JP2012082253A - Detergent for automatic dishwasher - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a detergent for automatic dishwasher, which causes no rubber material and is hardly separated even at the time of storage at normal and low temperatures.SOLUTION: The detergent for automatic dishwasher contains, as essential components: 0.1-20 wt.% of a low-foaming nonionic surfactant (A); 5-40 wt.% of a detergent builder (B); 0.1-15 wt.% of a 6-10C linear aliphatic carboxylic acid (C); and 0.1-15 wt.% of a 6-10C branched aliphatic carboxylic acid (D).

Description

The present invention relates to a cleaning agent for an automatic dishwasher.

Conventionally, as an automatic dishwasher cleaning agent, an automatic consisting of a surfactant such as a nonionic surfactant and a cleaning builder containing sodium hydroxide, potassium hydroxide, carbonate, phosphate, polyphosphoric acid, etc. Detergents for dishwashers are known.

For example, Patent Document 1 discloses an emulsification type automatic dishwashing detergent comprising a nonionic surfactant, a cleaning builder, and an emulsifier made of carboxyvinyl polymer.

Patent Document 2 discloses a soluble detergent for an automatic dishwasher comprising a nonionic surfactant, a cleaning builder, and a linear aliphatic carboxylic acid having 6 to 10 carbon atoms. ing.

Japanese Patent Laid-Open No. 06-80998 Japanese Patent Laid-Open No. 06-33100

The emulsification type automatic dishwasher cleaning agent described in Patent Document 1 has sufficient cleaning power against oil stains and the like peculiar to tableware, and can suppress water spots. Yes.

However, depending on the conditions of use of the detergent for automatic dishwashers, the emulsifier reacts with calcium contained in the water used for washing to form a rubbery substance, and this rubbery substance is inside the automatic dishwasher. In some cases, the detergency decreases due to deposition. Therefore, there has been a problem that the rubber-like substance must be removed periodically.

On the other hand, the soluble detergent for automatic dishwashers described in Patent Document 2 has sufficient cleaning power and foam suppression properties against oil stains and the like, and is considered to have no off-flavor. Yes.
Moreover, since the emulsifier is not used, it is thought that generation | occurrence | production of rubbery substance can be suppressed.

However, when stored at room temperature for a long time (hereinafter also simply referred to as room temperature storage) or when stored at a low temperature (hereinafter also referred to simply as low temperature storage), the detergent for automatic dishwashers is caused by salting out. It was easy to separate, and there was a problem that the cleaning power decreased when used in a separated state.
In particular, during low-temperature storage, there has been a problem that the detergent for automatic dishwashers is likely to freeze and solidify.

In view of the problems of such a conventional detergent for automatic dishwashers, the present inventor has developed a detergent for automatic dishwashers that does not generate a rubbery substance and is difficult to separate even at room temperature storage or low temperature storage. We conducted intensive studies for the purpose of development.
As a result, by using a straight chain aliphatic carboxylic acid having a predetermined carbon number and a branched aliphatic carboxylic acid having a predetermined carbon number based on a soluble type automatic dishwasher detergent that does not use an emulsifier, It has been found that no rubber-like substance is generated and that it is difficult to separate even at room temperature storage or low temperature storage. As a result of further studies based on such knowledge, the inventors have arrived at the present invention capable of solving the above-described problems.

That is, the cleaning agent for an automatic dishwasher of the present invention includes a low-foaming nonionic surfactant (A), a cleaning builder (B), and a linear aliphatic carboxylic acid (C) having 6 to 10 carbon atoms. , A detergent for automatic dishwashers containing, as an essential component, a branched aliphatic carboxylic acid having 6 to 10 carbon atoms (D),
The content of (A) is 0.1 to 20% by weight,
The content of (B) is 5 to 40% by weight,
The content of (C) is 0.1 to 15% by weight,
The content of (D) is 0.1 to 15% by weight.

The detergent for an automatic dishwasher of the present invention includes a low-foaming nonionic surfactant (A) that exhibits good detergency with less foaming, and a cleaning builder (B) that assists in the detergency of (A) above. Is contained in a predetermined amount, it is possible to exhibit sufficient detergency and foam suppression.

In addition, since a predetermined amount of a straight-chain aliphatic carboxylic acid (C) having 6 to 10 carbon atoms and a branched aliphatic carboxylic acid (D) having 6 to 10 carbon atoms is included, it can be stored at room temperature or at low temperature. Even so, it is difficult to separate.

In the cleaning agent for automatic dishwashers of the present invention, the content of (A) is 0.1 to 10% by weight, the content of (B) is 10 to 30% by weight, and the above (C) The content of is preferably 0.5 to 10% by weight, and the content of (D) is preferably 0.5 to 15% by weight.

In the detergent for automatic dishwashers of this invention, it is desirable that (D) is a branched aliphatic carboxylic acid having 8 carbon atoms.

In the cleaning agent for automatic dishwashers of the present invention, it is desirable that (C) is octanoic acid and (D) is 2-ethylhexanoic acid.

The cleaning agent for an automatic dishwashing machine of the present invention preferably further contains one saccharide (E) selected from the group consisting of monosaccharides, oligosaccharides, alkyl glucosides and alkyl polyglucosides, and the above alkyl glucosides Alternatively, the alkyl group of the alkyl polyglucoside preferably has 1 to 12 carbon atoms, and (E) is particularly preferably butyl glucoside.
The content of (E) is desirably 0.05 to 10% by weight.

In the cleaning agent for automatic dishwashing machine of the present invention, the above (A) is a polyoxyalkylene monoalkyl ether, polyoxyalkylene dialkyl ether, pluronic block polymer, reverse pluronic block polymer, tetronic block polymer, It is desirable to be one or more low-foaming nonionic surfactants selected from the group consisting of tronic block polymers and polyoxyalkylene alkylphenyl ethers.

The cleaning agent for an automatic dishwasher of the present invention can exhibit sufficient cleaning power and foam suppression, and is difficult to separate even during normal temperature storage or low temperature storage.

Hereinafter, the cleaning agent for automatic dishwashers of the present invention will be described in detail.
The detergent for an automatic dishwasher of the present invention is a low-foaming nonionic surfactant (A),
A cleaning builder (B);
Straight chain aliphatic carboxylic acid (C) having 6 to 10 carbon atoms;
A cleaning agent for an automatic dishwasher containing a branched aliphatic carboxylic acid having 6 to 10 carbon atoms (D) as an essential component,
The content of (A) is 0.1 to 20% by weight,
The content of (B) is 5 to 40% by weight,
The content of (C) is 0.1 to 15% by weight,
The content of (D) is 0.1 to 15% by weight.

Examples of the low-foaming nonionic surfactant (A) include polyoxyalkylene monoalkyl ethers, polyoxyalkylene dialkyl ethers, pluronic block polymers, reverse pluronic block polymers, tetronic block polymers, and reverse tetronic types. Mention may be made of one or more low-foaming nonionic surfactants selected from the group consisting of block polymers and polyoxyalkylene alkylphenyl ethers.
These polymers are desirable as the low-foaming nonionic surfactant (A) because they have less foaming and can exhibit better detergency.
Moreover, you may mix a low-foaming nonionic surfactant (A) and nonionic surfactant with comparatively good foaming, such as polyoxyalkylene fatty acid alkanolamide, for example. In this case, the blending amount of the polyoxyalkylene fatty acid alkanolamide in the mixture of the above (A) and the polyoxyalkylene fatty acid alkanolamide is desirably 50% by weight or less.

式中、ｘ、ｙはそれぞれ１以上の整数であり、Ｒはアルキル基である。特に好ましくは、ｘが約１０、ｙが約４であり、ＲがＣ１３〜Ｃ１５のアルキル基であるか、ｘが約５、ｙが約３．５であり、ＲがＣ１２〜Ｃ１４のアルキル基であるか、ｘが約２、ｙが約４であり、ＲがＣ１３〜Ｃ１５のアルキル基である。 Examples of the polyoxyalkylene monoalkyl ether include those having a structural formula represented by the following chemical formula (1).

In the formula, x and y are each an integer of 1 or more, and R is an alkyl group. Particularly preferably, x is about 10, y is about 4, and R is a C13 to C15 alkyl group, or x is about 5, y is about 3.5, and R is a C12 to C14 alkyl group. Or x is about 2, y is about 4, and R is a C13-C15 alkyl group.

式中、ｘは１以上の整数であり、Ｒはアルキル基である。
特に好ましくは、ｘが約３であり、ＲがＣ１２のアルキル基であるか、ｘが約５であり、ＲがＣ１２のアルキル基である。 Moreover, as another polyoxyalkylene monoalkyl ether, what has structural formula represented by following Chemical formula (2) is mentioned, for example.

In the formula, x is an integer of 1 or more, and R is an alkyl group.
Particularly preferably, x is about 3 and R is a C12 alkyl group, or x is about 5 and R is a C12 alkyl group.

式中、ｘは１以上の整数であり、特に好ましくは約５であり、Ｒはアルキル基であり、特に好ましくは、Ｃ８のアルキル基である。 Examples of the polyoxyalkylene dialkyl ether include those having a structural formula represented by the following chemical formula (3).

In the formula, x is an integer of 1 or more, particularly preferably about 5, and R is an alkyl group, particularly preferably a C8 alkyl group.

式中、ｘ、ｙ、ｘ’はそれぞれ１以上の整数を示している。
特に好ましくは、平均分子量が約３８００であり、エチレンオキサイド（ＥＯ）含有量が総分子量の約１０％であるか、平均分子量が約３５００であり、エチレンオキサイド（ＥＯ）含有量が総分子量の約４０％である。 Examples of the pluronic block polymer include those having a structural formula represented by the following chemical formula (4).

In the formula, x, y, and x ′ each represent an integer of 1 or more.
Particularly preferably, the average molecular weight is about 3800 and the ethylene oxide (EO) content is about 10% of the total molecular weight or the average molecular weight is about 3500 and the ethylene oxide (EO) content is about about the total molecular weight. 40%.

式中、ｘ、ｙ、ｘ’はそれぞれ１以上の整数を示している。
特に好ましくは、平均分子量が約３１００であり、エチレンオキサイド（ＥＯ）含有量が総分子量の約２０％である。 Examples of the reverse pluronic block polymer include those having a structural formula represented by the following chemical formula (5).

In the formula, x, y, and x ′ each represent an integer of 1 or more.
Particularly preferably, the average molecular weight is about 3100 and the ethylene oxide (EO) content is about 20% of the total molecular weight.

式中、ｘ、ｘ’ｘ’’、ｘ’’’、ｙ、ｙ’、ｙ’’、ｙ’’’は、それぞれ１以上の整数を示している。特に好ましくは、平均分子量が約３６００であり、エチレンオキサイド（ＥＯ）含有量が総分子量の約１０％である。 Moreover, as a tetronic type | mold block polymer, what has the structural formula represented by following Chemical formula (6) is mentioned, for example.

In the formula, x, x′x ″, x ′ ″, y, y ′, y ″, and y ′ ″ each represent an integer of 1 or more. Particularly preferably, the average molecular weight is about 3600 and the ethylene oxide (EO) content is about 10% of the total molecular weight.

式中、ｘ、ｘ’ｘ’’、ｘ’’’、ｙ、ｙ’、ｙ’’、ｙ’’’は、それぞれ１以上の整数を示している。特に好ましくは、平均分子量が約７７００であり、エチレンオキサイド（ＥＯ）含有量が総分子量の約２０％である。 Moreover, as a reverse tetronic block polymer, what has structural formula represented by following Chemical formula (7) is mentioned, for example.

In the formula, x, x′x ″, x ′ ″, y, y ′, y ″, and y ′ ″ each represent an integer of 1 or more. Particularly preferably, the average molecular weight is about 7700 and the ethylene oxide (EO) content is about 20% of the total molecular weight.

式中、ｘは１以上の整数であり、Ｒはアルキル基である。
特に好ましくは、ｘが約５であり、ＲがＣ９のアルキル基であるか、ｘが約７であり、ＲがＣ９のアルキル基であるか、ｘが約１０であり、ＲがＣ９のアルキル基である。 Examples of the polyoxyalkylene alkyl phenyl ether include those having a structural formula represented by the following chemical formula (8).

In the formula, x is an integer of 1 or more, and R is an alkyl group.
Particularly preferably, x is about 5 and R is a C9 alkyl group or x is about 7 and R is a C9 alkyl group or x is about 10 and R is a C9 alkyl group It is a group.

式中、ｘ、ｙはそれぞれ１以上の整数であり、Ｒはアルキル基である。
特に好ましくは、ｘが約７であり、ｙが約７であり、ＲがＣ９のアルキル基である。 Moreover, as another polyoxyalkylene alkyl phenyl ether, what has structural formula represented by following Chemical formula (9) is mentioned, for example.

In the formula, x and y are each an integer of 1 or more, and R is an alkyl group.
Particularly preferably, x is about 7, y is about 7, and R is a C9 alkyl group.

式中、ｘは１以上の整数であり、Ｒはアルキル基である。
特に好ましくは、ｘが約２であり、Ｒがヤシ油脂肪酸残基であるか、ｘが約５であり、Ｒがヤシ油脂肪酸残基である。 Examples of the polyoxyalkylene fatty acid alkanolamide include those having a structural formula represented by the following chemical formula (10).

In the formula, x is an integer of 1 or more, and R is an alkyl group.
Particularly preferably, x is about 2 and R is a coconut oil fatty acid residue, or x is about 5 and R is a coconut oil fatty acid residue.

The content of the low-foaming nonionic surfactant (A) is 0.1 to 20% by weight. Therefore, the cleaning agent for automatic dishwashers of the present invention has less foaming and can exhibit good cleaning power.
On the other hand, when the content of (A) is less than 0.1% by weight, the content of (A) is too small and sufficient detergency cannot be obtained. On the other hand, when the content of (A) exceeds 20% by weight, the amount of (A) is too large and the cleaning agent for an automatic dishwasher is separated.

The content of (A) is desirably 0.1 to 10% by weight. This is because such a cleaning agent for automatic dishwashers is superior in cleaning power.
The content of (A) is more preferably 0.5 to 5% by weight.

Examples of the cleaning builder (B) include alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium tripolyphosphate, potassium tripolyphosphate, sodium pyrophosphate, potassium pyrophosphate, and other phosphates. In addition, citrate, malate, silicate, EDTA (ethylenediaminetetraacetic acid) salt, nitrilotriacetic acid salt, polyacrylic acid salt and the like may be used.

The content of the cleaning builder (B) is 5 to 40% by weight. Therefore, in the cleaning agent for automatic dishwashers of the present invention, the cleaning builder (B) reinforces the cleaning power of the low-foaming nonionic surfactant (A) and can exhibit good cleaning power.

When the content of (B) is less than 5% by weight, the amount of the cleaning builder (B) is too small and the detergency becomes low. When the content of (B) exceeds 40% by weight, the cleaning builder There is too much quantity of (B), and the washing | cleaning agent for automatic dishwashers isolate | separates.

The content of (B) is desirably 10 to 30% by weight.
This is because such a cleaning agent for automatic dishwashers is superior in detergency and can reliably suppress separation of the cleaning agent for automatic dishwashers not only at room temperature storage but also at low temperature storage.

As the straight chain aliphatic carboxylic acid (C) having 6 to 10 carbon atoms, hexanoic acid (caproic acid), heptanoic acid (heptylic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (caprin) Acid).
On the other hand, if a straight chain aliphatic carboxylic acid having more than 10 carbon atoms is used, the cleaning agent for the automatic dishwasher is too foamed to wash the dishes using the automatic dishwasher, When a linear aliphatic carboxylic acid having a number of less than 6 is used, the solution stability during storage at room temperature and during storage at low temperature becomes low, and separation occurs.
In addition, the straight-chain aliphatic carboxylic acid (C) having 6 to 10 carbon atoms may form a salt with sodium, potassium or the like. May be summed up. The aqueous alkali solution for neutralization is not included in the cleaning builder (B).

Content of a C6-C10 linear aliphatic carboxylic acid (C) is 0.1 to 15 weight%.
Therefore, the cleaning agent for an automatic dishwasher according to the present invention is difficult to separate even during normal temperature storage or low temperature storage.

When the content of (C) is less than 0.1% by weight, the amount of (C) is too small, and the cleaning agent for an automatic dishwasher is separated.
If the content of (C) exceeds 15% by weight, the amount of (C) is too large and the content of other essential components is relatively small, so that sufficient detergency can be exerted. Can not.
In addition, when the above (C) is not included at all, the cleaning agent for the automatic dishwasher is separated.

The content of (C) is desirably 0.5 to 10% by weight. This is because such a cleaning agent for automatic dishwashers can exhibit a high detergency and can reliably suppress separation not only at room temperature storage but also at low temperature storage.
The content of (C) is more preferably 1 to 5% by weight.

The linear aliphatic carboxylic acid (C) is preferably octanoic acid.
This is because the stability of the solution can be further increased, so that the detergent for an automatic dishwasher becomes more difficult to separate.

Examples of the branched aliphatic carboxylic acid (D) having 6 to 10 carbon atoms include 2-ethylhexanoic acid, 4-isocaproic acid, and 4-ethyloctanoic acid.
Among the branched aliphatic carboxylic acids (D), a branched aliphatic carboxylic acid having 8 carbon atoms is desirable. When the above (D) is a branched aliphatic carboxylic acid having 8 carbon atoms, it becomes possible to further improve the solution stability during normal temperature storage and low temperature storage, and the washing agent for automatic dishwashers is further separated. It is difficult. Especially, it is more desirable that the (D) is 2-ethylhexanoic acid. In particular, when (C) is octanoic acid and (D) is 2-ethylhexanoic acid, the stability of the solution during normal temperature storage and low temperature storage can be further increased. Machine cleaners are extremely difficult to separate.
On the other hand, when a branched aliphatic carboxylic acid having a carbon number of more than 10 is used, the cleaning agent for the automatic dishwasher is too foamed to wash the dishes using the automatic dishwasher, and the carbon number When a branched aliphatic carboxylic acid having an A of less than 6 is used, the solution stability during normal temperature storage and low temperature storage is lowered, and the detergent for automatic dishwashers is separated.
In addition, the branched aliphatic carboxylic acid (D) having 6 to 10 carbon atoms may form a salt with sodium, potassium or the like, and when it does not form a salt, it is neutralized by adding an alkaline aqueous solution. May be. The alkaline aqueous solution for neutralization is not included in the cleaning builder (B).

Content of C6-C10 branched aliphatic carboxylic acid (D) is 0.1 to 15 weight%.
Therefore, the cleaning agent for an automatic dishwasher according to the present invention is difficult to separate even during normal temperature storage and low temperature storage.

When the content of (D) is less than 0.1% by weight, the amount of (D) is too small, and the detergent for an automatic dishwasher is easily separated during normal temperature storage and low temperature storage.
When the content of (D) exceeds 15% by weight, the amount of (D) is too large and the content of other essential components is relatively small, so that sufficient detergency cannot be exhibited. .

The content of the branched aliphatic carboxylic acid (D) having 6 to 10 carbon atoms is preferably 0.5 to 15% by weight. This is because such a detergent for automatic dishwashers can exhibit a high detergency and can reliably suppress separation during normal temperature storage and low temperature storage.
The content of the branched aliphatic carboxylic acid (D) having 6 to 10 carbon atoms is more preferably 2 to 8% by weight.

Moreover, it is desirable that the cleaning agent for an automatic dishwasher of the present invention further contains one saccharide (E) selected from the group consisting of monosaccharides, oligosaccharides, alkyl glucosides and alkyl polyglucosides.
When the said saccharide | sugar (E) is mix | blended, a low-foaming nonionic surfactant (A) can be mix | blended abundantly, without isolate | separating the washing | cleaning agent for automatic dishwashers. Therefore, higher cleaning power can be exhibited.

Examples of the monosaccharide include dihydroxyacetone, glyceraldehyde, erythrulose, erythrose, threose, ribulose, xylulose, ribose, arabinose, xylose, lyxose, deoxyribose, psicose, fructose, sorbose, tagatose, allose, altrose, glucose Mannose, growth, idose, galactose, talose, fucose, fucose, rhamnose and the like.

Examples of the oligosaccharide include disaccharides such as sucrose, lactose, maltose and trehalose, and trisaccharides such as raffinose and maltotriose.

Ｒ_１は、炭素数１〜１２のアルキル基であり、ｎは、１又は２である。 The alkyl glucoside and the alkyl polyglucoside (hereinafter also simply referred to as alkyl (poly) glucoside) can be represented by the following general formula (11).

R ₁ is an alkyl group having 1 to 12 carbon atoms, and n is 1 or 2.

In the alkyl (poly) glucoside, examples of the alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, Isobutyl group, n-pentyl group, s-pentyl group, t-pentyl group, isopentyl group, n-hexyl group, s-hexyl group, t-hexyl group, isohexyl group, n-heptyl group, s-heptyl group, t -Heptyl group, isoheptyl group, n-octyl group, s-octyl group, t-octyl group, isooctyl group, n-nonyl group, s-nonyl group, t-nonyl group, isononyl group, n-decyl group, s- Decyl group, t-decyl group, isodecyl group, n-undecyl group, s-undecyl group, t-undecyl group, isoundecyl group, n-dodecyl group, s-dodecyl group, t Dodecyl group, an alkyl group such as an isododecyl group.

Of these, the alkyl group is particularly preferably a butyl group. That is, the saccharide (E) is preferably butyl (poly) glucoside.
When the above (E) is butyl (poly) glucoside, the low-foaming nonionic surfactant (A) can be blended in a larger amount without separating the detergent for automatic dishwashers. Therefore, a higher cleaning power can be exhibited.
On the other hand, when the alkyl group has more than 12 carbon atoms in the alkyl (poly) glucoside, foaming may be a problem when washed using an automatic dishwasher.

The content of the saccharide (E) is desirably 0.05 to 10% by weight.
When the content of the saccharide (E) is 0.05 to 10% by weight, the low-foaming nonionic surfactant (A) is blended in a larger amount without separating the detergent for automatic dishwashers. Therefore, even higher detergency can be exhibited.
On the other hand, when the content of the saccharide (E) is less than 0.05% by weight, the content of the saccharide (E) is too small, and particularly the low-foaming nonionic surfactant (A). When the blending amount is increased, separation may become easier. In addition, when the content of the saccharide (E) exceeds 10% by weight, the content of the saccharide (E) is too much, and the contents of the (A) and (B) are relatively reduced, and washing is performed. The power may be reduced.
The content of the saccharide (E) is more preferably 0.5 to 10% by weight.

The cleaning agent for automatic dishwashing machine of the present invention includes, as components other than essential components, water, alcohol such as ethanol, antifoaming agent such as silicon, deodorant, antistatic agent and the like as auxiliary components. It can be blended appropriately within a range that does not hinder the cleaning power and solution stability of the cleaning agent for a cleaning machine.

Next, the manufacturing method of the cleaning agent for automatic dishwashers of this invention is demonstrated.

First, the low-foaming nonionic surfactant (A), the straight chain aliphatic carboxylic acid (C) having 6 to 10 carbon atoms, and the branching having 6 to 10 carbon atoms are added to the aqueous solution of the cleaning builder (B). Aliphatic carboxylic acid (D) and, if necessary, saccharide (E) are added and stirred using a mixer.
Thereby, the cleaning agent for automatic dishwashers of this invention can be manufactured.

Examples for more specifically explaining the present invention are shown below, but the present invention is not limited to these examples.

Example 1
1.0% by weight of polyoxyalkylene monoalkyl ether (purity: 100%) as a low-foaming nonionic surfactant and 10.0% by weight of aqueous KOH solution (purity: 49%) as a cleaning builder, cleaning builder NaOH aqueous solution (purity: 49%) as 10.0 wt%, and cleaning builder (chelating agent) trinitrile triacetate (purity: 100%) as 10.0 wt%, cleaning builder (scale inhibitor) Sodium polyacrylate (MW = 4000 to 8000, purity: 40%) as 4.0% by weight, 2-ethylhexanoic acid (purity: 100%) as 6.0% by weight, and octanoic acid (purity: 100) %) Was mixed with 4.0% by weight, neutralized NaOH aqueous solution (purity: 49%) 5.7% by weight and water 49.3% by weight, and the mixture was stirred. To produce a 1 for the automatic dishwasher detergent.

(Example 2)
Table 1 in which decanoic acid (capric acid, purity: 100%) is used instead of octanoic acid, ethylenediaminetetraacetic acid tetrasodium (purity: 100%) is used instead of nitrilotriacetic acid, and the blending ratio is shown below. A detergent for an automatic dishwasher was produced in the same manner as in Example 1 except that the changes were made as described in 1.

(Example 3)
A detergent for an automatic dishwasher was used in the same manner as in Example 1 except that tetrasodium ethylenediaminetetraacetate was used instead of trisodium nitrilotriacetate and the blending ratio was changed as described in Table 1 below. Manufactured.

Example 4
As a mixture of alkyl polyglucosides having an alkyl group having 4 to 8 carbon atoms, Simulsol AS48 (manufactured by SEPPIC, purity: 50%) was added, and tetrasodium ethylenediaminetetraacetate was used instead of trisodium nitrilotriacetate, A cleaning agent for an automatic dishwasher was produced in the same manner as in Example 1 except that the blending ratio was changed as described in Table 1 below.

(Example 5)
Nonioside (registered trademark) B-15 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., purity: 50%) is added as an alkylpolyglucoside (butylpolyglucoside) having an alkyl group having 4 carbon atoms, and the blending ratio is shown in Table 1 below. A detergent for an automatic dishwasher was produced in the same manner as in Example 1 except that the changes were made as described in 1.

(Example 6)
As a mixture of alkyl polyglucosides having an alkyl group having 10 to 12 carbon atoms, Mydol 12 (manufactured by Kao Corporation, purity: 50%) was added, and the blending ratio was changed as described in Table 1 below. Except for the above, a cleaning agent for an automatic dishwasher was produced in the same manner as in Example 1.

(Example 7)
A detergent for an automatic dishwasher was produced in the same manner as in Example 1 except that 1% by weight of glucose (purity: 100%) was added and the blending ratio was changed as described in Table 1 below.

(Example 8)
A detergent for an automatic dishwasher was produced in the same manner as in Example 1 except that 8% by weight of sucrose (purity: 100%) was added and the blending ratio was changed as described in Table 1 below.

(Comparative Example 1)
A detergent for an automatic dishwasher was produced in the same manner as in Example 1 except that 2-ethylhexanoic acid was not added and the blending ratio was changed as described in Table 1 below.

(Comparative Example 2)
Example except that low-foaming nonionic surfactant was not added, ethylenediaminetetraacetic acid tetrasodium was used instead of nitrilotriacetic acid trisodium, and the blending ratio was changed as described in Table 1 below. The washing | cleaning agent for automatic dishwashers was manufactured like 1.

(Comparative Example 3)
Dodecanoic acid (lauric acid, purity: 100%) was used instead of octanoic acid, tetrasodium ethylenediaminetetraacetate was used instead of trisodium nitrilotriacetate, and the blending ratio was changed as described in Table 1 below. A detergent for an automatic dishwasher was produced in the same manner as in Example 1 except that.

(Comparative Example 4)
Automatic as in Example 1, except that octanoic acid was not added, ethylenediaminetetraacetic acid tetrasodium was used in place of nitrilotriacetic acid trisodium, and the blending ratio was changed as described in Table 1 below. A detergent for dishwashers was produced.

(Evaluation of solution stability)
Solution stability was evaluated as follows using the detergent for automatic dishwashers manufactured in each Example and each Comparative Example.

100 ml of an automatic dishwasher detergent was placed in a clear polypropylene bottle and sealed with a cap.
Whether or not the detergent for the automatic dishwasher contained in the bottle is separated (i) Immediately after producing the detergent for the automatic dishwasher and filling the bottle (temperature of the detergent for the automatic dishwasher: (Iii) After the bottle was stored at room temperature for 1 day, (iii) Each state after the bottle was stored in a −7 ° C. refrigerator for one day was visually confirmed.

The evaluation results of the solution stability are shown in Table 2 below.
In Table 2, the case where the detergent for the automatic dishwasher is transparent and not separated is indicated by a circle, and the case where the detergent for the automatic dishwasher is separated into two or more layers or is frozen and solidified. X is shown.

(Evaluation of dishwashing performance)
Using the detergent for automatic dishwashers produced in each example and each comparative example, a dishwashing evaluation test was performed as follows.

(1) Sample pretreatment process A polypropylene box-shaped plastic tableware (170 mm long × 115 mm wide × 30 mm deep) was prepared.

The plastic tableware was hand-washed with a commercially available neutral detergent, rinsed with water, and then dried by wiping the surface with ethanol.

(2) Soil preparation process Wheat flour, milk, hen's egg, butter and tempura oil were prepared as soil materials.
10 g of flour was added to 90 g of purified water and stirred, and this was heated and kept at a temperature of 80 to 90 ° C. for 10 minutes to gelatinize the flour.
The obtained gelatinized aqueous solution was allowed to cool to room temperature.

20 g of milk, chicken egg, butter and tempura oil were each placed in the same beaker in order to prepare a mixed material.
20 g of the gelatinized aqueous solution was added to the mixed material, and the mixture was mixed using a round brush at a temperature of 20 to 30 ° C.
When the butter was completely dissolved, this was used as a dirt material.

(3) Dirt application process For plastic tableware, about 1 g of the dirt material was soaked in a round brush and applied to about 50% of the inner surface area of the plastic tableware to be cleaned.

(4) Automatic washing | cleaning process Next, the to-be-washed | cleaned tableware was wash | cleaned with the automatic dishwasher using the cleaning agent manufactured by each Example and each comparative example.
As the automatic dishwasher, a JW650 type automatic dishwasher manufactured by Hoshizaki Electric Co., Ltd. having a 45 L capacity washing tank was used, and the washing time was set as standard as described later.
Specifically, this automatic washing process was performed as follows.

First, water for washing (water temperature: 58 ± 3 ° C.) is supplied into the washing tank of the automatic dishwashing machine, and 90 g of one washing agent produced in Examples, Comparative Examples, etc. is added to the washing water. It was.
Separately, as a tableware to be cleaned, one plastic container was set on the rack with the mouth portion facing downward.

Next, a cleaning process is performed by spraying a cleaning agent solution for 1 minute, followed by a rinse process by spraying 80 ± 4 ° C. rinse water for 20 seconds, and then a cleaning process is performed by leaving it for 2 minutes. It was.
For each cleaning process, the dishes to be cleaned were replaced with new dishes to be cleaned, and a total of five cleaning processes were continuously performed.
Note that the cleaning agent was not replenished during the course of continuous cleaning. For this reason, it is considered that the concentration of the cleaning agent in the cleaning agent solution was sequentially diluted every time the cleaning process was performed. The concentration of the cleaning agent is 0.2% at the first cleaning and 0.1% at the fifth cleaning.

Table 2 shows the evaluation results of the dishwashing performance together with the evaluation results of the solution stability.
The evaluation of the dishwashing performance was performed by visually observing the tableware, and it was determined by checking whether or not the dirt was removed and confirming the degree of the dirt.
In Table 2, ◎ indicates that all the dirt has been removed, ◯ indicates that the dirt is slightly left, and △ indicates that much dirt remains. The case where a considerable amount of dirt remains is indicated by x.

As shown in the results of each Example, when the cleaning agent for an automatic dishwasher of the present invention was used, it was not separated even at normal temperature storage or low temperature storage, and sufficient cleaning power could be exhibited.
In particular, as shown in Examples 4 to 8, the low-foaming nonionic surfactant (A) is added in a larger amount without causing separation by adding a predetermined amount of saccharide (E) in addition to the essential components. Could be blended. As a result, in Examples 4-8, the detergency with respect to the plastic tableware was more excellent.

Since the detergent for the automatic dishwashing machine of Comparative Example 1 did not contain the branched aliphatic carboxylic acid, it was separated when it was liquid at room temperature storage, and was frozen and solidified at low temperature storage.
Since the detergent for an automatic dishwasher of Comparative Example 2 did not contain the low-foaming nonionic surfactant (A), the cleaning power for plastic tableware was extremely low.
In the cleaning agent for automatic dishwashing machine of Comparative Example 3, foaming occurred because the carbon number of the branched aliphatic carboxylic acid was 12, and it was not possible to wash the dishes using the automatic dishwashing machine.
Since the washing | cleaning agent for automatic dishwashers of the comparative example 4 did not contain C6-C10 linear aliphatic carboxylic acid (C), even if it is in the state immediately after manufacture, washing | cleaning for automatic dishwashers The agent separated.

Claims (9)

A low-foaming nonionic surfactant (A);
A cleaning builder (B);
Straight chain aliphatic carboxylic acid (C) having 6 to 10 carbon atoms;
A cleaning agent for an automatic dishwasher containing a branched aliphatic carboxylic acid having 6 to 10 carbon atoms (D) as an essential component,
The content of (A) is 0.1 to 20% by weight,
The content of (B) is 5 to 40% by weight,
The content of (C) is 0.1 to 15% by weight,
Content of said (D) is 0.1 to 15 weight%, The washing | cleaning agent for automatic dishwashers characterized by the above-mentioned. The content of (A) is 0.1 to 10% by weight,
The content of (B) is 10 to 30% by weight,
The content of (C) is 0.5 to 10% by weight,
The cleaning agent for an automatic dishwasher according to claim 1, wherein the content of (D) is 0.5 to 15% by weight. The cleaning agent for an automatic dishwasher according to claim 1 or 2, wherein (D) is a branched aliphatic carboxylic acid having 8 carbon atoms. (C) is octanoic acid,
Said (D) is 2-ethylhexanoic acid, The cleaning agent for automatic dishwashers in any one of Claims 1-3. The cleaning agent for automatic dishwashers according to any one of claims 1 to 4, further comprising one saccharide (E) selected from the group consisting of monosaccharides, oligosaccharides, alkyl glucosides and alkyl polyglucosides. The cleaning agent for an automatic dishwasher according to claim 5, wherein the alkyl group of the alkyl glucoside or the alkyl polyglucoside has 1 to 12 carbon atoms. Said (E) is a butyl glucoside, The cleaning agent for automatic dishwashers of Claim 5 or 6. The cleaning agent for an automatic dishwasher according to any one of claims 5 to 7, wherein the content of (E) is 0.05 to 10% by weight. The (A) is composed of polyoxyalkylene monoalkyl ether, polyoxyalkylene dialkyl ether, pluronic block polymer, reverse pluronic block polymer, tetronic block polymer, reverse tetronic block polymer and polyoxyalkylene alkyl phenyl ether. The cleaning agent for automatic dishwashers according to any one of claims 1 to 8, which is one or more low-foaming nonionic surfactants selected from the group consisting of: