JP7149838B2 - Liquid dish detergent composition and method for cleaning dishes - Google Patents

Description

TECHNICAL FIELD The present invention relates to a dishwashing liquid detergent composition and a dishwashing method.

There are a non-immersion method and an immersion method for washing tableware and cooking utensils (hereinafter sometimes referred to generally as tableware), which are kitchen utensils. The non-immersion method is a method in which a cleaning tool such as a sponge is applied with a liquid dishwashing detergent composition, and the object to be cleaned is rubbed with the cleaning tool. The immersion method is a method in which a dishwashing liquid detergent composition is dispersed in water to form a cleaning liquid, an object to be cleaned is immersed in this cleaning liquid, and then the object to be cleaned is rinsed. In the immersion method, the object to be cleaned may be rubbed with a cleaning tool in the cleaning liquid.

In both the immersion method and the non-immersion method, liquid dishwashing detergent compositions are required to have excellent detergency.
For example, Patent Document 1 discloses a dishwashing detergent containing a specific nonionic surfactant, a specific anionic surfactant, and at least one selected from semipolar surfactants and amphoteric surfactants in a specific ratio. Liquid detergents have been proposed. According to the invention of Patent Literature 1, an improvement in detergency against oil stains is achieved.
Further, Patent Document 2 describes a compound having a specific branched alkyl group, a specific anionic surfactant, and a surfactant selected from an amine oxide surfactant, an amphoteric surfactant and an alkanolamide surfactant. A liquid detergent composition has been proposed that contains specific ratios of an agent, an enzyme, and an enzyme stabilizer. According to the invention of Patent Document 2, the detergency in soaking and washing is improved.
Alternatively, Patent Document 3 proposes a liquid detergent composition containing specific amounts of a dialkyl sulfosuccinate, a linear amine oxide, and an alkyl or hydroxyalkyl sulfate or sulfonate. According to the invention of Patent Document 3, an improvement in detergency against oil stains at low temperature is achieved.

JP-A-2016-8276 JP-A-2005-325281 Japanese Patent Publication No. 2008-507611

However, conventional techniques are still unsatisfactory in detergency against strong stains such as complexes of oil, protein and starch. In addition, liquid dishwashing detergent compositions are required to foam rapidly and sustainably, and to leave no foam in drains (good defoaming properties).
Accordingly, an object of the present invention is to provide a liquid dishwashing detergent composition that has high detergency and excellent antifoaming properties.

［式中、Ｒ^１とＲ^２は、独立して、炭素数１～８のアルキル基であり、Ｒ^１とＲ^２との合計炭素数は、６～１６であり、Ｒ^３は、水素を表す。ＰＯはプロピレンオキシ基を表す。ＥＯはエチレンオキシ基を表す。ｐは、ＰＯの平均繰り返し数を表し、ｑは、ＥＯの平均繰り返し数を表し、ｐ＋ｑは０～１０である。Ｍは、対イオンであり、アルカリ金属、アルカリ土類金属、アルカノールアンモニウムから選ばれる１種である。］
［２］前記（ａ１）成分／前記（Ａ）成分で表される質量比は、０．０５～１である、［１］に記載の食器用液体洗浄剤組成物。
［３］前記（ａ１）成分／（前記（Ｃ）成分＋前記（Ｄ）成分）で表される質量比は、０．４～１６５である、［１］又は［２］に記載の食器用液体洗浄剤組成物。
［４］前記（Ｃ）成分／前記（Ｄ）成分で表される質量比は、０．２～２０である、［１］～［３］のいずれかに記載の食器用液体洗浄剤組成物。
［５］（Ｅ）成分：下記（ｅ１）式で表される化合物をさらに含有する、［１］～［４］のいずれかに記載の食器用液体洗浄剤組成物。

［６］前記（Ｅ）成分／（前記（Ａ）成分＋前記（Ｂ）成分）で表される質量比は、０．０１～５である、［５］に記載の食器用液体洗浄剤組成物。 The present invention has the following aspects.
[1] Component (A): an anionic surfactant containing at least one component (a1) selected from secondary alkanesulfonates, dialkylsulfosuccinates and compounds represented by the following formula (a1-1); ,
(B) component: an amine oxide surfactant;
(C) component: protease and
(D) component: amylase;
contains
A dishwashing liquid detergent composition, wherein the mass ratio represented by component (A)/component (B) is 0.7 to 2.

[In the formula, R ¹ and R ² are independently alkyl groups having 1 to 8 carbon atoms, the total number of carbon atoms of R ¹ and R ² is 6 to 16, and R ³ is hydrogen. show. PO represents a propyleneoxy group. EO represents an ethyleneoxy group. p represents the average repeating number of PO, q represents the average repeating number of EO, and p+q is 0-10. M is a counterion and is one selected from alkali metals, alkaline earth metals and alkanolammonium. ]
[2] The liquid dishwashing detergent composition according to [1], wherein the mass ratio represented by component (a1)/component (A) is 0.05 to 1.
[3] The tableware according to [1] or [2], wherein the mass ratio represented by component (a1)/(component (C) + component (D)) is 0.4 to 165. Liquid detergent composition.
[4] The liquid dishwashing detergent composition according to any one of [1] to [3], wherein the mass ratio represented by component (C)/component (D) is 0.2 to 20. .
[5] Component (E): The liquid dishwashing detergent composition according to any one of [1] to [4], further comprising a compound represented by the following formula (e1).

[6] The liquid dishwashing detergent composition according to [5], wherein the mass ratio represented by component (E)/(component (A) + component (B)) is 0.01 to 5. thing.

[7] The mass ratio represented by (the (a1) component + the (C) component + the (D) component)/(the (A) component + the (B) component + the (E) component) is The liquid dishwashing detergent composition according to [5] or [6], which is 0.03 to 1.
[8] The (A) component contains the (a2) component other than the (a1) component, and the (a2) component/(the (a1) component + the (C) component + the (D) component) The liquid dishwashing detergent composition according to any one of [1] to [7], wherein the mass ratio represented by is 0.1 to 10.

[9] After immersing the tableware in a cleaning liquid containing 0.01 to 50% by mass of the liquid detergent composition according to any one of [1] to [8] for 5 minutes to 10 hours, the tableware is washed with a cleaning tool. A method for washing tableware, comprising removing the tableware from the washing liquid with or without rubbing, and rinsing the removed tableware with purified water.

According to the dishwashing detergent composition of the present invention, it is possible to improve detergency and antifoaming properties.

(Dishwashing Liquid Detergent Composition)
The liquid dishwashing detergent composition of the present invention (hereinafter sometimes simply referred to as "liquid detergent composition") is a composition containing the following components (A) to (D).
Component (A): an anionic surfactant containing component (a1) at least one selected from secondary alkanesulfonates, dialkylsulfosuccinates and polyoxyethylene garbet-type alkyl ester sulfates.
(B) component: amine oxide type surfactant.
(C) Component: Protease.
(D) Component: amylase.

The liquid detergent composition is a so-called hand washing liquid detergent.
The pH (25° C.) of the liquid detergent composition is preferably 6-9, more preferably 6-8.
The pH (25°C) of the liquid detergent composition is a value measured by a method based on JIS Z8802-2011 using a pH meter.

The viscosity (25° C.) of the liquid detergent composition is preferably, for example, 10-2000 mPa. The viscosity of the liquid detergent composition is a value measured under the following conditions using a Brookfield viscometer.
≪Measurement conditions≫
· Rotor: No. 3 rotor (for less than 1000 mPa·s) or No. 4 rotor (for 1000 mPa·s or more).
- Rotation speed: 60 rpm.
- Measurement temperature: 25°C.
• Viscosity reading: 30 seconds after the rotor starts rotating.

<(A) component: anionic surfactant>
Component (A) is an anionic surfactant and contains component (a1), which is a specific anionic surfactant. A liquid detergent composition can improve detergency, foaming property, and defoaming property by containing (A) component.

<<(a1) component>>
Component (a1) is one or more selected from secondary alkanesulfonates, dialkylsulfosuccinates, and compounds represented by formula (a1-1) (component (a1-1)).

Examples of the salt form of component (a1) include alkali metal salts and alkanolammonium salts. Alkali metal salts include sodium salts, potassium salts and the like. Examples of alkanolammonium salts include monoethanolammonium salts and diethanolammonium salts.

The hydrocarbon group of the component (a1) is preferably an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms, and an alkyl group having 8 to 18 carbon atoms is preferable because the effect of the present invention can be easily obtained. more preferred. As the component (a1), secondary alkanesulfonates and dialkylsulfosuccinates are preferable, and secondary alkanesulfonates are more preferable.

These (a1) components have hydrophilic groups (SO ₃ groups, SO ₄ groups) and two hydrocarbon groups having 2 or more carbon atoms as hydrophobic groups (secondary alkyl, dialkyl type, branched alkyl type). common in By using an anionic surfactant having such a structure together with components (B), (C) and (D), it is believed that excellent foaming and excellent antifoaming properties are exhibited.

[Secondary alkanesulfonate]
As the secondary alkanesulfonate, a mixture of sodium secondary alkanesulfonates having 14 to 17 carbon atoms is preferred.
Commercially available products include "HOSTAPUR SAS30A" (trade name) manufactured by Clariant Japan, "MERSOLATE H-95" (trade name) manufactured by Bayer AG, and "Ramtel PS" (trade name) manufactured by Kao Corporation.

[Dialkyl sulfosuccinate]
Dialkyl sulfosuccinates include di(2-ethylhexyl) sodium sulfosuccinate, di(1,3-dimethylbutyl) sodium sulfosuccinate, dicyclohexyl sodium sulfosuccinate, di(1-methylheptyl) sodium sulfosuccinate, di(monooxyethylene-2-ethylhexyl)sodium sulfosuccinate, diisodecyl sodium sulfosuccinate and the like.
Commercially available products include di(2-ethylhexyl)sodium sulfosuccinate (trade name “Ripal 870P”) manufactured by Lion Specialty Chemicals Co., Ltd. and “Pelex” (trade name) manufactured by Kao Corporation.

[(a1-1) component]
The component (a1-1) is a compound represented by the following formula (a1-1) and is an anionic surfactant having a so-called branched alkyl group.

In formula (a1-1), R ¹ and R ² are independently alkyl groups having 1 to 8 carbon atoms, preferably alkyl groups having 2 to 7 carbon atoms. In formula (a1-1), the total carbon number of R ¹ and R ² is 6 to 16, preferably 6 to 14, more preferably 8 to 10, and particularly preferably 8. ^R3 is hydrogen.
The ratio of [carbon number of R ¹ ] and [carbon number of R ² ] is preferably [carbon number of R ¹ ]:[carbon number of R ² ] = 2: 6 to 6: 2, 3: 5 to 5:3 is more preferred.

PO represents a propyleneoxy group. EO represents an ethyleneoxy group.
p is a number representing the average repeating number of PO (that is, the average number of added moles of propylene oxide). q is a number representing the average repeating number of EO (that is, the average number of added moles of ethylene oxide).
p+q is 0-10, preferably 1-10. When both EO and PO are present, their arrangement state does not matter. That is, EO and PO may be random polymerized or block polymerized.
M is a counterion and is one selected from alkali metals, alkaline earth metals and alkanolammonium.

The component (a1-1) is preferably obtained by condensation of two molecules by the Garbet reaction, and more preferably a sulfate of an alkylene oxide adduct of an alcohol having a branched structure at the β-position (Garbet-type AES).
Garbet-type AES can be produced by sulfating an alkylene oxide adduct of Garbet alcohol and then neutralizing it with an alkali metal compound, alkaline earth metal compound, ammonium, alkanolamine, or the like. As a method for sulfation, for example, using a tank type reaction system, a film type reaction system, a tubular gas-liquid mixed phase flow reaction system, etc., an alkylene oxide adduct of garbet alcohol is mixed with liquid sulfuric anhydride, or SO ₃ methods of contacting with gas.
These (a1) components may be used singly or in combination of two or more.

The content of component (a1) is preferably 1 to 10% by mass, more preferably 1.5 to 8% by mass, even more preferably 2 to 5% by mass, relative to the total mass of the liquid detergent composition.
When the content of the component (a1) is equal to or less than the above upper limit, good foaming is obtained when the cleaning solution of the immersion method is applied to a sponge (the cleaning solution has a high foaming property), and the defoaming property can be further enhanced. When the content of the component (a1) is at least the above lower limit, the detergency in the immersion method can be further enhanced, and the antifoaming property can be further enhanced.

In the liquid detergent composition, the mass ratio (a1/A) represented by component (a1)/component (A) is preferably 0.05 to 1, more preferably 0.1 to 0.7, and 0 0.2 to 0.5 is more preferred. When the a1/A ratio is at least the above lower limit, the uniformity of the liquid can be further enhanced, and the foaming and defoaming properties of the cleaning liquid can be further enhanced. If the a1/A ratio is equal to or less than the above upper limit, the antifoaming property can be further enhanced. "Liquid uniformity" refers to the property of a liquid detergent composition that is resistant to precipitation, cloudiness, separation, and gelation.

<<(a2) component>>
The component (A) may contain an anionic surfactant (component (a2)) other than the component (a1).
Examples of component (a2) include linear alkylbenzene sulfonates, α-olefin sulfonates, linear alkyl sulfates, and higher fatty acid salts (soap).
Salt forms include alkali metal salts, alkanolammonium salts and the like. Alkali metal salts include sodium salts, potassium salts and the like. Examples of alkanolammonium salts include monoethanolammonium salts and diethanolammonium salts.

[Linear alkylbenzene sulfonate]
In the straight-chain alkylbenzenesulfonate, the number of carbon atoms in the straight-chain alkyl group bonded to the benzene ring is preferably 10-18, more preferably 12-14.
As the salt form, alkali metal salts are preferred, sodium salts and potassium salts are more preferred, and sodium salts are particularly preferred.

[α-olefin sulfonate]
The average carbon number of the alkyl group of the α-olefin sulfonate is preferably 10-18, more preferably 12-14. The salt form is preferably an alkali metal salt, more preferably a sodium salt or a potassium salt, and still more preferably a sodium salt.

[Polyoxyethylene alkyl sulfate]
Examples of polyoxyethylene alkyl sulfate salts include compounds represented by the following formula (a2-1).

R ¹⁰ -O-(EO) _n -SO ₃ M (a2-1)

[In the formula (a2-1), R ¹⁰ is a linear alkyl group having 8 to 18 carbon atoms. The carbon atoms bonded to the oxygen atoms in R ¹⁰ -O- are primary carbon atoms. EO represents an ethyleneoxy group. n represents the average number of repeating ethyleneoxy groups, and 0<n≦4. M is a cation other than a hydrogen ion. ]

In formula (a2-1), R ¹⁰ has 8 to 18 carbon atoms, preferably 10 to 14 carbon atoms, and more preferably 12 to 14 carbon atoms.
R ¹⁰ is preferably an alkyl group derived from an oil or fat raw material from the viewpoint of improving detergency and reducing environmental load. Suitable oil and fat raw materials include palm kernel oil, coconut oil, and the like.
In formula (a2-1), M may be any one capable of forming a water-soluble salt, and examples thereof include alkali metals, alkaline earth metals, ammonium, and alkanolammonium.
Alkali metals include sodium, potassium and the like. Alkaline earth metals include calcium, magnesium and the like. Examples of alkanolammonium include monoethanolammonium, diethanolammonium and triethanolammonium. When M is an alkaline earth metal, the alkaline earth metal ion is 0.5 mol per 1 mol of the anion (R ¹⁰ —O—(EO) _n —SO ₃ ⁻ ).

[Higher fatty acid salt]
Higher fatty acid salts include higher fatty acid salts having an acyl group of 10 to 20 carbon atoms, and higher fatty acid salts having an acyl group of 10 to 16 carbon atoms are preferred. The salt form is preferably an alkali metal salt, more preferably a sodium salt or a potassium salt, and still more preferably a sodium salt.

Component (a2) includes sodium salt of alkylbenzenesulfonate having 12 to 14 carbon atoms, sodium salt of polyoxyethylene (1) linear alkyl (C12) sulfate ester, and sodium salt of polyoxyethylene (2) linear alkyl (C12) sulfate ester. sodium salt, polyoxyethylene (4) linear alkyl (C12) sulfate sodium salt, polyoxypropylene (0.4) polyoxyethylene (1.5) linear alkyl (C12) sulfate sodium salt, polyoxyethylene (1) Linear alkyl (C12/14 = 75/25; derived from natural fats and oils) sulfate ester sodium salt, polyoxyethylene (2) Linear alkyl (C12/14 = 75/25; derived from natural fats and oils) sulfate ester sodium salt , polyoxyethylene (4) linear alkyl (C12/14=75/25; derived from natural fats and oils) sulfate ester sodium salt, sodium caprate, sodium laurate, sodium myristate and the like.
Among the above, polyoxyethylene (1) straight-chain alkyl (C12/14=75/25; derived from natural fats and oils) sulfate ester sodium salt is preferable because the effects of the present invention are particularly likely to be obtained.
Here, for example, "polyoxyethylene (1)" means that the average number of repeating ethyleneoxy groups is 1 (the average number of added moles of ethylene oxide is 1).
"Alkyl (C12)" means that the alkyl group has 12 carbon atoms.
"C12/14 = 75/25; derived from natural oils and fats" means a compound having a linear alkyl group with 12 carbon atoms and a compound having a linear alkyl group with 14 carbon atoms at a mass ratio of 75/25. It means that it is a mixture and that it is a straight-chain alkyl group derived from natural fats and oils.
These (a2) components may be used singly or in combination of two or more.

The content of component (a2) is preferably 1 to 28% by mass, more preferably 5 to 18% by mass, and even more preferably 7 to 12% by mass, relative to the total mass of the liquid detergent composition. If the content of the component (a2) is at least the above lower limit, the foamability of the cleaning liquid can be enhanced, and the detergency can be further enhanced. If the content of the component (a2) is equal to or less than the above upper limit, the uniformity of the liquid cleaning composition can be easily maintained, and the antifoaming property can be further enhanced.

The content of component (A) is preferably 5 to 30% by mass, more preferably 7 to 20% by mass, relative to the total mass of the liquid detergent composition. If the content of the component (A) is at least the above lower limit, the foamability of the cleaning liquid can be enhanced, and the detergency can be further enhanced. (A) If content of a component is below the said upper limit, the uniformity of the liquid of a liquid detergent composition will be improved more and an antifoaming property will be improved further.

<(B) component: amine oxide surfactant>
Component (B) is an amine oxide surfactant. By having both the component (A) and the component (B), the detergency against oil stains in the liquid detergent composition is enhanced, and good foaming is achieved.
"Amine oxide surfactants" include, for example, alkylamine oxides, alkanoylamide alkylamine oxides, and the like.
Preferred amine oxide surfactants include compounds represented by the following formula (b1).

[In formula (b1), R ⁶ represents a linear or branched alkyl group having 8 to 18 carbon atoms or a linear or branched alkenyl group having 8 to 18 carbon atoms. R ⁷ and R ⁸ each independently represent an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group. R ⁹ represents an alkylene group having 1 to 4 carbon atoms. B is -CONH-, -NHCO-, -COO-, -OCO- or -O-. r is 0 or 1; ]

In formula (b1), R ⁶ has 8 to 18 carbon atoms, preferably 10 to 14 carbon atoms. ^R6 is a linear or branched alkyl group or a linear or branched alkenyl group, preferably a linear or branched alkyl group.
In formula (b1), R ⁷ and R ⁸ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms. , a methyl group is more preferred. Among them, it is more preferable that both R ⁷ and R ⁸ are methyl groups.
In formula (b1), R ⁹ has 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms, and more preferably 3 carbon atoms.
In formula (b1), B is -CONH-, -NHCO-, -COO-, -OCO- or -O-, and -CONH- is preferred.
In formula (b1), r is 0 or 1, preferably 0.

Component (B) includes lauryldimethylamine oxide, coconutalkyldimethylamine oxide, lauryldiethylamine oxide, lauramidopropyldimethylamine oxide, and the like.
Among them, a compound in which r is 0 in the formula (b1) is preferable, and lauryldimethylamine oxide is more preferable, since the effect of the present invention can be particularly easily obtained.
Component (B) may be used alone or in combination of two or more.

The content of component (B) is preferably 2 to 20% by mass, more preferably 6 to 13% by mass, and even more preferably 8 to 10% by mass, relative to the total mass of the liquid detergent composition. If the content of component (B) is at least the above lower limit, detergency and foamability can be further enhanced. If the content of component (B) is equal to or less than the above upper limit, the uniformity and antifoaming properties of the liquid can be further enhanced.

In the liquid detergent composition, the mass ratio represented by component (A)/component (B) (A/B ratio) is 0.7 to 2, preferably 1 to 2, and 1.1 to 1.5. is more preferred. When the A/B ratio is at least the above lower limit, detergency, foaming properties and defoaming properties can be further enhanced. When the A/B ratio is equal to or less than the above upper limit, detergency and antifoaming properties can be further enhanced.

<(C) Component: Protease>
The (C) component is protease. Component (C) is preferably a protease having serine, histidine and aspartic acid in its molecule, such as serine protease.
Examples of protease preparations include Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everlase 16L TypeEX, Everlase Ultra 16L, Esperase 8L, Alcalase 2.5L, Alcalase 2.5L, and Ultraq 2.5L, which are available from Novozymes. , Liquanase Ultra 2.5L, Liquanase Ultra 2.5XL, Coronase 48L, Coronase Evity 48L and Progress Uno 100L, and the tradenames Purafect L, Purafect OX and Properase L available from Genencor.

The content of component (C) in the liquid detergent composition is preferably 0.01 to 2% by mass, more preferably 0.01 to 1% by mass, and 0.01 to 1% by mass, based on the total mass of the liquid detergent composition. 01 to 0.6% by mass is more preferable. If the content of component (C) is at least the above lower limit, the detergency in the immersion method can be further improved. If the content of the component (C) is equal to or less than the above upper limit, the uniformity of the liquid can be further improved.
In addition, content of (C)component is a compounding quantity as a formulation.

In addition, the protease activity Ep (kPU/g) per gram of the liquid detergent composition is preferably 0.1 to 40 (kPU/g), more preferably 0.1 to 20 (kPU/g), and 0.1 ~12 (kPU/g) is more preferred.

[Protease activity]
Protease activity is measured, for example, by the following method.
As used herein, "protease activity unit (PU)" represents a unit of activity for hydrolyzing peptide bonds in protein molecules.
The activity of releasing 1 μg of tyrosine in casein per minute is 1 PU.

<<Method for measuring protease activity Ep per 1 g of liquid detergent composition>>
1) Preparation of Casein Substrate Solution 0.6 g of casein (origin: Bovine Milk, manufactured by Merck) substrate is dissolved in 20 mM sodium tetraborate (manufactured by Kanto Chemical Co., Ltd.) solution. This is adjusted to pH 10.5 with 1N sodium hydroxide (1 mol/L sodium hydroxide solution, manufactured by Kanto Kagaku Co., Ltd.). A casein substrate solution is then prepared by making up to 100 mL with 20 mM sodium tetraborate solution.

2) Measurement of protease activity per 1 g of liquid detergent composition A liquid detergent composition containing no protease was prepared, and 1.0 g of this liquid detergent composition was dissolved in ion-exchanged water to make 1 liter. to obtain an aqueous detergent solution a containing no protease. Separately, a liquid detergent composition containing protease is prepared, and 1.0 g of this liquid detergent composition is dissolved in deionized water and the volume is adjusted to 1 L to obtain a detergent aqueous solution b containing protease.
0.5 mL of each of the detergent aqueous solutions a and b is collected in separate test tubes (φ15 mm, length 105 mm). These test tubes are immersed in a constant temperature bath at 35°C for 5 minutes. Then, 2.5 mL of 35° C. casein substrate solution is added to each test tube, stirred for 10 seconds with a vortex mixer, and returned to the 35° C. constant temperature bath to initiate the reaction.
10 minutes after the start of the reaction, each test tube was filled with an enzymatic reaction terminator TCA solution (0.11 mol/L trichloroacetic acid, 0.22 mol/L sodium acetate, 0.33 mol/L acetic acid (all special grade, Kanto Kagaku Co., Ltd.). After adding 2.5 mL of the product), the mixture is stirred with a vortex mixer for 10 seconds and allowed to stand at 20° C. for 30 minutes. After that, the unreacted substrate that precipitates is filtered with filter paper (No. 131 manufactured by Advantech, etc.), and the filtrate containing tyrosine is recovered. The absorbance at a wavelength of 275 nm in the collected filtrate is measured with an ultraviolet-visible spectrophotometer (UV-160 manufactured by Shimadzu Corporation, etc.). Next, the difference between the absorbance of the aqueous detergent solution b and the absorbance of the aqueous detergent solution a is obtained. This difference is taken as the absorbance value of the protease-containing liquid detergent composition b.
Then, based on a calibration curve prepared with a TCA solution of tyrosine (special grade, manufactured by Kanto Chemical Co., Ltd.), the tyrosine concentration is calculated, and the protease activity (PU) per 1 g of the liquid detergent composition is calculated.

<<Method for measuring activity per gram of protease>>
The activity per gram of component (C) (protease enzyme preparation) is, for example, a value measured by the following method.
0.1 g of the protease enzyme preparation is dissolved in deionized water and the volume is adjusted to 100 mL. By dissolving 1 mL of this enzyme solution in ion-exchanged water to a constant volume of 100 mL, an aqueous protease enzyme preparation solution having a concentration of 0.001% by mass is prepared.
0.5 mL of this protease enzyme preparation aqueous solution is dispensed into a test tube having a diameter of 15 mm and a length of 105 mm, and the test tube containing this protease enzyme preparation aqueous solution is immersed in a constant temperature bath at 35° C. for 5 minutes. After that, 2.5 mL of the casein substrate solution is added to the test tube, stirred for 10 seconds with a vortex mixer, returned to the thermostat at 35° C., and allowed to stand for 10 minutes to allow the enzymatic reaction to proceed.
Then, 2.5 mL of a TCA solution (0.11 mol/L trichloroacetic acid, 0.22 mol/L sodium acetate, 0.33 mol/L acetic acid (all special grade, manufactured by Kanto Kagaku Co., Ltd.)) of an enzyme reaction terminator was added to a test tube. is added, then stirred for 10 seconds with a vortex mixer and allowed to stand at 20° C. for 30 minutes. After that, it is filtered with a filter paper (No. 131 manufactured by Advantec Co., Ltd.), and the filtrate containing tyrosine is collected.
The absorbance at a wavelength of 275 nm in the collected filtrate is measured with an ultraviolet-visible spectrophotometer (UV-160 manufactured by Shimadzu Corporation, etc.). Based on a calibration curve prepared with a TCA solution of tyrosine (special grade, manufactured by Kanto Kagaku Co., Ltd.), the tyrosine concentration is calculated, and the protease activity (PU) per gram of component (C) is calculated.

<(D) component: amylase>
(D) Component is amylase. Component (D) includes, for example, Termamyl 300L, Termamyl Ultra 300L, Duramyl 300L, Stainzyme 12L, Stainzyme Plus 12L and AmplifyPrime 100L available from Novozymes; Maxamyl available from Genencore; available trade name Pullulanase Amano, trade name DB-250 available from Seikagaku Corporation, and the like.

Components (C) and (D) may be incorporated into one enzyme formulation. For example, as an enzyme preparation containing components (C) and (D), Medley Core 210L (trade name, manufactured by Novozymes) and the like can be suitably used.

The content of component (D) in the liquid detergent composition is preferably 0.01 to 1% by mass, more preferably 0.01 to 0.8% by mass, relative to the total mass of the liquid detergent composition. 0.01 to 0.6% by mass is more preferable. If the content of the component (D) is at least the above lower limit, the detergency in the immersion method can be further improved. If the content of the component (D) is equal to or less than the above upper limit, the uniformity of the liquid can be further improved.
In addition, content of (D)component is a compounding quantity as a formulation.

Further, the amylase activity Ea (kAU/g) per gram of the liquid detergent composition is preferably 0.035 to 3.5 (kAU/g), more preferably 0.035 to 2.8 (kAU/g). , 0.035 to 2.1 (kAU/g) is more preferred.

[Amylase activity]
Amylase activity is measured, for example, by the following method.
As used herein, "amylase activity unit (AU)" is the activity of α-amylase to hydrolyze α-1,4-glucosidic bonds in starch. The amylase activity unit (AU) is a value converted from an absorbance calibration curve (provided with the reagent) prepared with a standard enzyme "Phadebas Human α-Amylase Control" of known activity. Note that 1U/L is 1AU.

<<Method for measuring amylase activity Ea per 1 g of liquid detergent composition>>
The amylase activity Ea per 1 g of the liquid detergent composition is, for example, a value measured by the following method. The amylase activity Ea is measured using "Phadebas amylase test" (manufactured by Magle Life Sciences).

A standard enzyme solution diluted to each concentration is used to create a standard curve. The test tube containing the standard enzyme solution is heated in a constant temperature bath at 37°C for 5 minutes. To this test tube is then added one tablet containing a certain amount of bovine serum albumin in a blue starch polymer substrate. The tablet is mixed until it disintegrates, and is kept in a constant temperature bath at 37° C. for exactly 30 minutes for enzymatic reaction. Add 1 mL of 0.5 mol/L sodium hydroxide solution to terminate the enzymatic reaction, perform centrifugation (1500 G, 5 minutes), and measure the absorbance of the supernatant at a wavelength of 620 nm to obtain a standard curve.

2.59 g of potassium dihydrogen phosphate, 29.01 g of disodium phosphate dodecahydrate, 10 g of sodium sulfite, 1.322 g of calcium chloride dihydrate and 0.11 g of trihydroxymethylaminomethane were mixed with deionized water for 1.5 hours. The mixed solution made up to 1 L is used as a buffer solution.
A liquid detergent composition containing no amylase is prepared, and 1.0 g of the liquid detergent composition is dissolved in a buffer solution and the volume is adjusted to 1 L to obtain an aqueous detergent solution c containing no amylase. . Separately, a liquid detergent composition containing amylase is prepared, and 1.0 g of this liquid detergent composition is dissolved in a buffer solution and adjusted to 1 L to obtain an aqueous detergent solution d containing amylase.
1 mL of each of the detergent aqueous solutions c and d is collected in separate test tubes (φ15 mm, length 105 mm). Add 5 mL of 37° C. buffer to each tube and immerse the tubes in a 37° C. constant temperature bath for 10 minutes. Then, one tablet of Phadebas tablet is put into each test tube, stirred with a vortex mixer for 10 seconds, and returned to the constant temperature bath at 37° C. to initiate the reaction.
After 15 minutes from the start of the reaction, 1 mL of 1N NaOH, which is an enzyme reaction terminator, is added to each test tube, stirred for 10 seconds with a vortex mixer, and allowed to stand at 20° C. for 30 minutes. After that, it is filtered with a filter paper (No. 131 manufactured by Advantech Co., etc.), and the filtrate is recovered. The absorbance at a wavelength of 620 nm in the collected filtrate is measured with an ultraviolet-visible spectrophotometer (UV-160 manufactured by Shimadzu Corporation, etc.). Next, the difference between the absorbance of the detergent aqueous solution c and the absorbance of the detergent aqueous solution d is obtained, and this difference is taken as the absorbance value of the amylase-containing liquid detergent composition d.
Then, the amylase activity (AU) per 1 g of the liquid detergent composition is calculated from the concentration calculated based on the calibration curve created with amylase enzymes of known activity.

<<Method for measuring activity per gram of amylase>>
The activity per 1 g of component (D) (amylase enzyme preparation) is, for example, a value measured by the following method.
Dissolve 0.1 g of amylase enzyme preparation in buffer and make up to 100 mL. By dissolving 1 mL of this enzyme solution in ion-exchanged water to a constant volume of 100 mL, an aqueous solution of amylase enzyme preparation having a concentration of 0.001% by mass is prepared.
1 mL of this amylase enzyme preparation aqueous solution is dispensed into a test tube having a diameter of 15 mm and a length of 105 mm, and 5 mL of a buffer solution at 37° C. is added. After immersing these test tubes in a constant temperature bath at 37°C for 10 minutes, one tablet of Phadebas tablet was added to each test tube, stirred for 10 seconds with a vortex mixer, and returned to the constant temperature bath at 37°C to initiate the reaction. do.
After 15 minutes from the start of the reaction, 1 mL of 1N NaOH, which is an enzyme reaction terminator, is added to each test tube, stirred for 10 seconds with a vortex mixer, and allowed to stand at 20° C. for 30 minutes. After that, it is filtered with a filter paper (No. 131 manufactured by Advantech Co., etc.), and the filtrate is collected. The absorbance at a wavelength of 620 nm in the recovered filtrate is measured using a UV-visible spectrophotometer (UV-160 manufactured by Shimadzu Corporation, etc.).
Amylase activity (AU) per 1 g of component (D) is calculated from concentrations calculated based on a calibration curve prepared with amylase enzymes of known activity.

The total amount of components (C) and (D) in the liquid detergent composition (total amount of CD) is preferably 0.02 to 3% by mass, preferably 0.02 to 3% by mass, based on the total mass of the liquid detergent composition. 02 to 2% by mass is more preferable, and 0.02 to 1% by mass is even more preferable. If the total amount of CD is at least the above lower limit, the detergency can be further enhanced and the antifoaming property can be further enhanced. When the total amount of CD is equal to or less than the above upper limit, the uniformity of the liquid can be further improved.

In the liquid detergent composition, the mass ratio represented by component (C)/component (D) (C/D ratio) is preferably 0.2 to 20, more preferably 0.5 to 10, and 1 to 5. is more preferred. When the C/D ratio is within the above range, proteins and polysaccharides contained in dirt can be efficiently decomposed to further enhance detergency and defoaming properties.

The enzyme activity ratio (Ep/Ea ratio) represented by Ep/Ea in the liquid detergent composition is preferably 1-350, more preferably 2.6-175, and even more preferably 5-88. If the Ep/Ea ratio is within the above range, the protein and polysaccharide contained in the dirt can be efficiently decomposed, and the detergency in the immersion method can be further enhanced.

In the liquid detergent composition, the mass ratio (a1/(C+D)) represented by (a1) component/((C) component + (D) component) is preferably 0.4 to 165, and 3 to 20. is more preferred, and 8 to 12 are even more preferred. When the a1/(C+D) ratio is at least the above lower limit, the uniformity of the liquid can be further enhanced, and the foaming and defoaming properties of the cleaning liquid can be further enhanced. If the a1/(C+D) ratio is equal to or less than the above upper limit, the antifoaming property can be further enhanced.

In the liquid detergent composition, the mass ratio (a2/(a1+C+D) ratio) represented by (a2) component/((a1) component + (C) component + (D) component) is 0.1 to 10. It is preferably 0.4 to 5, more preferably 2.5 to 4. If the a2/(a1+C+D) ratio is within the above range, the detergency and antifoaming properties can be further enhanced.

<(E) component: branched polyoxyalkylene addition type nonionic surfactant>
Component (E) is a branched polyoxyalkylene addition type nonionic surfactant. By containing the component (E), the liquid detergent composition can further improve the uniformity of the liquid and further improve the foaming and defoaming properties of the cleaning liquid.

Examples of branched polyoxyalkylene addition type nonionic surfactants include compounds represented by the following formula (e1) (component (e1)). In the component (e1), both or one of an ethyleneoxy group and a propyleneoxy group are introduced into the alcohol, and the hydrophobic portion (hydrocarbon group) is branched into C _x H _2y+1 and C _y H _2y+1 at the β-position carbon atom. have a structure.

[In the formula, AO represents both or one of an ethyleneoxy group and a propyleneoxy group. m represents the average repetition number of AO and is a number from 6 to 12. Each of x and y is an integer of 1 to 6, and 6≦x+y≦12. ]

In formula (e1), AO is both or one of an ethyleneoxy group and a propyleneoxy group. Among them, AO preferably contains an ethyleneoxy group. By including an ethyleneoxy group, the foaming and defoaming properties of the cleaning liquid can be further enhanced. Among these, (AO) _m is more preferably composed of only ethyleneoxy groups, or a mixture of ethyleneoxy groups and propyleneoxy groups and containing more ethyleneoxy groups. Among them, those consisting only of ethyleneoxy groups are particularly preferable.
In (AO) _m , when an ethyleneoxy group and a propyleneoxy group are mixed, they may be mixed randomly or in blocks.

In formula (e1), m represents the average repeating number of AO and is a number of 6 to 12, preferably 8 to 11, more preferably 10. When m is 6 or more, the detergency in the immersion method can be further enhanced. When m is 12 or less, the detergency against oil stains in a non-immersion method can be further enhanced.
Note that m here denotes the "average" number of iterations of AO. Therefore, the compound represented by the general formula is an assembly of molecules having different AO repeating numbers.
In formula (a1), x and y are each integers of 1 to 6, and 6≦x+y≦12. Among them, 6≦x+y≦10 is preferable, 6≦x+y≦8 is more preferable, and x+y=8 is particularly preferable, because dirt does not easily remain on the sponge. If x+y is 6 or more, the detergency in the immersion method can be further enhanced. If x+y is 12 or less, the uniformity of the liquid detergent composition is further enhanced, the liquid detergent composition is easily dissolved in water, and the effect of detergency in the immersion method is more stably obtained.

C _x H _2x+1 and C _y H _2y+1 each include a straight-chain or branched-chain alkyl group, preferably a straight-chain alkyl group, such as a methyl group, an ethyl group, a propyl group, a butyl group, A pentyl group and a hexyl group are preferred. Among them, the combination of C _x H _2x+1 and C _y H _2y+1 is a combination of an ethyl group and a butyl group, and a combination of a propyl group and a pentyl group (in any combination, either group may be ) is preferred, and a combination of a propyl group and a pentyl group (one may be either group) is particularly preferred.

Among the above, as the component (E), an ethylene oxide adduct of an alcohol having a branched structure at the β-position obtained by condensation of two molecules by the Garbet reaction is particularly preferable.
Such commercial products include polyoxyethylene mono(2-propylheptyl) ether manufactured by BASF. Specifically, the product name "Lutensol XP60" which is a compound of m = 6 in the general formula (e1), the product name "Lutensol XP80" which is a compound of m = 8 in the general formula (e1), and the general formula Examples thereof include the product name “Lutensol XP90” which is a compound of m=9 in (e1) and the product name “Lutensol XP100” which is a compound of m=10 in the general formula (e1).
Component (E) includes polyoxyethylene mono(2-ethylhexyl) ether manufactured by Nippon Nyukazai Co., Ltd. A specific example is the product name "Newcol 1008" which is a compound of m=8 in formula (e1).
Component (E) also includes polyoxyethylene polyoxypropylene mono(2-propylheptyl) ether manufactured by BASF. Specifically, the product name "Lutensol XL90", which is a compound with m = 9 in formula (e1) (a mixture of an ethyleneoxy group and a propyleneoxy group), a compound with m = 10 in formula (e1) (ethylene A mixture of an oxy group and a propyleneoxy group), the trade name of which is "Lutensol XL100".

As the component (E), polyoxyalkylene alkyl ether is more preferable, and a compound represented by the following formula (e2) (component (e2)) is preferable.

R ¹⁶ —O—(R ¹⁷ O) _w —H (e2)

In formula (e2), R ¹⁶ is a linear hydrocarbon group having 10 to 18 carbon atoms or a branched hydrocarbon group having 10 to 18 carbon atoms. R ¹⁷ O is an alkyleneoxy group. R ¹⁷ is a hydrocarbon group having 1 to 3 carbon atoms, preferably an ethylene group or a propylene group. w represents the average repeating number of R ¹⁷ O and is a number of 1-20, preferably a number of 5-20, more preferably a number of 5-15. Among the components (e2), polyoxyalkylene alkyl ethers in which R ¹⁶ has 10 to 18 carbon atoms, R ¹⁷ has 2 or 3 carbon atoms, and w is 5 to 20 are preferred.

The content of component (E) in the liquid detergent composition is preferably 1 to 15% by mass, more preferably 2 to 12% by mass, more preferably 3 to 8% by mass, relative to the total mass of the liquid detergent composition. preferable. When the content of the component (E) is at least the above lower limit, the homogeneity of the liquid can be further improved, and the foamability and antifoaming properties can be further enhanced. If the content of the component (E) is equal to or less than the above upper limit, the antifoaming properties can be further enhanced.

In the liquid detergent composition, the mass ratio (E/(A+B) ratio) represented by (E) component/((A) component + (B) component) is preferably 0.01 to 5, and 0.05. ~2 is more preferred, and 0.1 to 1 is even more preferred. When the E/(A+B) ratio is at least the above lower limit, the homogeneity of the liquid can be further improved, and the antifoaming property can be further improved. When the E/(A+B) ratio is equal to or less than the above upper limit, the detergency can be further enhanced and the antifoaming property can be further enhanced.

In the liquid detergent composition, the mass ratio represented by ((a1) component + (C) component + (D) component) / ((A) component + (B) component + (E) component) ((a1 + C + D) /(A+B+E) ratio) is preferably 0.03 to 1, more preferably 0.05 to 0.3, and still more preferably 0.1 to 0.2. When the (a1+C+D)/(A+B+E) ratio is at least the above lower limit, the homogeneity of the liquid can be further improved and the defoaming properties can be further improved. If the (a1+C+D)/(A+B+E) ratio is equal to or less than the above upper limit, the foaming and defoaming properties of the purified liquid can be further enhanced.

<Optional component>
The cleaning agent of the present invention may contain optional components other than the components described above, if necessary, as long as the effects of the present invention are not impaired.
Optional ingredients are appropriately selected in consideration of the dosage form and the like. Optional components include surfactants (optional surfactants) excluding components (A), (B) and (E), solvents, enzymes (optional enzymes) excluding components (C) to (D), preservatives agents, hydrotropic agents, inorganic builders, pH adjusters, bleaching components, metal scavengers, radical trapping agents, fragrances, pigments, and other conventionally known components.

[solvent]
Water is preferred as the solvent for the liquid detergent composition. By using water as a solvent, the liquid detergent composition can be easily prepared and has better solubility in water.
The content of water in the liquid detergent composition is preferably 75% by mass or less, more preferably 40 to 70% by mass, even more preferably 50 to 70% by mass, relative to the total mass of the liquid detergent composition.
When the water content is at least the above lower limit, gelation is suppressed, and the uniformity of the liquid can be further enhanced. If the water content is equal to or less than the above upper limit, the blending amount of components (A) to (D) can be ensured, and the viscosity does not become too low, making it easier to use.

Optional enzymes include, for example, catalase. Catalase can decompose residual hydrogen peroxide derived from component (B). Therefore, in the liquid detergent composition, the stability of the components (C) and (D), which are susceptible to hydrogen peroxide, can be enhanced.
The content of catalase is preferably 0.001 to 1% by mass, more preferably 0.01 to 0.5% by mass, relative to the total mass of the liquid detergent composition. In addition, the content of catalase is the compounding amount as a formulation.

[Method for measuring activity per gram of catalase enzyme preparation]
In the present invention, catalase activity per gram of catalase is measured, for example, by the following method. As used herein, "catalase activity unit (CU)" represents a unit of activity for decomposing hydrogen peroxide. 1 CU is defined as the activity to decompose 1 μmol of hydrogen peroxide per minute.
A mixture of 2.66 g of potassium dihydrogen phosphate, 5.31 g of dipotassium hydrogen phosphate, and 950 mL of ion-exchanged water is adjusted to pH 7.00 with 1 M hydrochloric acid, and then diluted to 1 L as a buffer solution. .
122 μL of hydrogen peroxide (35% by mass, manufactured by Mitsubishi Gas Chemical Company, Inc.) is placed in a 100 mL volumetric flask, and the diluted solution diluted with the above buffer solution is used as a hydrogen peroxide substrate solution. Absorbance at a wavelength of 240 nm is measured with an ultraviolet-visible spectrophotometer (UV-160 manufactured by Shimadzu Corporation, etc.). This ensures that the buffer blank absorbance is in the range of 0.53 to 0.55. If the concentration is outside the above range, a buffer solution or hydrogen peroxide is added to adjust it so that it falls within the above range. The buffer solution and substrate solution are placed in a constant temperature water bath at 25° C. for 30 minutes or more to keep the temperature constant.

Dissolve 0.17 g of the catalase enzyme preparation in a buffer solution, adjust the volume to 100 mL, and stir with a stirrer for about 30 minutes to prepare an aqueous solution of the catalase enzyme preparation.
A cuvette containing 0.1 mL of the catalase enzyme preparation in water and 2.9 mL of the above buffer at 25° C. serves as a control. The time required for the absorbance at a wavelength of 240 nm to decrease from 0.450 to 0.400 in a mixture of 0.1 mL of the catalase enzyme preparation aqueous solution and 2.9 mL of the substrate solution is measured. The catalase enzyme preparation concentration in the catalase enzyme preparation aqueous solution is adjusted so that the measurement time is in the range of 0.267 minutes to 0.400 minutes. The activity of the catalase enzyme preparation per 1 g is calculated from the average value of time measured three times or more by the following formula (s).

Catalase activity per gram (kCU/g) = (3.45 x V x F)/(W x T x 0.1) (s)
V: Buffer dilution volume (mL) of catalase enzyme preparation.
F: Dilution factor.
W: Catalase enzyme preparation weighed value (g).
T: measurement time (minutes).

The catalase activity Ec (kCU/g) per 1 g of the detergent composition can be measured by changing the catalase enzyme preparation in the above measurement method to a detergent composition.
The catalase activity Ec (kCU/g) per gram of the detergent composition is preferably 0.0005 to 0.5 (kCU/g), more preferably 0.005 to 0.25 (kCU/g).

Examples of antiseptics include isothiazoline compounds. Examples of isothiazoline compounds include benzisothiazolinone, methylisothiazolinone, butylbenzisothiazolinone, chloromethylisothiazolinone, octylisothiazolinone, and dichlorooctylisothiazolinone. These may be used individually by 1 type, and may use 2 or more types together. The content of the preservative is preferably 0.0002 to 0.01% by mass (2 to 100 ppm by mass), and 0.0005 to 0.004% by mass ( 5 to 40 mass ppm) is more preferable.

[Optional surfactant]
Optional surfactants include amphoteric surfactants.
The total amount (total mass) of surfactants in the liquid cleaning composition is preferably 6 to 45% by mass, more preferably 10 to 40% by mass, more preferably 16 to 40% by mass, relative to the total mass of the liquid cleaning composition. % by mass is more preferred, and 16 to 35% by mass is particularly preferred.

[Hydrotropic agent]
Hydrotropic agents include monohydric alcohols having 2 to 4 carbon atoms, glyceryl ethers having 4 to 10 carbon atoms, toluenesulfonic acid, toluenesulfonate, cumenesulfonic acid, cumenesulfonate, benzoic acid, and benzoates. One or more selected are used (except for component (A)).
Monohydric alcohols having 2 to 4 carbon atoms include ethanol, n-propanol, isopropanol, normal butanol, secondary butanol and tertiary butanol.
Glyceryl ethers having 4 to 10 carbon atoms include glycerin and hexyl glyceryl ether.
Among these, monohydric alcohols having 2 to 4 carbon atoms, toluenesulfonic acid or salts thereof are preferred from the viewpoint of the effect of dissolving the components (A) to (E) in the liquid detergent composition and the feeling of use. Paratoluenesulfonate is more preferred.
These hydrotropic agents may be used singly or in combination of two or more.
The content of the hydrotrope agent is preferably 1 to 30% by mass, more preferably 1 to 20% by mass, based on the total mass of the liquid detergent composition.

[pH adjuster]
Examples of pH adjusters include hydrochloric acid, sulfuric acid, phosphoric acid, glycolic acid, citric acid, sodium hydroxide, potassium hydroxide, monoethanolamine, diethanolamine, and triethanolamine.
The pH adjusting agent may be used singly or in combination of two or more.

The sum of components (A) to (E) and optional components does not exceed 100% by mass.

(Production method)
A conventionally well-known method is mentioned as a manufacturing method of a liquid detergent composition.
As a method for producing the liquid detergent composition, for example, components other than the enzyme and the pH adjuster are added to a part of the solvent water, mixed, and adjusted to an arbitrary pH, and then the remainder of the enzyme and water is added. There is a method of adding

(how to use)
The method of using the liquid detergent composition (that is, the method of washing dishes) is described below.
Methods for washing tableware include a method of applying an arbitrary amount of liquid detergent composition to a cleaning tool and scrubbing the object to be cleaned with this cleaning tool (scrubbing operation).
The amount of the liquid detergent composition attached to the cleaning tool is, for example, 1 to 10 g.
Objects to be washed include tableware such as plates, chopsticks, and spoons. Also, objects to be cleaned may be cooking utensils such as pots and kitchen knives. In this paper, tableware and cooking utensils are collectively referred to as "tableware."
After the scrubbing operation, the object to be washed is rinsed with rinsing water to wash away the liquid detergent composition adhering to the object to be washed (rinsing operation). At this time, in the liquid detergent composition of the present invention, the generated foam does not stay in the drain port and quickly disappears.

Further, as a method for washing tableware, there is a method (immersion method) in which the liquid detergent composition is dispersed in water to form a washing liquid, and the object to be washed is immersed in the washing liquid for an arbitrary time (immersion time) (immersion operation). be done.

The content of the liquid detergent composition with respect to the total amount of the cleaning liquid is, for example, preferably 0.01 to 50% by mass (that is, 2 to 10,000-fold dilution), more preferably 0.05 to 20% by mass, and 0.1 to 0.1% by mass. 5% by mass is more preferred.
The immersion time in the immersion method is determined in consideration of the degree of contamination of the object to be cleaned, and is, for example, preferably 5 minutes or more, more preferably 5 minutes to 10 hours, 5 minutes to 1 hour, 15 minutes to 1 hour. More preferred. If the immersion time is at least the above lower limit, the detergency can be further improved. If the immersion time is equal to or less than the above upper limit, it is possible to prevent the dishwashing time from becoming excessively long.

In the immersion operation, the object to be cleaned may be scrubbed with a cleaning tool in the cleaning liquid or removed from the cleaning liquid, if desired. Examples of cleaning tools include sponges and brushes.
The object to be cleaned is immersed in the cleaning liquid for an arbitrary period of time, and then the object to be cleaned is removed from the cleaning liquid. The removed object to be washed is rinsed with purified water (rinsing water) containing no liquid detergent composition to wash away the cleaning liquid and foam adhering to the object to be washed (rinsing operation). The washed tableware is obtained through the rinsing operation. At this time, in the liquid detergent composition of the present invention, the generated foam does not stay in the drain port and quickly disappears.
In the rinsing operation, the time until defoaming measured by the evaluation method for "defoaming property" described later is preferably less than 70 seconds, more preferably less than 50 seconds, and even more preferably less than 40 seconds.

[EXAMPLES] Hereafter, although an Example is shown and this invention is demonstrated in detail, this invention is not limited by the following description.

(Raw materials used)
<(A) Component>
<<(a1) component>>
· A1-1: Sodium secondary alkanesulfonate having 14 to 17 carbon atoms, trade name "HOSTAPUR SAS 30A", manufactured by Clariant Japan KK.
A1-2: Sodium di(2-ethylhexyl)sulfosuccinate, trade name “Ripal 870P”, manufactured by Lion Specialty Chemicals.
A1-3: polyoxyethylene mono(2-propylheptyl) ether sulfate Na, R ¹ = propyl group, R ² = pentyl group, R ¹ and R ² carbon chain length 8, p = 0, q = 3, M = equivalent to sodium. Prepared according to Preparation Example 1 below.

[Preparation Example 1] Preparation of A1-1 290 g of “Lutensol XP30” manufactured by BASF was put into a 500 mL flask equipped with a stirrer. After purging the inside of the flask with nitrogen, 81 g of liquid sulfuric anhydride (sulfan) was slowly added dropwise while maintaining the temperature at 40°C. After the dropwise addition was completed, stirring was continued for 1 hour to obtain the desired polyoxyethylene alkyl ether sulfuric acid. Furthermore, A1-3 was obtained by neutralizing this with an aqueous sodium hydroxide solution.

<<(a2) component>>
· A2-1: AES (1EO), sodium polyoxyethylene alkyl ether sulfate. R ¹⁰ in formula (a2-1) = linear alkyl group having 12 to 14 carbon atoms, n = 1, M = sodium. Adjusted in the following adjustment example 2.

[Preparation Example 2] Preparation of A2-1 In a 4 L autoclave, 400 g of P&G brand name CO1270 alcohol (C12/C14 = 75%/25%, mass ratio) as raw alcohol and potassium hydroxide as a reaction catalyst 0.8 g of catalyst were charged respectively. After purging the inside of the autoclave with nitrogen, the temperature was raised while stirring. Subsequently, while maintaining the temperature at 180° C. and the pressure at 0.3 MPa or less, 91 g of ethylene oxide was introduced and reacted. The average number of added moles of ethylene oxide in the obtained polyoxyalkylene ether was 1.
Next, 237 g of the alcohol ethoxylate thus obtained was placed in a 500 mL flask equipped with a stirrer, replaced with nitrogen, and then 96 g of liquid sulfuric anhydride (sulfan) was slowly added dropwise while maintaining the reaction temperature at 40°C. did. After the dropwise addition was completed, stirring was continued for 1 hour (sulfation reaction) to obtain polyoxyethylene alkyl ether sulfuric acid.
Then, this was neutralized with an aqueous sodium hydroxide solution to obtain A2-1.

A2-2: Sodium alkylbenzenesulfonate having 10 to 14 carbon atoms, trade name "Taika Power L121" manufactured by Tayka Corporation, neutralized with sodium hydroxide.

<(B) Component>
B-1: AX, n-dodecyldimethylamine oxide, manufactured by Lion Specialty Chemicals, trade name "Cadenax DM12D-W". In formula (b1) above, R ⁶ = straight-chain alkyl group having 12 carbon atoms, R ⁷ = methyl group, R ⁸ = methyl group, r=0.

<(C) Component>
· C-1: Protease, trade name "Savinase Ultra 16XL", 2000 kPU/g, manufactured by Novozymes Japan.
C-2: Protease, trade name “ProgressUno 100L”, 1800 kPU/g, manufactured by Novozymes Japan.

<(D) Component>
· D-1: Amylase, trade name "Amplify Prime 100L", 350 kAU/g, manufactured by Novozymes Japan.
· D-2: amylase, trade name "Termamyl Ultra 300L", 115 kAU/g, manufactured by Novozymes Japan.

<(CD) Component: Mixture of (C) Component and (D) Component>
CD-1: A mixture of protease and amylase, trade name "Medley Core 210L", 1440 kPU/g, 70 kAU/g, manufactured by Novozymes Japan.

<(E) Component>
E-1: Polyoxyethylene mono(2-propylheptyl) ether (EO10), manufactured by BASF, trade name "Lutensol XP100". A compound of m = 10, x = 3, y = 5 in the general formula (e1).

<Optional component>
- Ethanol (EtOH): manufactured by Kanto Kagaku Co., Ltd.
· pTSH: p-toluenesulfonic acid, manufactured by Kanto Kagaku Co., Ltd.
- Catalase: trade name "Terminox Ultra 50L", 50 kCU/g, manufactured by Novozymes Japan.
- pH adjuster: Sodium hydroxide, manufactured by Kanto Kagaku Co., Ltd.
• Solvent: tap water.

(Examples 1 to 43, Comparative Examples 1 to 3)
According to the compositions shown in Tables 1 to 4, they were prepared by the following procedure.
The composition in the table is expressed in % by mass unless otherwise specified, and is in terms of pure content. However, the compounded amount of the enzyme is the compounded amount of the formulation. In addition, in the table, components without description of compounding amount are not compounded.
In the table, the blending amount of water “balance” is the amount necessary to make the whole to 100% by mass. In the table, the "appropriate amount" of the pH adjuster is the amount necessary to achieve the pH shown in the table.
The components (A), (B) and ethanol were placed in a 1 L beaker and stirred with a magnetic stirrer (manufactured by NISSIN, product name SW-R800). Then, water was added so that the total amount was 50% by mass, and after stirring, the component (E) was added and mixed. Appropriate amounts of pTSH and a pH adjuster were added so that the pH at 25° C. was in the range of 6 to 8, and then components (C), (D) and catalase were added and mixed.
After that, water was added so that the total amount was 100% by mass, and the mixture was stirred to obtain a liquid detergent composition of each example.
The pH of the liquid detergent composition was adjusted to 25° C., and a glass electrode pH meter (manufactured by Toa DKK Co., Ltd., product name HM-30G) was used, and the glass electrode was directly immersed in the composition for 1 minute. The values shown after the passage of time were measured. This pH at 25°C is shown in the table.
The liquid detergent composition of each example was evaluated for detergency, foaming property and defoaming property, and the results are shown in the table.
However, Examples 19 to 21, 26, 31, 32, 36 and 43 are reference examples.

(Evaluation method)
<Detergency>
Commercially available Basta sauce (manufactured by the Nisshin Seifun Group, Carbonara with plenty of milk) was diluted with tap water at a water:pasta sauce ratio of 8:2 to remove complex stains of oil, starch, and protein. and
15 g of the composite stain was spread evenly on an aluminum one-handed pan (diameter 18 cm x height 8 cm, manufactured by Pearl Metal Co., Ltd., H-2432) and fixed by heating on an IH hot plate at 160 ° C. for 7.5 minutes.
The liquid detergent composition of each example was diluted with tap water to prepare a cleaning solution containing 0.5% by mass of the liquid detergent composition. 1 L of cleaning liquid was put into the pan and left for 30 minutes. After that, lightly rub the entire bottom of the pot once with a dishwashing sponge (length 11.5 cm x width 7.5 cm x height 3 cm, trade name Scotch Bright, manufactured by Sumitomo 3M) soaked with water, then rinse with tap water. I rinsed the pan. An appointed inspector visually confirmed how much dirt remained on the bottom of the pot and evaluated it based on the following criteria. An evaluation score of 4 points or more was regarded as a pass.

≪Evaluation Criteria≫
5 points: No dirt remains on the bottom of the pan.
4 points: The entire bottom surface of the pot is clean, but a very small amount of dirt is observed upon closer inspection.
3 points: Adhesion of dirt is clearly observed on less than half the area of the bottom of the pan.
2 points: Adhesion of dirt is clearly recognized on half or more of the area of the bottom of the pan.
1 point: Dirt is observed on the entire bottom surface of the pot.

<Foamability>
For evaluation of "<detergency>", 6 g of the same composite stain was evenly spread on a ceramic dish (φ13 cm, height 7 cm) and left overnight to fix. The liquid detergent composition of each example was diluted with tap water at 25°C to obtain the "detergent concentration (%)" in the table. The concentration of the liquid detergent composition of each example is shown in "Detergent Concentration (%)" in the table. 200 mL of this washing solution was placed in an earthenware dish and left to soak for 30 minutes. After that, 50 g of the washing liquid in the ceramic dish was taken on a dishwashing sponge (length 11.5 cm×width 7.5 cm×height 3 cm, trade name: Scotch Bright, manufactured by Sumitomo 3M), and the sponge was rubbed 10 times by hand to create foam. The foam quality (foam feel) of the spongy foam generated at this time was visually observed, and the foamability was evaluated based on the following evaluation criteria.

≪Evaluation Criteria≫
I: Very fine, viscous, creamy foam that hardly drips from the sponge.
II: Fine-textured, creamy foam that does not easily drip from the sponge.
III: The foam has a fine texture but lacks a creamy feeling, and tends to drip off the sponge.
IV: Rough, watery lather that spills out of the sponge.

<Antifoaming>
In the same manner as in “<Foamability>”, a ceramic dish with adhered composite stains and a washing solution were prepared. A ceramic dish with adhered composite soil was immersed in the cleaning solution for 30 minutes. After that, a dishwashing sponge (length 11.5 cm x width 7.5 cm x height 3 cm, product name Scotch Bright, manufactured by Sumitomo 3M) is rubbed with the cleaning liquid in the ceramic dish 10 times to create a foam, and the foamed liquid is After pouring into the drain port, the time until the bubbles disappear with a constant water flow (0.1 L/min) was measured. Evaluation was made based on the following criteria, and I to III were regarded as acceptable.

≪Evaluation Criteria≫
I: Less than 40 seconds until foam disappears.
II: 40 seconds or more and less than 50 seconds until bubbles disappear.
III: The time until bubbles disappear is 50 seconds or more and less than 70 seconds.
IV: 70 seconds or more and less than 80 seconds until bubbles disappear.
V: The time required for bubbles to disappear is 80 seconds or longer.

As shown in Tables 1 to 4, Examples 1 to 43 to which the present invention was applied had a detergency evaluation of 4 to 5 points and an antifoaming evaluation of any of I to III.
Comparative Example 1 lacking the component (a1) was evaluated as V in antifoaming properties. Comparative Example 2 with an A/B ratio of 0.68 and Comparative Example 3 with an A/B ratio of 2.13 had a detergency of 2 to 3 points and an antifoaming evaluation of IV.
From the above results, it was confirmed that the detergency and antifoaming properties can be enhanced by applying the present invention.

Claims (8)

(A) component: an anionic surfactant containing at least one component (a1) selected from secondary alkanesulfonates, dialkylsulfosuccinates and compounds represented by the following formula (a1-1);
(B) component: an amine oxide surfactant;
(C) component: protease and
(D) component: amylase;
contains
The mass ratio represented by the component (A)/component (B) is 0.7 to 2 ,
A dishwashing liquid detergent composition, wherein the mass ratio represented by component (a1)/(component (C)+component (D)) is 3 to 20 .

[In the formula (a1-1) , R ¹ and R ² are independently alkyl groups having 1 to 8 carbon atoms, the total number of carbon atoms of R ¹ and R ² is 6 to 16, and R ³ represents hydrogen. PO represents a propyleneoxy group.
EO represents an ethyleneoxy group. p represents the average repeating number of PO, q represents the average repeating number of EO, and p+q is 0-10. M is a counterion and is one selected from alkali metals, alkaline earth metals and alkanolammonium. ] 2. The dishwashing liquid detergent composition according to claim 1, wherein the mass ratio represented by component (a1)/component (A) is 0.05 to 1. 3. The dishwashing liquid detergent composition according to claim 1, wherein the mass ratio represented by component (C)/component (D) is 0.2-20. (a2) component: contains an anionic surfactant other than the (a1) component, and is represented by the (a2) component/(the (a1) component + the (C) component + the (D) component) The liquid dishwashing detergent composition according to any one of claims 1 to 3, wherein the mass ratio is 0.4 to 5. (E) Component: The liquid dishwashing detergent composition according to any one of claims 1 to 4, further comprising a compound represented by the following formula (e1).

[In the formula (e1), AO represents both or one of an ethyleneoxy group and a propyleneoxy group. m represents the average repetition number of AO and is a number from 6 to 12. Each of x and y is an integer of 1 to 6, and 6≦x+y≦12. ] The liquid dishwashing detergent composition according to claim 5, wherein the mass ratio represented by component (E)/(component (A) + component (B)) is 0.01 to 5. (the (a1) component + the (C) component + the (D) component) / (the (A) component + the (B) component + the (E) component) is 0.1 7. The dishwashing liquid detergent composition according to claim 5 or 6, wherein the ratio is ~0.2. After immersing the tableware in a cleaning liquid containing 0.01 to 50% by mass of the liquid detergent composition according to any one of claims 1 to 7 for 5 minutes to 10 hours, the tableware is rubbed with a cleaning tool, or A method for washing tableware, comprising removing the tableware from the washing liquid without rubbing and rinsing the removed tableware with purified water.