JP6807273B2 - Dishwashing agent - Google Patents

Description

The present invention relates to a dishwashing agent.

Cleaning of tableware or cooking utensils is usually performed by adding a dishwashing agent to a sponge. Further, the dishwashing agent is required to have high detergency and foaming property (foaming amount, foaming speed) against oil stains adhering to tableware or cooking utensils.
In order to improve the detergency and foaming property against oil stains, the dishwashing agent exhibits cleaning effects such as anionic surfactant, nonionic surfactant, amphoteric surfactant, and semi-polar surfactant. The ingredients are appropriately combined and blended.
For example, Patent Document 1 discloses a liquid cleaning agent for kitchens containing an anionic surfactant having a specific structure, an alkylamine oxide, and butyl carbitol.

JP 2013-256593

However, although the liquid cleaning agent for kitchen described in Patent Document 1 has good foaming property, the foaming durability during cleaning is not sufficient.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a dishwashing agent having excellent foam durability.

The present invention has the following aspects.
[1] The following components (A), (B), (C) and (D) are contained, and the mass ratio represented by the component (C) / component (D) is 0.1 to 9. , Dishwashing agent.
(A) Ingredient: Anionic surfactant.
Component (B): At least one selected from the group consisting of amphoteric surfactants and semipolar surfactants.
Ingredient (C): 3-Methoxy-3-methyl-1-butanol.
Ingredient (D): Nonionic surfactant.
[2] The dishwashing agent according to [1], wherein the component (D) is a branched alkyl alkoxylate.
[3] The method according to [1] or [2], wherein the total content of the component (C) and the component (D) is 5 to 20% by mass with respect to the total mass of the dishwashing agent. Dishwashing agent.
[4] The mass ratio represented by ((C) component + (D) component) / ((A) component + (B) component + (C) component + (D) component) is 0.1 to 0.6. The dishwashing agent according to any one of [1] to [3].
[5] The dishwashing agent according to any one of [1] to [4], wherein the content of the component (A) is 4 to 25% by mass with respect to the total mass of the dishwashing agent. ..
[6] The dishwashing agent according to any one of [1] to [5], wherein the content of the component (B) is 2 to 20% by mass with respect to the total mass of the dishwashing agent. ..
[7] The tableware according to any one of [1] to [6], wherein the content of the component (C) is 0.1 to 15% by mass with respect to the total mass of the dishwashing agent. Washing soap.
[8] The dishwashing agent according to any one of [1] to [7], wherein the content of the component (D) is 1 to 15% by mass with respect to the total mass of the dishwashing agent. ..
[9] The dishwashing agent according to any one of [1] to [8], wherein the mass ratio represented by the component (A) / component (B) is 0.5 to 4.
[10] The total content of the component (A), the component (B), the component (C) and the component (D) is 10% by mass or more and less than 60% by mass with respect to the total mass of the dishwashing agent. The dishwashing agent according to any one of [1] to [9].
[11] The dishwashing agent according to any one of [1] to [10], which does not substantially contain butyl carbitol.
[12] The dishwashing cleaning agent according to [2], wherein the component (D) is a gerbet alcohol-type nonionic surfactant.

According to the present invention, it is possible to provide a dishwashing agent having excellent foam durability.

Hereinafter, the present invention will be described in detail.
The dishwashing agent of the present invention contains the following components (A), (B), (C) and (D).

<Ingredient (A)>
The component (A) is an anionic surfactant.
When the dishwashing agent contains the component (A), the cleaning power and foaming property against oil stains required as the basic performance of the dishwashing agent can be exhibited by the interaction with the component (B) and the component (D). ..

Examples of the component (A) include α-olefin sulfonate, linear or branched alkyl sulfate, alkyl ether sulfate or alkenyl ether sulfate, alkane sulfonate having an alkyl group, and α-sulfo. Examples thereof include fatty acid ester salts, sulfosuccinic acid alkyl ester salts, and linear alkylbenzene sulfonates. Examples of these salts include alkali metal salts such as sodium and potassium; alkanolamine salts such as monoethanolamine and diethanolamine.
As the component (A), one type may be used alone, or two or more types may be used in combination as appropriate.

As the component (A), an anionic surfactant represented by the following general formula (1), an alkane sulfonate, and a linear alkylbenzene sulfonate are preferable.
_{^{R 1 -O- (EO) n -SO}} 3 - 1 / X · M + ··· (1)
(In the general formula (1), R ¹ is a linear alkyl group having 8 to 18 carbon atoms, and the carbon atom bonded to the oxygen atom is the first carbon atom. EO is an oxyethylene group. n indicates the average number of repetitions of EO, and 0 <n ≦ 4. M ⁺ is a cation other than a hydrogen ion, and X is a valence of M ⁺ .)

In the general formula (1), the carbon number of R ¹ is 8 to 18, preferably 10 to 14, and more preferably 12 to 14. R ¹ is preferably an alkyl group derived from a fat or oil raw material from the viewpoint of detergency and environment. Suitable oil and fat raw materials include palm kernel oil, coconut oil and the like.

In the general formula (1), M ⁺ is a cation other than a hydrogen ion and has a valence of X. Examples of M ⁺ include those capable of forming water-soluble salts such as alkali metals, alkaline earth metals, ammonium or alkanolamines.
Examples of the alkali metal include sodium and potassium.
Examples of alkaline earth metals include calcium and magnesium.
Examples of the alkanolamine include monoethanolamine, diethanolamine, triethanolamine and the like.

Examples of the alkane sulfonate include alkane sulfonates having 10 to 20 carbon atoms, preferably alkane sulfonates having 14 to 17 carbon atoms, and particularly preferably secondary alkane sulfonates.
As the linear alkylbenzene sulfonate, a linear alkylbenzene sulfonate having 8 to 16 carbon atoms in the linear alkyl group is preferable, and a linear alkylbenzene sulfonate having 10 to 14 carbon atoms in the linear alkyl group is particularly preferable. preferable.

Specifically, as the component (A), polyoxyethylene (1) linear alkyl (C12) sulfate sodium salt, polyoxyethylene (2) linear alkyl (C12) sulfate sodium salt, polyoxyethylene (4) Linear alkyl (C12) sulfate sodium salt, polyoxyethylene (1) Linear alkyl (C12 / 14 = 75/25; derived from natural fats and oils) Sulfate sodium salt, polyoxyethylene (2) Linear alkyl (C12 /) 14 = 75/25; derived from natural fats and oils) Sulfate sodium salt, polyoxyethylene (4) linear alkyl (C12 / 14 = 75/25; derived from natural fats and oils) sodium sulfate ester, sodium alkane sulfonate, straight chain Examples thereof include alkyl (C12) benzene sulfonate and linear alkyl (C14) benzene sulfonate.
Among these, since the effects of the present invention are particularly easy to obtain, polyoxyethylene (1) linear alkyl (C12 / 14 = 75/25; derived from natural fats and oils) sulfate ester sodium salt, polyoxyethylene (2) direct Chain alkyl (C12 / 14 = 75/25; derived from natural fats and oils) Sulfate sodium salt, polyoxyethylene (4) Linear alkyl (C12 / 14 = 75/25; derived from natural fats and oils) Sulfate sodium salt, linear alkyl (C12) benzene sulfonate is preferable.

Here, for example, "polyoxyethylene (1)" means that the average number of repetitions of the oxyethylene group is 1 (the average number of moles of ethylene oxide added is 1).
"C12 / 14 = 75/25; derived from natural fats and oils" is a mixture of a mixture having a linear alkyl group having 12 carbon atoms and a mixture having a linear alkyl group having 14 carbon atoms (mixing ratio: mass ratio). It means that it is 75/25) and that it is a linear alkyl group derived from natural fats and oils.

The content of the component (A) is preferably 4 to 25% by mass, more preferably 8 to 15% by mass, based on the total mass of the dishwashing agent. When the content of the component (A) is at least the lower limit value, the detergency against oil stains is enhanced. On the other hand, when the content of the component (A) is not more than the upper limit value, the uniformity of the dishwashing agent can be maintained well, and the cleaning power against oil stains can be maintained.

<Ingredient (B)>
The component (B) is at least one selected from the group consisting of amphoteric surfactants and semi-polar surfactants.
When the dishwashing agent contains the component (B), the cleaning power and foaming property against oil stains required as the basic performance of the dishwashing agent can be exhibited by the interaction with the components (A) and (D). ..
The "semi-polar surfactant" refers to one that becomes cationic or nonionic depending on the pH of the solution in which the semi-polar surfactant is dissolved or the dispersion system in which the semipolar surfactant is dispersed.

Examples of the amphoteric tenside include a carboxylate type (also referred to as a betaine type), a sulfate ester salt type, a sulfonate type, and a phosphate ester salt type, and any of these can be used. Of these, the carboxylate type is preferable.
Specific examples of carboxylate-type amphoteric surfactants include lauryldimethylaminoacetate betaine, coconut alkyldimethylaminoacetic acid betaine, coconut oil fatty acid amide propyl betaine, lauric acid amide propyl dimethylamino acetate betaine, coconut alkyl amide propyl dimethylamino. Examples thereof include betaine acetate and coconut oil fatty acid amide propyl dimethylamino betaine acetate (cocamidopropyl betaine).
One amphoteric surfactant may be used alone, or two or more amphoteric surfactants may be used in combination as appropriate.

Examples of the semi-polar surfactant include amine oxide-type surfactants and amine alkylene oxide-type surfactants. Among these, amine oxide type surfactants are preferable.
Examples of the amine oxide type surfactant include alkylamine oxides and alkanoylamide alkylamine oxides, and among these, compounds represented by the following general formula (2) are preferable.

In the general formula (2), R ² 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 ³ and R ⁴ are respectively. It is independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, and R ⁵ is an alkylene group having 1 to 4 carbon atoms. A is -CONH-, -NHCO-, -COO-, -OCO- or -O-, and p is a number of 0 or 1.

In the general formula (2), R ² has 8 to 18 carbon atoms, preferably 10 to 14 carbon atoms. The R ^2, preferably a linear or branched alkyl group having 8 to 18 carbon atoms.
In the general formula (2), as R ³ and R ⁴ , alkyl groups having 1 to 3 carbon atoms are preferable, methyl groups are more preferable, and both R ³ and R ⁴ are more preferably methyl groups.
In the general formula (2), p is a number of 0 or 1, and 0 is preferable.

Specific examples of the compound represented by the general formula (2) include lauryldimethylamine oxide (n-dodecyldimethylamine oxide), coconut alkyldimethylamine oxide, lauryldiethylamine oxide, lauric acid amidopropyldimethylamine oxide and the like. .. Among these, lauryldimethylamine oxide is preferable because the effect of the present invention is particularly easy to obtain.
As the semi-polar surfactant, one type may be used alone, or two or more types may be used in combination as appropriate.

As the component (B), only the amphoteric surfactant may be used, only the semipolar surfactant may be used, or the amphoteric surfactant and the semipolar surfactant may be used in combination.

The content of the component (B) is preferably 2 to 20% by mass, more preferably 6 to 12% by mass, based on the total mass of the dishwashing agent. When the content of the component (B) is at least the lower limit value, the detergency against oil stains is enhanced. On the other hand, when the content of the component (B) is not more than the upper limit value, the uniformity of the dishwashing agent can be maintained well, and the cleaning power against oil stains can be maintained.

<Component (C)>
The component (C) is 3-methoxy-3-methyl-1-butanol.
When the dishwashing agent contains the component (C), good foam persistence can be exhibited by the interaction with the component (A), the component (B) and the component (D).

The content of the component (C) is preferably 0.1 to 15% by mass, more preferably 1 to 9% by mass, further preferably 2 to 6% by mass, and 3 to 5% by mass with respect to the total mass of the dishwashing agent. Mass% is particularly preferred. When the content of the component (C) is within the above range, the foam persistence is further improved. In particular, when the content of the component (C) is at least the lower limit value, the stability of the dishwashing agent is also enhanced.

<Ingredient (D)>
The component (D) is a nonionic surfactant.
When the dishwashing agent contains the component (D), good foam persistence can be exhibited by the interaction with the component (A), the component (B) and the component (C), and the dishwashing agent It can demonstrate the detergency and foaming properties required for oil stains as basic performance.

Examples of the component (D) include a polyoxyalkylene-added nonionic surfactant represented by the following general formula (3), a nonionic surfactant represented by the following general formula (4), an alkyl glycoside, a sorbitan fatty acid ester, and the like. Can be mentioned.
R ^6- O- (R ⁷ O) _q- H ... (3)
(In the general formula (3), R ⁶ is a linear or branched hydrocarbon group having 10 to 18 carbon atoms, R ⁷ is a hydrocarbon group having 1 to 3 carbon atoms, and q is (R ⁷ O). ) Indicates the average number of repetitions, and 1 ≦ q ≦ 20.)
R ^8- C (= O) -NH- (R ⁹ O) _r- H ... (4)
(In the general formula (4), R ⁸ is a linear or branched hydrocarbon group having 5 to ¹⁹ carbon atoms, R ⁹ is a hydrocarbon group having 2 to 4 carbon atoms, and r is (R ⁹ O). ) Indicates the average number of repetitions, and 1 ≦ r ≦ 20.)

In the general formula (3), the carbon number of R ⁶ is 10 to 18, preferably 10 to 16, and more preferably 10 to 14. As the hydrocarbon group of R ⁶ , an alkyl group or an alkenyl group is preferable.
In the general formula (3), as the hydrocarbon group of R ⁷ , an alkylene group is preferable, and an ethylene group and a propylene group are more preferable. Further, as (R ⁷ O), an oxyethylene group and an oxypropylene group may be mixed. When the oxyethylene group and the oxypropylene group are mixed, they may be mixed randomly or may be mixed in a block shape.
In the general formula (3), q is 1 to 20, preferably 5 to 20, and more preferably 5 to 15.

In the general formula (4), the number of carbon atoms in ^{R 8} is 5-19, preferably 9-13. As the hydrocarbon group of R ⁸ , an alkyl group or an alkenyl group is preferable.
In the general formula (4), as the hydrocarbon group of R ⁹ , an alkylene group is preferable, an ethylene group and a propylene group are more preferable, and an ethylene group is particularly preferable. As the (R 9 ^O), oxyethylene group, oxypropylene group may be mixed. When the oxyethylene group and the oxypropylene group are mixed, they may be mixed randomly or may be mixed in a block shape.
In the general formula (4), r is 1 to 20, preferably 1 to 4.

As the component (D), a compound in which R ⁶ in the general formula (3) is a branched-chain hydrocarbon group and a compound in which R ⁸ in the general formula (4) is a linear hydrocarbon group are preferable. Among the compounds in which R ⁶ in the general formula (3) is a hydrocarbon group of a branched chain, a nonionic surfactant in which R ⁶ in the general formula (3) is a hydrocarbon group derived from a branched primary alcohol ( Branched alkyl alkoxylates) are particularly preferred.

As the component (D), among the branched alkyl alkoxylates, a gerbet alcohol-type nonionic surfactant is preferable.
Examples of the gerbet alcohol type nonionic surfactant include compounds represented by the following general formula (5).
(R ¹⁰ ) (R ¹¹ ) CH-CH _2- O- (R ⁷ O) _q- H ... (5)
(In the general formula (5), R ⁷ is a hydrocarbon group having 1 to 3 carbon atoms, and R ¹⁰ and R ¹¹ each independently represent a chain hydrocarbon group, and the sum of R ¹⁰ and R ¹¹ is used. Has 8 to 16 carbon atoms, and q indicates the average number of repetitions of (R ⁷ O), and 1 ≦ q ≦ 20.)

In the general formula (5), the total number of carbon atoms of R ¹⁰ and R ¹¹ is 8 to 16, preferably 8 to 14, and more preferably 8 to 12. R ¹⁰ and R ¹¹ are preferably linear or branched alkyl groups or linear or branched alkenyl groups, respectively.
^{R 7} and q in the general formula (5) is the same as ^{R 7} and q in the general formula (3).

Examples of the compound represented by the general formula (5) include 2-propylheptyl alcohol ethoxylate and 2-ethylhexyl alcohol ethoxylate. Of these, 2-propylheptyl alcohol ethoxylate is preferable. The average number of moles of ethylene oxide added is preferably 6 to 14, more preferably 8 to 11, and most preferably 10.
Specific examples of 2-propylheptyl alcohol ethoxylate include trade names "Lutensol XP-100" and "Lutensol XP-80" manufactured by BASF.
Specific examples of 2-ethylhexyl alcohol ethoxylate include the trade name “Newcol 1008” manufactured by Nippon Emulsifier Co., Ltd.

The content of the component (D) is preferably 1 to 15% by mass, more preferably 2 to 12% by mass, still more preferably 4 to 8% by mass, based on the total mass of the dishwashing agent. When the content of the component (D) is at least the lower limit, the foam persistence is further improved. On the other hand, when the content of the component (D) is not more than the upper limit value, the detergency and foaming property against oil stains are improved.

<Mass ratio>
The mass ratio represented by the component (C) / component (D) (hereinafter, also referred to as “C / D ratio”) is 0.1 to 9, preferably 0.2 to 1.4, and 0.3. ~ 1 is more preferable. When the C / D ratio is within the above range, the foam persistence is improved.

The mass ratio represented by the component (A) / component (B) (hereinafter, also referred to as “A / B ratio”) is preferably 0.5 to 4, more preferably 0.5 to 1.5. When the A / B ratio is within the above range, the foam persistence is further improved. In addition, it has excellent detergency and foaming property against oil stains.

Mass ratio represented by ((C) component + (D) component) / ((A) component + (B) component + (C) component + (D) component) (hereinafter, "(C + D) / (A + B + C + D)) The ratio) is preferably 0.1 to 0.6, more preferably 0.25 to 0.45. When the (C + D) / (A + B + C + D) ratio is within the above range, the foam persistence is further improved.

The total content of the component (C) and the component (D) is preferably 5 to 20% by mass, more preferably 8 to 15% by mass, and 10 to 15% by mass with respect to the total mass of the dishwashing agent. More preferred. When the total content of the component (C) and the component (D) is within the above range, the foam persistence is further improved.

The total content of the component (A), the component (B), the component (C) and the component (D) is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the dishwashing agent. It is preferable, and more preferably 30% by mass or more. Further, the total content of the component (A), the component (B), the component (C) and the component (D) is preferably less than 60% by mass. When the total content of the component (A), the component (B), the component (C) and the component (D) is within the above range, the foam persistence is further improved. In addition, it has excellent detergency and foaming property against oil stains.

<Water>
The dishwashing cleaning agent of the present invention preferably contains water as a solvent from the viewpoints of ease of handling during production, solubility in water during use, and the like.

<Arbitrary ingredient>
The dishwashing agent contains components (arbitrary components) other than the components (A), (B), (C) and (D) as long as the effects of the present invention are not impaired. It may be contained.
Examples of optional components include components used in cleaning composition for dishwashing, kitchen, hard surface, etc., and examples thereof include cationic surfactants, preservatives, hydrotropes, and water-soluble solvents. Be done.

Examples of the cationic surfactant include didecyldimethylammonmon chloride, didecyldimethylammonmonmetosulfate, disstearyldimethylammonmon chloride, dioctyldimethylammonmon chloride, disstearyldihydroxyethylammonmonclide, didecylalkyldimethylammonmonm chloride, and di (stearoyl). Oxyethyl) dimethylammonmon chloride, di (oleoiloxyethyl) dimethylammonmon chloride, di (palmitoyloxyethyl) dimethylammonmonmethosulfate, di (stearoyloxyisopropyl) dimethylammonmon chloride, di (oleoiloxyisopropyl) dimethylammonmon chloride, Examples thereof include di (oleoiloxybutyl) dimethylammonmon chloride, di (stearoyloxyethyl) methylhydroxyethylammonmetosulfate, and tri (stearoyloxyethyl) methylmethosulfate. The carbon number of the "beef tallow alkyl" group is 14 to 18.
One type of cationic surfactant may be used alone, or two or more types may be used in combination as appropriate.

(Preservative)
Since the dishwashing agent contains a preservative, the growth of bacteria is suppressed even if microorganisms or the like are mixed in the dishwashing agent.
Examples of the preservative include isothiazoline compounds, and specific examples thereof include benzisothiazolinone (1,2-benzisothiazolin-3-one) and methylisothiazolinone (2-methyl-4-isothiazolin-3). -On), butylbenzisothiazolinone, chloromethylisothiazolinone, octylisothiazolinone, dichlorooctylisothiazolinone and the like. Among these, 1,2-benzisothiazolin-3-one and 2-methyl-4-isothiazolin-3-one are preferable.
As the preservative, one type may be used alone, or two or more types may be used in combination as appropriate.

(Hydrotrope agent)
When the dishwashing agent contains a hydrotrope agent, the storage stability (particularly low temperature stability) of the dishwashing agent is mainly improved, and it becomes easier to secure a transparent appearance more stably.
Hydrotropic agents include monovalent alcohols having 2 to 4 carbon atoms, glyceryl ethers having 4 to 10 carbon atoms, toluenesulfonic acid, toluenesulfonic acid salt, cumenesulfonic acid, cumenesulfonic acid salt, benzoic acid, benzoic acid salt and the like. Can be mentioned.
As the hydrotrope agent, one type may be used alone, or two or more types may be used in combination as appropriate.

In the hydrotrope agent, the toluene sulfonic acid, the toluene sulfonate, the cumene sulfonic acid, and the cumene sulfonate may be any of the o-form, m-form, and p-form triisomers, respectively.
Examples of monohydric alcohols having 2 to 4 carbon atoms include ethanol, n-propanol, isopropanol, n-butanol, secondary butanol, and tarshalbutanol.
Examples of the glyceryl ether having 4 to 10 carbon atoms include glycerin and hexyl glyceryl ether.

As the hydrotrope agent, ethanol and paratoluenesulfonate are used from the viewpoint of the dissolving effect of the components (A), (B), (C) and (D) in the dishwashing agent and the feeling of use. preferable.
The content of the hydrotrope agent is preferably 1 to 30% by mass, more preferably 1 to 20% by mass, based on the total mass of the dishwashing agent.

(Water-soluble solvent)
When the dishwashing agent contains a water-soluble solvent, the viscosity and transparency of the dishwashing agent are mainly improved.
Examples of the water-soluble solvent include an alcohol solvent and a glycol ether solvent (however, the component (C) is excluded).
As the water-soluble solvent, one type may be used alone, or two or more types may be used in combination as appropriate.

Examples of the alcohol-based solvent include ethanol, isopropanol, n-butanol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,3-butylene glycol, 1, Examples thereof include 4-butanediol, 1,5-pentanediol, hexylene glycol and glycerin.
Examples of the glycol ether solvent include ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, diethylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol).

However, from the viewpoint of further enhancing the foam persistence, it is preferable that the dishwashing agent does not substantially contain butyl carbitol.
Here, "substantially free" means less than 1% by mass with respect to the total mass of the dishwashing agent.

In addition to the above, the dishwashing agent of the present invention includes, as optional components, a pH adjuster such as sodium hydroxide and sulfuric acid; an inorganic builder such as magnesium sulfate, zinc sulfate and zinc oxide; and sodium citrate, sodium lactate and the like. Chelating agent; fragrance, pigment, etc. can also be blended.

It is assumed that the total content of all the components contained in the dishwashing agent is 100% by mass.

<Manufacturing method>
In the dishwashing agent of the present invention, for example, the above-mentioned components (A), (B), (C) and (D) and, if necessary, any component are dissolved in a solvent such as water. , Can be produced by adjusting the pH to a predetermined pH using a pH adjusting agent.

<pH>
The pH of the dishwashing agent of the present invention at 25 ° C. is preferably 6 to 8.
In the present invention, the pH (25 ° C.) of the dishwashing agent indicates a value measured by a method based on JIS Z 8802: 1984 "pH measurement method".
The pH of the dishwashing agent may be adjusted using a pH adjuster.

<Effect>
In the dishwashing agent of the present invention described above, at least one selected from the group consisting of an anionic surfactant as a component (A), an amphoteric surfactant as a component (B), and a semipolar surfactant. In combination with, the component (C) 3-methoxy-3-methyl-1-butanol and the component (D) nonionic surfactant are used in combination in a specific ratio, so that the foam durability is excellent.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following description. The blending amount of the components used in each example is a pure content conversion value unless otherwise specified.

"Ingredients used"
The following compounds were used as the component (A).
A-1: Sodium polyoxyethylene alkyl ether sulfate (AES), in the above general formula (1), R ¹ = linear alkyl group having 12 to 14 carbon atoms, n = 1, M = sodium, X = 1. .. Synthesized by the following synthesis method.
-A-2: Sodium polyoxyethylene alkyl ether sulfate (AES; manufactured by BASF, trade name "Texapon N70T"). In the above general formula (1), R ¹ = linear alkyl group having 12 to 14 carbon atoms (C12 / C14 = 75% / 25%, mass ratio), n = 2, M = sodium, X = 1.
A-3: Sodium polyoxyethylene alkyl ether sulfate (AES), in the above general formula (1), R ¹ = linear alkyl group having 12 to 14 carbon atoms, n = 4, M = sodium, X = 1. .. Synthesized by the following synthesis method.
A-4: Sodium secondary alkane sulfonate having 14 to 17 carbon atoms (SAS; manufactured by Clariant Japan Co., Ltd., trade name "HOSTAPUR SAS 30A").
A-5: Sodium alkylbenzene sulfonate (LAS) having 10 to 14 carbon atoms, and the trade name "Tayca Power L121" manufactured by TAYCA Corporation, neutralized with sodium hydroxide.
-A-6: Sodium α-olefin sulfonate (AOS; manufactured by Lion Specialty Chemicals Co., Ltd., trade name "Liporan LB440").

(Synthesis method of A-1)
In a 4L autoclave, 400 g of the trade name "CO1270 alcohol (C12 / C14 = 75% / 25%, mass ratio)" manufactured by P & G was charged as a raw material alcohol, and 0.8 g of potassium hydroxide was charged as a reaction catalyst. After replacing the inside of the autoclave with nitrogen, the temperature was raised while stirring. Subsequently, 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 ethylene oxide of the obtained polyoxyalkylene ether was taken in a 500 mL flask equipped with a stirrer, replaced with nitrogen, and then 96 g of liquid anhydrous sulfuric acid (sulfur) was slowly added dropwise while maintaining the reaction temperature at 40 ° C. After completion of the dropping, stirring was continued for 1 hour (sulfation reaction) to obtain polyoxyethylene alkyl ether sulfuric acid.
Then, the obtained polyoxyethylene alkyl ether sulfuric acid was neutralized with an aqueous sodium hydroxide solution to obtain A-1.

(A-3 synthesis method)
A-3 was obtained in the same manner as A-1 except that the amount of ethylene oxide was changed to 364 g.

The following compounds were used as the component (B).
B-1: n-dodecyldimethylamine oxide (AX; manufactured by Lion Specialty Chemicals Co., Ltd., trade name "Cadenax DM12D-W"). In the above general formula (2), R ² = a linear alkyl group having 12 carbon atoms, R ³ = a methyl group, R ⁴ = a methyl group, and p = 0.
B-2: Amidopropyl dimethylamine laurate oxide (APAX; manufactured by Clariant Japan Co., Ltd., trade name "GENAMINOX AP"). In the above general formula (2), R ² = a linear alkyl group having 11 carbon atoms, R ³ = a methyl group, R ⁴ = a methyl group, R ⁵ = a propylene group, A = -CONH-, p = 1.
-B-3: Betaine lauryldimethylaminoacetate (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name "Amigen S").
B-1 and B-2 are semi-polar surfactants, and B-3 is an amphoteric surfactant.

The following compounds were used as the component (C) or a substitute (C') component thereof.
-C-1: 3-Methoxy-3-methyl-1-butanol (manufactured by Kuraray Co., Ltd., trade name "Solfit MMB").
-C'-1: Butylcarbitol (manufactured by Nippon Emulsifier Co., Ltd., trade name "butyldiglycol").
-C'-2: Propylene glycol (manufactured by BASF).
-C'-3: Glycerin (manufactured by Kanto Chemical Co., Inc., trade name "glycerin").

The following compounds were used as the component (D).
-D-1: 2-Propyl heptyl alcohol ethoxylate (manufactured by BASF, trade name "Lutensol XP-100"). In the above general formula (3), R ⁶ = 2-propyl heptyl group, R ⁷ = ethylene group, q = 10.
-D-2: 2-Propylheptyl alcohol ethoxylate (manufactured by BASF, trade name "Lutensol XP-80"). In the above general formula (3), R ⁶ = 2-propyl heptyl group, R ⁷ = ethylene group, q = 8.
-D-3: 2-Ethylhexyl alcohol ethoxylate (manufactured by Nippon Emulsifier Co., Ltd., trade name "Newcol 1008"). In the above general formula (3), R ⁶ = 2-ethylhexyl group, R ⁷ = ethylene group, q = 8.
-D-4: Polyoxyethylene lauryl ether (manufactured by Lion Specialty Chemicals Co., Ltd., "LMAO-90"). In the above general formula (3), R ⁶ = a linear alkyl group having 12 to 14 carbon atoms, R ⁷ = an ethylene group, q = 15.
-D-5: Polyoxyethylene lauryl ether (manufactured by Nippon Emulsion Co., Ltd., "EMALEX710 Laureth-10"). In the above general formula (3), R ⁶ = a linear alkyl group having 12 carbon atoms, R ⁷ = an ethylene group, q = 10.
-D-6: Polyoxyethylene lauric acid monoethanolamide (manufactured by Kawaken Fine Chemical Co., Ltd., trade name "Amizet 2LY"). In the above general formula (4), R ⁸ = a linear alkyl group having 11 carbon atoms, R ⁹ = an ethylene group, and r = 3.
D-1, D-2 and D-3 are gerbet alcohol-type nonionic surfactants, and D-4 and D-5 are linear nonionic surfactants.

The following compounds were used as optional components.
<Hydrotrope agent>
-PTS: Paratoluenesulfonic acid, deer first grade (manufactured by Kanto Chemical Co., Inc.).
-Na benzoate: Sodium benzoate (manufactured by Toagosei Co., Ltd., trade name "sodium benzoate").
<Inorganic builder>
-Zinc oxide: (manufactured by Mitsui Mining & Smelting Co., Ltd.).
-Mg sulfate: Magnesium sulfate heptahydrate (manufactured by Junsei Chemical Co., Ltd.).
-Zinc sulfate: Zinc sulfate heptahydrate (manufactured by Junsei Chemical Co., Ltd.).
<Preservative>
-BIT: 1,2-benzisothiazolin-3-one (manufactured by Arch Chemicals, trade name "PROXEL XL2").
-MIT: 2-Methyl-4-isothiazolin-3-one (manufactured by Rohm and Haas, trade name "Neoron M-10").
<Water-soluble solvent>
PEG1000: Polyethylene glycol 1000 (manufactured by Lion Corporation, trade name "PEG # 1000", average molecular weight 1000).
<Chelating agent>
-Na lactate: Sodium lactate (manufactured by Kanto Chemical Co., Inc., trade name "sodium lactate").
<pH adjuster>
-PH regulator: sodium hydroxide (manufactured by Kanto Chemical Co., Inc.).
<Fragrance>
-Fragrance: The fragrance composition A shown in Tables 11 to 18 of JP-A-2002-146399.

"Examples 1 to 30, Comparative Examples 1 to 10"
<Preparation of dishwashing agent>
1000 g of the dishwashing agent having the composition shown in Tables 1 to 6 was prepared by the following procedure.
The component (A), the component (C), and the component (D) were placed in a 1 L beaker and sufficiently stirred with a magnetic stirrer (manufactured by Fine, trade name "F-606N"). Subsequently, the component (B) and an optional component (excluding the pH adjuster) were added and mixed. After the mixing is completed, an appropriate amount of a pH adjuster is added so that the pH at 25 ° C. becomes 6 to 8, and then water (distilled water) is added so that the total amount becomes 100% by mass. Stirring gave a dishwashing agent.
For the pH (25 ° C) of the dishwashing agent, adjust the temperature of the dishwashing agent to 25 ° C and use a glass electrode type pH meter (manufactured by Toa DKK Co., Ltd., trade name "HM-30G") to use a glass electrode. Immersed directly in the dishwashing agent, the pH shown after 1 minute was measured. The measuring method was carried out in accordance with JIS Z 8802: 1984 "pH measuring method".
The foam persistence of each of the obtained dishwashing agents was evaluated as follows. The results are shown in Tables 1-6.

<Evaluation of foam persistence>
A dish (21 cm in diameter) from which 1 g of olive oil and 5 g of water were collected as a model oil stain was used as a model oil stain dish, and 30 dishes of this model oil stain dish were prepared. To a dishwashing sponge (manufactured by Sumitomo 3M Ltd., trade name "Scotch-Brite") measuring 11.5 cm in length x 7.5 cm in width x 3 cm in height, add 38 g of tap water at 25 ° C and 2 g of dishwashing agent in each example. After rubbing by hand three times, the dishwashing sponge was brought into contact with the model oil stain dish to allow the model oil stain and the dishwashing sponge to blend in. After that, the dishwashing sponge was pressed against the model oil-stained dish and moved in a circular motion to scrub. Then, without adding tap water and dishwashing agent to the dishwashing sponge, the model oil stain dish is continuously scrubbed, and no bubbles remain on the model oil stain dish after scrubbing (). I continued to wash until it was in a state (cannot be confirmed). Next, transfer the foam existing in each model oil-stained dish after scrubbing (after washing) to a 10 mL graduated cylinder, measure the amount of foam (mL) for each dish, and use the following evaluation criteria. Evaluated based on.
⊚: The number of dishes in which the amount of foam of 5 mL or more could be confirmed after washing was 20 or more.
◯: The number of dishes in which the amount of foam of 5 mL or more could be confirmed after washing was 18 to 19.
Δ: The number of dishes on which the amount of foam of 5 mL or more could be confirmed after washing was 16 to 17.
X: The number of dishes for which a foam amount of 5 mL or more could be confirmed after washing was 15 or less.

In Tables 1 to 6, "balance" is the blending amount (mass%) of water (distilled water) required to make 100% by mass of the total dishwashing agent.
Further, (C) + (D) is the total content of the component (C) and the component (D) in the dishwashing agent. (C') + (D) is the total content of the (C') component and the (D) component in the dishwashing agent. (A) + (B) + (C) + (D) is the total content of the components (A), (B), (C) and (D) in the dishwashing agent. (A) + (B) + (C') + (D) is the total content of the (A) component, (B) component, (C') component and (D) component in the dishwashing agent. is there. The "C / D ratio" is a mass ratio represented by the component (C) / component (D). The "C'/ D ratio" is a mass ratio represented by the (C') component / (D) component. The "A / B ratio" is a mass ratio represented by the component (A) / component (B). The "(C + D) / (A + B + C + D) ratio" is the mass represented by ((C) component + (D) component) / ((A) component + (B) component + (C) component + (D) component). The ratio. "(C'+ D) / (A + B + C'+ D) ratio" is ((C') component + (D) component) / ((A) component + (B) component + (C') component + (D) component ) Is the mass ratio.

As is clear from Tables 1 to 4, the dishwashing agents of each example were excellent in foam persistence.
On the other hand, as is clear from Tables 5 and 6, the dishwashing agents of Comparative Examples 1 to 5 which do not contain any of the components (A), (B), (C) and (D) are foam. It was inferior in sustainability.
The dishwashing agents of Comparative Example 6 having a C / D ratio of less than 0.1 and Comparative Examples 6 and 7 having a C / D ratio of more than 9 were inferior in foam persistence.
The dishwashing agents of Comparative Examples 8 to 10 in which the component (C') was used instead of the component (C) were inferior in foam persistence.

Claims (4)

For tableware, which contains the following components (A), (B), (C) and (D), and has a mass ratio of 0.1 to 9 represented by the component (C) / component (D). Washing soap.
(A) Ingredient: Anionic surfactant.
Component (B): At least one selected from the group consisting of amphoteric surfactants and semipolar surfactants.
Ingredient (C): 3-Methoxy-3-methyl-1-butanol.
Ingredient (D): Nonionic surfactant. The dishwashing cleaning agent according to claim 1, wherein the component (D) is a branched alkyl alkoxylate. The dishwashing agent according to claim 1 or 2, wherein the total content of the component (C) and the component (D) is 5 to 20% by mass with respect to the total mass of the dishwashing agent. The mass ratio represented by ((C) component + (D) component) / ((A) component + (B) component + (C) component + (D) component) is 0.1 to 0.6. The dishwashing cleaning agent according to any one of claims 1 to 3.