TWI550081B - Automatic dishwashing detergent compositions - Google Patents

Description

Automatic dishwashing detergent composition

The present invention relates to a detergent composition for an automatic dishwashing machine. In particular, it relates to a detergent composition for an automatic dishwashing machine suitable for use in a commercial water-saving tableware washing machine.

The dishwashing machine is a device for washing dishes such as dirt plates, wave cups, cooking utensils, etc., and is used in kitchens such as homes, restaurants, cafes, and the like. Usually, the dishwashing is performed in the order of the washing step-rinsing step, and in the washing step, the detergent for the automatic dishwashing machine which is different from the hand-washing dishwashing agent in the non-foaming property or the low foaming property is used.

In recent years, with the popularization of a washing machine called a water-saving type washing machine, the use of flushing water has been greatly reduced compared with the previous type, and is reduced by about half. Therefore, there is a tendency that the amount of the dirt remaining in the washing tank increases due to the inflow of the flushing water, and the amount of the dirt remaining in the washing tank tends to increase, and under such conditions, the stain adhesion or the noticeable appearance such as water spots may be lowered. .

In the case where the adhesion of the tea scale is increased, it is necessary to additionally perform impregnation bleaching using a chlorine-based bleaching agent. However, there are cases where it is difficult to ensure a space for impregnation bleaching depending on the scale of the equipment. In addition, it is feared that deterioration of the tableware is promoted by repeated impregnation with a chlorine-based bleaching agent, and the state of the tea stain is more likely to adhere.

In order to make the adhesion of the tea scale not obvious, a washing agent for an automatic dishwashing machine containing hypochlorous acid as a bleaching component is proposed. It can inhibit the adhesion of tea scale when the amount of dirt is small. On the other hand, in the case of a large amount of dirt, hypochlorite Since the effective chlorine concentration of acid is deactivated due to organic matter, etc., it is not expected to suppress the bleaching function such as adhesion of tea scale.

The hardness components such as calcium, magnesium, and cerium oxide contained in the water droplets of the water washing water are dried and remain in the form of white spots, especially in the case of glass tableware, which may seriously detract from the appearance. Therefore, in a kitchen such as a restaurant or a coffee shop, when the tableware is washed by a commercial dishwashing machine, in addition to the detergent, a bright dish is used in the rinsing step in order to make the water droplets easily flow away from the tableware (Rinse Agent). ).

A usual non-ionic surfactant such as glycerin fatty acid ester or sorbitan fatty acid ester is blended in the brightening agent to emulsifie the rinse water to lower the surface tension with the tableware, so that the water droplets are easily dripped. As a result, the drying of the tableware can be accelerated and the water spots can be reduced.

On the other hand, although the effect of reducing water spots was confirmed in the bright disk, this effect was never satisfactory, and in a restaurant, a coffee shop, etc., in order to remove the water spot which adhered to a tableware, the wiping operation was performed by the towel. Further, since the brightener is used in the rinsing step, it is necessary to supply a supply device different from the detergent used in the washing step. Furthermore, the actual situation is that the purchase cost of the brightener or the warehouse management fee is a big burden for the restaurant or the coffee shop.

When the amount of dirt in the washing tank is increased due to the spread of the water-saving type washing machine, further development of the technology is required from the viewpoint of the effect of suppressing the adhesion of the scale and the suppression of the water spot.

Patent Document 1 discloses a detergent composition for a dishwashing machine comprising a chelating agent such as manganese or methylglycine diacetic acid or a polycarboxylic acid system. A polymeric bleach activator component (A), an inorganic peroxide (B), and a low foaming surfactant (C). Patent Document 2 describes a cleaning preparation for mechanical dishwashing, which contains a) a copolymer obtained by polymerization of a specific monomer such as a monoethylenically unsaturated monocarboxylic acid under specific conditions, and b) A specific complexing agent such as an amine-N,N-diacetic acid derivative, c) a nonionic surfactant, and further a bleaching agent, a builder, an enzyme, and the like. Patent Document 3 describes a detergent composition for a dishwashing machine which contains (A) an alkali metal salt, (B) a metal ion blocking agent, (C) a surfactant, and (D) carbonic acid under specific conditions. An alkali metal salt or (E) polymer electrolyte polymer. Patent Document 4 describes a mixed powder containing a specific polymer such as (a) a glycine-N,N-diacetic acid derivative or (b) polyethylene glycol, and is compatible with a kitchen detergent. in.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-149777

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2010-500431

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2008-50410

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2008-505236

The present invention relates to a detergent composition for an automatic dishwashing machine comprising: (A-1) one or more selected from the group consisting of methylglycine diacetate and an alkali metal salt thereof [hereinafter referred to as (A-1) component is 6% by mass or more and 18% by mass or less, and (A-2) is one or more selected from the group consisting of citric acid and an alkali metal salt thereof. [hereinafter referred to as (A-2) component] 20% by mass or more and 30% by mass or less, and (B-1) is selected from a block bond having an alkyl group having a branched carbon number of 10 or more and 14 or less. One or two or more kinds of nonionic surfactants of ethylene oxide and propylene oxide (hereinafter referred to as (B-1) component) are 3% by mass or more and 7% by mass or less; and (A-1) and The total content of (B-1) is 10% by mass or more and 25% by mass or less, and the mass ratio (A-1)/(B-1) of the content of (A-1) to the content of (B-1) is 1. Above and below 5.

In the washing of the tableware, the insoluble matter which is insoluble in the dirt component of the tableware due to the hardness component in the water is generated. Therefore, if the tableware is washed and insufficiently washed, the insoluble matter remains on the tableware, and the appearance of the dishware after washing is remarkably lowered. Specific examples of the insoluble compound include a casein Ca salt in which a protein component of a soil component is bonded to calcium ions as a hardness component, or a tannic acid and a hardness component which are caused by polyphenols in a beverage. Insoluble Ca salt such as tannic acid Ca salt which is bonded by calcium ions.

In the water-saving type washing machine, the amount of water supplied from the flushing water to the washing tank is smaller than that of the previous washing machine, so that insoluble salts such as insoluble Ca salts generated in the washing liquid are large compared with the previous one. The tendency to exist. Therefore, in the water-saving type washing machine, insoluble compounds such as insoluble Ca salts are likely to remain on the dishware or glass after washing, and as a result, it is easy to cause adhesion to the scale of the tableware or water spots on the surface of the glass. Therefore, the water-saving type washing machine tends to make the appearance of the washed tableware less noticeable.

In the technique of the detergent composition for a dishwashing machine of Patent Document 1, the water-saving washing is not performed, and the adhesion of the tea scale is not sufficient.

In the technique of the washing preparation for mechanical dishwashing of Patent Document 2, the rinse effect accompanying the improvement of wettability is not provided, and it is insufficient in suppressing water spots, and it is difficult to formulate.

In the technique of the detergent composition for a dishwashing machine of Patent Document 3, the effective chlorine concentration is lowered in the case where the dirt load is large, and the adhesion of the tea scale is insufficient.

In the technique of blending powders which can be blended with kitchen detergents in Patent Document 4, the showering effect accompanying the improvement in wettability is not provided, and it is insufficient in suppressing water spots.

In the above-mentioned disclosed technique, it is not sufficient from the viewpoint of suppressing the adhesion of the added scale and reducing the water spots.

An object of the present invention is to provide an excellent performance in suppressing the adhesion of tea scale and reducing the water spot even under the condition that the amount of the rinse water used is small in the case of washing with a water-saving type cleaner. The effect of the automatic dishwashing detergent composition for cleaning.

Hereinafter, the components (A-1) and (A-2) will be summarized and described as the component (A).

According to the present invention, it is provided that the use amount of the flushing water is small even in the case where the amount of the flushing water used in the case of washing with the water-saving type washing machine is small, and it is excellent in suppressing the adhesion of the tea scale and reducing the water spot. The effect of the automatic dishwashing detergent additive composition.

In the present invention, the water-saving type washing machine refers to an automatic tableware washing machine which can be washed as follows: 20 pieces of NaOH solution of 0.2% by mass of NaOH is set at 60 ° C, and 20 pieces of test pieces which are opposed to each other on the glass frame (1) The shape of the piece: 15 cm × 15 cm × 0.2 cm, soda-lime glass manufactured by Japan Test Panel Co., Ltd.) Washed for 40 seconds or more and 60 seconds or less, and then set the tableware to a water level of 2 L per 2500 cm ² After rinsing at 80 ° C, the amount of NaOH remaining on the test piece dried in the atmosphere at 25 ° C for 10 minutes is 0.15 μg / cm ² or less, preferably 0.12 μg / cm ² or less, more preferably 0.1 μg / cm. ² or less. Here, the NaOH residual amount is obtained by immersing the test piece piece by piece in 200 g of distilled water at 25 ° C for 10 seconds, extracting the NaOH remaining on the test piece, and neutralizing and titrating with 0.01 mol/L of hydrochloric acid (HCl). The NaOH in the extract was quantified, and the average value with respect to 20 test pieces was determined. Furthermore, the area of the horizontal surface of the tableware is defined by the area of the bottom surface of the bracket when the area of the horizontal surface is used. The detergent composition for an automatic dishwashing machine of the present invention can be used for washing with a water-saving type washing machine thus defined.

In the present invention, the water-saving type washing machine refers to an automatic tableware washing machine that can perform water-saving washing using less water than the previous automatic dish washing machine, and is not limited to a special machine for water-saving washing. It also includes a washing machine with a function to clean water. For example, in the previous automatic dishwashing machine, the amount of water required for each flushing was 4-6 L per 2500 cm ² of the tableware setting level, but in the water saving type washing machine, the amount of water required for each flushing was The tableware setting level is 2~3 L per 2500 cm ² . Therefore, an automatic tableware washing machine capable of performing a flushing of water per rinsing at a water level of 2 to 3 L per 2500 cm ^{2 can} be used as a water-saving type washing machine.

<(A) component>

[(A-1) ingredient]

The detergent composition for an automatic dishwashing machine of the present invention contains one or more selected from the group consisting of methylglycine diacetate and an alkali metal salt thereof as the component (A-1).

It is presumed that the detergent composition for automatic dishwashing machine of the present invention is easily washed by a water-saving type washing machine by methylglycin diacetate (MGDA, methylglycin diacetate) or an alkali metal salt thereof. The formation of insoluble Ca salt such as casein Ca salt or tannic acid Ca salt and crystal growth are increased to obtain an excellent inhibitory effect on the adhesion of the tea scale.

From the viewpoint of the general product, the type of the alkali metal salt of the component (A-1) may, for example, be a sodium salt or a potassium salt, and is preferably a sodium salt.

The content of the component (A-1) in the detergent composition for an automatic dishwashing machine of the present invention is 6% by mass or more, preferably 7% by mass or more, and more preferably It is preferably 8 mass% or more, and is 18 mass% or less, preferably 15 mass% or less, and more preferably 12 mass% or less. Further, for the same reason, the content of the component (A-1) is 6 to 18% by mass, preferably 7 to 15% by mass, and more preferably 8 to 12% by mass.

<(A-2) component>

The detergent composition for an automatic dishwashing machine of the present invention contains one or two or more selected from the group consisting of citric acid and an alkali metal salt thereof as the component (A-2). As the alkali metal salt, a sodium salt or a potassium salt is preferred, and a sodium salt is more preferred. As the component (A-2) of the present invention, trisodium citrate is preferred. As the component (A-2) of the present invention, a trihydrate of trisodium citrate is preferred.

The content of the component (A-2) in the detergent composition for an automatic dishwashing machine of the present invention is 20% by mass or more, preferably 23% by mass or more, and is 30% by mass or less, preferably 27% by mass or less. Further, for the same reason, the content of the component (A-2) is 20 to 30% by mass, preferably 23 to 27% by mass.

<(B-1) component>

The detergent composition for an automatic dishwashing machine of the present invention contains a selected from the group consisting of a hydrocarbon having a branched carbon number of 10 or more and 14 or less, from the viewpoint of having a shower effect and reducing water spots. One or two or more kinds of nonionic surfactants of ethylene oxide and propylene oxide are bonded as the component (B-1).

The average addition molar number of the ethylene oxide of the component (B-1) is preferably 4 or more, more preferably 4.5 or more, further preferably 5 or more, and preferably 10 or less, more preferably 9 or less. More preferably, it is 8 or less.

Further, the average addition molar number of the propylene oxide of the component (B-1) is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, still more preferably 5 or more, and preferably 10 Hereinafter, it is more preferably 9.5 or less, further preferably 9 or less.

The component (B-1) is preferably one or more selected from the group consisting of nonionic surfactants which are sequentially blocked on an alcohol having a branched carbon number of 10 or more and 14 or less. Ethylene oxide and propylene oxide are bonded to each other, and the average addition molar number of ethylene oxide is 4 or more and 10 or less, and the average addition molar number of propylene oxide is 2 or more and 10 or less.

The component (B-1) is preferably selected from ethylene oxide and a ring which are selected from a secondary carbon having a carbon number of 10 or more, preferably a carbon number of 12 or more and a carbon number of 14 or less. One or two of the nonionic surfactants of oxypropane on. Further, the component (B-1) is preferably one or more selected from the group consisting of nonionic surfactants having a carbon number of 10 or more, preferably a carbon number of 12 or more, and Ethylene oxide and propylene oxide are bonded to the secondary alcohol having a carbon number of 14 or less, and the average addition molar number of ethylene oxide is 4 or more and 10 or less, and the average addition ratio of propylene oxide is The number of moles is 2 or more and 10 or less.

From the viewpoint of the completeness, the component (B-1) is preferably a nonionic surfactant represented by the following formula (b-1).

R ¹ -O-(EO) _s -(PO) _t -H (b-1) wherein R ¹ represents a branched alkyl group having 10 or more and 14 or less carbon atoms, or a carbon number of 10 or more and 14 or less The branched alkenyl group, further, represents a branched alkyl group having 10 to 14 carbon atoms or a branched alkenyl group having 10 to 14 carbon atoms, EO represents a vinyloxy group, PO represents a propyleneoxy group, and s and t represent an average addition. The molar 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 -(PO) _t -" is a block bond].

In the formula (b-1), R ¹ is a branched alkyl group having 10 to 14 carbon atoms or a branched chain having 10 to 14 carbon atoms, preferably having a branched carbon number of 10 ~14 alkyl. 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 a secondary alkyl group having 10 to 14 carbon atoms. The secondary alkyl group may be a group represented by the following formula. R ¹ in the formula (b-1) may be a secondary alkyl group represented by the formula.

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

In the formula (b-1), s is preferably 5 or more and 9 or less, and t is preferably 5 or more and 9 or less, and further preferably s = 5 to 9, and preferably t = 5 to 9. . Specific examples of the nonionic surfactant of the formula (b-1) include polyoxyethylene (7) polyoxypropylene (8.5)-second-dodecyl ether and polyoxyethylene (7). One or more of polyoxypropylene (8.5)-second-tridecyl ether, polyoxyethylene (7) polyoxypropylene (8.5)-second-tetradecyl ether. Here, () is the average addition mole number of ethylene oxide or propylene oxide (the same is true in the nonionic surfactant of the formula (b-2)).

In the formula (b-1), t/s is preferably 0.3 or more, more preferably 0.5 or more, still more preferably 0.7 or more, still more preferably 0.9 or more, and further preferably 1.5 or less, more preferably 1.4. Hereinafter, it is more preferably 1.3 or less.

The compound of the formula (b-1) can be obtained by using an alcohol having a branched alkyl group having 10 to 14 carbon atoms (preferably a secondary alcohol) or an alcohol having a branched alkenyl group having a carbon number of 10 to 14. Jia is a secondary alcohol) is added to form ethylene oxide and then added to form propylene oxide for synthesis.

The weight average molecular weight of the component (B-1) is preferably 200 or more, and is preferably 5,000 or less, more preferably 2,000 or less. Further, the weight average molecular weight of the component (B-1) is preferably from 200 to 5,000, more preferably from 200 to 2,000. general formula The compound of (b-1) can be obtained from Nippon Shokubai Co., Ltd. under the trade name of "Softanol".

(B-1) in the detergent composition for automatic dishwashing machine of the present invention, from the viewpoint of reducing the physical properties of the water spot and the detergent composition for an automatic dishwashing machine of the present invention. The content of the component is 3% by mass or more, and is 7% by mass or less, preferably 6% by mass or less, and more preferably 5% by mass or less. Further, for the same reason, the content of the component (B-1) in the composition is from 3 to 7% by mass, preferably from 3 to 6% by mass, more preferably from 3 to 5% by mass.

The total content of the component (A-1) and the component (B-1) in the detergent composition for an automatic dishwashing machine of the present invention is 10% by mass in terms of the inhibition of the adhesion of the tea scale and the reduction of the water spot. The above is preferably 12% by mass or more, more preferably 14% by mass or more, further preferably 16% by mass or more, and 25% by mass or less, preferably 23% by mass or less, and further preferably 21% by mass. Hereinafter, it is more preferably 19% by mass or less. Further, for the same reason, the total content of the component (A-1) and the component (B-1) in the composition is 10 to 25% by mass, preferably 12 to 23% by mass, and more preferably 14 to 21%. The mass%, and more preferably 16 to 19% by mass.

The mass ratio of the content of the component (A-1) to the content of the component (B-1) in the detergent composition for an automatic dishwashing machine of the present invention, from the viewpoint of suppressing the adhesion of the tea scale and reducing the water spot. (A-1)/(B-1) is 1 or more, more preferably 1.5 or more, further preferably 2 or more, further preferably 2.5 or more, and 5 or less, more preferably 4.5 or less, and further preferably Preferably, it is 4 or less, More preferably, it is 3.5 or less. Further, for the same reason, the mass ratio (A-1)/(B-1) is 1 to 5, preferably 1.5 to 4.5, more preferably 2 to 4, still more preferably 2.5 to 3.5.

<(B) component>

The detergent composition for an automatic dishwashing machine of the present invention may contain a nonionic surfactant other than the component (B-1). Hereinafter, the nonionic surfactant which also includes the component (B-1) will be described as the component (B).

<(B-2) component>

The detergent composition for an automatic dishwashing machine of the present invention preferably contains, as the component (B-2), an alcohol having a hydrocarbon group having 8 or more and 18 or less carbon atoms, and a nonionic surfactant [(B-1) component having an ethylene oxide and a propylene oxide bonded to an alcohol having a hydrocarbon group having 8 to 18 carbon atoms; A nonionic surfactant other than the component (B-1) is added to the alcohol of 14 or less, except for the nonionic surfactant in which ethylene oxide and propylene oxide are sequentially bonded. The component (B-2) may be an alcohol having a hydrocarbon group having 8 or more carbon atoms and 18 or less, and an ethylene oxide and propylene oxide bonded to an alcohol having a hydrocarbon group having 8 to 18 carbon atoms. The nonionic surfactant [(B-1) component is not bonded to the secondary alcohol having a carbon number of 10 or more and 14 or less, except for the nonionic surfactant in which ethylene oxide and propylene oxide are bonded to each other] .

The component (B-2) is preferably a nonionic surfactant represented by the formula (b-2).

R ² -O-(EO) _p -(PO) _q -(EO) _r -H (b-2) [wherein R ² represents a hydrocarbon group having a carbon number of 8 or more and 18 or less, and a carbon number of 8 to 18 a hydrocarbon group, EO represents a vinyloxy group, PO represents a propyleneoxy group, p, q, and r represent an average addition mole number, p is 1 or more and 10 or less, q is 0.5 or more and 5 or less, and r is 1 or more. 10 or less, again, p=1~10, q=0.5~5, r=1~10; "-(EO) _p -(PO) _q -(EO) _r -" is a block bond].

In the formula (b-2), R ^{2 is} preferably a hydrocarbon group having 10 to 14 carbon atoms, more preferably an alkyl group having 10 to 14 carbon atoms, still more preferably a linear alkyl group having 10 to 14 carbon atoms. In the formula (b-2), p is preferably 2 or more and 8 or less, and further preferably 2 to 8. In the formula (b-2), q is preferably 0.5 or more, more preferably 1 or more, and is preferably 4.5 or less, more preferably 3 or less, still more preferably 2 or less. Further, q is preferably from 0.5 to 4.5, more preferably from 1 to 3, still more preferably from 1 to 2. In the formula (b-2), r is preferably 2 or more and 8 or less, and further preferably 2 to 8. In the formula (b-2), p+r is preferably 1 or more, further preferably 2 or more, further preferably 4 or more, and more preferably 30 or less, further preferably 20 or less, and further preferably It is 15 or less. Further, p + r is preferably from 1 to 30, more preferably from 2 to 20, still more preferably from 4 to 15.

Specific examples of the nonionic surfactant of the formula (b-2) include polyoxyethylene (3) polyoxypropylene (1.5) polyoxyethylene (3) lauryl ether, and polyoxyethylene (5) poly One or more of oxypropylene (1.5) polyoxyethylene (5) lauryl ether, polyoxyethylene (5) polyoxypropylene (4.5) polyoxyethylene (5) lauryl ether.

The weight average molecular weight of the component (B-2) is preferably 200 or more, and is preferably 5,000 or less, more preferably 2,000 or less. Further, the weight average molecular weight of the component (B-2) is preferably from 200 to 5,000, more preferably from 200 to 2,000. The compound of the formula (b-2) can be obtained from Kao Corporation under the trade name "Emulgen".

When the detergent composition for an automatic dishwashing machine of the present invention contains the component (B-2), the water plaque and the physical properties of the detergent composition for an automatic dishwashing machine of the present invention are reduced. In view of the above, the total content of the component (B-1) and the component (B-2) in the composition is preferably 3% by mass or more, and further It is preferably 3.5% by mass or more, more preferably 4% by mass or more, and is preferably 7% by mass or less, further preferably 6.5 mass% or less, and further preferably 6% by mass or less. Further, for the same reason, the total content of the component (B-1) and the component (B-2) in the composition is preferably from 3 to 7% by mass, more preferably from 3.5 to 6.5% by mass, still more preferably 4 to 6 mass%.

In the case where the detergent composition for an automatic dishwashing machine of the present invention contains the component (B-2), the content of the component (B-1) and the component (B-2) are reduced from the viewpoint of reducing water spots. The mass ratio (B-1)/(B-2) of the content is preferably 1 or more, more preferably 2 or more, and is preferably 15 or less, more preferably 10 or less, still more preferably 8 or less. More preferably, it is 6 or less. For the same reason, the mass ratio (B-1) / (B-2) is preferably from 1 to 15, more preferably from 1 to 10, still more preferably from 2 to 8, and still more preferably from 2 to 6.

In the detergent composition for an automatic dishwashing machine of the present invention, other nonionic surfactants can be used as the component (B) within the range having the effects of the present invention. Examples of other nonionic surfactants include glycerin fatty acid esters, polyglycerin fatty acid esters, propylene glycol fatty acid esters, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, sucrose fatty acid esters, and polyoxygenates. Ethylene sorbitan fatty acid ester.

In the component (B), the ratio of the total of the component (B-1) to the component (B-2) is preferably 90% by mass or more, more preferably 95% by mass or more, and still more preferably 98% by mass. The above is preferably 100% by mass or less, and may be 100% by mass. Further, in the component (B), the ratio of the total of the component (B-1) to the component (B-2) is preferably from 90 to 100% by mass, more preferably from 95 to 100% by mass, still more preferably from 98 to 8%. 100% by mass.

In the detergent composition for an automatic dishwashing machine of the present invention, the total content of the component (A) and the component (B-1) is more in the composition than the viewpoint of reducing water spots and inhibiting the adhesion of the tea scale. It is preferably 30% by mass or more, more preferably 35% by mass or more, and is preferably 50% by mass or less, and more preferably 45% by mass or less. For the same reason, the total content of the component (A) and the component (B-1) in the composition is preferably from 30 to 50% by mass, more preferably from 35 to 45% by mass.

Moreover, it is preferable that the component (A) component, (B-1) component, and (B) are used in the detergent composition for automatic dishwashing machines of this invention from the viewpoint of the water stain reduction and the adhesion of the tea scale. The total content of the component (2) is preferably 30% by mass or more, more preferably 35% by mass or more, and is preferably 50% by mass or less, and more preferably 45% by mass or less. For the same reason, the total content of the component (A), the component (B-1) and the component (B-2) in the composition is preferably from 30 to 50% by mass, more preferably from 35 to 45% by mass.

Further, in the detergent composition for automatic dishwashing machine of the present invention, the total content of the component (A) and the component (B) is more in the composition than the viewpoint of reducing water spots and inhibiting the adhesion of the tea scale. It is preferably 30% by mass or more, more preferably 35% by mass or more, and is preferably 50% by mass or less, and more preferably 45% by mass or less. For the same reason, the total content of the component (A) and the component (B) in the composition is preferably from 30 to 50% by mass, more preferably from 35 to 45% by mass.

The mass ratio of the content of the component (A) to the content of the component (B-1) in the detergent composition for an automatic dishwashing machine of the present invention, from the viewpoint of reducing the water spot and suppressing the adhesion of the tea scale ( A)/(B-1) is preferably 3 or more, more preferably 4 or more, still more preferably 5 or more, and is preferably 12 or less, more preferably 11 or less, still more preferably 10 or less. Again, for the same reason, the quality The amount ratio (A)/(B-1) is preferably from 3 to 12, more preferably from 4 to 11, more preferably from 5 to 10.

Further, in the detergent composition for an automatic dishwashing machine of the present invention, the content of the component (A) and the component (B-1), (B-), in terms of reducing water spots and inhibiting the adhesion of the tea scale. 2) The mass ratio (A) / [(B-1) + (B-2)] of the total content of the components is preferably 3 or more, more preferably 4 or more, still more preferably 5 or more, and preferably 12 or less, further preferably 11 or less, further preferably 10 or less. Further, for the same reason, the mass ratio (A) / [(B-1) + (B-2)] is preferably from 3 to 12, more preferably from 4 to 11, more preferably from 5 to 10.

Further, in the detergent composition for an automatic dishwashing machine of the present invention, the mass ratio of the content of the component (A) to the content of the component (B) in terms of reducing water spots and inhibiting the adhesion of the tea scale ( A)/(B) is preferably 3 or more, more preferably 4 or more, still more preferably 5 or more, and is preferably 12 or less, more preferably 11 or less, still more preferably 10 or less. Further, for the same reason, the mass ratio (A)/(B) is preferably from 3 to 12, more preferably from 4 to 11, more preferably from 5 to 10.

<(C) component>

The detergent composition for an automatic dishwashing machine of the present invention preferably contains a source selected from the group consisting of (C-1) polyacrylic acid and a salt thereof (hereinafter referred to as (C-1) component), and (C-2). One or more polymer compounds of a group consisting of a copolymer of a monomer unit of maleic acid and a salt thereof (hereinafter referred to as a component (C-2)) are used as the component (C).

The salt of the component (C-1) is preferably an alkali metal salt, more preferably a sodium salt or a potassium salt.

The component (C-2) is preferably a copolymer selected from the group consisting of acrylic acid and maleic acid; the carbon number is 1 or more, further 5 or more, and 10 or less, and the carbon number is 1 to 10, Further, a copolymer of olefin and maleic acid having a carbon number of 5 to 10; a copolymer of polystyrenesulfonic acid and maleic acid; and one or more of the salts, more preferably selected from the group consisting of acrylic acid and cis One or more copolymers of butenedioic acid and salts thereof.

The salt of the component (C-2) is preferably an alkali metal salt, more preferably a sodium salt or a potassium salt.

In the copolymer of acrylic acid and maleic acid of the component (C-2) or a salt thereof, the structural unit derived from acrylic acid or the structural unit derived from maleic acid is preferably 90/10 or more. Further, it is preferably 75/25 or more, and is preferably 50/50 or less, and more preferably 65/35 or less. Moreover, the molar is preferably 90/10~50/50, more preferably 75/25~65/35. Here, the molar ratio of the structural unit derived from acrylic acid or the structural unit derived from maleic acid can be obtained by detecting pyrolysis of the copolymer by pyrolysis gas Chromatography (PGC). Out.

The weight average molecular weight of the polyacrylic acid or a salt thereof of the component (C-1) is preferably 1,000 or more, more preferably 3,000 or more, and preferably 10,000 or less, and further preferably, from the viewpoint of the scale adhesion inhibitory property. It is 8,000 or less, more preferably 6,000 or less, and still more preferably 5,000 or less. Further, for the same reason, the polyacrylic acid or the salt thereof of the component (C-1) preferably has a weight average molecular weight of 1,000 to 10,000, more preferably 3,000 to 8,000, still more preferably 3,000 to 6,000, and still more preferably 3,000. ~5,000.

The weight average molecular weight of the copolymer of the component (C-2) having a unit derived from maleic acid or a salt thereof is preferably 1,000 or more, and more preferably 3,000 or more, from the viewpoint of the scale adhesion inhibitory property. It is preferably 10,000 or less, and more preferably 5,000 or less. Also, for the same reason, (C-2) The weight average molecular weight of the copolymer having a unit derived from maleic acid or a salt thereof is preferably from 1,000 to 10,000, more preferably from 3,000 to 5,000.

Moreover, the weight average molecular weight of the copolymer of the (C-2) component having a unit derived from maleic acid or a salt thereof is more than the viewpoint of the scale adhesion inhibitory property, the inhibition of the adhesion of the tea scale, and the reduction of the water spot. It is preferably 10,000 or more, more preferably 30,000 or more, further preferably 50,000 or more, and more preferably 150,000 or less, further preferably 120,000 or less, and further preferably 100,000 or less.

Here, the weight average molecular weight of the component (C) can be determined by a gel permeation chromatography using a mixed solvent of acetonitrile and water (phosphate buffer solution) as a standard substance.

In the present invention, it is preferred to contain both the component (C-1) and the component (C-2) as the component (C). That is, it is preferable to contain (C-1) component and (C-2) component as (C) component. In the combination of the component (C-1) and the component (C-2), the component (C-1) is preferably a polymer compound selected from the group consisting of polyacrylic acid and a salt thereof, (C- 2) The component is a polymer compound selected from the group consisting of a copolymer of acrylic acid and maleic acid and a salt thereof. When the (C-1) component and the (C-2) component are contained, the mass ratio (C-1)/(C-2) of the component (C-1) to the component (C-2) is preferably It is 1 or more, more preferably 2 or more, still more preferably 3 or more, and is preferably 30 or less, more preferably 20 or less, still more preferably 10 or less.

The content of the component (C) in the detergent composition for an automatic dishwashing machine of the present invention is preferably 5% by mass or more, and more preferably 6% by mass, based on the composition. The above is further preferably 7% by mass. The upper portion is preferably 15% by mass or less, more preferably 14% by mass or less, and still more preferably 13% by mass or less. Further, for the same reason, the content of the component (C) is preferably from 5 to 15% by mass, more preferably from 6 to 14% by mass, even more preferably from 7 to 13% by mass, based on the total amount of the composition.

Further, in the detergent composition for an automatic dishwashing machine of the present invention, the component (A-1), the component (A-2), and (C) are used for the purpose of suppressing the adhesion of the tea scale and reducing the water spot. The total content of the components is preferably 30% by mass or more, more preferably 33% by mass or more, further preferably 35% by mass, further preferably 40% by mass or more, and preferably 50% by mass or less, and further It is preferably 47% by mass or less, and more preferably 45% by mass or less. Further, for the same reason, the total content of the component (A-1), the component (A-2), and the component (C) in the composition is preferably 30 to 50% by mass, and more preferably 33 to 47% by mass. %, and more preferably 35 to 45 mass%.

<(D) component>

From the viewpoint of the formulation, the detergent composition for an automatic dishwashing machine of the present invention preferably contains an inorganic powder having a liquid supporting ability as the component (D). Further, it is preferable that the inorganic powder having one or more selected from the group consisting of amorphous ceria and crystalline calcium silicate has a liquid supporting ability as the component (D). Examples of the liquid which can be carried as the component (D) include a solution of water and a polymer, a surfactant which is a liquid at normal temperature (for example, 25 ° C), a solution of a surfactant, and the like.

In the present invention, the "liquid carrying ability" of the component (D) means that the oil absorption capacity measured by the method described in JIS K6220 (-1995) is 120 ml/100 g or more. The above oil absorption capacity of the component (D) is preferably 120. Ml/100 g or more, and preferably 1,000 ml/100 g or less, further preferably 600 ml/100 g or less. Further, the oil absorption capacity of the component (D) is preferably from 120 to 1,000 ml/100 g, more preferably from 120 to 600 ml/100 g.

The average particle diameter of the component (D) is preferably 0.5 μm or more, more preferably 1 μm or more, and is preferably 300 μm or less, and more preferably 150 μm or less. Further, the average particle diameter of the component (D) is preferably from 0.5 to 300 μm, more preferably from 1 to 150 μm.

The average particle diameter referred to herein is a value calculated by using a laser diffraction type flow distribution measuring device: LA-500 (manufactured by Horiba, Ltd.).

The specific surface area of the component (D) is preferably 30 m ² /g or more, more preferably 50 m ² /g or more, and is preferably 600 m ² /g or less, and further preferably 400 m ² /g or less. Further, the specific surface area of the component (D) is preferably from 30 to 600 m ² /g, more preferably from 50 to 400 m ² /g. This was measured by the BET (Brunauer-Emmett-Teller) type surface area meter.

As the amorphous ceria which is the component (D) of the present invention, synthetic amorphous ceria which is commercially available as the Tokusil series and the Finesil series (Tokuyama Co., Ltd.) can be used. Here, the amorphous ceria refers to a network structure containing Si—O and does not have a fixed crystal structure.

The crystalline calcium silicate as the component (D) of the present invention is preferably 2CaO. 3SiO ₂ . mSiO ₂ . In the case of nH ₂ O (m, n is a number of 1 < m < 2, 2 < n < 3), various crystal calcium silicates commercially available as the Florite series (Tokuyama Co., Ltd.) can be used.

From the viewpoint of formulation, a liquid having the component (D) of the present invention The inorganic powder having a supporting ability is preferably amorphous ceria.

The content of the component (D) in the detergent composition for an automatic dishwashing machine of the present invention is preferably 0.5% by mass or more, and more preferably 0.7% by mass or more, based on the composition. Further, it is preferably 1% by mass or more, and preferably 2% by mass or less. For the same reason, the content of the component (D) is preferably from 0.5 to 2% by mass, more preferably from 0.7 to 2% by mass, even more preferably from 1 to 2% by mass, based on the total amount of the composition.

<(E) component>

The detergent composition for an automatic dishwashing machine of the present invention is preferably an alkali agent containing at least one selected from the group consisting of anhydrides of phthalates and carbonates (wherein (D) (except for the ingredients) as the component (E).

The alkali agent as the component (E) is preferably one or more selected from the group consisting of an anhydride of an alkali metal citrate and an anhydride of an alkali metal carbonate, more preferably selected from the group consisting of anhydrous sodium carbonate, anhydrous potassium carbonate, and One or more alkali chemicals in anhydrous sodium citrate.

As the inorganic compound of the component (E), it is preferred to use an anhydride of a carbonate and an anhydride of a phthalate. That is, an anhydride containing a carbonate and an anhydride of a phthalate are preferable as the component (E). From the viewpoint of detergency, it is preferred to use an anhydride of an alkali metal carbonate and an alkali metal citrate, and it is more preferred to use anhydrous sodium carbonate and anhydrous sodium citrate. When the anhydrous sodium carbonate and the anhydrous sodium citrate are used in combination, the mass ratio of the content of the anhydrous sodium carbonate to the content of the anhydrous sodium citrate (the content of the anhydrous sodium carbonate) / (the content of the anhydrous sodium citrate) is preferably 1.5 or more. Further, it is preferably 2 or more, more preferably 2.5 or more, and is preferably 4 or less, more preferably 3.5 or less, still more preferably 3 or less. Further, the mass ratio (sodium anhydrous sodium carbonate) / (anhydrous sodium citrate) is preferably from 1.5 to 4, more preferably from 2 to 3.5, and further preferably 2.5~3.

The content of the component (E) in the detergent composition for an automatic dishwashing machine of the present invention is preferably 40% by mass or more, and preferably 70% by mass, based on the detergency. Hereinafter, it is more preferably 65 mass% or less, further preferably 60 mass% or less. For the same reason, the content of the component (E) is preferably 40 to 80% by mass, more preferably 40 to 70% by mass, still more preferably 40 to 60% by mass in the composition.

<Automatic dishwashing detergent composition>

The detergent composition for an automatic dishwashing machine of the present invention preferably contains one selected from the group consisting of (C) component, (D) component, and (E) component in addition to the component (A) and the component (B). Further, it is preferably a component containing (C) component, (D) component, and (E) component, or two or more components.

In the case where the detergent composition for an automatic dishwashing machine of the present invention contains the components (A) to (E), the content of the component (A) is relative to (A) from the viewpoint of reducing the adhesion of the tea scale. The total content of the component (E) is 100% by mass, preferably 20% by mass or more, more preferably 23% by mass or more, further preferably 26% by mass or more, and preferably 55% by mass or less, and more preferably It is preferably 50% by mass or less, and more preferably 45% by mass or less. Further, for the same reason, the content of the component (A) is preferably 100% by mass or more, more preferably 23% to 50% by mass, more preferably 23% to 50% by mass, based on the total of the contents of the components (A) to (E). It is preferably 26 to 45% by mass.

Further, when the detergent composition for an automatic dishwashing machine of the present invention contains the components (A) to (E), the content of the component (B) is further reduced from the viewpoint of reducing water spots (B- 1) the total content of the component and the component (B-2) relative to The total content of the components (A) to (E) is preferably 100% by mass, preferably 3% by mass or more, more preferably 10% by mass or less, still more preferably 9% by mass or less, still more preferably 8% by mass or less. . In addition, the content of the component (B) and the total content of the component (B-1) and the component (B-2) are 100% by mass based on the total content of the components (A) to (E). It is preferably 3 to 10% by mass, more preferably 3 to 9% by mass, still more preferably 3 to 8% by mass.

Further, when the detergent composition for an automatic dishwashing machine of the present invention contains the components (A) to (E), the content of the component (C) is relative to the viewpoint of reducing the adhesion of the tea scale. The total content of the components A) to (E) is 100% by mass, preferably 5% by mass or more, more preferably 6% by mass or more, further preferably 7% by mass or more, and preferably 15% by mass or less. Further, it is preferably 14% by mass or less, and more preferably 13% by mass or less. Further, for the same reason, the content of the component (C) is preferably 100% by mass, more preferably 5 to 15% by mass, even more preferably 6 to 14% by mass, based on the total of the contents of the components (A) to (E). It is preferably 7 to 13% by mass.

Further, when the detergent composition for an automatic dishwashing machine of the present invention contains the components (A) to (E), the content of the component (D) is relative to (A)~ from the viewpoint of formulation. The total content of the component (E) is 100% by mass, preferably 0.5% by mass or more, more preferably 0.7% by mass or more, further preferably 1% by mass or more, and preferably 2% by mass or less. Further, for the same reason, the content of the component (D) is preferably 100% by mass, more preferably 0.5% to 2% by mass, even more preferably 0.7% to 2% by mass, based on the total of the contents of the components (A) to (E). It is preferably 1 to 2% by mass.

Further, the detergent composition for an automatic dishwashing machine of the present invention contains In the case of the components (A) to (E), the content of the component (E) is preferably 100% by mass, preferably 40% by mass based on the total content of the components (A) to (E). % or more, and preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less. Further, for the same reason, the content of the component (A) is preferably 100% by mass or more, more preferably 40% to 70% by mass, more preferably 40% to 70% by mass, based on the total of the contents of the components (A) to (E). It is preferably 40 to 60% by mass.

The detergent composition for an automatic dishwashing machine of the present invention may further contain an organic polymer compound having a water-absorptive powder produced by hydrogen bonding. Specific examples thereof include dextrin, carrageenan, sin gum, guar gum, pectin, locust bean gum, or the like, and processed starch, methyl cellulose, carboxymethyl cellulose. Such as polysaccharides, synthetic polymer compounds such as polyvinyl alcohol, polypropylene decylamine, and polyethylene oxide. In the case of the organic polymer compound containing the water-absorptive powder, it is preferably contained in the detergent composition for an automatic dishwashing machine of the present invention from the viewpoint of storage stability. 0.1% by mass or more, and preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 5% by mass or less. For the same reason, the content of the organic polymer compound having such a water-absorptive powder is preferably from 0.1 to 20% by mass, more preferably from 0.1 to 15% by mass, even more preferably from 0.1 to 5% by mass in the composition. %.

Further, the composition of the present invention may contain an anionic surfactant (for example, an anionic surfactant described in International Publication No. 99/58633), an amphoteric surfactant, an enzyme, and a bleaching agent (other than the component (B)) ], defoamers, rust inhibitors, dissolution aids, surface modifiers, perfumes, etc.

The detergent composition for automatic dishwashing machine of the present invention can be used as a dishwashing machine for commercial and household use, and is particularly suitable for use in a short cleaning time (for example, 40 to 60 seconds) each time. A commercial dishwashing machine that washes a large amount of water and washes it several times a day. At this time, the composition of the present invention inhibits the adhesion of the tea scale and the water spot even under the condition that the amount of the flushing water is small (for example, the water level of the tableware is 2 to 3 L per 2500 cm ² per flush). The reduction has an excellent effect. In addition, as a tableware, a cup, a glass cup, a pot, a bowl, a chopstick, a plate, a knife, a fork, a spoon, etc. which are various materials, such as a ceramics, glass, a melamine resin, a polycarbonate resin, a wood, and a metal, can be used. The washing machine is washed.

When the washing is performed by a commercial dishwashing machine, for example, a container for plastics filled with a detergent composition for an automatic dishwashing machine is placed in a predetermined direction or filled in a hopper for a commercial dishwashing machine. The detergent composition for an automatic dishwashing machine in a bag container or the like is moved to a hopper for a business tableware washing machine. Further, the water or warm water is sprayed on the set composition in the form of a spray or a shower, and the dissolved washing liquid is supplied to the inside of the business dish washing machine to be used for washing the tableware.

The detergent composition for an automatic dishwashing machine of the present invention can be used as a cleaning liquid which is diluted with water or the like to a suitable concentration, and in this case, the concentration of the composition can be, for example, 0.05 to 0.3. It is diluted and used in the form of % by mass. In this case, the pH of the diluted washing solution at 25 ° C is preferably 10.5 or more and 11.5 or less. The pH of the 0.1% by mass aqueous solution of the detergent composition for an automatic dishwashing machine of the present invention at 25 ° C is preferably 10.5 or more and 11.5 or less.

The detergent composition for an automatic dishwashing machine of the present invention is preferably in the form of a solid, that is, a solid block, a granule, a powder or the like, and is more preferably in terms of operability and storage stability of the detergent. Powdery.

In the case where the detergent composition for an automatic dishwashing machine of the present invention is a powder or granule composition, the average particle diameter of the detergent composition for an automatic dishwashing machine of the present invention is preferably 200 μm. The above, and more preferably, it is 1000 μm or less, and more preferably 600 μm or less. Further, the average particle diameter is preferably from 200 to 1,000 μm, more preferably from 200 to 600 μm.

In addition, the average particle diameter here is a value measured by the volume of the laser-type flow distribution measuring apparatus: LA-500 (made by Horiba, Ltd.).

Further, in the case where the detergent composition for an automatic dishwashing machine of the present invention is a powder or a granulated composition, the detergent composition for an automatic dishwashing machine of the present invention is obtained by JIS K3362 (:2008) The apparent density measured is preferably 0.5 g/ml or more, more preferably 0.6 g/ml or more, and is preferably 1.2 g/ml or less, and further preferably 1 g/ml or less. Further, the apparent density is preferably from 0.5 to 1.2 g/ml, more preferably from 0.6 to 1 g/ml.

The detergent composition for an automatic dishwashing machine of the present invention can be produced according to a usual method, and is not particularly limited, and is preferably produced by a conical spiral mixer. In the case of producing a composition containing the components (A) to (E), that is, the components (A), (B), (C), (D), and (E), the automatic operation of the present invention From the viewpoint of workability in the production of the detergent composition for a dishwashing machine, it is preferred to employ a production method having the following steps: Step 1, mixing (A-2) component, (D) component, (E) ) an anhydride of the carbonate in the ingredient; step 2, The component obtained in the step 1 is mixed with the component (B); and in step 3, the mixture obtained in the step 2 is mixed with the ceric acid salt of the component (A-1), the component (C), and the component (E). Anhydride. When the anhydride of citrate and the anhydride of carbonate are used together as the component (E), that is, when the anhydride containing citrate and the anhydride of carbonate are used as the component (E), the anhydride of carbonate is preferably The mixture is mixed in step 1, and the phthalate anhydride is preferably mixed in step 3. Examples of the apparatus for mixing the respective components in the above steps 1 to 3 include a conical spiral mixer, a Henschel mixer, and the like, and a conical spiral mixer is preferable. Further, the component (B) as the liquid component is preferably mixed by dropping, and the dropping rate in this case is preferably 2 to 5 minutes, preferably in portions (intermittent addition). The mixing temperature is preferably 10 ° C or higher, more preferably 20 ° C or higher, and is preferably 50 ° C or lower, more preferably 40 ° C or lower. Further, the mixing temperature is preferably from 10 to 50 ° C, more preferably from 20 to 40 ° C.

Embodiments of the invention are shown below.

<item 1>

A detergent composition for an automatic dishwashing machine comprising: (A-1) one or more selected from the group consisting of methylglycine diacetate and an alkali metal salt thereof (hereinafter referred to as (A-) 1) Component] 6% by mass or more and 18% by mass or less, and (A-2) one or more selected from the group consisting of citric acid and an alkali metal salt thereof (hereinafter referred to as (A-2) component): 20% by mass or more And 30% by mass or less, and (B-1) is selected from a nonionic surfactant in which an ethylene oxide and a propylene oxide are sequentially bonded to an alcohol having a branched carbon number of 10 or more and 14 or less. One or two or more [hereinafter referred to as (B-1) components] 3 mass% or more and 7 masses The amount of the content of (A-1) and (B-1) is 10% by mass or more and 25% by mass or less, and the mass ratio of the content of (A-1) to the content of (B-1) (A) -1)/(B-1) is 1 or more and 5 or less.

<item 2>

In the detergent composition for an automatic dishwashing machine of the above-mentioned item 1, the content of the component (A-1) is 7% by mass or more, further preferably 8% by mass or more, and 15% by mass or less, and further 12 The mass% or less is 7 to 15% by mass, and further 8 to 12% by mass.

<item 3>

The detergent composition for an automatic dishwashing machine according to <1> or <2>, wherein the content of the component (A-2) is 23% by mass or more, and is 27% by mass or less, or 23 to 27%. quality%.

<item 4>

The detergent composition for an automatic dishwashing machine according to any one of the items 1 to 3, wherein (B-1) is one or more selected from the group consisting of nonionic surfactants described below. a nonionic surfactant, wherein the nonionic surfactant is bonded to ethylene oxide in a block having a branched carbon number of 10 or more, preferably a carbon number of 12 or more, and a carbon number of 14 or less; The average addition molar number of propylene oxide and ethylene oxide is 4 or more and 10 or less, and the average addition molar number of propylene oxide is 2 or more and 10 or less.

<item 5>

Washing the automatic dishwashing machine according to any one of <Item 1> to <Item 4> The component (B-1) is selected from the group consisting of a carbon number of 10 or more, preferably a carbon number of 12 or more, and a secondary carbon having a carbon number of 14 or less; One or more of propylene oxide nonionic surfactants.

<Item 6>

The detergent composition for an automatic dishwashing machine according to any one of the items 1 to 5, wherein the component (B-1) is selected from a carbon number of 10 or more, preferably a carbon number of 12 or more. And the secondary block having a carbon number of 14 or less is bonded to ethylene oxide and propylene oxide in sequence, and the average addition molar number of ethylene oxide is 4 or more and 10 or less, and the average propylene oxide is One or two or more kinds of nonionic surfactants having a molar amount of 2 or more and 10 or less of a nonionic surfactant are added.

<item 7>

The detergent composition for an automatic dishwashing machine according to any one of the above items, wherein the component (B-1) is a nonionic interface represented by the following formula (b-1). active _{^{agent, R 1 -O- (EO) s}} - (PO) t -H (b-1) [ in the formula, R ¹ represents more than 10 carbon atoms and branched chain alkyl group of 14 or less, or 10 or more carbon atoms, and a branched alkenyl group of 14 or less, further, a branched alkyl group having 10 to 14 carbon atoms or a branched alkenyl group having 10 to 14 carbon atoms; EO represents a vinyloxy group; PO represents a propyleneoxy group; and s and t respectively The average addition molar number is s, and s is 4 or more, preferably 5 or more, and 10 or less, preferably 9 or less, and t is 2 or more, preferably 5 or more, and 10 or less, preferably 9 Hereinafter, t/s is 0.3 or more, preferably 0.5 or more, more preferably 0.7 or more, further preferably 0.9 or more, and 1.5 or less, preferably 1.4 or less, more preferably 1.3 or less; and, s=4 ~10, preferably s=5~9, t=2~10, preferably t=5~9, 0.3≦(t/s)≦1.5, preferably 0.5≦(t/s)≦1.4, More preferably 0.7 ≦(t/s) ≦1.3; "-(EO) _s -(PO) _t -" is a block bond].

<item 8>

The detergent composition for an automatic dishwashing machine according to any one of the above-mentioned items, wherein the content of the component (B-1) is 3% by mass or more and 6% by mass or less, and further is 3 It is 5% by mass or more and 5% by mass or less, or 3 to 6% by mass, and further preferably 3 to 5% by mass.

<item 9>

The detergent composition for an automatic dishwashing machine according to any one of the above items, wherein the total content of the component (A-1) and the component (B-1) is 12% by mass or more. Further, it is 14% by mass or more, further 16% by mass or more, 23% by mass or less, further 21% by mass or less, further 19% by mass or less, 12 to 23% by mass, and further 14 to 21% by mass. Further, it is 16 to 19% by mass.

<item 10>

The detergent composition for an automatic dishwashing machine according to any one of <1> to <9>, wherein a mass ratio of the content of the component (A-1) to the content of the component (B-1) (A) -1) / (B-1) is 1.5 or more, further 2 or more, further 2.5 or more, and 4.5 or less, further 4 or less, further 3.5 or less, 1.5 to 4.5, and further 2 to 4. Furthermore, it is 2.5 to 3.5.

<item 11>

Automatic dishwashing machine washing machine according to any one of <Item 1> to <Item 10> The detergent composition contains a nonionic surfactant other than the component (B-1) [hereinafter, the nonionic surfactant including the component (B-1) is (B) component].

<item 12>

The detergent composition for an automatic dishwashing machine according to <11>, which comprises (B-2) an upper block of an alcohol having a hydrocarbon group having 8 or more and 18 or less and having an ethylene oxide and a ring bonded thereto. The nonionic surfactant of the oxypropane nonionic surfactant [(B-1) component is bonded to the alcohol having a branched carbon number of 10 or more and 14 or less, and the nonionic interface of ethylene oxide and propylene oxide is bonded in sequence. Except for the active agent] [hereinafter referred to as (B-2) component] as the component (B).

<item 13>

A detergent composition for an automatic dishwashing machine according to <12>, wherein the component (B-2) is a nonionic surfactant represented by the formula (b-2), and R ² -O-(EO) _p -(PO) _q -(EO) _r -H (b-2) [wherein R ² represents a hydrocarbon group having 8 or more and 18 or less carbon atoms, and further, a hydrocarbon group having 8 to 18 carbon atoms, and EO represents ethylene oxide. The base, PO represents a propyleneoxy group; p, q, and r represent the average addition molar number, p is 1 or more and 10 or less, q is 0.5 or more and 5 or less, and r is 1 or more and 10 or less, and p = 1~10, q=0.5~5, r=1~10; "-(EO) _p -(PO) _q -(EO) _r -" is a block bond].

<item 14>

The detergent composition for an automatic dishwashing machine according to <12> or <13>, wherein the total content of the component (B-1) and the component (B-2) is 3% by mass or more, and further 3.5 mass. % or more, further, 4 mass% or more, and 7% by mass or less, further 6.5 mass% or less, further 6% by mass or less, or 3 to 7 The mass% is further 3.5 to 6.5% by mass, and further 4 to 6% by mass.

<Item 15>

The detergent composition for an automatic dishwashing machine according to any one of the above items, wherein the ratio of the content of the component (B-1) to the content of the component (B-2) (B) -1)/(B-2) is 1 or more, further 2 or more, 15 or less, further 10 or less, further 8 or less, further 6 or less, or 1 to 15, and further 1 to 10. Further, it is 2 to 8, and further 2 to 6.

<Item 16>

The detergent composition for an automatic dishwashing machine according to any one of the items (1), wherein, in the component (B), the total of the components (B-1) and (B-2) The ratio is 90% by mass or more, further 95% by mass or more, further 98% by mass or more, and 100% by mass or less, or 90 to 100% by mass, further 95 to 100% by mass, and further 98 to 100% by mass. %.

<item 17>

The detergent composition for an automatic dishwashing machine according to any one of the above-mentioned items, wherein the component (A-1) and the component (A-2) are collectively referred to as The total content of the component (A) and the component (B-1) or the total content of the component (A) and the component (B) is 30% by mass or more, more preferably 35% by mass or more, and 50% by mass or less. It is 45 mass% or less, or 30-50 mass%, and 35-45% by mass.

<Item 18>

The detergent composition for an automatic dishwashing machine according to any one of <12>, wherein the total content of the component (A), the component (B-1), and the component (B-2) is 30% by mass or more, further 35% by mass or more, and 50% by mass % or less is further 45% by mass or less, or 30 to 50% by mass, and further 35 to 45% by mass.

<Item 19>

The detergent composition for an automatic dishwashing machine according to any one of <1> to <18>, wherein the mass ratio of the content of the component (A) to the content of the component (B-1) is (A)/ The mass ratio (A)/(B) of the content of the component (B-1) or the component (A) to the content of the component (B) is 3 or more, further 4 or more, further 5 or more, and 12 or less. It is 11 or less, further 10 or less, or 3 to 12, further 4 to 11, and further 5 to 10.

<item 20>

The detergent composition for an automatic dishwashing machine according to any one of <12>, wherein the content of the component (A) and the total of the components (B-1) and (B-2) are the same. The mass ratio (A)/[(B-1)+(B-2)] of the content is 3 or more, further 4 or more, further 5 or more, 12 or less, further 11 or less, and further 10 or less. Or 3~12, and then 4~11, and then 5~10.

<Item 21>

The detergent composition for an automatic dishwashing machine according to any one of the items 1 to 2, which further comprises (C-1) polyacrylic acid and a salt thereof (hereinafter referred to as (C-1) (Component) and (C-2) a polymer having one or more of a group consisting of a copolymer derived from a monomer unit of maleic acid and a salt thereof (hereinafter referred to as a component (C-2)] Compound (C) [hereinafter referred to as component (C)].

<Item 22>

The detergent composition for an automatic dishwashing machine according to <21>, wherein the component (C-2) is selected from the group consisting of copolymers of acrylic acid and maleic acid and salts thereof. One or more kinds of polymer compounds, wherein the structural unit derived from acrylic acid or the structural unit derived from maleic acid has a molar ratio of 90/10 or more, further 75/25 or more, and 50/50 or less, and further Below 65/35, or 90/10~50/50, and further 75/25~65/35.

<item 23>

The detergent composition for an automatic dishwashing machine according to the above, wherein the polyacrylic acid or the salt thereof of the component (C-1) has a weight average molecular weight of 1,000 or more, further 3,000 or more, and It is 10,000 or less, further 8,000 or less, further 6,000 or less, further 5,000 or less, or 1,000 to 10,000, and further 3,000 to 5,000.

<item 24>

The detergent composition for an automatic dishwashing machine according to any one of the above items, wherein the (C-2) component has a copolymer derived from a unit of maleic acid or The weight average molecular weight of the salt is 1,000 or more, further 3,000 or more, and 10,000 or less, further 5,000 or less, or 1,000 to 10,000, and further 3,000 to 5,000.

<Item 25>

The detergent composition for an automatic dishwashing machine according to any one of the above items, wherein the (C-2) component has a copolymer derived from a unit of maleic acid or The weight average molecular weight of the salt is 10,000 or more, further 30,000 or more, further 50,000 or more, and 150,000 or less, further 120,000 or less, and further 100,000 or less.

<Item 26>

Automatic dishwashing machine washing machine according to any one of <21> to <25> a detergent composition containing (C-1) component and (C-2) component as component (C), mass ratio of (C-1) component to (C-2) component (C-1)/(C -2) is 1 or more, preferably 2 or more, more preferably 3 or more, and is 30 or less, preferably 20 or less, more preferably 10 or less.

<item 27>

The detergent composition for an automatic dishwashing machine according to any one of the above-mentioned items, wherein the content of the component (C) is 5% by mass or more, further 6% by mass or more, and further 7 The mass% or more is 15% by mass or less, further 14% by mass or less, further 13% by mass or less, or 5 to 15% by mass, further 6 to 14% by mass, and further 7 to 13% by mass.

<Item 28>

The detergent composition for an automatic dishwashing machine according to any one of <21>, wherein the total content of the component (A-1), the component (A-2), and the component (C) is the total amount of the component. 30% by mass or more, further 33% by mass or more, further 35% by mass or more, further 40% by mass or more, 50% by mass or less, further 47% by mass or less, further 45% by mass or less, or 30 to 50% by mass, further 33 to 47% by mass, and further 35 to 45% by mass.

<Item 29>

The detergent composition for an automatic dishwashing machine according to any one of the above items, further comprising an inorganic powder (D) having a liquid carrying ability (hereinafter referred to as a component (D)) ].

<item 30>

The detergent composition for an automatic dishwashing machine according to <29>, wherein the component (D) is one or more selected from the group consisting of amorphous ceria and crystalline calcium citrate. An inorganic powder having a liquid carrying ability.

<item 31>

A detergent composition for an automatic dishwashing machine according to <Item 29> or <Item 30>, wherein the oil absorption capacity of the component (D) measured by the method described in JIS K6220 (-1995) is 120 ml. /100 g or more, and is 1,000 ml/100 g or less, and further 600 ml/100 g or less, or 120 to 1,000 ml/100 g, and further 120 to 600 ml/100 g.

<item 32>

The detergent composition for an automatic dishwashing machine according to any one of the above-mentioned items, wherein the content of the component (D) is 0.5% by mass or more, further 0.7% by mass or more, and further 1 The mass% or more is 2% by mass or less, or 0.5 to 2% by mass, further 0.7 to 2% by mass, and further 1 to 2% by mass.

<Item 33>

The detergent composition for an automatic dishwashing machine according to any one of the above items, further comprising an alkali agent selected from the group consisting of an anhydride of a phthalate and an anhydride of a carbonate ( E) [hereinafter referred to as (E) component].

<item 34>

The detergent composition for an automatic dishwashing machine according to the item (1), wherein the component (E) is one or more selected from the group consisting of an anhydride of an alkali metal citrate and an alkali metal salt of an alkali metal carbonate.

<Item 35>

The detergent composition for an automatic dishwashing machine according to the item <3>, wherein the component (E) is one or more selected from the group consisting of anhydrous sodium carbonate, anhydrous potassium carbonate, and anhydrous sodium citrate. .

<Item 36>

The detergent composition for an automatic dishwashing machine according to any one of the items of the present invention, which comprises a carbonate anhydride and a phthalate anhydride as the component (E).

<item 37>

The detergent composition for an automatic dishwashing machine according to any one of the above items, which comprises an anhydride selected from the group consisting of anhydrous sodium carbonate and anhydrous potassium carbonate, and anhydrous sodium citrate. (E) ingredient.

<item 38>

The detergent composition for an automatic dishwashing machine according to any one of <33>, which contains anhydrous sodium carbonate and anhydrous sodium citrate as the component (E), anhydrous sodium carbonate and anhydrous The mass ratio of the content of sodium citrate (content of anhydrous sodium carbonate) / (content of anhydrous sodium citrate) is 1.5 or more, further 2 or more, further 2.5 or more, 4 or less, further 3.5 or less, and further 3 Hereinafter, it is 1.5 to 4, further 2 to 3.5, and further 2.5 to 3.

<item 39>

The detergent composition for an automatic dishwashing machine according to any one of the above-mentioned items, wherein the content of the component (E) is 40% by mass or more, and further 70% by mass or less, and further 65. The mass% or less is further 60% by mass or less, or 40 to 70% by mass, further 40 to 65% by mass, and further 40 to 60% by mass.

<item 40>

The detergent composition for an automatic dishwashing machine according to any one of the items <3> to <39> which contains (A) to (E) components, and the content of the component (A) is relative to The total content of the components (A) to (E) is 100% by mass or more, further preferably 23% by mass or more, further preferably 26% by mass or more, and 55% by mass or less, and further 50% by mass or less. Further, it is 45 mass% or less, or 20 to 55 mass%, further 23 to 50 mass%, and further 26 to 45 mass%.

<item 41>

The detergent composition for an automatic dishwashing machine according to any one of the items of the present invention, which contains (A) to (E) components, (B) component content, and further (B-1) The total content of the component (B-2) is 100% by mass or more based on the total content of the components (A) to (E), and is 3% by mass or more, and 10% by mass or less, and further 9% by mass or less. Further, it is 8 mass% or less, or 3 to 10 mass%, further 3 to 9 mass%, and further 3 to 8 mass%.

<item 42>

The detergent composition for an automatic dishwashing machine according to any one of the above items, which contains the components (A) to (E), and the content of the component (C) is relative to (A)~ The total content of the component (E) is 100% by mass, more preferably 5% by mass or more, further 6% by mass or more, further 7% by mass or more, 15% by mass or less, further 14% by mass or less, and further 13 mass%. % or less, or 5 to 15% by mass, further 6 to 14% by mass, and further 7 to 13% by mass.

<item 43>

The detergent composition for an automatic dishwashing machine according to any one of the above items, which comprises (A) to (E) components, and the content of the component (D) is relative to (A)~ The total content of the component (E) is 100% by mass, and is 0.5% by mass or more, further 0.7% by mass or more, further 1% by mass or more, 2% by mass or less, 0.5% to 2% by mass, and further 0.7. ~2% by mass, and further 1~2 mass %.

<item 44>

The detergent composition for an automatic dishwashing machine according to any one of the above items, which contains (A) to (E) components, and the content of the component (E) is relative to (A)~ The total content of the component (E) is 100% by mass, and is 40% by mass or more, more preferably 80% by mass or less, further 70% by mass or less, further 60% by mass or less, or 40% to 80% by mass, and further 40%. ~70% by mass, and further 40 to 60% by mass.

<item 45>

The detergent composition for an automatic dishwashing machine according to any one of <1> to <44>, which is used for washing with a water-saving type washing machine as defined below.

[Water-saving washing machine]

It is an automatic tableware washing machine which can be washed as follows: 20 parts by mass of NaOH is set to 60 ° C, and 20 pieces of test pieces are opposed to each other on a glass frame (shape of one piece: 15 cm × 15 cm × 0.2 cm) , soda-lime glass manufactured by Tcst Panel Co., Ltd., Japan, washed for 40 seconds or more and 60 seconds or less, and then the tableware is placed at a water level of 2,500 cm ^{2 and} 2 L of water is set to 80 ° C for rinsing, at 25 ° C. The amount of NaOH remaining on the test piece dried in the atmosphere for 10 minutes is 0.15 μg/cm ² or less, preferably 0.12 μg/cm ² or less, more preferably 0.1 μg/cm ² or less. Here, the NaOH residual amount is obtained by immersing the test piece piece by piece in 200 g of distilled water at 25 ° C for 10 seconds, extracting the NaOH remaining on the test piece, and neutralizing and titrating with 0.01 mol/L of hydrochloric acid (HCl). The NaOH in the extract was quantified, and the average value with respect to 20 test pieces was determined. Furthermore, the area of the water level of the tableware is defined by the area of the bottom surface of the bracket when the bracket is used (the bracket for the tableware storage).

<item 46>

The invention relates to a method for producing a detergent composition for an automatic dishwashing machine, which is an automatic dishwashing machine according to any one of the above items <36> to <45>. The detergent composition contains (A) component, (B) component, (C) component, (D) component, and (E) component; and the production method has the following steps: Step 1, mixing (A -2) a component, a component of the component (D), and an anhydride of the carbonate in the component (E); a step 2 of mixing the component (B) in the mixture obtained in the step 1; and a step 3, in the step 2 The obtained mixture is mixed with the anhydride of the ceric acid salt of the component (A-1), the component (C), and the component (E).

<item 47>

A method for producing a detergent composition for an automatic dishwashing machine according to <46>, wherein the components are mixed by a conical spiral mixer.

<item 48>

A cleaning method for a tableware, comprising the steps of: using an automatic dishwashing detergent composition according to any one of the above items <1> to <45>, using an automatic dishwashing machine to wash the tableware And each rinse with the tableware set 2~3 L of water per 2500 cm ² of the water level, and rinse the tableware after the step.

<item 49>

A cleaning method for a tableware, comprising the following steps: using the detergent composition for an automatic dishwashing machine according to any one of the above items <1> to <45>, using a water-saving type as defined below Machine-washed tableware; and each rinse uses tableware to set the water level to 2~3 L per 2500 cm ² , and rinse the tableware after the step.

[Water-saving washing machine]

It is an automatic dishwashing machine which can be washed as follows: 20 pieces of NaOH solution of 0.2% by mass is set to 60° C., and 20 pieces of test pieces which are opposed to each other on the glass (shape of one piece: 15 cm×15 cm×0.2 cm, The soda-lime glass manufactured by Japan Test Panel Co., Ltd. is washed for 40 seconds or more and 60 seconds or less, and then the tableware is placed at a water level of 2,500 cm ^{2 and} 2 L of water is set to 80 ° C for rinsing, and then at 25 ° C. The amount of NaOH remaining on the test piece dried in the atmosphere for 10 minutes is 0.15 μg/cm ² or less, preferably 0.12 μg/cm ² or less, more preferably 0.1 μg/cm ² or less. Here, the NaOH residual amount is obtained by immersing the test piece piece by piece in 200 g of distilled water at 25 ° C for 10 seconds, extracting the NaOH remaining on the test piece, and neutralizing and titrating with 0.01 mol/L of hydrochloric acid (HCl). The NaOH in the extract was quantified, and the average value with respect to 20 test pieces was determined. Furthermore, the area of the horizontal surface of the tableware is defined by the area of the bottom surface of the bracket when the area of the horizontal surface is used.

<item 50>

A method of washing dishes according to <Item 48> or <Item 49>, wherein no light dish is added to the water used for rinsing.

<item 51>

A cleaning agent combination for an automatic dishwashing machine according to any one of items 1 to 45 The use of the material is used as a detergent for an automatic dishwashing machine.

<Item 52>

The use of the detergent composition for an automatic dishwashing machine according to any one of items 1 to 45, which is used as an automatic dishwashing machine for washing by a water-saving type washing machine having the following definition Use a detergent.

[Water-saving washing machine]

It is an automatic tableware washing machine which can be washed as follows: 20 pieces of NaOH solution of 0.2% by mass is set to 60° C., and 20 pieces of test pieces which are opposed to each other on the glass (shape of one piece: 15 cm×15 cm×0.2 cm, The soda-lime glass manufactured by Japan Test Panel Co., Ltd. is washed for 40 seconds or more and 60 seconds or less, and then the tableware is placed at a water level of 2,500 cm ^{2 and} 2 L of water is set to 80 ° C for rinsing, and then at 25 ° C. The amount of NaOH remaining on the test piece dried in the atmosphere for 10 minutes is 0.15 μg/cm ² or less, preferably 0.12 μg/cm ² or less, more preferably 0.1 μg/cm ² or less. Here, the NaOH residual amount is obtained by immersing the test piece piece by piece in 200 g of distilled water at 25 ° C for 10 seconds, extracting the residual NaOH on the test piece, and then neutralizing and titrating with 0.01 mol/L hydrochloric acid (HCl) for extraction. The NaOH in the solution was quantified, and the average value with respect to 20 test pieces was determined. Furthermore, the area of the horizontal surface of the tableware is defined by the area of the bottom surface of the bracket when the area of the horizontal surface is used.

Example

<Preparation of detergent composition for automatic dishwashing machine>

Stirring and mixing by the production method having the following steps: Step 1, mixing the components of the components (A-2), (D), and (E) among the components of Tables 1 and 2; , mixed in the mixture obtained in the step 1 (B) component; Step 3, mixing the component (A-1) in the mixture obtained in the step 2 (or sodium phosphamate, glutamic acid diacetic acid, glutamic acid diacetic acid, or EDTA) (ethylenediaminetetraacetic acid, ethylenediaminetetraacetic acid) 4Na. Dihydrate replaces the anhydride of the ceric acid salt of the component (A-1), (C), and (E). Thereby, the powdery automatic dishwashing detergent composition of Tables 1 and 2 (total amount of 10 kg) was obtained.

Examples of the apparatus for stirring and mixing the respective components include a conical spiral mixer, a Henkel mixer, and the like. Further, the dropping rate in the case where the component (B) as a liquid component is dropped and mixed is preferably 2 to 5 minutes, and preferably added in portions (intermittently added). The detergent composition for the automatic dishwashing machine of Tables 1 and 2 is a device using a conical spiral mixer "Hosokawa Micron Co., Ltd., model: DBY-10R" as a device, and the component (B) as a liquid component is added dropwise. In the case of mixing, the dropping acceleration was set to 3 minutes, and the addition method was carried out by batchwise addition (intermittent addition). Further, the screw was rotated to a speed of 8 (rpm/min) and the rotation speed was adjusted to 225 (rpm/min) to carry out mixing.

In the mixing method in the case of using the components of Tables 1 and 2, stirring of any one of the component (A-2), the component (D), the anhydrous sodium carbonate, and the anhydrous potassium carbonate is started until the final mixture is obtained. The mixing temperature is 10 to 50 °C. Moreover, the stirring time required for each step is 3 to 7 minutes, respectively. When preparing the detergent composition for automatic dishwashing machines of Tables 1 and 2, stirring (A-2) component, (D) component, anhydrous sodium carbonate, and anhydrous potassium carbonate (A-2) The mixing temperature from the composition to the final mixture is 20 to 40 °C. Further, the stirring time required for each step was set to 5 minutes.

<Detergency evaluation>

[1] Evaluation of the inhibition effect of tea scale adhesion

A specific amount (about 2 kg) of the detergent composition is put into a hopper of a single-door commercial dishwashing machine [SANYO DR53 manufactured by Sanyo Electric Co., Ltd.] so that the concentration of the washing machine in the washing liquid becomes 0.1. The operation was performed under the setting of mass %, and the operation was carried out for 50 times under the conditions of a washing temperature of 60 ° C, a detergent composition concentration of 0.1% by mass, a washing time of 40 seconds, a washing temperature of 80 ° C, and a washing time of 10 seconds. The adjustment is performed in such a manner that the concentration control during operation is not biased. In addition, the following method was used to set the sample dirt (casein Ca salt, tannic acid Ca salt, salad oil) in the washing tank (38 L) from the start of washing to the end of washing.

(washing conditions)

. Washing temperature: 60 ° C

. Detergent composition concentration: 0.1% by mass

. Washing time: 40 seconds

. Washing temperature: 80 ° C

. Washing time: 10 seconds

. The amount of water per rinse: 2 L

. Washing water hardness: German hardness (German Hardness) 3 ° dH or 6 ° dH

. Sample dirt in the tank: casein Ca salt, tannic acid Ca salt, and salad oil

[Method of inputting sample dirt into the cleaning tank]

As a sample of casein Ca salt, albumin is added continuously from the start of washing to the end of the albumin concentration of 25 ppm or 50 ppm (from egg, Wako Pure Chemical Industries Co., Ltd.) Manufactured reagent) Put it into the washing tank. Further, as a sample of the tannic acid Ca salt, the boiled roasted tea was continuously placed in the washing tank from the start of washing to the end so that the concentration of the roasted tea in the washing tank was 100 ppm. In addition, as a sample of the oily stain, the salad oil (made by Nisshin Oillio Group Co., Ltd., Nisshin Salad Oil) was continuously washed from the start of washing to the end as the concentration of the salad oil in the washing tank was 100 ppm. In the net slot.

(Evaluation method of tea scale adhesion inhibition effect)

The boiled tea boiled material (10 roast tea tea bags in 1.8 L boiling water, boiled in 10 minutes and cooled to room temperature) was added to 4 melamine cups (capacity of about 150 cc). In the middle to 80%, after standing for 10 to 20 seconds, the roasted tea is discarded and washed under the above washing conditions. This was repeated 50 times (50 times of baking tea was put in, discarded, and washed), and the appearance was visually observed, and the effect of suppressing the adhesion of the scale was determined by the following criteria. Further, in the washing with each detergent composition, the difference in the state between the four cups could not be confirmed.

*Evaluation criteria for inhibition of tea scale adhesion

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

4: Four melamine cups were slightly attached to the tea scale. (Compared with Evaluation 5, trace adhesion was confirmed)

3: Four melamine cups were confirmed to adhere to the brown color.

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

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

In the above evaluation criteria, 4 or more were judged as pass.

[2] Water spot evaluation

(production of glass for evaluation)

A new glass cup (inner diameter 55 mm, height 113 mm) will be applied to 1 g of commercially available beverage milk (Megmilk milk, Megmilk Snow Brand Co., Ltd.) and dried at 50 ° C for 1 hour as a sample attached. The evaluation of the dirt was carried out for the water spot evaluation using a glass.

(cleaning method)

30 g of the detergent composition for automatic dishwashing machine was put into a washing tank (38 L) of a commercial dishwashing machine [SANYO DR53 manufactured by Sanyo Electric Co., Ltd.], and dissolved in warm water of 55 ° C. . The above four evaluation glasses were placed on a dedicated holder, and after washing with a washing liquid of 55 ° C for 60 seconds, the bright disk was not used, and the mixture was rinsed with 2 L of washing water at 80 ° C for 10 seconds. It is equivalent to flushing with 2 L of water per 2500 cm ² of the water level with each cut. The glass for evaluation was taken out from a dedicated holder and dried at 25 °C.

In addition, the washing water of German hardness of 3 ° dH or 6 ° dH is used for washing. In the same manner as in the evaluation of the effect of suppressing the adhesion of the tea stain, the casein Ca salt soil, the tannic acid Ca salt soil, and the oil stain were set in the washing tank. In other words, as a sample of the casein Ca salt, the concentration of albumin in the washing tank is 25 ppm or 50 ppm, and the albumin is continuously washed from the start of washing to the end. Eggs, reagents manufactured by Wako Pure Chemical Industries Co., Ltd.) are put into the washing tank. In addition, as a sample of the tannic acid Ca salt, the concentration of the roasted tea in the washing tank is 100 ppm, and the washing is continued from the beginning to the end. The boiled roasted tea is put into a washing tank. In addition, as a result of the concentration of the salad oil in the washing tank, the salad oil (Nisshin Oillio Group Co., Ltd., Nisshin Salad Oil) was continuously put into the washing tank from the start of washing to the end. Inside.

(Water spot evaluation method)

The completion of the water spot number on the surface of the glass for evaluation by washing and drying by the above method was evaluated. The average number of water spots of the four glasses is shown in Table 1. The average number of water spots is preferably 20 or less, more preferably 10 or less.

The ingredients in the table are the following.

. Methylglycine diacetate: methylglycine diacetate 3Na, trade name "Trilon M Compactate" (manufactured by BASF Corporation)

. Trisodium citrate. Dihydrate: trade name "Purified Sodium Citrate M" (manufactured by Fuso Chemical Industry Co., Ltd.)

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

. Nonionic surfactant 1-2: R ¹ in the formula (b-1) is a secondary alkyl group having 12 to 14 carbon atoms, a s=5.0, t=4.5 nonionic surfactant, and the trade name is "Softanol". EP5045" (made by Nippon Shokubai Co., Ltd.)

. Nonionic surfactant 2-1: R ² in the formula (b-2) is a linear alkyl group having 12 to 14 carbon atoms, a nonionic surfactant having p = 3, q = 1.5, and r = 3, Product name "Emulgen LS-106" (made by Kao Corporation)

. Nonionic surfactant 2-2: an ethylene oxide or propylene oxide block adduct of a higher alcohol produced by the following synthesis example [if simply expressed by the formula (b-2), it is equivalent to R ² in the formula (b-2) is a nonionic surfactant having an alkyl group of 12 to 13 carbon atoms, p=3, q=3, and r=0]

. Nonionic surfactant 2-3: R ² in the formula (b-2) is a linear alkyl group having 12 to 14 carbon atoms, a nonionic surfactant having p=5, q=1.5, and r=5, Product name "Emulgen LS-110" (made by Kao Corporation)

. Nonionic surfactant 3: If it is simply represented by the formula (b-1), R ¹ in the formula (b-1) is a secondary alkyl group having 12 to 14 carbon atoms, s=7.0, t= 0 nonionic surfactant, trade name "Softanol 70" (manufactured by Nippon Shokubai Co., Ltd.)

. Nonionic surfactant 4: If simply represented by the formula (b-2), R ² in the formula (b-2) is a linear alkyl group having 12 to 14 carbon atoms, p=6, q= 0, r=0 nonionic surfactant, trade name "Emulgen 106" (made by Kao Co., Ltd.)

. Nonionic surfactant 5: propylene oxide-ethylene oxide-propylene oxide block polymer, weight average molecular weight 3,100, propylene oxide / ethylene oxide ratio = 80/20, trade name "Pluronic RPE2520" (Manufactured by BASF Japan)

. Polyacrylic acid: Sokalan PA25CL Granules (manufactured by BASF, weight average molecular weight 5,400)

. Acrylic acid-maleic acid copolymer: Sokalan CP5 Granules (manufactured by BASF, weight average molecular weight 85,000)

. Amorphous cerium oxide: Tokusil NR (manufactured by Tokuyama Co., Ltd.), oil absorption capacity 250 ml/100 g, average particle diameter 130 μm, specific surface area 195 m ² /g

. Anhydrous sodium carbonate: soda ash (light soda ash) (manufactured by Central Glass Co., Ltd.)

. Anhydrous Potassium Carbonate: Potassium Carbonate (Manufactured by Asahi Glass Co., Ltd.)

. Anhydrous sodium metasilicate: Sodium Metasilicate Anhydrous-D (manufactured by Guangrong Chemical Industry Co., Ltd.)

. Sodium tripolyphosphate: trade name "Soda Tripolyphosphate" (manufactured by Shimonoseki Mitsui Chemicals Co., Ltd.)

. GLDA: glutamic acid diacetic acid 4Na, trade name "Dissolvine GL-PD-S" (Manufactured by AkzoNobel)

. EDTA4Na. Dihydrate: sodium edetate, trade name "Triron B Powder" (manufactured by BASF)

<Synthesis Example: Synthesis Method of Nonionic Surfactant 2-2>

Dobanol 23 (manufactured by Mitsubishi Chemical Corporation, 1-dodecanol and its branched isomers, a mixture of 1-tridecanol and its branched isomers) 386.8 g and potassium hydroxide 1.12 g were added to 2 L high pressure The mixture was replaced with dry nitrogen gas, heated to 110 ° C, dehydrated under reduced pressure for 30 minutes, and then heated to 155 ° C. Ethylene oxide 263.48 g was slowly pressed in at a temperature of 155 ° C ± 5 ° C in such a manner that the internal pressure of the autoclave did not become 0.4 MPa or more. After the completion of the press-in, the reaction was carried out until no decrease in the internal pressure of the autoclave was observed. Thereafter, it was cooled to 120 °C. At 120 ° C ± 5 ° C, the internal pressure of the autoclave did not become 0.4 MPa or more, and 347.4 g of propylene oxide was slowly injected in 2 hours. After the completion of the press-in, the reaction was carried out until no decrease in the internal pressure of the autoclave was observed. After cooling to 80 ° C, 1.20 g of acetic acid was added, and after mixing for 30 minutes, filtration was carried out to obtain a block adduct of Dobanol 23, ethylene oxide 3 mol, and propylene oxide 3 mol.

Claims (19)

A detergent composition for an automatic dishwashing machine comprising: (A-1) one or more selected from the group consisting of methyl glycine diacetate and an alkali metal salt thereof, and 6% by mass or more and 18 masses (A-2) is selected from one or more of citric acid and an alkali metal salt thereof, 20% by mass or more and 30% by mass or less, and (B-1) is selected from a carbon number having 10 branches. One or more of ethylene oxide and propylene oxide nonionic surfactant are bonded to the above-mentioned 14 or less alcohols in an amount of 3% by mass or more and 7% by mass or less; and (A-1) And the total content of (B-1) is 10% by mass or more and 25% by mass or less, and the mass ratio of (A-1) content to (B-1) content (A-1)/(B-1) It is 1 or more and 5 or less. The detergent composition for an automatic dishwashing machine according to claim 1, wherein (B-1) is selected from the group consisting of an alcohol having a branched carbon number of 10 or more and 14 or less. Ethane and propylene oxide, and the average addition molar number of ethylene oxide is 4 or more and 10 or less, and the average addition molar number of propylene oxide is 2 or more and 10 or less in the nonionic surfactant. One or two or more nonionic surfactants. The detergent composition for an automatic dishwashing machine according to claim 1 or 2, which further comprises, selected from (C-1) polyacrylic acid and a salt thereof, and (C-2) having a source derived from maleic acid One or more polymer compounds (C) of a group consisting of a copolymer of a monomer unit and a salt thereof. An automatic dishwashing detergent composition according to claim 3, wherein The total content of (A-1), (A-2), and (C) is 30% by mass or more and 50% by mass or less. The detergent composition for an automatic dishwashing machine according to claim 1 or 2, which further comprises (B-2) an ethylene oxide block having an alkyl group having a carbon number of 8 or more and 18 or less bonded with ethylene oxide. And a nonionic surfactant of propylene oxide [(B-1) having a nonionic interface of ethylene oxide and propylene oxide sequentially bonded to an alcohol having a branched carbon number of 10 or more and 14 or less Except for active agents]. The detergent composition for an automatic dishwashing machine according to claim 5, wherein the total content of (B-1) and (B-2) is 3% by mass or more and 7% by mass or less, and the content of (B-1) The mass ratio (B-1)/(B-2) to the content of (B-2) is 1 or more and 15 or less. The detergent composition for an automatic dishwashing machine according to claim 1 or 2, which further comprises an inorganic powder (D) having a liquid supporting ability. The detergent composition for an automatic dishwashing machine according to claim 1 or 2, further comprising an alkali agent (E) selected from the group consisting of an anhydride of a phthalate and an anhydride of a carbonate. The detergent composition for an automatic dishwashing machine according to claim 8, which comprises a carbonate anhydride and a phthalate anhydride as the component (E). The detergent composition for an automatic dishwashing machine according to claim 1 or 2, wherein the mass ratio of the content of the component (A-1) to the content of the component (B-1) is (A-1)/(B-1) ) is 1.5 or more and 4 or less. The detergent composition for an automatic dishwashing machine according to claim 1 or 2, wherein the total content of the component (A-1) and the component (B-1) is 10% by mass or more and 19 mass The amount is below %. The detergent composition for an automatic dishwashing machine according to claim 3, wherein the total content of (A-1), (A-2), and (C) is 40% by mass or more and 47% by mass or less. The detergent composition for an automatic dishwashing machine according to claim 4, wherein the total content of (A-1), (A-2), and (C) is 40% by mass or more and 47% by mass or less. The detergent composition for an automatic dishwashing machine according to claim 1 or 2, wherein the component (B-1) is a nonionic surfactant represented by the following formula (b-1), R ¹ -O- (EO) _s -(PO) _t -H (b-1) [wherein R ¹ represents a secondary alkyl group having 10 or more and 14 or less carbon atoms, or a secondary alkyl group having 10 or more carbon atoms and 14 or less carbon atoms, EO represents a vinyloxy group, PO represents a propyleneoxy group; s and t respectively represent an average addition mole number, s is 4 or more and 10 or less, t is 2 or more and 10 or less, and t/s is 0.3 or more and 1.5 or less; "-(EO) _s -(PO) _t -" is a block bond]. The detergent composition for an automatic dishwashing machine according to claim 5, wherein the component (B-2) is a nonionic surfactant represented by the formula (b-2), R ² -O-(EO) _p -(PO) _q -(EO) _r -H (b-2) [wherein R ² represents a hydrocarbon group having 8 or more and 18 or less carbon atoms, EO represents a vinyloxy group, PO represents a propyleneoxy group; p, q, r denotes an average addition molar number, p is 1 or more and 10 or less, q is 0.5 or more and 5 or less, and r is 1 or more and 10 or less; "-(EO) _p -(PO) _q -(EO) _r -" is block bonding]. The detergent composition for an automatic dishwashing machine according to claim 6, wherein the component (B-2) is a nonionic surfactant represented by the formula (b-2), R ² -O-(EO) _p -(PO) _q -(EO) _r -H (b-2) [wherein R ² represents a hydrocarbon group having 8 or more and 18 or less carbon atoms, EO represents a vinyloxy group, PO represents a propyleneoxy group; p, q, r denotes an average addition molar number, p is 1 or more and 10 or less, q is 0.5 or more and 5 or less, and r is 1 or more and 10 or less; "-(EO) _p -(PO) _q -(EO) _r -" is block bonding]. A method for producing a detergent composition for an automatic dishwashing machine, wherein the detergent composition for an automatic dishwashing machine is a detergent combination for an automatic dishwashing machine according to any one of claims 9 to 16. The component (A), the component (B), the component (C), the component (D), and the component (E) are contained in the product; and the method has the following steps: Step 1, mixing the component (A-2), (D) component, and the anhydride of the carbonate in the component (E), step 2, mixing the component (B) in the mixture obtained in the step 1, and the step 3, in the mixture obtained in the step 2 An anhydride of the ceric acid salt of the component (A-1), the component (C), and the component (E) is mixed. A method for washing a tableware, comprising: using the detergent composition for an automatic dishwashing machine according to any one of claims 1 to 16, the step of washing the tableware with an automatic dishwashing machine; and the step After the tableware, rinse each time with 2~3L of water per 2500cm ² of the tableware. A use of the detergent composition for an automatic dishwashing machine according to any one of claims 1 to 16, which is used as a detergent for an automatic dishwashing machine.