KR20140136384A - Detergent for dishwasher - Google Patents

Abstract

A detergent for a dishwasher according to a first aspect of the present invention contains a surfactant (A) including a nonionic surfactant (A1) which is selected from the group consisting of fatty acid alkanolamide and polyoxyethylene fatty acid alkanolamide and also has a 8.5 or more and less than 12.0 of HLB, and in which the content of the nonionic surfactant (A1) in the surfactant (A) is 25 mass% or more. A detergent for a dishwasher according to a second aspect of the present invention contains: a component (A1); a nonionic surfactant (A1) which is selected from the group consisting of: fatty acid alkanolamides, and polyoxyethylene fatty acid alkanolamide, and also has an HLB that is 8.5 or more and less than 12.0, and a component (C): and a chelating agent (C), in which the mass ratio represented by component (C)/component (A1) ranges form 1 to 50.

Description

{DETERGENT FOR DISHWASHER}

The present invention relates to a dishwasher detergent.

The present application claims priority based on Japanese Patent Application No. 2013-106562, filed on May 20, 2013, and Japanese Patent Application No. 2013-106563, filed on May 20, 2013, the contents of which are incorporated herein by reference .

BACKGROUND ART [0002] In recent years, a dishwasher for washing dishes or cooking utensils has been spreading not only in a kitchen such as a hotel, a restaurant or a food service center but also in a home.

In the dishwasher, a dedicated cleaning agent (dishwasher detergent) is generally used, and hot water of about 55 to 65 ° C is used.

In the dishwasher, the cleaning liquid is discharged using a pump. When bubbles are generated in the cleaning liquid, the cleaning liquid is not discharged from the pump, and it is likely that the operation stop is undesirable. For this reason, a dishwasher detergent is required to have a low foaming property. In addition, detergents for dishwashing machines are also required to have a cleaning power capable of removing oil contamination and scale contamination (such as tap water or contaminated calcium that is insolubilized due to contamination and adhered to dishes or the like) attached to dishes and the like.

On the other hand, polyoxyethylene polyoxypropylene alkyl ethers are generally used as detergents for dishwashers with low foaming properties.

Conventionally, as a dishwasher detergent, there has been proposed a particulate detergent composition for dishwasher, which contains a polycarboxylic acid-based polymer compound and inorganic peroxide at a specific mixing ratio, as well as a low-foaming nonionic surfactant (see Patent Document 1) . Patent Document 1 discloses the use of a polyoxyalkylene polyoxyethylene alkyl ether as a nonionic surfactant having a low foaming property. The oxyalkylene group has 3 to 5 carbon atoms. In addition, there has been proposed a composition for dishwashing which contains an essential oil component such as terpene alcohol and an N-acyl amino acid salt for solubilizing the essential oil component and a fatty acid alkanolamide as a solubilization aid for the essential oil component (see Patent Document 2 ).

Japanese Patent Application Laid-Open No. 2010-159384 Japanese Patent Application Laid-Open No. 2000-96091

However, up to now, after washing (preliminary washing) in advance to some extent contamination or food left on the tableware or the like, washing treatment by the dishwasher has been carried out.

However, in recent years, the preliminary cleaning has been omitted, and a dishwashing machine, such as a dishwasher, which is highly contaminated, has been performed by a direct dishwasher. Therefore, the amount of contamination to be cleaned by the dishwasher is increasing. In addition, scale contamination from dishes or the like and oil contamination (oil / scale complex contamination) coexisting therewith are becoming difficult to remove as the contamination amount increases. In addition, in cleaning of a hydrophobic tableware (for example, a plastic container) made of a polypropylene (PP) resin or the like, oil contamination is likely to re-adhere (re-contaminate) during cleaning.

However, in the conventional cleaning agents such as Patent Documents 1 and 2, when washing treatment is carried out by the dishwasher without performing preliminary cleaning, the washing power against the oil / scale composite contamination is insufficient. Further, in the cleaning of the hydrophobic tableware, re-contamination is remarkable.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances and provides a dishwasher detergent having an excellent detergency against oil / scale composite contamination while ensuring a low foaming property and suppressing re-contamination, such as oil contamination, .

The inventors of the present invention have focused on a fatty acid alkanolamide represented by coconut fatty acid diethanolamide or the like or an ethylene oxide adduct thereof which is generally used for increasing the viscosity of a liquid detergent or the like and for increasing the solubilizing power, Among them, it has been found that the above problem can be solved by selecting a substance having a specific HLB and using it at a specific ratio with respect to the total amount of the surfactant. It has also been found that the above problems can be solved by mixing a fatty acid alkanolamide having a specific HLB or an ethylene oxide adduct thereof with a chelating agent in a specific ratio. The present invention has been completed based on the above findings.

That is, the dishwasher cleaner of the first aspect of the present invention comprises a nonionic surfactant (A1) selected from the group consisting of a fatty acid alkanolamide and a polyoxyethylene fatty acid alkanolamide and having an HLB of from 8.5 to less than 12.0 (A), and the content of the nonionic surfactant (A1) in the surfactant (A) is 25 mass% or more.

In the dishwasher detergent according to the first aspect of the present invention, the protease (B) is further contained, and the protease activity Ea (kPU / g) per 1 g of the cleaning agent and the content of the nonionic surfactant (A1) _A1 (mass%), it is preferable that the ratio represented by Ea / W _A1 is 1 to 30.

The cleaning agent for a dishwashing machine according to the second aspect of the present invention comprises (A1) a nonionic surfactant (A1) selected from the group consisting of fatty acid alkanolamides and polyoxyethylene fatty acid alkanolamides and having an HLB of from 8.5 to less than 12.0, And the component (C): chelating agent (C), and the mass ratio represented by the component (C) / (A1) is 1 to 50.

(Effects of the Invention)

According to the present invention, it is possible to provide a detergent for dishwasher having excellent detergency against oil / scale composite contamination while suppressing low contamination and restricting contamination such as oil contamination to the object to be cleaned.

(Detergent for dishwasher according to the first embodiment of the present invention)

The detergent for dishwashing machine according to the first embodiment 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 from 8.5 to less than 12.0 Contains the active agent (A).

Hereinafter, in the present specification, specific nonionic surfactant (A1) is also referred to as component (A1) and surfactant (A) as component (A).

The formulation of the dishwasher detergent according to the first embodiment of the present invention is not particularly limited as long as it contains the component (A1), and may be a solid such as a powdered granule or a tablet, or may be a liquid.

≪ Component (A): Surfactant >

(A) is a surfactant comprising a nonionic surfactant (A1) selected from the group consisting of fatty acid alkanolamides and polyoxyethylene fatty acid alkanolamides and having an HLB of from 8.5 to less than 12.0.

The content of the component (A1) in the component (A) is 25 mass% or more, preferably 50 mass% or more, more preferably 70 mass% or more and 100 mass% do. When the content of the component (A1) is 25 mass% or more, bubble formation is kept low when a dishwasher is used to clean dishes or the like, thereby suppressing re-contamination such as oil contamination to the object to be cleaned do.

≪ Component (A1): Specific nonionic surfactant >

(A1) is a nonionic surfactant selected from the group consisting of fatty acid alkanolamides and polyoxyethylene fatty acid alkanolamides, and having an HLB of from 8.5 to less than 12.0.

The "fatty acid alkanolamide" in the present invention means, for example, a fatty acid component such as a fatty acid, a fatty acid alkyl ester, a fatty acid chloride or a fat; Monoethanolamine, monoethanolamine, monoethanolamine, monoethanolamine, monoethanolamine, diethanolamine, diisopropanolamine and the like. Fatty acid monoalkanolamides, and / or fatty acid dialkanolamides.

&Quot; Polyoxyethylene fatty acid alkanolamide " means that an oxyethylene group is introduced into the fatty acid alkanolamide.

In the present invention, " HLB " is expressed by IOB x 10 in the organic conceptual diagram.

IOB in the organic conceptual diagram refers to the ratio of the inorganic value (IV) to the organic value (OV) in the organic conceptual diagram, that is, the "inorganic value (IV) / organic value (OV)".

The above organic conceptual diagram is proposed by Atsushi Fujita and is described in detail in "Pharmaceutical Bulletin ", 1954, vol. 2, 2, pp. 163-173; &Quot; Area of Chemistry ", 1957, vol. 11, 10, pp. 719-725; Fragrance Journal ", 1981, vol. 50, pp. 79-82. That is, it is assumed that the source of all the organic compounds is methane (CH ₄ ), all other compounds are considered to be derivatives of methane, certain numerical values are set for the carbon number, substituent, Value and inorganic value. Then, these values are plotted on the drawing with the organic value as the X axis and the inorganic value as the Y axis. This organic conceptual diagram is also shown in "The Concept of Organic Concept - Fundamentals and Applications" (Koda Yoshio, Sanko Publishing, 1984).

The HLB of the component (A1) is from 8.5 to less than 12.0, preferably from 9.0 to 11.0.

When the HLB of the component (A1) is in the range of 8.5 to less than 12.0, the detergency against oil contamination and oil / scale composite contamination increases, and the re-contamination such as oil contamination to 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 re-contamination such as oil contamination of the object to be cleaned is high. On the other hand, when the HLB of the component (A1) is less than 12.0, the low foaming property at the time of cleaning can be secured.

When two or more components (A1) are used, the HLB of these mixtures is required to have a weighted average value of HLB of each component (A1) within the range of 8.5 to less than 12.0.

The melting point of the component (A1) is preferably 35 to 70 占 폚, more preferably 40 to 65 占 폚.

When the melting point of the component (A1) is not lower than the preferable lower limit value, the low foaming property at the time of cleaning is easily ensured. On the other hand, if the melting point of the component (A1) is not more than the preferable upper limit value, the solubility of the dishwasher detergent becomes high, and the residue of the detergent dissolved after cleaning is less likely to be generated.

In the present invention, the term "melting point of the component (A1)" means a mixture obtained by mixing the component (A1) in which the mixing ratio is set to the component (A1) / the purified water = 9/1 , About 4 mg of the sample is sampled, and the temperature is set to a temperature that shows the minimum value of the endothermic peak observed when a differential scanning calorimeter (DSC8230D, manufactured by Rigaku Corporation) is used and the temperature is measured at a rate of 3 K / min.

The component (A1) may have a monoalkanolamide structure or may have a dialkanolamide structure. Particularly, since the effect of the present invention becomes higher, it is preferable to have a monoalkanolamide structure.

As the compound having a monoalkanolamide structure, for example, a compound represented by the following general formula (a1-1) or a compound represented by the general formula (a1-2) is preferably listed.

Wherein R ¹ represents an alkyl or 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 the alkenyl group in R ¹ may be linear or branched. In particular, R ¹ is preferably a linear or branched alkyl group.

The alkyl group and alkenyl group in R ^{1 preferably} have ⁷ to 19 carbon atoms and preferably 9 to 17 carbon atoms from the viewpoint of oil contamination and oil / 15.

Wherein R ² represents an alkyl 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 repeats]

R ^{2 in} the formula (a1-2) is 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 3 or less, more preferably 2 or less, from the viewpoints of detergency against oil contamination, oil / scale complex contamination, , More preferably not more than 1, and particularly preferably 1. [

The compound represented by the general formula (a1-2) is a mixture of different molecules in which the repeating number of (CH ₂ CH ₂ O) is different as n also indicates the average number of repeats.

Specific examples of the component (A1) include coconut fatty acid monoethanolamide, lauric acid monoethanolamide, myristic acid monoethanolamide, palmitic acid monoethanolamide, stearic acid monoethanolamide, isostearic acid monoethanolamide, lauric acid Fatty acid monoalkanolamides such as monoisopropanolamide; And polyoxyethylene coconut fatty acid monoethanol amide, polyoxyethylene lauric acid monoethanolamide, polyoxyethylene myristate monoethanolamide, polyoxyethylene palmitoic acid monoethanolamide, polyoxyethylene stearic acid monoethanolamide, poly Polyoxyethylene fatty acid monoalkanolamides such as oxyethylene isostearic acid monoethanolamide and polyoxyethylene lauric acid monoisopropanolamide.

Of these, fatty acid monoalkanolamides are preferred from the viewpoints of their detergency against oil contamination, oil / scale complex contamination, and the effect of inhibiting re-contamination such as oil contamination, particularly to hydrophobic tableware such as plastic containers, Monoethanol amide, lauric acid monoethanolamide and lauric acid monoisopropanolamide are more preferable, and palm oil fatty acid monoethanolamide is particularly preferable.

Among the polyoxyethylene fatty acid monoalkanolamides, from the viewpoints of the detergency against oil contamination and oil / scale composite contamination, and the effect of inhibiting re-contamination such as oil contamination, particularly to hydrophobic tableware such as plastic containers, Lauric acid monoethanolamide is preferable, and the average number of repeating oxyethylene groups is particularly preferably one.

The fatty acid alkanolamide in the component (A1) is prepared, for example, by an amidation reaction of a fatty acid or fatty acid alkyl ester with an alkanolamine. In addition, polyoxyethylene fatty acid alkanolamides are prepared by the addition reaction of fatty acid alkanolamides with ethylene oxide. Specifically, it can be produced by a synthesis method described in JP-A-2003-183693 or JP-A-2006-315977.

The synthesis of the fatty acid alkanolamide can be carried out, for example, by reacting an alkanolamine (monoethanolamine, monoethanolamine, etc.) with a fatty acid (palm oil fatty acid, lauric acid or myristic acid) or fatty acid alkyl ester (Alkali metal alcoholates such as sodium methylate, hydroxides of alkali metals such as potassium hydroxide and sodium hydroxide) are mixed with a fatty acid or a fatty acid such as hydrochloric acid or hydrobromic acid, The amidation reaction is carried out in an amount of 0.01 to 1 part by mass based on 100 parts by mass of the total of the alkyl ester and the alkanolamine.

Usually, an alkanolamine is added to a reaction vessel, and then a fatty acid or a fatty acid alkyl ester at room temperature or elevated temperature is added dropwise over 1 to 5 hours and reacted. The reaction temperature is higher than the melting point of the resulting fatty acid alkanolamide. The reaction pressure is in the range of normal pressure to reduced pressure, and it is preferable to set the pressure to a reduced pressure 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 pressure is gradually reduced to 1.2 kPa or less and held for 0.1 to 4 hours to complete the reaction.

The synthesis of the polyoxyethylene fatty acid alkanolamide is obtained by reacting the fatty acid alkanolamide obtained in the above " Synthesis of fatty acid alkanolamide " by adding ethylene oxide at a desired molar ratio. A step of introducing a fatty acid alkanolamide containing an alkali metal alcoholate catalyst into an autoclave reactor and performing nitrogen gas substitution and then heating a predetermined amount of ethylene oxide gas at a temperature not lower than the melting point of the fatty acid alkanolamide for 0.5 to 2 hours The reaction is carried out under normal pressure and under a pressure of 0.5 MPa. After the introduction of the ethylene oxide gas, the reaction is completed for 0.1 to 2 hours.

The component (A1) may be used singly or in a combination of two or more.

(A1), at least one member selected from the group consisting of palm oil fatty acid monoethanolamide, lauric acid monoethanol amide, lauric acid monoisopropanolamide and polyoxyethylene (average repeating number 1) myristic acid monoethanolamide Is preferably used.

In the dishwasher cleaning agent, the content of the component (A1) is preferably 0.1 to 10 mass%, more preferably 0.3 to 5 mass%, and still more preferably 0.5 to 3 mass%, based on the total mass of the cleaning agent.

If the content of the component (A1) is lower than the preferable lower limit value, the detergency against oil contamination and oil / scale composite contamination increases, and also the re-contamination such as oil contamination to the object to be cleaned is easily suppressed. On the other hand, if the content of the component (A1) is not more than the preferable upper limit value, bubble formation at the time of cleaning tends to be suppressed.

&Quot; Component (A2): Surfactant other than component (A1) "

The component (A) may contain a surfactant other than the component (A1) (hereinafter also referred to as "component (A2)"). (A2) are used in combination, it is possible to satisfactorily remove oil contamination or the like adhering to the object to be cleaned. The component (A2) may also function as a binder in the formulation on the powder particle.

The component (A2) is not particularly limited, and examples thereof include polyoxyalkylene alkyl ethers, glycerin fatty acid esters, sucrose fatty acid esters, alkyl glycosides, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene fatty acids Nonionic surfactants such as esters, fatty acid monoglycerides, higher alcohol polyoxyethylene (EO) adducts and amine oxides; anionic surfactants such as? -sulfo fatty acid alkyl esters, linear alkylbenzenesulfonic acid salts, alkylsulfates and soaps; Cationic surfactants such as monoalkylamines, dialkylamines, ethylene oxide adducts of monoalkylamines, ethylene oxide adducts of dialkylamines, mono long chain alkyl quaternary ammonium salts and di long chain alkyl quaternary ammonium salts; And amphoteric surfactants such as carbobetaine, sulfobetaine and hydroxysulfobetaine.

The dishwasher is characterized in that a cleaning liquid is sprayed by using a pump to perform a cleaning treatment. Therefore, when a cleaning agent containing a non-low-surfactant surfactant is used, bubbles are excessively generated, air entrainment occurs in the pump due to the bubbles, and the operation may be stopped. Therefore, 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 imposing an excessive burden on the pump of the dishwasher.

In the present invention, the term " low foaming surfactant " includes a surfactant having a foam height of 15 mm or less, preferably 10 mm or less, as measured by the following measuring method.

Method of Measuring Bubble Height:

0.12 g of a surfactant is added to 3 L of water at 15 캜 to prepare a surfactant solution. The surfactant solution is put into an automatic dishwasher-drier to carry out the operation. One minute after the start of cleaning, the operation is stopped and the door is opened. After 15 seconds, the generation of air bubbles in the interior is measured. At that time, three points in the hearth are randomly selected, and the bubble height (mm) at the above points are respectively measured, and the average value is obtained.

In the dishwasher, it is necessary to have a good cleaning force and to suppress the generation of bubbles during cleaning. Therefore, the content of the total of the components (A1) and (A2) in the dishwasher detergent (ie, the content of the component (A)) is preferably 11% by mass or less based on the total mass of the cleaning agent, More preferably from 11 to 11 mass%, further preferably from 0.3 to 5 mass%, particularly preferably from 0.5 to 3 mass%.

≪ Component (B): Protease >

It is preferable that the detergent for dishwasher according to the first embodiment of the present invention further contains a protease (B) (hereinafter also referred to as "component (B)").

As described above, in recent years, the preliminary washing has been omitted, and the amount of contamination to be cleaned by the dishwasher has been increased. Accordingly, oil contamination and protein contamination (contamination of oil / protein complex) coexisting therewith are becoming difficult to be removed. On the other hand, by using the component (B) together with the component (A), the detergency against the contamination of the oil / protein complex becomes higher. In addition, the effect of preventing re-contamination such as oil contamination on the object to be cleaned is further enhanced.

The component (B) is not particularly limited and may be blended with a conventional detergent. Examples thereof include pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, BPN, papain, promyelin, carboxypeptidases A and B, aminopeptidase, and aspergillop peptidase A and B are listed.

Examples of the component (B) in the present invention include those described in JP-A-51-8401, JP-A-46-43551, JP-A-46-42956, 59-59189, JP-A-54-62386, JP-A-48-2794, JP-A-50-16435, JP-A-53-18594, Japanese Patent Application Laid-Open No. 55-46711, Japanese Patent Application Laid-Open No. 57-42310, Japanese Patent Application Laid-Open No. 58-16200, Japanese Patent Application Laid-Open No. 56-24512, Japanese Patent Application Laid- JP-A-1832, JP-A-52-35758, JP-A-50-34633, JP-A-46-41596, JP-A-58-134990, JP- Japanese Patent Application Laid-Open No. 55-14086, Japanese Patent Application Laid-Open No. 51-82783, Japanese Patent Application Laid-Open No. 51-125407, 55-39794, 46-1840, 46-23989, 58-15282, 61-280278, JP-A-61-280278, JP- Those described in JP-A-4-197182, JP-A-3-79987, and JP-A-5-25492 can be used. These purified fractions or coenzymes or their granules can also be used.

Examples of the commercially available enzyme (B) that can be used as the enzyme include Savinase (registered trademark), Alcalase (registered trademark), Everlase (registered trademark), Kannase (registered trademark) And Esperaze; proteases from Novozymes; API21 (manufactured by Showa Denko K.K.); Proteases of the products of Genecor, Inc., such as Maxataze, Maxacal, Purafect (TM) and Maxapem; And proteases of Kao Corporation such as KAP and K-14 and K-16 described in JP-A-5-25492.

The component (B) may be used singly or in a combination of two or more.

(B) is prepared by a conventional method such as the method described in Japanese Patent Application Laid-open No. 60-262900, and the component (B) is mixed with a stabilizer, a filler, an extender, a brightener, a binder or a coating agent An assembly (enzyme assembly) can be used. Usually, the content of the component (B) in the enzyme granulate is about 0.1 to 10% by mass, preferably about 0.5 to 5% by mass, and more preferably about 1 to 3% by mass as the enzyme protein amount. The two or more kinds of enzymes may be assembled in the respective stages, or the enzymes may be mixed in the same stage.

In the dishwasher detergent according to the first embodiment of the present invention, the mixing ratio of the components (A1) and (B) is preferably such that the protease activity per gram of the detergent is Ea (kPU / g) when the content have been called _A1 W (mass%) (hereinafter, also referred to as "Ea / W ratio _A1") represented by Ea / W _A1 ratio is more preferable that the 1 to 30 is preferable, and 5 to 20 Do.

By setting the Ea / W _A1 ratio within the above range, the cleaning power against contamination of the oil / protein complex increases.

In addition, when the Ea / W _A1 ratio is less than 1, the detergency against oil / protein complex contamination is likely to deteriorate. This is presumably because the protein contamination tends to remain in tableware or the like as the protease activity (Ea) ratio per 1 g of detergent is reduced, and oil contamination remains in the residual protein contaminated portion. In addition, the foaming property derived from the component (A1) tends to increase, and the nozzle sprayability (jetting power) of the dishwasher is thereby weakened, which is considered to be one cause of the deterioration in the washing power. On the other hand, even if the Ea / W _A1 ratio exceeds 30, the detergency against oil / protein complex contamination tends to decrease. This is considered to be because, when the ratio of the protease activity (Ea) per 1 g of the cleaning agent is increased, the detergency against protein contamination is weakened by the self-digestion function of the protease.

In the present invention, the protease activity per g of the detergent shows, for example, a value measured as follows. In the present specification, the term " protease unit (PU) " refers to a unit of activity of hydrolyzing a peptide bond in a protein molecule.

The activity of 1 μg of tyrosine in casein for 1 minute is called 1 PU.

[Method for measuring protease activity per 1 g of detergent]

1) Preparation of casein substrate solution

0.6 g of casein (derived from Bovine Milk, manufactured by Merk) was dissolved in 20 mM sodium 4-borate (sodium tetraborate, manufactured by KANTO CHEMICAL CO., INC.) Solution, and 1 N sodium hydroxide (1 mol / L sodium hydroxide solution, KANTO CHEMICAL CO., INC.) Is adjusted to pH 10.5, and then 100 mL of 20 mM sodium borate is added to prepare a casein substrate solution.

2) Measurement of protease activity per 1 g of detergent

When a detergent on a powdery particle is used, a powdery particulate detergent composition containing no protease is prepared. Ten grams of the powdery particulate detergent composition is precisely weighed and dissolved in ion-exchanged water to be used in a volume of 1 L, whereby a protease- Thereby obtaining an aqueous solution (cleaning agent aqueous solution A) of the powdery particulate detergent composition. Separately, a powdery particulate detergent composition containing a protease is prepared. Ten grams of the powdery particulate detergent composition is precisely weighed, dissolved in ion-exchanged water, and adjusted to 1 liter. Of these, 30 mL is collected by a hole pipette, dissolved in a powdery particulate detergent composition not containing the above protease, and then diluted with 300 mL to obtain an aqueous solution of a powdery particulate detergent composition (detergent aqueous solution B) containing a protease.

When a liquid detergent is used, a liquid detergent composition containing no protease is prepared, and 1.0 g of this liquid detergent composition is precisely weighed and dissolved in ion-exchanged water to be used in a volume of 1 L to obtain a liquid detergent composition containing no protease To obtain an aqueous solution of the composition (cleaning agent aqueous solution C). (Liquid detergent solution D) of the liquid detergent composition in which the protease was blended was prepared by dissolving 1.0 g of the liquid detergent composition in ion-exchanged water, .

0.5 mL of the detergent solutions A and B, or the detergent solutions C and D are separately collected in a test tube (φ 15 mm, length 105 mm) with a hole pipette. These test tubes are immersed in a thermostat at 35 캜 for 5 minutes. Thereafter, 2.5 mL of the casein substrate solution previously adjusted to 35 DEG C was added to each test tube, stirred for 10 seconds with a vortex mixer, and returned to a 35 DEG C thermostat to start the reaction.

After 10 minutes from the initiation of the reaction, 2.5 mL of an enzyme-stoppered TCA solution (0.11 M trichloroacetic acid, 0.22 M sodium acetate, 0.33 M acetic acid (all grades, KANTO CHEMICAL CO., INC. Thereafter, the mixture was stirred for 10 seconds with a vortex mixer, and the mixture was allowed to stand at 20 DEG C for 30 minutes. Thereafter, the precipitated unreacted substrate was filtered with a filter paper (No. 131 of Advantech Co., Ltd.) The absorbance at a wavelength of 275 nm of the collected filtrate was measured using an ultraviolet visible spectrophotometer (UV-160 manufactured by Shimadzu Corporation, etc.). Then, 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 detergent solution A and the absorbance of the detergent solution C is obtained, and this difference is used as the absorbance value of the detergent composition containing the protease.

The protease activity (PU) per 1 g of the powdery particulate detergent composition or the protease activity (PU) per 1 g of the liquid detergent composition was calculated from the tyrosine concentration calculated based on the calibration curve previously prepared with the TCA solution of tyrosine (Kanto Chemical Co., Calculate activity (PU).

The activity per g of the protease indicates, for example, a value measured as follows.

[Determination of activity per 1 g of protease]

0.1 g of the protease enzyme preparation is precisely weighed, dissolved in ion-exchange water and adjusted to 100 mL. Thereafter, 1 mL of the above aqueous solution is collected with a hole pipette, dissolved in ion-exchanged water, and then diluted with 100 mL to prepare a 0.001% by weight aqueous solution of a protease enzyme preparation solution.

0.5 mL of the protease enzyme preparation aqueous solution was collected into a test tube having a diameter of 15 mm and a length of 105 mm with a hole pipette, and the test tube with the aqueous solution of the protease enzyme preparation was immersed in a thermostatic chamber at 35 ° C for 5 minutes. Thereafter, 2.5 mL of the casein substrate solution is added to the test tube, and the mixture is stirred for 10 seconds with a vortex mixer. Thereafter, the test tube is returned to a 35 ° C thermostatic chamber and allowed to stand for 10 minutes to allow the enzyme reaction to proceed.

Thereafter, 2.5 mL of an enzyme stopper, TCA solution (0.11 M trichloroacetic acid, 0.22 M sodium acetate and 0.33 M acetic acid (all grades, produced by KANTO CHEMICAL CO., INC.) Was added to the test tube, The mixture is stirred for 10 seconds. Thereafter, the mixture is allowed to stand at 20 占 폚 for 30 minutes and then filtered with a filter paper (No. 131 of Advantech Co., Ltd., etc.) to recover the filtrate containing tyrosine.

The absorbance of the recovered filtrate at a wavelength of 275 nm is measured using an ultraviolet visible spectrophotometer (UV-160 manufactured by Shimadzu Corporation). The protease activity (PU) per 1 g of the protease enzyme preparation is calculated from the tyrosine concentration calculated based on the calibration curve previously prepared with the TCA solution of tyrosine (manufactured by KANTO CHEMICAL CO., INC.).

The component (B) is preferably blended so that the protease activity Ea (kPU / g) is 1 to 80 (kPU / g) per 1 g of the detergent, more preferably 2.5 to 40 (kPU / g) 5 to 20 (kPU / g).

By combining the component (B) with the component (A1) such that Ea (kPU / g) is in the above range, the detergency against oil / protein complex contamination increases synergistically.

The content of the component (B) in the dishwasher detergent is preferably from 0.05 to 16 mass%, more preferably from 0.1 to 8 mass%, and still more preferably from 0.3 to 4 mass%, based on the total mass of the detergent.

When the content of the component (B) is less than the preferable lower limit value, the removal effect of oil contamination / protein complex contamination may be lowered. On the other hand, even if the content of the component (B) exceeds the preferable upper limit value, the removal effect of the oil contamination / protein complex contamination becomes a limit.

<Optional ingredients>

The detergent for dishwasher according to the first embodiment of the present invention may be optionally blended with components other than the above-mentioned components as needed within the range not impairing the effect of the present invention.

There are no particular limitations on such components which may optionally be blended, and those which have been used so far as cleaning agents for cleaning dishes are enumerated. For example, a chelating agent, a bleaching agent, a bleaching activator, an alkaline agent, an enzyme other than the component (B), a plant extract, a fragrance, an oil absorbing agent, a defoaming agent, a food protecting agent, a thickening agent, a colorant, Silicic acid, etc.), processing agents (sodium sulfate, potassium sulfate and sodium chloride), and the like.

(Manufacturing method)

The dishwasher detergent according to the first embodiment of the present invention can be produced by a conventionally known method.

The liquid detergent for dishwasher is produced by mixing a solvent and a component (A) containing the component (A1) and optionally an optional component. (B) after mixing the solvent and optional components other than the component (A) and the component (B) containing the component (A1) in order to maintain the activity of the component (B) It is preferable to mix the components.

The solvent is preferably water, and a water-miscible organic solvent other than water may be used.

&Quot; Water-miscible organic solvent &quot; 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 is a homogeneous solution when mixed with water. Among these, monohydric alcohols having 2 to 4 carbon atoms, polyhydric alcohols having 2 to 4 carbon atoms, and glycol ethers are exemplified.

Examples of monohydric alcohols having 2 to 4 carbon atoms include ethanol, 1-propanol, 2-propanol and 1-butanol.

Examples of the polyhydric alcohol having 2 to 4 carbon atoms include ethylene glycol, propylene glycol, butylene glycol and glycerin.

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, and diethylene glycol monobutyl ether.

The pH (25 캜) of the liquid dishwasher cleaning agent is preferably at least 6.5, more preferably from 7 to 11, and even more preferably from 8 to 10.

If the pH (25 DEG C) is higher than or equal to the lower limit value, the detergency against oil / protein complex contamination increases. Moreover, re-contamination such as oil contamination to the object to be cleaned is also easily suppressed. Further, the storage stability of the detergent composition is further improved.

In the present invention, the pH (25 DEG C) of the dishwasher detergent is measured in accordance with JIS K3362-1998 using a pH meter (HM-30G, manufactured by DKK-TOA CORPORATION) And the values measured by using the same.

As a method of producing a solid dishwasher detergent, for example, a dry blend method of powder mixing of each raw material, a dry granulation method of granulating while mixing the raw materials of the powder, a method of spraying a liquid binder while flowing the powder raw material An extrusion granulation method in which a raw material is kneaded and extruded by an extruder, a pulverization granulation method in which a raw material is pulverized, a spray drying method in which a slurry containing a raw material is spray dried, and the like.

The moisture content of the solid dishwasher detergent is not particularly limited and is preferably 8% by mass or less.

Tableware The bulk density of the detergent for washing of the powder particles is 0.3g / cm ³ or more is preferred and more preferred, 0.5~1.2g / cm ³ is more preferred, and 0.6~1.1g / cm ^3.

The bulk density is a value measured by JIS-K3362.

The mean particle diameter of the dishwasher cleaner on the powdery particle is preferably 200 to 1500 m, more preferably 300 to 1200 m. When the average particle diameter is less than the preferable lower limit value, dust tends to be generated. On the other hand, when the average particle diameter is more than the preferable upper limit value, it is difficult to dissolve or disperse in water.

In the present invention, the average particle diameter of the dishwasher detergent has a mesh size of 1680 탆, 1410 탆, 1190 탆, 1000 탆, 710 탆, 500 탆, 350 탆, 250 탆 and 149 탆, Is used.

In the classification operation, a mesh having a large mesh size was sequentially laminated on a receiving tray, a sample of 100 g / s from the top of a 1680 탆 sieve at the top was sequentially placed, and the RO-TAP type sieve shaker (IIDA SEISAKUSHO product, tapping: 156 times / minute, rolling: 290 times / minute) and vibrated for 10 minutes. Thereafter, the sample remaining on each sieve and the base plate is collected every sieve, and the mass of the sample is measured. Then, the mass frequency of the base plate and each body is integrated, and the mesh size of the first body having the mass frequency of integration of 50% or more is defined as "a 탆", and the mesh size of one- Mu m &quot;. Further, the integrated value of the mass frequency from the base plate to a mu m sieve is referred to as &quot; c% &quot;, and the mass frequency of the sieve of a mu m is referred to as &quot; d% &quot;. Then, the average particle diameter (50 mass% particle diameter) is determined by the following formula (1), and this is taken as the average particle diameter of the sample.

(How to use)

The detergent for dishwasher according to the first embodiment of the present invention may be used depending on the degree of contamination of the dishwasher, the dishware, and the like.

As a method of cleaning the object to be cleaned by the dishwasher using the above-described cleaning agent, there is listed a cleaning method having both of the steps of cleaning and rinsing.

As a preferable method of cleaning, for example, there is a method of cleaning the object to be cleaned (hereinafter referred to as &quot; cleaning step &quot;) while raising the temperature of the cleaning liquid to preferably 50 to 60 DEG C at a rate of 2 to 3 DEG C / (Hereinafter referred to as &quot; rinsing (1) step &quot;) of tap water (preferably about 5 to 30 占 폚) of tap water and room temperature tap water is preferably heated to 50 to 80 占 폚 at 2 to 3 占 폚 / , And a step of further rinsing the object to be cleaned after the rinsing (1) step (hereinafter referred to as &quot; rinsing (2) step &quot;).

In the cleaning process, it is preferable that the cleaning agent for dishwasher is used at a rate of 3 to 9 g per one liter of tap water.

The washing liquid in the dishwasher preferably contains 2 to 300 ppm (by mass) of the component (A), more preferably 3 to 200 ppm (on a mass basis), more preferably 10 to 100 ppm Is particularly preferable.

By controlling the concentration of the component (A) in the cleaning liquid to the above-mentioned range, re-contamination such as oil contamination to a hydrophobic tableware such as a plastic container is easily suppressed. In addition, the detergency against oil contamination increases. If the concentration of the component (A) in the cleaning liquid is less than 2 ppm (by mass), the above-mentioned re-contamination inhibiting effect or washing power may be insufficient. On the other hand, if the concentration exceeds 300 ppm (mass basis) The tendency tends to be undesirable.

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 detergent composition for a dishwashing machine according to the first embodiment of the present invention employs the component (A1) and uses the component (A1) in an amount of 25 mass% or more based on the total amount of the component (A) (Such as a plastic container) in which a hydrophobic material such as polypropylene is used while ensuring a low foaming property even when a washing process such as a tableware is performed by a dishwasher without performing washing .

Further, in the dishwasher detergent composition according to the first embodiment of the present invention, by using the components (A1) and (B) in combination and setting the ratio Ea / W _A1 to 1 to 30, detergency against oil / And the decontamination effect is excellent. Further, at the time of rinsing, oil contamination or protein contamination is hardly caused to re-adhere to dishes or the like, thereby remarkably suppressing re-contamination such as oil contamination to hydrophobic tableware.

(Detergent for dishwasher according to the second embodiment of the present invention)

The cleaning agent for a dishwashing machine according to the second embodiment of the present invention comprises (A1) component: a nonionic surfactant selected from the group consisting of fatty acid alkanolamides and polyoxyethylene fatty acid alkanolamides and having an HLB of 8.5 to less than 12.0 ) And component (C): chelating agent (C).

The formulation of the dishwasher detergent according to the second embodiment of the present invention is not particularly limited as long as it contains the component (A1) and the component (C), and may be a solid such as a powder particle or a tablet, or may be a liquid. The nonionic surfactant (A1) in the second embodiment of the present invention is the same as the nonionic surfactant (A1) in the first embodiment of the present invention.

&Lt; Component (C): chelating agent >

Component (C) is a chelating agent.

The component (C) is not particularly limited, and conventional chelating agents used in detergents for dishwashing machines are listed, and both polymer chelating agents and low molecular chelating agents can be used.

As the polymer chelating agent, a copolymer of maleic acid and acrylic acid (hereinafter referred to as &quot; maleic acid / acrylic acid copolymer &quot;) or a salt thereof is preferably listed.

The maleic acid / acrylic acid copolymer or its salt preferably has a molar ratio of maleic acid to acrylic acid of 70/30 to 30/70.

The maleic acid / acrylic acid copolymer or its salt preferably has a weight average molecular weight of 1,000 or more as measured by gel permeation chromatography using a standard material as sodium polyacrylate, more preferably 1,500 to 200,000, More preferably in the range of 10,000 to 100,000, and most preferably in the range of 40,000 to 60,000. When the weight average molecular weight is 1,000 or more, the effect of preventing re-adhesion of soap scum improves. On the other hand, when the weight average molecular weight is 200,000 or less, the caking property is improved when the formulation is a solid such as a powder particle.

When the maleic acid / acrylic acid copolymer is in the form of a salt, it is preferably an alkali metal salt, more preferably a sodium salt or a potassium salt.

Specific examples of the low-molecular chelating agent include citric acid, hydroxyethanedisulfonic acid, nitrilotriacetic acid, glutamic acid diacetic acid, methylglycine diacetic acid, and salts thereof.

The component (C) may be used singly or in a combination of two or more.

Among the components (C), at least one selected from the group consisting of maleic acid / acrylic acid copolymer, glutamic acid diacetic acid, methylglycine diacetic acid, citric acid and salts thereof is preferably used.

The content of the component (C) in the dishwasher detergent is preferably 4 to 20 mass%, more preferably 8 to 16 mass%, and even more preferably 8 to 13 mass% with respect to the total mass of the cleaning agent , And particularly preferably from 10 to 12.5 mass%.

When the content of the component (C) is lower than the lower limit, the cleaning performance against the oil / scale composite contamination increases. In particular, the cleaning power against scale contamination increases. On the other hand, when the content of the component (C) is not more than the preferable upper limit value, the caking property is improved when the formulation is a solid such as a powder particle. Further, when the liquid formulation is used, it is easy to maintain the uniformly dispersed state of the cleaning agent.

The component (C) may be a compound synthesized by a known method, or a compound available in the market. Acrylic acid copolymer sodium salt available on the market is NIPPON SHOKUBAI CO., LTD. (Weight average molecular weight: 50,000, CP5 = 70,000, CP12S = 3,000) and the like can be listed as the product of BASF Co., Ltd. As for the sodium glutamate diacetate, Dissolvine GL47-S or GL-PDS manufactured by Akzo Nobel NV, and Trilon M manufactured by BASF are listed as methylglycine diacetate sodium salt. Citric acid or sodium citrate, FUSO CHEMICAL CO., LTD. Product citric acid or sodium citrate.

In the present invention, the "mass ratio expressed by the component (C) / (A1)" means the ratio of the contained mass of the component (C) to the contained mass of the component (A1) in the dishwasher cleaning agent.

In the detergent for dishwashing machine of the present invention, the mixing ratio of the component (A1) and the component (C) is preferably 1 to 1 (hereinafter, also referred to as "C / A1 ratio" To 50, preferably 3 to 25, and more preferably 5 to 20.

By setting the C / A1 ratio within the above range, the detergency against oil / scale composite contamination increases.

In addition, when the C / A1 ratio is less than 1, the detergency against oil / scale composite contamination tends to decrease. This is because scale contamination can not be removed due to a decrease in the proportion of the component (C), scale contamination tends to remain on the tableware, and oil contamination tends to remain on the remaining scale contaminated portion. Further, the foaming property derived from the component (A1) tends to increase, and thus nozzle sprayability (jetting power) of the dishwasher is weakened, which is considered to be one cause of the deterioration of the washing power.

On the other hand, even if the C / A1 ratio exceeds 50, the detergency against oil / scale composite contamination tends to decrease. It is presumed that the cleaning power against the scale contamination is simply increased when the ratio of the component (C) is large. However, if the proportion of the component (A1) is low, the scale contamination dispersed in the cleaning liquid tends to adhere again to the tableware, It is thought that oil contamination adheres to the attached scale contamination part.

<Optional ingredients>

The detergent for dishwasher according to the second embodiment of the present invention may be optionally blended with components other than the above-mentioned components as needed within a range not to impair the effect of the present invention.

The optional components are not particularly limited, and those which have heretofore been used for a dishwasher detergent are listed. For example, a surfactant, a bleaching agent, a bleaching activator, an alkaline agent, an enzyme (protease, amylase, etc.), a plant extract, a fragrance, an oil absorbing agent, a defoaming agent, a dish protecting agent, a thickener, a colorant, (Such as anhydrous silicic acid), a processing agent (such as sodium sulfate, potassium sulfate, and sodium chloride), and the like.

However, in a dishwasher, it is necessary to suppress bubble generation during cleaning. Therefore, the content of the component (A1) and the content of the surfactant other than the other components in the cleaning agent for dishwasher is preferably 11% by mass or less, more preferably 0.2 to 11% by mass with respect to the total mass of the cleaning agent By mass, more preferably from 0.3 to 5% by mass, and particularly preferably from 0.5 to 3% by mass.

In addition, the content of the component (A1) in the total surfactant is preferably 25% by mass or more, more preferably 50% by mass or more, further preferably 70% by mass or more with respect to the total mass of the total surfactant , And 100 mass%.

When the content of the component (A1) is not less than the preferable lower limit value, the generation of bubbles is kept low when the dishwasher is subjected to a cleaning treatment such as a tableware. In addition, the detergency against oil contamination increases, and the re-contamination such as oil contamination with respect to the object to be cleaned (particularly, the hydrophobic tableware) is also easily suppressed.

(Manufacturing method)

The dishwasher detergent according to the second embodiment of the present invention can be manufactured by a conventionally known method.

The liquid dishwasher cleaning agent is produced by mixing a solvent, a component (A1), a component (C) and optional components as required. Particularly, since a homogeneous solution is easily obtained, it is preferable to previously prepare a solution of the component (A1) and a solution of the component (C), respectively, and mix the solution of the component (A1) and the solution of the component (C).

The solvent is preferably water, and a water-miscible organic solvent other than water may be used.

&Quot; Water-miscible organic solvent &quot; 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 is a homogeneous solution when mixed with water. Among these, monohydric alcohols having 2 to 4 carbon atoms, polyhydric alcohols having 2 to 4 carbon atoms, and glycol ethers are exemplified.

Examples of monohydric alcohols having 2 to 4 carbon atoms include ethanol, 1-propanol, 2-propanol and 1-butanol.

Examples of the polyhydric alcohol having 2 to 4 carbon atoms include ethylene glycol, propylene glycol, butylene glycol and glycerin.

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, and diethylene glycol monobutyl ether.

The pH (25 캜) of the liquid detergent for dishwasher is preferably 6 or more, more preferably 7 to 10, and even more preferably 7 to 8.

If the pH (25 DEG C) is higher than the lower limit value, the detergency against oil / scale composite contamination increases. Moreover, re-contamination such as oil contamination to the object to be cleaned is also easily suppressed.

In the present invention, the pH (25 ° C) of the detergent for dishwasher is measured in accordance with JIS K3362-1998 by using a pH meter (HM-30G, manufactured by DKK-TOA CORPORATION) And the values measured by using the same.

As a manufacturing method of a solid dishwasher detergent, the manufacturing method described in the first embodiment can be used.

(How to use)

The method of using the dishwasher detergent according to the second embodiment of the present invention differs depending on the degree of contamination of the dishwasher, the type of dishwasher, and the like. For example, the amount of the dishwasher detergent used once per 3 liters To 9 g.

The cleaning liquid in the dishwasher preferably contains 2 to 300 ppm (by mass) of the component (A1), more preferably 3 to 200 ppm (on a mass basis), more preferably 10 to 100 ppm Is particularly preferable.

By controlling the component concentration of the component (A1) in the cleaning liquid to the above range, the detergency against oil / scale composite contamination increases. In addition, re-contamination such as oil contamination to hydrophobic food containers such as plastic containers is likely to be suppressed. If the concentration of the component (A1) in the cleaning liquid is less than 2 ppm (mass basis), the cleaning power may be insufficient. On the other hand, if the concentration exceeds 300 ppm (mass basis), bubbles tend to be formed excessively during cleaning.

INDUSTRIAL APPLICABILITY As described above, the dishwasher detergent composition according to the second embodiment of the present invention has excellent detergency against oil / scale composite contamination by using the components (A1) and (C) in combination. In addition, by employing the component (A1), re-adhesion of oil contamination to dishes or the like at the time of rinsing is hardly caused, and particularly, re-contamination such as oil contamination to the hydrophobic tableware is greatly suppressed. Furthermore, the mass ratio of the component (C) / (A1) is 1 to 50, whereby the detergency against the oil / scale composite contamination is increased synergistically, so that the decontamination effect and the effect of preventing recontamination are excellent. Further, And the low foaming property is ensured.

INDUSTRIAL APPLICABILITY According to the detergent composition for a dishwashing machine of the present invention, even when a washing process such as a tableware is performed by a dishwasher without performing preliminary washing, an excellent cleaning effect is exhibited under severe conditions in which oil / do. In addition, recontamination of oil contamination to dishes (such as plastic containers) in which hydrophobic materials such as polypropylene are used is suppressed.

According to the detergent composition for a dishwasher, in addition to the water-contamination of the glassware, it is possible to satisfactorily remove the contamination of the glassware.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

&Lt; Preparation of a dishwasher detergent according to the first embodiment of the present invention >

According to the formulation compositions shown in Tables 1A to 5C, cleaning agents of the respective examples were prepared by the production method described below (when the ingredients of the blended ingredients were present, the ingredients were not blended).

The unit of the compounding amount in the table is &quot; mass% &quot;, and both components represent the net conversion amount.

In the table, &quot; suitable amount &quot; represents the total addition amount of 1N sulfuric acid and 1N sodium hydroxide used as a pH adjusting agent.

Means the component (sodium sulfate or ion-exchanged water) is blended so that the total amount (mass%) of the total ingredients contained in the cleaning agent of each example is 100% by mass.

The content (mass%) of the component (A1) in the component (A) means the ratio of the mass of the component (A1) to the total mass of the surfactant.

"Ea / W _A1 ratio" means the ratio of the protease activity (Ea) (kPU / g) per 1 g of the cleaning agent to the content (W _A1 ) (mass%) of the component (A1) in the cleaning agent.

The protease activity (Ea) per 1 g of the detergent was measured by the above-mentioned [method for measuring the protease activity per 1 g of detergent].

The components shown in the table are described below.

Component (A1):

A1-1: Coconut oil fatty acid monoethanolamide (Amisol CME, manufactured by Kawaken Fine Chemicals Co., Ltd.), HLB 10.3, melting point 43.7 캜.

A1-2: Lauric acid monoethanolamide (synthetic), HLB 10.7, melting point 61.2 ° C.

A1-3: Polyoxyethylene myristate monoethanolamide (ethylene oxide average moles adduct of myristate monoethanolamide, product of Synthesis), HLB 8.9, melting point 50.3 ° C.

A1-4: monoisopropanolamide laurate (Amisol PLME-A, manufactured by Kawaken Fine Chemicals Co., Ltd.), HLB 10.3, melting point 50.6 ° C.

A1-5: polyoxyethylene lauric acid monoethanolamide (ethylene oxide average 1 mole adduct of lauric acid monoethanolamide, product of Synthesis), HLB 10.0, melting point 51.3 deg.

Component (A2)

A2-1: Decanoic acid monoethanolamide (Synthesis), HLB 12.5, melting point 53.2 ° C.

A2-2: stearic acid monoethanolamide (synthetic), HLB 7.5, melting point 94 캜.

A2-3: Coconut oil fatty acid diethanolamide (Amizole CDE, manufactured by Kawaken Fine Chemicals Co., Ltd.), HLB 12.0, melting point 5.0 캜.

A2-4: C12, 13 polyoxyalkylene alkyl ether (a mixture of an alcohol having 12 carbon atoms and an alcohol having 13 carbon atoms added with 3 moles of an average of ethylene oxide and 3 moles of an average of propylene oxide) (manufactured by Lion Chemicals, NNAEP-3030), HLB 4.5.

A2-5: polyoxyethylene (5) lauryl ether, ethylene oxide average 5 moles adduct (manufactured by NIHON EMULSION Co., Ltd., Emulex 705), HLB 9.5, melting point 8.4 deg.

A2-6: Sodium straight-chain alkylbenzenesulfonate (straight-chain alkylbenzenesulfonic acid (Lion Corporation product, Lyfon LH-200) neutralized with sodium hydroxide).

[Method for synthesizing the components (A1) and (A2)] [

Examples of synthesis of A1-2, A2-1 and A2-2:

A1-2, A2-1, and A2-2 were synthesized by the reaction of each fatty acid methyl ester with monoethanolamine.

A 2-liter four-necked flask equipped with a stirrer and a cooling tube was charged with monoethanolamine at a molar ratio of 1.05 to the fatty acid methyl ester, and sodium methylate (28 mass% solution) as a catalyst was added to 100 parts by mass of fatty acid methyl ester 0.25 parts by mass (converted to pure water) was further added.

Then, at a reaction temperature of 100 占 폚 and a pressure of 40 kPa (under reduced pressure), a fatty acid methyl ester was added dropwise over 3 hours to carry out an amidation reaction. After completion of the dropwise addition, the mixture was reduced to 1.3 kPa and aged for 4 hours to obtain fatty acid monoethanolamide A1-2, A2-1 and A2-2.

As such fatty acid methyl esters, stearic acid methyl ester was used in the synthesis of A1-2, decanoic acid methyl ester in the case of synthesis of A2-1, and stearic acid methyl ester in the case of synthesis of A2-2.

Examples of synthesis of A1-3 and A1-5:

With respect to A1-3, the fatty acid monoethanolamide A2-2 (containing sodium methylate of the catalyst as it is) as obtained in the above Synthesis Example was placed in a 2 L autoclave, and the reaction temperature was 100 ° C. Under the conditions that the reaction was carried out by blowing ethylene oxide gas over 1.0 molar equivalent of the fatty acid monoethanolamide over 1 hour and aging was further carried out for 30 minutes until the pressure in the system was kept unchanged.

The procedure of synthesis of A1-3 was repeated except that A1-2 was used instead of A2-2 for A1-5.

Component (B)

The following () is active per unit g of each protease (unit: kPU / g).

B-1: Sabine U16XL, manufactured by Novo (2000 kPU / g).

B-2: Everera 16L, manufactured by Novo (1000 kPU / g).

B-3: Everera 8T, manufactured by Novo (500 kPU / g).

B-4: Purpefect OX6000E, manufactured by Genencor (1000 kPU / g).

Further, the activity per 1 g of each protease represents the value measured by the above-mentioned [activity measurement method per 1 g of protease].

· Optional ingredients

Na salt of maleic acid / acrylic acid copolymer: NIPPON SHOKUBAI CO., LTD. Product, Aquarix TL400 (weight average molecular weight 50000, active ingredient 40% by mass).

Sodium citrate: Fuso Chemical Co., Ltd. Product, Sodium citrate.

Anhydrous silicic acid (manufactured by Tokuyama Corporation, Tokusil NP).

Sodium sulfate (manufactured by Japan Chemical Industrial Co., Ltd., neutral anhydrous manganese K2).

pH adjusting agent: 1N sulfuric acid, 1N sodium hydroxide.

Ion exchange water.

[Method of producing detergent for dishwasher according to the first embodiment of the present invention]

(Liquid phase cleaning agent: Examples 1 to 18, Comparative Examples 1 to 9)

According to the compositions shown in Tables 1A to 3, 0.8 kg of each liquid cleaning agent of each example was produced as follows.

First, an aqueous solution (X) was prepared so that the Na salt or sodium citrate of maleic acid / acrylic acid copolymer was dissolved in ion-exchanged water in a 1 L capacity beaker and the total amount of these was 50 mass% of the total composition.

Separately, a surfactant solution was prepared so that the ion-exchanged water adjusted to 75 ° C and the component (A1) and / or the component (A2) were mixed in a 1 L beaker with a capacity of 40 mass% of the total amount of the composition.

Subsequently, the entire amount of the surfactant solution adjusted to 75 캜 was added while stirring the aqueous solution (X) heated to 75 캜 with an agitation homogenizer (6000 rpm), and then stirred for 30 seconds to obtain a mixed solution.

The mixture was cooled to 25 캜 and adjusted to pH 9.5 by using 1 N sulfuric acid or 1N sodium hydroxide. In Examples 9 to 14, 16 to 18 and Comparative Examples 6 to 9, after the pH was adjusted, the component (B) was added and stirred.

Subsequently, the remaining ion-exchanged water was added to the composition so as to make the entire composition 100 mass% and stirred to obtain a liquid phase cleaning agent.

The pH (25 ° C) of the composition was measured by using a glass electrode type pH meter (HM-30G, manufactured by DKK-TOA CORPORATION) as a liquid detergent adjusted to 25 ° C. The measurement was conducted in accordance with JIS K3362-1998.

(Powder particulate cleaner: Examples 19 to 41, Comparative Examples 10 to 15)

According to the compositions of Tables 4 and 5, 6 kg of powder particulate cleaner of each example was produced as follows.

First, sodium sulfate was placed in a ribbon mixer (YOSHIDA product, Ribbon mixer 1102-1500, width 900 mm x length 1800 mm x depth 1100 mm), and anhydrous silicic acid was added while stirring at 25 rpm and mixed for 10 minutes. Subsequently, the component (B) was added to the component (A1) or the component (A2) in Examples 19 to 38, 40, 41 and Comparative Examples 10 to 15, and mixed at 25 rpm for 10 minutes to obtain a powdery particulate cleaner.

&Lt; Evaluation of dishwasher detergent according to the first embodiment of the present invention >

Each example of the cleaning agent was evaluated by the following evaluation method, and the results are shown in Tables 1 to 5 ''.

As a dishwasher, an automatic dishwashing drier (model NP-40SX2 from Panasonic Corporation) was used. In each evaluation, the cleaning process was performed by operating the standard dish set in the automatic dishwashing and drying machine. The contents of the standard course are shown below.

Standard course:

The washing liquid was introduced into the automatic dishwashing drier with the use amount of the cleaning agent as shown in the table for 3 liters of tap water. The tap water was then introduced into the oven to prepare a cleaning liquid, and was rinsed for 20 minutes while being heated from room temperature to 55 캜 at a rate of 2 to 3 캜 / . Thereafter, rinsing (final rinse) was performed for 20 minutes while the tap water was heated from room temperature to 70 deg. C at a rate of 2 to 3 degrees / min, and then rinsed three times (two minutes / Drying of tableware or the like is performed while circulating hot air.

In the table, the concentration of component (A) (ppm, by mass) in the cleaning liquid in which the cleaning agent is dissolved in tap water is shown.

[Evaluation of low foaming property]

6 g of detergent was put into the automatic dishwasher-drier, and the operation was performed using the standard course.

From the start of cleaning, the operation was stopped at the time when the water temperature reached 55 캜, and at the same time, the door was opened.

At that time, three points in the hearth were randomly selected, and the height (mm) of the bubbles at the above places was measured, and the average value of these was determined. If the bubble height is 10 mm or less, it is said to be acceptable.

[Evaluation of prevention of re-contamination]

Two 15 cm diameter porcelain dishes loaded with 8 cm diameter of 8 cm diameter porcelain dish and two 8 cm porcelain dishes loaded with 8 grams of retort curry (this curry gold spicy taste) were prepared, and these were used as model porcelain 8 times the amount of contamination remaining after the preliminary washing).

Further, one lunch box (110 mm in length, 170 mm in width, and 35 mm in height) made of polypropylene (PP) of navy color confirmed to have no oil adhesion was prepared before the cleaning process.

Then, the automatic dishwasher-drier was filled with the above-mentioned model cup (two pieces of each porcelain dish) and one lunch box made of PP, and the above-mentioned standard course was operated to perform a washing process. This cleaning treatment was performed three times.

The degree of adhesion of oil in the box lunch box after the cleaning treatment (after drying) was visually observed by hand and hand, and the re-contamination prevention performance was evaluated based on the following evaluation criteria.

The three evaluation points of the evaluation were averaged, and when the average value was 3.0 or more, the evaluation was made acceptable.

(Evaluation standard)

4 points: The attachment of oil is not confirmed on the neck, and there is no feeling of oil sticking even when touched with a finger.

3 points: The attachment of oil is confirmed in the eyes, but when you touch it with your fingers, you feel a little feeling of oil sticking.

2 points: The attachment of oil is confirmed a little at the time of moxibustion, and the feeling that oil is attached even when it touched with a finger is felt.

1 point: The attachment of oil is clearly confirmed in the eyes, and the attachment of oil is clearly felt even when touched with a finger.

[Evaluation of detergency against contamination of oil / protein complex]

The Nisshin OilliO, Ltd. Product Two 20g eggs were cooked on a frying pan with a diameter of 25cm heated by adding 2g of salad oil.

Two eggs cooked in one side were placed on a black porcelain dish having a diameter of 12 cm and the egg yolk portion was divided using a knife and a fork. The salad oil and one side egg were mixed on the above-mentioned black porcelain dish and left for 2 hours at room temperature (Oil / protein complex contamination) which is a mixture of oil and protein.

This oil / protein complex contamination was divided into 8 parts, and each of the contaminated black small dishes with a diameter of 6 cm was contaminated and 8 pieces of black small plates with oil / protein complex contamination were produced (also, The amount of contamination of the attached oil / protein complex contamination is 10 times the amount of contamination remaining in the case of the prewash).

Subsequently, a black dish with eight pieces of oil / protein complex contamination was stored in one automatic dishwasher-drier, and the operation was performed with the above-mentioned standard course to perform a washing treatment.

The appearance of the black small dish after the cleaning treatment (after drying) was visually observed, and the washing power against the oil / protein complex contamination was evaluated based on the following evaluation criteria.

The evaluation points of 8 black small plates were averaged, and when the average value was 3.0 or more, the evaluation was made.

(Evaluation standard)

4 points: All oil and egg contamination on the black plate is completely removed, and water droplet marks are not confirmed.

3 points: Although all the oil and egg contamination that was attached to the black small dish is completely removed, the water droplet marks are slightly confirmed.

2 points: Residues of oil and egg contamination attached to a black small plate are slightly confirmed, and water droplet marks are also confirmed.

1 point: The residue of oil and egg contamination adhered to the black small plate is clearly confirmed, and water droplet marks are remarkably confirmed.

(Table 1)

(Table 1 ')

(Table 1 '')

From the results shown in Table 1, Table 1 'and Table 1' ', all of the cleaning agents of Examples 1 to 8 to which the present invention was applied were found to have low foaming properties while suppressing re-contamination such as oil contamination to the object to be cleaned Is confirmed.

(Table 2)

(Table 2 ')

(Table 3)

(Table 4)

(Table 4 ')

(Table 4 '')

(Table 5)

(Table 5 ')

(Table 5 '')

From the results shown in Tables 2 to 5, the cleaning agents of Examples 9 to 41 to which the first embodiment of the present invention was applied all had excellent cleaning power against contamination of oil / protein complex while securing low foaming properties, It is confirmed that re-contamination such as oil contamination to the object to be cleaned is suppressed.

&Lt; Preparation of a dishwasher detergent according to the second embodiment of the present invention >

Each of the cleaning agents of each example was produced by following the mixing compositions shown in Tables 1a to 4a and using the production method described later (when the ingredients of the blend are present, the components are not blended).

The unit of the compounding amount in the table is &quot; mass% &quot;, and all components represent the net conversion amount.

In the table, &quot; suitable amount &quot; represents the total addition amount of 1N sulfuric acid and 1N sodium hydroxide used as a pH adjusting agent.

"Remainder" means that the component (ion-exchanged water or sodium sulfate) is blended so that the total amount (mass%) of the total ingredients contained in the cleaning agent of each example is 100% by mass.

The "C / A1 ratio" is the same as the mass ratio of the component (C) / component (A1) and means the ratio of the content of the component (C) to the content of the component (A1) in the cleaning agent.

The components shown in the table are described below.

Component (A1):

A1-1: Coconut oil fatty acid monoethanolamide (Amisol CME, manufactured by Kawaken Fine Chemicals Co., Ltd.), HLB 10.3, melting point 43.7 캜.

A1-2: Lauric acid monoethanolamide (synthetic), HLB 10.7, melting point 61.2 ° C.

A1-3: Polyoxyethylene myristate monoethanolamide (ethylene oxide average moles adduct of myristate monoethanolamide, product of Synthesis), HLB 8.9, melting point 50.3 ° C.

A1-4: monoisopropanolamide laurate (Amisol PLME-A, manufactured by Kawaken Fine Chemicals Co., Ltd.), HLB 10.3, melting point 50.6 ° C.

A1-5: polyoxyethylene lauric acid monoethanolamide (ethylene oxide average 1 mole adduct of lauric acid monoethanolamide, product of Synthesis), HLB 10.0, melting point 51.3 deg.

(Hereinafter referred to as "(A2) component") of the component (A1)

A2-1: Decanoic acid monoethanolamide (Synthesis), HLB 12.5, melting point 53.2 ° C.

A2-2: stearic acid monoethanolamide (synthetic), HLB 7.5, melting point 94 캜.

A2-3: Coconut fatty acid diethanolamide (Amizole CDE, manufactured by Kawaken Fine Chemicals Co., Ltd.), HLB 12.0, melting point 5.0 캜.

A2-4: C12, 13 polyoxyalkylene alkyl ether (a mixture of an alcohol having 12 carbon atoms and an alcohol having 13 carbon atoms in which 3 moles of an average of ethylene oxide and 3 moles of an average of propylene oxide are added) (Lion Chemical product, NNAEP -3030), HLB 4.5.

A2-5: polyoxyethylene (5) lauryl ether, ethylene oxide average 5 moles adduct (manufactured by NIHON EMULSION Co., Ltd., Emulex 705), HLB 9.5, melting point 8.4 deg.

A2-7: lauric acid diethanolamide (Amizole LDE, manufactured by Kawaken Fine Chemicals Co., Ltd.), HLB 12.5, melting point 41 캜.

[Method for synthesizing the components (A1) and (A2)] [

Examples of synthesis of A1-2, A2-1 and A2-2:

A1-2, A2-1 and A2-2 were synthesized in the same manner as the synthesis method in the first embodiment of the present invention.

Examples of synthesis of A1-3 and A1-5:

A1-3 and A1-5 were synthesized in the same manner as in the synthesis method of the first embodiment of the present invention.

Component (C)

C-1: Sodium salt of maleic acid / acrylic acid copolymer (NIPPON SHOKUBAI CO., LTD., Aquarix TL400), weight average molecular weight 50000, active ingredient 40% by mass.

C-2: Sodium salt of glutamic acid diacetic acid (Dissolvine GL 47-S, product of Akzo Nobel N.V.) Active ingredient 47% by mass.

C-3: Sodium salt of methylglycine diacetic acid (Trilon M, manufactured by BASF) Active ingredient 40% by mass.

C-4: Sodium salt of maleic acid / acrylic acid copolymer (SOCALAN CP7 manufactured by BASF), weight average molecular weight 50000.

C-5: Sodium citrate (manufactured by Fuso Chemical Co., Ltd.).

· Optional ingredients

Anhydrous silicic acid (manufactured by Tokuyama Corporation, Tokusil NP).

Sodium sulfate (manufactured by Japan Chemical Industrial Co., Ltd., neutral anhydrous manganese K2).

pH adjusting agent: 1N sulfuric acid, 1N sodium hydroxide.

Ion-exchange water

[Method of producing detergent for dishwasher according to the second embodiment of the present invention]

(Liquid phase cleaning agent: Examples 1a to 19a, Comparative Examples 1a to 10a)

0.8 kg of liquid cleaner of each example was produced as follows according to the composition of Tables 1a to 3a.

First, the component (C) was dissolved in ion-exchanged water in a volume of 1 L of a beaker, and an aqueous chelating agent solution was prepared so that the total amount of these components was 50% by mass.

Separately, a surfactant solution was prepared so that the ion-exchanged water adjusted to 75 ° C and the component (A1) or the component (A2) were mixed in a 1 L beaker with a capacity of 40% by mass of the total composition.

Subsequently, the whole amount of the surfactant solution adjusted to 75 캜 was added while stirring the aqueous chelating agent solution heated to 75 캜 at 6000 rpm by an agitation homogenizer, and then the mixture was stirred for 30 seconds to obtain the component (A1) or the component (A2) C) was obtained.

The mixture was cooled to 25 DEG C and adjusted to pH 9.5 by using 1N sulfuric acid or 1N sodium hydroxide. The remaining ion-exchanged water was added and stirred so that the whole composition became 100% by mass To obtain a liquid phase cleaning agent.

The pH (25 ° C) of the composition was measured by using a glass electrode type pH meter (HM-30G, manufactured by DKK-TOA CORPORATION) as a liquid detergent adjusted to 25 ° C. The measuring method was based on JIS K3362-1998.

(Powder particulate cleaner: Examples 20a to 22a)

6 kg of the powder particulate cleaner of each example was produced as follows according to the composition of Table 4a.

First, sodium sulfate was placed in a ribbon mixer (YOSHIDA product, ribbon mixer 1102-1500, width 900 mm x length 1800 mm x depth 1100 mm), and anhydrous silicic acid was added while stirring at 25 rpm and mixed for 10 minutes. Subsequently, the components (A1) and (C) were added and mixed at 25 rpm for 10 minutes to obtain a powdery particulate cleaner.

&Lt; Evaluation of dishwasher detergent according to the second embodiment of the present invention >

Each example of the cleaning agent was evaluated by the following evaluation method, and the results are shown in Tables 1a to 4a.

As a dishwasher, an automatic dishwashing drier (model NP-40SX2 from Panasonic Corporation) was used. In each evaluation, the cleaning process was performed by operating the standard dish set in the automatic dishwashing and drying machine. The contents of the standard course are shown below.

Standard course:

After 6 g of cleaning agent (about 3 L of tap water) was poured into the automatic dishwasher-drier, tap water was introduced into the oven to prepare a cleaning liquid, and was rinsed for 20 minutes while raising the temperature from room temperature to 55 캜 at 2 to 3 캜 / Drainage. Thereafter, new tap water is introduced, and rinsing (two minutes / twice) with tap water at room temperature and repetition of drainage are carried out three times. Then, new tap water is introduced and the temperature is raised from room temperature to 70 DEG C at 2 to 3 DEG C / min The rinsing is performed once (final rinsing) for 20 minutes while the temperature is raised, and drying of the tableware or the like is performed while circulating hot air after the drainage.

[Evaluation of low foaming property]

The evaluation of low foaming was performed in the same manner as the evaluation of the dishwasher detergent of the first embodiment of the present invention.

[Evaluation of detergency against oil / scale composite contamination]

A glass cup (upper diameter: 63 mm, lower diameter: 53 mm, height: 100 mm) was placed in the automatic dishwashing and drying machine, 1.2 g of sodium carbonate was placed in the vat and the operation was performed using the standard course using 30- Water contamination (scale contamination) was attached.

Subsequently, 8 g of Uji was applied to the inner surface of the glass cup to which the scale contamination was attached, and the glass cup with this oil / scale composite contamination was used as a cleaning object.

Subsequently, eight such objects to be cleaned were housed in one automatic dishwasher-drier, and the cleaning was performed by operating the above-mentioned standard course.

The appearance of the glass cup after the cleaning treatment (after drying) was observed by naked eyes, and the cleaning power against the oil / scale composite contamination was evaluated based on the following evaluation criteria.

Eight evaluation points of the glass cups were averaged, and when the average value was 3.0 or more, the evaluation was made.

(Evaluation standard)

4 points: All oil contamination and scale contamination are completely removed from the glass cup and water droplet marks are not confirmed.

3 points: Although oil contamination and scale contamination are removed from the glass cup, a few drops of water are observed.

2 points: Residues of oil contamination and scale contamination are slightly observed in the glass cup, and water droplet marks are also confirmed.

1 point: Residual oil contamination and scale contamination in the glass cup is clearly identified.

[Evaluation of prevention of re-contamination]

Evaluation of re-contamination resistance was performed in the same manner as in the evaluation of the dishwasher detergent of the first embodiment of the present invention.

(Table 1a)

(Table 1a ")

(Table 2a)

(Table 2a ')

(Table 3a)

(Table 3a ')

(Table 4a)

From the results shown in Tables 1a to 4a, all of the cleaning agents of Examples 1a to 22a to which the second embodiment of the present invention is applied have excellent detergency against oil / scale composite contamination while ensuring low foaming property, It is confirmed that re-contamination such as oil contamination is suppressed.

Claims (3)

(A) comprising a nonionic surfactant (A1) selected from the group consisting of fatty acid alkanolamides and polyoxyethylene fatty acid alkanolamides and having an HLB of from 8.5 to less than 12.0,
Wherein the content of the nonionic surfactant (A1) in the surfactant (A) is 25 mass% or more. The method according to claim 1,
Further contains a protease (B), and further comprises
The ratio expressed by Ea / W _A1 is 1 to 30 when the protease activity per gram of the cleaning agent is Ea (kPU / g) and the content of the nonionic surfactant (A1) in the cleaning agent is W _A1 (mass% Features a dishwasher detergent. (A1): a nonionic surfactant (A1) selected from the group consisting of a fatty acid alkanolamide and a polyoxyethylene fatty acid alkanolamide and having an HLB of from 8.5 to less than 12.0 and
Component (C): Containing a chelating agent (C)
Wherein the mass ratio of the component (C) / component (A1) is 1 to 50.