JP6846275B2 - Dishwashing agent - Google Patents

Description

The present invention relates to a dishwashing agent.

In recent years, consumers have become more aware of bad odors due to increased hygiene awareness.
Examples of causes of microbial contamination in the kitchen at home include bacteria brought in from foodstuffs or the hands of cooks during cooking. It is considered that this bacterium is transferred to tableware and cooking utensils and proliferates as one of the factors such as food poisoning and sponge odor.

Conventionally, as a method of sterilizing kitchen utensils such as sponges and cutting boards, chlorine bleach or kitchen bleach based on sodium hypochlorite, or oxygen bleach containing sodium percarbonate or sodium perborate is used. There was a method of dipping kitchen utensils in the agent and processing it.
However, in the method of sterilizing kitchen utensils by immersing them in chlorine bleach, kitchen sterilizer, oxygen bleach, etc., prepare a treatment solution in which these bleach and sterilizer are dissolved in water, and use this treatment solution in the kitchen. It took time and effort to immerse the products. In addition, since these bleaching agents and disinfectants have a peculiar odor, they were sometimes avoided by some consumers.

In recent years, cleaning agents for kitchen utensils with sterilizing properties have been proposed. For example, Patent Document 1 describes a polyoxyethylene alkyl ether sulfate having a specific structure, an alkane sulfonic acid or a salt thereof, an amine oxide type surfactant, an aromatic sulfonic acid or a salt thereof, and a zinc compound. A liquid cleaning agent composition for kitchen containing a specific amount of is disclosed.

Japanese Unexamined Patent Publication No. 2008-156590

However, although the liquid cleaning agent composition for kitchen described in Patent Document 1 has good sterilizing properties, it is said that when the sponge is left after being used for cleaning dishes and the like, a foul odor is generated from the sponge. There was a problem.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a dishwashing cleaning agent that does not easily leave stains on the sponge after being used for washing dishes and the like and can suppress the generation of foul odors.

The present invention has the following aspects.
[1] A dishwashing agent containing the following components (A) and (B) and having a mass ratio of 5 to 250 represented by the component (A) / component (B).
Component (A): A surfactant containing the following components (a1) and (a2).
(A1) Ingredient: Anionic surfactant.
(A2) Ingredient: At least one selected from the group consisting of amphoteric surfactants and semipolar surfactants.
(B) Ingredient: Dichroic glass.
[2] The dishwashing cleaning agent according to [1], wherein the component (A) further contains the following component (a3).
(A3) Ingredient: Nonionic surfactant.
[3] The dishwashing agent according to [2], wherein the component (a3) is a branched alkyl alkoxylate.
[4] The dishwashing cleaning agent according to [2] or [3], wherein the mass ratio represented by (a3) component / ((a1) component + (a2) component) is 0.05 to 1.7. ..
[5] The dishwashing agent according to any one of [1] to [4], wherein the mass ratio represented by the component (a2) / component (a1) is 0.3 to 1.6.
[6] The dishwashing agent according to any one of [1] to [5], wherein the content of the component (A) is 10% by mass or more 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 (B) is 0.01 to 5% 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 (a1) is 1 to 25% 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 content of the component (a2) is 1 to 20% by mass with respect to the total mass of the dishwashing agent. ..
[10] The dishwashing agent according to any one of [2] to [4], wherein the content of the component (a3) is 1 to 20% by mass with respect to the total mass of the dishwashing agent. ..
[11] The dishwashing cleaning agent according to any one of [3], [4], and [10], wherein the component (a3) is a gerbet alcohol-type nonionic surfactant.

According to the present invention, it is possible to provide a dishwashing cleaning agent that does not leave stains on the sponge after being used for washing dishes and the like and can suppress the generation of foul odors.

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

<Ingredient (A)>
The component (A) is a surfactant containing the following components (a1) and (a2). The component (A) preferably further contains the following component (a3).
(A1) Ingredient: Anionic surfactant.
(A2) Ingredient: At least one selected from the group consisting of amphoteric surfactants and semipolar surfactants.
(A3) Ingredient: Nonionic surfactant.

The content of the component (A) is preferably 10% by mass or more, more preferably 10 to 50% by mass, still more preferably 15 to 45% 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, stains are less likely to remain on the sponge after being used for washing dishes and the like. When the content of the component (A) is not more than the upper limit value, the uniformity of the dishwashing agent can be maintained satisfactorily.

((A1) component)
The component (a1) is an anionic surfactant.
When the dishwashing agent contains the component (a1), 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 (a2).

Examples of the component (a1) 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 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 (a1), one type may be used alone, or two or more types may be used in combination as appropriate.

As the component (a1), 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 (a1), 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) sodium sulfate, polyoxyethylene (4) linear alkyl (C12 / 14 = 75/25; derived from natural fats and oils) sodium sulfate, sodium alkanesulfonic acid, linear 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 ester sodium salt, polyoxyethylene (4) linear alkyl (C12 / 14 = 75/25; derived from natural fats and oils) sulfate ester sodium salt are 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 (a1) is preferably 1 to 25% by mass, more preferably 5 to 15% by mass, based on the total mass of the dishwashing agent. When the content of the component (a1) is within the above range, stains are less likely to remain on the sponge after being used for washing dishes and the like, and the generation of foul odor from the sponge can be further suppressed.

((A2) component)
The component (a2) is at least one selected from the group consisting of amphoteric surfactants and semipolar surfactants.
When the dishwashing agent contains the component (a2), 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 (a1).
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 dissolves or the dispersion system in which the semipolar surfactant is dispersed.

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

As the component (a2), 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 (a2) is preferably 1 to 20% by mass, more preferably 5 to 12% by mass, based on the total mass of the dishwashing agent. When the content of the component (a2) is within the above range, stains are less likely to remain on the sponge after being used for washing dishes and the like, and the generation of foul odor from the sponge can be further suppressed. In addition, the detergency against oil stains is improved.

The mass ratio represented by the component (a2) / component (a1) (hereinafter, also referred to as “a2 / a1 ratio”) is preferably 0.3 to 1.6, more preferably 0.7 to 1.2. When the a2 / a1 ratio is within the above range, stains are less likely to remain on the sponge after being used for washing dishes and the like, and the stability of the dishwashing agent is improved.

((A3) component)
The component (a3) is a nonionic surfactant.
By further containing the component (a3) in addition to the components (a1) and (a2), the dishwashing agent further exhibits the detergency and foaming property against oil stains required as the basic performance of the dishwashing agent. it can.

Examples of the component (a3) include a polyoxyalkylene-added nonionic surfactant represented by the following general formula (3), an alkyl glycoside, a sorbitan fatty acid ester, and the like.
R ^6- O- (R ⁷ O) _q- H ... (3)
(In the general formula (3), R ⁶ is a linear or branched hydrocarbon group having 8 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.)

In the general formula (3), ^{the carbon number of R 6} is 8 to 18, preferably 8 to 16, and more preferably 8 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.

As the component (a3), the polyoxyalkylene-added nonionic surfactant represented by the general formula (3) is preferable because the effect of the present invention is particularly easy to obtain, and the polyoxyalkylene (2 to 3 carbon atoms) is preferable. Alkyl (10 to 18 carbon atoms) ether (average number of moles of alkylene oxide added 5 to 20) is more preferable, and branched alkyl alkoxylate is particularly preferable.
Here, the "branched alkyl alkoxylate" is ^{a nonionic surfactant in which R 6} in the general formula (3) is a hydrocarbon group derived from a branched primary alcohol.

As the component (a3), a gerbet alcohol-type nonionic surfactant is preferable among the branched alkyl alkoxylates.
Examples of the gerbet alcohol type nonionic surfactant include compounds represented by the following general formula (4).
(R ⁸ ) (R ⁹ ) CH-CH _2- O- (R ⁷ O) _q- H ... (4)
(In the general formula (4), R ⁷ is a hydrocarbon group having 1 to 3 carbon atoms, and R ⁸ and R ⁹ each independently represent a chain hydrocarbon group, and the sum of ^{R 8} and R ^{9 is used.} The number of carbon atoms in is 6 to 16, and q ^{indicates the average number of repetitions of (R 7} O), and 1 ≦ q ≦ 20.)

In the general formula (4), ^{the total number of carbon atoms of R 8} and R ⁹ is 6 to 16, preferably 6 to 14, and more preferably 6 to 12. R ⁸ and R ⁹ are preferably linear or branched alkyl groups or linear or branched alkenyl groups, respectively.
^{R 7} and q in the general formula (4) is the same as ^{R 7} and q in the general formula (3).

Examples of the compound represented by the general formula (4) 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 (a3) is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, based on the total mass of the dishwashing agent. When the content of the component (a3) is within the above range, stains are less likely to remain on the sponge after being used for washing dishes and the like, and the generation of foul odor from the sponge can be further suppressed. In addition, the detergency against oil stains is improved.

The mass ratio represented by (a3) component / ((a1) component + (a2) component) (hereinafter, also referred to as “a3 / (a1 + a2) ratio”) is preferably 0.05 to 1.7. 2 to 0.9 is more preferable. When the a3 / (a1 + a2) ratio is within the above range, the generation of malodor from the sponge can be suppressed for a longer period of time.

<Ingredient (B)>
The component (B) is 4,4'-dichloro-2'-hydroxydiphenyl ether (common name: diclosan).
When the dishwashing agent contains the component (B), antibacterial and bacteriostatic properties can be exhibited.

The content of the component (B) is preferably 0.01 to 5% by mass, more preferably 0.1 to 3% by mass, based on the total mass of the dishwashing agent. When the content of the component (B) is at least the above lower limit value, the antibacterial and bacteriostatic effects are sufficiently exhibited, and the generation of foul odor from the sponge can be further suppressed. The antibacterial property and bacteriostatic property tend to increase as the content of the component (B) increases, but the antibacterial property and bacteriostatic property may decrease if the content of the component (B) is too large.

The mass ratio represented by the component (A) / component (B) (hereinafter, also referred to as “A / B ratio”) is 5 to 250, preferably 15 to 130. When the A / B ratio is within the above range, the generation of foul odor from the sponge can be suppressed.

The total content of the component (A) and the component (B) is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, based on the total mass of the dishwashing agent. When the total content of the component (A) and the component (B) is at least the above lower limit value, it is excellent in suppressing the stain residue of the sponge and the malodor of the sponge. When the total content of the component (A) and the component (B) is not more than the above upper limit value, the ease of handling at the time of manufacturing the dishwashing agent is improved.

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

<Arbitrary ingredient>
The dishwashing agent may contain a component (arbitrary component) other than the component (A) and the component (B), if necessary, as long as the effect of the present invention is not impaired.
Examples of the optional component include components used in cleaning composition for dishwashing, kitchen, hard surface and the like, and examples thereof include cationic surfactants, preservatives and hydrotropes.

Examples of the cationic surfactant include didecyldimethylammonium chloride, didecyldimethylammonium metosulfate, distearyldimethylammonium chloride, dioctyldimethylammonium chloride, distearyldihydroxyethylammonium chloride, dibeef alkyldimethylammonium chloride, and di (stearoyl). Oxyethyl) dimethylammonium chloride, di (oleoyloxyethyl) dimethylammonium chloride, di (palmitoyloxyethyl) dimethylammoniummethsulfate, di (stearoyloxyisopropyl) dimethylammonium chloride, di (oleoyloxyisopropyl) dimethylammonium chloride, Examples thereof include di (oleoyloxybutyl) dimethylammonium chloride, di (stearoyloxyethyl) methylhydroxyethylammonium metosulfate, and tri (stearoyloxyethyl) methylmethosulfate. The carbon number of the "beef tallow alkyl" group is 14 to 18.
As the cationic surfactant, one type 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.

The content of the preservative is preferably 2 to 1000 mass ppm with respect to the total mass of the dishwashing agent. As long as the content of the preservative is within the above range, microbial contamination of the dishwashing detergent can be suppressed even if the dishwashing agent is stored for a long period of time.

(Hydrotrope)
When the dishwashing agent contains a hydrotropic 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, toluene sulfonic acid, toluene sulfonic acid salt, cumene sulfonic acid, cumene sulfonic 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 preferable from the viewpoint of the dissolving effect of the components (A) and (B) in the dishwashing agent and the feeling of use.
The content of the hydrotropic agent is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, based on 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; a dye, a radical trapping agent, a fragrance and the like. Can also be blended.

The total content of all the components contained in the dishwashing agent shall be 100% by mass.

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

<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, the surfactant as the component (A) is the anionic surfactant as the component (a1), and the amphoteric surfactant and the semipolar surfactant as the component (a2). In combination with at least one selected from the group consisting of agents, the component (B), diclosan, is used in combination, and the component (A) and the component (B) are contained in a specific ratio, so that the component (A) and the component (B) are contained in a specific ratio for a long period of time. Can exert antibacterial effect and bacteriostatic effect. Therefore, by the usual usage method, dirt is less likely to remain on the sponge after it is used for washing dishes and the like, and the generation of foul odor can be suppressed. Specifically, by washing the dishes on a daily basis, it is possible to suppress the residual stains on the sponge after washing the dishes and to suppress the generation of foul odors from the sponge. In particular, by newly adding the dishwashing agent of the present invention to the sponge after washing the dishes, kneading and leaving the sponge, the generation of foul odor from the sponge can be suppressed more effectively.
Moreover, with the dishwashing agent of the present invention, when sterilizing the sponge, it is not necessary to dissolve the sponge in water and prepare a treatment liquid as in the case of conventional bleaching agents, so that the sponge can be sterilized without any trouble. it can. In addition, the odor is less noticeable than conventional bleaching agents and disinfectants.

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. Examples 1 to 10, 15 and 16 are reference examples.

"Ingredients used"
The following compounds were used as the component (a1).
A1-1: 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.
-A1-2: 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.
-A1-3: 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.
-A1-4: Sodium secondary alkane sulfonate having 14 to 17 carbon atoms (SAS; manufactured by Clariant Japan Co., Ltd., trade name "HOSTAPUR SAS 30A").
-A1-5: 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.

(Synthesis method of a1-1)
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 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 a1-1.

(Synthesis method of a1-3)
A1-3 was obtained in the same manner as in a1-1 except that the amount of ethylene oxide was changed to 364 g.

The following compounds were used as the component (a2).
-A2-1: 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, p = 0.
-A2-2: 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.
-A2-3: Betaine lauryldimethylaminoacetate (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name "Amigen S").
In addition, a2-1 and a2-2 are semi-polar surfactants, and a2-3 is an amphoteric surfactant.

The following compounds were used as the component (a3).
-A3-1: 2-Propylheptyl 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.
-A3-2: 2-Propylheptyl alcohol ethoxylate (manufactured by BASF, trade name "Lutensol XP-80"). In the above general formula (3), R ⁶ = 2-propylheptyl group, R ⁷ = ethylene group, q = 8.
-A3-3: 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.
-A3-4: Polyoxyethylene lauryl ether (manufactured by Nippon Emulsion Co., Ltd., "EMALEX 710"). In the above general formula (3), R ⁶ = a linear alkyl group having 12 carbon atoms, R ⁷ = an ethylene group, q = 10.
In addition, a3-1, a3-2 and a3-3 are gerbet alcohol type nonionic surfactants, and a3-4 is a linear type nonionic surfactant.

The following compounds were used as the component (B).
-B-1: Dichrosan (manufactured by BASF, trade name "Tinosan HP100").

The following compounds were used as optional components.
<Inorganic builder>
-Zinc oxide: (manufactured by Mitsui Mining & Smelting 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").
<Dye>
・ Green No. 3: (manufactured by Ami Kasei Co., Ltd.).
<Hydrotrope>
-Ethanol: Ethanol 95%, 1st grade (manufactured by Kanto Chemical Co., Inc.).
-PTS-H: Paratoluenesulfonic acid monohydrate, Deer 1st grade (manufactured by Kanto Chemical Co., Inc.).
<pH adjuster>
-PH adjuster: sodium hydroxide (manufactured by Kanto Chemical Co., Inc.).
<Fragrance>
-Fragrance A: The fragrance composition A shown in Tables 1 to 6.
-Fragrance B: The fragrance composition B shown in Tables 1 to 6.

"Examples 1 to 30, Comparative Examples 1 to 6"
<Preparation of dishwashing agent>
1000 g of a dishwashing cleaning agent having the composition shown in Tables 7 to 10 was prepared by the following procedure.
The component (A), the component (B), and ethanol were placed in a 1 L beaker and sufficiently stirred with a magnetic stirrer (manufactured by Fine, trade name "F-606N"). Subsequently, the remaining optional components (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 7.8, and then water (distilled water) is added so that the total amount becomes 100% by mass, and even better. 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".
For each of the obtained dishwashing agents, the resistance to residual stains on the sponge and the deodorizing effect of the sponge were evaluated as follows. The results are shown in Tables 7-10.

<Evaluation of the difficulty of remaining dirt on the sponge>
Sudan IV (manufactured by Kanto Chemical Co., Inc.) 1 g of beef tallow (manufactured by Wako Junyaku Co., Ltd.) colored to a concentration of 1% by mass in a plastic container (Iwasaki Industry Inc.) measuring 10 cm in length, 15 cm in width, and 5 cm in height. It was applied evenly to the entire inside of the company-made product name "Neokeeper") to make a stain model. Take 38 g of tap water and 2 g of the dishwashing agent of each example in a dishwashing sponge (manufactured by Sumitomo 3M Ltd., trade name "Scotch-Brite") of 11.5 cm in length x 7.5 cm in width x 3 cm in height, and 10 After rubbing with a hand, the sponge was thoroughly rinsed with tap water after rubbing the bottom surface of the stain model 10 times, the side surface once, and the four corners 5 times for the above stain model. The sponge after rinsing was visually observed, and the remaining stains on the sponge were evaluated according to the following evaluation criteria. ◎ and ○ are accepted.
⊚: No stain residue of beef tallow colored on the sponge is visually recognized.
◯: Almost no stain residue of beef tallow colored on the sponge is visually recognized.
Δ: Residual stains of beef tallow colored on the sponge are visually observed.
X: A considerable amount of stain residue of beef tallow colored on the sponge is visually observed.

<Evaluation of deodorant effect of sponge>
50 g of sardine oil was put in a frying pan, 1 ball of onion and 100 g of minced meat were fried, and then 5 g of each was spread on 5 ceramic plates to make a stain model. Take 38 g of tap water and 2 g of the dishwashing agent of each example in a dishwashing sponge (manufactured by Sumitomo 3M Ltd., trade name "Scotch-Brite") of 11.5 cm in length x 7.5 cm in width x 3 cm in height, and 10 After rubbing with hand, each stain model was scrubbed 10 times, and then the sponge was thoroughly rinsed with tap water. The rinsed sponge was processed into a cylinder having a diameter of 2.4 cm and a height of 3 cm, and placed in a screw cap bottle having a capacity of 110 mL. The sponge in the screw cap bottle was ingested with 0.5 g of the dishwashing agent of each example, and was rubbed evenly with a glass rod. The screw cap bottle was sealed and left at 35 ± 1 ° C. for 48 hours. The malodor of the sponge after 24 hours and 48 hours was evaluated according to the following evaluation criteria. ◎ ◎, ◎ and ○ are passed.
◎◎: I do not feel any bad odor.
◎: I do not feel a bad smell.
◯: Almost no stench is felt.
Δ: A slight odor is felt.
×: I feel a bad smell.

In Tables 7 to 10, "balance" is the blending amount (mass%) of water (distilled water) required to make 100% by mass of the total dishwashing agent.
The "a2 / a1 ratio" is a mass ratio represented by the component (a2) / component (a1). The "A / B ratio" is a mass ratio represented by the component (A) / component (B). The "a3 / (a1 + a2) ratio" is a mass ratio represented by (a3) component / ((a1) component + (a2) component).

As is clear from Tables 7 to 9, the dishwashing agents of each example did not easily leave stains on the sponge after being used for washing dishes and the like. In addition, the generation of foul odors could be suppressed.
On the other hand, as is clear from Table 10, the dishwashing agents of Comparative Examples 1 and 2 having an A / B ratio of more than 250 and the dishwashing agent of Comparative Example 3 having an A / B ratio of less than 5 were used. If there was, a foul odor was likely to be generated from the sponge.
When the dishwashing agent of Comparative Example 4 containing no component (a1) and the dishwashing agent of Comparative Example 5 containing no component (a2) were used, stains tended to remain on the sponge. In addition, a foul odor was likely to be generated from the sponge.
(B) When the dishwashing agent of Comparative Example 6 containing no component was used, a foul odor was likely to be generated from the sponge.

Claims (3)

A dishwashing agent containing the following components (A) and (B) and having a mass ratio of 5 to 250 represented by the components (A) / (B).
Component (A): the following component (a1), the component (a2) and (a3) a component seen including, mass ratio represented by (a3) component / (component (a1) + (a2) component) 0.05 Surfactant of ~ 1.7 .
(A1) Ingredient: Anionic surfactant.
(A2) Ingredient: At least one selected from the group consisting of amphoteric surfactants and semipolar surfactants.
(A3) Ingredient: Nonionic surfactant.
(B) Ingredient: Dichroic glass. The dishwashing cleaning agent according to claim 1 , wherein the component (a3) is a branched alkyl alkoxylate. The dishwashing agent according to claim 1 or 2 , wherein the mass ratio represented by the component (a2) / component (a1) is 0.3 to 1.6.