JP2015131941A - Liquid detergent composition for dishwasher - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a detergent composition for dishwasher with excellent scale adhesion suppressing properties, washability, tea stain adhesion suppressing properties, blending properties, and low temperature storage stability.SOLUTION: There is provided a liquid detergent composition for dishwasher containing silicate, in which the composition contains the following ingredients (A)(B)(C) and water, furthermore contains silicate at 2.5 to 7.4 mass %, and contains potassium ion and arbitrarily sodium ion. A molar ratio [Na]/[K] of the content of sodium ion [Na] to the content of potassium ion [K] is 0 to 0.9. Ingredient (A): methylglycine diacetate, glutamine diacetate or salt thereof, ingredient (B): citric acid or salt thereof, and ingredient (C): polyacrylic acid or salt thereof. The content of ingredient (A) is 2.0 to 5.0 mass % in terms of acid, and the content of ingredient (B) is 1.5 to 5.4 mass % in terms of acid.

Description

  The present invention relates to a liquid detergent composition for a dishwasher. In particular, the present invention relates to a liquid detergent composition for a dishwasher suitably used in a commercial automatic dishwasher.

  Automatic washing machines are used for cleaning dishes such as dirty dishes, glasses and cooking utensils in kitchens such as homes, restaurants and coffee shops, as well as food containers used in food and beverage factories and plastic containers for products. . Main target soils include food-derived proteins, starches, fats and oils, and these soils are combined and adhered to dishes, glasses, dishes such as cooking utensils, and plastic containers. In addition, during cooking, these stains may be heat-denatured to become strong stains and be fixed.

  Usually, washing by an automatic washing machine is performed in the order of a washing process and a rinsing process. The time required for these processes is as short as about 40 to 60 seconds for the washing process and about 5 to 20 seconds for the rinsing process in business use.

  For cleaning, tap water and well water containing hardness components such as Ca ions and Mg ions are often used. Calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, etc. produced by these hardness components in water are insoluble in water, so they adhere to the washing liquid tank in the automatic washing machine or the side wall in the automatic washing machine, and are called scales. A smooth coating is formed. The scale adhering to each part in the cleaning liquid tank causes troubles such as a decrease in thermal efficiency of the heat exchange unit, blockage of the circulation pump, malfunction of the concentration sensor, and the like. In addition, organic contamination easily accumulates on the scale attached to the side wall, which may cause 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 can be increased, but in the case of a liquid detergent, the blending amount of the chelating agent in terms of obtaining a stable liquid composition There are limitations.

  Patent Document 1 discloses that a detergent composition containing a chelate component such as methylglycine diacetate, a metal citrate, a metal carbonate, and a metal silicate has excellent detergency characteristics, for example, a dish compared to a conventional composition. It has been disclosed to reduce film formation and spots on the top.

Patent Document 2 contains a predetermined amount of a chelating agent such as citrate, a surfactant, and an aromatic hydrotrope, has a pH of 3 to less than 7 at 25 ° C., and contains sodium ions (Na ⁺ ) and potassium. It is disclosed that a liquid detergent composition having a predetermined molar ratio of ions (K ⁺ ) is excellent in low-temperature stability, reduces clogging of discharge ports, and exhibits excellent detergency against hard surface dirt. Has been.

  Patent Document 3 includes one or more selected from methyl glycine diacetate and its alkali metal salt, one or more selected from citric acid and its alkali metal salt, and a specific nonionic surfactant. The cleaning composition for automatic dishwashers containing one or more selected from the above is excellent in suppressing tea astringency and reducing water spots even under conditions where the amount of rinsing water used is small It is disclosed to show the effect.

Special table 2013-518983 gazette JP 2007-23210 A International Publication No. 2013/175659

  As described above, when the scale adheres, it causes a decrease in the heat efficiency of the heat exchanging part, a clogging of the circulation pump, a malfunction of the concentration sensor, a deterioration of the sanitary condition due to organic matter accumulation, and the like.

  Although the detergent composition of patent document 1 can be used as a detergent for automatic dishwashers (ADD), scale adhesion inhibitory property was insufficient. Moreover, the liquid cleaning composition of patent document 2 does not have a concrete disclosure about the cleaning property and the scale adhesion inhibiting property when used as a dishwasher composition.

  The present invention provides a silicate-containing liquid detergent composition for a dishwasher that not only excels in detergency, tea astringent adhesion inhibitory properties, blendability and low-temperature storage stability, but also has excellent scale adhesion inhibitory properties.

The present invention is a liquid detergent composition for a dishwasher containing a silicate, the following (A) component, (B) component, (C) component:
(A) component: methylglycine diacetate, glutamine diacetate or a salt thereof (B) component: citric acid or a salt thereof (C) component: polyacrylic acid or a salt thereof, and water,
(A) The content of the component is 2.0% by mass or more and 5.0% by mass or less in terms of acid,
The content of the component (B) is 1.5% by mass or more and 5.4% by mass or less in terms of acid,
The content of silicate is 2.5% by mass or more and 7.4% by mass or less,
Contains potassium ions and optionally sodium ions,
The content of sodium ion content of potassium ions in the [Na ^{+] [K +]} molar ratio ^{[Na +] / [K +} ] 0 or more and 0.9 or less,
The present invention relates to a liquid detergent composition for a dishwasher.

  Further, the present invention is a cleaning liquid obtained by diluting the liquid detergent composition for a dishwasher of the present invention with water, and the content of the component (A) in the cleaning liquid is 0.0017% by mass or more in terms of acid. , 0.017% by mass or less.

  In addition, the present invention provides the liquid detergent composition for dishwashers of the present invention to a washing liquid tank of an automatic dishwasher, mixes the composition and water, and the content of component (A) is acid. The present invention relates to a tableware cleaning method in which a cleaning liquid that is 0.0017% by mass or more and 0.017% by mass or less in terms of conversion is prepared in a cleaning liquid tank, and dishes are cleaned using the cleaning liquid.

  According to the present invention, there is provided a silicate-containing liquid detergent composition for a dishwasher that not only has excellent cleaning properties, tea astringent adhesion inhibitory properties, compoundability and low-temperature storage stability, but also has excellent scale adhesion inhibitory properties. The

  Hereinafter, in the present specification, “the liquid detergent composition for a dishwasher of the present invention” is referred to as “the liquid detergent composition of the present invention”, “the detergent composition of the present invention”, “the liquid detergent”. Also referred to as “composition” or “cleaning composition”.

The liquid detergent composition for dishwashers containing the silicate of the present invention comprises (A) component: methylglycine diacetate, glutamine diacetate or a salt thereof, (B) component: citric acid or a salt thereof, (C ) Component: Polyacrylic acid or a salt thereof, and water in a predetermined amount, a silicate content is a predetermined amount, and a sodium ion content [Na ⁺ ] potassium ion content [K ⁺ ] When the molar ratio [Na ⁺ ] / [K ⁺ ] is 0 or more and 0.9 or less, not only is cleaning property, tea astringent adhesion inhibiting property, compounding property and low temperature storage stability excellent, but also the scale adhesion inhibiting property. Excellent.

  The liquid detergent composition for tableware washing machines containing the silicate of this invention is excellent in scale adhesion inhibitory property. The reason is not clear, but think as follows.

  The present inventor has found the following with respect to the problem of suppression of scale adhesion in the cleaning liquid tank and the inner wall of the cleaning machine. The scale is composed of a silicate that is hardly soluble in water such as calcium silicate and magnesium silicate (hereinafter referred to as silicate scale) and a carbonate that is hardly soluble in water such as calcium carbonate and magnesium carbonate (hereinafter referred to as carbonate scale). Call). The silicate scale adhering to the stainless steel (SUS) surface in the cleaning machine becomes a binder on the SUS surface, and the carbonate scale existing in the cleaning liquid tank adheres thereto. The scale is formed by the crystal growth of the carbonate scale. Also, the silicate scale and carbonate scale form a layer and adhere.

Scale occurs when the amount of water hardness components such as Ca ions and Mg ions exceeds the cation exchange capacity (CEC) of the chelating agent. Furthermore, it has been found that the carbonate scale remaining on the SUS surface of the inner wall of the cleaning machine causes crystal growth, and the scale becomes stronger.
Therefore, it is necessary to sufficiently capture the hardness component of water in order to suppress the adhesion of scale, in particular, to suppress the adhesion of carbonate scale.

The silicate ion monomer undergoes a structural change to dimer or multimer and polymerizes, so that the scale easily adheres to the SUS surface. This silicic acid polymer takes in divalent cations such as Ca ions and Mg ions and converts them into a more complicated three-dimensional network structure. The polymer converted into a network structure is further fixed on the SUS surface as a silicate scale.
Compared with Na, K has a smaller first ionization energy and electron affinity, and is considered to suppress the polymerization of silicate ions. Therefore, it is important that a certain amount of K ions is present in the cleaning liquid in order to suppress silicate scale adhesion.

In an alkaline solution, unlike other organic acids, citric acid exists only in a dissociated form and is considered to be easily dissolved in a silica gel polymer. Therefore, it is considered that citric acid in the alkaline liquid captures hardness components such as Ca ions and Mg ions and effectively suppresses the scale.
In addition, since K has lower first ionization energy and electron affinity than Na, potassium citrate is slightly more dissociated than sodium citrate. Due to this slight difference, it is considered that a larger amount of potassium ions has a higher scale suppression effect due to dissociated citric acid than a case where there are many sodium ions.

  Therefore, in order to suppress scale adhesion, it is important to capture hardness components and to suppress the polymerization of silicate ions. In the present invention, by combining the three specific compounds (A), (B), and (C), and defining the molar ratio of the sodium ion content to the potassium ion content, The hardness component in the silicic acid polymer can be suppressed. By limiting the content of silicate and defining the molar ratio between the content of sodium ions and the content of potassium ions, polymerization of silicate ions can be suppressed. As a result, scale adhesion is suppressed.

<(A) component>
The component (A) of the present invention is methylglycine diacetate, glutamine diacetate or a salt thereof from the viewpoints of scale adhesion inhibition and tea astringent adhesion inhibition. The salt of the component (A) is preferably an alkali metal salt, more preferably a sodium salt, from the viewpoint of easy availability. Moreover, from a viewpoint of the further improvement of scale adhesion inhibitory property, potassium salt is more preferable.

  The liquid detergent composition of this invention can contain 1 type, or 2 or more types of (A) component.

  (A) Content of a component is 2.0 mass% or more and 5.0 mass% or less in a detergent composition from a viewpoint of scale adhesion inhibitory property, detergency, tea astringent adhesion inhibitory property, and a compounding property. The content of the component (A) is preferably 2.6% by mass or more, more preferably 3.3% by mass or more, more preferably in the liquid detergent composition from the viewpoints of scale adhesion inhibition and tea astringent adhesion inhibition. Is 3.6% by mass or more, more preferably 4.2% by mass or more, and from the viewpoint of blendability, it is preferably 4.7% by mass or less, more preferably 4.0% by mass or less, more preferably 3.6% by mass or less. Further, the content of the component (A) is preferably 2.6 to 5.0% by mass, more preferably 3 in the liquid detergent composition from the viewpoints of scale adhesion inhibition, tea astringent adhesion inhibition, and blendability. It is 0.3-5.0 mass%, More preferably, it is 3.3-4.7 mass%, More preferably, it is 3.3-4.0 mass%, More preferably, it is 3.3-3.6 mass%. In addition, all content of (A) component is a value of acid conversion.

<(B) component>
(B) component of this invention is a citric acid or its salt from a viewpoint of scale adhesion inhibitory property. The component (B) is preferably citric acid from the viewpoint of easy availability and further improvement in 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 easy availability. From the viewpoint of further improving the scale adhesion inhibiting property, potassium salt is more preferable.

  (B) Content of a component is 1.5 mass% or more and 5.4 mass% or less in a cleaning composition from a viewpoint of scale adhesion inhibitory, compounding property, and low-temperature storage stability. The content of component (B) is preferably 2.5% by mass or more, more preferably 3.0% by mass or more, more preferably 3. The content is 5% by mass or more, more preferably 4.5% by mass or more, and preferably 5.2% by mass or less from the viewpoint of further improving the blendability and low-temperature storage stability. In addition, the content of the component (B) is preferably 2.5 to 5.4% by mass, more preferably 2 in the liquid detergent composition from the viewpoints of scale adhesion inhibition, compoundability, and low-temperature storage stability. 0.5 to 5.2% by mass, more preferably 3.0 to 5.2% by mass, more preferably 3.5 to 5.2% by mass, and even more preferably 4.5 to 5.2% by mass. The content of the component (B) is 1.5 to 5.4% by mass, preferably 1.5 to 5.2% by mass, more preferably 1.5 to 4.5% by mass, more preferably 1.5 to 3.5% by mass. In addition, all content of (B) component is a value of acid conversion.

  (A) Mass ratio [(A) / (B)] of acid equivalent content of component (B) to acid equivalent content of component (B) is scale adhesion inhibitory, washability, tea astringent adhesion inhibitory, and low temperature storage. From the viewpoint of further improving the stability, it is preferably 0.65 or more, more preferably 0.70 or more, more preferably 1.0 or more, more preferably 1.25 or more, and scale adhesion suppression and blending From a viewpoint of the further improvement of property, Preferably it is 1.9 or less, More preferably, it is 1.7 or less, More preferably, it is 1.55 or less.

<(C) component>
The component (C) of the present invention is polyacrylic acid or a salt thereof from the viewpoints of detergency 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, more preferably from the viewpoint of further improvement in scale adhesion inhibition, from the viewpoint of easy availability. Potassium salt.

  As for the molecular weight of component (C), the weight average molecular weight is preferably 1,000 or more, more preferably 3,000 or more, and preferably 10,000 or less, more preferably 8,000 or less, more preferably It is 6,000 or less, more preferably 5,000 or less. For the same reason, the weight average molecular weight of the component (C) is preferably 1,000 to 10,000, more preferably 3,000 to 8,000, more preferably 3,000 to 6,000, and more. Preferably it is 3,000-5,000.

  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 polyacrylic acid as a standard substance 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, more preferably 2.5% by mass in the cleaning composition from the viewpoint of further improving the detergency. % Or more, more preferably 3.5 mass% or more, more preferably 4.5 mass% or more, and preferably 5.5 mass% or less, more preferably 2.8 mass% or less, more preferably 2 .2% by mass or less. Further, the content of the component (C) is preferably 0.8 to 5.5% by mass, more preferably 1.8 to 5.5% by mass in the liquid detergent composition from the viewpoint of further improving the detergency. %, More preferably 2.5 to 5.5% by mass, more preferably 3.5 to 5.5% by mass, and even more preferably 4.5 to 5.5% by mass. In addition, from the viewpoint of coexistence of scale adhesion inhibition, low-temperature storage stability, detergency, tea astringent adhesion inhibition and compounding properties, in the liquid detergent composition, preferably 0.8 to 5.5% by mass, more preferably It is 0.8-2.8 mass%, More preferably, it is 1.8-2.8 mass%, More preferably, it is 1.8-2.2 mass%.

  (B) Mass ratio (B) / (C) of content of acid conversion of component to content of (C) component is scale adhesion inhibitory, washability, tea astringent adhesion inhibitory, compoundability and low temperature storage stability. From the viewpoint of further improvement, the ratio is preferably 0.5 or more, more preferably 0.8 or more, more preferably 1.2 or more, and from the viewpoint of blendability, it is preferably 2.5 or less.

  The mass ratio (A) / (C) of the content of the acid equivalent of the component (A) to the content of the component (C) is preferably from the viewpoint of further improvement in scale adhesion inhibitory property, detergency and tea astringent adhesion inhibitory property. Is 0.7 or more, more preferably 0.8 or more, more preferably 1.0 or more, more preferably 1.3 or more, more preferably 1.6 or more, and from the viewpoint of easy availability , Preferably 3.4 or less, more preferably 2.5 or less.

  In the liquid detergent composition of the present invention, the sum of the component (A) in terms of acid, the component (B) in terms of acid, and the sum of the components (C) is scale adhesion inhibitory and detergency. And preferably from 6.0% by weight or more, more preferably from 7.5% by weight or more, and from the viewpoint of further improving the blendability and low-temperature stability, It is 12.0 mass% or less, More preferably, it is 10 mass% or less, More preferably, it is 9 mass% or less, More preferably, it is 8.5 mass% or less.

<Water>
The liquid detergent composition of the present invention contains water.

<Silicate>
The liquid detergent composition of the present invention contains silicate as an alkaline agent from the viewpoint of anodizing corrosion resistance.

The content of the silicate is 2.5% by mass or more and 7.4% by mass or less in the liquid detergent composition from the viewpoints of detergency, tea astringent adhesion inhibition, alumite corrosion prevention and scale adhesion inhibition. .
From the same viewpoint, the content of the silicate 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 in the liquid detergent composition. % Or less.

The silicate is preferably one or more selected from alkali metal silicates from the viewpoint of further improving the anodizing corrosion prevention property, blendability, and availability. The alkali metal silicate is preferably No. 1 silicate, No. 2 silicate, from the viewpoint of further improvement of scale adhesion inhibitory, washability, tea astringent adhesion inhibitory, blendability, low-temperature storage stability and availability. 1 type or 2 types or more of silicates selected from No. 3 silicate and No. 4 silicate, more preferably 1 type or 2 types or more selected from No. 1 silicate, No. 2 silicate and No. 3 silicate Silicates, more preferably one or more silicates selected from No. 1 silicate and No. 2 silicates, more preferably one or more silicates selected from No. 1 silicate. Here, the alkali metal silicate is represented by the formula M ₂ O · nSiO ₂ (M is an alkali metal, n is a molar ratio SiO ₂ / M ₂ O), and No. 1 silicate has an average molar ratio of 1. Silicates of 7 or more and 2.3 or less, No. 2 silicate has an average molar ratio n of 2.4 or more, 2.7 or less of silicate, No. 3 silicate has an average molar ratio n of 2.8 or more Silicates of 3.3 or less and No. 4 silicates are silicates having an average molar ratio n of 3.7 or more and 3.9 or less.

  The silicate is preferably one or more selected from potassium silicate and sodium silicate from the viewpoint of availability. The alkali metal silicate is preferably a salt selected from sodium salts and potassium salts. The silicate is preferably one or more alkali metal silicates selected from No. 1 sodium silicate and No. 1 potassium silicate, and preferably No. 1 sodium silicate from the viewpoint of availability. The alkali metal silicate is preferably No. 1 potassium silicate from the viewpoint of scale adhesion inhibition.

The alkali metal silicate is represented by the formula M ₂ O · nSiO ₂ (M is an alkali metal, n is a molar ratio SiO ₂ / M ₂ O), and the change in properties due to M and n is complicated, It was thought difficult to suppress and remove. For example, in an aqueous solution of sodium metasilicate (M is sodium in the above formula, n = 1) or an aqueous alkali silicate solution containing more sodium, silicate ion monomers are mainly present, and n (molar ratio SiO ₂ / M ₂ O In the case of an aqueous solution of sodium silicate having a larger molecular weight of), a monomer (monomer), a dimer, and a higher silicate ion micelle are included. The ratio of this polysilicate ion micelle increases as n (molar ratio SiO ₂ / M ₂ O) increases. As a result, it is known that when n (molar ratio SiO ₂ / M ₂ O) is 2 or more, silicate ions tend to be converted from monomeric anions to more complex polymer structures. These silicic acid polymers are oriented and adsorbed on the SUS surface, and form a scale by combining with calcium, magnesium, etc. that are usually present in water used for cleaning (for example, tap water or groundwater). When n is 2 or more, the formed scale is considered to adhere in a stronger state. Alkali metal silicates are desirable components for improving detergency, but there was a tendency to promote scale generation. The liquid detergent composition of the present invention can suppress scale even when it contains an alkali metal silicate effective for improving the detergency.

<PH>
The pH (JIS K 3362) at 25 ° C. of the 0.2% by weight water dilution of the liquid detergent composition of the present invention is preferably 9 or more, more preferably from the viewpoint of further improvement in scale adhesion suppression and detergency. Is 9.5 or more, more preferably 10 or more, more preferably 10.5 or more, and preferably 12 or less, more preferably 11.5 or less from the viewpoint of detergency.

<Other ingredients>
The liquid detergent composition of the present invention preferably contains an alkaline agent other than silicate. The alkali agent other than silicate is preferably one or more alkali agents selected from alkali metal hydroxides and alkali metal carbonates from the viewpoint of easy availability.

  The alkali metal hydroxide is preferably potassium hydroxide or sodium hydroxide, more preferably potassium hydroxide.

  The alkali metal carbonate is preferably potassium carbonate or sodium carbonate, more preferably potassium carbonate.

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

  The liquid detergent composition of the present invention preferably contains one or more selected from alkali metal hydroxides and alkali metal carbonates as the alkali agent, more preferably alkali metal hydroxides and alkali metals. Contains two or more selected from carbonates.

  The liquid detergent composition of the present invention is an alkaline agent other than silicate from the viewpoints of further improvement in scale adhesion inhibition, detergency, tea astringent adhesion inhibition, blendability, low temperature storage stability, and availability. As (1) 1 type (s) or 2 or more types chosen from alkali metal hydroxide, and (2) 1 type (s) or 2 or more types chosen from alkali metal carbonate are contained preferably. That is, it contains both (1) and (2).

  The liquid detergent composition of the present invention preferably contains one or more selected from potassium hydroxide, sodium hydroxide, potassium carbonate and sodium carbonate, more preferably potassium hydroxide and sodium hydroxide. And two or more selected from potassium carbonate and sodium carbonate.

  In addition, the liquid detergent composition of the present invention preferably contains one or more selected from potassium hydroxide, sodium hydroxide, potassium carbonate, and sodium carbonate as an alkaline agent, more preferably hydroxylated. 1 type or 2 or more types chosen from potassium and sodium hydroxide and 1 sort or 2 types or more chosen from potassium carbonate and sodium carbonate are contained.

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

  From the viewpoint of further improving the detergency, the alkaline agent is preferably contained so that the pH at 25 ° C. of a 0.2% by weight water dilution of the liquid detergent composition of the present invention falls within the above range. The content of the alkali agent is preferably 10% by mass or more, more preferably 15% by mass or more, from the viewpoint of further improving the detergency in the liquid detergent composition, including the content of silicate. From the viewpoint of low-temperature storage stability, it is preferably 25% by mass or less, more preferably 20% by mass or less.

  In the total alkali agent, the proportion of silicate is preferably 15% by mass or more, more preferably, from the viewpoint of further improvement of anodizing corrosion prevention, tea astringent adhesion suppression, detergency, blendability and low-temperature storage stability. 20% by mass or more, more preferably 25% by mass or more, and preferably 45% by mass or less, more preferably 40% by mass or less, from the viewpoint of further improvement in scale adhesion inhibition, blendability and low-temperature storage stability. More preferably, it is 35 mass% or less.

  Preferably, the liquid detergent composition of the present invention is a nonionic surfactant in which ethylene oxide and propylene oxide are bonded in this order to a branched chain alcohol having 10 to 14 carbon atoms in order. 1 type or 2 types or more selected from active agent (I).

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

  In addition, in the nonionic surfactant (I), the average number of moles of propylene oxide added is preferably 2 or more, more preferably 4 or more, more preferably from the viewpoint of further improving the detergency and low foamability. 5 or more, and preferably 10 or less, more preferably 9 or less.

  Preferably, in the liquid detergent composition of the present invention, the nonionic surfactant (I) is a nonionic surfactant (I) in which ethylene oxide and propylene oxide are bonded in block order in this order to a branched chain alcohol having 10 to 14 carbon atoms. One or more ionic surfactants selected from nonionic surfactants having an average addition mole number of ethylene oxide of 4 or more and 10 or less and an average addition mole number of propylene oxide of 2 or more and 10 or less. contains.

  Preferably, the liquid detergent composition of the present invention is a secondary ion having 10 or more carbon atoms, more preferably 12 or more carbon atoms, and preferably 14 or less carbon atoms as the nonionic surfactant (I). 1 type, or 2 or more types chosen from the nonionic surfactant which ethylene oxide and propylene oxide couple | bonded with alcohol in this order in alcohol are contained.

  Preferably, the liquid detergent composition of the present invention is a secondary ion having 10 or more carbon atoms, more preferably 12 or more carbon atoms, and preferably 14 or less carbon atoms as the nonionic surfactant (I). A nonionic surfactant in which ethylene oxide and propylene oxide are combined in this order in block form with an alcohol, and the average addition mole number of ethylene oxide is 4 or more and 10 or less, and the average addition mole number of propylene oxide is 2 or more and 10 or less. 1 type (s) or 2 or more types chosen from a nonionic surfactant are contained.

The liquid detergent composition of the present invention preferably contains a nonionic surfactant represented by the following general formula (1) as the nonionic surfactant (I).
R ¹ —O— (EO) _s — (PO) _t —H (1)
[Wherein, R ¹ represents a branched alkyl group having 10 to 14 carbon atoms, a branched alkenyl group having 10 to 14 carbon atoms, or a branched alkyl group having 10 to 14 carbon atoms. Or a branched alkenyl group having 10 to 14 carbon atoms, EO represents an ethyleneoxy group, and PO represents a propyleneoxy group. s and t each represent an average added mole number, s is 4 or more and 10 or less, t is 2 or more and 10 or less, t / s is 0.3 or more and 1.5 or less, and s = 4 to 10, t = 2 to 10, and 0.3 ≦ (t / s) ≦ 1.5. “(EO) _s ” and “(PO) _t ” are connected in a block form. ]

In the general formula (1), R ¹ is preferably a branched alkyl group having 10 to 14 carbon atoms or a branched chain alkenyl group having 10 to 14 carbon atoms, and more preferably, It is a C10-C14 alkyl group having a branched chain. From the same viewpoint, R ¹ is preferably a secondary alkyl group having 10 to 14 carbon atoms or a secondary alkenyl group having 10 to 14 carbon atoms, more preferably, It is a secondary alkyl group having 10 to 14 carbon atoms. From the same viewpoint, the secondary alkyl group is preferably a group represented by the following formula. From the same viewpoint, R ¹ in the general formula (1) is preferably a secondary alkyl group represented by this formula.

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

  In the general formula (1), s is preferably 5 or more and 9 or less, and t is 5 or more and 9 or less. Specific examples of the nonionic surfactant of the general formula (1) are preferably polyoxyethylene (7) polyoxypropylene (8.5) -sec-dodecyl ether, polyoxyethylene from the viewpoint of easy availability. (7) 1 type, or 2 or more types chosen from polyoxypropylene (8.5) -sec-tridecyl ether and polyoxyethylene (7) polyoxypropylene (8.5) -sec-tetradecyl ether are mentioned. . Here, the value in () is the average number of moles of ethylene oxide or propylene oxide added.

  In the general formula (1), t / s is preferably 0.3 or more, more preferably 0.7 or more, more preferably 0.9 or more, and preferably 1.5 or less, more preferably 1. 3 or less.

  The compound of the general formula (1) has an alcohol having a branched alkyl group having 10 to 14 carbon atoms, preferably a secondary alcohol, or a branched alkenyl group having 10 to 14 carbon atoms. It can be synthesized by adding ethylene oxide to an alcohol, preferably a secondary alcohol, and then adding propylene oxide.

  The weight average molecular weight of the nonionic surfactant of the general formula (1) is preferably 200 or more, and preferably 5,000 or less, more preferably 2,000 or less. Moreover, the weight average molecular weight of the compound of the general formula (1) is preferably 200 to 5,000, more preferably 200 to 2,000 from the viewpoints of detergency and low foamability. The compound of the general formula (1) is available 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 detergency, low foamability and compoundability. It is 0.4 mass% or more, and preferably 0.7 mass% or less, more preferably 0.6 mass% or less. For the same reason, the content of the nonionic surfactant (I) in the cleaning composition is preferably 0.3 to 0.7% by mass, more preferably 0.3 to 0.6% by mass. More preferably, it is 0.4-0.6 mass%.

The liquid detergent composition of the present invention preferably contains one or more selected from fatty acids or salts thereof and alkenyl succinic acids or salts thereof.
From the same viewpoint, the number of carbon atoms of the fatty acid is preferably 6 or more, more preferably 8 or more, and preferably 12 or less, more preferably 10 or less. Moreover, carbon number of a fatty acid becomes like this. Preferably it is 6-12, More preferably, it is 8-10.
From the same viewpoint, the number of carbon atoms of the alkenyl succinic acid is preferably 10 or more, more preferably 12 or more, and preferably 16 or less, more preferably 14 or less. Moreover, carbon number of alkenyl succinic acid becomes like this. Preferably it is 10-16, More preferably, it is 12-14.

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

  When the fatty acid or its salt and the alkenyl succinic acid or its salt are contained, the mass ratio of the content of the fatty acid or its salt to the alkenyl succinic acid or its salt is (fatty acid or its salt) / (Alkenyl succinic acid or a salt thereof), preferably 50/50 or more, more preferably 60/40 or more, more preferably 67/33 or more, and preferably 99/1 or less, more preferably 90/10. Below, more preferably 80/20 or less. The mass ratio of the content of the fatty acid or salt thereof and the alkenyl succinic acid or salt thereof is (fatty acid or salt thereof) / (alkenyl succinic acid or salt thereof), and preferably from 50/50 to 99 from the same viewpoint. / 1, more preferably 50/50 to 90/10, more preferably 67/33 to 80/20.

The total content of fatty acid or salt thereof and alkenyl succinic acid or salt thereof is preferably 0.5% by mass or more, more preferably 0.75% by mass or more, from the viewpoint of low-temperature stability in the detergent composition. Yes, and preferably 5% by mass or less, more preferably 3% by mass or less, more preferably 1.5% by mass or less.
In addition, the total content of the fatty acid or salt thereof and the alkenyl succinic acid or salt thereof is preferably 0.5 to 5% by mass, more preferably 0.75 to 0.5% in the detergent composition from the viewpoint of low-temperature stability. It is 3 mass%, More preferably, it is 0.75-1.5 mass%.
In addition, all content of a fatty acid or its salt and alkenyl succinic acid or its salt is an acid conversion value.

  The liquid detergent composition of the present invention includes a solvent, a hydrotrope agent, a dispersant, a pH adjuster, a thickener, a viscosity adjuster, a fragrance, a colorant, and an antioxidant as long as the object of the present invention is not impaired. Ingredients such as preservatives, foam inhibitors, bleaches, bleach activators (except for those corresponding to the components (A) to (C) and silicates) can be blended.

  The remaining component of the liquid detergent composition of the present invention is water. Unless otherwise specified, the content is mass% with respect to the total amount of components including water.

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

<Potassium ion>
The liquid detergent composition of the present invention contains potassium ions from the viewpoints of scale adhesion inhibition, detergency, tea astringent 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), the potassium silicate, or the potassium salt of the optional alkali agent.

<Sodium ion>
The liquid detergent composition of the present invention can contain sodium ions so that the molar ratio with respect to the potassium ion content [K ⁺ ] is within a predetermined range. That is, it can optionally contain sodium ions. The liquid detergent composition of the present invention can 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), the sodium silicate or the sodium salt of the optional component.

<Molar ratio [Na ⁺ ] / [K ⁺ ]>
The content of sodium ions in the liquid detergent composition of the present invention the content of potassium ions in the [Na ^{+] [K +]} molar ratio ^{[Na +] / [K +} ] is the scale adhesion prevention properties, detergency, From the viewpoint of tea astringent adhesion inhibitory, blendability and low-temperature storage stability, it is 0 or more and 0.9 or less.
The content of sodium ion content of potassium ions in the [Na ^+] [K ^+] molar ratio ^{[Na +] / [K +} ] is the viewpoint of the easy availability of further improvement and ingredients of scale adhesion inhibitory Therefore, it is preferably 0.1 or more, more preferably 0.2 or more, more preferably 0.25 or more, and preferably 0.85 from the viewpoint of further improvement in scale adhesion suppression and low-temperature storage stability. Hereinafter, it is more preferably 0.70 or less, and more preferably 0.65 or less.
Further, the content of sodium ion content of potassium ions in the [Na ^{+] [K +]} molar ratio ^{[Na +] / [K +} ] is the scale adhesion prevention properties, detergency, Chashibu adhesion inhibitory, formulation properties And from the viewpoint of low-temperature storage stability, it is preferably 0.1 to 0.9, more preferably 0.2 to 0.85, more preferably 0.25 to 0.70, and more preferably 0.25 to 0.00. 65.

The content [K ⁺ ] of potassium ions in the liquid detergent composition of the present invention is such that scale adhesion inhibitory, detergency, tea astringent adhesion inhibitory, compoundability, low-temperature storage stability is further improved and From the viewpoint of availability, it is preferably 1 mol / L or more, more preferably 1.5 mol / L or more, more preferably 1.8 mol / L or more, and preferably 3 mol / L or less, More preferably, it is 2.7 mol / L or less, More preferably, it is 2.4 mol / L or less.

The content of sodium ions [Na ⁺ ] in the liquid detergent composition of the present invention is such that scale adhesion inhibitory, detergency, tea astringent adhesion inhibitory, compoundability, low-temperature storage stability is further improved and From the viewpoint of availability, it is preferably 0.3 mol / L or more, more preferably 0.4 mol / L or more, more preferably 0.6 mol / L or more, more preferably 0.9 mol / L or more. More preferably 1.2 mol / L or more, and preferably 3 mol / L or less, more preferably 2 mol / L or less, more preferably 1.6 mol / L or less, more preferably 1.3 mol / L or less. Mol / L or less.

<Cleaning liquid>
This invention is the washing | cleaning liquid which diluted the liquid cleaning composition for dishwashers of this invention with water, Comprising: Content of (A) component in washing | cleaning liquid is 0.0017 mass% or more in acid conversion, 0.00. Provided is a cleaning liquid of 017% by mass or less. As the water for dilution, water having a German hardness of 2 ° dH or more, and further 3 ° dH or more can be used.
Regarding the cleaning solution of the present invention, the concentration corresponding to the dilution ratio and the like is described below in the description of the cleaning method below. The molar ratio [Na ⁺ ] / [K ⁺ ] of the sodium ion content [Na ⁺ ] to the potassium ion content [K ⁺ ] in the cleaning liquid is 0 as in the liquid cleaning composition of the present invention. Above, it is 0.9 or less.

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

  The content of the component (B) in the cleaning liquid of the present invention is preferably 0.00125% by mass or more, more preferably 0.00475% by mass or more, in terms of acid, from the viewpoint of further improving scale adhesion inhibition. And, Preferably it is 0.0125 mass% or less, More preferably, it is 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 cleaning property and scale adhesion inhibition property, And from a further improvement viewpoint of tea astringency adhesion inhibitory property, Preferably it is 0.011 mass% or less, More preferably, it is 0.0042 mass% or less.

  The content of the silicate in the cleaning liquid of the present invention is preferably 0.0025% by mass or more, more preferably 0, from the viewpoint of further improving the cleaning performance, tea astringent adhesion suppression, alumite corrosion prevention and scale adhesion suppression. .0095% by mass or more, and preferably 0.025% by mass or less, more preferably 0.0105% by mass or less.

  These cleaning liquids can also contain the aforementioned components and other components, and the preferred embodiments are also the same. Moreover, it is preferable that a washing | cleaning liquid is a composition which mix | blended the essential component and arbitrary component of this invention with the said content.

The present invention
water and,
The component (A) in terms of acid is preferably 0.0017% by mass or more, more preferably 0.0065% by mass or more, and preferably 0.017% by mass or less, as a ratio in all blended components. Preferably it is 0.0072 mass% or less,
The component (B) in terms of acid is preferably 0.00125% by mass or more, more preferably 0.00475% by mass or more, and preferably 0.0125% by mass or less, as a ratio in the total formulation components. Preferably it is 0.00525 mass% or less,
The component (C) is preferably 0.001% by mass or more, more preferably 0.0038% by mass or more, and preferably 0.011% by mass or less, more preferably 0 as a ratio in the total blending components. .0042 mass% or less,
The ratio of silicate is preferably 0.0025% by mass or more, more preferably 0.0095% by mass or more, and preferably 0.025% by mass or less, and more preferably 0.0105% by mass as a ratio in all the ingredients. Mass% or less,
The manufacturing method of the liquid detergent composition which mixes can be provided.
Also in this manufacturing method, the above-mentioned components and other components can be used as components to be mixed, and the preferred embodiments are also the same. Also in this production method, water having a German hardness of 2 ° dH or more, and further 3 ° dH or more can be used.

<Washing method>
The liquid detergent composition of the present invention is suitably used for washing with a dishwasher, and further with a commercial dishwasher. The cleaning liquid of the present invention is preferably prepared from the liquid cleaning composition of the present invention. In washing with a commercial dishwasher, the liquid detergent composition of the present invention is used as a washing liquid mixed with water. At that time, the composition is arbitrarily transferred into the commercial dishwasher by the supply device to maintain a proper concentration of the cleaning liquid. The liquid detergent composition of the present invention is supplied by, for example, inserting a tube dedicated to a commercial dishwasher directly into a plastic container filled with the composition and sucking it up. Thereafter, the cleaning liquid is supplied into the commercial dishwasher.

  In general, the cleaning liquid of the present invention is preferably prepared while maintaining a constant concentration in a storage tank provided in an automatic cleaning machine.

  According to the present invention, the liquid detergent composition of the present invention is preferably 200 mass times or more, more preferably 333 mass times or more, more preferably 400 mass times or more, more preferably 455 mass times or more, more preferably with water. Is 476 mass times or more, and from the viewpoints of scale adhesion inhibitory property, detergency and tea astringent adhesion inhibitory property, preferably 2000 mass times or less, more preferably 1000 mass times or less, more preferably 769 mass times or less, more preferably There is provided a washing method for washing dishes by an automatic washing machine using a washing liquid diluted at a dilution ratio of 667 mass times or less, more preferably 556 mass times or less, more preferably 526 mass times or less. This cleaning method includes a step of preparing a cleaning liquid by diluting the liquid cleaning composition of the present invention with water so as to achieve the dilution ratio, and a step of cleaning dishes using an automatic cleaning machine using the cleaning liquid. Good.

  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, more preferably 0, from the viewpoint of further improvement in scale adhesion inhibition, detergency and tea astringent adhesion inhibition. 10 mass% or more, more preferably 0.13 mass% or more, more preferably 0.15 mass% or more, more preferably 0.18 mass% or more, more preferably 0.19 mass% or more, and Preferably it is 0.5 mass% or less, More preferably, it is 0.30 mass% or less, More preferably, it is 0.25 mass% or less, More preferably, it is 0.22 mass% or less, More preferably, it is 0.21 mass% or less. .

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

  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 improving the cleaning performance, and preferably 3 minutes from the viewpoint of work efficiency. Below, more preferably 2 minutes or less, 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 improving productivity and cleaning performance, and preferably 80 ° C. or lower, more preferably from the viewpoint of cleaning performance. It is 70 degrees C or less.
After the dishes are washed, they are usually rinsed immediately in the same commercial dishwasher with water, hot water or hot water, for example, hot water of 70 ° C. or higher and 90 ° C. or lower for 5 seconds or longer and 15 seconds or shorter. Is called.

  The cleaning agent of the present invention can exhibit an effect even when a high hardness water having a German hardness of 2 ° dH or higher or a German hardness of 3 ° dH or higher is used as water for preparation and / or rinsing of the cleaning liquid. That is, in the cleaning method of the present invention, the cleaning liquid can be prepared by mixing the liquid detergent composition of the present invention with water having a German hardness of 2 ° dH or higher or a German hardness of 3 ° dH or higher. In the cleaning method of the present invention, rinsing can be performed using water having a German hardness of 2 ° dH or higher.

  In a commercial dishwasher, the cleaning liquid is usually used repeatedly by circulating it with a pump.

  When washing dishes with a commercial dishwasher, the cleaning liquid in the cleaning liquid storage tank (that is, the cleaning liquid used for cleaning) is brought together with the number of cleanings by taking out the cleaning liquid by tableware or carrying over the rinsing water to the cleaning liquid storage tank. ) Concentration decreases. When the concentration of the cleaning liquid is lowered, an appropriate amount of the liquid cleaning composition is supplied to the cleaning liquid storage tank by the automatic supply device so that the concentration of the cleaning liquid is maintained in an appropriate range.

  The automatic supply device for the liquid detergent composition is not limited, but is controlled by sensing the concentration of the cleaning liquid and receiving a signal. In the liquid composition of the present invention, the tube pump is driven to supply the required amount of the liquid detergent composition.

  This automatic supply device is suitable for use in a commercial washing machine with a very large number of cleanings per day. In addition to the advantage that the use of the automatic supply device saves a lot of time compared to manual operation for each cleaning frequency. If the automatic supply device is used, there is an advantage that it is easy to maintain the concentration of the cleaning liquid within an appropriate concentration range throughout the day (during cleaning).

  As a tableware cleaning method of the present invention, a tableware cleaning method for cleaning tableware with an automatic washing machine comprising a cleaning liquid storage means and a means for bringing the cleaning liquid stored in the storage means into contact with the tableware, The cleaning liquid is the cleaning liquid according to the present invention, and the cleaning liquid after contacting the tableware is circulated to the storage means, and the concentrated composition is obtained using the electrical conductivity of the cleaning liquid stored in the storage means as an index. A method of supplying and controlling the concentration of the cleaning liquid (hereinafter referred to as method 1).

  In general, an automatic washing machine, in particular, an automatic washing machine for business use includes a cleaning liquid storage means and a means for bringing the cleaning liquid stored in the storage means into contact with tableware. The cleaning liquid storage means may be referred to as a cleaning liquid tank, a cleaning liquid tank, or the like, for example. In addition, the means for bringing the cleaning liquid stored in the storage means into contact with the tableware may include a cleaning liquid transporting means (such as a pipe) and a means for applying the cleaning liquid to the tableware (such as a shower nozzle). The means for bringing the cleaning liquid stored in the storage means into contact with the tableware may include a defined space (sometimes referred to as a cleaning room or the like) for bringing the cleaning liquid into contact with the tableware. In the method 1, the liquid cleaning composition of the present invention is supplied to the cleaning liquid stored in the storage means using the electric conductivity of the cleaning liquid as an index so that the concentration of the cleaning liquid is maintained at the set concentration. It is preferable to control.

  According to the present invention, the liquid detergent composition for a dishwasher of the present invention is supplied to a washing liquid tank of an automatic dishwasher, the composition and water are mixed, and the content of component (A) is 0 in terms of acid. A cleaning method for tableware is provided in which a cleaning liquid of not less than 0017% by mass and not more than 0.017% by mass is prepared in a cleaning liquid tank, and dishes are cleaned using the cleaning liquid.

  In relation to the above-described embodiment, the present invention discloses the following liquid detergent composition for dishwasher, cleaning liquid, dishwashing method and use.

<Section 1>
A liquid detergent composition for a dishwasher containing a silicate, the following (A) component, (B) component, (C) component:
(A) component: methylglycine diacetate, glutamine diacetate or a salt thereof (B) component: citric acid or a salt thereof (C) component: polyacrylic acid or a salt thereof, and water,
(A) The content of the component is 2.0% by mass or more and 5.0% by mass or less in terms of acid,
The content of the component (B) is 1.5% by mass or more and 5.4% by mass or less in terms of acid,
The content of silicate is 2.5% by mass or more and 7.4% by mass or less,
Contains potassium ions and optionally sodium ions,
The content of sodium ion content of potassium ions in the [Na ^{+] [K +]} molar ratio ^{[Na +] / [K +} ] 0 or more and 0.9 or less,
Liquid detergent composition for dishwashers.

<Section 2>
(A) The mass ratio (A) / (B) of the acid-converted content of the component to the acid-converted content of the (B) component is 0.65 or more and 1.9 or less, according to <Section 1>. A detergent composition for dishwashers.

<Section 3>
<Item 1> or <Item 2> in which the mass ratio (B) / (C) of the content in terms of acid of component (B) to the content of component (C) is 0.5 or more and 2.5 or less. A liquid detergent composition for a dishwasher according to any one of the above.

<Section 4>
<Claim 1> to <Claim 3>, wherein the mass ratio (A) / (C) of the content in terms of acid of component (A) to the content of component (C) is 0.7 or more and 3.4 or less. A liquid detergent composition for a dishwasher according to any one of the above.

<Section 5>
(A) The acid equivalent content of the component, the (B) acid equivalent content and the (C) component content is 6.0% by mass or more and 12.0% by mass or less. 1>-<item 4> Liquid detergent composition for tableware washing machines given in any 1 paragraph.

<Section 6>
The liquid detergent composition for a dishwasher according to any one of <Item 1> to <Item 5>, wherein the pH of the 0.2% by weight diluted water at 25 ° C. is 9 or more.

<Section 7>
The content of sodium ion content of potassium ions in the [Na ^{+] [K +]} molar ratio ^{[Na +] / [K +} ] is preferably 0.1 or more, more preferably 0.2 or more, more preferably Is at least 0.25, preferably at most 0.85, more preferably at most 0.70, more preferably at most 0.65, <1> to <6> Liquid detergent composition for dishwashers.

<Section 8>
In the liquid detergent composition, the content of the component (A) is preferably 2.6% by mass or more, more preferably 3.3% by mass or more, more preferably 3.6% by mass or more, and more preferably in the liquid detergent composition. Is 4.2% by mass or more, and is preferably 4.7% by mass or less, more preferably 4.0% by mass or less, and more preferably 3.6% by mass or less. In the liquid detergent composition, the content is preferably 2.6 to 5.0% by mass, more preferably 3.3 to 5.0% by mass, and more preferably 3.3 to 4.7% by mass in terms of acid. %, More preferably 3.3 to 4.0% by mass, and more preferably 3.3 to 3.6% by mass, for a dishwasher according to any one of <Item 1> to <Item 7> Liquid detergent composition.

<Section 9>
The content of the component (B) citric acid or a salt thereof is preferably 2.5% by mass or more, more preferably 3.0% by mass or more, more preferably 3.5% by mass or more in the cleaning composition. More preferably, the content is 4.5% by mass or more, and preferably 5.2% by mass or less, and the content of the component (B) is preferably 2.5 to 5 in the liquid detergent composition. .4 mass%, more preferably 2.5-5.2 mass%, more preferably 3.0-5.2 mass%, more preferably 3.5-5.2 mass%, more preferably 4.5 The content of the component (B) is 1.5 to 5.4% by mass, preferably 1.5 to 5.2% by mass, and more preferably 1.5 to 5.2% by mass. The food according to any one of <Claim 1> to <Claim 8>, which is ˜4.5 mass%, more preferably 1.5 to 3.5 mass%. Washer liquid detergent composition.

<Section 10>
The content of the component (C) polyacrylic acid or a salt thereof is preferably 0.8% by mass or more, more preferably 1.8% by mass or more, more preferably 2.5% by mass or more in the cleaning composition. More preferably 3.5% by mass or more, more preferably 4.5% by mass or more, and preferably 5.5% by mass or less, more preferably 2.8% by mass or less, more preferably 2.2% by mass. The content of the component (C) is preferably 0.8 to 5.5% by mass, more preferably 1.8 to 5.5% by mass, and more preferably 2.5 to 5%. 0.5% by mass, more preferably 3.5-5.5% by mass, more preferably 4.5-5.5% by mass, and the content of component (C) is preferably 0.8- 5.5% by mass, more preferably 0.8 to 2.8% by mass, more preferably 1.8 to 2.8%. The amount%, more preferably from 1.8 to 2.2 wt%, <claim 1> to <claim 9> any one dishwasher liquid detergent composition according to.

<Section 11>
The total of the content in terms of acid of component (A), the content in terms of acid of component (B), and the content of component (C) is more preferably 6.5% by mass or more, and more preferably 7.0% by mass. % Or more, more preferably 7.5% by mass or more, and preferably 12.0% by mass or less, more preferably 11.5% by mass or less, more preferably 10% by mass or less, more preferably 9.5%. The liquid detergent composition for a dishwasher according to any one of <Item 1> to <Item 10>, wherein the composition is at most 10% by mass, more preferably at most 9% by mass, and even more preferably at most 8.5% by mass.

<Section 12>
The silicate is preferably an alkali metal silicate, and preferably one or more silicates selected from No. 1 silicate, No. 2 silicate, No. 3 silicate and No. 4 silicate, and more Preferably one or more silicates selected from No. 1 silicate, No. 2 silicate, and No. 3 silicate, more preferably one or more selected from No. 1 silicate and No. 2 silicate Silicate, more preferably one or more silicates selected from No. 1 silicate, and the silicate is preferably one or more selected from potassium silicate and sodium silicate In addition, it is preferably one or more alkali metal silicates selected from No. 1 sodium silicate and No. 1 potassium silicate, preferably No. 1 sodium silicate, and preferably No. 1 potassium silicate. <Section 1><Claim11> any one dishwasher liquid detergent composition according to.

<Section 13>
The content of silicate 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 in the liquid detergent composition. <Claim 1>-<Claim 12> Liquid detergent composition for tableware washing machines in any one of <1>.

<Section 14>
As an alkali agent other than silicate, one or more alkali agents selected from alkali metal hydroxides and alkali metal carbonates, preferably 1 selected from potassium hydroxide, sodium hydroxide, potassium carbonate and sodium carbonate Species or two or more alkali agents, more preferably one or more selected from potassium hydroxide and sodium hydroxide, and one or more selected from potassium carbonate and sodium carbonate, more preferably potassium hydroxide A liquid detergent composition for a dishwasher according to any one of <Item 1> to <Item 13>, further comprising potassium carbonate.

<Section 15>
The total content of silicate and alkali agent other than silicate is preferably 10% by mass or more, more preferably 15% by mass or more, and preferably 25% by mass or less, more preferably in the liquid detergent composition. The liquid detergent composition for a dishwasher according to <Item 14>, preferably 20% by mass or less.

<Section 16>
The pH at 25 ° C. of the 0.2% by weight water dilution is preferably 9 or higher, more preferably 9.5 or higher, more preferably 10 or higher, more preferably 10.5 or higher, and preferably 12 or lower. The liquid detergent composition for dishwashers according to any one of <Item 1> to <Item 15>, more preferably 11.5 or less.

<Section 17>
One or more selected from nonionic surfactants (hereinafter referred to as nonionic surfactant (I)) in which ethylene oxide and propylene oxide are bonded in this order to a branched chain alcohol having 10 to 14 carbon atoms The liquid detergent composition for a dishwasher according to any one of <Item 1> to <Item 16>, comprising two or more.

<Section 18>
The average addition mole number of ethylene oxide of the nonionic surfactant (I) is preferably 4 or more, more preferably 4.5 or more, more preferably 5 or more, and preferably 10 or less, more preferably 9 or less. The liquid detergent composition for a dishwasher according to <Item 17>, more preferably 8 or less.

<Section 19>
The average added mole number of propylene oxide of the nonionic surfactant (I) is preferably 2 or more, more preferably 3 or more, more preferably 4 or more, more preferably 5 or more, and preferably 10 or less, The liquid detergent composition for a dishwasher according to any one of <Item 17> or <Item 18>, more preferably 9.5 or less, more preferably 9 or less.

<Section 20>
The content of the nonionic surfactant (I) in the liquid detergent composition is preferably 0.3% by mass or more, more preferably 0.4% by mass or more, and preferably 0.7% by mass. Hereinafter, the content of the nonionic surfactant is preferably 0.6% by mass or less, and the content of the nonionic surfactant in the liquid detergent composition is preferably 0.3 to 0.7% by mass, more preferably 0.00. The liquid detergent composition for a dishwasher according to any one of <Item 17> to <Item 19>, which is 3 to 0.6 mass%, more preferably 0.4 to 0.6 mass%.

<Section 21>
The liquid detergent composition for dishwashers according to any one of <Item 1> to <Item 20>, comprising one or more selected from fatty acids or salts thereof and alkenyl succinic acids or salts thereof. .

<Section 22>
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. The carbon number of the fatty acid is preferably 6 to 12, more preferably The liquid detergent composition for a dishwasher according to <Item 21>, wherein is 8 to 10.

<Section 23>
The carbon number of the alkenyl succinic acid is preferably 10 or more, more preferably 12 or more, and preferably 16 or less, more preferably 14 or less. The carbon number of the alkenyl succinic acid is preferably 10 to 10 The liquid detergent composition for dishwashers according to <Item 21> or <Item 22>, which is 16, more preferably 12-14.

<Section 24>
Fatty acid or its salt, and alkenyl succinic acid or its salt, and the mass ratio of the content of fatty acid or its salt and alkenyl succinic acid or its salt is (fatty acid or its salt) / (alkenyl succinic acid) Acid or salt thereof), preferably 50/50 or more, more preferably 60/40 or more, more preferably 67/33 or more, and preferably 99/1 or less, more preferably 90/10 or less, more It is preferably 86/14 or less, more preferably 80/20 or less, and it contains a fatty acid or a salt thereof, and alkenyl succinic acid or a salt thereof, and the content of the fatty acid or a salt thereof and alkenyl succinic acid or a salt thereof. The mass ratio is (fatty acid or salt thereof) / (alkenyl succinic acid or salt thereof), preferably 50/50 to 99/1, more preferably 50/50 to <10>, more preferably 60/40 to 86/14, more preferably 67/33 to 80/20, <21> to <23> The liquid cleaning for dishwashers according to any one of <23> Agent composition.

<Section 25>
The total content of fatty acid or salt thereof and alkenyl succinic acid or salt thereof is preferably 0.5% by mass or more, more preferably 0.75% by mass or more, and preferably 5% by mass in terms of acid. In the following, the total content of fatty acids or salts thereof and alkenyl succinic acids or salts thereof is preferably 0.3% by mass or less, more preferably 3% by mass or less, more preferably 1.5% by mass or less. The dish washing according to any one of <Item 21> to <Item 24>, which is 5 to 5% by mass, more preferably 0.75 to 3% by mass, and more preferably 0.75 to 1.5% by mass. Liquid detergent composition for machinery.

<Section 26>
<Claim 1> to <Claim 25> A cleaning liquid for a dishwasher according to any one of <1> to <25>, wherein the cleaning liquid is diluted with water, and the content of the component (A) in the cleaning liquid is converted to an acid. A cleaning liquid of 0.0017% by mass or more and 0.017% by mass or less.

<Section 27>
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, more preferably 0.0044% by mass or more, more preferably 0.004% by mass or more in terms of acid. 0051% by mass or more, more preferably 0.0061% by mass or more, more preferably 0.0065% by mass or more, and preferably 0.010% by mass or less, more preferably 0.0094% by mass or less, more preferably The cleaning liquid according to <Item 26>, wherein is 0.0085 mass% or less, more preferably 0.0075 mass% or less, and more preferably 0.0072 mass% or less.

<Section 28>
The content of the component (B) in the cleaning liquid is preferably 0.00125% by mass or more, more preferably 0.0025% by mass or more, more preferably 0.0030% by mass or more, more preferably 0.005% by mass or more in terms of acid. 00325% by weight or more, more preferably 0.00375% by weight or more, more preferably 0.0045% by weight or more, more preferably 0.00475% by weight or more, and preferably 0.0125% by weight or less, more preferably Is 0.011% by mass or less, more preferably 0.010% by mass or less, more preferably 0.009% by mass or less, more preferably 0.0075% by mass or less, more preferably 0.0070% by mass or less, more preferably Is 0.00625 mass% or less, more preferably 0.0060 mass% or less, more preferably 0.0055 mass% or less, more preferably Is properly or less 0.00525 wt%, <claim 26> or <claim 27> any one wash described.

<Section 29>
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 0.0020% by mass or more, more preferably 0.0026% by mass or more. More preferably 0.0030% by mass or more, more preferably 0.0036% by mass or more, more preferably 0.0038% by mass or more, and preferably 0.011% by mass or less, more preferably 0.010%. % By mass or less, more preferably 0.009% by mass or less, more preferably 0.007% by mass or less, more preferably 0.005% by mass or less, more preferably 0.0044% by mass or less, more preferably 0.0042%. The cleaning liquid according to any one of <Item 26> to <Item 28>, wherein the cleaning solution is not more than mass%.

<Section 30>
The content of silicate in the cleaning liquid is preferably 0.0025% by mass or more, more preferably 0.005% by mass or more, more preferably 0.006% by mass or more, more preferably 0.0065% by mass or more, more Preferably it is 0.0075 mass% or more, More preferably, it is 0.0080 mass% or more, More preferably, it is 0.009 mass% or more, More preferably, it is 0.0095 mass% or more, and Preferably it is 0.025 mass% Or less, more preferably 0.015 mass% or less, more preferably 0.014 mass% or less, more preferably 0.0125 mass% or less, more preferably 0.012 mass% or less, more preferably 0.0110 mass%. Hereinafter, the cleaning liquid according to any one of <Item 26> to <Item 29>, which is more preferably 0.0105% by mass or less.

<Section 31>
The liquid detergent composition for a dishwasher according to any one of <Item 1> to <Item 25> is preferably 200 mass times or more, more preferably 333 mass times or more, more preferably 400 mass with water. Times or more, more preferably 455 mass times or more, more preferably 476 mass times or more, and preferably 2000 mass times or less, more preferably 1000 mass times or less, more preferably 769 mass times or less, more preferably 667 times. A cleaning liquid obtained by diluting at a dilution ratio of not more than mass times, more preferably not more than 556 times mass, more preferably not more than 526 times mass.

<Section 32>
<Claim 1> to <Claim 25> The liquid detergent composition for a dishwasher according to any one of the above is supplied to a washing liquid tank of an automatic dishwasher, and the composition and water are mixed (A) A cleaning method for tableware, in which a cleaning liquid having a component content of 0.0017% by mass or more and 0.017% by mass or less is prepared in a cleaning liquid tank, and dishes are cleaned using the cleaning liquid.

<Section 33>
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, more preferably 0.0044% by mass or more, more preferably 0.004% by mass or more in terms of acid. 0051% by mass or more, more preferably 0.0061% by mass or more, more preferably 0.0065% by mass or more, and preferably 0.010% by mass or less, more preferably 0.0094% by mass or less, more preferably The cleaning method for tableware according to <Item 32>, wherein is 0.0085% by mass or less, more preferably 0.0075% by mass or less, and more preferably 0.0072% by mass or less.

<Section 34>
The content of the component (B) in the cleaning liquid is preferably 0.00125% by mass or more, more preferably 0.0025% by mass or more, more preferably 0.0030% by mass or more, more preferably 0.005% by mass or more in terms of acid. 00325% by weight or more, more preferably 0.00375% by weight or more, more preferably 0.0045% by weight or more, more preferably 0.00475% by weight or more, and preferably 0.0125% by weight or less, more preferably Is 0.011% by mass or less, more preferably 0.010% by mass or less, more preferably 0.009% by mass or less, more preferably 0.0075% by mass or less, more preferably 0.0070% by mass or less, more preferably Is 0.00625 mass% or less, more preferably 0.0060 mass% or less, more preferably 0.0055 mass% or less, more preferably Is properly or less 0.00525 wt%, <claim 32> or <33.> tableware cleaning method according to any one of.

<Section 35>
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 0.0020% by mass or more, more preferably 0.0026% by mass or more. More preferably 0.0030% by mass or more, more preferably 0.0036% by mass or more, more preferably 0.0038% by mass or more, and preferably 0.011% by mass or less, more preferably 0.010%. % By mass or less, more preferably 0.009% by mass or less, more preferably 0.007% by mass or less, more preferably 0.005% by mass or less, more preferably 0.0044% by mass or less, more preferably 0.0042%. The method for washing tableware according to any one of <Item 32> to <Item 34>, wherein the amount is less than or equal to mass%.

<Section 36>
The content of silicate in the cleaning liquid is preferably 0.0025% by mass or more, more preferably 0.005% by mass or more, more preferably 0.006% by mass or more, more preferably 0.0065% by mass or more, more Preferably it is 0.0075 mass% or more, More preferably, it is 0.0080 mass% or more, More preferably, it is 0.009 mass% or more, More preferably, it is 0.0095 mass% or more, and Preferably it is 0.025 mass% Or less, more preferably 0.015 mass% or less, more preferably 0.014 mass% or less, more preferably 0.0125 mass% or less, more preferably 0.012 mass% or less, more preferably 0.0110 mass%. Hereinafter, the washing | cleaning method of the tableware in any one of <paragraph 32>-<paragraph 35> which is 0.0105 mass% or less more preferably.

<Section 37>
<Claim 1> to <Claim 25> The liquid detergent composition for a dishwasher according to any one of the above items is supplied to a washing liquid tank of an automatic dishwasher, and the composition and water are mixed, preferably 200 mass times or more, more preferably 333 mass times or more, more preferably 400 mass times or more, more preferably 455 mass times or more, more preferably 476 mass times or more, and preferably 2000 mass times or less, more preferably Is prepared in a washing liquid tank at a dilution ratio of 1000 mass times or less, more preferably 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, A method for washing dishes, in which dishes are washed with a cleaning solution.

<Section 38>
The tableware according to any one of items <32> to <37>, wherein the composition is mixed with water having a German hardness of 2 ° dH or higher, a German hardness of 3 ° dH or higher, or a German hardness of 4 ° dH or higher. Cleaning method.

<Section 39>
Use of the liquid detergent composition for a dishwasher according to any one of <Item 1> to <Item 25> as a liquid detergent for a dishwasher.

  About the liquid cleaning composition of Tables 1-4, scale adhesion suppression (1), scale adhesion inhibition (2), scale adhesion inhibition (3), detergency, tea astringency adhesion inhibition, The compoundability and low-temperature storage stability were evaluated, and the results are shown in Tables 1 to 4. Moreover, pH at 25 degreeC of 0.2 mass% water dilution aqueous solution was measured by JISK3362, and it described in Tables 1-4.

  In addition, the preparation method of the liquid detergent composition of the mixing | blending composition shown in Examples 1-19 and Comparative Examples 1-18 is as follows.

<Method for preparing liquid detergent composition>
Examples 1-15, Comparative Examples 1, 2, 5, 6, 17
The blending amount was calculated so that the total amount of each component was 500 g. Each composition was put into a 500 mL beaker in the following order. Using a stirrer (manufactured by TOKYO DRIKAKIKAI, Type Z-2200) and a stirring blade (three blades: 4 cm in diameter), mixing was performed at a rotation speed of 200 (rpm / min). The temperature at the time of preparation was adjusted in the range of 25 ° C. to 35 ° C. in consideration of heat generation due to heat of neutralization.

  Ion-exchanged water, potassium hydroxide, caprylic acid (Lunac 8-98), alkenyl succinic acid (Latemul DSK), and nonionic surfactant (Softanol EP7085) were added and mixed until evenly dissolved. Thereafter, potassium carbonate, No. 1 sodium silicate, and sodium polyacrylate (Socaran PA25CL-FR) were added and mixed until they were uniformly dissolved. Thereafter, MGDA and citric acid were added and mixed until dissolved uniformly to obtain a liquid detergent composition.

Example 16, Comparative Examples 3, 4
A liquid detergent composition was prepared in the same manner as in Example 1 except that instead of MGDA, the amount of GLDA described in the table was used at the same addition time.

Examples 17 and 18
Instead of No. 1 sodium silicate, a liquid detergent composition was prepared in the same manner as in Example 1 except that No. 1 sodium silicate or No. 1 potassium silicate described in the table was used at the same time of addition.

Example 19
Instead of sodium polyacrylate, use the potassium polyacrylate listed in the table at the same time of addition, and use No. 1 potassium silicate listed in the table at the same time of addition instead of No. 1 sodium silicate Except for this, a liquid detergent composition was prepared in the same manner as in Example 1.

Comparative Example 7
Instead of MGDA, a liquid detergent composition was prepared in the same manner as in Example 1 except that the amount of EDTA described in the table was used at the same addition time.

Comparative Example 8
A liquid detergent composition was prepared in the same manner as in Example 1 except that citric acid was not blended.

Comparative Example 9
A liquid detergent composition was prepared in the same manner as in Example 1 except that malic acid was used at the same addition time instead of citric acid.

Comparative Example 10
A liquid detergent composition was prepared in the same manner as in Example 1 except that gluconic acid was used at the same addition time instead of citric acid.

Comparative Example 11
A liquid detergent composition was prepared in the same manner as in Example 1 except that succinic acid was used at the same addition time instead of citric acid.

Comparative Example 12
A liquid detergent composition was prepared in the same manner as in Example 1 except that instead of citric acid, the amount of trisodium citrate described in the table was used at the same addition time.

Comparative Examples 13, 14,
A liquid detergent composition was prepared in the same manner as in Example 1 except that the amount of potassium hydroxide or sodium hydroxide described in the table was used at the same addition time instead of potassium hydroxide.

Comparative Examples 15 and 16
A liquid detergent composition was prepared in the same manner as in Example 1 except that potassium carbonate or sodium carbonate in the amount shown in the table was used at the same addition time instead of potassium carbonate.

Comparative Example 18
A liquid detergent composition was prepared in the same manner as in Example 1 except that sodium polyacrylate (Socaran PA25CL-FR) was not used.

  In the above, potassium hydroxide or sodium hydroxide forms a neutralized salt of caprylic acid (Lunac 8-98), citric acid, malic acid, gluconic acid or succinic acid. It was determined. In addition, the remainder as an unneutralized part of the potassium hydroxide or sodium hydroxide in a composition was all 4.8 mass%.

<Scale adhesion suppression (1)>
A cleaning liquid tank (38L) of a one-door type commercial dishwasher (SANYO DR53) was filled with a cleaning liquid prepared from the cleaning composition shown in the table. The conditions of a washing temperature of 70 ° C., a washing time of 40 seconds, a rinsing temperature of 80 ° C., and a rinsing time of 6 seconds were defined as one cycle (70 seconds). Continuous operation of 500 cycles (about 10 hours) was performed. A cleaning liquid was prepared by diluting the cleaning composition 500 times with water so that the concentration of the cleaning composition in the cleaning liquid was 0.2% by mass. In this dishwasher, the concentration of each component of the cleaning liquid stored in the cleaning liquid tank is controlled to be constant during cleaning.
In addition, hard water adjusted to 10000 ° dH (German hardness) with calcium chloride is added to the water used for the preparation and rinsing of the washing solution so that the hardness during operation of the dishwasher becomes 1 to 7 ° dH. To 0.5 ° dH.
Each cycle was operated for 500 cycles using water of each hardness, and after completion of the operation, the degree of scale adhesion on the cleaning chamber side wall and the strainer was visually determined. The upper limit hardness at which scale adhesion is suppressed is shown in the table as hardness resistance (° dH). The higher the hardness resistance, the higher the effect of suppressing scale adhesion.

  Here, the fact that scale adhesion is suppressed means that no discoloration or alteration is observed at all compared to before the operation, and there is a gloss equivalent to the initial level or slightly discolored, but the scale does not adhere and is glossy. Indicates that there is a state. When the scale is attached, the gloss is lost and the surface becomes rough.

In addition, content of (A) component in a washing | cleaning liquid was as follows in acid conversion.
Examples 1 and 19: 0.0046% by mass
Example 2: 0.0060 mass%
Examples 3, 6-18: 0.0068% by mass
Example 4: 0.0076 mass%
Example 5: 0.0090 mass%
Comparative examples 1 and 3: 0.0030 mass%
Comparative Example 2: 0.0106% by mass
Comparative Example 4: 0.0104% by mass
Comparative Examples 5, 6, 8-18: 0.0068% by mass
Comparative Example 7: 0% by mass

<Scale adhesion suppression (2)>
Except for preparing the cleaning liquid by diluting the cleaning composition with water so that the concentration of the cleaning composition in the cleaning liquid is 0.15% by mass, the scale adhesion inhibiting property (1) and Evaluation was performed in the same manner.

In addition, content of (A) component in a washing | cleaning liquid was as follows in acid conversion.
Examples 1 and 19: 0.00345% by mass
Example 2: 0.0045% by mass
Example 3, 6-18: 0.0051 mass%
Example 4: 0.0057 mass%
Example 5: 0.00675 mass%
Comparative Examples 1 and 3: 0.00225 mass%
Comparative example 2: 0.00795 mass%
Comparative example 4: 0.0078 mass%
Comparative Examples 5, 6, 8 to 18: 0.0051% by mass
Comparative Example 7: 0% by mass

<Scale adhesion suppression (3)>
Except for preparing the cleaning liquid by diluting the cleaning composition 1000 times with water so that the concentration of the cleaning composition in the cleaning liquid is 0.1% by mass, Evaluation was performed in the same manner.
In addition, content of (A) component in a washing | cleaning liquid was as follows in acid conversion.
Examples 1 and 19: 0.0023 mass%
Example 2: 0.0030% by mass
Examples 3, 6-18: 0.0034% by mass
Example 4: 0.0038 mass%
Example 5: 0.0045% by mass
Comparative Examples 1 and 3: 0.0015 mass%
Comparative example 2: 0.0053 mass%
Comparative example 4: 0.0052 mass%
Comparative Examples 5, 6, 8-18: 0.0034% by mass
Comparative Example 7: 0% by mass

<Detergency>
To a magnetic dish having a peripheral wall with an inner diameter of 200 mm and a height of 30 mm, 2 g of egg yolk colored with a red pigment as a model stain was uniformly applied to a radius of 7 cm in the center. Thereafter, drying was performed at 80 ° C. for 30 minutes, and four magnetic dishes used for evaluation were prepared. They were set in a one-door type commercial dishwasher (SANYO DR53 manufactured by Sanyo Electric Co., Ltd.). The cleaning liquid tank (38L) of the cleaning machine was prepared from the cleaning composition shown in the table, and the cleaning composition having a cleaning composition concentration of 0.15% by mass (however, diluted with water having a German hardness of 4 ° dH). Satisfied. Washing was performed under conditions of a washing temperature of 50 ° C., a washing time of 40 seconds, a rinsing temperature of 80 ° C., and a rinsing time of 10 seconds. In this dishwasher, the concentration of the cleaning liquid stored in the cleaning liquid tank is controlled to be constant during cleaning. The washed magnetic dish was taken out, dried in a room adjusted to 25 ° C. ± 5 ° C., and the area of the model stain remaining in the 7 cm radius of the central part of the magnetic dish was determined by image processing. The area of the obtained model dirt is taken as the area after the test, and the area before the test is taken as the area of a circle having a radius of 7 cm (the area of the central part where the dirt is applied). / (Area before test)] × 100], the cleaning rate (%) was obtained. The average value of 4 sheets was shown to Tables 1-4.

  In addition, content of (A) component in a washing | cleaning liquid was the same as that of the said scale adhesion inhibitory property (2) in conversion of an acid.

<Adhesion to tea astringency>
The liquid detergent composition was put into a one-door type commercial dishwasher [SANYO DR53 manufactured by Sanyo Electric Co., Ltd.]. The washing machine was operated under the conditions of a washing temperature of 60 ° C., a concentration of the detergent composition in the washing liquid of 0.15% by mass, a washing time of 40 seconds, a rinsing temperature of 80 ° C., a rinsing time of 10 seconds, and a water volume of 2 L per rinsing. The operation was continued 50 times. Adjustment was made so that there was no fluctuation in the concentration of the cleaning composition in the cleaning solution during the test. After the adjustment, during the tea astringent adhesion inhibitory test, the following method was used. From the start of cleaning to the end of cleaning, the model was set so that model dirt (casein Ca salt) was present in the cleaning tank (38L).
(Cleaning conditions)
・ Cleaning temperature: 60 ℃
-Detergent composition concentration 0.15% by mass
-Washing time: 40 seconds-Rinsing temperature: 80 ° C
・ Rinse time: 10 seconds ・ Water volume per rinse: 2 L
・ Washing water hardness: German hardness 2 ° dH
・ Model dirt in cleaning solution tank: Casein Ca salt

[How to put model dirt into the cleaning solution tank]
As a model of casein Ca salt, albumin (egg derived, manufactured by Wako Pure Chemical Industries, Ltd .: Reagent) is continuously washed from start to finish so that the concentration of albumin in the wash tank is 50 ppm. I put it in.

[Evaluation method of tea astringent adhesion suppression effect]
Boiled Hojicha (10 Hojicha tea bags for 1.8 L of boiling water, boiled for 10 minutes and cooled to room temperature) into 4 melamine cups (capacity approx. 150 cc) for 8 minutes each I put it in my eyes. After standing for 10 to 20 seconds, hojicha was discarded and washed under the above washing conditions. This was repeated 50 times (hoji tea was charged, discarded and washed 50 times). Then, the external appearance was observed visually and the tea astringent adhesion inhibitory effect was determined on the following reference | standard. In addition, in the washing | cleaning by each cleaning composition, the difference of the state between four cups was not able to be confirmed.
In addition, content of (A) component in a washing | cleaning liquid was the same as that of the said scale adhesion inhibitory property (2) in conversion of an acid.

* Evaluation Criteria for Tea Astringency Inhibition Effect 5: All 4 melamine cups have no tea astringency attached.
4: All four melamine cups have a slight amount of tea astringent attached. (Slight adhesion can be confirmed from Evaluation 5)
3: Brown partial adhesion is recognized by all four melamine cups.
2: Adherence to tea astringency is observed in all four melamine cups. (It can be confirmed that there is more adhesion than evaluation 3 and less adhesion than evaluation 1)
1: Adhesion of dark tea astringency is recognized in all four melamine cups.

<Compoundability>
When preparing the liquid detergent composition by the above method, check the time from immediately after mixing the final raw materials MGDA, GLDA, EDTA, citric acid, or trisodium citrate until uniform dissolution. It was evaluated with.
* Evaluation criteria 5 of compoundability: dissolved in less than 2 minutes after mixing of the final raw materials.
4: Dissolve in 2 minutes to less than 5 minutes after mixing the final raw materials.
3: Dissolved in 5 minutes or more and less than 10 minutes after mixing of the final raw materials.
2: Dissolved in 10 minutes to less than 20 minutes after final raw material mixing.
1: Dissolve in 20 minutes or more after final raw material mixing.

<Low temperature storage stability>
200 ml of the liquid detergent composition shown in the table was placed in a 250 ml polypropylene container, sealed, stored at −5 ° C. for 10 days, and the appearance of the liquid was evaluated according to the following criteria.
(Criteria)
5: Uniform and transparent (no turbidity is observed).
4: Slight turbidity is observed.
3: Slight turbidity is observed.
2: Turbidity is observed.
1: Turbidity is observed and two-layer separation occurs.

(Note) The components in the table are as follows. In the table, the mass ratio is shown for convenience, with the comparative component of component (A) as component (A) and the comparative component of component (B) as component (B).
<(A) component or its comparative component>
MGDA: trisodium methylglycine diacetate, “Trilon M Powder” (manufactured by BASF)
GLDA: glutamine diacetate tetrasodium, “Dissolvine GL-PD-S” (manufactured by AkzoNobel)
EDTA: ethylenediaminetetraacetic acid tetrasodium, “Kyrest 400” [manufactured by Kyrest Co., Ltd.]

<(B) component or its comparative component>
Citric acid: Reagent (first grade)
・ Trisodium citrate: “Purified sodium citrate M” (manufactured by Fuso Chemical Co., Ltd.)
-Malic acid: Reagent (DL-malic acid) (special grade)
-Gluconic acid: Reagent (50% gluconic acid aqueous solution), the numbers in the table indicate the compounding amount of the effective amount.
・ Succinic acid: Reagent (special grade)

<(C) component>
-Sodium polyacrylate: “Socaran PA25CL FR” [manufactured by BASF Japan Ltd., sodium salt of acrylic acid homopolymer, weight average molecular weight 4,000]
Poly potassium acrylate: “Oligomer M3” (Kao Corporation, potassium salt of acrylic acid homopolymer, weight average molecular weight 9000)

<Other ingredients>
Caprylic acid: “Lunac 8-98” (manufactured by Kao Corporation)
・ Alkenyl succinic acid: “Latemul DSK” (manufactured by Kao Corporation)
・ Potassium hydroxide: Reagent (special grade)
・ Sodium hydroxide: Reagent (special grade)
・ Potassium carbonate: Reagent (special grade)
・ Sodium carbonate: Reagent (special grade)
・ No. 1 potassium silicate: manufactured by Nippon Chemical Industry Co., Ltd., SiO ₂ / K ₂ O molar ratio = 2.0 to 2.3 [from Nippon Chemical Industry Co., Ltd. pamphlet]
・ No. 1 sodium silicate: manufactured by Nippon Chemical Industry Co., Ltd., SiO ₂ / Na ₂ O molar ratio = 2.0 to 2.3 [from Nippon Chemical Industry Co., Ltd. pamphlet]
And non-ionic surfactants: ^{R 1} in the general formula (1) is secondary alkyl group having 12 to 14 carbon atoms, s = 7.0, nonionic surfactants t = 8.5, trade name " SOFTANOL EP7085 "(manufactured by Nippon Shokubai Co., Ltd.)

 As is clear from the comparison between Examples and Comparative Examples shown in Tables 1 to 4, the liquid detergent composition of the present invention has good cleanability and tea astringent adhesion inhibitory property against dirt containing protein. It has not only excellent blendability and low-temperature stability, but also excellent scale adhesion inhibition properties.

  The liquid detergent compositions of Examples 1 to 19 and Comparative Examples 1 to 18 were evaluated for anodizing corrosion resistance by the following method. As a result, no damage was observed and the anodizing corrosion resistance was good. .

<Anodizing corrosion resistance>
In a 100 ml glass standard bottle (No. 11), 30 mL of 0.2% by mass water diluted cleaning solution obtained by diluting the liquid cleaning composition 500 times by mass with ion-exchanged water was placed. A 3 cm × 5 cm test plate cut from an aluminum anodized aluminum can (AIHO) was immersed therein to about half in the longitudinal direction and held at a liquid temperature of 60 ° C. for 1 hour. After holding, the test plate was taken out, rinsed with running water at 20 ° C. ± 5 ° C. for 30 seconds, water droplets were removed with 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 dishwasher containing a silicate, the following (A) component, (B) component, (C) component:
(A) component: methylglycine diacetate, glutamine diacetate or a salt thereof (B) component: citric acid or a salt thereof (C) component: polyacrylic acid or a salt thereof, and water,
(A) The content of the component is 2.0% by mass or more and 5.0% by mass or less in terms of acid,
The content of the component (B) is 1.5% by mass or more and 5.4% by mass or less in terms of acid,
The content of silicate is 2.5% by mass or more and 7.4% by mass or less,
Contains potassium ions and optionally sodium ions,
The content of sodium ion content of potassium ions in the [Na ^{+] [K +]} molar ratio ^{[Na +] / [K +} ] 0 or more and 0.9 or less,
Liquid detergent composition for dishwashers. The tableware of Claim 1 whose mass ratio (A) / (B) with respect to acid conversion content of (B) component of acid conversion content of (A) component is 0.65 or more and 1.9 or less. A cleaning composition for a cleaning machine. The mass ratio (B) / (C) of the content of the component (B) in terms of acid to the content of the component (C) is 0.5 or more and 2.5 or less, either 1 or 2. A liquid detergent composition for a dishwasher according to Item. Any one of Claims 1-3 whose mass ratio (A) / (C) of content of the acid conversion of (A) component with respect to content of (C) component is 0.7 or more and 3.4 or less. A liquid detergent composition for a dishwasher according to Item. The total of (A) component acid content, (B) component acid content, and (C) component content is 6.0 mass% or more and 12.0 mass% or less. The liquid detergent composition for tableware washing machines of any one of 1-4. The liquid detergent composition for dishwashers in any one of Claims 1-5 whose pH in 25 degreeC of 0.2 mass% water dilution liquid is 9 or more. It is the washing | cleaning liquid which diluted the liquid cleaning composition for tableware washing machines of any one of Claims 1-6 with water, Comprising: Content of (A) component in washing | cleaning liquid is 0.0017 mass in conversion of an acid % Or more and 0.017% by mass or less. The liquid detergent composition for dishwashers according to any one of claims 1 to 6 is supplied to a washing liquid tank of an automatic dishwasher, and the composition and water are mixed to contain the component (A). A cleaning method for tableware, in which a cleaning liquid having an acid conversion of 0.0017% by mass or more and 0.017% by mass or less is prepared in a cleaning liquid tank, and the tableware is cleaned using the cleaning liquid.