JP2014227442A - Detergent for dishwasher - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a detergent for a dishwasher in which recontamination such as oil stain to the object to be cleaned is suppressed while securing low foam properties.SOLUTION: Provided is a detergent for a dishwasher comprising: a surfactant (A) including a nonionic surfactant (A1) selected from the group consisting of fatty acid alkanolamide and polyoxyethylene fatty acid alkanolamide and having an HLB of 8.5 or more to below 12.0, and in which the content of the nonionic surfactant (A1) in the surfactant (A) is 25 mass% or more.

Description

  The present invention relates to a detergent for a dishwasher.

In recent years, dishwashers for washing dishes, cooking utensils, and the like have become widespread not only in kitchens such as hotels, restaurants, and lunch centers, but also in general households.
In the dishwasher, a dedicated cleaning agent (cleaning agent for dishwasher) is generally used, and hot water of about 55 to 65 ° C. is used.
Moreover, in the dishwasher, the cleaning liquid is discharged using a pump. If the cleaning liquid is bubbled, the cleaning liquid is not discharged from the pump, and problems such as operation stop are likely to occur. For this reason, the dishwasher detergent is required to have low foaming properties.
On the other hand, polyoxyethylene polyoxypropylene alkyl ether is widely used as a low-foaming surfactant in dishwasher detergents.

Conventionally, as a detergent for a dishwasher, a granular detergent composition for a dishwasher containing a polycarboxylic acid polymer compound and an inorganic peroxide in a specific mixing ratio together with a low-foaming nonionic surfactant Has been proposed (see Patent Document 1). Patent Document 1 discloses the use of polyoxyethylene polyoxyalkylene (3 to 5 carbon atoms) alkyl ether as a low-foaming nonionic surfactant.
There is also a dishwashing composition containing an essential oil component such as a terpene alcohol, an N-acylamino acid salt for solubilizing the essential oil component, and a fatty acid alkanolamide as a solubilizing aid for the essential oil component. It has been proposed (see Patent Document 2).

JP 2010-159384 A JP 2000-96091 A

By the way, until now, dirt or uneaten food adhering to tableware or the like has been removed to some extent in advance (preliminary washing), and then a washing process using a dishwasher has been performed.
However, recently, the preliminary washing has been omitted, and a dishwashing machine or the like that has been subjected to a washing process is being directly performed by a dishwasher. For this reason, the amount of dirt to be cleaned by the dishwasher is increasing. In addition, along with the increase in the amount of dirt, especially in the washing of hydrophobic dishes (for example, plastic containers) made of polypropylene (PP) resin or the like, oil dirt is likely to transfer or reattach (recontamination) during washing. It is becoming an environment.
However, in the conventional cleaning agents such as Patent Documents 1 and 2, re-contamination is significant in hydrophobic dishes when the washing process is performed by a dishwasher without pre-washing.
This invention is made | formed in view of the said situation, and makes the subject the washing | cleaning agent for dishwashers in which recontamination, such as oil stains with respect to a washing | cleaning target, was suppressed, ensuring low foaming property.

  As a result of studies, the present inventors have generally used a fatty acid alkanolamide represented by coconut oil fatty acid diethanolamide or the like, which is used to increase the viscosity of a liquid detergent or the like, or to increase the solubilizing power. Among the ethylene oxide adducts, the one having a specific HLB was selected, and it was found that the above problem could be solved by using this in a specific ratio with respect to the total amount of the surfactant, and the present invention was completed. .

That is, the dishwasher cleaning agent of the present invention is selected from the group consisting of fatty acid alkanolamides and polyoxyethylene fatty acid alkanolamides, and has a HLB of 8.5 or more and less than 12.0 (A1). And a surfactant (A) containing the nonionic surfactant (A1) in the surfactant (A) is 25% by mass or more.
In the dishwasher detergent of the present invention, the protease (B) is further contained, the protease activity per gram of the detergent is Ea (kPU / g), and the nonionic surfactant (A1) in the detergent When the content of is W _A1 (mass%), the ratio represented by Ea / W _A1 is preferably 1 to 30.

  ADVANTAGE OF THE INVENTION According to this invention, the washing | cleaning agent for dishwashers in which recontamination, such as oil stains with respect to a washing | cleaning target, was suppressed, can be provided, ensuring low-foam property.

The dishwasher cleaning agent of the present invention comprises a nonionic surfactant (A1) selected from the group consisting of fatty acid alkanolamides and polyoxyethylene fatty acid alkanolamides and having an HLB of 8.5 or more and less than 12.0. Contains surfactant (A).
Hereinafter, in the present specification, the specific nonionic surfactant (A1) is also referred to as component (A1), and the surfactant (A) is also referred to as component (A).
The dosage form of the dishwasher detergent of the present invention is not particularly limited as long as it contains the component (A1), and may be a solid such as a powder or tablet, or a liquid.

<(A) component: Surfactant>
The component (A) is a surfactant selected from the group consisting of fatty acid alkanolamides and polyoxyethylene fatty acid alkanolamides, and containing a nonionic surfactant (A1) having an HLB of 8.5 or more and less than 12.0. is there.
The content of the component (A1) in the component (A) is 25% by mass or more, preferably 50% by mass or more, more preferably 70% by mass or more with respect to the total mass of the component (A). 100 mass%. If the content of the component (A1) is 25% by mass or more, foaming is kept low when washing dishes with a dishwasher, and recontamination such as oil stains on the object to be washed (especially hydrophobic dishes). Is suppressed.

<< (A1) component: About specific nonionic surfactant >>
The component (A1) is a nonionic surfactant selected from the group consisting of fatty acid alkanolamides and polyoxyethylene fatty acid alkanolamides and having an HLB of 8.5 or more and less than 12.0.
In the present invention, the “fatty acid alkanolamide” is produced, for example, by a reaction between a fatty acid, a fatty acid alkyl ester, a fatty acid chloride, an oil or the like, and an alkanolamine (monoethanolamine, monoisopropanolamine, diethanolamine, diisopropanolamine, etc.). Or fatty acid monoalkanolamides and / or fatty acid dialkanolamides.
“Polyoxyethylene fatty acid alkanolamide” refers to an oxyethylene group introduced into the fatty acid alkanolamide.

In the present invention, “HLB” is represented by IOB × 10 in the organic conceptual diagram.
The IOB in the organic conceptual diagram means the ratio of the inorganic value (IV) to the organic value (OV) in the organic conceptual diagram, that is, “inorganic value (IV) / organic value (OV)”.
The organic conceptual diagram was proposed by Satoshi Fujita, and details thereof are described in “Pharmaceutical Bulletin”, 1954, vol. 2,2, pp. 163-173; "Area of Chemistry", 1957, vol. 11, 10, pp. 719-725; "Fragrance Journal", 1981, vol. 50, pp. 79-82. That is, the source of all organic compounds is methane (CH ₄ ), all other compounds are all regarded as derivatives of methane, and certain numbers are set for the carbon number, substituent, transformation part, ring, etc. Add scores to determine organic and inorganic values. These values are plotted on a diagram with the organic value as the X axis and the inorganic value as the Y axis. This organic conceptual diagram is also shown in “Organic Conceptual Diagram-Basics and Applications” (by Yoshio Koda, Sankyo Publishing, 1984).
The HLB of the component (A1) is 8.5 or more and less than 12.0, and preferably 9.0 to 11.0.
When the HLB of the component (A1) is 8.5 or more and less than 12.0, the detergency against oil stains is increased, and re-contamination such as oil stains on the object to be cleaned is also suppressed.
In particular, when the HLB of the component (A1) is 8.5 or more, the effect of suppressing recontamination such as oil stains on the object to be cleaned is high. On the other hand, if the HLB of the component (A1) is less than 12.0, low foamability during cleaning can be ensured.
In addition, when using 2 or more types of (A1) component, the HLB of these mixtures requires that the value of the weighted average of HLB of each (A1) component is in the range of 8.5 or more and less than 12.0. Shall.

The melting point of the component (A1) is preferably 35 to 70 ° C, more preferably 40 to 65 ° C.
If the melting point of the component (A1) is equal to or greater than the preferred lower limit, it is easy to ensure low foaming properties during cleaning. On the other hand, if the melting point of the component (A1) is equal to or less than the preferable upper limit, the solubility of the detergent for dishwashers increases, and the undissolved residue of the detergent is less likely to occur after washing.
In the present invention, “the melting point of the component (A1)” means that the component (A1) with the mixing ratio set to (A1) component / purified water = 9/1 (mass ratio) and the purified water were mixed in a mortar. The sample is sampled and about 4 mg of the sample is collected, and the minimum value of the endothermic peak observed when measured with a differential scanning calorimeter (DSC8230D, manufactured by Rigaku Corporation) at a temperature rising rate of 3 K / min. The indicated temperature.

The component (A1) may have a monoalkanolamide structure or a dialkanolamide structure. Especially, since the effect of this invention increases more, what has a mono alkanolamide structure is preferable.
As what has a monoalkanolamide structure, the compound represented by the following general formula (a1-1) or the compound represented by general formula (a1-2) is mentioned suitably, for example.

［式中、Ｒ^１は炭素数７〜１９のアルキル基又はアルケニル基を表す。Ｒ^１’は水素原子又はメチル基を表す。］

[Wherein, R ¹ represents an alkyl group or an alkenyl group having 7 to 19 carbon atoms. R ¹ ′ represents a hydrogen atom or a methyl group. ]

In the formula (a1-1), the alkyl group and alkenyl group in R ¹ may be linear or branched. Among these, R ¹ is preferably a linear or branched alkyl group.
The alkyl group or alkenyl group in R ¹ has 7 to 19 carbon atoms, and preferably has 9 to 17 carbon atoms, more preferably 11 to 15 carbon atoms, from the viewpoint of detergency against oil stains. .

［式中、Ｒ^２は炭素数７〜１９のアルキル基又はアルケニル基を表す。Ｒ^２’は水素原子又はメチル基を表す。ｎは平均繰返し数である。］

[Wherein R ² represents an alkyl group or alkenyl group having 7 to 19 carbon atoms. R ² ′ represents a hydrogen atom or a methyl group. n is the average number of repetitions. ]

In the formula (a1-2), examples of R ² include the same as R ¹ in the formula (a1-1).
In the formula (a1-2), n is an average number of repetitions, and is preferably a number of 3 or less, more preferably a number of 2 or less, from the viewpoint of the detergency against oil stains and the effect of suppressing recontamination. More preferably, the number is 1 or less, and particularly preferably 1.
The compound represented by the general formula (a1-2) is a mixture of molecules having different (CH ₂ CH ₂ O) repeating numbers, as can be seen from the fact that n represents the average repeating number.

Specific examples of the component (A1) include coconut oil fatty acid monoethanolamide, lauric acid monoethanolamide, myristic acid monoethanolamide, palmitic acid monoethanolamide, stearic acid monoethanolamide, isostearic acid monoethanolamide, lauric acid monoethanol Fatty acid monoalkanolamides such as isopropanolamide; polyoxyethylene coconut oil fatty acid monoethanolamide, polyoxyethylene lauric acid monoethanolamide, polyoxyethylene myristic acid monoethanolamide, polyoxyethylene palmitic acid monoethanolamide, polyoxyethylene stearin Acid monoethanolamide, polyoxyethylene isostearic acid monoethanolamide, polyoxyethylene lauric acid monoisopropanol Polyoxyethylene fatty acid monoalkanolamides, such as amide.
Among these, fatty acid monoalkanolamides are preferable from the viewpoint of the detergency against oil stains and the like, and the effect of suppressing recontamination of oil stains such as plastic containers, particularly hydrophobic dishes. Among them, coconut oil fatty acid is preferable. Monoethanolamide, lauric acid monoethanolamide, and lauric acid monoisopropanolamide are more preferable, and coconut oil fatty acid monoethanolamide is particularly preferable.
Among the polyoxyethylene fatty acid monoalkanolamides, polyoxyethylene myristic acid monoethanol is used in terms of its detergency against oil stains and the effect of suppressing recontamination of oil stains such as plastic containers, especially hydrophobic dishes. Amides are preferred, and those having an average number of repeating oxyethylene groups of 1 are particularly preferred.

  Among the components (A1), the fatty acid alkanolamide is produced, for example, by an amidation reaction between a fatty acid or a fatty acid alkyl ester and an alkanolamine. Polyoxyethylene fatty acid alkanolamide is produced by an addition reaction between a fatty acid alkanolamide and ethylene oxide. Specifically, it can be produced by a synthesis method described in JP2003-183893A, JP2006-315977A, and the like.

The synthesis of a fatty acid alkanolamide is, for example, a fatty acid (such as coconut oil fatty acid, lauric acid or myristic acid) or a fatty acid alkyl ester (such as methyl laurate or methyl myristate), alkanolamine (monoethanolamine, monoisopropanolamine, Diethanolamine, etc.) in an amount of 1.0 to 1.5 molar times, and an alkali catalyst (an alkali metal alcoholate such as sodium methylate; an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide), a fatty acid or a fatty acid The amidation reaction is performed by adding 0.01 to 1 part by mass with respect to 100 parts by mass in total of the alkyl ester and the alkanolamine.
Usually, after charging alkanolamine into a reaction vessel, a normal temperature or warmed fatty acid or fatty acid alkyl ester is dropped over 1 to 5 hours and reacted. The reaction temperature is higher than the melting point of the fatty acid alkanolamide to be produced. The reaction pressure is in the range from normal pressure to reduced pressure, and setting the reduced pressure is preferable because the by-produced alkyl alcohol can be efficiently distilled off. After completion of the dropwise addition of the fatty acid or fatty acid alkyl ester, the reaction is completed by gradually reducing the pressure to 1.2 kPa or less and holding for about 0.1 to 4 hours.

  The synthesis of polyoxyethylene fatty acid alkanolamide can be obtained by adding ethylene oxide at a desired molar ratio and reacting with the fatty acid alkanolamide obtained in the above-mentioned “synthesis of fatty acid alkanolamide”. A fatty acid alkanolamide containing an alkali metal alcoholate catalyst is charged into an autoclave reactor, nitrogen gas replacement is performed, and then a predetermined amount of ethylene oxide gas is pressurized for 0.5 to 2 hours at a temperature equal to or higher than the melting point of the fatty acid alkanolamide. While introducing, the reaction is carried out under normal pressure to 0.5 MPa. After the introduction of ethylene oxide gas, the reaction is completed for an additional 0.1 to 2 hours.

(A1) A component may be used individually by 1 type and may be used in combination of 2 or more types as appropriate.
Among the components (A1), at least one selected from the group consisting of coconut oil fatty acid monoethanolamide, lauric acid monoethanolamide, lauric acid monoisopropanolamide and polyoxyethylene (average number of repetitions 1) myristic acid monoethanolamide It is preferable to use it.
In the dishwasher detergent, the content of the component (A1) is preferably 0.1 to 10% by mass, more preferably 0.3 to 5% by mass, and more preferably 0.5 to 0.5% by mass with respect to the total mass of the detergent. 3% by mass is more preferable.
When the content of the component (A1) is equal to or more than the preferred lower limit, the cleaning power against oil stains is increased, and re-contamination of the oil stains on the object to be cleaned is easily suppressed. On the other hand, if the content of the component (A1) is equal to or less than the preferable upper limit, foaming at the time of washing is easily suppressed.

<< (A2) component: About surfactants other than (A1) component >>
The component (A) may contain a surfactant other than the component (A1) (hereinafter also referred to as “component (A2)”). By using the component (A2) in combination, oil stains and the like adhering to the object to be cleaned can be removed well. In addition, the component (A2) can also function as a binder in a granular dosage form.
The component (A2) is not particularly limited, and for example, polyoxyalkylene alkyl ether, glycerin fatty acid ester, sucrose fatty acid ester, alkyl glycoside, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester, fatty acid Nonionic surfactants such as monoglycerides, higher alcohol polyoxyethylene (EO) adducts, amine oxides; anionic surfactants such as α-sulfo fatty acid alkyl esters, linear alkylbenzene sulfonates, alkyl sulfates, soaps; Monoalkylamine, dialkylamine, ethylene oxide adduct of monoalkylamine, ethylene oxide adduct of dialkylamine, mono long chain alkyl quaternary ammonium salt, di long chain alkyl quaternary ammonium Cationic surfactants such as ium salts; carboxymethyl betaine, sulfobetaine, such as amphoteric surfactants such as sulfobetaine can be used.
Because of the features of the dishwasher (the point that the cleaning liquid is sprayed using a pump), if a detergent containing a non-low-foaming surfactant is used, excessive foam will be generated and the foam will cause the pump to There is a risk of air spilling and stopping operation. For this reason, it is preferable to use a low-foaming surfactant for the component (A2). If the surfactant used in combination with the component (A1) is low-foaming, the object to be cleaned can be cleaned without placing an excessive burden on the pump of the dishwasher.

In the present invention, the “low-foaming surfactant” includes a surfactant having a foam height of 15 mL or less, which is measured by the following measurement method.
Bubble height measurement method:
A surfactant solution is prepared by adding 0.12 g of a surfactant to 3 L of water at 15 ° C. The surfactant solution is put into an automatic dishwasher and operated. Stop the operation 1 minute after the start of washing and open the door at the same time, and measure the foaming in the chamber after 15 seconds. In that case, three places in a store | warehouse | chamber are selected at random, the bubble height (mL) of this place is measured, respectively, and the average value is calculated | required.

  In a dishwasher, since it is necessary to have good detergency and to suppress foaming during washing, the total content of the components (A1) and (A2) in the dishwasher detergent ( That is, the content of the component (A) is preferably 11% by mass or less, more preferably 0.2 to 11% by mass, and more preferably 0.3 to 5% with respect to the total mass of the cleaning agent. It is more preferable to set it as mass%, and it is especially preferable to set it as 0.5-3 mass%.

<Optional component>
In the dishwasher cleaning agent of the present invention, components other than the above-described component (A) may be optionally blended as necessary within a range not impairing the effects of the present invention.
The dishwasher detergent of the present invention preferably further contains protease (B) (hereinafter also referred to as “component (B)”).
As described above, recently, pre-washing has been omitted, and the amount of dirt to be washed by the dishwasher has increased. Along with this, it is difficult to remove oil stains and protein stains (oil / protein composite stains) coexisting therewith. On the other hand, by using the component (B) together with the component (A), the detergency against the oil / protein composite soil is further increased. In addition, the effect of preventing recontamination such as oil stains on the object to be cleaned is further enhanced.

≪ (B) component: About protease≫
The component (B) is not particularly limited, and those usually blended in detergents can be used. For example, pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, sptilisin, BPN, papain, promeline, carboxy Peptidases A and B, aminopeptidases, aspergillopeptidases A and B and the like can be mentioned.
In addition, as the component (B) in the present invention, JP-A 51-8401, JP-A 46-43551, JP-A 46-42956, JP-A 59-59189, JP JP 54-62386, JP 48-2794, JP 50-16435, JP 53-18594, 55-46711, 57-42310 JP, 58-16200, JP 56-24512, JP 47-1832, JP 52-35758, JP 50-34633, JP 46 -41596, JP-A-58-134990, JP-A-55-14086, JP-A-51-82783, JP-A-51-125407, JP-A-55-39794 JP-A 46-1840, JP-A 46-23989, JP-A 58-15282, JP-A 61-280278, JP-A 4-197182, JP 3-79987. Those described in Japanese Patent Laid-Open No. 5-25492 and the like can also be used. Furthermore, not only these purified fractions but also crude enzymes or their granulated products can be used.
Regarding the component (B), commercially available enzymes include savinase, alcalase, evalase, cannase, esperase (above, Novozymes); API21 (Showa Denko) (Manufactured by Co., Ltd.); Maxatase, Maxcal, Maxacal, Purefect, Maxapem (manufactured by Genencor Corp.); KAP (manufactured by Kao Corporation), described in JP-A-5-25492 Proteases K-14 and K-16
Etc.
(B) A component may be used individually by 1 type and may be used in combination of 2 or more types as appropriate.

  In the case of using a granulated product containing the component (B), the component (B) is added to a stabilizer, a filler, an extender, an increase agent based on a normal granulation method such as the method described in JP-A-60-262900. A granulated product (enzyme granulated product) with a whitening agent, a binder, a coating agent, or the like can be used. Usually, the content of the component (B) in the enzyme granulated product is about 0.1 to 10% by mass, preferably about 0.5 to 5% by mass, more preferably 1 to 3% by mass as the amount of enzyme protein. %. When granulating two or more kinds of enzymes, they may be granulated separately, or the enzymes may be mixed to form the same granulated product.

In the dishwasher cleaning agent of the present invention, the mixing ratio of the component (A1) and the component (B) is such that the protease activity per gram of the cleaning agent is Ea (kPU / g), and the component (A1) in the cleaning agent. When the content of is W _A1 (% by mass), the ratio represented by Ea / W _A1 (hereinafter also referred to as “Ea / W _A1 ratio”) is preferably 1 to 30, preferably 5 to 20. More preferably.
By setting the Ea / W _A1 ratio in the above range, the detergency against oil / protein composite soil is increased.
In addition, if the Ea / W _A1 ratio is less than 1, the detergency against the oil / protein composite soil tends to decrease. This is presumably because protein stains tend to remain on tableware and the like as the ratio of protease activity Ea per gram of cleaning agent decreases, and oil stains also tend to remain on the remaining protein stains. Furthermore, the foaming property derived from the component (A1) tends to increase, and this also weakens the nozzle jetting property (spraying force) of the dishwasher, which is considered to be a cause of the reduction of the cleaning power. On the other hand, even if the Ea / W _A1 ratio exceeds 30, the detergency against oil / protein composite stains tends to decrease. This is considered to be because if the ratio of the protease activity Ea per 1 g of the cleaning agent increases, the cleaning power against the protein soil is weakened by the self-digestion action of the protease.

In the present invention, the protease activity per 1 g of the cleaning agent indicates a value measured as follows, for example. In the present specification, the “protease unit (PU)” represents a unit of activity for hydrolyzing a peptide bond in a protein molecule.
The activity of releasing 1 μg of tyrosine in casein per minute is defined as 1PU.

[Measurement method for protease activity per gram of detergent]
1) Preparation of casein substrate solution 0.6 g of casein (origin: Bovine Milk, manufactured by Merck & Co., Inc.) substrate was dissolved in a 20 mM sodium tetraborate (sodium tetraborate, manufactured by Kanto Chemical Co.) solution, and 1N sodium hydroxide ( After adjusting the pH to 10.5 with a 1 mol / L sodium hydroxide solution (manufactured by Kanto Chemical Co., Inc.), a casein substrate solution is prepared by adjusting the volume to 100 mL with 20 mM sodium tetraborate.

2) Measurement of protease activity per gram of detergent In the case of granular detergent, a granular detergent composition not containing protease is prepared, 10 g of this granular detergent composition is precisely weighed, and ion-exchanged water To obtain a 1 L volume, thereby obtaining an aqueous solution (detergent aqueous solution A) of the granular detergent composition not containing protease. Separately, a granular detergent composition containing protease was prepared, 10 g of this granular detergent composition was precisely weighed, dissolved in ion-exchanged water, and made up to a volume of 1 L. An aqueous solution (cleaning agent aqueous solution B) of the granular cleaning agent compounded with protease is obtained by separating and dissolving in the granular detergent composition not containing the protease and making a constant volume of 300 mL. .
In the case of a liquid detergent, a liquid detergent composition containing no protease is prepared, 1.0 g of this liquid detergent composition is precisely weighed, dissolved in ion-exchanged water, and made up to a volume of 1 L. As a result, an aqueous solution (detergent aqueous solution C) of the liquid detergent composition not containing protease is obtained. Separately, a liquid detergent composition containing a protease was prepared, 1.0 g of this liquid detergent composition was precisely weighed, dissolved in ion-exchanged water, and made up to a volume of 1 L. An aqueous solution (detergent aqueous solution D) of the liquid detergent composition is obtained.
0.5 mL of the cleaning solution A and B or the cleaning solution C and D is collected in a separate test tube (φ15 mm, length 105 mm) with a whole pipette. After immersing these test tubes in a constant temperature bath at 35 ° C. for 5 minutes, 2.5 mL of the casein substrate solution adjusted to 35 ° C. in advance is added to each test tube, stirred for 10 seconds with a vortex mixer, and again It returns to a 35 degreeC thermostat and reaction is started.
Ten minutes after the start of the reaction, 2.5 mL of TCA solution (0.11 M trichloroacetic acid, 0.22 M sodium acetate, 0.33 M acetic acid (all of which are special grades, manufactured by Kanto Chemical Co., Inc.)) in each test tube After each is added, the mixture is stirred for 10 seconds with a vortex mixer and allowed to stand at 20 ° C. for 30 minutes. Thereafter, the unreacted substrate that precipitates is filtered through a filter paper (No. 131 manufactured by Advantech Co., Ltd.), and the filtrate containing tyrosine is recovered. The absorbance of the collected filtrate at a wavelength of 275 nm is measured using an ultraviolet-visible spectrophotometer (UV-160 manufactured by Shimadzu Corporation). Next, the difference between the absorbance of the cleaning agent aqueous solution B and the absorbance of the cleaning agent aqueous solution A, or the difference between the absorbance of the cleaning agent aqueous solution D and the absorbance of the cleaning agent aqueous solution C is obtained, and this difference is determined to contain protease. The absorbance value of the cleaning composition is used.
Then, from the tyrosine concentration calculated based on a calibration curve prepared in advance with a TCA solution of tyrosine (special grade, manufactured by Kanto Chemical Co., Inc.), protease activity (PU) per 1 g of granular detergent composition, or liquid washing The protease activity (PU) per gram of the agent composition is calculated.

The activity per gram of protease indicates a value measured as follows, for example.
[Measurement method for activity per gram of protease]
Weigh precisely 0.1 g of protease enzyme preparation, dissolve in ion-exchanged water and adjust to a volume of 100 mL, then dispense 1 mL with a whole pipette, dissolve in ion-exchanged water, and adjust to a volume of 100 mL. A 0.001 mass% protease enzyme preparation aqueous solution is prepared.
After 0.5 mL of this protease enzyme preparation aqueous solution was dispensed into a test tube having a diameter of 15 mm and a length of 105 mm with a whole pipette, the test tube containing the protease enzyme preparation aqueous solution was immersed in a constant temperature bath at 35 ° C. for 5 minutes, To the test tube, 2.5 mL of the casein substrate solution is added, stirred for 10 seconds with a vortex mixer, then returned to a 35 ° C. constant temperature bath and allowed to stand for 10 minutes to proceed with the enzyme reaction.
Thereafter, 2.5 mL of a TCA solution (0.11 M trichloroacetic acid, 0.22 M sodium acetate, 0.33 M acetic acid (all special grades, manufactured by Kanto Chemical Co., Ltd.)) of an enzyme reaction stopper was added to the test tube, and vortexed. After stirring for 10 seconds with a mixer, the mixture is allowed to stand at 20 ° C. for 30 minutes. Thereafter, the mixture is filtered with a filter paper (No. 131 manufactured by Advantech Co., Ltd.), and the filtrate containing tyrosine is recovered.
The absorbance of the collected filtrate at a wavelength of 275 nm is measured using an ultraviolet-visible spectrophotometer (UV-160 manufactured by Shimadzu Corporation). Then, the protease activity (PU) per gram of the protease enzyme preparation is calculated from the tyrosine concentration calculated based on a calibration curve prepared in advance with a TCA solution of tyrosine (special grade, manufactured by Kanto Chemical Co., Inc.).

The component (B) is preferably blended so that the protease activity Ea (kPU / g) per 1 g of the cleaning agent is 1 to 80 (kPU / g), more preferably 2.5 to 40 (kPU / g). ), Particularly preferably 5 to 20 (kPU / g).
By combining the component (B) with the component (A1) so that Ea (kPU / g) falls within the above range, the detergency against oil / protein composite soil is synergistically increased.

In the dishwasher detergent, the content of the component (B) is preferably 0.05 to 16% by mass, more preferably 0.1 to 8% by mass, more preferably 0.3 to the total mass of the detergent. More preferably, 4% by mass.
If the content of component (B) is less than the preferred lower limit, the effect of removing oil stains / protein composite stains may be reduced. On the other hand, even if the content of the component (B) exceeds the preferable upper limit value, the effect of removing the oil stain / protein composite stain may reach its peak.

You may mix | blend components other than the component mentioned above arbitrarily with the washing | cleaning agent for dishwashers of this invention as needed in the range which does not impair the effect of this invention.
The component that may be optionally blended is not particularly limited, and examples thereof include those that have been used in detergents for washing dishes. For example, chelating agent, bleaching agent, bleach activator, alkaline agent, enzyme other than component (B), plant extract, fragrance, oil absorbing agent, antifoaming agent, dish protection agent, thickener, colorant, preservative , PH adjusting agents, powdering agents (such as silicic anhydride), process agents (such as sodium sulfate, potassium sulfate, and sodium chloride) can be used.

(Production method)
The detergent for dishwashers of this invention can be manufactured by a conventionally well-known method.
As a manufacturing method of the detergent for liquid dishwashers, it prepares by mixing a solvent, (A) component containing (A1) component, and an arbitrary component as needed. (B) When mix | blending component, from the point which maintains the activity of (B) component, after mixing a solvent, (A) component containing (A1) component, and arbitrary components other than (B) component ( It is preferable to mix the component B).
As the solvent, water is preferable, and a water-miscible organic solvent may be used in addition to water.
“Water-miscible organic solvent” refers to an organic solvent that dissolves 50 g or more in 1 L of ion-exchanged water at 25 ° C. The water-miscible organic solvent is not particularly limited as long as it becomes a uniform solution when mixed with water, and among them, a monohydric alcohol having 2 to 4 carbon atoms, a polyhydric alcohol having 2 to 4 carbon atoms, and glycol. Examples include ether.
Examples of the monohydric alcohol having 2 to 4 carbon atoms include ethanol, 1-propanol, 2-propanol, 1-butanol and the like.
Examples of the polyhydric alcohol having 2 to 4 carbon atoms include ethylene glycol, propylene glycol, butylene glycol, glycerin and the like.
Examples of the glycol ether include ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether and the like.

The pH (25 ° C.) of the liquid dishwasher detergent is preferably 6.5 or more, more preferably 7 to 11, and still more preferably 8 to 10.
If this pH (25 degreeC) is more than a preferable lower limit, the detergency with respect to oil / protein composite dirt will increase. In addition, recontamination such as oil stains on the object to be cleaned is easily suppressed. Moreover, the storage stability of the cleaning composition is further improved.
In the present invention, the pH of the dishwasher detergent (25 ° C.) is based on JIS K3362-1998, and the pH of the liquid detergent adjusted to 25 ° C. is adjusted to a pH meter (HM-30G, Toa DKK Corporation). The value measured using the product etc. is shown.

As a manufacturing method of a solid dishwasher cleaning agent, for example, if it is a powdery dosage form, a dry blend method in which each raw material is powder-mixed, a dry granulation method in which the powder raw material is granulated while flowing, Agitation granulation method in which a liquid binder is sprayed and granulated while flowing the powder raw material, extrusion granulation method in which the raw material is kneaded and extruded with an extruder, and the raw material is kneaded and pulverized Examples thereof include a grain method and a spray drying method in which a slurry containing a raw material is spray dried.
The moisture content of the solid dishwasher detergent is not particularly limited, and is preferably 8% by mass or less.
The bulk density of the dishwasher detergent powder granular, 0.3 g / cm ³ or more, more preferably 0.5 to 1.2 g / cm ^3, more preferably 0.6~1.1g / cm ³ .
The bulk density is a value measured according to JIS-K3362.
200-1500 micrometers is preferable and, as for the average particle diameter of the detergent for powdery dishwashers, 300-1200 micrometers is more preferable. When the average particle size is less than the preferred lower limit, dust is likely to be generated, while when it exceeds the preferred upper limit, it becomes difficult to dissolve or disperse in water.

In the present invention, the average particle size of the dishwasher detergent is determined by a classification operation using a 9-stage sieve having openings of 1680 μm, 1410 μm, 1190 μm, 1000 μm, 710 μm, 500 μm, 350 μm, 250 μm and 149 μm, and a tray. Measured.
In the classification operation, a sieve having a small mesh size is stacked on a tray in order, and a sample of 100 g / time is placed on the top of the top 1680 μm sieve, and the lid is capped and a low-tap type sieve shaker ( (Made by Iida Seisakusho, tapping: 156 times / minute, rolling: 290 times / minute) and vibrating for 10 minutes. Thereafter, the sample remaining on each sieve and the tray is collected for each sieve, and the mass of the sample is measured. Then, the mass frequency of the tray and each sieve is integrated, the opening of the first sieve where the integrated mass frequency is 50% or more is “a μm”, and the opening of the sieve that is one step larger than a μm is “b μm”. To do. In addition, the integrated value of the mass frequency from the tray to the a μm sieve is “c%”, and the mass frequency on the a μm sieve is “d%”. And an average particle diameter (50 mass% particle diameter) is calculated | required by the following Formula (1), and let this be an average particle diameter of a sample.

(how to use)
What is necessary is just to use the detergent for dishwashers of this invention according to the model of a dishwasher, and the grade of stain | pollution | contamination of tableware.
Examples of a method for washing an object to be washed with a dishwasher using the detergent include a method having both washing and rinsing steps.
As a preferable cleaning method, for example, a step of cleaning the cleaning object while raising the temperature of the cleaning liquid to preferably 50 to 60 ° C. at 2 to 3 ° C./min (hereinafter referred to as “cleaning step”), and after cleaning The object to be cleaned is rinsed with tap water at room temperature (preferably about 5 to 30 ° C.) (hereinafter referred to as “rinse (1) step”), and tap water at room temperature is preferably 2 to 50 to 80 ° C. There is a method of further rinsing the object to be cleaned after the rinsing (1) step (hereinafter referred to as “rinsing (2) step”) while raising the temperature at ˜3 ° C./min.
In the washing step, it is preferable that the amount of the dishwasher detergent used once is 3 to 9 g for about 3 liters of tap water.
Moreover, it is preferable that the washing | cleaning liquid in a dishwasher contains 2-300 ppm (mass basis) of (A) component, It is more preferable to contain 3-200 ppm (mass basis), and 10-100 ppm (mass basis) contains. Is particularly preferred.
By controlling the concentration of component (A) in the cleaning liquid within the above range, recontamination such as oil stains on hydrophobic dishes such as plastic containers can be easily suppressed. In addition, the detergency against oil stains is increased. If the concentration of the component (A) in the cleaning liquid is less than 2 ppm (mass basis), the effect of suppressing the recontamination or the cleaning power may be insufficient. On the other hand, if the concentration exceeds 300 ppm (mass basis), There is a tendency for foaming to be excessive, which is not preferable.
The washing time in the washing step is preferably 3 to 50 minutes, more preferably 5 to 30 minutes.
The rinsing time in the rinsing (1) step is preferably 0.5 to 10 minutes, more preferably 1 to 7 minutes.
The rinsing time in the rinsing (2) step is preferably 3 to 50 minutes, more preferably 5 to 30 minutes.

  As described above, the dishwasher detergent composition of the present invention employs the component (A1), and the component (A1) is used in an amount of 25% by mass or more based on the total amount of the component (A). Oil stains on dishes (such as plastic containers) that use hydrophobic materials such as polypropylene while ensuring low foaming even when dishes are washed with a dishwasher without washing Re-contamination of is suppressed.

In addition, in the dishwasher detergent composition of the present invention, the combination of the component (A1) and the component (B) and the Ea / W _A1 ratio of 1 to 30 makes it possible to prevent oil / protein composite stains. Detergency increases synergistically and excels in dirt removal effect. Further, since it becomes difficult for redeposition of oil stains or protein stains to tableware or the like at the time of rinsing, recontamination of oil stains or the like particularly on hydrophobic tableware is greatly suppressed.

  Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples.

<Preparation of dishwasher detergent>
According to the composition shown in Tables 1 to 5, each example of the cleaning agent was prepared by the below-described production method (when there is an unblended component, the component is not blended).
The unit of the blending amount in the table is “mass%”, and all the components indicate the amount in terms of pure content.
In the table, “appropriate amount” indicates the total amount of 1N sulfuric acid and 1N sodium hydroxide used as a pH adjuster.
“Balance” means that the component (sodium sulfate or ion-exchanged water) is blended so that the total blended amount (mass%) of all the blended components contained in the cleaning agent of each example is 100 mass%. means.
“Content (mass%) of component (A1) in component (A)” means the ratio of the mass occupied by component (A1) to the total mass of the surfactant.
“Ea / W _A1 ratio” means the ratio of protease activity Ea (kPU / g) per 1 g of the cleaning agent with respect to the content W _A1 (mass%) of the component (A1) in the cleaning agent.
The protease activity Ea per 1 g of the cleaning agent was measured by the above-mentioned [Method for measuring protease activity per 1 g of cleaning agent].
Below, the component shown in the table | surface is demonstrated.

-(A1) component A1-1: Coconut oil fatty acid monoethanolamide (manufactured by Kawaken Fine Chemicals, Amisol CME), HLB10.3, melting point 43.7 ° C.
A1-2: Lauric acid monoethanolamide (synthetic product), HLB 10.7, melting point 61.2 ° C.
A1-3: Polyoxyethylene myristic acid monoethanolamide (ethylene oxide average 1 mol adduct of myristic acid monoethanolamide, synthetic product), HLB 8.9, melting point 50.3 ° C.
A1-4: Lauric acid monoisopropanolamide (manufactured by Kawaken Fine Chemicals, Amizole PLME-A), HLB10.3, melting point 50.6 ° C.
A1-5: Polyoxyethylene lauric acid monoethanolamide (ethylene oxide average 1 mol adduct of lauric acid monoethanolamide, synthetic product), HLB 10.0, melting point 51.3 ° C.

-(A2) component A2-1: Decanoic acid monoethanolamide (synthetic product), HLB12.5, melting | fusing point 53.2 degreeC.
A2-2: Stearic acid monoethanolamide (synthetic product), HLB 7.5, melting point 94 ° C.
A2-3: Palm oil fatty acid diethanolamide (manufactured by Kawaken Fine Chemicals, Amizole CDE), HLB 12.0, melting point 5.0 ° C.
A2-4: C12,13 polyoxyalkylene alkyl ether (a mixture of an alcohol having 12 carbons and an alcohol having 13 carbons added with an average of 3 moles of ethylene oxide and an average of 3 moles of propylene oxide) NNAEP-3030), HLB4.5.
A2-5: Polyoxyethylene (5) lauryl ether, ethylene oxide average 5 mol adduct (manufactured by Nippon Emulsion, Emalex 705), HLB 9.5, melting point 8.4 ° C.
A2-6: Sodium linear alkylbenzene sulfonate (a product obtained by neutralizing linear alkylbenzene sulfonic acid (Lypon LH-200, manufactured by Lion Corporation) with sodium hydroxide).

[Method for synthesizing synthetic product in component (A1) or component (A2)]
Synthesis example of A1-2, A2-1, A2-2:
They were synthesized by reacting each fatty acid methyl ester with monoethanolamine.
A stirrer and a condenser were installed in a 2 L four-necked flask, charged with 1.05 times the molar ratio of monoethanolamine to fatty acid methyl ester, and sodium methylate (28% by mass solution) as a catalyst. 0.25 mass part (pure part conversion) was prepared with respect to 100 mass parts of fatty acid methyl ester.
Here, at a reaction temperature of 100 ° C. and a pressure of 40 kPa (under reduced pressure), fatty acid methyl ester was added dropwise over 3 hours to carry out an amidation reaction. Fatty acid monoethanolamides A1-2, A2-1 and A2-2 were obtained by reducing the pressure to 1.3 kPa and aging for 4 hours after completion of the dropwise addition.
As the fatty acid methyl ester, lauric acid methyl ester was used when A1-2 was synthesized, decanoic acid methyl ester was used when A2-1 was synthesized, and stearic acid methyl ester was used when A2-2 was synthesized.

Synthesis examples of A1-3 and A1-5:
For A1-3, the fatty acid monoethanolamide of A2-2 obtained in the above synthesis example (including sodium methylate as a catalyst) is charged into a 2 L autoclave, the reaction temperature is 100 ° C., and the reaction pressure is from normal pressure to 0. Under conditions up to 4 MPa, ethylene oxide gas is reacted by blowing 1.0 mole equivalent over 1 hour with respect to the fatty acid monoethanolamide, and further aged for 30 minutes until the pressure in the system does not change. It was obtained by performing.
A1-5 was obtained in the same manner as the synthesis method of A1-3 except that A1-2 was used instead of A2-2.

-(B) component The inside of () shown below is the activity per 1g of each protease (unit: kPU / g).
B-1: Sabinase U 16XL, manufactured by Novo Corporation (2000 kPU / g).
B-2: Everase 16L, manufactured by Novo Corporation (1000 kPU / g).
B-3: Evalase 8T, manufactured by Novo Corporation (500 kPU / g).
B-4: Purefect OX6000E, manufactured by Genencor (1000 kPU / g).
In addition, the activity per 1 g of each protease indicates the value measured by the above-mentioned [Measurement method for activity per 1 g of protease].

-Optional component Na salt of maleic acid / acrylic acid copolymer: manufactured by Nippon Shokubai Co., Ltd., AQUALIC TL400 (weight average molecular weight 50000, active ingredient 40% by mass).
Sodium citrate: manufactured by Fuso Chemical, sodium citrate.
Silicic anhydride (manufactured by Tokuyama Corporation, Tokuseal NP).
Sodium sulfate (Nippon Chemical Co., Ltd., neutral anhydrous sodium sulfate K2).
pH adjuster: 1N sulfuric acid, 1N sodium hydroxide.
Ion exchange water.

[Manufacturing method of dishwasher detergent]
(Liquid detergent: Examples 1-18, Comparative Examples 1-9)
According to the composition of Tables 1 to 3, 0.8 kg of the liquid cleaning agent of each example was prepared as follows.
First, in a 1 L beaker, a maleic acid / acrylic acid copolymer Na salt or sodium citrate is dissolved in ion-exchanged water, and an aqueous solution (so that the total amount thereof becomes 50% by mass of the entire composition) X) was prepared.
Separately, ion-exchanged water adjusted to 75 ° C. and (A1) component and / or (A2) component are mixed in a 1 L beaker so that the total amount thereof is 40% by mass of the entire composition. A surfactant solution was prepared.
Next, the whole amount of the surfactant solution adjusted to 75 ° C. was added to the aqueous solution (X) heated to 75 ° C. while stirring at 6000 rpm, and then stirred for 30 seconds to obtain a mixed solution.
After cooling this mixed liquid to 25 degreeC, it adjusted so that pH (25 degreeC) of a composition might be set to 9.5 using 1N sulfuric acid or 1N sodium hydroxide. In Examples 9-14, 16-18, and Comparative Examples 6-9, after adjusting pH, (B) component was added and stirred.
Subsequently, the remaining ion exchange water was added and stirred so that the whole composition might be 100 mass%, and the liquid cleaning agent was obtained.
The pH (25 ° C.) of the composition was measured by using a liquid detergent adjusted to 25 ° C. using a glass electrode type pH meter (HM-30G, manufactured by Toa DKK Corporation). The measuring method was performed based on JIS K3362-1998.

(Granular detergent: Examples 19 to 41, Comparative Examples 10 to 15)
According to the composition of Tables 4 and 5, 6 kg of the granular detergent for each example was prepared as follows.
First, sodium sulfate was put into a ribbon mixer (manufactured by Yoshida Manufacturing Co., Ltd., ribbon mixer 1102-1500 type, width 900 mm × length 1800 mm × depth 1100 mm), and anhydrous silicic acid was added while stirring at 25 rpm, and mixed for 10 minutes. . Next, the (A1) component or the (A2) component and the components (B) are added in Examples 19 to 38, 40, and 41 and Comparative Examples 10 to 15, and the mixture is mixed at 25 rpm for 10 minutes. Obtained.

<Evaluation of dishwasher detergent>
About the cleaning agent of each example, each evaluation was performed by the evaluation method shown below, and the result was written together in Tables 1-5.
An automatic dishwasher (manufactured by Panasonic Corporation, model NP-40SX2) was used as the dishwasher. In each evaluation, the washing process was performed by operating on a standard course set in the automatic dishwasher. The contents of the standard course are shown below.
Standard course:
Into the automatic dishwasher, the amount of cleaning agent described in the table is added to 3 L of tap water, and then tap water is introduced into the cabinet to prepare a cleaning solution. A cleaning process is performed for 20 minutes while the temperature is raised at a temperature of ° C / min. Thereafter, rinsing with room temperature tap water is performed 3 times (2 minutes / time), and then rinsing (final rinse) for 20 minutes is performed while raising the tap water from room temperature to 70 ° C. at a rate of 2 to 3 ° C./min. After being broken, the dishes are dried while circulating warm air.
In the table, (A) component concentration (ppm, based on mass) in the cleaning liquid obtained by dissolving the cleaning agent in tap water is shown.

[Evaluation of low foaming properties]
The automatic dishwasher was charged with 6 g of detergent and operated on the standard course.
When the water temperature reached 55 ° C. from the start of washing, the operation was stopped and the door was opened at the same time, and foaming in the cabinet was measured 15 seconds later.
At that time, three locations in the warehouse were selected at random, and the bubble height (mm) at each location was measured with a ruler, and the average value was obtained. If this bubble height was 10 mm or less, it was judged as acceptable.

[Evaluation of recontamination prevention]
Prepare 2 pieces of 21cm diameter ceramic dish with 8g of beef tallow and 2 pieces of 15cm diameter ceramic dish with 8g of retort curry (bon curry gold 21 dry). These were used as model dirt. The amount of dirt is eight times the amount of dirt remaining when pre-washing).
Also, one amber-colored polypropylene (PP) lunch box (110 mm long, 170 mm wide, 35 mm high), which was confirmed to have no oil adhesion before the cleaning treatment, was prepared.
And the said model dirt (each 2 pieces of earthenware dishes) and one said PP lunch box were accommodated in the said automatic dishwasher, and it drive | operated in the said standard course, and performed the washing process. Such washing treatment was performed three times.
The degree of oil adhesion was observed by touching the PP lunch box after washing (after drying) with the naked eye and by hand, and the anti-contamination property was evaluated based on the following evaluation criteria.
The three evaluation points were averaged, and if the average value was 3.0 points or more, it was regarded as acceptable.
(Evaluation criteria)
4 points: No adhesion of oil was observed visually, and there was no oily touch even when touched with a finger.
3 points: The adhesion of oil is not recognized visually, but a slight touch of oil is felt when touched with a finger.
2 points: A slight amount of oil was visually observed, and even when touched with a finger, a feeling of oil was felt.
1 point: The adhesion of oil is clearly recognized visually, and even when touched with a finger, the adhesion of oil is clearly felt.

[Evaluation of detergency against oil / protein complex dirt]
On a frying pan with a diameter of 25 cm, heated by drawing 20 g of Nisshin Oilio salad oil, two half-boiled fried eggs were cooked by dividing 2 egg M sizes.
Place the two half-boiled fried eggs on a black ceramic dish with a diameter of 12 cm, split the yolk using a knife and fork, mix the salad oil and the half-boiled fried egg on the black ceramic dish, and leave it at room temperature for 2 hours. Thus, a soil (oil / protein composite soil) in which oil and protein were mixed was prepared.
This oil / protein composite soil was divided into 8 parts, and a black small plate having a diameter of 6 cm was contaminated with each of the soils to prepare 8 black small plates to which the oil / protein composite soil was adhered (the oil / protein composite soil adhered to the black small plate / The amount of soil of the protein composite soil is 10 times the amount of soil remaining when prewashed).
Next, the black dish with the 8 oil / protein composite stains was stored in one automatic dishwasher and operated on the standard course for washing treatment.
The appearance of the black small dish after the washing treatment (after drying) was visually observed, and the detergency against the oil / protein composite soil was evaluated based on the following evaluation criteria.
The evaluation score of 8 black small dishes was averaged, and if the average value was 3.0 points or more, it was judged as acceptable.
(Evaluation criteria)
4 points: Both oil and egg stains adhering to the black small dish are removed, and no trace of water drops is observed.
3 points: Both oil and egg stains adhering to the black small dish are cleanly removed, but traces of water droplets are observed.
2 points: A slight residue of oil and egg stains adhering to the black pan was observed, and traces of water droplets were also observed.
1 point: Residue of oil and egg stains adhering to the black small dish is clearly observed, and traces of water droplets are also remarkably observed.

  From the results shown in Table 1, it can be seen that all of the cleaning agents of Examples 1 to 8 to which the present invention is applied have low foaming properties and suppresses recontamination such as oil stains on the object to be cleaned. .

  From the results shown in Tables 2 to 5, the detergents of Examples 9 to 41 to which the present invention is applied have excellent detergency against oil / protein composite stains while ensuring low foaming properties. It can be seen that recontamination of the object to be cleaned, such as oil stains, is suppressed.

Claims (2)

A surfactant (A) containing a nonionic surfactant (A1) selected from the group consisting of fatty acid alkanolamides and polyoxyethylene fatty acid alkanolamides and having an HLB of 8.5 or more and less than 12.0,
A dishwasher cleaning agent, wherein the content of the nonionic surfactant (A1) in the surfactant (A) is 25% by mass or more. Further containing protease (B), and
When the protease activity per 1 g of the cleaning agent is Ea (kPU / g) and the content of the nonionic surfactant (A1) in the cleaning agent is W _A1 (mass%), it is expressed by Ea / W _A1. The dishwasher cleaning agent according to claim 1, wherein the ratio is 1-30.