JP7178936B2 - Dishwashing Liquid Detergent Composition - Google Patents

Description

The present invention relates to liquid dishwashing detergent compositions.

In recent years, due to changes in consumer lifestyles, "quickness" is emphasized in dishwashing behavior. Important factors that lead to "quickness" include high "detergency" that firmly removes oil stains, good "foaming" that gives a sense of detergency, and good "drainage" after washing. If all of "detergency", "foaming" and "drainage" are good, it is easy to realize "quickness".

Patent Document 1 proposes a dishwashing detergent containing an anionic surfactant, at least one of a semipolar surfactant and an amphoteric surfactant, a cationized cellulose, and a specific nonionic surfactant. there is According to the invention described in Patent Document 1, suppression of nulliness during washing and rinsing is achieved.
US Pat. No. 6,200,005 proposes a dishwashing detergent composition containing a hydrophobic emollient and a specific amount of protease. According to the invention described in Patent Document 2, it is intended to provide hand skin care benefits without affecting detergency and lathering.

JP 2018-35251 A Japanese Patent Publication No. 2013-536279

However, in the conventional technique, when rinsing is insufficient, the water drainability is lowered. By "insufficient rinsing" is meant low rinsing water or low rinsing frequency. In addition, liquid dishwashing detergent compositions are required to further improve the feeling of "quickness".
Accordingly, an object of the present invention is to provide a liquid dishwashing detergent composition that is superior in detergency, foamability, and drainability.

［式（ａ１）中、Ｒ^１は、炭素数５～１８のアルキル基を表し、Ｒ^２は、炭素数１～１８のアルキル基を表す。Ａ^１、Ａ^２は、それぞれ独立に炭素数２～４のアルキレン基を表し、ｘ、ｙは、平均繰り返し数を表し、それぞれ独立に０～６であり、Ｍ^１は陽イオンを表す。］
＜２＞前記（Ａ）成分／前記（Ｄ）成分で表される質量比が０．０５～０．３である、＜１＞に記載の食器用液体洗浄剤組成物。
＜３＞前記（Ａ）成分／前記（Ｃ）成分で表される質量比が４～５０である、＜１＞又は＜２＞に記載の食器用液体洗浄剤組成物。
＜４＞さらに（Ｅ）成分：下記式（ｅ１）で表される化合物を含有する、＜１＞～＜３＞のいずれかに記載の食器用液体洗浄剤組成物。

［式（ｅ１）中、ＥＯはオキシエチレン基を表す。ｍはＥＯの平均繰返し数を表し、８～１２の数である。ｊとｋはそれぞれ１～６の整数であり、６≦ｊ＋ｋ≦１２である。
ＥＯはオキシエチレン基である。］
＜５＞さらに（Ｆ）成分：酵素を含有する、＜１＞～＜４＞のいずれかに記載の食器用液体洗浄剤組成物。
＜６＞界面活性剤の総質量が１６～３５質量％以上である、＜１＞～＜５＞のいずれかに記載の食器用液体洗浄剤組成物。
＜７＞アルキルポリグリコシドの含有量が５質量％以下である、＜１＞～＜６＞のいずれかに記載の食器用液体洗浄剤組成物。
＜８＞前記（Ａ）成分の含有量が、食器用液体洗浄剤組成物の総質量に対して、０．５～５質量％である、＜１＞～＜７＞のいずれかに記載の食器用液体洗浄剤組成物。
＜９＞前記（Ｂ）成分の含有量が、食器用液体洗浄剤組成物の総質量に対して、５～２０質量％である、＜１＞～＜８＞のいずれか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: a dialkyl sulfosuccinate represented by the following formula (a1) or a salt thereof;
(B) component: at least one selected from semipolar surfactants and amphoteric surfactants;
(C) component: cationized cellulose;
(D) component: an anionic surfactant excluding the (A) component,
contains
The mass ratio represented by the component (A)/component (B) is 0.05 to 0.5,
A dishwashing liquid detergent composition, wherein the mass ratio represented by component (D)/component (B) is 0.5 to 1.5.

[In formula (a1), R ¹ represents an alkyl group having 5 to 18 carbon atoms, and R ² represents an alkyl group having 1 to 18 carbon atoms. A ¹ and A ² each independently represent an alkylene group having 2 to 4 carbon atoms, x and y each independently represent an average repeating number of 0 to 6, and M ¹ represents a cation. ]
<2> The dishwashing liquid detergent composition according to <1>, wherein the mass ratio of component (A)/component (D) is 0.05 to 0.3.
<3> The dishwashing liquid detergent composition according to <1> or <2>, wherein the mass ratio of component (A)/component (C) is 4 to 50.
<4> The liquid dishwashing detergent composition according to any one of <1> to <3>, further comprising (E) component: a compound represented by the following formula (e1).

[In the formula (e1), EO represents an oxyethylene group. m represents the average repetition number of EO and is a number from 8 to 12. Each of j and k is an integer from 1 to 6, and 6≤j+k≤12.
EO is an oxyethylene group. ]
<5> The dishwashing liquid detergent composition according to any one of <1> to <4>, further comprising (F) component: an enzyme.
<6> The liquid dishwashing detergent composition according to any one of <1> to <5>, wherein the total weight of the surfactant is 16 to 35% by weight or more.
<7> The liquid dishwashing detergent composition according to any one of <1> to <6>, wherein the content of the alkyl polyglycoside is 5% by mass or less.
<8> The content of the component (A) is 0.5 to 5% by mass with respect to the total mass of the dishwashing liquid detergent composition, according to any one of <1> to <7> A dishwashing liquid detergent composition.
<9> For tableware according to any one of <1> to <8>, wherein the content of the component (B) is 5 to 20% by mass with respect to the total mass of the liquid dishwashing detergent composition. Liquid detergent composition.

The liquid dishwashing detergent composition of the present invention is excellent in detergency, foaming ability and drainability. A liquid dishwashing detergent composition is intended.

(Dishwashing Liquid Detergent Composition)
The dishwashing liquid detergent composition (hereinafter sometimes simply referred to as liquid detergent composition) of the present invention contains the following components (A) to (D).
(A) Component: Dialkyl sulfosuccinate or its salt.
(B) Component: At least one selected from semipolar surfactants and amphoteric surfactants.
(C) Component: cationized cellulose.
(D) Component: an anionic surfactant other than the (A) component.

The pH of the liquid detergent composition of the present invention at 25°C is preferably 6-8. If the pH of the liquid detergent composition at 25°C is within the above range, the drainage property can be further enhanced.
In the present invention, the pH (25°C) of the liquid detergent composition is a value measured by a method conforming to JIS Z 8802:1984 "pH measurement method".

Although the viscosity of the liquid detergent composition of the present invention is not particularly limited, it is preferably 30 to 400 mPa·s, more preferably 100 to 300 mPa·s. If the viscosity is within the above range, the liquid cleaning composition is easy to handle.

<(A) Component>
Component (A) is a dialkyl sulfosuccinate represented by the following formula (a1) or a salt thereof.

[In formula (a1), R ¹ represents an alkyl group having 5 to 18 carbon atoms, and R ² represents an alkyl group having 1 to 18 carbon atoms. A ¹ and A ² each independently represent an alkylene group having 2 to 4 carbon atoms, x and y each independently represent an average repeating number of 0 to 6, and M ¹ represents a cation. ]

R ¹ is an alkyl group having 5 to 18 carbon atoms. The number of carbon atoms in R ¹ is preferably 6-14, more preferably 7-10.
R ¹ may be linear or branched. R ¹ is preferably branched.

R ² is an alkyl group having 1 to 18 carbon atoms. The carbon number of R ² is preferably 6-14, more preferably 7-10.
^R2 may be linear or branched. ^R2 is preferably branched.

A ¹ and A ² are each independently an alkylene group having 2 to 4 carbon atoms. A ¹ and A ² are preferably C 2-3 alkylene groups. When the number of carbon atoms of A ¹ and A ² is 2 to 3, high drainage can be exhibited even if rinsing is insufficient.

The content of component (A) is preferably 0.5 to 5% by mass, more preferably 1 to 3% by mass, relative to the total mass of the liquid detergent composition. If the content of component (A) is within the above range, detergency and foamability will be better, and drainability will be further enhanced.

<(B) Component>
Component (B) is at least one selected from semipolar surfactants and amphoteric surfactants. A liquid detergent composition can improve drainage property by containing the (B) component.
In addition, the term "semipolar surfactant" refers to a surfactant having a semipolar bond (a bond having intermediate properties between a nonpolar bond and a polar bond), and a solution in which the semipolar surfactant dissolves or A substance that becomes cationic or nonionic depending on the pH of the dispersion system to be dispersed.
Examples of semipolar surfactants (hereinafter also referred to as "component (b1)") include amine oxide surfactants and amine alkylene oxide surfactants. Among these, amine oxide surfactants are preferred as the component (b1).
Examples of amine oxide surfactants include alkylamine oxides and alkanoylamide alkylamine oxides, among which compounds represented by the following formula (b1) are preferred.

[In the formula (b1), R ²¹ is 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, and R ²² and R ²³ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, and R ²⁴ is an alkylene group having 1 to 4 carbon atoms. B is -CONH-, -NHCO-, -COO-, -OCO- or -O-, and r is the number 0 or 1; ]

Examples of the compound represented by formula (b1) include lauryldimethylamine oxide (n-dodecyldimethylamine oxide), coconutalkyldimethylamine oxide, lauryldiethylamine oxide, lauramidopropyldimethylamine oxide, and the like. Among these, lauryl dimethylamine oxide is preferable from the viewpoint of the balance between improvement in drainage property and suppression of nulliness.
The component (b1) may be used alone or in combination of two or more.

Amphoteric surfactants (hereinafter also referred to as "component (b2)") include, for example, carboxylate type (also referred to as betaine type), sulfate type, sulfonate type, phosphate type, and the like. is mentioned. Among these, the carboxylate type is preferable as the component (b2).
Carboxylate type amphoteric surfactants include betaine lauryldimethylaminoacetate, betaine coconutalkyldimethylaminoacetate, betaine coconut fatty acid amidopropyl betaine, betaine lauramidopropyldimethylaminoacetate, betaine coconutalkylamidopropyldimethylaminoacetate, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine (cocamidopropyl betaine);
The component (b2) may be used alone or in combination of two or more.

The component (B) may be the component (b1) alone, the component (b2) alone, or a combination of the component (b1) and the component (b2). Component (B) is preferably component (b1).

The content of component (B) is preferably 5 to 20% by mass, more preferably 5 to 15% by mass, relative to the total mass of the liquid detergent composition. If the content of component (B) is within the above range, detergency and foamability will be better, and drainability will be further enhanced.

The mass ratio represented by component (A)/component (B) (A/B ratio) is 0.05 to 0.5, preferably 0.1 to 0.4, and 0.15 to 0.3. is more preferred. If the A/B ratio is at least the above lower limit, the water drainage property can be further enhanced, and better foaming can be obtained. If the A/B ratio is equal to or less than the above upper limit, the detergency can be further enhanced.

<(C) Component>
(C) Component is cationized cellulose. The liquid detergent composition can improve the drainage property by containing the (C) component.
Component (C) includes, for example, a compound represented by the following formula (c1), a compound represented by the following formula (c2), a compound represented by the following formula (c3), and the like. Component (C) includes cation-modified hydroxyethyl cellulose such as hydroxytrimethylammoniopropyl hydroxyethyl cellulose chloride and hydroxyethyl cellulose dimethyldiallylammonium chloride polymer. Among these, the compound represented by the formula (c1) is preferable as the component (C) from the viewpoint of the balance between the improvement of the drainage property and the suppression of the sliminess.

[In formula (c1), t, u, and s are numbers representing the number of repetitions. ]

[In formula (c2), v and w are numbers representing the number of repetitions. ]

The average molecular weight of the compound represented by formula (c1) is 10,000 to 10,000,000.
The average molecular weight of the compound represented by formula (c2) is 10,000 to 1,000,000.
The average molecular weight of the compound represented by formula (c3) is 10,000 to 1,000,000.
An average molecular weight is a weight average molecular weight measured by a gel permeation method.

The degree of cationization of component (C) is preferably 0.5 to 3.5% by mass, more preferably 1.5 to 2.5% by mass. If the degree of cationization is within the above range, the water-removability is enhanced.
Here, the “degree of cationization” is the content (% by mass) of nitrogen atoms derived from the cationizing agent in the molecule of component (C). That is, the degree of cationization is the content of nitrogen atoms with respect to the total mass of component (C).
The degree of cationization of component (C) is calculated based on the specified chemical structure.
When the chemical structure of component (C) is not specified, such as when the ratio of any monomer in component (C) is unknown, the degree of cationization of component (C) can be determined from the nitrogen content obtained experimentally. Calculated. Examples of the method for measuring the nitrogen content in component (C) include the Kjeldahl method.

The viscosity of the 2% by mass aqueous solution of component (C) at 25° C. is preferably 1000 mPa·s or less, more preferably 500 mPa·s or less, and even more preferably 200 mPa·s or less. In addition, when the viscosity of 2 mass % aqueous solution exceeds 1000 mPa*s, the viscosity of 1 mass % aqueous solution is measured. The viscosity of the 1% by mass aqueous solution at 25° C. is preferably 2000 mPa·s or less, more preferably 500 mPa·s or less. If the viscosity of the 2% by mass aqueous solution or the viscosity of the 1% by mass aqueous solution of component (C) is within the above range, the drainage property can be further enhanced, and the viscosity of the liquid detergent composition can be made more appropriate.

Viscosity is a value obtained by measuring an object to be measured (aqueous solution of component (C)) at 25°C with a Brookfield viscometer. The viscosity measurement conditions are as follows.
≪Measurement conditions≫
[rotor]
The rotor numbers corresponding to the viscosities to be measured are as follows.
・When the viscosity of the object to be measured is less than 300 mPa·s: Rotor No. No. 2.
・When the viscosity of the object to be measured is 300 mPa·s or more and 1200 mPa·s: Rotor No. No. 3.
・When the viscosity of the object to be measured is 1200 mPa·s or more: Rotor No. No. 4.
[Rotor speed]
60 rpm.
[Read Number]
60 seconds after the start of rotation of the rotor.

(C) component, for example, trade name "Leoguard GP (cationization degree 1.8% by mass, manufactured by Lion Specialty Chemicals Co., Ltd.)", trade name "Leoguard MGP (cationization degree 1.8% by mass, Lion Specialty Chemicals Co., Ltd.)”, trade name “Leogard MLP (cationization degree 0.6 mass%, Lion Specialty Chemicals Co., Ltd.)”, trade name “UCARE JR125 (cationization degree 1.9 mass %, manufactured by Dow Chemical Co.)”, trade name “UCARE JR400 (degree of cationization 1.9% by mass, manufactured by Dow Chemical Co.)”, trade name “UCARE LR30M (degree of cationization 1.0% by mass, manufactured by Dow Chemical Co.)” chemical company)” and the like. Among these, as component (C), "UCARE JR125" and "UCARE JR400" are preferable, and "UCARE JR125" is more preferable, from the viewpoint of further increasing drainage.
Component (C) may be used alone or in combination of two or more.

The content of component (C) is preferably 0.04 to 1% by mass, more preferably 0.1 to 0.5% by mass, relative to the total mass of the liquid detergent composition. (C) If content of a component is more than the said lower limit, drainability will be improved more. If the content of component (C) is equal to or less than the above upper limit, foaming can be improved.

The mass ratio (A/C ratio) represented by component (A)/component (C) is preferably 4-50, more preferably 8-25. If the A/C ratio is at least the above lower limit, foaming can be made better, and drainage can be further enhanced. If the A/C ratio is equal to or less than the above upper limit, the detergency can be further enhanced, and the drainability can be further enhanced.

<(D) Component>
Component (D) is an anionic surfactant other than component (A). Component (D) may be any anionic surfactant conventionally used in liquid detergent compositions and the like. Component (D) includes, for example, linear alkylbenzene sulfonic acid or its salt, α-olefin sulfonic acid or its salt, linear or branched alkyl sulfate or its salt, polyoxyalkylene alkyl ether sulfate or its salt. , polyoxyalkylene alkenyl ether sulfate esters or salts thereof, alkanesulfonic acids having alkyl groups or salts thereof, α-sulfo fatty acid esters or salts thereof, and the like.
Examples of the salt form of the anionic surfactant include alkali metal salts such as sodium and potassium; alkaline earth metal salts such as calcium and magnesium; alkanolamine salts such as monoethanolammonium, diethanolammonium and triethanolamine. .

As the straight-chain alkylbenzenesulfonic acid or its salt, a straight-chain alkylbenzenesulfonic acid having a straight-chain alkyl group having 8 to 16 carbon atoms or a salt thereof is preferable, and a straight-chain alkylbenzenesulfonic acid having a straight-chain alkyl group having 10-14 carbon atoms. or salts thereof are particularly preferred.
As the α-olefin sulfonic acid or its salt, an α-olefin sulfonic acid having 10 to 20 carbon atoms or its salt is preferable.
As the linear or branched alkyl sulfate or its salt, an alkyl sulfate having 10 to 20 carbon atoms or its salt is preferable.
Examples of polyoxyalkylene alkyl ether sulfate esters or salts thereof include compounds represented by the following general formula (d1).

R ¹¹ —O—[(PO) _p /(EO) _q ]—SO ₃ ⁻ 1/X·M ⁺ (d1)

[In the formula (d1), R ¹¹ is a linear or branched alkyl group having 8 to 18 carbon atoms, and the carbon atom bonded to the oxygen atom is a primary carbon atom. PO represents an oxypropylene group and EO represents an oxyethylene group. p represents the average repetition number of PO and is a number that satisfies 0≦p<1. q represents the average repetition number of EO and is a number that satisfies 0<q≦4. M ⁺ is the counterion and X is the valence of M. ]

The carbon number of R ¹¹ is 8 to 18, preferably 10 to 14, more preferably 12 to 14.

The average repeating number of PO (that is, the average number of added moles of propylene oxide) is 0 or more and less than 1, preferably 0.
The average repeating number of EO (that is, the average number of added moles of ethylene oxide) is more than 0 and 4 or less, preferably 1-3.

Examples of M ⁺ include alkali metal ions, alkaline earth metal ions, alkanolammonium, and the like. Alkali metal ions include sodium ions and potassium ions. Alkaline earth metal ions include calcium ions and magnesium ions. Alkanolammonium includes monoethanolammonium, diethanolammonium and triethanolammonium.

In (PO) _p /(EO) _q , EO and PO may be added at random or added in blocks, and the arrangement state does not matter.

Examples of the compound represented by formula (d1) include polyoxyethylene (1) linear alkyl (C12) ether sulfate sodium salt, polyoxyethylene (2) linear alkyl (C12) ether sulfate sodium salt, Polyoxyethylene (4) linear alkyl (C12) ether sulfate sodium salt, polyoxypropylene (0.4) polyoxyethylene (1.5) linear alkyl (C12) ether sulfate sodium salt, polyoxyethylene ( 1) Linear alkyl (C12/14 = 75/25; derived from natural fat) ether sulfate sodium salt, polyoxyethylene (2) Linear alkyl (C12/14 = 75/25; derived from natural fat) ether sulfate sodium salt, polyoxyethylene (4) linear alkyl (C12/14 = 75/25; derived from natural fats and oils) ether sulfate ester sodium salt, polyoxypropylene (0.4) polyoxyethylene (1.5) linear alkyl ( C12/14=75/25; derived from natural oils and fats) ether sulfate ester sodium salt and the like.
The polyoxyalkylene alkenyl ether sulfate ester or salt thereof has a linear or branched alkenyl group having 8 to 18 carbon atoms, and has an average of 1 to 10 mol of ethyleneoxy group (EO) added, and an average Preferred is one to which 0 to 6 mol of propyleneoxy group (PO) is added (that is, polyoxyethylene (propylene) alkenyl ether sulfate).
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.

Alkanesulfonic acids having an alkyl group or salts thereof include alkanesulfonic acids having 10 to 20 carbon atoms or salts thereof, preferably alkanesulfonic acids having 14 to 17 carbon atoms or salts thereof, and secondary alkanesulfones. Acids or salts thereof are particularly preferred.

As α-sulfo fatty acid esters or salts thereof, α-sulfo fatty acid ester salts having 10 to 20 carbon atoms are preferable.
These anionic surfactants are readily available on the market. Moreover, you may use what was synthesize|combined by the well-known method.

From the viewpoint of further improving drainage, the component (D) preferably contains at least a polyoxyalkylene alkyl ether sulfate ester or a salt thereof (hereinafter also referred to as "component (d1)"), and polyoxyethylene (1 ) linear alkyl (C12/14=75/25; derived from natural fats and oils) ether sulfate ester sodium salt is more preferred.
Component (D) may be used alone or in combination of two or more.

The content of component (D) is preferably 5 to 15% by mass, more preferably 8 to 15% by mass, even more preferably 8 to 12% by mass, relative to the total mass of the liquid detergent composition. If the content of component (D) is within the above range, detergency and foamability will be improved, and drainability will be further enhanced.

The mass ratio (A/D ratio) represented by component (A)/component (D) is preferably 0.05 to 0.3, more preferably 0.14 to 0.22. If the A/D ratio is at least the above lower limit, the drainage property can be further enhanced. If the A/D ratio is equal to or less than the above upper limit, foaming can be improved.

The mass ratio (D/B ratio) represented by component (D)/component (B) is 0.5 to 1.5, preferably 0.9 to 1.4. If the D/B ratio is at least the above lower limit, detergency and foamability can be improved. If the D/B ratio is equal to or less than the above upper limit, the drainage property can be further enhanced.

<(E) component>
The (E) component is a compound represented by the following general formula (e1).
Liquid detergent composition can aim at the further improvement of drainability by containing (E) component.

[In the formula (e1), EO represents an ethyleneoxy group. m represents the average repetition number of EO and is a number from 8 to 12. Each of j and k is an integer from 1 to 6, and 6≤j+k≤12. ]

m is preferably 8-10, more preferably 9-10. If m is within the above range, the drainage property can be further enhanced. Note that m here indicates the average repetition number of EO. Therefore, the compound represented by formula (d1) may be a compound having a single EO repeating number, or may be an aggregate of molecules having different EO repeating numbers.

Each of j and k is an integer from 1 to 6, and 6≤j+k≤12. Among them, 6≦j+k≦10 is preferable, 6≦j+k≦8 is more preferable, and j+k=8 is even more preferable, because the drainage property becomes better.

C _j H _2j+1 and C _k H _2k+1 in formula (e1) each include a linear or branched alkyl group, preferably a linear alkyl group. Suitable examples of C _j H _2j+1 and C _k H _2k+1 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Among them, C _j H _2j+1 and C _k H _2k+1 include a combination of an ethyl group and a butyl group, and a combination of a propyl group and a pentyl group (either group may be used in any combination). A combination of a propyl group and a pentyl group (one can be either group) is particularly preferred.

As the component (E), an ethylene oxide adduct of an alcohol having a branched structure at the β-position, which is obtained by condensation of two molecules by the Garbet reaction, is particularly suitable.
Suitable (E) component includes, for example, polyoxyethylene mono(2-propylheptyl) ether manufactured by BASF. Specifically, Lutensol XP90 (trade name, j = 5, k = 3, m = 9 in formula (e1)), Lutensol XP100 (trade name, j = 5, k = in formula (e1) 3, m=10 compounds).

The content of component (E) is preferably 3 to 10% by mass, more preferably 5 to 8% by mass, relative to the total mass of the liquid detergent composition. If the content of component (E) is at least the above lower limit, foaming can be improved and drainage can be improved. (E) If the content of the component is equal to or less than the above upper limit, the detergency can be further enhanced.

<(F) Component>
The (F) component is an enzyme.
By containing the component (F), the liquid detergent composition can further enhance the detergency and drainability.

Component (F) includes protease, amylase, cellulase, pectinase, mannanase, catalase and the like. Among them, protease and amylase are preferable from the viewpoint of further improving water drainage and detergency.

As the protease, a protease having serine, histidine and aspartic acid in the molecule, such as serine protease, is preferred.
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, Progress Uno 101L; trade names Purafect L, Purafect OX, Properase L available from Genencore.

Examples of amylase preparations include Termamyl 300L, Termamyl Ultra 300L, Duramyl 300L, Stainzyme 12L, Stainzyme Plus 12L and Amplify Prime available from Novozymes; Maxamyl available from Genencore; name Pullulanase Amano; trade name DB-250 available from Seikagaku Corporation;
When protease or amylase is contained, it is preferable to contain catalase for the purpose of enhancing its stability. As a result, residual hydrogen peroxide derived from the amine oxide surfactant can be decomposed.

The content of component (F) is preferably 0.01 to 0.5% by mass, more preferably 0.1 to 0.5% by mass, more preferably 0.2 to 0.2% by mass, relative to the total mass of the liquid detergent composition. 0.3% by mass is more preferred. If the content of the component (F) is at least the above lower limit, the detergency can be further enhanced and the drainage property can be further enhanced. (F) If content of a component is below the said upper limit, precipitation etc. will not arise easily in a liquid detergent composition.

<Optional component>
The liquid detergent composition may contain components other than components (A), (B), (C), (D), (E) and (F) as long as they do not impair the effects of the present invention. A component (optional component) may be contained.
Examples of optional components include components used in liquid detergent compositions for dishes and clothes. Active agents (optional surfactants), hydrotropic agents, preservatives, pH adjusters, bleaching components, metal trapping components, radical trapping agents, fragrances and the like.

<<Optional surfactant>>
Examples of optional surfactants include nonionic surfactants other than component (E), cationic surfactants, and the like.
Examples of nonionic surfactants (optional nonions) other than the component (E) include polyoxyalkylene alkyl ethers and alkyl polyglycosides. Optional nonions may be used singly or in combination of two or more.
Cationic surfactants include, for example, didecyldimethylammonium chloride, didecyldimethylammonium methosulfate, distearyldimethylammonium chloride, dioctyldimethylammonium chloride, distearyldihydroxyethylammonium chloride, ditallowalkyldimethylammonium chloride, di(stearoyl oxyethyl)dimethylammonium chloride, di(oleoyloxyethyl)dimethylammonium chloride, di(palmitoyloxyethyl)dimethylammonium methosulfate, di(stearoyloxyisopropyl)dimethylammonium chloride, di(oleoyloxyisopropyl)dimethylammonium chloride, di(oleoyloxybutyl)dimethylammonium chloride, di(stearoyloxyethyl)methylhydroxyethylammonium methosulfate, tri(stearoyloxyethyl)methylmethosulfate and the like. The "beef tallow alkyl" group has 14 to 18 carbon atoms.
Cationic surfactants may be used singly or in combination of two or more.

However, an alkyl polyglycoside having an alkyl group with 10 to 14 carbon atoms tends to reduce water drainage. Therefore, the content of the alkyl polyglycoside having 10 to 14 carbon atoms in the alkyl group is preferably 5% by mass or less, more preferably less than 3% by mass, and 1% by mass with respect to the total mass of the liquid detergent composition. Less than is more preferred, and no content is particularly preferred.

The total amount of surfactants (total surfactant amount) is preferably 16 to 35% by mass, more preferably 20 to 30% by mass, more preferably 22 to 27% by mass, relative to the total mass of the liquid detergent composition. preferable. If the total amount of surfactant is at least the above lower limit, the cleansing power and foamability will be excellent. If the total amount of surfactant is equal to or less than the above upper limit, the drainage property can be further enhanced.

≪Hydrotropic agent≫
Containing a hydrotrope agent in the liquid detergent composition mainly improves the storage stability (especially low-temperature stability) of the liquid detergent composition, making it easier to stably ensure a transparent appearance.
Hydrotropic agents include, for example, toluenesulfonic acid, toluenesulfonate, cumenesulfonic acid, cumenesulfonate, ethanol and the like.
The hydrotrope agent may be used singly or in combination of two or more.
In the hydrotropic agent, toluenesulfonic acid, toluenesulfonate, cumenesulfonic acid, and cumenesulfonate may be any of the three isomers of o-isomer, m-isomer, and p-isomer, and among these, they are readily available. The p-isomer is preferred because it is possible, and among them, p-toluenesulfonic acid and p-toluenesulfonate are more preferred.
The content of the hydrotrope agent is preferably 2-30% by mass, more preferably 3-10% by mass, relative to the total mass of the liquid detergent composition. If the content of the hydrotrope agent is within the above range, it is possible to sufficiently obtain the blending effect without lowering the detergency and water-removability.

≪Preservative≫
By containing a preservative, the liquid detergent composition can suppress the growth of microbes even if the liquid detergent composition is contaminated with microorganisms.
Examples of antiseptics include isothiazoline compounds, and specific examples include benzisothiazolinone (1,2-benzisothiazolin-3-one), methylisothiazolinone (2-methyl-4-isothiazolin-3 -on), butylbenzisothiazolinone, chloromethylisothiazolinone, octylisothiazolinone, dichlorooctylisothiazolinone, and the like.
Preservatives may be used singly or in combination of two or more.
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 preferred. If the content of the antiseptic is within the above range, it is possible to sufficiently obtain the effects of the combination without deteriorating the detergency and drainage.

≪pH adjuster≫
Examples of pH adjusters include inorganic alkaline agents and organic alkaline agents.
Examples of inorganic alkaline agents include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like. Among these, hydroxides such as sodium hydroxide and potassium hydroxide are preferable because they tend to improve the storage stability of the liquid detergent.
Examples of organic alkaline agents include monoethanolamine, diethanolamine, triethanolamine, N-methylpropanol, 2-amino-2-methyl-1-propanol, N-(β-aminoethyl)ethanolamine, diethylenetriamine, morpholine, and amine compounds such as N-ethylmorpholine. Among these, monoethanolamine is preferred because it tends to improve the storage stability of the liquid detergent.
When the pH of the liquid detergent is too high, inorganic acids such as hydrochloric acid and sulfuric acid; and acids such as carboxylic acids such as acetic acid and citric acid may be used as pH adjusters.
In addition, the sum total of content of all the components contained in a liquid detergent composition shall be 100 mass %.

(Production method)
The liquid detergent composition of the present invention comprises, for example, the above-described components (A), (B), (C) and (D), and optionally components (E), (F) or optional components can be dissolved in water and adjusted to a predetermined pH using a pH adjuster.

(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). The rinsing operation includes, for example, a method of rinsing the object to be washed with running water, a method of immersing the object to be washed in rinsing water stored in a container or the like, and then pulling it out. At this time, with the liquid detergent composition of the present invention, even if the amount of rinsing water is small or the number of times of rinsing is small, the water adhering to the object to be cleaned is quickly washed down.

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, with the liquid detergent composition of the present invention, even if the amount of rinsing water is small or the number of times of rinsing is small, the water adhering to the object to be cleaned is quickly washed down.

In the liquid detergent composition of the present invention described above, the component (D) in a specific ratio to the component (A), the component (C) in a specific ratio to the component (A), and the component (D) Since it contains the component (B) in a specific ratio, it has excellent detergency and foamability, and also has excellent drainage even with insufficient rinsing. For this reason, after washing the tableware, even if the tableware is immersed in water and pulled up in a "preliminary rinse", water shortage occurs in a small number of times. The reason for this is considered as follows.
The drainability is determined by the fact that the components (C) and (D) form a complex (aggregate), the aggregate adsorbs to the surface of objects to be washed such as tableware, and the component (D) is removed from the component (C) during rinsing. Drainability is expressed by detachment. However, since the aggregate of the (C) component and the (D) component has a strong binding force, it is difficult to separate with a small physical force such as "rinse", and the drainage property is not exhibited. On the other hand, the aggregate of components (A) and (C) has a relatively weak binding force and is likely to be detached, but may impair detergency and foamability. Therefore, by setting the A/B ratio and the D/B ratio within specific ranges, the number of aggregates of the (C) component and the (D) component is relatively reduced. As a result, the components (A) and (D) can be easily separated from the component (C) without deteriorating the detergency and foamability, and the detergency and foamability are good, and excellent drainability is exhibited. It is considered that
Furthermore, the addition of component (E) improves the ease of detachment of aggregates of components (A) and (C) due to structural similarity, so it is thought that even more insufficient rinsing will exhibit drainage properties. be done.
In addition, although the reason is not clear, it is believed that the addition of an enzyme improves the ease of detachment of aggregates of components (C) and (D), so that the water-removability is exhibited even with fewer rinsing times.

[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: dialkyl sulfosuccinate (salt)>
A-1: Di-2-ethylhexyl sodium sulfosuccinate (trade name: Lipal 870P, manufactured by Lion Specialty Chemicals Co., Ltd.). A compound of formula (a1) wherein R ¹ and R ² are 2-ethylhexyl groups, M ¹ is sodium, x=0 and y=0.

<(B) component: semipolar surfactant, amphoteric surfactant>
B-1: n-dodecyldimethylamine oxide (trade name: Cadenax DM12D-W, manufactured by Lion Specialty Chemicals Co., Ltd.). In formula (b1), a compound in which R ²¹ is a linear alkyl group having 12 carbon atoms, R ²² is a methyl group, R ²³ is a methyl group, and r=0.
B-2: Lauramidopropyl dimethylamine oxide (trade name: GENAMINOX AP, manufactured by Clariant Japan Co., Ltd.). In the formula (b1), a compound in which R ²¹ is a linear alkyl group having 12 carbon atoms, R ²² is a methyl group, R ²³ is a methyl group, r = 1, and R ²⁴ = a propylene group.
B-3: Cocamidopropyl betaine (Ovasolin CAB-30, manufactured by Toho Chemical Industry Co., Ltd.).

<(C) component: cationized cellulose>
C-1: Cationized cellulose (degree of cationization: 1.9% by mass, trade name: UCARE JR 125, manufactured by Rohm and Haas Japan Co., Ltd.).
C-1: Cationized cellulose (degree of cationization: 1.9% by mass, trade name: UCARE JR 400, manufactured by Rohm and Haas Japan Co., Ltd.).

<Component (D): anionic surfactant excluding component (A)>
D-1: Sodium polyoxyethylene alkyl ether sulfate (synthesized in Synthesis Example 1 below). In formula (d1), R ¹¹ is a linear alkyl group having 12 to 14 carbon atoms, q=1, and M ⁺ is sodium.

<<Synthesis Example 1>> Synthesis of D-1 In a 4 L autoclave, 400 g of CO1270 alcohol (trade name, manufactured by Procter & Gamble Co., Ltd. (C12/C14 = 75%/25%, mass ratio)) as raw material alcohol, and a catalyst for reaction and 0.8 g of a potassium hydroxide catalyst were charged as . 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, D-1 was obtained by neutralizing this with an aqueous sodium hydroxide solution.

D-2: Sodium alkylbenzene sulfonate having 10 to 14 carbon atoms (trade name "Taika Power L121" manufactured by Tayka Co., Ltd. neutralized with sodium hydroxide).
D-3: Sodium secondary alkanesulfonate having 14 to 17 carbon atoms (HOSTAPUR SAS 30A, manufactured by Clariant Japan KK).

<(E) component: specific nonionic surfactant>
E-1: Polyoxyethylene mono(2-propylheptyl) ether (EO10) (trade name: Lutensol XP100, manufactured by BASF Japan Ltd.). A compound of formula (E1) where m=10, j=3, and k=5.
E-2: Polyoxyethylene mono(2-propylheptyl) ether (EO9) (trade name: Lutensol XP90, manufactured by BASF Japan Ltd.). A compound of formula (E1) wherein m=9, j=3 and k=5.

<(F) component: enzyme>
F-1: Protease (trade name: ProgressUno, manufactured by Novozymes Japan Co., Ltd.).
F-2: Amylase (trade name: Amplify Prime, manufactured by Novozymes Japan Co., Ltd.).

<Optional component>
E'-1 (optional nonion): Alkyl polyglycoside having an alkyl group with 12 to 14 carbon atoms (trade name: GLUCOPON600CSUP, manufactured by BASF Japan Ltd.).
Ethanol (Kanto Kagaku Co., Ltd.).
p-toluenesulfonic acid (pTS-H, manufactured by Kanto Kagaku Co., Ltd.).
Sodium benzoate (manufactured by Kanto Kagaku Co., Ltd.).
2-methyl-4-isothiazolin-3-one (MIT, trade name: Neoron M-10, manufactured by Rohm and Haas Japan Co., Ltd.)
1,2-benzisothiazolin-3-one (BIT, trade name: PROXEL XL2, manufactured by Arch Chemicals).
Citric acid (citric acid (anhydrous), manufactured by Fuso Chemical Co., Ltd.).
Zinc oxide (manufactured by Mitsui Mining & Smelting Co., Ltd.).
Sulfamic acid (manufactured by Fuso Chemical Industry Co., Ltd.).
Fragrance: Fragrance composition A or fragrance composition B described in Tables 1 to 6 of Japanese Patent Application 2017-085282.
pH adjuster: sodium hydroxide or sulfuric acid.
Water: distilled water.

(Evaluation method)
<Drainability>
≪Item to be washed≫
φ18.5cm pottery plate (no dirt).
≪Evaluation method≫
38 g of tap water and 2 g of the liquid detergent composition of each example are placed on a dishwashing sponge measuring 11.5 cm x 7.5 cm x 3 cm. I scrubbed and washed it several times. After that, the earthenware dish was immersed in a washing tub containing 5 L of tap water at 25° C. for 30 seconds for rinsing. This earthenware plate was made almost vertical and leaned against a commercially available dish basket. After that, the ceramic dish was visually observed to confirm whether or not the water flowed down from the ceramic dish and 100% of the surface of the ceramic dish was free of water within 30 seconds.
If water does not adhere to 100% of the entire surface of the ceramic dish within 30 seconds, immerse it in a washing tub containing 5 L of tap water at 25 ° C for 30 seconds again, and evaluate the above-mentioned drainage. Carried out. Confirmation of drainability was performed up to 10 times and evaluated according to the following evaluation criteria.

≪Evaluation Criteria≫
A: Rinsing is 3 times or less.
B: 4 to 6 times of preliminary rinsing.
C: 7 to 10 rinsing times.
D: The entire surface of the ceramic dish does not become free of water within 30 seconds even after 10 times.

<Detergency>
≪Preparation of oil stains≫
As the oil stain, beef tallow (manufactured by Wako Pure Chemical Industries, Ltd.) and Sudan IV (manufactured by Kanto Chemical Co., Ltd.), which are solid fats, were mixed to prepare colored beef tallow (colored beef tallow). The Sudan IV concentration in the colored beef tallow was set at 1% by weight.

≪Preparation of dirt model≫
1 g of the colored beef tallow was evenly applied to the entire inner surface of a plastic container (trade name: Neo Keeper, manufactured by Iwasaki Kogyo Co., Ltd.) measuring 10 cm long, 15 cm wide, and 5 cm high. and

≪Washing test≫
38 g of tap water and 2 g of the liquid detergent of each example were placed on a dishwashing sponge (trade name: Scotch-Brite, manufactured by Sumitomo 3M) measuring 11.5 cm long, 7.5 cm wide, and 3 cm high. After kneading with, it was scrubbed and washed. Specifically, with a sponge containing tap water and a liquid detergent, rub the inner bottom surface of the dirt model 10 times, the inner surface once, and the inner four corners 5 times, then rinse with tap water. operated.

≪Evaluation of detergency against oil stains≫
After scrubbing, the degree of removal of oil stains on the inner surface of the container was evaluated.
This evaluation was performed based on the following evaluation criteria (four-grade evaluation), and was used as an evaluation of detergency against oil stains.

≪Evaluation Criteria≫
A: No residual staining of colored beef tallow was visually observed, and no sliminess due to residual colored beef oil.
B: Stain residue of colored beef tallow is not visually observed, but there is slight sliminess due to residual colored beef tallow.
C: Residual stains of colored beef tallow are visually observed, and there is sliminess due to residual colored beef tallow.
D: Quite a lot of residual stains of colored beef tallow are observed.

<foaming>
38 g of tap water at 25° C. and 2 g of a liquid detergent are placed on a dishwashing sponge (manufactured by Sumitomo 3M Co., Ltd., trade name: Scotch Bright) measuring 11.5 cm long, 7.5 cm wide, and 3 cm high. The state after rubbing (the degree of foaming) was evaluated according to the following evaluation criteria.

≪Evaluation Criteria≫
A: Foam covered the entire surface of the sponge.
B: The proportion of foam covering the sponge surface was less than 50-80% of the surface area of the sponge.
C: The proportion of foam covering the sponge surface was less than 30-50% of the surface area of the sponge.
D: The proportion of foam covering the sponge surface was less than 30% of the surface area of the sponge.

(Examples 1 to 26, Comparative Examples 1 to 8)
1000 g of liquid detergent compositions shown in Tables 1 to 3 were prepared by the following procedure.
Components (A), (D), ethanol, pTS-H, sodium benzoate, and citric acid were placed in a 1 L beaker and stirred with a magnetic stirrer (“F-606N” manufactured by Fine). Subsequently, components (B), (C), (E) and other optional components were added and mixed. After that, after adding an appropriate amount of a pH adjuster as necessary so that the pH at 25° C. is 7.8, water is added so that the total amount becomes 100% by mass, and the mixture is stirred well. A liquid detergent composition was obtained.
The pH (25° C.) of the liquid detergent composition was measured by adjusting the temperature of the liquid detergent composition to 25° C., using a glass electrode pH meter (manufactured by Toa DKK Co., Ltd., "HM-30G"). The sample was directly immersed in the liquid detergent composition, and the pH was measured after 1 minute. The measurement method was performed in accordance with JIS Z 8802:1984 "pH measurement method".
The compounding amount (% by mass) in the table is a pure content conversion value (however, component (F) is the amount as a formulation). Ingredients whose blending amounts are not listed in the table are not blended. The "appropriate amount" of the pH adjuster is the amount necessary to adjust the pH of the liquid detergent composition to 7.8. The blending amount of water “balance” is the amount necessary to make the total amount of the liquid detergent composition 100% by mass.
The liquid detergent composition of each example was evaluated for drainage, detergency and foamability, and the results are shown in the table.

As shown in Tables 1 to 3, Examples 1 to 26 to which the present invention was applied were "A" to "C" in all of the water drainage, detergency and foamability.
Comparative Examples 1 to 3 lacking any of the components (A) to (C), Comparative Example 5 having an A/B ratio of 0.03, and Comparative Example 8 having a D/B ratio of 1.9 are all The drainage property was "D".
Comparative Example 4 lacking component (D) and Comparative Example 6 having an A/B ratio of 0.85 had a detergency of "D".
Comparative Example 7 with a D/B ratio of 0.4 had a "D" foam.
From these results, it was confirmed that the detergency, foaming ability, and drainability can be enhanced by applying the present invention.

Claims (7)

(A) component: a dialkyl sulfosuccinate represented by the following formula (a1) or a salt thereof;
(B) component: at least one selected from semipolar surfactants and amphoteric surfactants;
(C) component: cationized cellulose;
Component (D): linear alkylbenzene sulfonic acid or its salt, α-olefin sulfonic acid or its salt, linear or branched alkyl sulfate or its salt, polyoxyalkylene alkyl ether sulfate or its salt, polyoxyalkylene at least one selected from alkenyl ether sulfate esters or salts thereof, alkanesulfonic acids having alkyl groups or salts thereof, and α-sulfo fatty acid esters or salts thereof;
and no alkyl polyglycosides,
The content of component (A) is 0.5 to 5% by mass, the content of component (B) is 5 to 15% by mass, and the content of (C) is based on the total mass of the dishwashing liquid detergent composition. The content of the component is 0.04 to 0.5% by mass, the content of the component (D) is 5 to 15% by mass,
The mass ratio represented by the component (A)/component (B) is 0.05 to 0.5,
A dishwashing liquid detergent composition, wherein the mass ratio represented by component (D)/component (B) is 0.5 to 1.5.

[In formula (a1), R ¹ represents an alkyl group having 5 to 18 carbon atoms, and R ² represents an alkyl group having 1 to 18 carbon atoms. A ¹ and A ² each independently represent an alkylene group having 2 to 4 carbon atoms, x and y each independently represent an average repeating number of 0 to 6, and M ¹ represents a cation. ] 2. The dishwashing liquid detergent composition according to claim 1, wherein the mass ratio represented by component (A)/component (D) is 0.05 to 0.3. 3. The dishwashing liquid detergent composition according to claim 1, wherein the mass ratio represented by component (A)/component (C) is 4 to 50. Furthermore, (E) component: containing a compound represented by the following formula (e1),
The liquid dishwashing detergent composition according to any one of claims 1 to 3, wherein the content of the component (E) is 5 to 8% by mass relative to the total mass of the liquid dishwashing detergent composition. thing.

[In the formula (e1), EO represents an oxyethylene group. m represents the average repetition number of EO and is a number from 8 to 12. Each of j and k is an integer from 1 to 6, and 6≤j+k≤12. EO is an oxyethylene group. ] The liquid dishwashing detergent composition according to any one of claims 1 to 4, further comprising (F) component: an enzyme. The dishwashing liquid detergent composition according to claim 5 , wherein the component (F) is one or more selected from protease and amylase . The liquid dishwashing detergent composition according to any one of claims 1 to 6 , wherein the total weight of the surfactant is 16 to 35% by weight with respect to the total weight of the liquid dishwashing detergent composition.