JP2017119762A - Detergent composition for dishwasher - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a detergent composition for a dishwasher excellent in detergency against oil stains and also in foam inhibition.SOLUTION: A detergent composition for a dishwasher comprises a component (a): a compound represented by the general formula (a1) in the figure, and a component (b): an anionic surfactant. In the formula (a1), at least one of Rto Ris a C12-16 linear or branched alkyl group, or a C12-16 linear or branched alkenyl group, and the remainder are C1-3 linear or branched alkyl groups.SELECTED DRAWING: None

Description

  The present invention relates to a detergent composition 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. For washing with a dishwasher, a dedicated detergent (a dishwasher detergent composition, hereinafter also simply referred to as “composition”) is generally used.

In this dishwasher detergent composition, an effect of suppressing foaming (foam suppression) is required.
Insufficient foam suppression of the dishwasher detergent composition results in a phenomenon called “overflow” that bubbles overflow during operation of the dishwasher, and sufficient jetting due to bubbles entangled in the circulating water. A phenomenon called “air biting” may occur where force cannot be obtained. If "overflow" or "air biting" occurs, the dishwasher may stop abnormally or break down.

In order to solve such problems, a polyoxyalkylene alkyl ether type nonionic surfactant having an oxypropylene group is widely used as a low foaming surfactant in dishwasher detergent compositions.
In addition, a dishwasher cleaning agent that employs a combination of a silicone compound and a specific short chain (C 6-10) alkylamine surfactant as a foam inhibitor has been proposed (see Patent Document 1).

JP 2000-5009078

By the way, with eco-friendliness such as power saving and water saving, not only the standard course (normal mode) in which hot water of about 55 to 65 ° C circulates in the dishwasher but also hot water whose water temperature is about 10 ° C lower than this. Some have power-saving modes such as a "low-temperature course" and "clear course" that circulate.
When such a power saving mode is selected and cleaning is performed using a conventional dishwasher cleaning composition containing a polyoxyalkylene alkyl ether having an oxypropylene group, etc., the cleaning power against oil stains is insufficient. .

In order to improve the cleaning power of the cleaning agent when cleaning dishes and the like in such a power saving mode, it is considered effective to use an anionic surfactant that has a small temperature effect on the cleaning power. .
However, an anionic surfactant has a high foaming property, and there is a problem that bubbles are easily formed by adding an anionic surfactant in washing with a dishwasher.
Moreover, even if it uses together the foam inhibitor (combination of a silicone compound and a specific short chain (C6-C10) alkylamine surfactant) of patent document 1 with an anionic surfactant, it is foam-suppressing property. Cannot be obtained sufficiently.
This invention is made | formed in view of the said situation, and makes it a subject to provide the washing | cleaning agent composition for dishwashers which has the outstanding cleaning power with respect to oil stains, and is excellent also in foam suppression property.

  As a result of intensive studies, the present inventor has used an anionic surfactant having a high detergency against oil stains, and the problem of a decrease in foam suppression due to the use of the anionic surfactant is a long chain (12 to 16 carbon atoms). ) It has been found that the problem can be solved by using a mono long chain alkyl dishort chain alkylamine having an alkyl group, and the present invention has been completed.

式中、Ｒ^１〜Ｒ^３のうち少なくとも１つは炭素数１２〜１６の直鎖若しくは分岐鎖のアルキル基、又は炭素数１２〜１６の直鎖若しくは分岐鎖のアルケニル基であり、残りは炭素数１〜３の直鎖又は分岐鎖のアルキル基である。
［２］前記（ａ）成分と前記（ｂ）成分の質量比が、（ａ）成分／（ｂ）成分で表して、０．２〜３である［１］に記載の食器洗い機用洗浄剤組成物。
［３］前記（ａ）成分が、式（ａ１）中、Ｒ^１〜Ｒ^３のうち１つが炭素数１２〜１４の直鎖のアルキル基であり、残りがメチル基である化合物である［１］又は［２］に記載の食器洗い機用洗浄剤組成物。
［４］前記（ｂ）成分が、直鎖アルキルベンゼンスルホン酸塩、及びセカンダリーアルカンスルホン酸塩からなる群から選ばれる少なくとも一種の陰イオン界面活性剤である［１］〜［３］のいずれか一項に記載の食器洗い機用洗浄剤組成物。 The detergent composition for dishwashers of this invention has the following aspects.
[1] Dishwasher detergent composition comprising (a) component: a compound represented by the following general formula (a1) and (b) component: an anionic surfactant.

In the formula, at least one of R ^{1 to} R ³ is a linear or branched alkyl group having 12 to 16 carbon atoms, or a linear or branched alkenyl group having 12 to 16 carbon atoms, and the rest is carbon. A linear or branched alkyl group of 1 to 3;
[2] The dishwasher cleaning agent according to [1], wherein the mass ratio of the component (a) to the component (b) is 0.2 to 3 in terms of the component (a) / (b). Composition.
[3] The component (a) is a compound in which, in formula (a1), ^one of R ^{1 to} R ³ is a linear alkyl group having 12 to 14 carbon atoms, and the rest is a methyl group. ] Or the detergent composition for dishwashers as described in [2].
[4] Any one of [1] to [3], wherein the component (b) is at least one anionic surfactant selected from the group consisting of a linear alkylbenzene sulfonate and a secondary alkane sulfonate. The detergent composition for dishwashers as described in a term.

  ADVANTAGE OF THE INVENTION According to this invention, the cleaning composition for dishwashers which is excellent in the detergency with respect to oil stains, and is excellent also in foam suppression property can be provided.

  The detergent composition for dishwashers of this invention is a composition containing the following (a) component and (b) component.

<(A) Component: Compound Represented by General Formula (a1)>
The component (a) is a compound represented by the following general formula (a1).

In the formula, at least one of R ^{1 to} R ³ is a linear or branched alkyl group having 12 to 16 carbon atoms, or a linear or branched alkenyl group having 12 to 16 carbon atoms, and the rest is carbon. A linear or branched alkyl group of 1 to 3;

In the formula (a1), at least one of R ^{1 to} R ³ is a linear or branched alkyl group having 12 to 16 carbon atoms, or a linear or branched alkenyl group having 12 to 16 carbon atoms. The remainder represents a straight-chain or branched alkyl group having 1 to 3 carbon atoms.
Examples of the linear or branched alkyl group having 12 to 16 carbon atoms include dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, and hexadecyl group.
Examples of the linear or branched alkenyl group having 12 to 16 carbon atoms include dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, and hexadecenyl group.
Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

Among these, it is preferable that one of R ^{1 to} R ³ is a linear or branched alkyl group having 12 to 14 carbon atoms and the remaining is an alkyl group having 1 to 3 carbon atoms. Moreover, it is more preferable that one of R ^{1 to} R ³ is a linear or branched alkyl group having 12 to 14 carbon atoms, and the rest is a methyl group.

  Specific examples of the component (a) include N, N-dimethyllaurylamine, N, N-dimethyltridecylamine, N, N-dimethylcoconutamine, N, N-dimethylmyristylamine, N, N-dimethylpalmityl. And N, N-dimethyllarlylamine, N, N-dimethylcoconutamine, N, N-dimethylmyristylamine, and N, N-dimethylpalmitylamine are preferable. N, N-dimethyllaurylamine, N, N-dimethylcoconutamine, and N, N-dimethylmyristylamine are particularly preferable. Here, N, N-dimethyl coconut amine means a mixture of tertiary amines having an alkyl group having 12, 14 or 16 carbon atoms and two methyl groups.

(A) A component may be used individually by 1 type and may be used in combination of 2 or more type as appropriate.
(A) 0.01-10 mass% is preferable with respect to the total mass of the detergent composition for dishwashers, as for content of a component, 0.1-5 mass% is more preferable, 0.2-3 mass% Is more preferable.
When the content of the component (a) is equal to or more than the preferable lower limit value, it is easy to improve foam suppression. On the other hand, if content of (a) component is below a preferable upper limit, it will be easy to improve the detergency with respect to oil stains.

<(B) component: anionic surfactant>
The component (b) is an anionic surfactant.
Examples of the component (b) include a sulfonate type, a sulfate ester salt type, a carboxylate salt type, and a phosphate ester salt type.
Examples of the sulfonate type include alkane sulfonate, alkylbenzene sulfonate, α-olefin sulfonate, α-sulfo fatty acid salt, α-sulfo fatty acid alkyl ester salt, alkyl sulfosuccinate, and dialkyl sulfosuccinate. It is done.
Examples of the sulfate ester type include alkyl sulfate ester salts, alkenyl sulfate ester salts, polyoxyalkylene alkyl ether sulfate ester salts, polyoxyalkylene alkenyl ether sulfate ester salts, and the like.
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.
In addition, the component (b) preferably has an alkyl group having 8 to 18 carbon atoms, or has an alkenyl group having 8 to 18 carbon atoms, and particularly has an alkyl group having 8 to 18 carbon atoms. More preferred. The alkyl group or the alkenyl group may be linear or branched.
(B) Examples of the salt 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.

(B) A component may be used individually by 1 type and may be used in combination of 2 or more types as appropriate.
Among these, as the component (b), the sulfonate type and the sulfate ester type are preferable, and the sulfonate type is particularly preferable because the detergency against oil stains and the foam suppression property are easily improved.
Among them, alkane sulfonate, alkylbenzene sulfonate, and dialkyl sulfosuccinate are preferable, and alkane sulfonate and alkyl benzene sulfonate are more preferable, and alkane sulfonic acid because detergency against oil stains is particularly easily increased. Salts and linear alkylbenzene sulfonates are more preferred, and alkane sulfonates are most preferred. Of the alkane sulfonates, secondary alkane sulfonates having a structure in which a sulfo group is bonded to a secondary alkyl group are particularly preferred.

(B) 0.1-10 mass% is preferable with respect to the total mass of the detergent composition for dishwashers, as for content of a component, 0.1-5 mass% is more preferable, 0.5-3 mass% Is more preferable.
When the content of the component (b) is equal to or more than the preferred lower limit, it is easy to improve the detergency against oil stains. On the other hand, if the content of the component (b) is equal to or less than the preferable upper limit value, it is easy to improve foam suppression.

In the dishwasher detergent composition of the present invention, the mixing ratio of the component (a) and the component (b) is a mass ratio represented by the component (a) / component (b) (hereinafter referred to as “a / b ratio”). Is also preferably 0.2-3.
If the a / b ratio is at least the preferred lower limit, it is easy to improve foam suppression. On the other hand, when the a / b ratio is less than or equal to the preferable upper limit value, it is easy to improve the cleaning power against oil stains.
In the present invention, the “mass ratio represented by component (a) / component (b)” is the ratio of the mass of component (a) to the mass of component (b) in the dishwasher detergent composition. Represents.

<Optional component>
In the dishwasher detergent composition of the present invention, components other than the components (a) and (b) described above may be blended as necessary within a range not impairing the effects of the present invention.

Such components that may be optionally blended are not particularly limited, and include components that have been blended in detergents for washing dishes.
For example, surfactants other than the components (a) and (b), hydrotropes, chelating agents, antioxidants, pH adjusters, water-soluble inorganic salts such as sodium sulfate, colorants, enzymes, perfumes, water, etc. These solvents can be used.
However, in a dishwasher, it is necessary to suppress foaming during washing. For this reason, it is preferable that the total content of the component (a) and the component (b) and the surfactant other than these is 12% by mass or less based on the total mass of the dishwasher detergent composition. It is more preferable to set it as 10 mass% or less, and it is still more preferable to set it as 8 mass% or less.
In addition, the content of the component (a) and the component (b) in the total surfactant is preferably 50% by mass or more, more preferably 70% by mass or more, based on the total mass of all the surfactants. It may be 100% by mass. If content of (a) component and (b) component is more than a preferable lower limit, foaming will be kept low when performing washing processing of tableware etc. with a dishwasher. In addition, it is easy to improve the detergency against oil stains.
The total content of each component contained in the dishwasher detergent composition does not exceed 100% by mass.

The concentration of the component (a) in the dishwasher during use is preferably 4 to 60 ppm.
If it is within the above numerical range, it is easy to improve detergency and foam suppression.
It is preferable that the density | concentration of (b) component in the dishwasher at the time of use is 10-60 ppm.
If it is within the above numerical range, it is easy to improve detergency and foam suppression.
The pH during use is preferably 5 or more from the viewpoint of corrosiveness to the dishwasher, and preferably 8 or less from the viewpoint of influence on aluminum or glass tableware.

<Method for producing detergent composition for dishwasher>
The detergent composition for dishwashers of this invention can be manufactured by a conventionally well-known method.
As a manufacturing method of the detergent composition for liquid dishwashers, it prepares by mixing a solvent, (a) component, (b) component, and another arbitrary component as needed.

The solvent is preferably water, and a water-miscible organic solvent may be used in addition to water.
“Water-miscible organic solvent” refers to an organic solvent that dissolves 50 g or more in 1 L of ion-exchanged water at 25 ° C. The water-miscible organic solvent is not particularly limited as long as it becomes a uniform solution when mixed with water, and among them, a monohydric alcohol having 2 to 4 carbon atoms, a polyhydric alcohol having 2 to 4 carbon atoms, and glycol. Examples include ether.
Examples of the monohydric alcohol having 2 to 4 carbon atoms include ethanol, 1-propanol, 2-propanol, 1-butanol and the like.
Examples of the polyhydric alcohol having 2 to 4 carbon atoms include ethylene glycol, propylene glycol, butylene glycol, glycerin and the like.
Examples of the glycol ether include ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether and the like.

The pH (25 ° C.) of the liquid dishwasher detergent composition is preferably 5 or more from the viewpoint of corrosiveness to the dishwasher, preferably 8 or less, more preferably pH (25). ° C) 6-8.
In this invention, pH (25 degreeC) of the detergent composition for liquid dishwashers shows the value measured by the method based on JISZ8802: 1984 "pH measuring method".
In order to adjust the pH of the liquid dishwasher detergent composition of the present invention, a pH adjuster such as an inorganic alkali agent, an organic alkali agent, or an inorganic acid is preferably used. Examples of the inorganic alkaline agent include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like. Of these, hydroxides such as sodium hydroxide and potassium hydroxide are preferred because the storage stability of the composition is easily improved. Examples of the organic alkali agent include monoethanolamine, diethanolamine, triethanolamine, N-methylpropanol, 2-amino-2-methyl-1-propanol, N- (β-aminoethyl) ethanolamine, diethylenetriamine, morpholine, N- Examples thereof include amine compounds such as ethylmorpholine. Among them, monoethanolamine is preferable because the storage stability of the composition is easily improved. Examples of inorganic acids include hydrochloric acid and sulfuric acid.

As a method for producing a solid dishwasher detergent composition, for example, in the case of a granular dosage form, a dry blend method in which each raw material is powder-mixed, and a dry granulation in which the powder raw material is granulated while flowing Granulation method, stirring granulation method in which liquid raw material is sprayed and granulated while fluidizing powder material, extrusion granulation method in which raw material is kneaded and extruded with extruder, raw material is kneaded and pulverized Examples thereof include a pulverizing granulation method, a spray drying method in which a slurry containing a raw material is spray dried.
The moisture content of the solid dishwasher detergent composition is not particularly limited, and is preferably 8% by mass or less.
The bulk density of the dishwashing detergent composition of the particulate is, 0.3 g / cm ³ or more, more preferably 0.5 to 1.2 g / cm ^3, is 0.6~1.1g / cm ³ Further preferred.
The bulk density is a value measured according to JIS-K3362.
200-1500 micrometers is preferable and, as for the average particle diameter of the detergent composition for powdery dishwashers, 300-1200 micrometers is more preferable. When the average particle size is less than the preferred lower limit, dust is likely to be generated, while when it exceeds the preferred upper limit, it becomes difficult to dissolve or disperse in water.

In the present invention, the average particle size of the powdery dishwasher detergent composition is 9-stage sieve with openings of 1680 μm, 1410 μm, 1190 μm, 1000 μm, 710 μm, 500 μm, 350 μm, 250 μm and 149 μm, and a saucer. It is measured by the classification operation used.
In the classification operation, a sieve having a small mesh size is stacked on a tray in order, and a sample of 100 g / time is placed on the top of the top 1680 μm sieve, and the lid is capped and a low-tap type sieve shaker ( (Made by Iida Seisakusho, tapping: 156 times / minute, rolling: 290 times / minute) and vibrating for 10 minutes. Thereafter, the sample remaining on each sieve and the tray is collected for each sieve, and the mass of the sample is measured. Then, the mass frequency of the tray and each sieve is integrated, the opening of the first sieve where the integrated mass frequency is 50% or more is “a μm”, and the opening of the sieve that is one step larger than a μm is “b μm”. To do. In addition, the integrated value of the mass frequency from the tray to the a μm sieve is “c%”, and the mass frequency on the a μm sieve is “d%”. And an average particle diameter (50 mass% particle diameter) is calculated | required by the following Formula (1), and let this be an average particle diameter of a sample.

<How to use the detergent composition for dishwashers>
The detergent composition for a dishwasher of the present invention may be used by changing the amount of use etc. according to the model of the dishwasher and the degree of dirt on the dishwasher.
Examples of a method for washing an object to be washed with a dishwasher using the composition include a method having both washing and rinsing steps.
As a preferred washing method, for example, a washing liquid prepared by introducing tap water at room temperature (preferably about 5 to 30 ° C.) into the dishwasher, preferably 35 to 60 ° C. at 2 to 3 ° C./min. A process of cleaning the object to be cleaned while raising the temperature (hereinafter referred to as “cleaning process”), and a process of rinsing the object to be cleaned after cleaning with tap water at room temperature (hereinafter referred to as “rinsing (1) process”). While rinsing room temperature tap water preferably at 50 to 80 ° C. at 2 to 3 ° C./min, further rinsing the object to be cleaned after the rinsing (1) step (hereinafter referred to as “rinsing (2) step”. And the like).
In the washing step, it is preferred that the amount of the dishwasher detergent composition used once is 3 to 9 g for about 3 liters of tap water.
The washing time in the washing step is preferably 3 to 50 minutes, more preferably 5 to 30 minutes. The rinsing time in the rinsing (1) step is preferably 0.5 to 10 minutes, more preferably 1 to 7 minutes. The rinsing time in the rinsing (2) step is preferably 3 to 50 minutes, more preferably 5 to 30 minutes.

  The dishwasher cleaning composition of the present invention described above uses the component (b) when washing with a dishwasher, so that the washing is performed at a temperature lower than that of the standard course (normal mode). Even when a power saving mode such as “Clear Course” is selected, it has excellent cleaning power against oil stains. In addition, by using the component (b) in combination with the component (b), foaming of the component (b) can be suppressed and excellent foam suppression can be obtained.

  The detergent composition for a dishwasher according to the present invention is suitable for dishwashers. In particular, when washing is performed under conditions lower than the standard course (normal mode), for example, the water temperature is higher than that in the normal mode. Is a composition suitable for washing dishes and the like in a power-saving mode such as a “low temperature course” or a “clear course” which is about 10 ° C. lower.

  Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples.

<< Examples 1-18, Comparative Examples 1-7 >>
<Preparation of detergent composition for dishwasher>
According to the compounding composition shown in Tables 1-3, the composition of each example was prepared by the below-mentioned manufacturing method (when there is an unblended component, the component is not blended).
In Examples 1 to 13, 15 to 18, and Comparative Examples 1, 2, and 4 to 7, the components are mixed according to the compositions shown in Tables 1 to 3, and a pH adjuster is added to adjust the pH to 7.0. Each liquid composition was obtained.
In Example 14 and Comparative Example 3, each component was mixed according to the composition shown in Tables 2 and 3, and each granular composition was obtained.
The unit of the blending amount in the table is “mass%”, and all the components indicate the amount in terms of pure content.
A blank in the table indicates that the component is not blended.
In the table, “appropriate amount” indicates the amount of pH adjuster added.
“Balance” means that water or anhydrous sodium sulfate is blended so that the total blending amount (mass%) of all blending components contained in the composition of each example is 100 mass%.
"A / b ratio" is synonymous with the mass ratio represented by (a) component / (b) component, and the ratio of the mass of component (a) to the mass of component (b) in the composition Means.
Below, the component shown in the table | surface is demonstrated.

[(A) component]
A-1: N, N-dimethyllaurylamine (manufactured by Lion Specialty Chemicals, product name “Lipomin DM12D”, in formula (a1), R ¹ is a linear alkyl group having 12 carbon atoms, and R ² is a methyl group , Compounds in which R ³ is a methyl group).
A-2: N, N-dimethylmyristylamine (manufactured by Lion Specialty Chemicals, product name “Lipomin DM14D”, in formula (a1), R ¹ is a linear alkyl group having 14 carbon atoms, and R ² is a methyl group , Compounds in which R ³ is a methyl group).
A-3: N, N-dimethylpartimylamine (manufactured by Lion Specialty Chemicals, product name “Lipomin DM16D”, in formula (a1), R ¹ is a linear alkyl group having 16 carbon atoms, R ² is methyl Group wherein R ³ is a methyl group).

[Comparative component of component (a) (hereinafter referred to as “component (a ′)”)]
A′-1: Silicone compound (manufactured by Dow Corning Toray, product name “2-4248S”).
A′-2: polyoxyethylene (2) beef tallow alkylamine (manufactured by Lion Specialty Chemicals, product name “Liponol T12”, tallow amine (monoalkylamine having 16 and 18 carbon atoms, and monoalkenylamine having 18 carbon atoms) A tertiary amine having an average of 2 moles of ethylene oxide added to a mixture of
A′-3: N, N-dimethyloctylamine (manufactured by Lion Specialty Chemicals, product name “Lipomin DM8D”, in formula (a1), R ¹ is a linear alkyl group having 8 carbon atoms, R ² is methyl Group wherein R ³ is a methyl group).
A′-4: N, N-dimethylstearylamine (manufactured by Lion Specialty Chemicals, product name “Lipomin DM18D”, in formula (a1), R ¹ is a linear alkyl group having 18 carbon atoms, R ² is methyl Group wherein R ³ is a methyl group).

[Component (b)]
B-1: Secondary alkane sulfonate having 14 to 17 carbon atoms (manufactured by Clariant Japan, product name “HOSTAPUR SAS 30A”).
B-2: Sodium linear alkylbenzene sulfonate having a linear alkyl group having 10 to 15 carbon atoms (manufactured by Teika Co., Ltd., product name “Taika Power L121”).
B-3: linear alkylbenzene sulfonate having a linear alkyl group having 10 to 14 carbon atoms: linear alkyl (10 to 14 carbon atoms) benzenesulfonic acid (manufactured by Lion Corporation, product name “Lypon LH-200”) (LAS-H, pure content 96%)) at the time of preparation with a compound neutralized with a 48% aqueous sodium hydroxide solution (LAS-Na) and a compound neutralized with a 48% aqueous potassium hydroxide solution instead of sodium hydroxide ( LAS-K) mixed at a mass ratio of 2: 1. The composition ratio in a table | surface shows the value (mass%) as these mixtures.
B-4: Sodium polyoxyethylene alkyl ether sulfate having an alkyl group having 12 to 13 carbon atoms (average added mole number of ethylene oxide (EO) 2); Raw alcohol (product name “Neodol 23”, carbon A mixture of alcohol of number 12 / alcohol of carbon number 13 = 40/60 (mass ratio), linear chain ratio of 80 mass%) and an average of 2 mol of ethylene oxide are reacted with anhydrous sulfuric acid, and then sodium hydroxide Neutralized compound.

[Comparison component of component (b) (hereinafter referred to as “component (b ′)”)]
B′-1: polyoxyalkylene alkyl ether (a mixture of an alcohol having 12 carbon atoms and an alcohol having 13 carbon atoms added with an average of 3 mol of ethylene oxide and an average of 3 mol of propylene oxide) (manufactured by Lion Corporation, Product name "NNAEP-3030").

[Optional ingredients]
PH adjuster (1): sodium hydroxide, manufactured by Tsurumi Soda Co., Ltd.
PH adjuster (2): sulfuric acid, manufactured by Kanto Chemical Co., Inc.
・ Anhydrous mirabilite: Product name Anhydrous mirabilite K (2), manufactured by Nippon Chemical Co.
-Water: Ion exchange water.

<Evaluation of dishwasher detergent composition>
About the composition of each example, each evaluation was performed with the evaluation method shown below, and the result was written together in Tables 1-3.
A dishwasher (manufactured by Panasonic Corporation, model 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 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 putting 6 g of the composition (relative to 3 L of tap water) into the dishwasher, the temperature of the cleaning solution prepared by introducing tap water of about 5 ° C. into the cabinet is raised to 40 ° C. at 2-3 ° C./min. Wash for 20 minutes while draining the cleaning solution. 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.

  The standard course (normal mode) is the same as the standard course (power saving mode). The standard course (power saving mode) is the same as the standard course (power saving mode). It is the same.

[Evaluation method of foam suppression]
6 g of the composition was put into the dishwasher and operated in the standard course (normal mode).
The water used was pre-adjusted tap water at 5 ° C., and the state of foaming at the time of 1, 5, 10, 20 minutes elapsed from the start of washing was visually observed based on the following foam evaluation criteria. Evaluation was made and scored.
<Evaluation criteria for foam>
4 points: Foam occupies 0-25% of the bottom of the dishwasher.
3 points: Foam occupies 26-50% of the bottom of the dishwasher.
2 points: Foam occupies 51 to 75% of the bottom of the dishwasher.
1 point: Foam occupies 76 to 100% of the bottom of the dishwasher.
0 point: Air biting occurs and the dishwasher stops abnormally.
Furthermore, based on the sum total of the evaluation score of foam, it evaluated on the basis of the following foam suppression property. Here, the air biting refers to a state in which bubbles enter the propeller portion of the dishwasher and the rotation of the propeller is slow.
Evaluations of ◎ to ○ were regarded as acceptable. The results are shown in Tables 1-3.
<Evaluation criteria for foam suppression>
(Double-circle): The sum total of the evaluation score of a bubble is 14-16 points.
A: The sum total of the evaluation score of bubbles is 11 to 13 points.
(Triangle | delta): The sum total of the evaluation score of a bubble is 8-10 points.
X: The score which became 0 points at any time or the score of bubbles became 7 points or less.

[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 with 3 g of the mixed oil and 6 g of the retort curry was loaded into the dishwasher and charged with 6 g of the composition. Washing treatment was performed in the 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. Evaluations of ◎ to ○ were regarded as acceptable. The results are shown in Tables 1-3.
(Evaluation criteria)
(Double-circle): Oil does not remain at all and does not feel uncomfortable feelings, such as with a null.
○: Residual oil is not visually recognized, but feels a little uncomfortable when touched.
Δ: Some oil residue is visually observed.
X: It can be visually confirmed that oil remains.

Examples 1 to 18 to which the present invention was applied were all excellent in foam suppression and detergency against oil stains.
(A) The comparative example 1 which does not contain a component was inferior in foam suppression property.
The comparative example 2 which does not contain (b) component was inferior in the detergency with respect to oil stains.
In Comparative Examples 3 to 6 in which the component (a) was replaced with the component (a ′), all of the foam suppression properties were inferior.
Comparative Example 7 in which the component (b) was replaced with the component (b ′) was inferior in cleaning power against oil stains.
From the above results, it was confirmed that the dishwasher detergent composition to which the present invention was applied was excellent in cleaning power against oil stains and foam suppression.

Claims (2)

A detergent composition for a dishwasher comprising (a) component: a compound represented by the following general formula (a1) and (b) ingredient: an anionic surfactant.

In the formula, at least one of R ^{1 to} R ³ is a linear or branched alkyl group having 12 to 16 carbon atoms, or a linear or branched alkenyl group having 12 to 16 carbon atoms, and the rest is carbon. A linear or branched alkyl group of 1 to 3;   The detergent composition for a dishwasher according to claim 1, wherein the mass ratio of the component (a) to the component (b) is 0.2 to 3 as expressed by the component (a) / component (b).