JP2937635B2 - Cleaning agents for automatic dishwashers - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a new composition of detergents suitable for use in automatic dishwashers.

[0002]

2. Description of the Related Art In general, a detergent contains, in addition to sodium hydroxide, potassium hydroxide, carbonate and phosphate, silicate and other alkali components.
Many contain bleaching agents such as hypochlorite or chlorinated isocyanurate.

[0003] In particular, detergents for automatic dishwashers are liquid detergents containing no solid components and are uniform and stable in order to automatically inject the detergents and maintain the running water system. There was a restriction that it be a solution.
For this reason, for example, cleaning performance such as removal of oil and dirt and prevention of generation of water spots was not sufficient. Further, as a cleaning agent for an automatic dishwasher, it is necessary to have a sufficient foam suppressing property in order to maintain a flowing water system based on a pump or the like.

For this reason, conventionally, a method of using a cleaning builder and a surfactant in combination has been developed to improve the cleaning power.

[0005]

However, it has generally been considered that the washing builder and the surfactant are difficult to uniformly mix due to a salting-out effect or the like. For this reason, conventionally, a means for simultaneously supplying an appropriate amount of the washing builder and the surfactant to the flowing water system of the automatic dishwasher in a separated state, respectively, has been adopted.

In the above-mentioned conventional method,
Not only is the operation of supplying each component inconvenient, but also the concentration of each component in the washing water is not always constant, and therefore, it is difficult to stabilize the cleaning effect. There are drawbacks such as the need for an apparatus.

Accordingly, the present invention has complete solubility and solution stability as a single detergent, exhibits an effective detergency against oils and the like, and has a sufficient foam-suppressing property. An object of the present invention is to provide a cleaning agent for an automatic dishwasher which does not have any adverse effects such as generation of an unpleasant odor.

[0008]

Means for Solving the Problems In order to achieve the above-mentioned object, the present invention has the following constitution as a cleaning agent for an automatic dishwasher. 0.1 to 30% by weight of a low-foaming nonionic surfactant, 20 to 60% by weight of a washing builder, and 0.1 to 30% by weight.
4545% by weight of an aliphatic carboxylic acid having 6 to 10 carbon atoms as an essential component. Hereinafter, the weight% is simply described as%.

In the present invention, the low-foaming nonionic surfactant includes, for example, polyoxyalkylene monoalkyl ether, polyoxyalkylene dialkyl ether, pluronic block polymer, reverse pluronic block polymer, and tetronic. Examples include, but are not limited to, a type block polymer, a reverse stetronic type block polymer, and a polyoxyalkylene alkyl phenyl ether. These surfactants may be used alone or in combination of two or more. In addition, it is possible to use the above-mentioned low-foaming nonionic surfactant by mixing other nonionic surfactants having relatively high foaming, for example, in a ratio of 10 to 20% with respect to the low-foaming nonionic surfactant. it can.

If the amount of the low-foaming nonionic surfactant is less than 0.1%, the cleaning effect cannot be sufficiently exhibited, and if it exceeds 30%, the detergent solution becomes unstable. As a result, the washing builder cannot be blended in an amount of 20% or more, so that improvement in the washing power cannot be expected.

An aliphatic carboxylic acid having 6 to 10 carbon atoms is
It can be incorporated in an amount of 0.1 to 45%. The amount
If less than 0.1%, use low-foaming nonionic surfactant
0.1% or more cannot be blended stably, and if it exceeds 45%,
The mixing ratio of other essential components decreases, and the detergency as a detergent decreases.

The washing builder includes sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, sodium tripolyphosphate, potassium tripolyphosphate, sodium pyrophosphate, potassium pyrophosphate, and other alkaline phosphates. In addition to those, common ones such as citrate, malate, EDTA, nitrilotriacetate, and polyacrylate can be used.

The cleaning builder can be incorporated in an amount of 20 to 60%. When the amount is less than 20%, the detergency against oil and the like cannot be sufficiently exhibited, and when it is more than 60%, the solution of the detergent becomes unstable.

Further, in the present invention, other functional components such as silicon, other defoamers, deodorants, antistatic agents, etc., are added as auxiliary components to the solution stability, cleaning performance, etc. of the detergent. It can be appropriately compounded within a range that does not cause any trouble. Further, water is mixed in for solution.

[0015]

In the present invention, the following effects are obtained.
First, the low-bubble nonionic surfactant and the cleaning builder become a uniform and transparent aqueous solution in the presence of an aliphatic carboxylic acid having 6 to 10 carbon atoms. That is, the aliphatic carboxylic acid acts as a solubilizing agent for both.

Further, in this detergent solution, the number of carbon atoms is 6;
The blending of an aliphatic carboxylic acid of ~ 10 allowed the blending of a larger amount of a washing builder while maintaining the stable dissolution state of other components. Therefore, a sufficient cleaning effect is exerted on food-borne dirt adhering to dishes and the like.

In addition, the low-foaming nonionic surfactant acts to exhibit a foam-suppressing property at the time of washing, and at the same time, has a washing action such as eliminating spots on the tableware surface and improving a finished state due to a rinsing effect. Occurs.

In particular, when heptylic acid, which is an aliphatic carboxylic acid having 7 carbon atoms, is used, foam damage at the time of washing is further reduced as compared with the case where other kinds of aliphatic carboxylic acids are used. Also, it acts so as to hardly generate an off-flavor peculiar to lower fatty acids.

[0019]

Next, an embodiment of the cleaning agent for an automatic dishwasher according to the present invention will be described. (Embodiment 1) First, in this embodiment, No. 1
To No. 9 were prepared as detergents, and all the detergents were obtained in the form of transparent solutions.

[Table 1] In Table 1, column A shows a surfactant, and column B shows heptylic acid and potassium hydroxide required for neutralizing heptylic acid.
% Aqueous solution. In addition, values calculated as potassium heptylate are shown in parentheses.

The respective surfactants listed in the table are specifically as follows. That is, the polyoxyalkylene monoalkyl ether 1 has the following chemical structural formula.

Embedded image The polyoxyalkylene monoalkyl ether 2 has the following chemical structural formula.

Embedded image The polyoxyalkylene dialkyl ether has the following chemical structural formula.

Embedded image The polyoxyalkylene alkyl phenyl ether has the following chemical structural formula.

Embedded image Further, the Pluronic type block polymer 1 has the following chemical structural formula.

Embedded image The Pluronic type block polymer 2 has the following chemical structural formula.

Embedded image The reverse pluronic block polymer has the following chemical structural formula.

Embedded image The tetronic type block polymer has the following chemical structural formula.

Embedded image The reverse stetronic block polymer has the following chemical structural formula.

Embedded image

Then, glass dishes and polypropylene plastic dishes (200 × 150 mm) were used as dishes to be washed.
Large) was processed as follows. (Pretreatment) First, for glass cups,
% Alkali detergent for about 2 hours, then take out the glass cup, rinse with hot water,
Drying was performed for 1 hour in a constant temperature dryer at 0 ° C., and then this was allowed to cool to room temperature. The plastic tableware was hand-washed with a commercially available neutral detergent, rinsed with water, and then its surface was wiped with ethanol and dried.

(Preparation of Soil Material) Flour, milk, chicken eggs, butter, tempura oil and lipstick are prepared as the soil material.
These materials were processed as follows. 10 g of the flour was added to 90 g of purified water and stirred, and the mixture was heated and maintained at a temperature of 80 to 90 ° C. for 10 minutes. In this state, the flour was gelatinized, and then allowed to cool to room temperature.

In addition, milk, chicken eggs, butter, and tempura oil were each fed in the same beaker in an amount of 20 g each. Next, 20 g of the above gelatinized aqueous solution of flour was added to the mixture. Then, mix this mixture with 30 ~
The mixture was mixed with a round brush at a temperature of 40 ° C., and it was confirmed that the butter was completely dissolved.

(Application of Soil) The above-mentioned soil material was applied to a pretreated glass cup and plastic tableware in the following manner. For glass cups, about 1 piece of dirty material
g was immersed in a round brush, and this was applied on the inner wall surface of the glass cup in a helical manner from the edge to the bottom. A lipstick was adhered to the outer wall surface of the glass cup so as to lightly touch the lip near the lip. The glass cup thus treated was used as dishware to be washed. Also, for plastic tableware, soak about 1 g of dirty material in a round brush,
What was applied to about 50% of the inner surface area of the tableware was used as the tableware to be washed.

Next, the above-mentioned cleaning operation for the tableware to be cleaned was performed as follows using each of the above-mentioned cleaning agents. In addition, as an automatic dishwasher, a WM30 type device manufactured by Daikin Co., Ltd. equipped with a 24-liter capacity washing tank was used, and the washing time was set to a standard as described later.

The specific contents of this washing operation were as follows. First, water for washing (water temperature: 57 ± 3 ° C.) was previously supplied into a washing tank of an automatic dishwasher, and 50 g of one of the above-mentioned washing agents was poured into the washing tank to obtain a washing liquid. In addition, one of the above-mentioned dishes to be washed was set on a rack in a state in which each mouth portion is directed downward.

Next, the cleaning process by spraying the above-mentioned cleaning agent liquid is performed for 1 minute and 45 seconds, the rinsing process by spraying cleaning water at 80 ± 4 ° C. is performed for 15 seconds, and then left for 2 minutes as one cycle. The tableware to be washed was replaced with a new one every cycle, and this cycle was repeated a total of five times. Since the cleaning agent is not replenished at all in the repetition of each cycle, the concentration of the cleaning agent in the cleaning agent solution is sequentially diluted and decreased in each cycle. The cleaning operation for the plastic container was performed only for the first and fifth cycles.

Tables 2-1 and 2-2 show the results of cleaning the dishes to be cleaned by the above-described cleaning operation.

[Table 2-1]

[Table 2-2] The No. in each table corresponds to the cleaning agent No. in Table 1 respectively.

In Comparative Example 1 in Table 1, 10 parts by weight of a 48% aqueous potassium hydroxide solution (hereinafter simply referred to as "parts"), 20 parts of potassium carbonate, 10 parts of sodium tripolyphosphate and 3 parts of sodium nitrilotriacetate were used. Was used as a cleaning agent consisting of the following cleaning builder-1 and the balance of water. The results obtained when the cleaning operation was carried out in the same manner as described above using this was also shown in Table 2-2.

The symbols in Tables 2-1 and 2-2 indicate, firstly, the degree of washing against artificial stains and lipsticks. ◎ indicates that no dirt was attached, and ○ indicates that dirt was slightly attached. , 少 し means a little dirt, ▲ means a lot of dirt, × means a lot of dirt, and second, the degree of adhesion of water spots is ◎ When there is no, when ○ is slightly, △
Is when there is a little, ▲ is when there are many, X is when it is remarkable.

The measurement of the degree of foam suppression was performed as follows.
That is, when there is no contamination, a detergent aqueous solution equivalent to a concentration of 0.2% is supplied into the washing tank of the automatic dishwasher, and after confirming that the solution temperature is 41 to 43 ° C, A cleaning operation was performed for 1 minute with this aqueous solution of the cleaning agent, and the state of the liquid level was confirmed. In addition, in the case of contamination, a cleaning solution aqueous solution equivalent to 0.2% concentration is fed into the washing tank of the automatic dishwasher, and after confirming that the temperature of the solution is 51 to 53 ° C,
The chicken eggs were thoroughly disintegrated, and 10 g of the eggs were mixed as dirt. A washing operation was performed for 1 minute with this solution, and the state of the liquid level was immediately confirmed.

The degree of foam suppression was measured according to the following criteria by measuring the height of generated foam at each of the above liquid levels. That is,
○: when less than 10 mm, △: when more than 10 mm and less than 30 mm, ×
Is when it is 30 mm or more.

From the results of Tables 2-1 and 2-2, the cleaning agent according to the present invention has more detergency than the comparative example 1 with respect to the detergency, and also has a defoaming degree. Can be confirmed to be excellent. In addition, no off-flavor was generated when using the cleaning agents No. 1 to No. 9 according to the present invention.

Further, the storage stability of the detergent is as follows when cold (−6).
° C) and warming (50 ° C) for 30 days, ○ indicates stable, X indicates separation, cloudiness, etc., respectively. From the results of Table 2-1 and Table 2-2, No. 1 to
It can be confirmed that all the cleaning agents of No. 9 had good storage stability.

(Embodiment 2) First, in this embodiment, the following Table 3
No. 10 to No. 14 were prepared as detergents, and all the detergents were obtained as transparent solutions.

[Table 3]

In Table 3, column A indicates the amount of a surfactant, and column B indicates the amount of heptylic acid and a 48% aqueous solution of potassium hydroxide required for neutralizing heptyl acid. The values calculated in parentheses are calculated as potassium heptylate. In addition, each surfactant listed in the table is as described above. Comparative Example 2 in Table 3 is a cleaning agent comprising the cleaning builder 2 composed of 10 parts by weight of a 48% aqueous potassium hydroxide solution, 20 parts by weight of potassium carbonate, and 10 parts by weight of EDTA-4Na, and the remaining water.

The dishes to be washed were glass cups and plastic dishes made of polypropylene (larger than 200 × 150 mm), which were treated in the same manner as in Example 1 and washed in the same manner.

Table 4 shows the results of cleaning the dishes to be cleaned.

[Table 4] In the table, No. Are No. in Table 3, respectively.
Respectively. Further, the symbols indicating the degree of cleaning, the method of measuring the degree of suppression of foaming and the symbols used, and the symbols regarding the storage stability of the detergent are the same as those in Example 1. Comparative Example 2 is based on the cleaning agent composed of the cleaning builder 2 and the balance of water.

From the results shown in Table 4, the cleaning agent according to the present invention is:
It can be confirmed that the composition has excellent storage stability and, in comparison with Comparative Example 2, has higher detergency and more excellent foam control. In addition, no off-flavor was generated when using the cleaning agents No. 10 to No. 14 according to the present invention.

(Embodiment 3) First, in this embodiment, the following Table 5
No. 15 to No. 19 shown in Table 1 were prepared as detergents, and all the detergents were obtained in the form of transparent solutions.

[Table 5]

In Table 5, column A shows the amount of surfactant, and column B shows the amount of heptylic acid and the amount of 48% aqueous potassium hydroxide required for neutralizing heptylic acid. Also in parentheses,
The value calculated as heptyl acid is shown. Comparative Example 3 in Table 5 is a cleaning agent composed of 10 parts by weight of a 48% aqueous solution of potassium hydroxide, 5.2 parts by weight of potassium carbonate, and 10 parts by weight of potassium pyrophosphate, and the remaining part of water. .

The dishes to be washed were glass cups and plastic dishes made of polypropylene (larger than 200 × 150 mm), which were treated in the same manner as in Example 1 and washed in the same manner.

The results of cleaning the dishes to be cleaned are shown in Table 6 below.

[Table 6] In Table 6, No. Is N in Table 5
o. Respectively. Further, the symbols indicating the degree of cleaning, the method of measuring the degree of suppression of foaming and the symbols used, and the symbols regarding the storage stability of the detergent are the same as those in Example 1. Comparative Example 3 is based on the cleaning agent composed of the cleaning builder 3 and the balance of water.

From the results shown in Table 6, the cleaning agent according to the present invention is:
It can be confirmed that the storage stability is excellent, and in comparison with Comparative Example 3, the detergency is more effective and the defoaming degree is excellent. In addition, no off-flavor was generated when the cleaning agents Nos. 15 to 19 according to the present invention were used.

(Example 4) In this example, each of the components contained in Nos. 20 to 28 shown in Table 7 was prepared as a cleaning agent. Obtained as.

[Table 7] These detergents use, in particular, caproic acid, which is an aliphatic carboxylic acid having 6 carbon atoms, as a component in column B. Also, C
The cleaning builder 1 in the column is the same as that in Example 1.

As a result of applying these detergents in the same manner as in Example 1, almost the same effects as those of Example 1 were obtained with respect to the storage stability, the degree of washing, and the degree of foam suppression.

(Example 5) In this example, each of the components contained in No. 29 to No. 37 shown in Table 8 was prepared as a cleaning agent. Obtained as.

[Table 8] These cleaning agents are those in which caprylic acid, which is an aliphatic carboxylic acid having 8 carbon atoms, is used as a component in column B. Also, C
The cleaning builder 1 in the column is the same as that in Example 1.

As a result of applying these detergents in the same manner as in Example 1, almost the same effects as in Example 1 were obtained with respect to the storage stability, the degree of washing, and the degree of foam suppression.

(Example 6) In this example, each of the components contained in No. 39 to No. 46 shown in Table 9 below was prepared as a cleaning agent, and each cleaning agent was in the form of a transparent solution. Obtained as.

[Table 9] These detergents use pelargonic acid, which is an aliphatic carboxylic acid having 9 carbon atoms, as a component in column B. Also,
The cleaning builder 1 in column C is the same as that in Example 1.

As a result of applying these detergents in the same manner as in Example 1, almost the same effects as in Example 1 were obtained with respect to the storage stability, the degree of washing, and the degree of foam suppression.

Example 7 In this example, each of the components contained in Nos. 47 to 50 shown in Table 10 below was prepared as a cleaning agent, and each cleaning agent was a transparent solution. Obtained as.

[Table 10] These detergents use, in particular, capric acid, which is an aliphatic carboxylic acid having 10 carbon atoms, as a component in column B. Also, C
The cleaning builder 1 in the column is the same as that in Example 1.

As a result of applying these detergents in the same manner as in Example 1, almost the same effects as in Example 1 were obtained with respect to the storage stability, the degree of washing, and the degree of foam suppression.

[0053]

As described above, the present invention is constituted, and the following effects are exhibited. First, in the detergent according to the present invention, as described above, particularly a stable blending of a surfactant is possible, and in this case, each blending component exhibits complete solubility and solubility stability. In addition, the automatic dishwasher can always be supplied with a constant amount. Therefore, the cleaning effect can be obtained in a more stable state.

Further, in the cleaning agent according to the present invention, since a relatively large amount of a cleaning builder can be contained in the low-foaming surfactant, it is possible to prevent various types of tableware from being stained with an oily component that has adhered strongly. Can also exert an effective detergency.

Further, since the detergent according to the present invention is particularly excellent in terms of the degree of foam suppression, it has a drawback that foaming occurs during operation of the automatic dishwasher and that the foam overflows outside the machine. Does not occur.

When the detergent according to the present invention contains heptyl acid in particular, it is possible to obtain more excellent storage stability and more excellent detergency against oil stains. In order to stably mix a certain amount of surfactant, a relatively small amount is required. Therefore,
From this point, it is possible to further improve the cleaning power by reducing the cost and further increasing the number of cleaning builders.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ identification symbol FI C11D 3/20 C11D 3/20 (58) Fields investigated (Int.Cl. ⁶ , DB name) C11D 17/00 C11D 1/72 -1/722 C11D 3/04-3/20 WPI / L (QUESTEL)

Claims (3)

(57) [Claims] 1. A low foaming nonionic surfactant of 0.1 to 30% by weight, a washing builder of 20 to 60% by weight, and 0.1 to 45% by weight.
A detergent for an automatic dishwasher, comprising, as an essential component, 6% by weight of an aliphatic carboxylic acid having 6 to 10 carbon atoms. 2. The low-foaming nonionic surfactant is a polyoxyalkylene monoalkyl ether, a polyoxyalkylene dialkyl ether, a pluronic block polymer, a reverse pluronic block polymer, a tetronic block polymer, or a reverse stetronic block. The detergent for an automatic dishwasher according to claim 1, wherein the detergent is one or more surfactants selected from a polymer and a polyoxyalkylene alkylphenyl ether. 3. The detergent for an automatic dishwasher according to claim 1, wherein the aliphatic carboxylic acid is heptyl acid.