TWI613291B - Liquid detergent composition for tableware cleaning machine - Google Patents

Description

Liquid detergent composition for tableware cleaning machine

The present invention relates to a liquid detergent composition for a dishwashing machine. More particularly, it relates to a liquid detergent composition for a dishwashing machine which is preferably used in a commercial automatic tableware cleaning machine.

The automatic cleaning machine is used for cleaning dishes such as soiled dishes, glasses, cooking utensils, etc. in kitchens such as homes, restaurants, teahouses, etc., and cleaning of food containers used in food and beverage factories and plastic containers for products. As a main target stain, there are proteins, starches, fats and the like derived from foods, and these stains are combined and adhered to dishes, plastic containers such as dishes, glasses, and cooking utensils. Moreover, there is also a case where the stains are thermally modified when heated and conditioned, and the stains are firmly fixed.

Usually, the cleaning system using the automatic cleaning machine is carried out in the order of the cleaning step and the washing step. The time required for these steps is very short for commercial use, the cleaning step is about 40 to 60 seconds, and the washing step is about 5 to 20 seconds.

When cleaning, tap water or well water containing a hardness component such as Ca ion or Mg ion is repeatedly used. Calcium carbonate, magnesium carbonate, calcium citrate, magnesium citrate and the like which are produced by the hardness components in the water are insoluble in water, and therefore adhere to the cleaning liquid tank in the automatic cleaning machine or the side wall in the automatic cleaning machine to form a A strong film called scale. The scale adhering to each portion in the cleaning liquid tank is a cause of failure such as a decrease in thermal efficiency of the heat exchange portion, clogging of the circulation pump, and malfunction of the concentration sensor. Further, it is a state in which organic matter stains are easily deposited on the scale adhering to the side wall, and there is a possibility of causing problems in hygiene management.

In order to reduce the influence of hardness components such as Ca ions and Mg ions, the content of the chelating agent may be increased, but in the case of a liquid detergent, there is a limitation in the amount of the chelating agent in terms of obtaining a stable liquid composition.

In the Japanese Patent Publication No. 2013-518983, it is disclosed that a lotion composition comprising a chelate component such as methylglycine diacetic acid, a metal citrate, a metal carbonate or a metal citrate has excellent cleaning. Force characteristics, such as film formation and fouling on the disc, are reduced compared to previous compositions.

Japanese Patent Publication No. 2007-23210 discloses a chelating agent such as a specific amount of citrate, a surfactant, and an aromatic dissolution aid. The pH at 25 ° C is 3 or more and less than 7, and The liquid detergent composition having a specific molar ratio of sodium ion (Na ⁺ ) and potassium ion (K ⁺ ) is excellent in low-temperature stability, reduces clogging of the discharge port, and exhibits excellent cleaning power against stains on hard surfaces.

In International Publication No. 2013/175659, it is disclosed that one or more selected from the group consisting of methylglycine diacetic acid and an alkali metal salt thereof are selected from a citric acid and an alkali metal salt thereof in a specific amount ratio. One or two or more kinds of detergent compositions for automatic dishwashing machines selected from one or more of specific nonionic surfactants, even under conditions in which the amount of washing water used is small, The suppression of the adhesion of the tea scale and the reduction of the water spots show an excellent effect.

The present invention relates to a liquid detergent composition for a dishwashing machine which contains a bismuth citrate and which comprises the following components (A), (B), (C) and water: (A): A Glycine diacetic acid, glutamic acid diacetic acid or the like (B) component: citric acid or a salt thereof (C) component: polyacrylic acid or a salt thereof, and the content of the component (A) is 2.0 mass in terms of acid % or more and 5.0% by mass or less, the content of the component (B) is 1.5% by mass or more and 5.4% by mass or less based on the acid, and the content of the citrate is 2.5% by mass or more and 7.4% by mass or less, and the tableware cleaning machine is used. The liquid detergent composition contains potassium ions and optionally contains sodium ions, and the molar ratio of the sodium ion content [Na ⁺ ] to the potassium ion content [K ⁺ ] is [Na ⁺ ] / [K ⁺ ] is 0 or more. Below 0.9.

Moreover, the present invention relates to a cleaning liquid obtained by diluting the liquid detergent composition for a dishwashing machine of the present invention with water, and the content of the component (A) in the cleaning liquid is converted into an acid of 0.0017. The mass% or more and 0.017% by mass or less.

Moreover, the present invention relates to a method for cleaning a dishware, which comprises supplying the liquid detergent composition for a dishwashing machine of the present invention to a cleaning liquid tank of an automatic tableware cleaning machine, mixing the composition with water, and cleaning the liquid tank. The content of the component (A) in the preparation is converted into a cleaning liquid having an acid content of 0.0017 mass% or more and 0.017 mass% or less, and the tableware is cleaned using the cleaning liquid.

In the past, if scale is attached, it causes a decrease in thermal efficiency of the heat exchange unit, clogging of the circulation pump, malfunction of the concentration sensor, deterioration of the sanitary state due to deposition of organic matter, and the like.

The lotion composition of JP-A-2013-518983 can be used as an automatic dishwasher detergent (ADD), but the scale adhesion inhibiting property is not sufficient.

Further, the cleansing property and the scale adhesion inhibiting property in the case of using the liquid detergent composition of the Japanese Patent Laid-Open Publication No. 2007-23210 as a dishwashing machine composition are not specifically disclosed.

The present invention provides a liquid detergent composition for a tableware cleaning machine containing a phthalate which is excellent in not only cleanability, tea scale adhesion inhibiting property, formulation property, and low-temperature storage stability, but also excellent in scale adhesion inhibition property.

According to the present invention, there is provided a liquid detergent composition for a tableware cleaning machine containing a phthalate which is excellent in not only cleanability, tea scale adhesion inhibiting property, blending property, and low-temperature storage stability, but also excellent in scale adhesion inhibiting property.

In the present specification, the "liquid detergent composition for tableware cleaning machine of the present invention" is also referred to as "the liquid detergent composition of the present invention", "the detergent composition of the present invention", and "liquid detergent". "Composition" or "detergent composition".

The liquid detergent composition for a phthalate-containing dishwashing machine of the present invention contains the component (A) in a specific amount: methyl glycine diacetic acid, glutamic acid diacetic acid or the like thereof, and (B) component: citric acid or a salt thereof, (C) component: polyacrylic acid or a salt thereof, and water, and the content of a specific amount of silicate, the content of sodium ions [Na ^+] with respect to the potassium content of [K ^+] Mok ear than the ^{[Na +] / [K +} ] is 0 or more and 0.9 or less, whereby not only cleaning performance, tea scale adhesion-inhibiting, low-temperature deployment property and excellent storage stability, and also excellent in inhibiting scale adhesion.

The liquid detergent composition for a phthalate-containing dishwashing machine of the present invention is excellent in scale adhesion inhibition property. The reason is not clear, but it is considered as follows.

The present inventors have found the following problems with respect to the problem of scale adhesion suppression in the cleaning liquid tank and the inner side wall of the cleaning machine. The scale includes a hardly soluble calcium silicate such as calcium citrate or magnesium citrate (hereinafter referred to as citrate scale), and a water-insoluble carbonate such as calcium carbonate or magnesium carbonate (hereinafter referred to as carbonate scale). . The bismuth scale adhered to the surface of the stainless steel (SUS) in the cleaning machine becomes a binder on the surface of the SUS, and the carbonate scale present in the cleaning liquid tank is attached thereto. Scale is formed by crystal growth of carbonate scale. Further, the citrate scale adheres to the carbonate scale to form a layer.

If the amount of the hardness component of water such as Ca ion or Mg ion exceeds the cation exchange capacity (CEC) of the chelating agent, scale is generated. Further, it was found that the carbonate scale remaining on the SUS surface of the inner side wall of the cleaner crystallized and the scale became stronger.

Therefore, in order to suppress the adhesion of scale and to particularly inhibit the adhesion of carbonate scale, it is necessary to sufficiently capture the hardness component of water.

Since the monomer of the citrate ion polymerizes to the dimer and the polymer, the scale becomes easy to adhere to the SUS surface. The phthalic acid polymer introduces a divalent cation such as a Ca ion or a Mg ion, and is converted into a more complicated three-dimensional network structure. The polymer converted into a network structure is further fixed to the SUS surface as a phthalate scale.

Since the first ionization energy and electron affinity of K are smaller than Na, it is considered that the polymerization of the citrate ion is suppressed. Thus, in order to inhibit the adhesion of citrate scale, it is important to have a fixed amount of K ions in the cleaning solution.

It is considered that, in the alkaline solution, unlike other organic acids, citric acid only has a dissociated type and is easily dissolved in a gelled state of a citric acid polymer. Therefore, it is considered that citric acid in the alkaline liquid captures hardness components such as Ca ions or Mg ions, and the scale is effectively suppressed.

Moreover, since the first ionization energy and electron affinity of K are smaller than Na, potassium citrate is slightly easier to dissociate than sodium citrate. It is considered that by this slight difference, the case where the potassium ions are large is higher than the case where the sodium ions are large, and the scale inhibition effect by the dissociated citric acid is higher.

Therefore, in suppressing the adhesion of scale, it is important to capture the hardness component and inhibit the polymerization of the citrate ion. In the present invention, by combining the specific three compounds of the component (A), the component (B), and the component (C), and by specifying the molar ratio of the content of the sodium ion to the content of the potassium ion, the cleaning liquid and the hydrazine can be suppressed. The hardness component of the acid polymer. By limiting the content of the citrate and specifying the molar ratio of the content of the sodium ion to the content of the potassium ion, the macromolecularization of the citrate ion can be suppressed. As a result, scale adhesion can be suppressed.

<(A) component>

The component (A) of the present invention is a salt of methylglycine diacetic acid, glutamic acid diacetic acid or the like from the viewpoint of scale adhesion inhibiting property and tea scale adhesion inhibiting property. The salt of the component (A) is preferably an alkali metal salt, more preferably a sodium salt, from the viewpoint of easiness of availability. Further, from the viewpoint of further improving the scale adhesion inhibiting property, a potassium salt is more preferable.

The liquid detergent composition of the present invention may contain one or more components (A).

The content of the component (A) is 2.0% by mass or more and 5.0% by mass or less in the detergent composition from the viewpoint of scale adhesion inhibitory property, cleanability, tea scale adhesion inhibiting property, and blending property. The content of the component (A) is preferably 2.6 mass% or more, more preferably 3.3 mass% or more, more preferably in terms of scale adhesion inhibitory property and tea scale adhesion inhibitory property. The content is 3.6 mass% or more, more preferably 4.2 mass% or more, and from the viewpoint of blending property, it is preferably 4.7 mass% or less, more preferably 4.0 mass% or less, still more preferably 3.6 mass% or less. In addition, the content of the component (A) is preferably 2.6 to 5.0% by mass, more preferably 3.3, in the liquid detergent composition from the viewpoint of scale adhesion inhibitory property, tea scale adhesion inhibitory property, and formulation property. ~5.0% by mass, more preferably 3.3 to 4.7 mass%, more preferably 3.3 to 4.0 mass%, still more preferably 3.3 to 3.6 mass%. Further, the content of the component (A) is a value converted into an acid.

<(B) component>

The component (B) of the present invention is citric acid or a salt thereof from the viewpoint of scale adhesion inhibition. The component (B) is preferably citric acid from the viewpoint of further improvement in availability and scale adhesion inhibition. The salt of the component (B) is preferably an alkali metal salt, more preferably a sodium salt or a potassium salt, and more preferably a sodium salt, from the viewpoint of availability. The potassium salt is more preferable from the viewpoint of further improvement in scale adhesion inhibition.

The content of the component (B) is 1.5% by mass or more and 5.4% by mass or less in the detergent composition from the viewpoint of scale adhesion inhibiting property, blending property, and low-temperature storage stability. The content of the component (B) is preferably 2.5% by mass or more, more preferably 3.0% by mass or more, and still more preferably 3.5% by mass in terms of the detergent composition. The amount is more preferably 4.5% by mass or more, and is preferably 5.2% by mass or less from the viewpoint of further improvement in blending property and low-temperature storage stability. In addition, the content of the component (B) is preferably from 2.5 to 5.4% by mass, more preferably from 2.5 to 5% by mass, in terms of scale adhesion inhibitory, formulation, and low-temperature storage stability. 5.2% by mass, more preferably 3.0 to 5.2% by mass, more preferably 3.5 to 5.2% by mass, more Good is 4.5~5.2% by mass. Further, the content of the component (B) is from 1.5 to 5.4% by mass, preferably from 1.5 to 5.2% by mass, more preferably from 1.5 to 4.5% by mass, still more preferably from 1.5 to 3.5% by mass. Further, the content of the component (B) is a value converted into an acid.

The mass ratio of the content of the component (A) to the acid content of the component (B) is proportional to the content of the acid ([A)/(B)], and the scale adhesion inhibition property, the cleanliness property, and the tea scale adhesion inhibitory property. From the viewpoint of further improving the low-temperature storage stability, it is preferably 0.65 or more, more preferably 0.70 or more, still more preferably 1.0 or more, still more preferably 1.25 or more, and further improved in scale adhesion inhibition property and blendability. From the viewpoint, it is preferably 1.9 or less, more preferably 1.7 or less, still more preferably 1.55 or less.

<(C) component>

The component (C) of the present invention is a polyacrylic acid or a salt thereof from the viewpoint of cleanability and scale adhesion inhibition. The salt of the component (C) is preferably an alkali metal salt, more preferably a sodium salt or a potassium salt, from the viewpoint of ease of availability, and more preferably from the viewpoint of further improving the scale adhesion inhibiting property. Potassium salt.

The molecular weight of the component (C) preferably has a weight average molecular weight of 1,000 or more, more preferably 3,000 or more, and is preferably 10,000 or less, more preferably 8,000 or less, still more preferably 6,000 or less, still more preferably 5,000 or less. Further, for the same reason, the weight average molecular weight of the component (C) is preferably from 1,000 to 10,000, more preferably from 3,000 to 8,000, still more preferably from 3,000 to 6,000, still more preferably from 3,000 to 5,000.

Here, the weight average molecular weight of the component (C) can be determined by using a mixed solvent of acetonitrile and water (phosphate buffer solution) as a developing solvent and using polyacrylic acid as a standard material by size exclusion chromatography.

The content of the component (C) is preferably 0.8% by mass or more, more preferably 1.8% by mass or more, and still more preferably 2.5% by mass or more, from the viewpoint of further improving the cleanability. More preferably, it is 3.5 mass% or more, more preferably 4.5 mass% or more, and is preferably 5.5 mass% or less, more preferably 2.8 mass% or less, still more preferably 2.2 mass%. under. Further, the content of the component (C) is preferably from 0.8 to 5.5% by mass, more preferably from 1.8 to 5.5% by mass, more preferably from 1.8 to 5.5% by mass, more preferably from the viewpoint of further improvement in cleanability. 2.5 to 5.5% by mass, more preferably 3.5 to 5.5% by mass, still more preferably 4.5 to 5.5% by mass. In addition, it is preferably from 0.8 to 5.5% by mass, more preferably from 0.8 to 5.5% by mass in the liquid detergent composition, from the viewpoints of scale adhesion inhibition property, low-temperature storage stability, cleanability, tea scale adhesion inhibition property, and formulation property. It is 0.8 to 2.8% by mass, more preferably 1.8 to 2.8% by mass, still more preferably 1.8 to 2.2% by mass.

The mass ratio (B)/(C) of the content of the component (B) to the content of the component (C), the scale adhesion inhibition property, the cleanliness, the tea scale adhesion inhibition property, the formulation property, and the cryopreservation From the viewpoint of further improvement of the stability, it is preferably 0.5 or more, more preferably 0.8 or more, still more preferably 1.2 or more, and from the viewpoint of blending property, it is preferably 2.5 or less.

The mass ratio (A)/(C) of the content of the component (A) to the content of the component (C) is further improved in terms of scale adhesion inhibition property, cleanability, and tea scale adhesion inhibition property. In particular, it is preferably 0.7 or more, more preferably 0.8 or more, still more preferably 1.0 or more, still more preferably 1.3 or more, still more preferably 1.6 or more, and from the viewpoint of easiness of acquisition, preferably 3.4 or less, more preferably Good is below 2.5.

In the liquid detergent composition of the present invention, the amount of the component (A) converted to the acid content, the component of the component (B) converted to the acid content, and the content of the component (C) are combined in terms of scale adhesion inhibition property and cleanability. From the viewpoint of further improving the adhesion inhibition property of the tea scale, it is preferably 6.0% by mass or more, more preferably 7.5% by mass or more, and is preferably 12.0 from the viewpoint of further improvement in blendability and low-temperature stability. The mass% or less is more preferably 10% by mass or less, more preferably 9% by mass or less, and still more preferably 8.5 mass% or less.

<water>

The liquid detergent composition of the present invention contains water.

<Citrate>

The liquid detergent composition of the present invention contains from the viewpoint of preventing corrosion resistance of acid aluminum There is a citrate as an alkali agent.

The content of the bismuth salt is 2.5% by mass or more and 7.4% by mass or less in the liquid detergent composition from the viewpoints of cleanability, inhibition of the adhesion of the scale, adhesion prevention of the acid-resistant aluminum, and scale adhesion inhibition.

The content of the citrate is preferably 3% by mass or more, more preferably 4% by mass or more, and particularly preferably 7% by mass or less, more preferably in the liquid detergent composition. 6 mass% or less.

The citrate is preferably one or more selected from the group consisting of alkali metal citrates, from the viewpoint of further improving the corrosion resistance, the formulation, and the ease of acquisition. The alkali metal silicate is preferably selected from the group consisting of No. 1 in terms of scale adhesion inhibition, cleanability, tea scale adhesion inhibition, blendability, low-temperature storage stability, and ease of acquisition. One or more of the acid salts, the No. 2 citrate, the No. 3 citrate and the No. 4 citrate, more preferably selected from the group consisting of No. 1 citrate, No. 2 citrate One or more of the citrates of the citrate No. 3, more preferably one or more citrates selected from the group consisting of citrate No. 1 and bismuth citrate No. 2, more preferably One or two or more types of citrate selected from the group consisting of citrate No. 1. Here, the alkali metal citrate is of the formula M ₂ O. nSiO ₂ (M is an alkali metal, n is a molar ratio of SiO ₂ /M ₂ O), and the No. 1 citrate is a citrate having an average molar ratio of 1.7 or more and 2.3 or less. The molar ratio of the molar ratio n is 2.4 or more and 2.7 or less. The citrate of the No. 3 citrate is an average of 2.8 or more and 3.3 or less of the citrate, and the No. 4 citrate is the molar ratio of the molar ratio n. It is a citrate of 3.7 or more and 3.9 or less.

The citrate is preferably one or more selected from the group consisting of potassium citrate and sodium citrate from the viewpoint of easiness of availability. Further, as the alkali metal ruthenate, a salt selected from the group consisting of a sodium salt and a potassium salt is preferred. The citrate is preferably one or more alkali metal silicates selected from the group consisting of sodium citrate No. 1 and potassium citrate No. 1 and is preferably one in terms of ease of availability. Sodium citrate. Further, the alkali metal citrate is preferably potassium citrate No. 1 from the viewpoint of scale adhesion inhibition.

The alkali metal silicate is of the formula M ₂ O. nSiO ₂ (M is an alkali metal, n is the molar ratio of SiO ₂ / M ₂ O) represented, and it is believed, based on the change in the M n of the trait, or more complex, it is difficult to suppress and remove scale. For example, in an aqueous solution of sodium metasilicate (in the above formula, M is sodium, n=1) or an aqueous solution of sodium citrate more than the above, mainly a citrate ion monomer is present in n (mole ratio) The SiO ₂ /M ₂ O) larger sodium citrate aqueous solution contains, in addition to a monomer, a dimer, and further a cerium ion microcapsule containing a polymer thereof. The ratio of the polycaprate ion micelles increases as n (mola ratio SiO ₂ /M ₂ O) increases. As a result, it is understood that when n (mol ratio SiO ₂ /M ₂ O) is 2 or more, there is a tendency for the ruthenate ion to switch from the anion of the monomer to the more complicated polymer structure. These tannic acid polymers are adsorbed on the surface of SUS, and are combined with calcium or magnesium which is usually present in water used for cleaning (for example, tap water or ground water) to form scale. It is considered that if n is 2 or more, the scale formed is adhered to a more firm state. Alkali metal citrate is a desirable component for improving cleaning power, but has a tendency to promote scale formation. The liquid detergent composition of the present invention can inhibit scale even when it contains an alkali metal silicate which is effective for improving the cleaning power.

<pH value>

The pH value (JIS K 3362) of the 0.2% by mass aqueous dilution of the liquid detergent composition of the present invention at 25 ° C is preferably 9 or more from the viewpoint of further improvement in scale adhesion inhibition property and cleanability. More preferably, it is 9.5 or more, more preferably 10 or more, still more preferably 10.5 or more, and from the viewpoint of cleanability, it is preferably 12 or less, more preferably 11.5 or less.

<Other ingredients>

The liquid detergent composition of the present invention preferably contains an alkali agent other than phthalate. The alkali agent other than the bismuth acid salt is preferably one or more alkali chemicals selected from the group consisting of an alkali metal hydroxide and an alkali metal carbonate from the viewpoint of easiness of availability.

As the alkali metal hydroxide, potassium hydroxide or sodium hydroxide is preferred, and potassium hydroxide is more preferred.

As the alkali metal carbonate, potassium carbonate or sodium carbonate is preferred, and potassium carbonate is more preferred.

The liquid detergent composition of the present invention may contain one or more alkali agents other than decanoate.

In the liquid detergent composition of the present invention, the alkaline agent preferably contains one or more selected from the group consisting of an alkali metal hydroxide and an alkali metal carbonate, and more preferably contains an alkali metal hydroxide. And two or more kinds of alkali metal carbonates.

The liquid detergent composition of the present invention is used as a mites for the purpose of further improving scale adhesion inhibition, cleanability, tea scale adhesion inhibition, blendability, and low-temperature storage stability, and ease of acquisition. The alkali agent other than the acid salt is preferably one or more selected from the group consisting of (1) one or more selected from the group consisting of alkali metal hydroxides, and (2) one selected from the group consisting of alkali metal carbonates. That is, both of (1) and (2) are contained.

Further, the liquid detergent composition of the present invention preferably contains one or more selected from the group consisting of potassium hydroxide, sodium hydroxide, potassium carbonate and sodium carbonate, and more preferably contains potassium hydroxide and hydroxide. Two or more of sodium, potassium carbonate and sodium carbonate.

Further, in the liquid detergent composition of the present invention, the alkaline agent preferably contains one or more selected from the group consisting of potassium hydroxide, sodium hydroxide, potassium carbonate, and sodium carbonate, and more preferably contains the selected ones. One or two or more kinds selected from the group consisting of potassium hydroxide and sodium hydroxide, and one or more selected from the group consisting of potassium carbonate and sodium carbonate.

The liquid detergent composition of the present invention preferably contains potassium hydroxide and potassium carbonate as an alkali agent other than phthalate.

In view of further improvement of the cleanability, it is preferred to contain an alkaline agent in such a manner that the pH of the 0.2% by mass aqueous dilution of the liquid detergent composition of the present invention at 25 ° C is within the above range. In the liquid detergent composition, the content of the alkalinity agent is preferably 10% by mass or more, and more preferably 15% by mass or more from the viewpoint of further improving the cleanability. In view of low-temperature storage stability, it is preferably 25% by mass or less, and more preferably 20% by mass or less.

Furthermore, regarding the ratio of citrate in all alkaline agents, it is resistant to acid aluminum corrosion, It is preferably 15% by mass or more, more preferably 20% by mass or more, and still more preferably 25% by mass or more, from the viewpoint of further improving the scale adhesion inhibition, cleanability, blendability, and low-temperature storage stability, and more preferably From the viewpoint of further improving the scale adhesion inhibiting property, the formulation property, and the low-temperature storage stability, it is preferably 45 mass% or less, more preferably 40 mass% or less, still more preferably 3 mass% or less.

Preferably, the liquid detergent composition of the present invention contains an alcohol having a carbon number of 10 or more and 14 or less having a branched chain, and the nonionic interfacial activity of ethylene oxide and propylene oxide is bonded in a block type. One or two or more of the agents (hereinafter referred to as nonionic surfactant (I)).

In the nonionic surfactant (I), the average addition mole number of ethylene oxide is preferably 4 or more, more preferably 4 or more, from the viewpoint of further improvement in cleanability and low foaming property. 5 or more, and preferably 10 or less, more preferably 8 or less.

Further, in the nonionic surfactant (I), the average addition mole number of propylene oxide is preferably 2 or more, and more preferably from the viewpoint of further improvement of cleanability and low foaming property. It is 4 or more, more preferably 5 or more, and is preferably 10 or less, more preferably 9 or less.

Preferably, the liquid detergent composition of the present invention contains one or more selected from the group consisting of nonionic surfactants (I), which are branched carbon. The alcohol having a number of 10 or more and 14 or less is bonded with ethylene oxide and propylene oxide in a block type, and the average addition molar number of ethylene oxide is 4 or more and 10 or less, and the average propylene oxide is propylene oxide. The addition molar number is 2 or more and 10 or less.

It is preferable that the liquid detergent composition of the present invention contains one or more selected from the group consisting of nonionic surfactants, such as a nonionic surfactant (I), having a carbon number of 10 or more. More preferably, the secondary alcohol having a carbon number of 12 or more and preferably having a carbon number of 14 or less is bonded to ethylene oxide and propylene oxide in a block type.

It is preferable that the liquid detergent composition of the present invention contains one or more selected from the group consisting of nonionic surfactants, such as a nonionic surfactant (I), having a carbon number of 10 or more. More preferably, it has a carbon number of 12 or more, and preferably has a carbon number of 14 or less. The alcohol is bonded with ethylene oxide and propylene oxide in a block type, and the average addition molar number of ethylene oxide is 4 or more and 10 or less, and the average molar addition of propylene oxide is 2 Above and 10 or less.

The liquid detergent composition of the present invention preferably contains a nonionic surfactant represented by the following formula (1) as the nonionic surfactant (I).

R ¹ -O-(EO) _s -(PO) _t -H (1)

In the formula, R ¹ represents a branched alkyl group having 10 or more and 14 or less carbon atoms, a branched alkenyl group having 10 or more and 14 or less carbon atoms, and a branched alkyl group having 10 to 14 carbon atoms or carbon. a branched alkenyl group of 10 to 14, EO represents an ethoxy group, PO represents a propoxy group; s and t represent an average addition molar number, s is 4 or more and 10 or less, and t is 2 or more and 10 or less, t / s is 0.3 or more and 1.5 or less, and, s = 4 ~ 10, t = 2 ~ 10,0.3 ≦ (t / s) ≦ 1.5; "(EO) _s 'and' (PO) _t" in Block type bond]

In the formula (1), R ^{1 is} preferably an alkyl group having a branched carbon number of 10 or more and 14 or less or an alkenyl group having a branched carbon number of 10 or more and 14 or less, more preferably a branched chain. An alkyl group having 10 or more carbon atoms and 14 or less carbon atoms. Further, R ¹ is preferably a secondary alkyl group having 10 or more and 14 or less carbon atoms or a secondary alkenyl group having 10 or more and 14 or less carbon atoms, more preferably 10 or more carbon atoms. A secondary alkyl group of 14 or less. As the secondary alkyl group, from the same viewpoint, it is preferably a group represented by the following formula. With respect to R ¹ in the formula (1), from the same viewpoint, a secondary alkyl group represented by the formula is preferred.

Wherein R ¹¹ and R ¹² are each an alkyl group or an alkenyl group which may have a branch, preferably a linear alkyl group or an alkenyl group, more preferably a linear alkyl group, and a carbon number of R ¹¹ and R ¹² The total is 9 or more and 13 or less]

In the general formula (1), s is preferably 5 or more and 9 or less, and further, t is 5 or more and 9 or less. Specific examples of the nonionic surfactant of the formula (1) are preferably selected from the group consisting of polyoxyethylene (7) polyoxypropylene (8.5) and second to twelve from the viewpoint of easiness of acquisition. 1 of an alkyl ether, polyoxyethylene (7) polyoxypropylene (8.5)-second-tridecyl ether, polyoxyethylene (7) polyoxypropylene (8.5)-second-tetradecyl ether Kind or more than two. Here, () is the average addition mole number of ethylene oxide or propylene oxide.

In the formula (1), t/s is preferably 0.3 or more, more preferably 0.7 or more, still more preferably 0.9 or more, and is preferably 1.5 or less, more preferably 1.3 or less.

The compound of the formula (1) can be synthesized by using an alcohol having a branched alkyl group having 10 or more and 14 or less carbon atoms, preferably a secondary alcohol, or having a carbon number of 10 or more and 14 or less. The branched alkenyl alcohol, preferably a secondary alcohol, is added to the ethylene oxide to form propylene oxide.

The weight average molecular weight of the nonionic surfactant of the formula (1) is preferably 200 or more, and preferably 5,000 or less, more preferably 2,000 or less. Further, the weight average molecular weight of the compound of the formula (1) is preferably from 200 to 5,000, more preferably from 200 to 2,000, from the viewpoint of cleanability and low foaming property. The compound of the formula (1) can be obtained from Nippon Shokubai Co., Ltd. under the trade name "Softanol".

The content of the nonionic surfactant (I) in the liquid detergent composition of the present invention is preferably 0.3% by mass or more, more preferably from the viewpoint of further improvement of cleanability, low foaming property and blending property. It is 0.4% by mass or more, and preferably 0.7% by mass or less, more preferably 0.6% by mass or less. Further, for the same reason, the content of the nonionic surfactant (I) in the detergent composition is preferably from 0.3 to 0.7% by mass, more preferably from 0.3 to 0.6% by mass, still more preferably from 0.4 to 0.6% by mass.

The liquid detergent composition of the present invention preferably contains a selected from a fatty acid or a salt thereof and an alkene. One or more of succinic acid or a salt thereof.

The carbon number of the fatty acid is preferably 6 or more, more preferably 8 or more, and is preferably 12 or less, and more preferably 10 or less, from the same viewpoint. Further, the carbon number of the fatty acid is preferably from 6 to 12, more preferably from 8 to 10.

The carbon number of the alkenyl succinic acid is preferably 10 or more, more preferably 12 or more, and is preferably 16 or less, and more preferably 14 or less from the same viewpoint. Further, the number of carbon atoms of the alkenyl succinic acid is preferably from 10 to 16, more preferably from 12 to 14.

The salt of a fatty acid or an alkenyl succinic acid is preferably an alkali metal salt, more preferably a sodium salt or a potassium salt, from the viewpoint of availability, and further preferably from the viewpoint of scale adhesion inhibition. It is a potassium salt.

In the case of containing a fatty acid or a salt thereof and an alkenyl succinic acid or a salt thereof, the mass ratio of the fatty acid or a salt thereof to the content of the alkenyl succinic acid or a salt thereof, in terms of low foaming property, The salt/(alkenyl succinic acid or a salt thereof) is preferably 50/50 or more, more preferably 60/40 or more, still more preferably 67/33 or more, and still more preferably 99/1 or less, more preferably 90/10 or less, more preferably 80/20 or less. Further, the mass ratio of the content of the fatty acid or its salt to the alkenyl succinic acid or its salt is (yield of a fatty acid or its salt) / (alkenyl succinic acid or its salt) From the same viewpoint, it is preferably 50/50 to 99/1, more preferably 50/50 to 90/10, and even more preferably 67/33 to 80/20.

The total content of the fatty acid or a salt thereof and the alkenyl succinic acid or a salt thereof is preferably 0.5% by mass or more, and more preferably 0.75% by mass or more, from the viewpoint of low-temperature stability in the detergent composition. It is preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 1.5% by mass or less.

Further, the total content of the fatty acid or a salt thereof and the alkenyl succinic acid or a salt thereof is preferably from 0.5 to 5% by mass, more preferably from 0.75 to 3, in terms of low-temperature stability in the detergent composition. The mass% is more preferably 0.75 to 1.5% by mass.

Further, the content of the fatty acid or its salt and the alkenyl succinic acid or its salt are converted into an acid. The value.

In the liquid detergent composition of the present invention, the solvent, the dissolution aid, the dispersant, the pH adjuster, the tackifier, the viscosity adjuster, the fragrance, the colorant, and the anti-adhesion can be formulated within the range not impairing the object of the present invention. An oxidizing agent, a preservative, a suds suppressor, a bleaching agent, a bleach activator, and the like (excluding the components (A) to (C) and bismuth citrate).

The remaining component of the liquid detergent composition of the present invention is water. The content is the mass % relative to the total amount of the components including water unless otherwise specified.

The liquid detergent composition of the present invention is preferably a composition in which the essential components of the present invention and optional components are blended in the above amounts.

<potassium ion>

The liquid detergent composition of the present invention contains potassium ions from the viewpoints of scale adhesion inhibition, cleanability, tea scale adhesion inhibition, and low-temperature storage stability.

The potassium ion is preferably derived from the potassium salt of the component (A), the potassium salt of the component (B), the potassium salt of the component (C), or the potassium salt of the potassium citrate or the alkaline agent of any of the above components.

<sodium ion>

The liquid detergent composition of the present invention can contain sodium ions in such a manner that the molar ratio of the potassium ion content [K ⁺ ] becomes a specific range. That is, sodium ions can be arbitrarily contained. The liquid detergent composition of the present invention may contain potassium ions and sodium ions.

The sodium ion is preferably derived from the sodium salt of the component (A), the sodium salt of the component (B), the sodium salt of the component (C), or the sodium salt of the above sodium citrate or any of the above components.

<Morbi [Na ⁺ ] / [K ⁺ ]>

The content of the sodium ion content [Na ⁺ ] relative to the potassium ion of the liquid detergent composition of the present invention from the viewpoints of scale adhesion inhibition, cleanability, tea scale adhesion inhibition, blendability, and low-temperature storage stability [K ^+] the molar ratio of ^{[Na +] / [K +} ] is 0 or more and 0.9 or less.

Regarding the molar ratio [Na ⁺ ] of the content of sodium ions [Na ⁺ ] to the content of potassium ions [K ⁺ ] [Na ⁺ ] / [K ⁺ ], the scale adhesion inhibition property is further improved and the ease of obtaining the formulation components is obtained. In view of the above, it is preferably 0.1 or more, more preferably 0.2 or more, and still more preferably 0.25 or more, and from the viewpoint of further improving scale adhesion inhibition property and low-temperature storage stability, it is preferably 0.85 or less, more preferably 0.70 or less, more preferably 0.65 or less.

In addition, the molar ratio [Na ⁺ ]/[K ⁺ ] of the sodium ion content [Na ⁺ ] to the potassium ion content [K ⁺ ] is in terms of scale adhesion inhibition property, cleanliness, and tea scale adhesion inhibition property, From the viewpoint of blending property and low-temperature storage stability, it is preferably 0.1 to 0.9, more preferably 0.2 to 0.85, still more preferably 0.25 to 0.70, still more preferably 0.25 to 0.65.

The content of the potassium ion [K ⁺ ] in the liquid detergent composition of the present invention is a viewpoint of further improvement of scale adhesion inhibition property, cleanliness, tea scale adhesion inhibition property, blending property, and low-temperature storage stability, and a blending component. From the viewpoint of easiness of obtaining, it is preferably 1 mol/L or more, more preferably 1.5 mol/L or more, still more preferably 1.8 mol/L or more, and preferably 3 mol/L or less, more preferably 2.7 mol. Below /L, it is more preferably 2.4 mol/L or less.

The content of the sodium ion in the liquid detergent composition of the present invention [Na ⁺ ], the viewpoint of the improvement of scale adhesion inhibition property, cleanliness, tea scale adhesion inhibition property, blending property, and low-temperature storage stability, and the blending component From the viewpoint of easiness of obtaining, it is preferably 0.3 mol/L or more, more preferably 0.4 mol/L or more, still more preferably 0.6 mol/L or more, still more preferably 0.9 mol/L or more, still more preferably 1.2. The mol/L or more is preferably 3 mol/L or less, more preferably 2 mol/L or less, still more preferably 1.6 mol/L or less, still more preferably 1.3 mol/L or less.

<cleaning liquid>

The present invention provides a cleaning liquid obtained by diluting a liquid detergent composition for a dishwashing machine of the present invention with water, and the content of the component (A) in the cleaning liquid is 0.0017 mass% or more in terms of acid. 0.017 mass% or less. Water for dilution may be water having a German hardness of 2°dH or more and further 3°dH or more.

In the cleaning liquid of the present invention, the concentration corresponding to the dilution ratio or the like is described below in the description of the cleaning method described below. Further, the content of sodium ions in the cleaning solution of [Na ^+] with respect to the content of potassium ion [K ^+] The molar ratio of ^{[Na +] / [K +} ] and the liquid detergent composition of the present invention in the same manner as 0 or more and 0.9 or less.

The content of the component (A) in the cleaning liquid of the present invention is 0.0017 mass% or more, and more preferably 0.0065 mass% or more, from the viewpoint of further improving scale adhesion inhibition property and tea scale adhesion inhibition property. It is 0.017% by mass or less, and more preferably 0.0072% by mass or less.

The content of the component (B) in the cleaning liquid of the present invention is preferably 0.001255% by mass or more, more preferably 0.00475% by mass or more, and more preferably from the viewpoint of further improving the scale adhesion inhibiting property. It is 0.0125 mass% or less, more preferably 0.00525 mass% or less.

The content of the component (C) in the cleaning liquid of the present invention is preferably 0.001% by mass or more, more preferably 0.0038% by mass or more, from the viewpoint of further improving the cleanability and the scale adhesion inhibiting property. The viewpoint of further improving the scale adhesion inhibiting property is preferably 0.011% by mass or less, and more preferably 0.0042% by mass or less.

The content of the phthalate in the cleaning liquid of the present invention is preferably 0.0025% by mass or more from the viewpoint of further improving the cleanability, the adhesion inhibition property, the resistance to acid-aluminum corrosion, and the scale adhesion inhibition property. More preferably, it is 0.0095% by mass or more, and is preferably 0.025% by mass or less, more preferably 0.0105% by mass or less.

The cleaning liquid may also contain the above components and other components, and the preferred embodiment is also the same. Further, the cleaning liquid is preferably a composition in which the essential components and optional components of the present invention are blended at the above contents.

The present invention can provide a method for producing a liquid detergent composition, which comprises mixing water with (A) component, (B) component, (C) component, and silicate, wherein (A) component is converted into an acid. The ratio of the total blending component is preferably 0.0017 mass% or more, more preferably 0.0065 mass% or more, and is preferably 0.017 mass% or less, more preferably 0.0072 mass% or less, and the component (B) is converted into an acid. , based on the ratio of the total blending ingredients, preferably 0.00125 The amount is more than or equal to 0.00475% by mass, more preferably 0.0125% by mass or less, still more preferably 0.00525% by mass or less, and the component (C) is preferably 0.001% by mass or more based on the total blending component. More preferably, it is 0.0038 mass% or more, and is preferably 0.011 mass% or less, more preferably 0.0042 mass% or less, and the ceric acid salt is preferably 0.0025 mass% or more, more preferably 0.0095 mass, based on the ratio of the total compounding component. % or more, and preferably 0.025% by mass or less, more preferably 0.0105% by mass or less.

In the production method, as the component to be mixed, the above components and other components may be used, and preferred embodiments are also the same. Further, in the production method, water having a German hardness of 2° dH or more and further 3° dH or more may be used as the water.

<Cleaning method>

The liquid detergent composition of the present invention can be preferably used for cleaning using a tableware cleaning machine and further using a commercial tableware cleaning machine. The cleaning liquid of the present invention is preferably prepared from the liquid detergent composition of the present invention. The liquid detergent composition of the present invention is used as a cleaning liquid mixed with water when it is cleaned by a commercial tableware cleaner. At this time, the composition is transferred to the inside of the commercial dishwashing machine by the supply device in an arbitrary fixed amount while maintaining the concentration of the appropriate cleaning liquid. In the liquid detergent composition of the present invention, for example, a special tube for a commercial tableware cleaner is directly inserted into a container of plastic or the like filled with the composition, and the composition is sucked up and supplied. Thereafter, the cleaning liquid is supplied to the inside of the commercial dish cleaning machine.

The cleaning liquid of the present invention is usually preferably prepared by maintaining a fixed concentration in a storage box provided in the automatic cleaning machine.

According to the present invention, there is provided a cleaning method for cleaning dishes by an automatic cleaning machine using a cleaning liquid which utilizes water of the liquid detergent composition of the present invention to be preferably 200 times or more, more preferably 333. More than the mass, more preferably 400 times the mass In the above, it is more preferably 455 times by mass or more, more preferably 476 times by mass or more, and is preferably 2,000 times by mass or less, more preferably 1,000 or less, from the viewpoints of scale adhesion inhibitory property, cleanability, and tea scale adhesion inhibiting property. The mass is less than 769 mass times, more preferably 667 mass times or less, more preferably 556 mass times or less, and more preferably diluted to a dilution ratio of 526 times or less. The cleaning method may include a step of preparing a cleaning liquid by diluting the liquid detergent composition of the present invention by using water to be the above-described dilution ratio, and a step of cleaning the tableware by an automatic cleaning machine using the cleaning liquid.

The concentration in the cleaning liquid at the time of use of the liquid detergent composition of the present invention is preferably 0.05% by mass or more, from the viewpoint of further improving the scale adhesion inhibiting property, the cleanability, and the tea scale adhesion inhibiting property. It is preferably 0.10% by mass or more, more preferably 0.13% by mass or more, more preferably 0.15% by mass or more, still more preferably 0.18% by mass or more, still more preferably 0.19% by mass or more, and more preferably 0.5% by mass or less, more preferably It is 0.30% by mass or less, more preferably 0.25 mass% or less, still more preferably 0.22% by mass or less, still more preferably 0.21% by mass or less.

In addition, the content of the component (A) in the cleaning liquid used in the cleaning method of the present invention is preferably 0.0017 mass% or more and 0.017% mass% or less in terms of acid.

In addition, the cleaning time is preferably 10 seconds or longer, more preferably 20 seconds or longer, more preferably 30 seconds or longer, from the viewpoint of further improvement in cleanability, and is preferable from the viewpoint of work efficiency. It is 3 minutes or less, more preferably 2 minutes or less, and still more preferably 1 minute or less.

The cleaning temperature of the cleaning liquid is preferably 40° C. or higher, more preferably 50° C. or higher, from the viewpoint of further improvement in productivity and cleanability, and is preferably 80° C. or less from the viewpoint of cleanability. More preferably, it is 70 ° C or less.

After the tableware is cleaned, it is usually quickly washed with water, warm water or hot water, for example, hot water of 70 ° C or higher and 90 ° C or lower for 5 seconds or more and 15 seconds or less in the same commercial tableware cleaning machine.

The cleaning agent of the invention has a hardness of 2°dH or more or a hardness of 3°dH or more in Germany. The high hardness water can also be used as a cleaning liquid preparation and/or washing water. That is, in the cleaning method of the present invention, the liquid detergent composition of the present invention can be mixed with water having a German hardness of 2° dH or more or a German hardness of 3° dH or more to prepare a cleaning liquid. Further, the cleaning method of the present invention can be carried out using water having a German hardness of 2 ° dH or more.

Commercial tableware cleaners typically use the cleaning fluid over the pump cycle.

In the case of cleaning the tableware by the commercial tableware cleaning machine, the cleaning liquid is brought out by the tableware or the washing water is carried-over to the storage tank of the cleaning liquid, etc., and as the number of cleaning times increases, the cleaning is performed. The concentration of the cleaning liquid (ie, the cleaning liquid used for cleaning) in the liquid storage tank is lowered. When the concentration of the cleaning liquid is lowered, an appropriate amount of the liquid detergent composition is supplied to the storage tank of the cleaning liquid by the automatic supply device so that the concentration of the cleaning liquid is maintained within an appropriate range.

The automatic supply device for the liquid detergent composition is not limited, and the concentration of the cleaning liquid is sensed, and the signal is received and controlled. The liquid composition of the present invention is such that the tube pump is driven to supply the necessary amount of liquid detergent composition.

The automatic feeding device can be preferably used for a commercial cleaning machine with a very large number of cleaning times per day, and if an automatic feeding device is used, it has the advantage of being labor-saving compared with the hand-input for each cleaning, and further, if The use of an automatic supply device has the advantage that it is easy to maintain the concentration of the cleaning liquid within an appropriate concentration range within one day (cleaning).

The cleaning method of the tableware of the present invention includes the following method (hereinafter referred to as the method 1), that is, the automatic use of the storage mechanism provided with the cleaning liquid and the mechanism for contacting the cleaning liquid contained in the storage mechanism with the tableware a cleaning method for cleaning a tableware of a cleaning machine, wherein the cleaning liquid is any one of the cleaning liquids of the present invention, and the cleaning liquid after contact with the tableware is circulated to the storage mechanism, and the cleaning liquid contained in the storage mechanism is The conductivity is used as an index to supply a thick composition to control the concentration of the cleaning liquid.

Generally, an automatic cleaning machine, in particular, an automatic cleaning machine for commercial use, has a storage mechanism for a cleaning liquid, and a mechanism for bringing the cleaning liquid contained in the storage unit into contact with the tableware. clean The liquid accommodating mechanism is sometimes referred to as, for example, a cleaning liquid tank, a cleaning liquid tank, or the like. Further, the mechanism for bringing the cleaning liquid accommodated in the storage unit into contact with the dishes may include a cleaning liquid transfer mechanism (tube or the like) and an application mechanism (a head or the like) of the cleaning liquid to the dishes. Further, the mechanism for contacting the cleaning liquid contained in the storage mechanism with the dishes may include a defined space (sometimes referred to as a clean room or the like) for bringing the cleaning liquid into contact with the dishes. In the method 1, it is preferable to supply the liquid detergent composition of the present invention to the cleaning liquid contained in the storage means by using the conductivity of the cleaning liquid as an index, and to control the concentration of the cleaning liquid so as to maintain the set concentration.

According to the present invention, there is provided a cleaning method for a tableware, which comprises supplying a liquid detergent composition for a dish cleaning machine of the present invention to a cleaning liquid tank of an automatic tableware cleaning machine, mixing the composition and water, and preparing the liquid in a cleaning liquid tank. The content of the component (A) is converted into a cleaning liquid having an acid content of 0.0017 mass% or more and 0.017 mass% or less, and the tableware is cleaned using the cleaning liquid.

In the above embodiment, the present invention discloses the following liquid detergent composition for a dish cleaning machine, a cleaning liquid, a cleaning method for tableware, and use.

<item 1>

A liquid detergent composition for a dishwashing machine comprising a bismuth citrate and comprising the following components (A), (B), (C) and water: (A) component: methylglycine Diacetic acid, glutamic acid diacetic acid or the like (B) component: citric acid or a salt thereof (C) component: polyacrylic acid or a salt thereof, and the content of the component (A) is 2.0% by mass or more in terms of acid. 5% by mass or less, the content of the component (B) is 1.5% by mass or more and 5.4% by mass or less, and the content of the citrate is 2.5% by mass or more and 7.4% by mass or less, and the liquid detergent combination for the dishwashing machine contains potassium ions and optionally containing sodium ions, the content of sodium ions [Na ^+] with respect to the content of potassium ion [K ^+] the molar ratio of ^{[Na +] / [K +} ] is 0 or more and 0.9 or less.

<item 2>

The detergent composition for dishwashing machine according to <1>, wherein the mass ratio (A)/(B) of the component (A) to the acid content of the component (B) is 0.65 or more and 1.9 or less.

<item 3>

The liquid detergent composition for a dishwashing machine according to any one of the items 1 to 2, wherein the component (B) is converted into a mass ratio of the content of the acid to the content of the component (C) (B) ) / (C) is 0.5 or more and 2.5 or less.

<item 4>

The liquid detergent composition for a dishwashing machine according to any one of the items 1 to 3, wherein the component (A) is converted into a mass ratio of the content of the acid to the content of the component (C) (A) ) / (C) is 0.7 or more and 3.4 or less.

<item 5>

The liquid detergent composition for a dishwashing machine according to any one of the items 1 to 4, wherein the component (A) is converted into an acid content, and the component (B) is converted into an acid content and ( The total content of the component C) is 6.0% by mass or more and 12.0% by mass or less.

<Item 6>

The liquid detergent composition for a dishwashing machine according to any one of the items 1 to 5, wherein the pH of the 0.2% by mass aqueous dilution at 25 ° C is 9 or more.

<item 7>

The liquid detergent composition for a dishwashing machine according to any one of <1> to <6>, wherein a molar ratio of sodium ion content [Na ⁺ ] to potassium ion content [K ⁺ ] is [ Na ⁺ ] / [K ⁺ ] is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.25 or more, and is preferably 0.85 or less, more preferably 0.70 or less, still more preferably 0.65 or less.

<item 8>

The liquid detergent composition for a dishwashing machine according to any one of the above items, wherein the content of the component (A) is converted into an acid, and is preferably 2.6% by mass in the liquid detergent composition. More preferably, it is 3.3 mass% or more, more preferably 3.6 mass% or more, more preferably 4.2 mass% or more, and preferably 4.7 mass% or less, more preferably 4.0 mass% or less, still more preferably 3.6 mass% or less. Further, the content of the component (A) is preferably 2.6 to 5.0% by mass, more preferably 3.3 to 5.0% by mass, still more preferably 3.3 to 4.7% by mass, more preferably in the liquid detergent composition. 3.3 to 4.0% by mass, more preferably 3.3 to 3.6% by mass.

<item 9>

The liquid detergent composition for a dishwashing machine according to any one of the above items, wherein the content of the citric acid or the salt thereof of the component (B) is preferably 2.5 in the detergent composition. More preferably, it is 3.0% by mass or more, more preferably 3.5% by mass or more, more preferably 4.5% by mass or more, and preferably 5.2% by mass or less, and further, the content of the component (B) is in the liquid detergent composition. The amount is preferably 2.5 to 5.4% by mass, more preferably 2.5 to 5.2% by mass, still more preferably 3.0 to 5.2% by mass, still more preferably 3.5 to 5.2% by mass, still more preferably 4.5 to 5.2% by mass, and further, (B) The content of the component is from 1.5 to 5.4% by mass, preferably from 1.5 to 5.2% by mass, more preferably from 1.5 to 4.5% by mass, still more preferably from 1.5 to 3.5% by mass.

<item 10>

The liquid detergent composition for a dishwashing machine according to any one of the above-mentioned item, wherein the content of the polyacrylic acid or the salt thereof of the component (C) is preferably 0.8 mass in the detergent composition. More preferably, it is 1.8% by mass or more, more preferably 2.5% by mass or more, more preferably 3.5% by mass or more, still more preferably 4.5% by mass or more, and more preferably 5.5% by mass or less, still more preferably 2.8% by mass. More preferably, it is 2.2% by mass or less, and the content of the component (C) is preferably 0.8 to 5.5% by mass, more preferably 1.8 to 5.5% by mass, still more preferably 2.5 to 5.5% by mass, still more preferably 3.5 to 5% by mass. 5.5% by mass, more preferably 4.5 to 5.5% by mass, and the content of the component (C) is preferably 0.8 to 5.5% by mass, more preferably 0.8 to 2.8% by mass, still more preferably 1.8 to 2.8% by mass, more preferably It is 1.8 to 2.2% by mass.

<item 11>

The liquid detergent composition for a dishwashing machine according to any one of the items 1 to 3, wherein the component (A) is converted into an acid content, and the component (B) is converted into an acid content and ( The total content of the component C) is more preferably 6.5 mass% or more, more preferably 7.0 mass% or more, still more preferably 7.5% by mass or more, and preferably 12.0 mass% or less, more preferably 11.5% by mass or less, more preferably It is 10% by mass or less, more preferably 9.5 mass% or less, still more preferably 9% by mass or less, still more preferably 8.5 mass% or less.

<item 12>

The liquid detergent composition for a dishwashing machine according to any one of the preceding claims, wherein the bismuth citrate is preferably an alkali metal ruthenate, and further preferably selected from the group consisting of citric acid No. 1 One or more of the salts of the salt, the No. 2 citrate, the No. 3 citrate and the No. 4 citrate, more preferably selected from the group consisting of No. 1 citrate, No. 2 citrate and 3 One or more of the citrates of the citrate are more preferably one or more citrates selected from the group consisting of citrate No. 1 and bismuth citrate No. 2, more preferably selected And one or more of the citrates of the citrate No. 1 and the citrate are preferably one or more selected from the group consisting of potassium citrate and sodium citrate, and more preferably One or more alkali metal silicates selected from the group consisting of sodium citrate No. 1 and potassium citrate No. 1 are preferably sodium citrate No. 1, and further preferably potassium citrate No. 1.

<item 13>

The liquid detergent composition for a dishwashing machine according to any one of the items of the present invention, wherein the content of the ceric acid salt is preferably 3% by mass or more, more preferably 4% by mass or more, and preferably 7% by mass or less, more preferably 6% by mass or less.

<item 14>

The liquid detergent composition for a dishwashing machine according to any one of the items 1 to 3, wherein the alkali agent other than the bismuth acid salt is selected from the group consisting of alkali metal hydroxides and alkali metal carbonates. One or more alkaline agents, preferably selected from the group consisting of potassium hydroxide and hydrogen hydroxide One or two or more kinds of alkali chemicals of sodium, potassium carbonate and sodium carbonate are more preferably one or more selected from the group consisting of potassium hydroxide and sodium hydroxide, and selected from potassium carbonate and sodium carbonate. One type or two or more types are more preferably potassium hydroxide and potassium carbonate.

<Item 15>

The liquid detergent composition for a dishwashing machine according to the item [1], wherein the total content of the bismuth salt and the alkali agent other than the bismuth citrate is preferably 10% by mass or more in the liquid detergent composition. It is preferably 15% by mass or more, and more preferably 25% by mass or less, and still more preferably 20% by mass or less.

<Item 16>

The liquid detergent composition for a dishwashing machine according to any one of the above-mentioned items, wherein the pH of the 0.2% by mass water dilution solution at 25 ° C is preferably 9 or more, more preferably 9.5. The above is more preferably 10 or more, still more preferably 10.5 or more, and is preferably 12 or less, more preferably 11.5 or less.

<item 17>

The liquid detergent composition for a dishwashing machine according to any one of the above-mentioned items, wherein the alcohol-containing detergent composition having a branched carbon number of 10 or more and 14 or less has a block type. One or two or more kinds of nonionic surfactants (hereinafter referred to as nonionic surfactants (I)) of ethylene oxide and propylene oxide are bonded to each other.

<Item 18>

The liquid detergent composition for a dishwashing machine according to <17>, wherein the average addition molar number of the ethylene oxide of the nonionic surfactant (I) is preferably 4 or more, more preferably 4.5 or more. More preferably, it is 5 or more, and is preferably 10 or less, more preferably 9 or less, still more preferably 8 or less.

<Item 19>

The liquid detergent composition for a dishwashing machine according to any one of the items <1>, wherein the average addition mole number of the propylene oxide of the nonionic surfactant (I) is It is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, still more preferably 5 or more, and more preferably 10 or less, more preferably 9.5 or less, still more preferably 9 or less.

<item 20>

The liquid detergent composition for a dishwashing machine according to any one of the items of the present invention, wherein the content of the nonionic surfactant (I) is preferably 0.3% by mass in the liquid detergent composition. More preferably, it is 0.4% by mass or more, and preferably 0.7% by mass or less, more preferably 0.6% by mass or less, and further, the content of the nonionic surfactant is preferably 0.3 to 0.7 by mass in the liquid detergent composition. % is more preferably 0.3 to 0.6% by mass, still more preferably 0.4 to 0.6% by mass.

<Item 21>

The liquid detergent composition for a dishwashing machine according to any one of the above-mentioned item, which contains one or more selected from the group consisting of a fatty acid or a salt thereof and an alkenyl succinic acid or a salt thereof. .

<Item 22>

The liquid detergent composition for a dishwashing machine according to the invention, wherein the carbon number of the fatty acid is preferably 6 or more, more preferably 8 or more, and is preferably 12 or less, more preferably 10 or less, and further, fatty acid. The carbon number is preferably from 6 to 12, more preferably from 8 to 10.

<item 23>

The liquid detergent composition for a dishwashing machine according to the invention, wherein the alkenyl succinic acid has a carbon number of preferably 10 or more, more preferably 12 or more, and preferably 16 or less. Preferably, the number of carbon atoms of the alkenyl succinic acid is from 10 to 16, more preferably from 12 to 14.

<item 24>

A liquid detergent composition for a dishwashing machine according to any one of the above-mentioned items, comprising a fatty acid or a salt thereof, an alkenyl succinic acid or a salt thereof, and a fatty acid or a salt thereof and an alkenyl amber The mass ratio of the content of the acid or its salt is converted into an acid to (fatty acid or The salt) / (alkenyl succinic acid or a salt thereof) is preferably 50/50 or more, more preferably 60/40 or more, still more preferably 67/33 or more, and further preferably 99/1 or less, more preferably 90/. 10 or less, more preferably 86/14 or less, more preferably 80/20 or less, further containing a fatty acid or a salt thereof and an alkenyl succinic acid or a salt thereof, and a fatty acid or a salt thereof and an alkenyl succinic acid or a salt thereof The mass ratio is preferably 50/50 to 99/1, more preferably 50/50 to 90/10, still more preferably 60/40, based on (fatty acid or a salt thereof) / (alkenyl succinic acid or a salt thereof). ~86/14, more preferably 67/33~80/20.

<Item 25>

The liquid detergent composition for a dishwashing machine according to any one of the above-mentioned items, wherein the total content of the fatty acid or a salt thereof and the alkenyl succinic acid or a salt thereof is converted into an acid, preferably 0.5. More preferably, the mass is at least 0.75% by mass, more preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 1.5% by mass or less, and further, a fatty acid or a salt thereof and an alkenyl succinic acid or the same The total content of the salt is converted into an acid, preferably 0.5 to 5% by mass, more preferably 0.75 to 3% by mass, still more preferably 0.75 to 1.5% by mass.

<Item 26>

A liquid detergent composition for a dishwashing machine according to any one of <1> to <25> which is diluted with water, and the component (A) in the cleaning liquid The content is converted into an acid of 0.0017% by mass or more and 0.017% by mass or less.

<item 27>

In the cleaning liquid according to the above item, the content of the component (A) in the cleaning liquid is preferably 0.0034% by mass or more, more preferably 0.0040% by mass or more, even more preferably 0.0044% by mass or more, more preferably converted to an acid. It is preferably 0.0051% by mass or more, more preferably 0.0061% by mass or more, still more preferably 0.0065% by mass or more, and more preferably 0.010% by mass or less, still more preferably 0.009% by mass or less, still more preferably 0.0085% by mass or less, more preferably It is 0.0075 mass% or less, more preferably 0.0072 mass% or less.

<Item 28>

The cleaning liquid according to any one of <26> or <27>, wherein the cleaning liquid is in the cleaning liquid The content of the component (B) is preferably 0.001255% by mass or more, more preferably 0.0025% by mass or more, even more preferably 0.0030% by mass or more, even more preferably 0.00325% by mass or more, and still more preferably 0.00375% by mass or more. More preferably, it is 0.0045 mass% or more, more preferably 0.00475 mass% or more, and is preferably 0.0125 mass% or less, more preferably 0.011 mass% or less, still more preferably 0.010 mass% or less, still more preferably 0.009 mass% or less. More preferably, it is 0.0075 mass% or less, more preferably 0.0070 mass% or less, still more preferably 0.00625 mass% or less, still more preferably 0.0060 mass% or less, still more preferably 0.0055 mass% or less, still more preferably 0.00525 mass% or less.

<Item 29>

The cleaning liquid according to any one of the above-mentioned items, wherein the content of the component (C) in the cleaning liquid is preferably 0.001% by mass or more, more preferably 0.0016% by mass or more, and still more preferably 0.0020%. The mass% or more is more preferably 0.0026% by mass or more, more preferably 0.0030% by mass or more, still more preferably 0.0036% by mass or more, still more preferably 0.0038% by mass or more, and still more preferably 0.011% by mass or less, still more preferably 0.010% by mass. % or less is more preferably 0.009% by mass or less, still more preferably 0.007% by mass or less, still more preferably 0.005% by mass or less, still more preferably 0.0044% by mass or less, still more preferably 0.0042% by mass or less.

<item 30>

The cleaning liquid according to any one of the above-mentioned items, wherein the content of the ceric acid salt in the cleaning liquid is preferably 0.0025 mass% or more, more preferably 0.005 mass% or more, still more preferably 0.006 mass. More preferably, it is 0.0065 mass% or more, more preferably 0.0075 mass% or more, more preferably 0.0080 mass% or more, still more preferably 0.009 mass% or more, more preferably 0.0095% by mass or more, and preferably 0.025% by mass. The amount is more preferably 0.015% by mass or less, more preferably 0.014% by mass or less, still more preferably 0.0125% by mass or less, still more preferably 0.012% by mass or less, still more preferably 0.0110% by mass or less, still more preferably 0.0105% by mass or less.

<item 31>

A liquid detergent composition for a dishwashing machine according to any one of the items 1 to 2, which is preferably 200 mass times or more, more preferably 333 mass times or more. More preferably, it is 400 mass times or more, more preferably 455 mass times or more, more preferably 476 mass times or more, and more preferably 2,000 mass times or less, more preferably 1000 mass times or less, and even more preferably 769 mass times or less. More preferably, it is diluted by 667 mass times or less, more preferably 556 mass times or less, more preferably 526 mass times or less.

<item 32>

A cleaning method for a tableware according to any one of the items 1 to 2, wherein the liquid detergent composition for a dishwashing machine is supplied to a cleaning liquid tank of an automatic tableware cleaning machine, and the composition is mixed with Water is used to prepare a cleaning liquid having a content of the component (A) of 0.0017 mass% or more and 0.017 mass% or less in a cleaning liquid tank, and the tableware is cleaned using the cleaning liquid.

<Item 33>

The cleaning method of the tableware according to the item [32], wherein the content of the component (A) in the cleaning liquid is preferably 0.0034% by mass or more, more preferably 0.0040% by mass or more, and still more preferably 0.0044% by mass or more. More preferably, it is 0.0051% by mass or more, more preferably 0.0061% by mass or more, still more preferably 0.0065% by mass or more, and more preferably 0.010% by mass or less, still more preferably 0.009% by mass or less, still more preferably 0.0085% by mass or less. More preferably, it is 0.0075 mass% or less, more preferably 0.0072 mass% or less.

<item 34>

The method for cleaning a tableware according to any one of the above items, wherein the content of the component (B) in the cleaning liquid is converted into an acid, preferably 0.00125 mass% or more, more preferably 0.0025 mass%. The above is more preferably 0.0030% by mass or more, more preferably 0.00325% by mass or more, still more preferably 0.00375% by mass or more, still more preferably 0.0045% by mass or more, still more preferably 0.00475% by mass or more, and still more preferably 0.0125% by mass or less. More preferably, it is 0.011 mass% or less, more preferably 0.010 mass% or less, still more preferably 0.009 mass% or less, more preferably 0.0075 mass% or less, more preferably 0.0070 mass% or less, more preferably 0.00625 mass% or less, still more preferably 0.0060 mass% or less, still more preferably 0.0055 mass% or less, still more preferably 0.00525 mass% or less.

<Item 35>

The method for cleaning a tableware according to any one of the above-mentioned items, wherein the content of the component (C) in the cleaning liquid is preferably 0.001% by mass or more, more preferably 0.0016% by mass or more, more preferably It is 0.0020% by mass or more, more preferably 0.0026% by mass or more, more preferably 0.0030% by mass or more, still more preferably 0.0036% by mass or more, still more preferably 0.0038% by mass or more, and further preferably 0.011% by mass or less, more preferably It is 0.010% by mass or less, more preferably 0.009% by mass or less, more preferably 0.007% by mass or less, still more preferably 0.005% by mass or less, still more preferably 0.0044% by mass or less, still more preferably 0.0042% by mass or less.

<Item 36>

The method for cleaning a tableware according to any one of the items of the present invention, wherein the content of the citrate in the cleaning liquid is preferably 0.0025 mass% or more, more preferably 0.005 mass% or more, more preferably 0.006 mass% or more, more preferably 0.0065 mass% or more, more preferably 0.0075 mass% or more, still more preferably 0.0080 mass% or more, still more preferably 0.009 mass% or more, more preferably 0.0095% by mass or more, and preferably 0.025 mass%. The mass % or less is more preferably 0.015% by mass or less, more preferably 0.014% by mass or less, still more preferably 0.0125% by mass or less, still more preferably 0.012% by mass or less, still more preferably 0.0110% by mass or less, still more preferably 0.0105% by mass. the following.

<item 37>

A cleaning method for a tableware according to any one of the items 1 to 2, wherein the liquid detergent composition for a dishwashing machine is supplied to a cleaning liquid tank of an automatic tableware cleaning machine, and the composition is mixed with The water is preferably 200 mass times or more, more preferably 333 mass times or more, more preferably 400 mass times or more, still more preferably 455 mass times or more, more preferably 476 mass times or more, and more preferably 2000 mass times. The following, more preferably 1000 mass times or less, more Preferably, the cleaning liquid is prepared in the cleaning liquid tank at a dilution ratio of 769 mass times or less, more preferably 667 mass times or less, more preferably 556 mass times or less, more preferably 526 mass times or less, and the tableware is cleaned using the cleaning liquid.

<item 38>

The method for cleaning a tableware according to any one of the above items, wherein the composition is made of water having a hardness of 2°dH or more or a German hardness of 3°dH or more and a German hardness of 4°dH or more. mixing.

<item 39>

The use of the liquid detergent composition for a dishwashing machine according to any one of the items 1 to 2, which is used as a liquid detergent for a dishwashing machine.

Example

The following examples are illustrative of the practice of the invention. The examples are intended to be illustrative of the invention and are not intended to limit the invention.

With respect to the liquid detergent composition described in Tables 1 to 4, the scale adhesion inhibitory property (1), the scale adhesion inhibitory property (2), the scale adhesion inhibitory property (3), the cleanability, and the tea scale adhesion were evaluated by the following methods. Inhibition, formulation, and low temperature storage stability, the results are shown in Tables 1-4. Further, the pH of the 0.2% by mass water-diluted aqueous solution at 25 ° C was measured by JIS K 3362, and is shown in Tables 1 to 4.

Further, the preparation methods of the liquid detergent compositions of the blending compositions shown in Examples 1 to 19 and Comparative Examples 1 to 18 are as follows.

<Preparation method of liquid detergent composition> Examples 1 to 15, Comparative Examples 1, 2, 5, 6, and 17

The blending amount was calculated in such a manner that the total amount of each component became 500 g. The compositions were placed in a 500 mL beaker in the following order. The mixture was mixed at a number of revolutions of 200 (rpm/min) using a stirrer (manufactured by TOKYO DRIKAKIKAI, model Z-2200) and a stirring blade (three blades: 4 cm in diameter). Furthermore, the temperature at the time of preparation considers the exotherm generated by the neutralization heat at 25 ° C to Adjust the range of 35 °C.

Ion-exchanged water, potassium hydroxide, octanoic acid (Lunac 8-98), alkenyl succinic acid (Latemul DSK), and a nonionic surfactant (Softanol EP7085) were added and mixed until homogeneously dissolved. Thereafter, potassium carbonate, sodium citrate No. 1 and sodium polyacrylate (Sokalan PA25CL-FR) were added and mixed until homogeneously dissolved. Thereafter, MGDA (methyl glycine diacetic acid) and citric acid were added and mixed until homogeneously dissolved to obtain a liquid detergent composition.

Example 16, Comparative Example 3, 4

A liquid detergent composition was prepared in the same manner as in Example 1 except that GLDA (glutamate diacetic acid) was used in the same manner as in the above-mentioned addition period instead of MGDA.

Examples 17, 18

A liquid detergent composition was prepared in the same manner as in Example 1 except that sodium citrate No. 1 or potassium citrate No. 1 described in the table was used instead of sodium citrate No. 1 in the same addition period.

Example 19

In the same addition period, potassium polyacrylate described in the table was used instead of sodium polyacrylate, and in addition, potassium citrate No. 1 described in the table was used instead of sodium citrate No. 1 in the same addition period, and the same was carried out. Example 1 A liquid detergent composition was prepared in the same manner.

Comparative Example 7

A liquid detergent composition was prepared in the same manner as in Example 1 except that EDTA (ethylenediaminetetraacetic acid) was used instead of MGDA in the same manner.

Comparative Example 8

A liquid detergent composition was prepared in the same manner as in Example 1 except that citric acid was not prepared.

Comparative Example 9

A liquid detergent composition was prepared in the same manner as in Example 1 except that malic acid was used instead of citric acid in the same addition period.

Comparative Example 10

A liquid detergent composition was prepared in the same manner as in Example 1 except that gluconic acid was used instead of citric acid in the same addition period.

Comparative Example 11

A liquid detergent composition was prepared in the same manner as in Example 1 except that succinic acid was used instead of citric acid in the same addition period.

Comparative Example 12

A liquid detergent composition was prepared in the same manner as in Example 1 except that trisodium citrate was used in place of citric acid in the same addition period.

Comparative Examples 13, 14

A liquid detergent composition was prepared in the same manner as in Example 1 except that potassium hydroxide or sodium hydroxide in an amount described in the table was used instead of potassium hydroxide in the same addition period.

Comparative Examples 15, 16

A liquid detergent composition was prepared in the same manner as in Example 1 except that potassium carbonate or sodium carbonate in an amount described in the table was used instead of potassium carbonate in the same addition period.

Comparative Example 18

A liquid detergent composition was prepared in the same manner as in Example 1 except that sodium polyacrylate (Sokalan PA25CL-FR) was not used.

As described above, in order to form a neutralizing salt of octanoic acid (Lunac8-98), citric acid, malic acid, gluconic acid or succinic acid, potassium hydroxide or sodium hydroxide determines the blending amount in consideration of the AV equivalent. Further, the remainder of the unneutralized amount of potassium hydroxide or sodium hydroxide in the composition was 4.8% by mass.

<scale adhesion inhibition (1)>

The cleaning liquid prepared by the detergent composition of the watch is filled with a cleaning liquid tank (38L) of a commercial tableware cleaning machine (Sanyo Electric SANYO DR53). The conditions of the cleaning temperature of 70 ° C, the cleaning time of 40 seconds, the washing temperature of 80 ° C, and the washing time of 6 seconds were set to one cycle (70 seconds). Continuous operation of 500 cycles (about 10 hours) was carried out. The cleaning liquid was prepared by diluting the detergent composition to 500 times by mass with water so that the concentration of the detergent composition in the cleaning liquid became 0.2% by mass. Further, the dish cleaning machine is controlled such that the concentration of each component of the cleaning liquid contained in the cleaning liquid tank during cleaning is fixed.

Moreover, hard water adjusted to 10000 ° dH (German hardness) by using calcium chloride is added to water used for preparation and washing of the cleaning liquid, and the hardness in the operation of the above-mentioned dish cleaning machine is 1 to 7 ° dH, Adjusted in units of 0.5°dH.

Each of the hardness waters was used for 500 cycles, and after the operation was completed, the degree of adhesion of the scale in the side walls of the clean room and the filter was visually determined. The upper limit hardness which inhibits the adhesion of scale is shown in the table as the hardness resistance (°dH). The higher the hardness resistance, the higher the effect of inhibiting scale adhesion.

Here, the scale-inhibiting system has a state in which it has no discoloration or deterioration, and has a gloss equivalent to that in the initial stage, or a slight discoloration, but does not adhere to scale, and has a luster state. Further, when scale is adhered, the gloss disappears and the surface becomes rough.

Further, the content of the component (A) in the cleaning liquid is converted into an acid as follows.

Example 1, 19: 0.0046% by mass

Example 2: 0.0060% by mass

Example 3, 6~18: 0.0068 mass%

Example 4: 0.0076 mass%

Example 5: 0.0090% by mass

Comparative Example 1, 3: 0.0030% by mass

Comparative Example 2: 0.0106% by mass

Comparative Example 4: 0.0104% by mass

Comparative Example 5, 6, 8~18: 0.0068 mass%

Comparative Example 7: 0% by mass

<scale adhesion inhibition (2)>

In the same manner as the above-described scale adhesion inhibitory property (1), the detergent composition was diluted to 670 times by mass with water to prepare a cleaning liquid, in a manner that the concentration of the detergent composition in the cleaning liquid was 0.15% by mass. Evaluation.

Further, the content of the component (A) in the cleaning liquid is converted into an acid as follows.

Example 1, 19: 0.00345% by mass

Example 2: 0.0045% by mass

Example 3, 6~18: 0.0051% by mass

Example 4: 0.0057% by mass

Example 5: 0.00675 mass%

Comparative Example 1, 3: 0.00225 mass%

Comparative Example 2: 0.00795 mass%

Comparative Example 4: 0.0078% by mass

Comparative Example 5, 6, 8~18: 0.0051% by mass

Comparative Example 7: 0% by mass

<scale adhesion inhibition (3)>

In the same manner as the above-described scale adhesion inhibitory property (1), the detergent composition was diluted to 1000 times by mass with water to prepare a cleaning liquid, and the concentration of the detergent composition in the cleaning liquid was 0.1% by mass. Evaluation.

Further, the content of the component (A) in the cleaning liquid is converted into an acid as follows.

Example 1, 19: 0.0023% by mass

Example 2: 0.0030% by mass

Example 3, 6~18: 0.0034% by mass

Example 4: 0.0038% by mass

Example 5: 0.0045% by mass

Comparative Example 1, 3: 0.0015% by mass

Comparative Example 2: 0.0053 mass%

Comparative Example 4: 0.0052% by mass

Comparative Example 5, 6, 8~18: 0.0034% by mass

Comparative Example 7: 0% by mass

<cleanliness>

For a porcelain dish having a peripheral wall having an inner diameter of 200 mm and a height of 30 mm, 2 g of egg yolk colored by a red pigment as a sample stain was uniformly applied at a central portion of a radius of 7 cm. Thereafter, drying was carried out at 80 ° C / 30 minutes, and 4 pieces of porcelain plates for evaluation were prepared. They are placed in a door type commercial tableware cleaning machine (made by Sanyo Electric Co., Ltd., SANYO DR53). The cleaning liquid tank (38L) of the cleaning machine was filled with a cleaning liquid having a concentration of 0.15 mass% of the detergent composition prepared from the detergent composition of the table (wherein diluted with water having a German hardness of 4 ° dH). The cleaning was carried out under the conditions of a cleaning temperature of 50, a cleaning time of 40 seconds, a washing temperature of 80 ° C, and a washing time of 10 seconds. Further, the dish cleaner is controlled such that the concentration of the cleaning liquid accommodated in the cleaning liquid tank during cleaning is fixed. After the cleaned porcelain dish was taken out, it was dried in a room adjusted to 25 ° C ± 5 ° C, and the area of the sample stain remaining in the 7 cm radius of the center portion of the porcelain plate was determined by image processing. The area of the sample stain remaining after the determination is set as the area after the test, and the area before the test is set to the area of the circle having a radius of 7 cm (the area of the center portion to which the stain is applied), by the formula [[(before the test) Area - area after test / (area before test)] × 100] The cleaning rate (%) was determined. The average of the four pieces is shown in Tables 1 to 4.

In addition, the content of the component (A) in the cleaning liquid is converted into an acid, which is the same as the above-described scale adhesion inhibitory property (2).

<tea scale adhesion inhibition>

The liquid detergent composition was put into a commercial type tableware cleaning machine [manufactured by Sanyo Electric Co., Ltd., SANYO DR53]. The cleaning machine is continuously operated at a cleaning temperature of 60 ° C, a detergent composition concentration of 0.15 mass% in the cleaning liquid, a cleaning time of 40 seconds, a washing temperature of 80 ° C, a washing time of 10 seconds, and a water quantity of 2 L per washing. Run 50 times. During the test, the concentration of the detergent composition in the cleaning liquid was adjusted without deviation. After the adjustment, the tea scale adhesion inhibition test was carried out in the following manner. From the start of self-cleaning to the end of cleaning, set the sample stain (casein Ca salt) in the cleaning tank (38L).

(cleaning conditions)

‧ Cleaning temperature: 60 ° C

‧ detergent composition concentration: 0.15 mass%

‧ Cleaning time: 40 seconds

‧ Washing temperature: 80 ° C

‧ Washing time: 10 seconds

‧Water volume per wash: 2L

‧The hardness of clean water: German hardness 2°dH

‧Sample stains in the cleaning tank: Casein Ca salt

[Method of putting sample stains into the cleaning tank]

As a sample of the casein Ca salt, albumin (derived from Egg, Wako Pure Chemical Industries, Ltd.: reagent) was continuously supplied from the beginning to the end of the cleaning in such a manner that the concentration of albumin in the cleaning liquid tank became 50 ppm. Into the cleaning tank.

[Evaluation method of tea scale adhesion inhibition effect]

The boiled tea boiled material (added to 1000 tea bags of boiling water to 10 liters of tea, and the boiled tea was cooled to room temperature for 10 minutes) was placed in 8 melamine cups (capacity: 150 cc). to make. After standing for 10 to 20 seconds, the roasted tea is discarded and cleaned under the above-mentioned cleaning conditions. This was repeated 50 times (50 times of baking, input, disposal, and cleaning). Thereafter, The appearance was visually observed, and the tea scale adhesion inhibiting effect was judged by the following criteria. Further, in the cleaning using the respective detergent compositions, the difference in state between the four cups could not be confirmed.

In addition, the content of the component (A) in the cleaning liquid is converted into an acid, which is the same as the above-described scale adhesion inhibitory property (2).

*Evaluation criteria for inhibition of tea scale adhesion

5: None of the 4 melamine cups were attached to the tea scale.

4: 4 melamine cups are slightly attached to the tea scale. (Compared with evaluation 5, it can be confirmed that it is slightly attached)

3: Four cups of melamine were found to be partially attached to the brown color.

2: Four melamine cups were found to adhere to the tea scale. (It can be confirmed that the adhesion is more than the evaluation 3, and the adhesion is less than the evaluation 1)

1:4 melamine cups were found to adhere to the thicker tea scale.

<Materiality>

When the liquid detergent composition was prepared by the above method, it was confirmed that the time until the MGDA, GLDA, EDTA, citric acid, or trisodium citrate as the final raw material was mixed until it was uniformly dissolved was evaluated on the following basis.

*Assessment benchmark for blending

5: After the final raw materials were mixed, they dissolved after less than 2 minutes.

4: After the final raw materials are mixed, they are dissolved in 2 minutes or more and less than 5 minutes.

3: After the final raw materials were mixed, they dissolved after 5 minutes or more and less than 10 minutes.

2: After the final raw materials were mixed, they were dissolved at 10 minutes or more and less than 20 minutes.

1: After the final raw materials are mixed, they are dissolved in 20 minutes or more.

<Cryogenic storage stability>

A liquid detergent composition of 200 ml of a watch was placed in a 250 ml polypropylene container and sealed, and stored at -5 ° C for 10 days, and the appearance of the liquid was evaluated on the basis of the following criteria.

(judgment basis)

5: Uniform and transparent (no turbidity was found at all).

4: Very little turbidity is found.

3: Slightly found turbid.

2: Found turbid.

1: turbidity was found and two layers of separation were produced.

(Note) The components in the table are the following. In the table, the comparative component of the component (A) is referred to as the component (A), and the comparative component of the component (B) is referred to as the component (B), thereby conveniently indicating the mass ratio.

<(A) component or its comparative component>

‧MGDA: Trisodium methylglycine diacetate, "Trilon M Powder" [manufactured by BASF Corporation]

‧GLDA: tetrasodium glutamate diacetate, "Dissolvine GL-PD-S" [AkzoNobel)

‧EDTA: tetrasodium edetate, "Chelest400" [manufactured by Chelest Co., Ltd.]

<(B) component or its comparative component>

‧ Citric acid: reagent (Grade 1)

‧ Trisodium citrate: "Refined sodium citrate M" (manufactured by Fuso Chemical Industry Co., Ltd.)

‧ Malic acid: reagent (DL-malic acid) (special grade)

‧ Gluconic acid: Reagent (50% aqueous gluconate solution), the numbers in the table indicate the amount of active ingredient.

‧Succinic acid: reagent (special grade)

<(C) component>

‧Sodium polyacrylate: "Sokalan PA25CL FR" [manufactured by BASF JAPAN Co., Ltd., sodium salt of acrylic acid homopolymer, weight average molecular weight 4,000]

‧Polyacrylic acid potassium: "Oigomer M3" [manufactured by Kao Co., Ltd., potassium salt of acrylic acid homopolymer, weight average molecular weight 9000]

<Other ingredients>

‧ bitterness: "Lunac8-98" [made by Kao Co., Ltd.]

‧ Alkenyl succinic acid: "Latemul DSK" [Manufactured by Kao Corporation]

‧ Potassium Hydroxide: Reagent (Special)

‧Sodium hydroxide: reagent (special grade)

‧ Potassium carbonate: reagent (special grade)

‧Sodium carbonate: Reagent (special grade)

‧1 potassium citrate: manufactured by Nippon Chemical Industry Co., Ltd., SiO ₂ /K ₂ O molar ratio = 2.0~2.3 [according to the specifications of Nippon Chemical Industry Co., Ltd.]

‧1 sodium citrate: manufactured by Nippon Chemical Industry Co., Ltd., SiO ₂ /Na ₂ O molar ratio = 2.0~2.3 [according to the specifications of Nippon Chemical Industry Co., Ltd.]

‧Nonionic surfactant: R ¹ in the formula (1) is a secondary alkyl group having 12 to 14 carbon atoms, a nonionic surfactant having s=7.0 and t=8.5, and the trade name is "Softanol EP7085" (Japan) Catalyst Co., Ltd.)

From the comparison of the examples shown in Tables 1 to 4 and the comparative examples, it is understood that the liquid detergent composition of the present invention not only has good cleansing property and stain adhesion inhibition, blending property and low temperature stability for protein-containing stains. Excellent and excellent in scale adhesion inhibition.

With respect to the liquid detergent compositions of Examples 1 to 19 and Comparative Examples 1 to 18, the corrosion resistance of the acid-resistant aluminum was evaluated by the following method, and as a result, no damage was observed, and the acid-resistant aluminum corrosion resistance was excellent.

<Anti-acid aluminum corrosion resistance>

To a 100 ml glass standard bottle (No. 11), 30 mL of a 0.2% by mass water-diluted cleaning liquid obtained by diluting the liquid detergent composition with ion-exchanged water to a mass of 500 times was added. to Among them, a test piece of 3 cm × 5 cm cut out from an aluminum tableware (manufactured by AIHO Co., Ltd.) which was subjected to an alumite treatment was immersed in about half of the longitudinal direction, and kept at a liquid temperature of 60 ° C for 1 hour. After the holding, the test plate was taken out, rinsed in running water at 20 ° C ± 5 ° C for 30 seconds, and the water was removed in the air and dried at 25 ° C ± 5 ° C. After drying, the appearance of the obtained test plate was visually observed and evaluated.

Claims (8)

A liquid detergent composition for a dishwashing machine comprising a bismuth citrate and comprising the following components (A), (B), (C) and water: (A) component: methylglycine Diacetic acid, glutamic acid diacetic acid or the like (B) component: citric acid or a salt thereof (C) component: polyacrylic acid or a salt thereof, and the content of the component (A) is 2.0% by mass or more in terms of acid. 5% by mass or less, the content of the component (B) is 1.5% by mass or more and 5.4% by mass or less, and the content of the citrate is 2.5% by mass or more and 7.4% by mass or less, and the liquid detergent combination for the dishwashing machine contains potassium ions and optionally containing sodium ions, the content of sodium ions [Na ^+] with respect to the potassium content of [K ^+] the molar ratio of ^{[Na +] / [K +} ] is 0 or more and 0.9 or less. The liquid detergent composition for a dishwashing machine according to claim 1, wherein the mass ratio (A)/(B) of the component (A) to the acid content of the component (B) is 0.65. Above and above 1.9. The liquid detergent composition for a dishwashing machine according to claim 1 or 2, wherein the mass ratio (B)/(C) of the component (B) to the content of the component (C) is 0.5 or more and 2.5 or less. The liquid detergent composition for a dishwasher according to claim 1 or 2, wherein the mass ratio (A)/(C) of the component (A) to the content of the component (C) is 0.7 or more and 3.4 or less. The liquid detergent composition for a dishwashing machine according to claim 1 or 2, wherein the total amount of the component (A) converted to the acid content, the component (B) converted to the acid content, and the (C) component is 6.0. The mass% or more and 12.0 mass% or less. A liquid detergent composition for a dishwashing machine according to claim 1 or 2, wherein the 0.2% by mass aqueous dilution has a pH of 9 or higher at 25 °C. A cleaning liquid obtained by diluting a liquid detergent composition for a dishwasher according to any one of claims 1 to 6 with water, and converting the content of the component (A) in the cleaning liquid into an acid of 0.0017 The mass% or more and 0.017% by mass or less. A cleaning method for a tableware, which is characterized in that the liquid detergent composition for a dishwashing machine according to any one of claims 1 to 6 is supplied to a cleaning liquid tank of an automatic tableware cleaning machine, and the composition and water are mixed with the cleaning liquid. The content of the component (A) in the tank is adjusted to a cleaning liquid having an acid content of 0.0017 mass% or more and 0.017 mass% or less, and the tableware is cleaned using the cleaning liquid.