JP2024084979A - Liquid dishwashing detergent composition - Google Patents

Abstract

[Problem] To provide a liquid dishwashing detergent composition which has high detergency and foaming properties, and in which the foam adhering to the object to be cleaned easily washes off after cleaning, thereby eliminating the step of rinsing the foam off the object to be cleaned with water.
[Solution] A liquid dishwashing detergent composition comprising: component (A): one or more selected from secondary alkyl ether sulfate salts represented by a specific structure and dialkyl sulfosuccinate salts represented by a specific structure; component (B): one or more selected from semi-polar surfactants and amphoteric surfactants; and component (C): a nonionic surfactant represented by a specific structure, wherein the content of component (A) is 0.1 mass% or more and less than 5.0 mass%, relative to the total mass of the liquid dishwashing detergent composition.
[Selection diagram] None

Description

The present invention relates to a liquid dishwashing detergent composition.

In addition to having a strong cleaning power, liquid dishwashing detergent compositions are also required to generate abundant foam during washing (foaming ability).
In recent years, from the viewpoints of reducing the environmental load and effectively utilizing water resources, there has been a demand for reducing the amount of water used in hand washing. For this reason, in liquid dishwashing detergent compositions, it is required to reduce the amount of rinsing water used after washing as much as possible.

For example, Patent Document 1 proposes a liquid dishwashing detergent composition that contains a sulfosuccinic acid alkyl ester or its salt having a specific structure, an anionic surfactant having a sulfate ester group or a sulfonate group, and a sulfobetaine surfactant. According to the invention of Patent Document 1, the composition produces abundant foam during washing and the foam lasts for a long time, but the foam disappears instantly during rinsing, allowing rinsing to be completed with a small amount of water.

JP 2013-100462 A

However, the invention of Patent Document 1 requires an initial step of rinsing the foam adhering to the object to be cleaned with water, and does not take into consideration reducing the amount of water used in this step.

Therefore, the present invention aims to provide a liquid dishwashing detergent composition that has high cleaning power and foaming properties, and allows the foam adhering to the object to be cleaned to easily wash off after cleaning, thereby eliminating the need for a process of rinsing the foam off the object with water.

The present invention has the following aspects.
[1] Component (A): at least one selected from a secondary alkyl ether sulfate salt represented by the following formula (a1) and a dialkyl sulfosuccinate salt represented by the following formula (a2),
Component (B): one or more surfactants selected from semi-polar surfactants and amphoteric surfactants;
Component (C): A nonionic surfactant represented by the following formula (c1),
A liquid dishwashing detergent composition, wherein the content of the component (A) is 0.1 mass % or more and less than 5.0 mass % based on the total mass of the liquid dishwashing detergent composition.

[In formula (a1), R ¹ and R ² each independently represent a linear or branched alkyl group having 1 to 20 carbon atoms, the total number of carbon atoms in R ¹ and the total number of carbon atoms in R ² is 7 to 21, R ³ O represents an oxyalkylene group having 2 to 5 carbon atoms, n is a number from 1 to 20 representing the average number of repetitions of R ³ O, and M represents a counter ion.]

[In formula (a2), R ⁴ represents an alkyl group having 5 to 18 carbon atoms, R ⁵ 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 the average number of repetitions and are 0 to 6, and M ¹ represents a cation.]

[In formula (c1), EO represents an oxyethylene group, m is a number between 8 and 12 representing the average number of EO repeats, j and k are integers between 1 and 6, and 6≦(j+k)≦12.]

[2] The liquid dishwashing detergent composition according to [1], further comprising a component (D): a fatty acid having 8 to 24 carbon atoms or a salt thereof.
[3] The liquid dishwashing detergent composition according to [1] or [2], wherein the mass ratio represented by (the content of the (A) component)/(the content of the (B) component) is 0.1 to 1.0.
[4] The dishwashing liquid detergent composition according to any one of [1] to [3], wherein a mass ratio represented by (the content of the (A) component)/(the content of the (C) component) is 0.1 to 1.0.

The liquid dishwashing detergent composition of the present invention has high cleaning power and foaming properties, and after cleaning, the foam adhering to the object to be cleaned easily washes off, eliminating the need for a process of rinsing the foam off the object with water.

[Liquid dishwashing detergent composition]
The liquid dishwashing detergent composition of the present invention (hereinafter, also simply referred to as liquid detergent) is a composition containing components (A), (B) and (C).

<Component (A)>
The component (A) is at least one selected from a secondary alkyl ether sulfate salt represented by the following formula (a1) (hereinafter also referred to as the component (a1)) and a dialkyl sulfosuccinate salt represented by the following formula (a2) (hereinafter also referred to as the component (a2)):
The liquid detergent containing component (A) can enhance the cleaning power and can also more easily wash off foam adhering to the object to be cleaned (improve the adhesiveness of the foam).

[In formula (a1), R ¹ and R ² each independently represent a linear or branched alkyl group having 1 to 20 carbon atoms, the total number of carbon atoms in R ¹ and the total number of carbon atoms in R ² is 7 to 21, R ³ O represents an oxyalkylene group having 2 to 5 carbon atoms, n is a number from 1 to 20 representing the average number of repetitions of R ³ O, and M represents a counter ion.]

[In formula (a2), R ⁴ represents an alkyl group having 5 to 18 carbon atoms, R ⁵ 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 the average number of repetitions and are 0 to 6, and M ¹ represents a cation.]

In formula (a1), R ¹ and R ² each independently represent a linear or branched alkyl group having 1 to 20 carbon atoms. The number of carbon atoms in the alkyl group of R ¹ is 1 to 20, preferably 1 to 16, and more preferably 1 to 12. When the number of carbon atoms in the alkyl group of R ¹ is equal to or greater than the above lower limit, the foam adhesion can be improved. When the number of carbon atoms in the alkyl group of R ¹ is equal to or less than the above upper limit, the viscosity of the liquid detergent can be reduced, and ease of use (usability) can be improved.
The number of carbon atoms in the alkyl group of ^R2 is the same as the number of carbon atoms in the alkyl group of ^R1 .

In formula (a1), the alkyl group for ^R1 is preferably a linear alkyl group. The same applies to the alkyl group for ^R2 .
In formula (a1), the sum of the number of carbon atoms in ^R1 and the number of carbon atoms in ^R2 is 7 to 21, preferably 9 to 17, and more preferably 11 to 13. When the sum of the number of carbon atoms in ^R1 and the number of carbon atoms in ^R2 is within the above numerical range, high detergency can be maintained and foam adhesion can be improved.

In formula (a1), (R ¹ )(R ² )CH- is a hydrophobic group derived from a higher secondary alcohol. It is believed that the fact that component (a1) has such a hydrophobic group containing a secondary carbon contributes to improving the adhesiveness of the foam.

In formula (a1), R ³ O is an oxyalkylene group having 2 to 5 carbon atoms, and n represents the average number of repetitions of R ³ O.
When n is 2 or more, the multiple (R ³ O) may be the same as or different from each other. R ³ O is preferably an oxyethylene group (hereinafter also referred to as EO) or an oxypropylene group (hereinafter also referred to as PO). When n is 2 or more, the oxyalkylene chain represented by (R ³ O) _n is preferably an EO chain consisting of only EO, or a block chain or random chain consisting of EO and PO.

n is 1 to 20, preferably 2 to 15, and more preferably 3 to 12. A larger n value tends to improve foam adhesion, and a smaller n value tends to provide excellent foamability. When n is within the above numerical range, both adhesion and foamability are excellent.

In formula (a1), M is a counter ion. Examples of the counter ion include an alkali metal ion, an ammonium ion, and a protonated amine. In particular, an alkali metal ion is preferred.
Examples of the alkali metal that can serve as the counter ion include sodium and potassium.
Examples of amines that can serve as the counter ion include primary to tertiary amines (monomethylamine, dimethylamine, trimethylamine, etc.) and alkanolamines (monoethanolamine, diethanolamine, triethanolamine, etc.).

The component (a1) is a compound obtained by sulfating an alcohol alkoxylate obtained by adding an alkylene oxide to a secondary alcohol having a carbon number of 8 to 22, followed by neutralization. The component (a1) may be produced by a conventional method, or a commercially available product may be used.
The component (a1) may be used alone or in combination of two or more types.

The component (a1) preferably has a narrow ratio calculated by the following formula (S) of 40 to 80 mass %, more preferably 50 to 70 mass %. A higher narrow ratio means a narrower distribution of the repeat number (n) of the oxyalkylene group (R ³ O).
When the narrow ratio of the (a1) component is within the above range, it is effective in improving both adhesion and foaming properties in a well-balanced manner.

In formula (S), i represents the number of repetitions (n) of the oxyalkylene group (R ³ O). s _max represents the number of repetitions of the oxyalkylene group in the compound present in the greatest amount in component (a1). Yi represents the proportion (unit: mass%) of the compound present in component (a1) having the added mole number of oxyalkylene groups of i relative to the entire component (a1).
The narrow ratio of the component (a1) can be controlled by a known method, for example, by the production method of the component (a1).
When a mixture of two or more compounds represented by the above formula (a1) is used as the component (a1), the narrow ratio of the component (a1) is the value in the mixture.

The content of the (a1) component is, for example, preferably 0.1% by mass or more and less than 5.0% by mass, and more preferably 1.0% by mass or more and 4.5% by mass or less, based on the total mass of the liquid detergent. When the content of the (a1) component is equal to or more than the above lower limit, the cleaning power can be further improved and the foam adhesion can be further improved. When the content of the (a1) component is less than the above upper limit, the foaming property can be further improved.

In formula (a2), R ⁴ represents an alkyl group having 5 to 18 carbon atoms, and R ⁵ represents an alkyl group having 1 to 18 carbon atoms.
The carbon number of ^R4 is 5 to 18, preferably 6 to 14, and more preferably 7 to 10. ^R4 may be a linear alkyl group or a branched alkyl group. ^R4 is preferably a branched alkyl group.
The carbon number of ^R5 is 1 to 18, preferably 6 to 14, and more preferably 7 to 10. ^R5 may be a linear alkyl group or a branched alkyl group. ^R5 is preferably a branched alkyl group.

In formula (a2), specific examples of R ⁴ and R ⁵ include a hexyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tridecyl group, a 2-ethylhexyl group, an n-octyl group, a sec-octyl group, an isopentyl group, an isononyl group, an isodecyl group, a cyclohexyl group, etc. R ⁴ and R ⁵ are preferably groups selected from an n-octyl group, a sec-octyl group, a decyl group, an isodecyl group, and a 2-ethylhexyl group, and more preferably a 2-ethylhexyl group.

In formula (a2), A ¹ and A ² are each independently an alkylene group having 2 to 4 carbon atoms, and the carbon numbers of A ¹ and A ² are preferably 2 to 3. When the carbon numbers of A ¹ and A ² are 2 to 3, the detergency can be further improved.

In formula (a2), x and y each independently represent an average repeat number of 0 to 6, preferably 0 to 3, and more preferably 0. When x and y are 0 to 3, the cleaning power of the liquid detergent can be further improved. When x is 0, ^R4 is directly bonded to the oxygen atom, and when y is 0, ^R5 is directly bonded to the oxygen atom.

In formula (a2), ^M1 is a cation. Examples of ^M1 include hydrogen ion, sodium ion, ammonium ion, potassium ion, magnesium ion, monoethanolamine, diethanolamine, triethanolamine, etc. ^M1 is preferably a sodium ion, ammonium ion, potassium ion, or magnesium ion, and more preferably a sodium ion or potassium ion.

The method for preparing the compound in which R ⁴ and R ⁵ are the same in the component (a2) is not particularly limited. For example, the compound can be prepared by referring to the method described in U.S. Pat. No. 2,028,091.
As a method for preparing an asymmetric compound having different R ⁴ and R ⁵ , for example, JP-A-58-24555 can be referred to. When using a commercially available compound, Lipar (registered trademark) 870P (a compound in which R ⁴ and R ⁵ are both 2-ethylhexyl groups) manufactured by Lion Specialty Chemicals Co., Ltd., Luensit A-BO (a compound in which R ⁴ and R ⁵ are both 2-ethylhexyl groups) manufactured by BASF Corporation, Aerosol AY-100 (a compound in which R ⁴ and R ⁵ are both amyl groups) and Aerosol A-196 (a compound in which R ⁴ and R ⁵ are both cyclohexyl groups) available from Mitsui Cytec Co., Ltd. can be used.
The component (a2) may be used alone or in combination of two or more types.

The content of the (a2) component is, for example, preferably 0.1% by mass or more and less than 3.0% by mass, and more preferably 1.0% by mass or more and 2.6% by mass or less, based on the total mass of the liquid detergent. When the content of the (a2) component is equal to or more than the above lower limit, the cleaning power can be further improved and the foam adhesion can be further improved. When the content of the (a2) component is less than the above upper limit, the foaming property can be further improved.

The content of component (A) (the sum of the content of components (a1) and (a2)) is, for example, 0.1% by mass or more and less than 5.0% by mass, and preferably 0.1% by mass or more and less than 3.0% by mass, relative to the total mass of the liquid detergent. When the content of component (A) is equal to or more than the lower limit, the cleaning power can be further improved and the foam adhesion can be further improved. When the content of component (A) is less than the upper limit, the foaming property can be further improved.

<Component (B)>
The component (B) is at least one selected from the group consisting of semi-polar surfactants and amphoteric surfactants. By including the component (B), the liquid detergent can have improved cleaning power and foaming properties.

Examples of the semi-polar surfactant include alkyl dimethylamine oxide type semi-polar surfactants, alkanoyl amido alkyl dimethylamine oxide type semi-polar surfactants, and the like.
Examples of the alkyl dimethyl amine oxide type semi-polar surfactant include lauryl dimethyl amine oxide, coconut alkyl dimethyl amine oxide, lauryl diethyl amine oxide, and n-dodecyl dimethyl amine oxide.
Examples of the alkanoyl amido alkyl dimethyl amine oxide type semi-polar surfactants include lauric acid amido propyl amine oxide.
Among these, alkyldimethylamine oxide-type semi-polar surfactants are preferred, and n-dodecyldimethylamine oxide is more preferred, because they have superior cleaning power and foaming properties.
The semi-polar surfactant may be used alone or in combination of two or more kinds.

Examples of the amphoteric surfactant include betaine-based amphoteric surfactants and amino acid-based amphoteric surfactants.
Examples of betaine-based amphoteric surfactants include carbobetaine-based amphoteric surfactants, amidobetaine-based amphoteric surfactants, sulfobetaine-based (hydroxysulfobetaine-based, amidosulfobetaine-based) amphoteric surfactants, imidazolinium betaine-based amphoteric surfactants, phosphobetaine-based amphoteric surfactants, and aminopropionic acid-based amphoteric surfactants.

Examples of the carbobetaine amphoteric surfactant include lauric acid dimethylaminoacetate betaine, myristyl dimethylaminoacetate betaine, and stearyl dimethylaminoacetate betaine.
Examples of amidobetaine amphoteric surfactants include coconut oil fatty acid amidopropyl betaine (cocamidopropyl betaine), lauric acid amidopropyl betaine, and isostearamidopropyl betaine.
Examples of sulfobetaine-based amphoteric surfactants include coconut oil fatty acid dimethylaminohydroxysulfobetaine, lauryl dimethylaminohydroxysulfobetaine, lauryl hydroxysulfobetaine, coconut oil fatty acid dimethylsulfopropylbetaine, lauryl sulfobetaine, stearyl sulfobetaine, and myristyl sulfobetaine.
Examples of the imidazolinium betaine amphoteric surfactant include coconut oil alkyl-N-hydroxyethyl imidazolinium betaine, coconut oil alkyl-N-carboxyethyl-N-hydroxyethyl imidazolinium betaine, and 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine.
An example of the phosphobetaine amphoteric surfactant is lauryl hydroxyphosphobetaine.
Examples of the aminopropionic acid-based amphoteric surfactant include sodium laurylaminodipropionate and triethanolamine laurylaminodipropionate.

Examples of amino acid-based amphoteric surfactants include laurylamino fatty acid salts, stearylamino fatty acid salts, and myristylamino fatty acid salts.

Of these amphoteric surfactants, aminopropionic acid-based amphoteric surfactants are preferred, and sodium laurylaminodipropionate is more preferred, due to their superior cleaning power and foaming properties.
The amphoteric surfactant may be used alone or in combination of two or more kinds.

The content of component (B) is, for example, preferably 0.1 to 20% by mass, more preferably 1 to 15% by mass, and even more preferably 3 to 10% by mass, based on the total mass of the liquid detergent. When the content of component (B) is equal to or greater than the lower limit, the cleaning power and foaming properties can be further improved. When the content of component (B) is equal to or less than the upper limit, the foam adhesion can be improved.

<Component (C)>
The component (C) is a nonionic surfactant represented by the following formula (c1).
The liquid detergent can have improved foaming properties by containing the component (C). In addition, the liquid detergent can have better foam adhesion by using the components (A) and (C) in combination.

[In formula (c1), EO represents an oxyethylene group, m is a number between 8 and 12 that represents the average number of EO repeats, j and k are integers between 1 and 6, and 6≦(j+k)≦12.]

m is preferably 8 to 10, more preferably 9 to 10. When m is within the above numerical range, the foam adhesion can be improved. Here, m represents the average number of EO repeats. Therefore, the nonionic surfactant represented by formula (c1) may be a compound with a single number of EO repeats, or may be an aggregate of molecules with different numbers of EO repeats.

j and k are each an integer from 1 to 6, and 6≦(j+k)≦12. Among these, 6≦(j+k)≦10 is preferred, 6≦(j+k)≦8 is more preferred, and j+k=8 is even more preferred, as this can improve the adhesion of the foam.

In formula (c1), C _j H _2j+1 and C _k H _2k+1 each may be a linear or branched alkyl group, with linear alkyl groups being preferred. 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. Of these, C _j H _2j+1 and C _k H _2k+1 are preferably a combination of an ethyl group and a butyl group, or a combination of a propyl group and a pentyl group (each of the above combinations may be either group), and particularly preferably a combination of a propyl group and a pentyl group (each of the above combinations may be either group).

Particularly preferred examples of component (C) include ethylene oxide adducts of alcohols having a branched structure at the β-position, which are obtained by bimolecular condensation via the Guerbet reaction.
Suitable examples of the component (C) include polyoxyethylene mono(2-propylheptyl)ether manufactured by BASF Corp. Specific examples include Lutensol XP90 (trade name, a compound in formula (c1) where j = 5, k = 3, and m = 9) and Lutensol XP100 (trade name, a compound in formula (c1) where j = 5, k = 3, and m = 10).

The content of component (C) is, for example, preferably 1 to 20% by mass, more preferably 2 to 12% by mass, and even more preferably 4 to 8% by mass, based on the total mass of the liquid detergent. When the content of component (C) is equal to or greater than the above lower limit, the foaming properties can be further improved. In addition, when the content of component (C) is equal to or greater than the above lower limit, the foam adhesion can be further improved. When the content of component (C) is equal to or less than the above upper limit, the cleaning power can be further improved.

In liquid detergents, the mass ratio expressed by (content of component (A))/(content of component (B)) (hereinafter also referred to as "(A)/(B) ratio") is preferably 0.05 to 1.0, more preferably 0.2 to 0.8. When the (A)/(B) ratio is equal to or greater than the above lower limit, the cleaning power can be further improved. In addition, when the (A)/(B) ratio is equal to or greater than the above lower limit, the foam adhesion can be improved. When the (A)/(B) ratio is equal to or less than the above upper limit, gelation can be suppressed, and the liquid stability can be further improved.

In liquid detergents, the mass ratio expressed by (content of component (A))/(content of component (C)) (hereinafter also referred to as "(A)/(C) ratio") is preferably 0.05 to 1.0, more preferably 0.2 to 0.9, and even more preferably 0.2 to 0.45. When the (A)/(C) ratio is equal to or greater than the above lower limit, the cleaning power can be further improved. In addition, when the (A)/(C) ratio is equal to or greater than the above lower limit, the foam adhesion can be further improved. When the (A)/(C) ratio is equal to or less than the above upper limit, the foaming property can be further improved.

<Component (D)>
Component (D) is a fatty acid having 8 to 24 carbon atoms or a salt thereof. That is, component (D) is a higher fatty acid or a salt thereof, that is, a so-called soap.
By including component (D), the liquid detergent can improve foam-breaking properties (make foam easier to disappear) and improve the adhesiveness of foam.

The component (D) is preferably a chain monocarboxylic acid.
Examples of component (D) include single fatty acids such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, and oleic acid, and mixed fatty acids such as coconut oil fatty acid and beef tallow fatty acid.
The carbon number of component (D) is preferably 8 to 18, and more preferably 10 to 16. When the carbon number of component (D) is equal to or greater than the above lower limit, the foam adhesion can be improved. When the carbon number of component (D) is equal to or less than the above upper limit, the cleaning power can be further improved.

The content of component (D) is, for example, preferably 0.1 to 2.0% by mass, more preferably 0.1 to 1.0% by mass, and even more preferably 0.1 to 0.7% by mass, based on the total mass of the liquid detergent. When the content of component (D) is equal to or greater than the lower limit, the adhesion of the foam can be improved. When the content of component (D) is equal to or less than the upper limit, the foaming property can be improved.

<Optional ingredients>
The liquid detergent may contain components (optional components) other than the components (A), (B), (C) and (D) as long as the effects of the present invention are not impaired.
The optional components include those typically used in liquid dishwashing detergent compositions, such as surfactants other than the components (A), (B) and (C) (optional surfactants), water, water-miscible organic solvents, surface modifiers, hydrotropic agents, preservatives, pH adjusters, bleaching components, metal scavenger components, radical trapping agents, fragrances and the like.

Optional surfactants include, for example, anionic surfactants other than component (A), nonionic surfactants other than component (C), cationic surfactants, etc.

Examples of the anionic surfactant other than the component (A) include linear alkylbenzene sulfonic acid or a salt thereof, α-olefin sulfonic acid or a salt thereof, linear alkyl sulfate or a salt thereof, polyoxyalkylene alkyl ether sulfate or a salt thereof, polyoxyalkylene alkenyl ether sulfate or a salt thereof, and α-sulfofatty acid ester or a salt thereof.
Examples of the salt form of the anionic surfactant other than component (A) include alkali metal salts such as sodium and potassium; alkaline earth metal salts such as calcium and magnesium; and alkanolamine salts such as monoethanolamine, diethanolamine, and triethanolamine.

As the linear alkylbenzenesulfonic acid or a salt thereof, a linear alkylbenzenesulfonic acid or a salt thereof having a linear alkyl group with 8 to 16 carbon atoms is preferred, and a linear alkylbenzenesulfonic acid or a salt thereof having a linear alkyl group with 10 to 14 carbon atoms is more preferred.
The α-olefin sulfonic acid or a salt thereof is preferably an α-olefin sulfonic acid having 10 to 20 carbon atoms or a salt thereof.
As the linear alkyl sulfate or its salt, an alkyl sulfate having 10 to 20 carbon atoms or its salt is preferred.

The polyoxyalkylene alkyl ether sulfate or its salt is preferably one having a linear alkyl group having 8 to 18 carbon atoms and having an average of 1 to 10 moles of ethyleneoxy groups (EO) added thereto.
Examples of polyoxyalkylene alkyl ether sulfates or salts thereof 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 ... Examples of the alkyl ether sulfate include sodium kyl (C12/14=75/25; derived from natural fats and oils) ether sulfate, sodium polyoxyethylene (2) linear alkyl (C12/14=75/25; derived from natural fats and oils) ether sulfate, sodium polyoxyethylene (4) linear alkyl (C12/14=75/25; derived from natural fats and oils) ether sulfate, and sodium polyoxypropylene (0.4) polyoxyethylene (1.5) linear alkyl (C12/14=75/25; derived from natural fats and oils) ether sulfate.
Here, for example, "polyoxyethylene (1)" means that the average number of repeating ethyleneoxy groups is 1 (the average number of moles of ethylene oxide added is 1).
"Alkyl(C12)" means that the alkyl group has 12 carbon atoms.
"C12/14=75/25; derived from natural fats and oils" means a mixture of a compound having a linear alkyl group with 12 carbon atoms and a compound having a linear alkyl group with 14 carbon atoms in a mass ratio of 75/25, and means that the linear alkyl groups are derived from natural fats and oils.

Preferred polyoxyalkylene alkenyl ether sulfates or salts thereof are those having a linear or branched alkenyl group with 8 to 18 carbon atoms, with an average of 1 to 10 moles of ethyleneoxy groups (EO) added, and further with an average of 0 to 6 moles of propyleneoxy groups (PO) added (i.e., polyoxyethylene (propylene) alkenyl ether sulfates).

The α-sulfofatty acid ester or its salt is preferably an α-sulfofatty acid ester salt having 10 to 20 carbon atoms.
These anionic surfactants are readily available on the market, and those synthesized by known methods may also be used.

Nonionic surfactants other than component (C) include, for example, polyoxyalkylene alkyl ethers, alkyl polyglycosides, etc.

Examples of cationic surfactants include didecyl dimethyl ammonium chloride, didecyl dimethyl ammonium methosulfate, distearyl dimethyl ammonium chloride, dioctyl dimethyl ammonium chloride, distearyl dihydroxyethyl ammonium chloride, di-tallow alkyl dimethyl ammonium chloride, di(stearoyloxyethyl)dimethyl ammonium chloride, di(oleoyloxyethyl)dimethyl ammonium chloride, di(palmitoyloxyethyl)dimethyl ammonium methosulfate, di(stearoyloxyisopropyl)dimethyl ammonium chloride, di(oleoyloxyisopropyl)dimethyl ammonium chloride, di(oleoyloxybutyl)dimethyl ammonium chloride, di(stearoyloxyethyl)methyl hydroxyethyl ammonium methosulfate, and tri(stearoyloxyethyl)methyl methosulfate. The number of carbon atoms in the "tallow alkyl" group is 14 to 18.

When the liquid detergent contains an optional surfactant, the content of the optional surfactant is preferably, for example, 0.1 to 3.0 mass % relative to the total mass of the liquid detergent.
The optional surfactants may be used alone or in combination of two or more kinds.

The liquid detergent preferably contains water as a solvent, since this makes it easier to handle and improves the adhesiveness of the foam.
The water content is not particularly limited, but is preferably, for example, 50 to 99 mass %, and more preferably 70 to 99 mass %, based on the total mass of the liquid detergent.

Examples of the water-miscible organic solvent include alcohols, glycols, polyglycols, alkyl ethers, and phenoxyethanol.
Examples of the alcohols include ethanol, 1-propanol, 2-propanol, and 1-butanol.
Examples of glycols include propylene glycol, butylene glycol, and hexylene glycol.
Examples of polyglycols include dipropylene glycol and polypropylene glycol.
Examples of alkyl ethers include diethylene glycol monobutyl ether (butyl carbitol), diethylene glycol dimethyl ether, and 3-methoxy-3-methyl-1-butanol.
In this specification, the water-miscible organic solvent refers to an organic solvent that dissolves in an amount of 50 g or more in 1 L of ion-exchanged water at 25°C.

When the liquid detergent contains a water-miscible organic solvent, the content of the water-miscible organic solvent is preferably, for example, 0.1 to 3.0% by mass relative to the total mass of the liquid detergent.
The water-miscible organic solvents may be used alone or in combination of two or more kinds.

The liquid detergent may contain a surface modifier to improve the adhesion of the foam. Examples of the surface modifier include cationic cellulose.
Examples of cationic cellulose include cationic modified hydroxyethyl cellulose such as hydroxytrimethylammoniopropyl hydroxyethyl cellulose chloride and hydroxyethyl cellulose dimethyl diallyl ammonium chloride polymer.

When the liquid detergent contains a surface modifier, the content of the surface modifier is preferably, for example, 0.1 to 1.0 mass % relative to the total mass of the liquid detergent.
The surface modifier may be used alone or in combination of two or more kinds.

Examples of the hydrotropic agent include toluenesulfonic acid, toluenesulfonate salts, cumenesulfonic acid, and cumenesulfonate salts.
In the hydrotropic agent, toluenesulfonic acid, toluenesulfonate, cumenesulfonic acid, and cumenesulfonate may each be any of the three isomers, o-, m-, and p-isomers.
When the liquid detergent contains a hydrotrope agent, the content of the hydrotrope agent is preferably, for example, 0.1 to 1.0 mass % based on the total mass of the liquid detergent.
The hydrotropic agent may be used alone or in combination of two or more kinds.

Examples of preservatives include isothiazoline compounds, such as benzisothiazolinone (1,2-benzisothiazolin-3-one), methylisothiazolinone (2-methyl-4-isothiazolin-3-one), butylbenzisothiazolinone, chloromethylisothiazolinone, octylisothiazolinone, and dichlorooctylisothiazolinone.
When the liquid detergent contains a preservative, the content of the preservative is preferably, for example, 0.0002 to 0.01 mass % (2 to 100 mass ppm) relative to the total mass of the liquid detergent.
The preservatives may be used alone or in combination of two or more kinds.

Examples of the pH adjuster include inorganic alkaline agents and organic alkaline agents.
Examples of inorganic alkaline agents include sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate.
Examples of the organic alkaline agent include amine compounds such as monoethanolamine, diethanolamine, triethanolamine, N-methylpropanol, 2-amino-2-methyl-1-propanol, N-(β-aminoethyl)ethanolamine, diethylenetriamine, morpholine, and N-ethylmorpholine.
If the pH of the liquid cleaning agent is too high, a pH adjuster may be used, for example, an inorganic acid such as hydrochloric acid or sulfuric acid; or an acid such as a carboxylic acid such as acetic acid or citric acid.
The total content of all components contained in the liquid detergent is assumed to be 100% by mass.

<Physical Properties>
The pH of the liquid detergent at 25° C. is preferably, for example, 6 to 8.
The pH of the liquid detergent at 25° C. is a value measured by a method in accordance with JIS Z8802:1984 "pH measurement method."

The viscosity of the liquid detergent at 25°C is, for example, preferably 10 to 200 mPa·s, and more preferably 50 to 150 mPa·s. If the viscosity is equal to or greater than the lower limit, dripping from the spout of the container can be effectively prevented. If the viscosity is equal to or less than the upper limit, the liquid detergent can be more easily dispensed from the container.

The viscosity of the liquid detergent at 25° C. can be adjusted by the water content, addition of a thickener, etc.
The viscosity of a liquid detergent at 25°C is a value measured at 25°C using a Brookfield viscometer with rotor number 1 at a rotor rotation speed of 60 rpm, 60 seconds after the rotor starts rotating.

[Method of manufacturing liquid detergent]
The liquid detergent of the present invention can be produced, for example, by dissolving the above-mentioned components (A), (B) and (C) and, if necessary, the component (D) or any optional components, in water and adjusting the pH to a predetermined value using a pH adjuster.

[how to use]
The method of using the liquid detergent (i.e., for cleaning dishes) is described below.
An example of a method for washing tableware is a method in which a given amount of liquid detergent is applied to a washing tool and the washing tool is used to scrub the object to be washed (scrubbing operation).
The amount of liquid detergent applied to the cleaning tool is, for example, 1 to 10 g.
Examples of the objects to be washed include tableware such as plates, chopsticks, spoons, etc. The objects to be washed may also be cooking utensils such as pots, knives, etc. In this specification, tableware and cooking utensils are collectively referred to as "tableware".
The liquid detergent of the present invention has good foam adhesion (foam adhering to the object to be cleaned can be easily washed off), so that the foam adhering to the object to be cleaned can be removed by tilting the object to be cleaned after scrubbing. This makes it possible to omit the step of rinsing the foam off the object to be cleaned with water. As a result, the amount of water used to wash dishes can be further reduced.
If any foam remains on the object to be cleaned, it may be washed away with purified water (rinsing water) that does not contain the liquid detergent (rinsing operation). Since the liquid detergent of the present invention has good foam adhesion, even if any foam remains on the object to be cleaned, the foam adhering to the object to be cleaned can be quickly washed away with a small amount of rinsing water or a small number of rinses.

Another method for washing tableware is, for example, a method (immersion method) in which a liquid detergent is dispersed in water to prepare a cleaning liquid, and the object to be washed is immersed in the cleaning liquid for a desired time (immersion time) (immersion operation).

The content of the liquid detergent relative to the total amount of the cleaning liquid is, for example, preferably 0.01 to 50 mass % (i.e., 2 to 10,000 times diluted), more preferably 0.05 to 20 mass %, and even more preferably 0.1 to 5 mass %.
The immersion time in the immersion method is determined taking into consideration the degree of dirt on the object to be washed, and is, for example, preferably 5 minutes or more, more preferably 5 minutes to 10 hours, even more preferably 5 minutes to 1 hour, and even more preferably 15 minutes to 1 hour. When the immersion time is equal to or more than the above lower limit, the cleaning power can be further improved. When the immersion time is equal to or less than the above upper limit, the washing time for the tableware can be prevented from being excessively long.

During the immersion operation, the object to be cleaned may be scrubbed with a cleaning tool, such as a sponge or a brush, in the cleaning solution or after being removed from the cleaning solution, as necessary.
The object to be cleaned is immersed in the cleaning liquid for a desired time, and then removed from the cleaning liquid. Since the liquid cleaning agent of the present invention has good foam adhesion, the foam adhering to the object to be cleaned can be removed by tilting the object to be cleaned after the immersion operation. This makes it possible to omit the step of rinsing the foam on the object to be cleaned with water. As a result, the amount of water required to wash dishes can be further reduced.
By using a cleaning liquid, foam adhering to the object to be cleaned can be washed away more effectively.
If any foam remains on the object to be cleaned, a rinsing operation may be carried out.

The liquid detergent of the present invention described above contains components (A), (B), and (C), and since the content of component (A) is a specific amount, it has high cleaning power and foaming properties, and after washing, the foam attached to the object to be washed easily flows off, making it possible to omit the step of rinsing the foam on the object to be washed with water. This makes it possible to further reduce the amount of water used when washing dishes. The reasons for this are thought to be as follows.
Component (A) is a bulky compound having secondary carbon. Therefore, it is considered that it is difficult to adhere to the cleaning object having a slippery surface such as pottery, and the foam flows down by its own weight even without water. Similarly, components (B) and (C) are also bulky compounds having branched chains, and it is considered that it is difficult to adhere to the cleaning object, and the foam flows down by its own weight even without water.
Furthermore, by adjusting the (A)/(B) ratio and the (A)/(C) ratio, the balance between cleaning power, foaming property, and foam adhesion can be adjusted, making it possible to further exhibit the effects of the present invention.

The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following description.
The raw materials and evaluation methods used in each of the examples and comparative examples are as follows.

[Ingredients used]
<Component (A)>
A-1: Secondary AES (3EO), Taipol SFES-326 (product name), manufactured by Taiko Yushi Chemical Industries Co., Ltd., sodium sulfate ester of secondary alcohol (average 3 moles of EO added), the carbon number of the secondary alcohol is 12 to 14, narrow ratio 78.5%.
A-2: Secondary AES (7EO), Taipol SFES-733 (product name), manufactured by Taiko Yushi Chemical Industries Co., Ltd., sodium sulfate ester of secondary alcohol (average 7 moles of EO added), the carbon number of the secondary alcohol is 12 to 14, narrow ratio 67.8%.
A-3: sodium di-2-ethylhexyl sulfosuccinate, Reparl (registered trademark) 870P (product name), manufactured by Lion Specialty Chemicals Co., Ltd., a compound in which, in the formula (a2), R ⁴ and R ⁵ are 2-ethylhexyl groups, M ¹ is sodium, x = 0, and y = 0.

<Component (A') (Comparative Component for Component (A))>
A'-1: Linear AES, synthesized by the following synthesis method.
A'-2: Sodium monoalkyl sulfosuccinate, alkyl group having 12 to 14 carbon atoms, Kohacool (registered trademark) L-400 (product name), manufactured by Toho Chemical Industry Co., Ltd.

(Method of Synthesizing A'-1)
In a 4L autoclave, 400 g of P&G's product name "CO1270 alcohol (C12/C14 = 75%/25%, mass ratio)" was charged as the raw material alcohol, and 0.8 g of potassium hydroxide was charged as the reaction catalyst. The atmosphere in the autoclave was replaced with nitrogen, and the temperature was raised while stirring. Next, 91 g of ethylene oxide was introduced and reacted while maintaining the temperature at 180°C and the pressure at 0.3 MPa or less. The average number of moles of ethylene oxide added to the obtained polyoxyalkylene ether was 1.
Next, 237 g of the obtained ethylene oxide polyoxyalkylene ether was placed in a 500 mL flask equipped with a stirrer, and after replacing with nitrogen, 96 g of liquid sulfuric anhydride (Sulfane (registered trademark), manufactured by Nisso Engineering Co., Ltd.) was slowly added dropwise while maintaining the reaction temperature at 40° C. After completion of the dropwise addition, stirring was continued for 1 hour (sulfation reaction) to obtain polyoxyethylene alkyl ether sulfate. Next, the obtained polyoxyethylene alkyl ether sulfate was neutralized with an aqueous sodium hydroxide solution to obtain A'-1.

<Component (B)>
B-1: n-dodecyldimethylamine oxide (AX), Cadenax (registered trademark) DM12D-W (product name), manufactured by Lion Specialty Chemicals Co., Ltd., an alkyldimethylamine oxide type semi-polar surfactant.
B-2: Sodium laurylaminodipropionate, Energical (registered trademark) DP-30 (product name), manufactured by Lion Specialty Chemicals Co., Ltd., an aminopropionic acid-based amphoteric surfactant.

<Component (C)>
C-1: Polyoxyethylene mono(2-propylheptyl)ether (EO10), Lutensol XP100 (product name), manufactured by BASF Japan Ltd., a compound in which m = 10, j = 3, and k = 5 in the formula (c1).

<Component (C') (Comparative Component for Component (C))>
C'-1: AE (15EO), nonionic surfactant, polyoxyethylene alkyl ether, LMAO-90 (product name), manufactured by Lion Chemical Co., Ltd., a compound having a linear alkyl group having 12 carbon atoms (C12) and a linear alkyl group having 14 carbon atoms (C14) (mass ratio of C12:C14 = 75:25), and having an average repeat number of oxyethylene groups (EO) of 15.

<Component (D)>
D-1: Palmitic acid, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
D-2: Myristic acid, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
D-3: Coconut oil fatty acid, coconut fatty acid (product name), manufactured by NOF Corporation.

<Optional ingredients>
LAS: anionic surfactant, linear alkylbenzene sulfonic acid having an alkyl group having 10 to 14 carbon atoms, Lipon (registered trademark) LH-200 (product name), manufactured by Lion Specialty Chemicals Co., Ltd.
PPG 4000: Polyoxypropylene glyceryl ether, Actocol (registered trademark) T-4000 (product name), manufactured by Mitsui Chemicals, Inc., mass average molecular weight 4000.
CC: Cationic cellulose, UCARE JR125 (product name), manufactured by The Dow Chemical Company.
GE: glycol ether solvent, water-miscible organic solvent, diethylene glycol monobutyl ether, butyl diglycol (product name), manufactured by Nippon Nyukazai Co., Ltd.
pH adjuster: sodium hydroxide, 48% sodium hydroxide solution (product name), manufactured by Kanto Chemical Co., Ltd.
・Water: Purified water.

[Evaluation method]
<Evaluation of Foamability>
38 g of tap water at 25°C and 2 g of each liquid detergent were placed in a dishwashing sponge (Scotch-Brite (registered trademark) (product name), manufactured by Sumitomo 3M Limited, 115 mm x 75 mm x 30 mm), and the sponge was rubbed with the hands 10 times. The amount of foam generated was then visually checked and the sponge was given the following scores to evaluate the foaming ability based on the following evaluation criteria.
《Score》
5+ points: The foam covers the entire surface area of the sponge (100%) and there is more foam than a point 5.
5 points: Foam covers the entire surface area of the sponge (100%).
Score 4: Foam covers 80% to less than 100% of the surface area of the sponge.
Score 3: Foam covers 50% to less than 80% of the sponge's surface area.
Score 2: Foam covers 30% to less than 50% of the sponge's surface area.
Score 1: No foaming (less than 30% of the sponge surface area).
"Evaluation criteria"
◎: The above score is 5+ points.
○: The above score is 5 points.
×: The above score is 4 points or less.

<Evaluation of cleaning power>
38 g of tap water at 25°C and 2 g of the liquid detergent of each example were placed in a dishwashing sponge (Scotch-Brite (registered trademark) (trade name) manufactured by Sumitomo 3M Limited) and rubbed with hands 10 times. Using this sponge, a polypropylene food container (NEO Keeper M (trade name) manufactured by Iwasaki Kogyo Co., Ltd., 870 mL, 127 mm x 179 mm x 55 mm) with 1 g of beef tallow evenly spread over the entire inside surface was rubbed with hands 10 times on the bottom inside, 10 times on each side inside, and 5 times on each of the four corners. After rinsing with tap water, the condition of the inside surface of the food container and the condition of the remaining oil on the sponge were evaluated by touching with hands, and the following scores were assigned to evaluate the cleaning power based on the following evaluation criteria.
《Score》
5 points: No matter where you touch the food container, there is absolutely no slimy feeling due to residual oil, and no oily residue can be felt on the sponge.
4+ points: There is a slimy feeling due to residual oil on the sides and some of the corners of the food container, but no oil residue can be felt on the sponge.
4 points: The sides or corners of the food container are sticky due to residual oil, but no oil remains in the sponge.
3 points: The entire inside of the food container feels slimy due to residual oil, but no oil remains on the sponge.
2 points: The entire inside of the food container feels slimy due to residual oil, and oil residue is visually visible on more than 0% but less than 50% of the sponge's surface area.
Score 1: The entire inside of the food container feels slimy due to residual oil, and oil residue is visually visible on more than 50% but less than 100% of the sponge's surface area.
"Evaluation criteria"
◎: The above score is 5 points.
○: The above score is 4+ points.
△: The above score is 4 points.
×: The above score is 3 points or less.

<Evaluation of foam adhesion>
1g of tap water was dropped onto a circular ceramic dish (diameter 240 mm) to wet the entire surface of the dish. A cleaning solution prepared by diluting each liquid detergent with tap water to 5% by mass was filled into a KIREI KIREI (registered trademark) pump foamer (250 mL), and three pumps of foam were placed horizontally at equal intervals in the center of the dish. The dish was tilted vertically, and the amount (mass) of foam remaining on the dish after 5 seconds was measured, and the foam remaining rate (%) on the dish was calculated using the following formula (i), and the foam adhesion was evaluated based on the following evaluation criteria.
Percentage of foam remaining on dish (%) = foam remaining (g) / (1 g of tap water + mass of foam dropped on dish (g)) × 100 (i)
"Evaluation criteria"
⊚: The foam remaining on the plate is less than 10%.
◯: The foam remaining on the plate is 10% or more but less than 20%.
△: The remaining foam rate on the plate is 20% or more but less than 30%.
×: The foam remaining on the plate is 30% or more.

[Examples 1 to 27, Comparative Examples 1 to 11]
1000 g of each of the liquid dishwashing detergent compositions (liquid detergents) shown in Tables 1 to 6 was prepared according to the following procedure.
500 g of component (A), PPG4000, CC, and water were placed in a 1 L beaker and stirred with a magnetic stirrer (Fine Corp., "F-606N"). Next, components (B), (C), (D), and other optional components were added and mixed. Thereafter, an appropriate amount of pH adjuster was added as necessary so that the pH at 25°C was 7.8, and the remaining water was added so that the total amount was 100% by mass, and further stirring was performed thoroughly to obtain a liquid detergent of each example.
The pH (25°C) of the liquid detergent was measured by adjusting the temperature of the liquid detergent to 25°C, and measuring the pH value after 1 minute by using a glass electrode pH meter (manufactured by DKK-TOA Corporation, "HM-30G") by directly immersing the glass electrode in the liquid detergent. The measurement was performed in accordance with JIS Z8802:1984 "pH measurement method."
The amounts (mass %) in the table are calculated as pure contents. In addition, "-" in the table means that the component is not contained. The "appropriate amount" of pH adjuster is the amount required to adjust the pH of the liquid detergent to 7.8. The "balance" amount of water is the amount required to make the total amount of the liquid detergent 100 mass %.
The liquid detergent of each example was evaluated for foaming ability, cleaning power, and foam adhesion, and the results are shown in the table.

As shown in Tables 1 to 6, Examples 1 to 27 in which the present invention was applied were rated as "Excellent" to "Fair" in terms of foaming ability, cleaning power, and foam adhesion.
In contrast, Comparative Example 1 lacking the (A) component was rated as "x" for cleaning power and foam adhesion. Comparative Example 2 lacking the (B) component was rated as "x" for cleaning power. Comparative Examples 3 and 4 lacking the (C) component were rated as "x" for foaming and cleaning power. Comparative Examples 5 and 7 using the (A') component instead of the (A) component were rated as "x" for foam adhesion. Comparative Example 6 using the (A') component instead of the (A) component was rated as "x" for cleaning power and foam adhesion. Comparative Example 8 using the (A') component instead of the (A) component was rated as "x" for all evaluations. Comparative Examples 9 and 10 using the (C') component instead of the (C) component were rated as "x" for foaming and foam adhesion. Comparative Example 11, in which the content of the (A) component is outside the range of the present invention, was rated as "x" for foam adhesion.

These results show that the present invention has high cleaning power and foaming properties, and after cleaning, the foam adhering to the object to be cleaned easily washes off, making it possible to omit the step of rinsing the foam off the object with water.

Claims (4)

Component (A): at least one selected from the group consisting of a secondary alkyl ether sulfate salt represented by the following formula (a1) and a dialkyl sulfosuccinate salt represented by the following formula (a2),
Component (B): one or more surfactants selected from semi-polar surfactants and amphoteric surfactants;
Component (C): A nonionic surfactant represented by the following formula (c1),
A liquid dishwashing detergent composition, wherein the content of the component (A) is 0.1 mass % or more and less than 5.0 mass % based on the total mass of the liquid dishwashing detergent composition.

[In formula (a1), R ¹ and R ² each independently represent a linear or branched alkyl group having 1 to 20 carbon atoms, the total number of carbon atoms in R ¹ and the total number of carbon atoms in R ² is 7 to 21, R ³ O represents an oxyalkylene group having 2 to 5 carbon atoms, n is a number from 1 to 20 representing the average number of repetitions of R ³ O, and M represents a counter ion.]

[In formula (a2), R ⁴ represents an alkyl group having 5 to 18 carbon atoms, R ⁵ 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 the average number of repetitions and are 0 to 6, and M ¹ represents a cation.]

[In formula (c1), EO represents an oxyethylene group, m represents the average number of repeats of EO and is a number from 8 to 12, j and k each represent an integer from 1 to 6, and 6≦(j+k)≦12.] The liquid dishwashing detergent composition according to claim 1, further comprising component (D): a fatty acid having 8 to 24 carbon atoms or a salt thereof. The liquid dishwashing detergent composition according to claim 1 or 2, in which the mass ratio represented by (content of said component (A))/(content of said component (B)) is 0.1 to 1.0. The liquid dishwashing detergent composition according to claim 1 or 2, in which the mass ratio represented by (content of said component (A))/(content of said component (C)) is 0.1 to 1.0.