of component (d) (d′-1): sodium chloride (d′-2): sodium carbonate

(E) Component / (e-1); Sabinase Ultra 16L (manufactured by Novozyme)
(E-2); alkaline protease (KAP, manufactured by Kao Corporation)

(F) Ingredients (f-1): Propylene glycol (f-2): Glycerin (f-3): Diethylene glycol (f-4): Triethylene glycol

(G) component * (g-1): Calcium chloride. The content of calcium ions in 1 mol of calcium chloride is 36% by mass.

<Evaluation of cleaning power>
After putting 4 sheets of AS-10 artificially contaminated cloth (made by Testfabrics, cut into 10 cm × 10 cm) (12 g in total) into 1 L of a cleaning liquid obtained by mixing a liquid cleaning composition for clothing and water, Washing was performed at 100 r / min for 3 minutes with a targotometer (MS-8212 manufactured by Ueshima Co., Ltd., inner diameter 12 cm, height 17.5 cm). The concentration of the liquid detergent composition in the cleaning liquid was 0.4% by mass. The water used for the preparation of the cleaning liquid was water in which calcium chloride was added to ion-exchanged water and the German hardness was adjusted to 10 ° DH (178 mg CaCO ₃ / L). The water temperature of the cleaning liquid was 30 ° C., and this temperature was maintained during the immersion of the artificially contaminated cloth. After washing, rinsing was performed for 30 seconds with water adjusted to 10 ° DH.

The detergency was determined by measuring the reflectance at 550 nm of the raw cloth before contamination and the contaminated cloth before and after washing with a self-recording colorimeter (Shimadzu Corporation), and obtaining the washing rate (%) by the following formula. The table shows the average value of the washing rate of the four artificially contaminated cloths.
A higher cleaning rate is preferred. In this evaluation, it can be recognized more clearly that the average value of the cleaning rate is 55% or more, which is superior to a cleaning composition having a cleaning power at a general level.

<Evaluation of enzyme activity stability>
After holding 1.0 mL of 50 mM borate buffer (pH 10.5) containing 1% (w / v) casein (Hammerstein; manufactured by Merck) for 5 minutes at 30 ° C., 0.1 mL of the enzyme solution was added. The mixture was added and reacted at 30 ° C. for 15 minutes. Next, 2.0 mL of a TCA solution (0.11 M trichloroacetic acid, 0.22 M sodium acetate, 0.33 M acetic acid), which is a reaction stop solution, is added and left at room temperature for 10 minutes, and then the acid-denatured protein is removed by filtration. The acid-soluble proteolysate contained in the filtrate was quantified by the Raleigh method. That is, to 0.5 mL of the filtrate, 2.5 mL of an alkaline copper solution [1% (w / v) potassium sodium tartrate aqueous solution, 1% (w / v) copper sulfate aqueous solution, sodium carbonate 0.1 M sodium hydroxide aqueous solution After adding a lysate (sodium carbonate concentration 2% (w / v) mixed at 1: 1: 100 (v / v)) and incubating at 30 ° C. for 10 minutes, 0.25 mL of diluted phenol reagent ( Phenol reagent (Kanto Chemical Co., Ltd. diluted twice with ion-exchanged water) was further added, and the mixture was kept at 30 ° C. for 30 minutes. Then, the absorbance at 660 nm was measured, and the enzyme activity was determined from the absorbance value. The result of adding the enzyme solution after adding the TCA solution and allowing to stand at room temperature for 10 minutes was used as a blank.
For the liquid detergent composition of Table 1, the enzyme activity before storage and the enzyme activity after 14 days of storage at 40 ° C. were measured by the above methods, and the enzyme activity stability was determined by the following equation. The enzyme activity stability is preferably as high as possible. In this evaluation, 70% or more is a practically preferred level.
Enzyme activity stability (%) = (enzyme activity after storage) / (enzyme activity before storage) × 100

In Table 2, (a) / (b) is a mass ratio of [content of (a) component] / [content of (b) component], and (c) / [(a) + (b) ] Is a mass ratio of (c) component content / [(a) component content + (b) component content].
The content of the component (a) and the content of the component (b) in Table 2 are 2 after the decimal point in the sum of the content based on the composition in Table 1 and the content in (a-1) in Table 2. The value rounded to the first digit is shown. Moreover, in Table 2, each mass ratio calculated | required from the value is shown.
The number in parentheses of the component (d) is mass% as sulfate ion.
Further, the mass% of the component (e) is mass% as the amount of enzyme protein.
The number in parentheses of the component (g) is mass% as calcium ions.
These are the same in Table 3.

<Test Examples 1 to 4>
With reference to the liquid detergent composition for clothing of Comparative Example 1 and Examples 1, 3, and 5, a liquid detergent composition for clothing having respective compositions changed as shown in Table 3 was prepared. Similarly, the cleaning power was evaluated. The results are shown in Table 3. The pH of the composition was adjusted with monoethanolamine or citric acid.

Comparative Examples 7 and 8 do not contain the component (d), and are represented by a mass ratio between the content of the component (a) and the content of the component (b) in the liquid cleaning composition for clothing. (A) / (b) is a composition outside the scope of the present invention. Although (a) / (b) is outside the scope of the present invention and (d) the cleaning rate of the composition of Comparative Example 8 not containing the component, (a) / (b) is outside the scope of the present invention. The difference in the cleaning rate from the cleaning rate of Comparative Example 7 containing the component (d) is about 4%, and the improvement in the cleaning rate due to the inclusion of the component (d) is low.
On the other hand, although (a) / (b) is within the scope of the present invention, the composition of Comparative Examples 8, 9, and 10 that does not contain the component (d), the component (d) is added to each comparative example. It turns out that the washing | cleaning rate of Example 1, 3, 5 to contain improves dramatically.
Moreover, it turns out from Test Examples 2-4 that the improvement degree of the washing | cleaning rate by containing (d) component is so large that (a) / (b) is large.

<Formulation Examples 1-7>
Using the blending components used in Example 1 and the like, liquid detergent compositions for clothing of Formulation Examples 1 to 7 in Table 4 were prepared. The pH of the composition was adjusted with monoethanolamine or citric acid. All of the compositions of Formulation Examples 1 to 7 are considered to have the effects of the present invention.
In addition, in Formulation Examples 5 to 7, the enzyme activity stability is highest in Formulation Example 7, followed by Formulation Example 5, and then considered as Formulation Example 6. In terms of further improving the effect of the component (d) to improve the protein stain detergency with protease, Formulation Examples 5 and 6 are the highest, followed by Formulation Example 7. Formulation Example 6 is preferable in that the above two effects are balanced.

Claims (10)

Contains the following (a) component, (b) component, (c) component, (d) component, (e) component and water,
The total content of the content of the component (a) and the content of the component (b) is 5% by mass or more and 40% by mass or less,
(D) The content of the component is 2% by mass or more and 8% by mass or less,
The mass ratio of the content of the component (a) and the content of the component (b) is 0.5 or more and 10 or less in [(a) component content] / [(b) component content].
Liquid detergent composition for clothing.
(A) Component: Alkyl sulfate ester salt having 10 to 18 carbon atoms (b) Component: Alkyl ether sulfate salt represented by the following general formula (1) R—O— (AO) _n —SO ₃ M (1 )
[In the formula, R is an aliphatic hydrocarbon group having 10 to 18 carbon atoms, AO is an alkyleneoxy group selected from an alkyleneoxy group having 2 carbon atoms and an alkyleneoxy group having 3 carbon atoms, and n is 1 It is an integer of 20 or more and M is a cation. ]
(C) Component: Nonionic surfactant (d) Component: One or more sulfates (e) selected from organic ammonium sulfates having 1 to 8 carbon atoms and inorganic sulfates (excluding calcium sulfate) Ingredient: Protease   The mass ratio of the content of (c) component and the total content of (a) component and (b) component is (c) component content / [(a) component content The liquid detergent composition for clothing according to claim 1, which is 0.02 or more and 2 or less in terms of “amount + content of component (b)”. The liquid detergent composition for clothes according to claim 1 or 2, 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 _n H _{2n + 1} ) _x N (C ₂ H ₄ OH) _y ] ^{2 +} · SO ₄ ²⁻ (d1)
[In the formula, n is an integer of 0 or more and 2 or less, x and y are each a number of 0 or more and 4 or less, and x + y is 4, except when n is 0 and x is 4. When there are a plurality of C _n H _{2n + 1} groups, they may be the same or different. ]   (D) The component inorganic sulfate (excluding calcium sulfate) is one or more inorganic sulfates selected from ammonium sulfate, alkali metal sulfate, and alkaline earth metal sulfate excluding calcium sulfate. The liquid cleaning composition for clothes according to any one of claims 1 to 3.   (D) The liquid cleaning composition for clothing in any one of Claims 1-4 whose content of a component is 1.4 to 7 mass% as a sulfate ion.   Furthermore, the liquid cleaning composition for clothes in any one of Claims 1-5 containing the polyhydric alcohol of 2 to 8 carbon atoms having 2 to 8 carbon atoms as the component (f).   Furthermore, calcium ion donor is contained as (g) component, and content of (g) component is 0.01 mass% or more and 0.15 mass% or less as calcium ion, Any of Claims 1-6 A liquid detergent composition for clothing according to claim 1.   The liquid detergent composition for clothing according to any one of claims 1 to 7, wherein the component (c) is a nonionic surfactant having a polyoxyalkylene group having an average addition mole number of 3 to 50 moles.   Use of the liquid cleaning composition for clothing according to any one of claims 1 to 8 for pickling washing. The washing | cleaning method of the clothing containing the following processes 1-3.
Step 1: Mixing the liquid cleaning composition for clothing according to any one of claims 1 to 8 and a dipping solution containing water, and a step Step 2: After step 1, the dipping solution is added to the dipping solution. Step 3 for soaking clothes: Step after step 2, washing and stirring clothes in a cleaning solution containing a cleaning composition for clothes and water