JP2017119742A - Detergent for dishwasher - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a detergent for a dishwasher that is of a compact type but keeps detergency on tea staining and also has excellent transparency.SOLUTION: A detergent for dishwasher has (A) component: surfactant, (B) component: chelator, (C) component: water-soluble solvent, (D) component: at least one selected from aromatic sulfonic acid and salt thereof, and (E) component: water. A content of (B) component is 18 mass% or more, in terms of the acid type, relative to the total mass of the detergent for a dishwasher, and a mass ratio represented by ((C) component +(D) component)/(B) component is 0.3-1.7.SELECTED DRAWING: None

Description

  The present invention relates to a detergent for a dishwasher.

In recent years, dishwashers for washing dishes, cooking utensils, etc. (objects to be washed) have become widespread not only in kitchens such as hotels, restaurants, and lunch centers, but also in general households.
In a dishwasher, when washing and rinsing, several liters of hot water circulates while being strongly ejected from the nozzle. In addition, a dedicated cleaning agent (cleaning agent for dishwashers) is generally used for cleaning by the dishwasher.

For example, Patent Document 1 discloses a dishwasher wash containing a nonionic surfactant, an organic acid (chelating agent), an enzyme, a water-soluble solvent, a solubilizer, a calcium additive, and water. Agents are disclosed.
Patent Document 2 discloses a dishwasher cleaning agent containing an anionic surfactant, a chelating agent, an enzyme, propylene glycol and the like.

JP 2008-127490 A Japanese Patent Laying-Open No. 2015-10187

  The conventional dishwasher cleaning agent requires a large amount of cleaning agent for each cleaning, so that it can be used more than a predetermined number of times. It tends to be heavy. For this reason, a compact type cleaning agent with a small amount of use per time is required from the viewpoint of accommodation in a kitchen or the like and usability when putting the cleaning agent into a dishwasher.

A dishwasher detergent is required to have a high detergency against dirt that is difficult to remove, such as tea astringent dirt. In order to exert a cleaning power equivalent to or higher than that of a conventional cleaning agent in a compact type cleaning agent, it is necessary to increase the content of components that contribute to cleaning properties (for example, surfactants and chelating agents).
However, in the cleaning agents described in Patent Documents 1 and 2, if the content of the chelating agent is simply increased, the cleaning agent becomes cloudy and the transparency is lowered. Since a cleaning agent having a transparent appearance is easy to obtain a high-class feeling and a clean feeling, the cleaning agent is also required to have transparency.

  This invention is made | formed in view of the said situation, and it aims at providing the washing | cleaning agent for dishwashers which is excellent also in transparency, maintaining the cleaning power with respect to tea astringent dirt, although it is a compact type.

The present invention has the following aspects.
[1] Component (A): Surfactant, Component (B): Chelating agent, Component (C): Water-soluble solvent, Component (D): At least one selected from aromatic sulfonic acids and salts thereof A dishwasher detergent containing seeds and component (E): water, wherein the content of component (B) is 18% by mass in terms of acid type with respect to the total mass of the dishwasher detergent. A dishwasher cleaning agent, wherein the mass ratio represented by ((C) component + (D) component) / (B) component is 0.3 to 1.7.
[2] The dishwasher cleaning agent according to [1], wherein the total content of the component (C) and the component (D) is 7 to 35% by mass with respect to the total mass of the dishwasher cleaning agent.
[3] The dishwasher cleaning agent according to [1] or [2], wherein the mass ratio represented by (C) component / (D) component is 2 to 10.
[4] The component (A) includes any one of [1] to [3], including the compound (A1) represented by the following general formula (a-1) and the anionic surfactant (A2). Detergent for dishwasher as described in 1.

In the formula (a-1), R ¹ is a linear or branched alkyl group having 11 to 21 carbon atoms or a linear or branched alkenyl group having 11 to 21 carbon atoms, and R ² is A hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group having 1 to 4 carbon atoms, R ³ is an alkylene group having 1 to 4 carbon atoms, and R ⁴ and R ⁵ are each independently a hydrogen atom. Or it is a C1-C4 alkyl group.

[5] The total content of the component (B), the component (C), and the component (D) is 25 to 55% by mass with respect to the total mass of the dishwasher detergent [1] to [4] The cleaning agent for dishwashers as described in any one of these.
[6] The dishwasher cleaning agent according to any one of [1] to [5], wherein the component (C) is at least one selected from propylene glycol, dipropylene glycol, and tripropylene glycol. .
[7] The component (D) according to any one of [1] to [6], wherein the component is at least one selected from benzenesulfonic acid, toluenesulfonic acid, cumenesulfonic acid, and salts thereof. Detergent for dishwasher.
[8] The detergent for a dishwasher according to any one of [1] to [7], further comprising an enzyme.
[9] The dishwasher cleaning agent according to [8], wherein the pH at 25 ° C is 6 to 8.

  The detergent for dishwashers of the present invention is excellent in transparency while maintaining a cleaning power against tea astringent stains while being a compact type.

Hereinafter, the present invention will be described in detail.
The dishwasher cleaning agent of the present invention (hereinafter also simply referred to as “cleaning agent”) includes the following components (A), (B), (C), (D), and (E): Containing.

<(A) component>
The component (A) is a surfactant. When the cleaning agent contains the component (A), high cleaning power (particularly cleaning power against oil stains) is exhibited.
(A) Although it does not specifically limit as a component, It is preferable to use the low-foaming surfactant normally used for the washing | cleaning agent for dishwashers, and it is sufficient to use surfactant individually or in combination of 2 or more types. it can. Among them, alkylamide amine (hereinafter referred to as “(A1) component”) which is a compound (A1) represented by the following general formula (a-1) because it has low foaming properties and has higher detergency against oil stains. And an anionic surfactant (A2) (hereinafter also referred to as “component (A2)”) are preferably used in combination.

In formula (a-1), R ¹ is a linear or branched alkyl group having 11 to 21 carbon atoms or a linear or branched alkenyl group having 11 to 21 carbon atoms.
The carbon number of the alkyl group and the alkenyl group in R ¹ is 11 to 21 respectively, and the defoaming effect to suppress foaming and the detergency against oil stains are further increased, and therefore the carbon number is preferably 13 to 21 and more preferably. Has 15 to 21 carbon atoms, particularly preferably 15 to 19 carbon atoms.
R ¹ is preferably a linear or branched alkyl group having 13 to 21 carbon atoms.

R ² is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 1 to 4 carbon atoms.
The number of hydroxy groups in the hydroxyalkyl group for R ² may be one or two or more.
R ² is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

R ³ is an alkylene group having 1 to 4 carbon atoms.
The alkylene group in R ³ has 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms, more preferably 2 or 3 carbon atoms, and particularly preferably 3 carbon atoms.

R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
The alkyl groups in R ⁴ and R ⁵ each have 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms, more preferably 1 or 2 carbon atoms, and particularly preferably 1 carbon atom. is there.
R ⁴ and R ⁵ are each preferably an alkyl group having 1 to 4 carbon atoms, and preferably the same as each other.

Examples of the component (A1) include lauric acid dimethylaminoethylamide, lauric acid diethylaminoethylamide, lauric acid dipropylaminoethylamide, lauric acid dimethylaminopropylamide, lauric acid diethylaminopropylamide, and lauric acid dipropylaminopropylamide. , Myristic acid dimethylaminoethylamide, myristic acid diethylaminoethylamide, myristic acid dipropylaminoethylamide, myristic acid dimethylaminopropylamide, myristic acid diethylaminopropylamide, myristic acid dipropylaminopropylamide, palmitic acid dimethylaminoethylamide, Palmitic acid diethylaminoethylamide, palmitic acid dipropylaminoethylamide, palmitic acid dimethylamino Lopyramide, palmitic acid diethylaminopropylamide, palmitic acid dipropylaminopropylamide, stearic acid dimethylaminoethylamide, stearic acid diethylaminoethylamide, stearic acid dipropylaminoethylamide, stearic acid dimethylaminopropylamide, stearic acid diethylaminopropylamide, Stearic acid dipropylaminopropylamide, behenic acid dimethylaminoethylamide, behenic acid diethylaminoethylamide, behenic acid dipropylaminoethylamide, behenic acid dimethylaminopropylamide, behenic acid diethylaminopropylamide, behenic acid dipropylaminopropylamide, Lauric acid dimethylaminoethylmethylamide, myristic acid dimethylaminoethylmethylamide Palmitic acid dimethylaminoethylmethylamide, stearic acid dimethylaminoethylmethylamide, behenic acid dimethylaminoethylmethylamide, lauric acid dimethylaminopropylmethylamide, myristic acid dimethylaminopropylmethylamide, palmitic acid dimethylaminopropylmethylamide, stearic acid Examples thereof include dimethylaminopropylmethylamide and behenic acid dimethylaminopropylmethylamide.
Among these, myristate dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, stearic acid dimethylaminopropylamide, and behenic acid dimethylaminopropylamide are preferable because a foam-suppressing effect is more easily obtained.
These (A1) components may be used individually by 1 type, and may use 2 or more types together.

  The content of the component (A1) is preferably 0.02 to 5% by mass, more preferably 0.2 to 5% by mass, and still more preferably 0.2 to 3% by mass with respect to the total mass of the cleaning agent. If content of (A1) component is in the said range, detergency and transparency will increase more. In addition, a defoaming effect is obtained, and a cleaning agent having excellent low foaming properties is obtained.

Examples of the component (A2) include sulfonate type, sulfate ester type, carboxylate type, and phosphate ester salt type.
The sulfonate type includes alkylbenzene sulfonate, alkyl sulfate, alkane sulfonate, α-olefin sulfonate, α-sulfo fatty acid salt, α-sulfo fatty acid alkyl ester salt, alkyl sulfosuccinate, dialkyl sulfosuccinic acid. Etc.
Examples of the sulfate ester type include alkyl sulfate ester salts, alkenyl sulfate ester salts, polyoxyalkylene alkyl ether sulfate ester salts, and polyoxyalkylene alkenyl ether sulfate ester salts.
Examples of the carboxylate type include alkyl ether carboxylates, amide ether carboxylates, sulfosuccinates, amino acid anionic surfactants, and the like.
Examples of the phosphoric acid ester salt type include alkyl phosphoric acid ester salts and alkyl ether phosphoric acid ester salts.

As the component (A2), those having an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms are preferable, and those having an alkyl group having 8 to 18 carbon atoms are more preferable. The alkyl group and alkenyl group may be linear or branched.
Among these, the sulphonate type is preferable because the detergency against oil stains is good, it is easy to ensure low foaming properties, and transparency is easily obtained, and linear alkylbenzene sulphonate, alkane sulphonate and α-olefin sulfonates are particularly preferred.
These (A2) components may be used individually by 1 type, and may use 2 or more types together.

  (A2) Salts constituting the component include alkali metal salts such as sodium salt and potassium salt; alkaline earth metal salts such as magnesium salt and calcium salt; monoethanolamine salt (monoethanolammonium), diethanolamine salt (diethanolammonium salt) ), Alkanolamine salts such as triethanolamine salt (triethanolammonium); ammonium salts and the like.

  The content of the component (A2) is preferably 0.02 to 5% by mass, more preferably 0.2 to 5% by mass, and still more preferably 0.2 to 3% by mass with respect to the total mass of the cleaning agent. If content of (A2) component exists in the said range, detergency and transparency will increase more. In addition, a defoaming effect is obtained, and a cleaning agent having excellent low foaming properties is obtained.

  Regarding the mixing ratio of the component (A1) and the component (A2), the mass ratio represented by the component (A1) / the component (A2) is preferably 0.6 to 1.4, more preferably 0. 8 to 1.2. When the mass ratio represented by (A1) component / (A2) component is within the above range, the foam suppression effect is easily exhibited.

  The component (A) may further contain an amphoteric surfactant, a nonionic surfactant, a semipolar surfactant, a cationic surfactant (excluding the component (A1)), and the like. Furthermore, (A) component can contain the surfactant used for a normal cleaning agent besides these. However, it is preferable to use a combination in which the average value of the foam height when mixing all the surfactants contained in the dishwasher detergent is 10 mm or less.

  The content of the component (A) is preferably 0.1 to 5.02% by mass, more preferably 1 to 3% by mass, and still more preferably 1 to 2% by mass with respect to the total mass of the cleaning agent. If content of (A) component is in the said range, detergency and transparency will increase more. In addition, a defoaming effect is obtained, and a cleaning agent having excellent low foaming properties is obtained.

<(B) component>
(B) A component is a chelating agent. When the cleaning agent contains the component (B), the cleaning power against cloudy dirt such as a glass cup and the cleaning power against tea astringent dirt are increased.
The molecular weight of the component (B) is preferably 800 or less. When the molecular weight is 800 or less, the compatibility with other components is good, and a large amount of the component (B) can be easily blended.

Examples of the component (B) include ethylenediaminetetraacetic acid, nitrilotriacetic acid, β-alanine diacetic acid, ethylenediaminedisuccinic acid, L-aspartic acid-N, N-diacetic acid, dihydroxyethylethylenediaminediacetic acid, hydroxyethyliminodiacid. Acetic acid, citric acid, hydroxyethylethylenediaminetriacetic acid, glycol etherdiaminetetraacetic acid, L-glutamic acid diacetic acid, 1,3-diamino-2-hydroxypropanetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, dihydroxyethylglycine, Examples include 3-hydroxy-2,2′-iminodisuccinic acid, serine diacetic acid, asparagine diacetic acid, methylglycine diacetic acid, hydroxyethane diphosphonic acid, aminotrimethylenephosphonic acid, tripolyphosphoric acid, and salts thereof. It is.
(B) As a salt which comprises a component, an alkali metal salt is preferable and a sodium salt and potassium salt are more preferable.

Among these, since the detergency against both cloudy stain and tea astringent stain is likely to increase, ethylenediaminetetraacetic acid, nitrilotriacetic acid, β-alanine diacetic acid, ethylenediamine disuccinic acid, L-aspartic acid-N, N-diacetic acid, Dihydroxyethylethylenediaminediacetic acid, hydroxyethyliminodiacetic acid, citric acid, hydroxyethylethylenediaminetriacetic acid, glycol etherdiaminetetraacetic acid, L-glutamic acid diacetic acid, 1,3-diamino-2-hydroxypropanetetraacetic acid, diethylenetriaminepentaacetic acid, Triethylenetetramine hexaacetic acid, dihydroxyethylglycine, 3-hydroxy-2,2′-iminodisuccinic acid, serine diacetic acid, asparagine diacetic acid, methylglycine diacetic acid, and salts thereof are preferred. Among them, citric acid, L-glutamic acid diacetic acid, methylglycine diacetic acid, diethylenetriaminepentaacetic acid, or a salt thereof is preferable, and citric acid or a salt thereof is particularly preferable because the detergency against cloudy stain and tea astringent stain is further increased. .
These (B) components may be used individually by 1 type, and may use 2 or more types together.

(B) Content of a component is 18 mass% or more in conversion of an acid type with respect to the gross mass of a cleaning agent, 18-30 mass% is preferable, 20-24 mass% is more preferable, 20-22 mass % Is more preferable. If the content of the component (B) is within the above range, it is useful for making the cleaning agent compact. In addition, the detergency against tea astringent stains is increased and the transparency is improved.
In the present invention, “acid type conversion” means that the component (B) is calculated as an acid type. For example, when the cleaning agent contains citrate or L-glutamic acid diacetate as the component (B), the content as acid corresponding to these (that is, citric acid or L-glutamic acid diacetate) is calculated.

<(C) component>
Component (C) is a water-soluble solvent. Transparency improves because a cleaning agent contains (C) component.
In the present invention, “water-soluble” means that when 1 g of a solvent is mixed with 1 liter of water at 25 ° C., it is transparently dissolved.

Examples of the component (C) include alcohol solvents and glycol ether solvents.
Examples of alcohol solvents include ethyl alcohol, isopropanol, 3-methoxybutanol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, and 1,3-butylene glycol. 1,4-butanediol, 1,5-pentanediol, hexylene glycol, glycerin and the like.

  Examples of glycol ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, and diethylene glycol. Dimethyl ether, diethylene glycol diethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol mono Chirueteru, propylene glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, and 3-methyl-3-methoxybutanol and the like.

Among these, propylene glycol, dipropylene glycol, and tripropylene glycol are preferable because of increased transparency, and propylene glycol is particularly preferable.
These components (C) may be used alone or in combination of two or more.

  (C) 0.1-30 mass% is preferable with respect to the total mass of a cleaning agent, as for content of a component, 5-24 mass% is more preferable, 10-20 mass% is more preferable, 12-18 mass % Is particularly preferred. If the content of the component (C) is 0.1% by mass or more, the transparency is further improved. However, if the content exceeds 30% by mass, further improvement in transparency cannot be expected, and only the cost increases. It is.

<(D) component>
The component (D) is at least one selected from aromatic sulfonic acids and salts thereof. Transparency improves because a cleaning agent contains (D) component.
The aromatic ring in the aromatic sulfonic acid may or may not have a substituent. When the aromatic ring has a substituent, examples of the substituent include a hydrocarbon group having 1 to 5 carbon atoms.

Examples of the aromatic sulfonic acid include benzene sulfonic acid, toluene sulfonic acid, xylene sulfonic acid, cumene sulfonic acid, substituted or unsubstituted naphthalene sulfonic acid, or salts thereof.
(D) As a salt constituting the component, alkali metal salts such as sodium salt and potassium salt; alkaline earth metal salts such as magnesium salt and calcium salt; monoethanolamine salt (monoethanolammonium), diethanolamine salt (diethanolammonium salt) ), Alkanolamine salts such as triethanolamine salt (triethanolammonium); ammonium salts and the like.

Among these, benzene sulfonic acid, toluene sulfonic acid, cumene sulfonic acid, and salts thereof are preferable, and toluene sulfonic acid or a salt thereof is particularly preferable because of higher transparency.
These (D) components may be used individually by 1 type, and may use 2 or more types together.

  (D) As for content of a component, 0.1-10 mass% is preferable with respect to the gross mass of a cleaning agent, 2-6 mass% is more preferable, and 3-5 mass% is further more preferable. If the content of the component (D) is 0.1% by mass or more, the transparency is further improved. However, if the content exceeds 10% by mass, further improvement in transparency cannot be expected and only the cost increases. It is. In addition, the risk of separation and precipitation increases.

  The mass ratio represented by (component (C) + component (D)) / component (B) is 0.3 to 1.7, preferably 0.4 to 1.5, and 0.6 to 1. 5 is more preferable, and 0.8 to 1.2 is more preferable. If the mass ratio represented by ((C) component + (D) component) / (B) component is within the above range, the transparency is improved.

  The total content of the component (C) and the component (D) is preferably 7 to 35% by mass, more preferably 10 to 30% by mass, and still more preferably 15 to 25% by mass with respect to the total mass of the cleaning agent. . If the sum total of content of (C) component and (D) component is in the said range, transparency will improve more.

  2-10 are preferable, as for mass ratio represented by (C) component / (D) component, 2.5-8 are more preferable, 3-7 are more preferable, and 3-6 are especially preferable. When the mass ratio represented by the component (C) / component (D) is within the above range, the transparency is further improved.

  The total content of the component (B), the component (C), and the component (D) is preferably 20 to 60% by mass, more preferably 25 to 55% by mass, and more preferably 35 to 50% with respect to the total mass of the cleaning agent. More preferred is mass%. If the sum total of content of (B) component, (C) component, and (D) component is in the said range, the detergency and transparency with respect to tea astringent dirt will improve more.

<(E) component>
(E) A component is water.
The content of the component (E) is preferably less than 70% by mass, more preferably 60% by mass or less, and even more preferably 50% by mass or less with respect to the total mass of the cleaning agent. If content of (E) component is less than 70 mass%, a cleaning agent can be compactized. In addition, the detergency and transparency against oil stains and tea astringent stains are further improved.
(E) Although the lower limit of content of a component is not specifically limited, 25 mass% or more is preferable with respect to the total mass of a cleaning agent, and 35 mass% or more is more preferable.

<Optional component>
Unless it is contrary to the objective of this invention, the cleaning agent of this invention can contain the component normally contained in the cleaning agent for wash | cleaning tableware as an arbitrary component.
Optional ingredients include, for example, enzymes, plant extracts, oil-absorbing agents, antifoaming agents, tableware protecting agents, thickeners, coloring agents, hydrotropes excluding component (D), antioxidants, pH adjusting agents, and fragrances. And bleach.

The enzyme is not particularly limited, and an enzyme that is usually mixed in a detergent for washing dishes and the like can be used. For example, cellulase, α-amylase, pullulanase, lipase, hemicellulase, β-glycosidase, Examples thereof include glucose oxidase, cholesterol oxidase, and protease.
Among these, β-glycosidase, glucose oxidase, and protease are preferable, and protease is particularly preferable because the detergency against protein soil and starch soil is particularly increased.
These enzymes may be used alone or in combination of two or more.

  In addition, the sum total of content of all the components contained in a cleaning agent shall be 100 mass%.

<Physical properties>
The pH at 25 ° C. of the cleaning agent is preferably 2-8. In particular, when the cleaning agent contains an enzyme, the pH of the cleaning agent is preferably 6 to 8, and more preferably 6 to 7 from the viewpoint of transparency. If pH of a cleaning agent is 6-8, it can suppress that the activity of an enzyme falls, maintaining the transparency of a cleaning agent favorable. Moreover, corrosion of the metal part of the dishwasher can be suppressed.
The pH of the cleaning agent may be adjusted using a pH adjuster such as sulfuric acid, sodium hydroxide, potassium hydroxide, monoethanolamine or the like.

<Manufacturing method>
The manufacturing method of the cleaning agent of the present invention is not particularly limited. For example, after mixing the component (E) and the component (C), the component (A), the component (B), and the component (D) are necessary. A method of adjusting to a predetermined pH by adding an optional component accordingly is mentioned.

<Effect>
In the cleaning agent of the present invention described above, since it contains (A) component, (E) component, and specific amounts of (B) component, (C) component and (D) component, it is a compact type. It also has excellent transparency while maintaining its detergency against tea astringent stains.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated in detail, this invention is not limited by the following description. In addition, the compounding quantity of the component used in each example is a pure conversion value unless there is particular notice.

"Raw material"
As the component (A), the following compounds were used.
A1-1: C18 dimethylaminopropylamide (manufactured by Toho Chemical Co., Ltd., trade name: “Catinal MPAS”, R ^{1 in} general formula (a-1) = a molecule having a linear alkyl group having 15 carbon atoms C16: C18 = 3: 7 by mass ratio of (C16) and R ¹ = molecule (C18) which is a linear alkyl group having 17 carbon atoms R ² = hydrogen atom, R ³ = propylene Group ((CH ₂ ) ₃ ), R ⁴ = methyl group, R ⁵ = methyl group).
A1-2: C14 dimethylaminopropylamide (synthetic product), R ¹ in the general formula (a-1) = linear alkyl group having 13 carbon atoms, R ² = hydrogen atom, R ³ = propylene group ( (CH ₂ ) ₃ ), R ⁴ = methyl group, R ⁵ = methyl group.
A1-3: C18 diethylaminoethylamide (manufactured by Nikko Chemicals Co., Ltd., trade name: “NIKKOL amidoamine SV”, molecule in which R ¹ in the general formula (a-1) is a linear alkyl group having 15 carbon atoms A mixture of (C16) and a molecule (C18) in which R ¹ = a linear alkyl group having 17 carbon atoms R ² = hydrogen atom, R ³ = ethylene group, R ⁴ = ethyl group, R ⁵ = ethyl Group).
A1-4: C12 dimethylaminopropylamide (synthetic product), R ¹ in the general formula (a-1) = linear alkyl group having 11 carbon atoms, R ² = hydrogen atom, R ³ = propylene group ( (CH ₂ ) ₃ ), R ⁴ = methyl group, R ⁵ = methyl group.
A2-1: Secondary alkane sulfonate sodium (manufactured by Clariant Japan KK, trade name: “HOSTAPUR SAS 30A”, sodium contained in an average molecular weight of 328 g / mol is 22.99 g / mol).
A2-2: Linear alkylbenzene sulfonic acid (manufactured by Teika Co., Ltd., trade name: “Taika Power L121”).
A2-3: Polyoxyethylene lauryl ether sulfate sodium salt (manufactured by Lion Co., Ltd., trade name: “Sanol LMT-1430”, average molecular weight 383 g / mol containing sodium 2.99 g / mol).
A2-4: α-olefin sulfonate (manufactured by Lion Corporation, trade name: “Lipolane LB-440”).
A3-1: Polyoxyalkylene alkyl ether (manufactured by Lion Co., Ltd., trade name: “NNAEP-3030”, a mixture of alcohol having 12 carbon atoms and alcohol having 13 carbon atoms, average 3 ethylene oxide and average 3 propylene oxide Mole added, nonionic surfactant).

(Synthesis method of A1-2)
In a 3 L four-necked flask, 907.0 g (3.97 mol) of methyl myristate (molecular weight 228.4), 121.6 g (1.19 mol) of dimethylaminopropylamine (DMAPA, molecular weight 102.2) and The reaction vessel was purged with nitrogen twice under reduced pressure and then heated to 185 ° C. After aging for 1.5 hours at the start of the reaction when reaching 180 ° C., 405.7 g (3.97 mol) of DMAPA (molecular weight 102.2) was added dropwise over 4 hours. After completion of dropping, the mixture was aged for 7 hours, and then heated to 195 ° C., and excess DMAPA was removed under reduced pressure (treated for 1 hr after reaching 2.4 kPa) to obtain 1183 g of myristic acid (C14) dimethylaminopropylamide. It was.

(Synthesis method of A1-4)
The synthesis was carried out in the same manner as the synthesis method of A1-2 except that methyl laurate was used instead of methyl myristate to obtain 1100 g of lauric acid (C12) dimethylaminopropylamide.

As the component (B), the following compounds were used.
B-1: Citric acid (manufactured by Fuso Chemical Industry Co., Ltd., trade name: “purified citric acid (anhydrous)”).
B-2: L-glutamic acid diacetate (manufactured by Akzo Nobel Co., Ltd., trade name: “GL-47-S”).

As the component (C), the following compounds were used.
C-1: Propylene glycol (trade name: “Propylene glycol for cosmetics” manufactured by ADEKA Corporation).
-C-2: Dipropylene glycol (made by Wako Pure Chemical Industries, Ltd.).
C-3: Tripropylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.).

As the component (D), the following compounds were used.
D-1: Paratoluenesulfonic acid (manufactured by Teika Co., Ltd., trade name: “Taikatox 300”).
D-2: sodium cumene sulfonate (manufactured by Teika Co., Ltd., trade name: “Teikatox N5040”).
D-3: Sodium benzenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.).

(E) Ion exchange water was used as a component.
The following compounds were used as optional components.
・ PH adjuster: Sodium hydroxide (made by Wako Pure Chemical Industries, special grade), potassium hydroxide (made by Wako Pure Chemical Industries, special grade), sulfuric acid (made by Kanto Chemical Co., Inc.), monoethanolamine ( One or more of Wako Pure Chemical Industries, Ltd.
Protease: (Novozymes Japan K.K., trade name: “Sabinase 16XL”).

"Examples 1-31, Comparative Examples 1-4"
<Preparation of cleaning agent>
According to the composition shown in Tables 1 to 4, cleaning agents were prepared as follows.
In a 1 L beaker (diameter 12 cm), the components (E) and (C) are charged, and a stirrer (manufactured by Shinto Kagaku Co., Ltd., product name: “HEIDON FBL1200 Three-One Motor”) is 7.5 cm in diameter and 1 width. (A) component, (B) component, (D) while stirring at a rotational speed of 300-900 rpm so that the contents in the beaker are not scattered, using a one equipped with a 4 cm paddle of .5 cm and an angle of 45 degrees. ) The ingredients were added in order and mixed. The mixture was adjusted with a pH adjuster so that the pH at 25 ° C. was 7, and further stirred for 5 minutes. Subsequently, an enzyme (protease) was added at 25 ° C., and the mixture was stirred for 1 minute at a rotation speed of 650 rpm of the stirrer to obtain a cleaning agent.
The pH of the mixed solution was measured using a glass electrode type pH meter (manufactured by Toa DKK Corporation, product name: “HM-30G”) adjusted to 25 ° C. The measuring method was performed according to JIS Z 8802: 1984 “pH measuring method”.
In addition, when using A1-1, A1-2, A1-3, and A1-4 as the component (A), these are separately put into a 1 L beaker (diameter 12 cm) and heated to 40 to 50 ° C and dissolved. Used.

<Evaluation of dishwasher detergent>
Each of the cleaning agents in each example was evaluated by the following evaluation method. The results are shown in Tables 1-4.
An automatic dishwasher (manufactured by Panasonic Corporation, model name: “NP-40SX2”) was used as the dishwasher. In each evaluation, the washing process was performed by operating in a standard course (power saving mode or normal mode) set in the automatic dishwasher. In the power saving mode, the water temperature in the cleaning process is set to be 15 ° C. lower than that in the normal mode. The contents of the standard course (power saving mode) are shown below.

Standard course (power saving mode):
After 3 to 4 g of cleaning agent (relative to 3 L of tap water) is added to the automatic dishwasher, the cleaning liquid prepared by introducing tap water at about 5 ° C. into the cabinet is kept at 2 to 3 ° C./min up to 40 ° C. Washing is performed for 20 minutes while the temperature is raised at, and the washing liquid is drained. Next, new tap water is introduced, and rinsing (2 minutes / times) and draining are repeated three times. After draining, tap water is introduced and rinsed once (final rinse) for 20 minutes while raising the temperature to 70 ° C at 2-3 ° C / min. After draining, the dishes are dried while circulating hot air. To do.
In addition, the usage-amount (g / 3L) of the cleaning agent in each case is shown to Tables 1-4.

  In the standard course (normal mode), in the standard course (power saving mode), cleaning is performed for 20 minutes while raising the temperature of the cleaning liquid to 55 ° C. at 2-3 ° C./min. Other operations are the same as in the standard course (power saving mode).

(Evaluation of detergency against tea astringency)
After drinking tea, 3 cups of tea stains (inner diameter 70mm, height 70mm) with tea stain left overnight at 25 ° C and relative humidity 50% RH are loaded into the automatic dishwasher. Then, 3 to 4 g of a cleaning agent was added and cleaning treatment was performed in a standard course (power saving mode).
After the cleaning treatment, the finish of the coffee cup was observed, and the cleaning power against tea astringent stains was evaluated based on the following evaluation criteria. If the average score of three coffee cups was 3.0 or more, it was considered acceptable.
4 points: Dirt was completely removed.
3 points: Slight dirt was observed, but it was not necessary to wash again.
2 points: Dirt remained and was a level that had to be washed again.
1 point: Dirt remained almost unremoved.

(Evaluation of detergency against oil stains)
As oil stains, mixed oil of beef tallow / lard / butter / salad oil = 3/3/3/1 (mass ratio) and retort curry (bon curry gold 21 dry) were used.
A polypropylene lunch box (110 mm long, 170 mm wide, 35 mm high) contaminated by adhering 3 g of the mixed oil and 6 g of the retort curry was loaded into the automatic dishwasher, and 3-4 g of cleaning agent was added. It was put in and washed in the standard course (power saving mode).
After the cleaning treatment, the finish of the polypropylene lunch box was observed, and the cleaning power against oil stains was evaluated based on the following evaluation criteria. If the evaluation score was 3 points or more, it was determined to be acceptable.
4 points: Oil stains were completely removed.
3 points: Some oil stains remained, but at a level that did not require re-washing.
2 points: Oil stains remained and the level required to be washed again.
1 point: Oil stains remained sticky.

(Evaluation of transparency)
A PS cell (12.5 × 12.5 × 45 mm) filled with about 2.5 mL of a cleaning agent and a PS cell filled with ion-exchanged water as a reference were obtained by an ultraviolet-visible absorbance meter (manufactured by HITACHI, product name: “ U-2910 "), and the transmittance was measured at a wavelength of 660 nm. Transparency was evaluated from the measured transmittance based on the following evaluation criteria. Appearance observation was performed at room temperature of 25 ° C. If the evaluation score was 3 points or more, it was determined to be acceptable.
5 points: Transparent (transmittance is 95% or more)
4 points: Transparent (transmittance is 90% or more and less than 95%)
3 points: Transparent (transmittance is 70% or more and less than 90%)
2 points: Turbidity (transmittance is 50% or more and less than 70%)
1 point: Separation or turbidity (transmittance is less than 50%)

(Evaluation of low foam properties)
The automatic dishwasher was charged with 3 to 4 g of a detergent and operated in the standard course (normal mode).
When the water temperature reached 50 ° C. from the start of washing, the operation was stopped and the door was opened at the same time, and foaming in the cabinet was measured 15 seconds later.
At that time, three locations in the warehouse were selected at random, and the height of the bubbles (mm) at each location was measured with a ruler, the average value of these was determined, and the low bubble properties were evaluated based on the following evaluation criteria. did. If the bubble height was 10 mm or less, it was considered acceptable.
4 points: Bubble height is 5 mm or less.
3 points: The foam height is more than 5 mm and 10 mm or less.
2 points: Bubble height is more than 10 mm and 15 mm or less.
1 point: Foam height is over 15 mm, or automatic dishwasher stopped abnormally.

In Tables 1 to 4, “balance” is the amount (% by mass) of water necessary to make the entire cleaning agent 100% by mass.
“(C + D) / B” is a mass ratio represented by ((C) component + (D) component) / (B) component. “C + D” is the total content of the component (C) and the component (D) in 100% by mass of the cleaning agent. “C / D” is a mass ratio represented by (C) component / (D) component. “B + C + D” is the total content of the component (B), the component (C), and the component (D) in 100% by mass of the cleaning agent.

As is clear from Tables 1 to 3, the cleaning agents of each Example were excellent in cleaning power and transparency against tea astringent stains, while being compact.
In particular, as the component (A), the general formula (a-1) number of carbon atoms of ^{R 1} in is 13 or more (A1) component and, in Example was used in combination with component (A2) 1～18,20～24 , 26 to 31 were low in foaming properties and excellent in detergency against oil stains.

On the other hand, as is clear from Table 4, the cleaning agent of Comparative Example 1 containing no component (B) was inferior in cleaning power against tea astringent stains.
(C) The cleaning agent of Comparative Example 2 containing no component was inferior in transparency.
The cleaning agents of Comparative Examples 3 and 4 in which the mass ratio represented by ((C) component + (D) component) / (B) component was 0.25 or 1.81 were inferior in transparency.

Claims (4)

(A) component: surfactant,
(B) component: a chelating agent,
(C) component: water-soluble solvent,
Component (D): at least one selected from aromatic sulfonic acids and salts thereof;
(E) Ingredient: A dishwasher detergent containing water,
(B) Content of a component is 18 mass% or more in conversion of an acid type with respect to the total mass of the washing | cleaning agent for dishwashers,
The dishwasher cleaning agent whose mass ratio represented by ((C) component + (D) component) / (B) component is 0.3-1.7.   The sum total of content of (C) component and (D) component is 7-35 mass% with respect to the total mass of the detergent for dishwashers, The cleaning agent for dishwashers of Claim 1 characterized by the above-mentioned.   The detergent for dishwashers of Claim 1 or 2 whose mass ratio represented by (C) component / (D) component is 2-10. The (A) component contains the compound (A1) represented with the following general formula (a-1), and an anionic surfactant (A2), The dishwashing as described in any one of Claims 1-3 Cleaning agent for machine.

(In Formula (a-1), R ¹ is a linear or branched alkyl group having 11 to 21 carbon atoms or a linear or branched alkenyl group having 11 to 21 carbon atoms; R ² Is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group having 1 to 4 carbon atoms, R ³ is an alkylene group having 1 to 4 carbon atoms, and R ⁴ and R ⁵ are each independently hydrogen. It is an atom or an alkyl group having 1 to 4 carbon atoms.)