JP5797829B1 - Cleaning composition and cleaning method - Google Patents

Abstract

An object of the present invention is to clean an object to be cleaned using an automatic dishwasher equipped with a control mechanism that monitors the electrical conductivity of a cleaning liquid containing a cleaning composition and determines whether or not the cleaning composition needs to be supplied. A cleaning composition suitable for the above is provided. The object to be cleaned is cleaned using an automatic dishwasher equipped with a control mechanism that monitors the electrical conductivity of a cleaning liquid containing the cleaning composition and determines whether or not the cleaning composition needs to be supplied. A liquid or solid detergent composition for use, comprising (A) a nonionic surfactant, (B) a polymer electrolyte, (C) an alkali agent, and (D) a chelating agent, wherein the detergent composition is solid In this case, when 0.5 g of the cleaning composition is dissolved in 1 L of water, the electrical conductivity at 60 ° C. is 1.2 mS / cm or more, and when the cleaning composition is liquid, the cleaning composition is added to 1 L of water. A detergent composition, wherein the electrical conductivity at 60 ° C. when 1 g of the product is dissolved is 0.7 mS / cm or more. [Selection] Figure 1

Description

The present invention relates to a cleaning composition and a cleaning method.

Conventionally, as a detergent for an automatic dishwasher, a detergent composition having low foaming property is used, and a detergent composition mainly containing a nonionic surfactant as a surfactant is known.

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

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

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

When supplying a cleaning composition to an automatic dishwasher, the user often supplies the cleaning composition manually in an automatic household dishwashing machine for home use. Some have a mechanism for automatically supplying a cleaning composition.

An example of a mechanism for automatically supplying a cleaning composition in a commercial automatic dishwashing machine is to monitor the concentration of the cleaning composition in the automatic dishwashing machine so that the concentration of the cleaning composition is lower than the set value. The control mechanism of supplying the cleaning composition when it comes to it can be mentioned.
Here, as a method of monitoring the concentration of the detergent composition in the automatic dishwasher, a method of monitoring the electrical conductivity of the cleaning liquid in the automatic dishwasher can be used.
The cleaning liquid is a mixture containing at least water and a cleaning composition in an automatic dishwasher.

When automatically supplying a cleaning composition in a commercial automatic dishwasher, it is preferable that the concentration of the cleaning composition in the automatic dishwasher can be kept constant by monitoring the electrical conductivity of the cleaning liquid. Depending on the composition of the cleaning composition and the operation method, the supply amount of the cleaning composition may become excessive or insufficient.
However, at present, there is no knowledge about what kind of cleaning composition is suitable for an automatic dishwasher equipped with such a control mechanism, and the electrical conductivity of the cleaning liquid containing the cleaning composition is monitored. Thus, there has been a demand for a cleaning composition suitable for cleaning an object to be cleaned using an automatic dishwashing machine equipped with a control mechanism that determines whether or not it is necessary to supply the cleaning composition.
Also,
In view of the above, an object of the present invention is to provide a cleaning composition that satisfies the above requirements.

The inventors of the present invention have come up with the present invention as a result of intensive studies on a cleaning composition that satisfies the above requirements.
That is, the cleaning composition of the present invention uses an automatic dishwasher equipped with a control mechanism that monitors the electrical conductivity of a cleaning liquid containing the cleaning composition and determines whether or not the cleaning composition needs to be supplied. A liquid or solid cleaning composition for cleaning an object to be cleaned,
(A) a nonionic surfactant (B) a polymer electrolyte (C) an alkali agent (D) a chelating agent,
When the cleaning composition is solid, the electrical conductivity at 60 ° C. when 1.2 g of the cleaning composition is dissolved in 1 L of water is 1.2 mS / cm or more,
When the cleaning composition is a liquid, the electrical conductivity at 60 ° C. when 1 g of the cleaning composition is dissolved in 1 L of water is 0.7 mS / cm or more.
In the present specification, when there is “water” unless otherwise specified, it is assumed to be artificial tap water. Artificial tap water is obtained by dissolving 0.20 g of calcium chloride dihydrate and 0.14 g of magnesium chloride hexahydrate in 4 L of ion-exchanged water. The total hardness of this artificial tap water is equivalent to 50 ppm (CaCO ₃ ).

The cleaning composition of the present invention contains an alkaline agent. Since the alkaline agent contains an electrolyte such as sodium ion, the electrical conductivity of the cleaning liquid containing the cleaning composition increases when the alkaline agent is included.
Specifically, when the cleaning composition is solid, the electric conductivity at 60 ° C. when 0.5 g of the cleaning composition is dissolved in 1 L of water is 1.2 mS / cm or more, and the cleaning composition When 1 is a liquid, the electric conductivity at 60 ° C. when 1 g of the detergent composition is dissolved in 1 L of water is 0.7 mS / cm or more.
When such a cleaning composition is supplied, the electrical conductivity of the cleaning liquid is quickly increased, so that excessive supply of the cleaning composition can be prevented.
On the other hand, when a cleaning composition that does not increase the electrical conductivity of the cleaning liquid is supplied, the electrical conductivity does not change much even if the cleaning composition is supplied. It is not detected that the concentration of the object has increased. Therefore, there is a possibility of causing an excessive supply of the cleaning composition. In addition, when the cleaning composition diffuses from the supply position of the cleaning composition to the sensor for measuring the electrical conductivity, the increase in the electrical conductivity is reduced, so that the electrical conductivity of the cleaning liquid is high. In the case of supplying a cleaning composition that does not become necessary, there is a high possibility of causing an excessive supply of the cleaning composition.
In addition, the quality of the water used varies seasonally, and the electrical conductivity of the water itself also fluctuates. Therefore, the electrical conductivity of the cleaning composition is lower than the electrical conductivity of the water used. Damage.
That is, the cleaning composition of the present invention has a configuration in which the electrical conductivity when used as a cleaning liquid is increased, whereby the electrical conductivity of the cleaning liquid containing the cleaning composition is monitored to supply the cleaning composition. The composition is suitable for an automatic dishwasher equipped with a control mechanism for determining necessity.

In the cleaning composition of this invention, it is preferable to contain the said nonionic surfactant (A) 0.5weight% or more.
When the nonionic surfactant is contained in an amount exceeding 0.5% by weight, the detergency can be further increased and drying of the tableware can be promoted.

In the cleaning composition of the present invention, the polymer electrolyte (B) is preferably a sodium salt or potassium salt of polyacrylic acid.
When the polymer electrolyte is used, the cleaning power can be further increased and the drying of the tableware can be promoted.

In the cleaning composition of the present invention, the nonionic surfactant (A) is preferably an alcohol ethylene oxide and propylene oxide adduct.
This type of surfactant is preferred because it has a good balance between low foaming properties and detergency.
Moreover, it is preferable that the molar ratio (PO / EO ratio) of propylene oxide (PO) to ethylene oxide (EO) contained in the nonionic surfactant (A) is 1/2 or more.
When the nonionic surfactant has such a composition, the low-foaming property is further increased, and a suitable detergency can be obtained.

In the cleaning composition of the present invention, the weight ratio [(B) / (A)] of the polymer electrolyte (B) to the nonionic surfactant (A) is 5/4 to 7/1. preferable.
That is, when [(B) / (A)] is 5/4 or more, the detergency of the surfactant can be enhanced. In addition, when [(B) / (A)] exceeds 7/1, the storage stability is lowered, and further interaction with other components may not be obtained.

It is preferable that the alkaline agent (C) contains at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium orthosilicate and potassium orthosilicate.
These alkali agents are preferable because they increase detergency and have high electrical conductivity per unit weight.

When the cleaning composition of the present invention is a solid cleaning composition, the electrical conductivity at 60 ° C. when 1.4 g of the cleaning composition is dissolved in 1 L of water is 1.4 mS / cm or more. It is preferable.
In the case of a solid cleaning composition, it is preferable to use a small amount as a composition that increases the electrical conductivity when 0.5 g of the cleaning composition is dissolved in 1 liter of water. In this case, it is preferable that the electric conductivity when 0.5 g of the cleaning composition is dissolved in 1 L of water is within such a range.
The concentration range in which the cleaning agent is dissolved at a ratio of 0.5 g of solid cleaning composition to 1 L of water is a concentration range that is often used in an automatic dishwashing machine. This is because the concentration of the cleaning composition can be suitably adjusted.

When the cleaning composition of the present invention is a liquid cleaning composition, the electrical conductivity at 60 ° C. when 1 g of the cleaning composition is dissolved in 1 L of water is 0.9 mS / cm or more. preferable.
In the case of a liquid detergent composition, the electrical conductivity when 1 g of the detergent composition is dissolved in 1 liter of water is lower than that of the solid detergent composition. It is preferable to use a large amount of the detergent composition. As a result, the electrical conductivity of the cleaning liquid is approximately the same when the solid cleaning composition is used and when the liquid cleaning composition is used.
In consideration of such a method of use, it is preferable that the electric conductivity when 1 g of the detergent composition is dissolved in 1 L of water is within such a range.
The concentration range in which the cleaning agent is dissolved at a ratio of 1 g of the liquid cleaning composition to 1 L of water is a concentration range that is often used in an automatic dishwasher, and has a predetermined electrical conductivity under these conditions. This is because the concentration of the cleaning composition can be suitably adjusted.

The cleaning method of the present invention uses an automatic dishwasher equipped with a control mechanism that determines the necessity of supplying the cleaning composition by monitoring the electrical conductivity of the cleaning liquid containing the cleaning composition. A cleaning method for cleaning, wherein the cleaning composition of the present invention is used as the cleaning composition.
When the cleaning composition of the present invention is used, when the cleaning composition is supplied, the electrical conductivity of the cleaning liquid is quickly increased, so that excessive supply of the cleaning composition is difficult to occur.
By monitoring the electrical conductivity of the cleaning liquid containing such a detergent composition and operating the automatic dishwasher, the automatic dishwashing machine continuously in a state where the concentration of the detergent composition in the automatic dishwasher is stable. The washing machine can be operated.

In the cleaning method of the present invention, the automatic dishwasher is preferably a water-saving automatic dishwasher.
In a water-saving automatic dishwasher, since the amount of rinsing water is small, the electrical conductivity of the washing liquid is unlikely to decrease during washing. Therefore, the control line is set to a value close to the most preferable electric conductivity (for example, 1.0 mS / cm) (for example, set to 0.95 mS / cm).
In this example, the cleaning composition is supplied when the electrical conductivity of the cleaning liquid falls below 0.95 mS / cm.
Here, if the electrical conductivity of the cleaning composition is high, the electrical conductivity of the cleaning liquid increases immediately after the supply of the cleaning composition, and the sensor for detecting the electrical conductivity immediately exceeds 0.95 mS / cm. Therefore, the supply of the cleaning composition is stopped, and the concentration of the cleaning composition in the cleaning liquid is controlled within a preferable range.
On the other hand, if the electrical conductivity of the cleaning composition is low, the electrical conductivity does not increase immediately even if the cleaning composition is supplied (it takes time for diffusion), so a sensor for detecting the electrical conductivity is 0.95 mS. At the time when / cm is detected, the concentration of the cleaning composition in the cleaning liquid becomes higher than the concentration corresponding to electric conductivity = 0.95 mS / cm. That is, the cleaning composition is excessively supplied.
From this, it can be said that the cleaning composition of the present invention capable of preventing the excessive supply of the cleaning composition is particularly suitable for a water-saving automatic dishwasher.
By the way, in the case of an automatic dishwasher that is not water-saving, the amount of rinsing water is large, so the concentration below the control line is large. For example, the conductivity decreases to 0.8 mS / cm by setting the cleaning agent to be supplied when it is below 0.95 mS / cm.
In this case, even if a large amount of the cleaning composition is supplied, the preferred electrical conductivity is not immediately exceeded, so that the problem of excessive supply of the cleaning composition hardly occurs.

In the washing | cleaning method of this invention, it is preferable to perform the drying process, without performing the rinse process using water and performing the rinse process using the rinse agent after the said rinse process.
In “non-rinse cleaning”, which is a cleaning method that does not perform a rinsing step, if the hardness of water is high, the scale may remain on the cleaning object, and sufficient cleaning may not be achieved. Contains polyelectrolyte and chelating agent. By blending these components, sufficient cleaning can be achieved even in non-rinse cleaning.
That is, it can be said that the cleaning composition of the present invention is a cleaning composition particularly suitable for non-rinsing cleaning.

In the cleaning method of the present invention, it is preferable to use a solid cleaning composition and to control the electrical conductivity of the cleaning liquid so that the electrical conductivity of the cleaning liquid during cleaning is 1.4 mS / cm or more. In addition, it is preferable to use a liquid cleaning composition and to control the electrical conductivity of the cleaning liquid so that the electrical conductivity of the cleaning liquid during cleaning is 0.9 mS / cm or more.
When the electrical conductivity is controlled within such a range, the concentration of the cleaning composition in the automatic dishwasher can be easily controlled.

The cleaning composition of the present invention is suitable for an automatic dishwasher equipped with a control mechanism that monitors the electrical conductivity of a cleaning liquid containing the cleaning composition and determines whether or not it is necessary to supply the cleaning composition. When the cleaning composition of the present invention is used, the concentration of the cleaning composition in the automatic dishwashing machine can be kept constant by preventing excessive supply of the cleaning composition.

FIG. 1 is a schematic diagram showing an example of an automatic dishwasher equipped with a control mechanism that monitors the electrical conductivity of a cleaning liquid containing a cleaning composition and determines whether or not the cleaning composition needs to be supplied. FIG. 2 is a flowchart illustrating a method for determining whether or not it is necessary to supply a cleaning composition based on a signal of electrical conductivity.

Hereinafter, the cleaning composition of the present invention will be described in detail.
That is, the cleaning composition of the present invention uses an automatic dishwasher equipped with a control mechanism that monitors the electrical conductivity of a cleaning liquid containing the cleaning composition and determines whether or not the cleaning composition needs to be supplied. A liquid or solid cleaning composition for cleaning an object to be cleaned,
(A) a nonionic surfactant (B) a polymer electrolyte (C) an alkali agent (D) a chelating agent,
When the cleaning composition is solid, the electrical conductivity at 60 ° C. when 1.2 g of the cleaning composition is dissolved in 1 L of water is 1.2 mS / cm or more,
When the cleaning composition is a liquid, the electrical conductivity at 60 ° C. when 1 g of the cleaning composition is dissolved in 1 L of water is 0.7 mS / cm or more.

Examples of the nonionic surfactant (A) include polyoxyalkylene monoalkyl ether, polyoxyalkylene dialkyl ether, pluronic block polymer, reverse pluronic block polymer, tetronic block polymer, reverse tetronic block polymer, poly Oxyalkylene alkyl phenyl ether, fatty acid alkanolamide, polyoxyalkylene fatty acid alkanolamide, polyoxyalkylene fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, alkyl polyglycoside, polyoxy Consists of ethylene methyl ether fatty acid ester and polyoxyalkylene alkylamine One or more nonionic surfactants selected from and the like.
These polymers are preferable as the nonionic surfactant (A) because they have less foaming and are suitable for use in an automatic dishwasher.
These nonionic surfactants (A) can be used singly or in appropriate combination of two or more.

式中、ｘ、ｙはそれぞれ１以上の数であり、オキシエチレン基又はオキシプロピレン基の平均付加モル数を表す。Ｒはアルコールの残基であるアルキル基である。ＲはＣ８〜Ｃ１５のアルキル基であることが好ましい。ｙとｘの比率（ＰＯ／ＥＯ比）はｙ／ｘ＝１／２以上であることが好ましく、２／３以上であることがより好ましい。また、ｙとｘの比率（ＰＯ／ＥＯ比）はｙ／ｘ＝５／１以下であることが好ましく、７／２以下であることがより好ましい。
また、数平均分子量が５００〜２０００であるものが好ましい。 Examples of the polyoxyalkylene monoalkyl ether include an alkylene oxide adduct of an alcohol obtained by adding an alkylene oxide (ethylene oxide (EO), propylene oxide (PO), butylene oxide (BO), etc.) to an alcohol.
Preferable examples of the alkylene oxide adduct of alcohol include ethylene oxide and propylene oxide adducts of alcohol.
As an example of the ethylene oxide and propylene oxide adduct of alcohol, what has structural formula represented by following Chemical formula (1) is mentioned.

In the formula, each of x and y is a number of 1 or more, and represents the average number of added moles of oxyethylene group or oxypropylene group. R is an alkyl group which is a residue of alcohol. R is preferably a C8 to C15 alkyl group. The ratio of y to x (PO / EO ratio) is preferably y / x = 1/2 or more, and more preferably 2/3 or more. The ratio of y to x (PO / EO ratio) is preferably y / x = 5/1 or less, and more preferably 7/2 or less.
Moreover, the thing whose number average molecular weight is 500-2000 is preferable.

式中、ｘは１以上の数であり、オキシエチレン基の平均付加モル数を表す。Ｒはアルコールの残基であるアルキル基である。ＲはＣ８〜Ｃ１５のアルキル基であることが好ましい。 Another example of the alkylene oxide adduct of alcohol is an ethylene oxide adduct of alcohol.
As an example of the ethylene oxide adduct of alcohol, what has structural formula represented by following Chemical formula (2) is mentioned.

In the formula, x is a number of 1 or more, and represents the average number of added moles of oxyethylene groups. R is an alkyl group which is a residue of alcohol. R is preferably a C8 to C15 alkyl group.

式中、ｘは１以上の数であり、オキシエチレン基の平均付加モル数を表す。ｘは好ましくは約５であり、Ｒはアルキル基であり、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 a number of 1 or more, and represents the average number of added moles of oxyethylene groups. x is preferably about 5 and R is an alkyl group, preferably a C8 alkyl group.

式中、ｘ、ｙ、ｘ’はそれぞれ１以上の数であり、オキシエチレン基又はオキシプロピレン基の平均付加モル数を表す。
特に好ましくは、数平均分子量が３５００〜４５００であり、オキシエチレン基の含有量が総分子量の５〜１５％であるか、数平均分子量が３０００〜３５００であり、オキシエチレン基の含有量が総分子量の３０〜５０％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, each of x, y, and x ′ is a number of 1 or more, and represents the average added mole number of an oxyethylene group or an oxypropylene group.
Particularly preferably, the number average molecular weight is 3500 to 4500 and the content of oxyethylene groups is 5 to 15% of the total molecular weight, or the number average molecular weight is 3000 to 3500 and the content of oxyethylene groups is 30-50% of the molecular weight.

式中、ｘ、ｙ、ｘ’はそれぞれ１以上の数であり、オキシエチレン基又はオキシプロピレン基の平均付加モル数を表す。
好ましくは、数平均分子量が２０００〜４０００であり、オキシエチレン基の含有量が総分子量の１０〜３０％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, each of x, y, and x ′ is a number of 1 or more, and represents the average added mole number of an oxyethylene group or an oxypropylene group.
Preferably, the number average molecular weight is 2000 to 4000, and the content of oxyethylene groups is 10 to 30% of the total molecular weight.

式中、ｘ、ｘ’ｘ’’、ｘ’’’、ｙ、ｙ’、ｙ’’、ｙ’’’は、それぞれ１以上の数であり、オキシエチレン基又はオキシプロピレン基の平均付加モル数を表す。
好ましくは、数平均分子量が３５００〜４５００であり、オキシエチレン基の含有量が総分子量の５〜２０％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 ″, y ′ ″ are each a number of 1 or more, and an average addition mole of oxyethylene group or oxypropylene group Represents a number.
Preferably, the number average molecular weight is 3500-4500, and the content of oxyethylene groups is 5-20% of the total molecular weight.

式中、ｘ、ｘ’ｘ’’、ｘ’’’、ｙ、ｙ’、ｙ’’、ｙ’’’は、それぞれ１以上の数であり、オキシエチレン基又はオキシプロピレン基の平均付加モル数を表す。
好ましくは、数平均分子量が６０００〜８０００であり、オキシエチレン基の含有量が総分子量の１５〜３０％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 ″, y ′ ″ are each a number of 1 or more, and an average addition mole of oxyethylene group or oxypropylene group Represents a number.
Preferably, the number average molecular weight is 6000 to 8000, and the content of oxyethylene groups is 15 to 30% of the total molecular weight.

式中、ｘは１以上の数であり、オキシエチレン基の平均付加モル数を表す。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 a number of 1 or more, and represents the average number of added moles of oxyethylene groups. 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以上の数であり、オキシエチレン基又はオキシプロピレン基の平均付加モル数を表す。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, each of x and y is a number of 1 or more, and represents the average number of added moles of oxyethylene group or oxypropylene group. 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以上の数であり、オキシエチレン基の平均付加モル数を表す。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 a number of 1 or more, and represents the average number of added moles of oxyethylene groups. 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 nonionic surfactant (A) is preferably 0.5% by weight or more, and more preferably 1% by weight or more. Further, the content of the nonionic surfactant (A) is preferably 15% by weight or less, and more preferably 8% by weight or less.
When the content of the nonionic surfactant (A) is 0.5% by weight or more, suitable cleaning results can be obtained.

(B) As a polymer electrolyte, the salt of polycarboxylate is preferable. Specifically, polyacrylic acid, polymaleic acid, acrylic acid / maleic acid copolymer, acrylic acid / methacrylic acid copolymer, acrylic acid / itaconic acid copolymer, acrylic acid / acrylic acid ester copolymer, acrylic Examples include acid / methyl vinyl ether copolymers, acrylic acid / olefin copolymers, maleic acid / olefin copolymers, maleic acid / styrene sulfonic acid copolymers, sulfonic acid / acrylic acid copolymers, and salts thereof. It is done.
Examples of the salt include alkali metal salts such as potassium and sodium, and alkaline earth metal salts such as magnesium and calcium. Among these, alkali metal salts are preferable, and sodium salts or potassium salts are more preferable.
These polymer electrolytes (B) can be used singly or in appropriate combination of two or more.

Among these, polyacrylic acid or a salt thereof is preferable, and a sodium salt or potassium salt of polyacrylic acid is more preferable.
The weight average molecular weight of the polyacrylic acid or a salt thereof is preferably 3,000 to 200,000, and more preferably 3,000 to 50,000.
In the present specification, the weight average molecular weight and the number average molecular weight can be measured by gel permeation chromatography (GPC). Specifically, Tosoh Co., Ltd. TSKgelα-M (two linked) is used for the column, a differential refractometer is used for the detector, and the eluent is 60 mmol / L phosphoric acid and 50 mmol / L lithium bromide. The weight average molecular weight and the number average molecular weight are measured under the condition that the added dimethylformamide and the preparation is polyethylene glycol.

The content of the polymer electrolyte (B) is preferably 0.6 to 20% by weight, and more preferably 1 to 8% by weight.
When the content of (B) is in the above range, a cleaning composition suitable for non-rinsing cleaning without rinsing using a rinsing agent is performed after rinsing.
The weight ratio [(B) / (A)] of the polymer electrolyte (B) to the nonionic surfactant (A) is preferably 5/4 to 7/1, and is preferably 5/3 to 7/1. More preferably.

(C) As an alkali agent, an alkali metal salt or an alkaline earth metal salt can be used, and the kind thereof is not particularly limited, but sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, carbonate Sodium hydrogen, potassium hydrogen carbonate, sodium metasilicate, sodium sesquisilicate, sodium orthosilicate, potassium metasilicate, potassium sesquisilicate, potassium orthosilicate and the like are preferable. Moreover, the hydrate of these alkali agents may be sufficient.
Since these alkali agents supply alkali metal ions or alkaline earth metal ions into the cleaning liquid, when these alkali agents are blended, a cleaning composition having high electrical conductivity can be obtained.
Among these, at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium orthosilicate and potassium orthosilicate is preferable.
Moreover, these alkali agents (C) can be used individually by 1 type or in combination of 2 or more types.

The content of the alkali agent (C) is preferably 8 to 20% by weight when the cleaning composition is a liquid, and preferably 30 to 60% by weight when the composition is a solid. Moreover, it is preferable to contain the quantity which does not exceed 5% of either or both of sodium hydroxide and potassium hydroxide, respectively.
When the content of (C) is in the above range, the electrical conductivity can be sufficiently increased, and a detergent composition having a high detergency against oil stains can be obtained by adding an alkali agent. .

(D) As a chelating agent, ethylenediaminetetraacetic acid (EDTA), hydroxyethylethylenediaminetriacetic acid (HEDTA), nitrilotriacetic acid (NTA), diethylenetriaminepentaacetic acid (DTPA), 2-phosphonobutane-1,2,4-tricarboxylic acid, Ethylenediamine succinic acid (EDDS), hydroxyethyliminodiacetic acid (HIDA), glutamic acid diacetic acid (GLDA), methylglycine diacetic acid (MGDA), aspartic acid diacetic acid (ASDA), citric acid and salts thereof (sodium salt, potassium) Salt).
These chelating agents (D) can be used individually by 1 type or in combination of 2 or more types as appropriate.

The content of the chelating agent (D) is preferably 3 to 25% by weight when the cleaning composition is a liquid, and preferably 15 to 50% by weight when the composition is a solid. Further, when the cleaning composition is a liquid, it is more preferably 6 to 20% by weight in the case of a liquid, and more preferably 17 to 40% by weight in the case of a solid.
When the content of (D) is in the above range, when the hardness of water is high, the chelating agent (D) can capture calcium ions and the like in the water, and thus a rinsing step using a rinse agent after rinsing Even when non-rinse cleaning is performed without performing cleaning, sufficient cleaning is achieved.
This effect is specifically exhibited when the polymer electrolyte (C) and the chelating agent (D) are used in combination.

In addition to the above components (A) to (D), the cleaning composition of the present invention includes water, sodium sulfate as a processing agent (sodium sulfate), alcohols such as ethanol, silicon and the like. With the use of a defoaming agent, deodorant, antistatic agent, or the like as auxiliary components, it can be appropriately blended within a range that does not hinder the cleaning power and solution stability of the cleaning composition.
Moreover, it is preferable that the detergent composition of the present invention is substantially free of phosphate.

The cleaning composition of the present invention is a solid or liquid cleaning composition.
When the cleaning composition is solid, the electrical conductivity at 60 ° C. when 0.5 g of the cleaning composition is dissolved in 1 L of water is 1.2 mS / cm or more, and 1.4 mS / cm or more. It is preferably 1.5 mS / cm or more. Moreover, it is preferable that the electrical conductivity in 60 degreeC at the time of dissolving 0.5g of solid cleaning composition in 1L of water is 7 mS / cm or less.

When the cleaning composition is liquid, the electrical conductivity at 60 ° C. when 1 g of the cleaning composition is dissolved in 1 L of water is 0.7 mS / cm or more, and 0.9 mS / cm or more. Preferably, it is 1.0 mS / cm or more. Moreover, it is preferable that the electrical conductivity in 60 degreeC at the time of dissolving 1g of liquid cleaning composition in 1L of water is 3 mS / cm or less.

When using a solid detergent composition, it is preferable to use it by supplying it to an automatic dishwashing machine so that the electric conductivity of the washing liquid during washing is 1.4 mS / cm or more.
Moreover, when using a liquid cleaning composition, it is preferable to supply and use to an automatic dishwashing machine so that the electrical conductivity of the said washing | cleaning liquid in washing | cleaning may be 0.9 mS / cm or more.

Although the manufacturing method of the cleaning composition of this invention is not specifically limited, It manufactures by the method of mixing the said (A)-(D) component and other components (E), and stirring using a mixer. can do.
In the case of a solid detergent composition, it may be formed into a desired shape by processing such as granulation and pelletization.

Next, the cleaning method of the present invention will be described.
The cleaning method of the present invention uses an automatic dishwasher equipped with a control mechanism that determines the necessity of supplying the cleaning composition by monitoring the electrical conductivity of the cleaning liquid containing the cleaning composition. A cleaning method for cleaning, wherein the cleaning composition of the present invention is used as the cleaning composition.

FIG. 1 is a schematic diagram showing an example of an automatic dishwasher equipped with a control mechanism that monitors the electrical conductivity of a cleaning liquid containing a cleaning composition and determines whether or not the cleaning composition needs to be supplied.
The automatic dishwashing machine 1 shown in FIG. 1 is an apparatus provided with a cleaning composition automatic supply device 10 having a mechanism for automatically supplying a cleaning composition, and a cleaning tank 20 for cleaning. A cleaning composition supply pipe 40 for supplying the cleaning composition to the cleaning tank 20 is connected from the cleaning composition automatic supply apparatus 10, and rinse water is supplied to the cleaning tank 20 in the cleaning tank. A drain pipe 60 for draining water from the rinse water supply pipe 50 and the cleaning tank 20 is connected.

The cleaning tank 20 includes a concentration measurement sensor 30 that can measure the concentration of the cleaning composition in the cleaning liquid containing the cleaning composition inside the cleaning tank 20.
The concentration measurement sensor 30 is a sensor that measures the electrical conductivity of the cleaning liquid, and a signal of the measured electrical conductivity is sent to the cleaning composition automatic supply device 10.
The cleaning composition automatic supply device 10 includes a computer as a control mechanism for determining whether or not it is necessary to supply the cleaning composition, and it is necessary to supply the cleaning composition based on the transmitted electrical conductivity signal. Determine no.

FIG. 2 is a flowchart illustrating a method for determining whether or not it is necessary to supply a cleaning composition based on a signal of electrical conductivity.
Step S1 is measurement of the electrical conductivity of the cleaning liquid in the cleaning tank, and the electrical conductivity of the cleaning liquid is measured using the concentration measuring sensor 30 during the operation of the automatic dishwasher.

Data indicating the relationship between the electrical conductivity and the concentration of the cleaning composition in the cleaning liquid is recorded in the ROM of the computer as the control mechanism, and the electrical conductivity measured in step S1 is collated with the data. Determine the concentration of the cleaning composition.
In addition, the lower limit value of the electrical conductivity preferable for cleaning is determined from the lower limit value of the concentration of the detergent composition suitable for cleaning dishes and the like. A "is recorded.

In step S2, it is determined whether or not the electrical conductivity of the cleaning liquid measured by the concentration measurement sensor is lower than the control line A by executing a program that functions as electrical conductivity determination means installed in the computer.

In the case of NO, that is, when the electric conductivity is the same as or higher than that of the control line A, it is not necessary to supply the cleaning composition, but the cleaning composition supplying process described later may be continued. Therefore, the process proceeds to the next step, and in step S3, it is determined whether or not the cleaning composition supply process is being performed.

In step S3, when the cleaning composition supply process is not performed, that is, in the case of NO, the process returns to step S1, and the electrical conductivity of the cleaning liquid is measured again after a predetermined time.
On the other hand, if YES, that is, if it is determined that the cleaning composition supply process is being performed, the cleaning composition supply process is stopped in step S4. Specifically, the process of closing the opened electromagnetic valve and the process of stopping the motor of the pump are performed, and the supply of the cleaning composition to the cleaning tank 20 through the cleaning composition supply pipe 40 is stopped.
Thereafter, the process returns to step S1, and the electrical conductivity of the cleaning liquid is measured again after a predetermined time.

If YES in step S2, that is, if the electrical conductivity is lower than the control line A, it is necessary to supply the cleaning composition, and the process proceeds to the next step S5.

In step S <b> 5, the solenoid valve or the like is driven by executing a program installed in the computer, and the cleaning composition is supplied to the cleaning tank 20 through the cleaning composition supply pipe 40.
Specifically, a process of opening a closed electromagnetic valve or a process of rotating a pump motor is performed, and the cleaning composition is supplied to the cleaning tank 20 through the cleaning composition supply pipe 40.
In addition, the cleaning composition here may be supplied as a cleaning solution in which the cleaning composition is dissolved in water in advance, or the cleaning composition itself may be supplied. In the case where the cleaning composition is solid, the cleaning liquid obtained by dissolving the cleaning composition in water may be stored directly or once in the cleaning composition automatic supply device to supply the cleaning liquid. The solid cleaning composition may be directly supplied to the cleaning tank.

Thereafter, the process returns to step S1, and the electrical conductivity of the cleaning liquid is measured again after a predetermined time.

By using the cleaning composition of the present invention according to the above procedure, a control mechanism is provided to monitor the electrical conductivity of the cleaning liquid containing the cleaning composition and determine whether or not the cleaning composition needs to be supplied. The object to be cleaned can be cleaned using an automatic dishwasher.

According to the above procedure, the value of electrical conductivity as a control line to be specifically set can be arbitrarily set according to the type of the cleaning composition and the specifications of the automatic dishwasher.
In general, when a solid cleaning composition is used, it is preferable to define the control line A so that the electrical conductivity of the cleaning liquid during cleaning is 1.4 mS / cm or more. When used, it is preferable to define the control line A so that the electrical conductivity of the cleaning liquid during cleaning is 0.9 mS / cm or more.

As an example of an automatic dishwasher, FIG. 1 shows an apparatus in which a cleaning composition automatic supply device is included in the washing machine. However, as an automatic dishwasher used in the cleaning method of the present invention, a cleaning agent is used. An automatic composition supply device may be provided after the cleaning machine.

The automatic dishwasher is preferably a water-saving automatic dishwasher.
As a water-saving automatic dishwasher, in the case of a door-type automatic dishwasher, there is one in which rinse water is 3 L / cycle or less with respect to a passing area of 3600 cm ² where the tableware is present. Moreover, in the case of a rack conveyor type automatic dishwasher, the thing whose rinse water is 2.5 L / rack or less is mentioned.
In addition, in the case of an automatic dishwasher of a single tank type, the rinse water is 3 L / min or less. In the case of a double tank type of automatic dishwasher, the rinse water is 9 L / min or less. Things.
As described above, in the case of a water-saving automatic dishwasher, since the problem of excessive supply of the cleaning composition is likely to occur, the use of the cleaning composition of the present invention is effective for the excessive supply of the cleaning composition. Can be prevented.

Moreover, in the washing | cleaning method of this invention, it is preferable to perform the drying process without performing the rinse process using a rinse agent after performing the rinse process by water and the said rinse process.
In “non-rinse cleaning”, which is a cleaning method that does not perform a rinsing step, if the hardness of water is high, the scale may remain on the cleaning object, and sufficient cleaning may not be achieved. Contains polyelectrolyte and chelating agent. By blending these components, sufficient cleaning can be achieved even in non-rinse cleaning.
Specifically, when the rinse water has a hardness of 60 mg / L or more, the effect of using the cleaning composition of the present invention is remarkably exhibited.

Examples for more specifically explaining the present invention are shown below, but the present invention is not limited to these examples.
The raw materials used in the preparation of the cleaning compositions in the examples and comparative examples are as follows: (A) Nonionic surfactant surfactant (1): “Pull lafac LF403” manufactured by BASF Japan Ltd., alcohol ethylene Oxide and propylene oxide adducts, PO / EO ratio 1/1, pure content 100%
Surfactant (2): “Adecanol B722” manufactured by ADEKA Corporation, ethylene oxide and propylene oxide adducts of alcohol, PO / EO ratio 5/3, pure content 100%
Surfactant (3): “Adecanol BO901” manufactured by ADEKA Corporation, alcohol ethylene oxide and propylene oxide adduct, PO / EO ratio 1/10, pure content 100%
(B) Polymer electrolyte Polymer electrolyte (1): “Socaran PA25CLG” manufactured by BASF Japan Ltd., sodium polyacrylate, Mw = 4,500, resin pure content 92% by weight
Polymer electrolyte (2): “Acuzole 460N” manufactured by Dow Chemical, maleic acid / olefin copolymer, Mw = 10,000, resin pure content 25% by weight
Polymer electrolyte (3): “Aron A-6019N” manufactured by Toa Gosei Co., Ltd., sulfonic acid / acrylic acid copolymer, Mw = 100,000, resin pure content 25% by weight
(C) Alkaline agent sodium hydroxide: “Tosoh Pearl” manufactured by Tosoh Corporation Potassium hydroxide: “potassium hydroxide” Nippon Soda Co., Ltd. sodium orthosilicate: “Sodium orthosilicate 80”: Nippon Chemical Industry Co., Ltd. Sodium metasilicate pentahydrate: ADEKA Corporation sodium silicate No. 3: Nippon Chemical Industry Co., Ltd. sodium carbonate: Tokuyama Corporation (D) chelating agent NTA-3 sodium: "Trilon A92R" BASF Japan EDTA-4 sodium manufactured by Co., Ltd .: “Trilon B powder” GLDA-3 sodium manufactured by BASF Japan Co., Ltd .: “Dissolvin GL-PD-S” Akzo Nobel Co., Ltd. Trisodium citrate: Fuso Chemical Industry Co., Ltd. Manufactured (E) Other ingredients Snorra: Shikoku Kasei Kogyo Co., Ltd. Water: Artificial tap water It is displayed in mixing weight percent for displacement of the material.

[Measurement of electrical conductivity and concentration control of cleaning liquid]
(Examples 1 and 2, Comparative Examples 1 and 2)
As shown in Table 1, the raw materials of the cleaning composition were mixed to prepare cleaning compositions according to the examples and comparative examples.
The cleaning composition prepared in Example 1 and Comparative Example 1 is liquid, and the cleaning composition prepared in Example 2 and Comparative Example 2 is solid.
About these detergent compositions, the electrical conductivity of the washing | cleaning liquid was measured and the density | concentration control test was done in the automatic dishwasher.

[Measurement of electrical conductivity]
For the liquid cleaning composition (Example 1 and Comparative Example 1), 1 g of the cleaning composition was dissolved in 1 L of water to prepare a cleaning liquid. About the solid cleaning composition (Example 2 and Comparative Example 2) Prepared a cleaning solution by dissolving 0.5 g of the cleaning composition in 1 L of water.
The electrical conductivity of each cleaning liquid was measured at a liquid temperature of 60 ° C. using D54 Navi h manufactured by Horiba.
The measurement results of electric conductivity are shown in Table 1.

[Density control test]
The automatic dishwasher (Dishwasher DWE680A manufactured by Hoshizaki Electric Co., Ltd.) is equipped with a control device that monitors the electrical conductivity of the cleaning liquid containing the cleaning composition and determines whether or not the cleaning composition needs to be supplied. Operate a control mechanism that controls the lower concentration limit of the cleaning composition to 0.5 g / L or more for a solid cleaning composition and 1 g / L or more for a liquid cleaning composition. The washing test was conducted for 15 minutes.
By monitoring the electrical conductivity of the cleaning liquid, the concentration of the cleaning composition during the cleaning test is monitored, and the upper limit (maximum value) and the lower limit of the concentration of the cleaning composition measured during the cleaning test ( The minimum value was determined and the ratio is shown in Table 1.
It can be said that the concentration of the cleaning composition during the cleaning test is kept constant as the ratio (upper concentration limit / lower concentration limit) shown in Table 1 is smaller.

From Table 1, when the cleaning composition of Examples 1 and 2 having a high electrical conductivity of the cleaning liquid is used, the concentration of the cleaning composition during the cleaning test is higher than that of Comparative Examples 1 and 2. It can be seen that the ratio of (density upper limit / density lower limit) becomes smaller. Therefore, the cleaning compositions of Examples 1 and 2 are automatic dishes having a control mechanism for determining the necessity of supplying the cleaning composition by monitoring the electrical conductivity of the cleaning liquid containing the cleaning composition. It can be said that the composition is suitable for a washing machine.

[Cleanability test, quick drying test, foam suppression test, scale adhesion prevention test]
(Examples 1-13, Comparative Examples 1-6)
As shown in Table 2 and Table 3, the raw materials of the cleaning composition were mixed to prepare cleaning compositions according to the examples and comparative examples.
The cleaning composition prepared in Examples 1, 3 to 10 and Comparative Examples 1, 3, and 4 shown in Table 2 is a liquid, and Examples 2, 11 to 13 and Comparative Examples 2, 5, and 6 shown in Table 3 are liquid. The cleaning composition prepared in (1) is a solid.
About these cleaning composition, the electrical conductivity of the washing | cleaning liquid was measured by the method mentioned above, and also the detergency test, the quick-drying test, the foam suppression test, and the scale adhesion prevention test were done.

[Cleanability test]
Using the detergent compositions according to each of the examples and comparative examples, a dishwashability evaluation test was performed as follows.
(1) Sample pretreatment step: Toyo Sasaki glass tempered glass (170 mL) and polypropylene box-shaped plastic tableware (length 170 mm × width 115 mm × depth 30 mm) were prepared.
The glass was rubbed with a sponge using an alkaline cleaner, rinsed with water and then dried.
Plastic dishes were rubbed with a sponge using a neutral detergent, rinsed with water and then dried.
(2) Soil (mixed food soil) preparation process As a soil material, flour, milk, chicken egg, butter and tempura oil were prepared. 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 put in the same beaker in order to prepare a mixed material.
20 g of gelatinized aqueous solution was added to the mixed material, and the mixture was mixed at a temperature of 20 to 30 ° C. to make it uniform.
(3) Dirt application process A glass and plastic tableware was coated with about 1 g of a dirt material using a round brush as a dish 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 an automatic dishwasher, a JW-650UF type automatic dishwasher manufactured by Hoshizaki Electric Co., Ltd. having a 45 L capacity washing tank was used.
Specifically, this automatic washing process was performed as follows.
First, cleaning water (water temperature 58 ± 3 ° C.) was supplied into the cleaning tank of the automatic dishwasher, and the cleaning compositions according to the respective examples and comparative examples were added to the cleaning water. When the cleaning composition was liquid, 90 g was added, and when it was solid, 40 g was added.
Further, 10 g of dirt was added to the cleaning liquid.
Further, calcium chloride dihydrate was added to the washing solution. The total hardness of the cleaning liquid is 65 ppm, including the hardness originally possessed by tap water.
Premixing by the washing operation was performed for 1 minute, and the detergent composition was uniformly dissolved and dispersed in the washing solution.
As the tableware to be cleaned, a glass and one plastic tableware were set on the rack with the opening facing downward.
Next, a cleaning step by spraying the cleaning liquid was performed for 1 minute, followed by a rinse by spraying 80 ± 4 ° C. rinse water for 8 seconds.
The evaluation of the dishwashing performance was performed by visually observing the tableware, and judged by checking whether or not the dirt was removed and the extent to which the dirt was removed.
The evaluation criteria for the detergency test are as follows.
◎: Residue of dirt is not confirmed in glass or plastic tableware. ○: Slight dirt remains in either or both of glass and plastic tableware.
Δ: A lot of dirt remains in either or both of glass and plastic tableware.
X: A considerable amount of dirt remains in one or both of glass and plastic tableware.
Tables 2 and 3 show the results of the detergency test in each example and comparative example.

[Quick drying test]
(1) The glass was pretreated in the same manner as in the sample pretreatment step [detergency test].
(2) Dirt (coffee / milk component soil) preparation process Coffee / milk component mixed soil was prepared as a soil material.
70 g of hot water was added to 1 g of commercially available instant cappuccino (Nescafe Gold Blend Instant Cappuccino) and mixed to make uniform.
(3) Dirt application process A tableware to be cleaned was prepared by applying about 0.3 g of a dirt material to a glass using a round brush.
(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 an automatic dishwasher, a JW-650UF type automatic dishwasher manufactured by Hoshizaki Electric Co., Ltd. having a 45 L capacity washing tank was used.
Specifically, this automatic washing process was performed as follows.
First, cleaning water (water temperature 58 ± 3 ° C.) was supplied into the cleaning tank of the automatic dishwasher, and the cleaning compositions according to the respective examples and comparative examples were added to the cleaning water. When the cleaning composition was liquid, 45 g was added, and when it was solid, 25 g was added.
Furthermore, 10 g of the same kind of dirt (mixed food stain) as used in the cleaning test was added to the cleaning liquid.
Further, calcium chloride dihydrate was added to the washing solution. The total hardness of the cleaning liquid is 65 ppm, including the hardness originally possessed by tap water.
Premixing by the washing operation was performed for 1 minute, and the detergent composition was uniformly dissolved and dispersed in the washing solution.
Glass as a dish to be cleaned was set on a rack with the opening facing downward.
Next, a cleaning process by spraying a cleaning liquid was performed for 50 seconds, and then a rinse by spraying 80 ± 4 ° C. rinse water was performed for 7 seconds.
The quick-drying evaluation was performed by visually observing tableware, and was determined by confirming the number of water droplets adhering to the glass surface 10 minutes after the end of washing.
The evaluation criteria for the quick-drying test are as follows.
○: 15 or less Δ: More than 15 and 25 or less ×: More than 25 Tables 2 and 3 show the results of the quick-drying test in each Example and Comparative Example.

[Foam suppression test]
In the [Detergency Test], immediately after adding the cleaning composition to the cleaning water and premixing for 1 minute by the cleaning operation, open the door and measure the height of foaming with a ruler. I confirmed air smearing.
The evaluation criteria of the foam suppression test are as follows.
○: Foaming is 10 mm or less, pumping noise is not recognized Δ: Foaming is more than 10 mm, but pumping noise is not recognized ×: Pumping air noise is recognized Table 2 and In 3, the result of the foam suppression test in each Example and the comparative example was shown.

[Scale adhesion prevention test]
(1) Sample pretreatment step A stainless steel beaker (capacity: 250 mL) was prepared.
The stainless steel beaker was rubbed with a sponge using an acidic detergent, rinsed with water and then dried.
(2) Preparation of artificial high hardness water 5.88 g of calcium chloride dihydrate and 4.06 g of magnesium chloride hexahydrate were dissolved in deionized water to prepare a 4 L solution to obtain artificial high hardness water. The total hardness of the artificial high hardness water is 1500 mg / L (= 1500 ppm) in terms of calcium carbonate concentration.
(3) Preparation of test solution 200 g of a test solution was prepared so as to contain each component as follows.
The cleaning composition according to each of Examples and Comparative Examples was included in the case of liquid at 0.1% and in the case of solid at 0.05%.
21 g of artificial high hardness water was added. This adds a total hardness of 160 ppm to the 200 g test solution. Since the tap water having a total hardness of 40 ppm was used for the preparation of the test liquid, the total hardness of the test liquid is about 200 ppm.
A 0.02% diluted solution of a commercially available silicic acid No. 3 aqueous solution (manufactured by ADEKA, purity 38%) is prepared. 155 g of this liquid is contained in 200 g. Thereby, 60 ppm was added as silicon dioxide.
Dissolve 2.54 g of sodium bicarbonate (Asahi Glass Co., Ltd.) in 1 L to prepare a 30 mM aqueous solution. 10 g of this liquid is contained in 200 g. Thereby, 1.5 mM carbonate ions were added.
(4) The test liquid prepared in the heating step (3) of the test liquid was put into a stainless steel beaker and heated at 85 ° C. for 5 hours.
After 5 hours, it was returned to room temperature overnight.
The test solution was discarded, and it was naturally dried with a stainless steel beaker turned upside down.
Evaluation of scale adhesion prevention was performed by visually observing a stainless steel beaker, and was judged by confirming the degree of deposits on the inner wall of the beaker.
The evaluation criteria for the scale adhesion prevention test are as follows.
○: Adherence of scale is not recognized or very small Δ: A lot of scale adheres ×: A considerable amount of scale adheres
Tables 2 and 3 show the results of the scale adhesion prevention test in each example and comparative example.

The cleaning composition of each example has an electrical conductivity of 0.7 ms / cm or more in the case of a liquid cleaning composition, and an electrical conductivity of 1.2 ms in the case of a solid cleaning composition. / Cm or more.
Based on the results of the concentration control test shown in Table 1, the cleaning composition of each example determines the necessity of supplying the cleaning composition by monitoring the electrical conductivity of the cleaning liquid containing the cleaning composition. It can be said that the composition is suitable for an automatic dishwasher equipped with a control mechanism.

In addition, as shown in Tables 2 and 3, the cleaning composition of each Example is a well-balanced cleaning composition without any evaluation item being x. Even if there are items for which the evaluation result is Δ, the number is one.

When the results of each example are compared in more detail with reference to Table 2, the component ratio (B) / (A) is 5/4 to 7 in Examples 4 and 5 having different component ratios (B) / (A). In Example 4, which is included in / 1, the result of the detergency test is higher.
In Examples 1 to 7 and 10 using polyacrylic acid sodium salt as the polymer electrolyte, the results of the quick-drying test were higher than those in Examples 8 and 9 using other polymer electrolytes. Are better.
Moreover, in Examples 1-9 using the ethylene oxide and propylene oxide adducts of alcohol as the nonionic surfactant and having a PO / EO ratio of 1/2 or more, the PO / EO ratio is 1 / Compared to Example 10 using less than 2, the results of the foam suppression test are superior.

On the other hand, the cleaning composition of each comparative example has an evaluation item whose evaluation result is x because it does not satisfy any of the invention-specific matters of the present invention, or an evaluation item whose evaluation result is Δ There are multiple places. Therefore, it is not preferable as a cleaning composition for an automatic dishwasher.

DESCRIPTION OF SYMBOLS 1 Automatic dishwashing machine 10 Cleaning composition automatic supply apparatus 20 Cleaning tank 30 Concentration measurement sensor 40 Cleaning composition supply pipe 50 Rinsing water supply pipe 60 Drain pipe

Claims (9)

Cleaning the object to be cleaned using a water-saving automatic dishwasher equipped with a control mechanism that determines the necessity of supplying the cleaning composition by monitoring the electrical conductivity of the cleaning liquid containing the cleaning composition. A solid cleaning composition for
(A) Nonionic surfactant (B) Sodium salt of polyacrylic acid as polymer electrolyte (C) As alkali agent, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, At least one (D) chelating agent selected from the group consisting of sodium metasilicate, sodium sesquisilicate, sodium orthosilicate, potassium metasilicate, potassium sesquisilicate, orthosilicate, and hydrates of these alkaline agents Including
The weight ratio [(B) / (A)] of the polymer electrolyte (B) to the nonionic surfactant (A) is 5/4 to 7/1,
The electric conductivity at 60 ° C. when 0.5 g of the cleaning composition is dissolved in 1 L of water is 1.2 mS / cm or more,
The content of the sodium salt of polyacrylic acid Ri der least 2.76 wt%,
The water-saving automatic dishwasher is
A door-type automatic dishwasher in which rinse water is 3 L / cycle or less for a passing area of 3600 cm ² where the tableware is present ,
Rack conveyor type automatic dishwasher with rinse water less than 2.5L / rack,
1 tank type automatic dishwasher with rinse water of 3L / min or less, or
A detergent composition, characterized in that it is a double-tank conveyor type automatic dishwasher with a rinse water of 9 L / min or less . The cleaning composition according to claim 1, comprising 0.5% by weight or more of the nonionic surfactant (A). The cleaning composition according to claim 1 or 2, wherein the nonionic surfactant (A) is an adduct of alcohol with ethylene oxide and propylene oxide. The cleaning composition according to claim 3, wherein a molar ratio (PO / EO ratio) of propylene oxide (PO) to ethylene oxide (EO) contained in the nonionic surfactant (A) is 1/2 or more. The cleaning composition according to any one of claims 1 to 4, wherein the alkaline agent (C) includes at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium orthosilicate, and potassium orthosilicate. The cleaning composition according to any one of claims 1 to 5, wherein the electrical conductivity at 60 ° C when 0.5 g of the cleaning composition is dissolved in 1 L of water is 1.4 mS / cm or more. Cleaning that cleans an object to be cleaned using a water-saving automatic dishwasher equipped with a control mechanism that determines the necessity of supplying the cleaning composition by monitoring the electrical conductivity of the cleaning liquid containing the cleaning composition A method,
The water-saving automatic dishwasher is
A door-type automatic dishwasher in which rinse water is 3 L / cycle or less for a passing area of 3600 cm ² where the tableware is present ,
Rack conveyor type automatic dishwasher with rinse water less than 2.5L / rack,
1 tank type automatic dishwasher with rinse water of 3L / min or less, or
It is an automatic dishwasher of a double tank type conveyor type in which rinse water is 9 L / min or less,
A cleaning method using the cleaning composition according to any one of claims 1 to 6 as the cleaning composition. The washing | cleaning method of Claim 7 which performs the rinse process by water and performs a drying process after not performing the rinse process using a rinse agent after the said rinse process. The cleaning method according to claim 7 or 8 , wherein the electrical conductivity of the cleaning liquid is controlled so that the electric conductivity of the cleaning liquid during the cleaning is 1.4 mS / cm or more.

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