JP7138557B2 - Dishwashing Liquid Detergent Composition - Google Patents

Description

The present invention relates to liquid dishwashing detergent compositions.

As a method for washing kitchen utensils such as tableware and cooking utensils (hereinafter sometimes referred to generally as tableware), there is a method of applying a liquid dishwashing detergent composition to a cleaning tool such as a sponge and rubbing the object to be cleaned with the cleaning tool. Yes (non-immersion method). Non-immersion methods are perceived by consumers as physically and time-intensive.
In order to facilitate washing of tableware, there is a method (immersion method) in which a liquid dishwashing detergent composition is dispersed in water to form a washing solution, the dishes are immersed in this washing solution, and then the dishes are scrubbed with a sponge or the like. be.

For example, Patent Document 1 proposes a dishwashing liquid detergent containing a specific surfactant and a specific alcohol in a specific ratio. According to the invention of Patent Literature 1, an attempt is made to improve the performance of removing oil stains in washing by soaking (immersion method).

JP 2016-14102 A

However, in the conventional technique, although the cleaning power in the immersion method is improved, the bubbles washed away by rinsing after cleaning accumulate in the drain port of the sink and are difficult to disappear.
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、ｎは１～６の整数である。Ｒ ^１１ は、直鎖もしくは分岐鎖のアルキル基、又は直鎖もしくは分岐鎖のアルケニル基である。Ｒ ^１２ は、水素原子又は（ＣＨ_２）_ｍＮＨ_２であり、ｍは１～６の整数である。］
［２］前記（Ａ）成分／（前記（Ｃ）成分＋前記（Ｄ）成分）で表される質量比は、１．３～３０である、［１］に記載の食器用液体洗浄剤組成物。
［３］前記（Ｄ）成分は、プロテアーゼ及びアミラーゼから選ばれる１種以上である、［１］又は［２］に記載の食器用液体洗浄剤組成物。
［４］前記（Ｄ）成分は、前記プロテアーゼ及び前記アミラーゼの双方を含み、前記プロテアーゼ／前記アミラーゼで表される質量比が０．２～２０である、［３］に記載の食器用液体洗浄剤組成物。 The present invention has the following aspects.
[1] (A) component: an anionic surfactant,
(B) component: one or more selected from amphoteric surfactants and amine oxide surfactants;
(C) component: a compound represented by the following formula (c1);
(D) component: an enzyme,
contains
A dishwashing liquid detergent composition, wherein the mass ratio represented by component (A)/component (B) is 0.5 to 2.

[In the formula, n is an integer of 1 to 6. R ¹¹ is a linear or branched alkyl group or a linear or branched alkenyl group. R ¹² is a hydrogen atom or (CH ₂ ) _m NH ₂ , where m is an integer of 1-6. ]
[2] The liquid dishwashing detergent composition according to [1], wherein the mass ratio represented by component (A)/(component (C) + component (D)) is 1.3 to 30. thing.
[3] The liquid detergent composition for dishes according to [1] or [2], wherein the component (D) is one or more selected from protease and amylase.
[4] The dish washing liquid according to [3], wherein the component (D) contains both the protease and the amylase, and the mass ratio of the protease/amylase is 0.2 to 20. agent composition.

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).
(A) Component: Anionic surfactant.
(B) component: one or more selected from amphoteric surfactants and amine oxide surfactants.
(C) component: a compound represented by the following formula (c1).
(D) Component: Enzyme.

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 using a pH meter according to JIS Z 8802:2011 "pH measurement method".

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>
(A) Component is an anionic surfactant.
Component (A) is, for example, a straight-chain alkyl ether sulfate or alkenyl ether sulfate, a straight-chain alkyl sulfate, a straight-chain alkylbenzenesulfonate, an α-olefinsulfonate, an α-sulfofatty acid ester, Straight-chain alkanesulfonates, higher fatty acid salts and the like can be mentioned. These salts include alkali metal salts such as sodium and potassium, alkanolamine salts such as monoethanolamine and diethanolamine, and the like.
The (A) component of the present invention includes polyoxyalkylene alkyl ether sulfate represented by the following general formula (a1), linear alkylbenzene sulfonate represented by the following general formula (a2), and α-olefin sulfonic acid. Anionic surfactants selected from salts are preferred.

R ³ —O—(PO) _x —(EO) _y —SO ₃ M (a1)

In formula (a1), R ³ is preferably a linear alkyl group having 8 to 18 carbon atoms, more preferably 10 to 16 carbon atoms, even more preferably 12 to 14 carbon atoms. R ³ is preferably an alkyl group derived from a vegetable oil raw material from the standpoints of detergency and environment. Suitable oil and fat raw materials include palm kernel oil, coconut oil, and the like.
PO represents a propyleneoxy group and EO represents an ethyleneoxy group.
x represents the repeating number of PO (average added mole number of polyoxypropylene). y represents the average repeating number of EO (that is, the average added mole number of polyoxyethylene).
0≦x<1 and 0≦y≦4 are preferred, more preferably x is 0 and 0≦y≦2, and when both EO and PO are present, their arrangement state does not matter.

R ⁴ —C ₆ H ₄ —SO ₃ M (a2)

In formula (a2), ^R4 is a linear or branched alkyl group, preferably a linear alkyl group. The number of carbon atoms in R ⁴ is 8 to 18, and is preferred.
The average carbon number of R ⁴ is preferably 10-18, more preferably 12-14.
M is a counterion and represents an alkali metal such as sodium or potassium, or an alkanolammonium such as monoethanolammonium, diethanolammonium or triethanolammonium.

Examples of component (A) include polyoxyethylene (1) linear alkyl (C12) sulfate sodium salt, polyoxyethylene (2) linear alkyl (C12) sulfate sodium salt, polyoxyethylene (3) linear Chain 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 (3) linear alkyl (C12/14 = 75/25; derived from natural fats and oils) Sulfuric acid ester sodium salt, polyoxypropylene (0.4) polyoxyethylene (1.5) linear alkyl (C12/14 = 75/25; derived from natural fats and oils) Sulfuric acid ester sodium salts, linear alkyl (C10-14) benzenesulfonic acid sodium salts, C 12-14 α-olefin sulfonic acid sodium salts, and the like.
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 an alkyl group having 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 (A) components may be used individually by 1 type, and may be used in combination of 2 or more types as appropriate.

The content of component (A) is preferably 5 to 18% by mass, more preferably 7 to 18% by mass, even more preferably 9 to 15% 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 washing liquid after the immersion operation can be enhanced. If the content of the component (A) is equal to or less than the above upper limit, the uniformity of the liquid in the liquid detergent composition is enhanced, the liquid detergent composition is rapidly dissolved in water, and the washing effect by the immersion method is obtained. can be exhibited more stably. "Liquid uniformity" refers to the property of a liquid detergent composition that is resistant to precipitation, cloudiness, separation, and gelation.

<(B) component: one or more selected from amphoteric surfactants and amine oxide surfactants>
Component (B) is one or more selected from amphoteric surfactants and amine oxide surfactants.
Examples of amphoteric surfactants include betaine surfactants, and one or more selected from the group consisting of betaine alkyldimethylaminoacetate, betaine fatty acid amidopropyldimethylaminoacetate, alkylhydroxysulfobetaine, and fatty acid amide hydroxysulfobetaine. amphoteric surfactants can be used.
Among them, a betaine-type amphoteric interface selected from the group consisting of fatty acid (8 or more and 22 or less carbon atoms) amidopropyldimethylaminoacetic acid betaine and fatty acid (8 or more and 22 or less carbon atoms) amidopropyl hydroxysulfobetaine having a fatty acid amide group. Activators are preferred.
As the fatty acid (8 or more and 22 or less carbon atoms) amidopropyldimethylaminoacetate betaine, lauramidopropyldimethylaminoacetate betaine and coconut oil fatty acid amidopropyldimethylaminoacetate betaine are more preferred. Component (B) preferably has 8 to 22 carbon atoms, more preferably 10 to 18 carbon atoms, still more preferably a betaine type amphoteric surfactant having an alkyl group of 12 to 16 carbon atoms.

Amine oxide surfactants include, for example, alkylamine oxides and alkylamidopropyldimethylamine oxides.
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 6 to 18% by mass, more preferably 6 to 15% by mass, and even more preferably 7 to 12% by mass, relative to the total mass of the liquid detergent composition. (B) If the content of the component is at least the above lower limit, the detergency in the immersion method can be further enhanced. If the content of the component (B) 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 represented by component (A)/component (B) (A/B ratio) is 0.5 to 2, preferably 0.7 to 1.8, and 1 to 1. .6 is more preferred. If the A/B ratio is at least the above lower limit, the detergency in the immersion method can be further enhanced. If the A/B ratio is equal to or less than the above upper limit, the antifoaming properties can be further enhanced.

<(C) Component>
The component (C) is a compound represented by the following formula (c1).

[In the formula, n is an integer of 1 to 6. R ¹¹ is a linear or branched alkyl group or a linear or branched alkenyl group. R ¹² is a hydrogen atom or (CH ₂ ) _m NH ₂ , where m is an integer of 1-6. ]

In formula (c1), n is preferably 1 to 4, more preferably 3. If n is within the above range, the detergency and antifoaming properties in the immersion method can be further enhanced.

R ¹¹ is preferably a linear or branched alkyl group. The number of carbon atoms in the alkyl group or alkenyl group of R ¹¹ is preferably 8-18, more preferably 8-16, even more preferably 10-14. If the number of carbon atoms is within the above range, the detergency and antifoaming properties in the immersion method can be further enhanced.
Examples of R ¹¹ include a cocoalkyl (coconut oil)-derived hydrocarbon group, a beef tallow-derived hydrocarbon group, a lauryl group, a myristyl group, a palmityl group, an oleyl group, etc. Among these, cocoalkyl (coconut oil) A derived hydrocarbon group and a lauryl group are preferred, and a lauryl group is more preferred.

R ¹² is preferably (CH ₂ ) _m NH ₂ . If R ¹² is (CH ₂ ) _m NH ₂ , the detergency and antifoaming properties in the immersion method can be further enhanced.
m is an integer of 1 to 6, preferably an integer of 1 to 4, more preferably 3.

As the component (C), N,N-bis(3-aminopropyl)alkylamine with m=n=3 is preferable because of its excellent detergency and antifoaming properties in the immersion method.

The content of component (C) is preferably 0.02 to 3% by mass, more preferably 0.2 to 2% by mass, relative to the total mass of the liquid detergent composition. If the content of component (C) is at least the above lower limit, the detergency in the immersion method can be further improved. (C) If content of a component is below the said upper limit, the antifoaming property can be improved further.

<(D) component: enzyme>
The (D) component is an enzyme. Component (D) includes, for example, protease, amylase, lipase, cellulase, pullulanase, and the like.
Component (D) may be used alone or in combination of two or more.
Component (D) is preferably one or more selected from protease (component (d1)) and amylase (component (d2)), and more preferably contains both component (d1) and component (d2). The combination of the (d1) component and the (d2) component further enhances the antifoaming properties.

The content of component (D) in the liquid detergent composition is preferably 0.05 to 5% by mass, more preferably 0.5 to 5% by mass, and 1 to 5% by mass, relative to the total mass of the liquid detergent composition. 4% by mass is more preferred. If the content of component (D) is at least the above lower limit, the detergency can be further enhanced and the antifoaming property can be further enhanced. When 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.

<<(d1) component: protease>>
Component (d1) 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 (d1) in the liquid detergent composition is preferably 0.05 to 5% by mass, more preferably 0.5 to 5% by mass, and 1 to 5% by mass, relative to the total mass of the liquid detergent composition. 4% by mass is more preferred. If the content of the component (d1) is at least the above lower limit, it is possible to further improve the detergency and antifoaming properties in the immersion method. If the content of the component (d1) is equal to or less than the above upper limit, the uniformity of the liquid can be further improved.
In addition, content of (d1) component is a compounding quantity as a formulation.

The protease activity Ep (kPU/g) per gram of the liquid detergent composition is preferably 1-100 kPU/g, more preferably 10-100 kPU/g, and even more preferably 20-80 kPU/g.

[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 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.). 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 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.). 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.

<<(d2) component: amylase>>
(d2) component includes, for example, Termamyl 300L, Termamyl Ultra 300L, Duramyl 300L, Stainzyme 12L, Stainzyme Plus 12L and AmplifyPrime 100L available from Novozymes; available trade name Pullulanase Amano, trade name DB-250 available from Seikagaku Corporation, and the like.

The (d1) component and the (d2) component may be incorporated into one enzyme. For example, Medley Core 210L (trade name, manufactured by Novozymes) and the like can be preferably used as an enzyme preparation containing the (d1) component and the (d2) component.

The content of component (d2) in the liquid detergent composition is preferably 0.05 to 5% by mass, more preferably 0.5 to 5% by mass, and 1 to 5% by mass, relative to the total mass of the liquid detergent composition. 4% by mass is more preferred. If the content of the component (d2) is at least the above lower limit, the detergency in the immersion method can be further improved. If the content of the component (d2) is equal to or less than the above upper limit, the uniformity of the liquid can be further improved.
In addition, content of (d2) component is a compounding quantity as a formulation.

Further, the amylase activity Ea (kAU/g) per gram of the liquid detergent composition is preferably 0.18 to 18 kAU/g, more preferably 1.8 to 18 kAU/g, and further preferably 3.5 to 14 kAU/g. preferable.

[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.

In the liquid detergent composition, the mass ratio (d1/d2 ratio) represented by component (d1)/component (d2) is preferably 0.2 to 20, more preferably 0.5 to 10, and 1 to 5. is more preferred. If the d1/d2 ratio is within the above range, the detergency and antifoaming properties in the immersion method can be further enhanced.

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 detergency and antifoaming properties in the immersion method can be further enhanced.

In the liquid detergent composition, the mass ratio (A/(C+D)) represented by (A) component/((C) component + (D) component) is preferably 1.3 to 30, and 1.3 ~12 is more preferred, and 2.0 to 6.0 is even more preferred. If the A/(C+D) ratio is at least the above lower limit, the antifoaming property can be further enhanced. If the A/(C+D) ratio is equal to or less than the above upper limit, detergency and antifoaming properties 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) to (C), solvents, preservatives, disinfectants, hydrotropes, inorganic builders, pH adjusters, bleaching components, and metal capture. Conventionally known components such as components, radical trapping agents, fragrances, and pigments can be used.

[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.

[Preservative]
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% by mass) relative to the total mass of the liquid detergent composition. mass ppm) is more preferred.

[Disinfectant]
Examples of disinfectants include zinc sulfate, zinc chloride, and zinc oxide.
[Inorganic builder]
Examples of inorganic builders include magnesium sulfate.

[Optional surfactant]
Optional surfactants include cationic surfactants.
The total amount (total mass) of surfactants in the liquid cleaning composition is preferably 4 to 45% by mass, more preferably 10 to 35% by mass, more preferably 15 to 30% by mass, relative to the total mass of the liquid cleaning composition. % by mass is more 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 (C)).
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 0.5 to 30% by mass, more preferably 2 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 (D) 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.
Examples of the method for producing a liquid detergent composition include a method in which components other than a pH adjuster are added to a portion of water as a solvent, mixed, adjusted to an arbitrary pH, and then the rest of the water is added. be done.

(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 concentration of the liquid detergent composition in the cleaning liquid in the immersion method is preferably 0.5 to 30% by mass with respect to the total mass of the cleaning liquid. 1 to 20% by mass is more preferable, and 1 to 10% by mass is even more preferable. If the concentration of the liquid detergent composition is within the above range, it is possible to further improve the detergency and antifoaming properties in the immersion method.

In the present invention, the cleaning solution of the immersion method has a component (A) of 250 to 54,000 mass ppm, a component (B) of 300 to 54,000 mass ppm, a component (C) of 20 to 3,000 mass ppm, and a component of (D) of 50 to 5000 mass ppm. Cleaning liquids containing 9000 ppm by weight and having an A/B ratio of 0.5 to 2.0 are preferred.

The concentration of component (A) in the cleaning liquid is preferably 350 to 36,000 ppm by mass, more preferably 450 to 18,000 ppm by mass, relative to the total mass of the cleaning liquid.
The concentration of component (B) in the cleaning liquid is preferably 300 to 36,000 ppm by mass, more preferably 350 to 18,000 ppm by mass, relative to the total mass of the cleaning liquid.
The concentration of component (C) in the cleaning liquid is preferably 30 to 1500 mass ppm.
The concentration of component (D) in the cleaning liquid is preferably 100 to 3000 mass ppm.

By adjusting the contents of the components (A) to (D) in the cleaning solution within the above ranges, the cleaning power and antifoaming properties in the immersion method can be further improved.

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 longer, more preferably 5 minutes to 10 hours, and even more preferably 15 minutes to 1 hour. 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, if necessary, the object to be cleaned may be scrubbed with a cleaning tool in the cleaning liquid.
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 water containing no liquid detergent composition (rinsing water) to wash away the cleaning liquid 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.

[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>
· A-1: Sodium polyoxyethylene alkyl ether sulfate (AES). In formula (a1), R ³ = linear alkyl group having 12 to 14 carbon atoms, x = 0, y = 1, M = sodium ion, prepared by the following method.

<<Production Example 1>> Preparation of A-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 A-1.

A-2: Sodium α-olefin sulfonate (AOS) having 14 carbon atoms. Lion Specialty Chemicals, trade name "Liporan LB440".
A-3: Sodium alkylbenzenesulfonate (LAS) having 10 to 14 carbon atoms. Tayka's trade name "Tayka Power L121" is neutralized with sodium hydroxide.

<(B) Component>
· B-1: n-dodecyldimethylamine oxide (AX). In formula (b1), R ⁶ = n-dodecyl group, R ⁷ = methyl group, R ⁸ = methyl group, r = 0, manufactured by Lion Akzo Co., Ltd., trade name "Aromox DM12D-W".
· B-2: cocamidopropyl betaine (CAPB). Toho Chemical Industry Co., Ltd., trade name "Obazoline CAB-30".

<(C) Component>
· C-1: N-(3-aminopropyl)-N-dodecylpropane-1,3-diamine. In formula (c1), R ¹¹ =lauryl group, R ¹² =(CH ₂ ) _m NH ₂ , m=n=3, manufactured by Lonza Japan, trade name “Lonzabac 12.100”.
· C-2: N-cocoalkyl-1,3-diaminopropane. In formula (c1), R ¹¹ =alkyl group derived from coconut oil (having 12 and 14 carbon atoms), R ¹² =H, n=3, product name “Lipomin DA-CD” manufactured by Lion Specialty Chemicals.

<(D) Component>
• D-1: A mixture of protease and amylase. Novozymes Japan Co., Ltd., trade name "Medley Core 210L" (1440 kPU/g, 70 kAU/g).
• D-2: Protease. Novozymes Japan Co., Ltd., trade name “ProgressUno 100L” (1800 kPU/g).
• D-3: Protease. Novozymes Japan Co., Ltd., trade name “Savinase Ultra 16XL” (2000 kPU/g).
• D-4: Amylase. Novozymes Japan Co., Ltd., trade name “Amplify Prime 100L” (350 kAU/g).
• D-5: Amylase. Novozymes Japan Co., Ltd., trade name "TermamylUltra 300L" (115 kAU/g).

<Optional component>
- Ethanol (EtOH): Trade name "Ethyl alcohol fermentation Traceable 95 1st class" manufactured by Japan Alcohol Sangyo Co., Ltd.
- Citric acid: manufactured by Fuso Chemical Industry Co., Ltd., trade name "purified citric acid (anhydrous)".
• Perfume composition A: Perfume composition A described in Tables 1-6.
• Perfume composition B: Perfume composition B described in Tables 1-6.
· p-toluenesulfonic acid (pTSH): manufactured by Meiyu Sangyo Co., Ltd.
- Water: deionized water.

(Examples 1 to 28, Comparative Examples 1 to 4)
According to the composition shown in Tables 7-9, it was 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 adjust the pH of the liquid detergent composition to 7.8.
The components (A), (B) and ethanol were placed in a 200 mL beaker and stirred with a magnetic stirrer. Then, water was added and stirred so that the total amount was 50% by mass. After that, add citric acid, component (C) and p-toluenesulfonic acid to adjust the pH, add perfume and component (D), then add the remaining water so that the total amount becomes 100 parts by mass, A liquid detergent composition for each example was prepared.
The pH was measured by adjusting the detergent to 25° C. and using a glass electrode pH meter (product name: Horiba F-22, manufactured by Horiba, Ltd.). The measurement method was performed according to JISZ8802:2011.
The liquid detergent composition of each example was evaluated for detergency, foaming property and defoaming property, and the results are shown in the table.

(Evaluation method)
<Detergency>
A stainless plate (10 cm×10 cm) was coated with 3 g of carbonara sauce (starch/protein/oil composite stain) and heated at 130° C. for 5 minutes to bake the stain. The mass of the stainless steel plate on which the dirt was baked was measured, and this was taken as the mass of the stainless steel plate before cleaning.
The liquid detergent composition was diluted with water to prepare a cleaning liquid having the "detergent concentration (%)" in the table. A stainless steel plate on which stains were baked was immersed in this cleaning liquid.
After 30 minutes from the start of the immersion, the stainless steel plate was pulled out of the cleaning liquid, and after repeating the operation of immersing the stainless steel plate three times, the stainless steel plate was pulled out of the cleaning liquid. After the stainless plate was left to stand for one day to dry, the mass of the stainless plate was measured, and this was taken as the mass of the stainless plate after washing.
The washing rate was obtained from the following formulas (1) and (2), and evaluated according to the following evaluation criteria. Evaluations I to III were regarded as pass.
(Weight of stainless steel plate after cleaning) - (Weight of stainless steel plate before cleaning) = (remaining amount of dirt) (1)
Cleaning rate (%) = 100 - (remaining dirt (g) / 3 (g)) x 100 (2)

≪Evaluation Criteria≫
I: Cleaning rate of 90% or more.
II: Cleaning rate of 70% or more and less than 90%.
III: Cleansing rate of 40% or more and less than 70%.
IV: Cleaning rate of 10% or more and less than 40%.
V: Less than 10% cleaning rate.

<Foamability>
1 g of olive oil, 3 g of rice porridge, and 3 g of milk were added to a ceramic plate (φ13 cm, height cm) to prepare a dirt plate.
The liquid detergent composition was diluted with water to prepare a cleaning liquid having the "detergent concentration (%)" in the table. 200 mL of this cleaning solution was placed in a dirt dish and left to soak for 30 minutes.
After 30 minutes, 50 g of the washing liquid in the dirt dish was taken on a sponge (length 11.5 cm×width 7.5 cm×height 3 cm) and 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 I or II was taken as a pass.

≪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 (soiling dish) to which composite stains adhered and a washing solution were prepared. The soiled dishes were soaked 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 7 to 9, Examples 1 to 28, to which the present invention was applied, had a detergency evaluation of I to III and an antifoaming evaluation of I to III.
Comparative Example 1 lacking component (C), Comparative Example 2 lacking component (D), Comparative Example 3 having an A/B ratio of 0.31, and Comparative Example 4 having an A/B ratio of 4.25 Also, the detergency evaluation was IV or V, and the antifoaming evaluation was IV or V.
From the above results, it was confirmed that the detergency and antifoaming properties can be enhanced by applying the present invention.

Claims (4)

(A) component: an anionic surfactant;
(B) component: one or more selected from amphoteric surfactants and amine oxide surfactants;
(C) component: a compound represented by the following formula (c1);
(D) component: an enzyme,
contains
A dishwashing liquid detergent composition, wherein the mass ratio represented by component (A)/component (B) is 0.5 to 2.

[In the formula, n is an integer of 1 to 6. R ¹¹ is a linear or branched alkyl group or a linear or branched alkenyl group. R ¹² is a hydrogen atom or (CH ₂ ) _m NH ₂ , where m is an integer of 1-6. ] The liquid dishwashing detergent composition according to claim 1, wherein the mass ratio represented by component (A)/(component (C) + component (D)) is 1.3 to 30. The liquid detergent composition for tableware according to claim 1 or 2, wherein the component (D) is one or more selected from protease and amylase. 4. The dishwashing liquid detergent composition according to claim 3, wherein the component (D) contains both the protease and the amylase, and the mass ratio represented by the protease/amylase is 0.2 to 20. .