JP2014227441A - Detergent for dishwasher - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a detergent for a dishwasher having excellent detergency to oil/scale composite stains while securing its low foam properties, and in which recontamination such as oil stains to the object to be cleaned is suppressed.SOLUTION: Provided is a detergent for a dishwasher comprising: component (A): a nonionic surfactant selected from the group consisting of fatty acid alkanolamide and polyoxyethylene fatty acid alkanolamide and also having an HLB of 8.5 to below 12.0; and component (B): a chelating agent, and the mass ratio represented by the component (B)/the component (A) is 1 to 50.

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. In addition, the dishwasher cleaning agent can remove oil stains and scale stains that adhere to dishes (such as tap water or calcium in the stains that become carbonate and become insoluble and adhere to the dishes). Power is also required.
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. Further, as the amount of dirt increases, it becomes difficult to remove scale dirt and oil dirt (oil / scale composite dirt) coexisting with the dish from tableware and the like. In addition, particularly in the cleaning of hydrophobic dishes (for example, plastic containers) made of polypropylene (PP) resin, etc., it has become an environment in which oil stains are easily transferred or reattached (recontamination) during cleaning. .
However, conventional cleaning agents such as Patent Documents 1 and 2 have insufficient cleaning power against oil / scale composite dirt when the washing process is performed by a dishwasher without pre-washing. In addition, recontamination is significant in the cleaning of hydrophobic tableware.
The present invention has been made in view of the above circumstances, and has excellent detergency against oil / scale composite dirt while ensuring low foamability, and recontamination such as oil dirt on the object to be cleaned. An object is to suppress a dishwasher detergent.

  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. It has been found that the above problems can be solved by selecting an ethylene oxide adduct having a specific HLB and mixing it with a chelating agent in a specific ratio, and the present invention has been completed.

  That is, the dishwasher cleaning agent of the present invention is selected from the group consisting of component (A): fatty acid alkanolamide and polyoxyethylene fatty acid alkanolamide, and has an HLB of 8.5 to less than 12.0. It contains an activator and (B) component: chelating agent, and the mass ratio represented by (B) component / (A) component is 1-50.

  According to the present invention, there is provided a dishwasher cleaning agent that has excellent detergency against oil / scale composite stains while ensuring low foaming properties, and that suppresses recontamination of oil stains and the like on an object to be cleaned. Can be provided.

The dishwasher cleaning agent of the present invention is a nonionic surfactant selected from the group consisting of component (A): fatty acid alkanolamide and polyoxyethylene fatty acid alkanolamide, and having an HLB of 8.5 or more and less than 12.0. And (B) component: a chelating agent.
The dosage form of the dishwasher cleaning agent of the present invention is not particularly limited as long as it contains the component (A) and the component (B), and may be solid such as powder or tablet, or may be liquid.

<(A) component: specific nonionic surfactant>
The component (A) 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 (A) is 8.5 or more and less than 12.0, and preferably 9.0 to 11.0.
When the HLB of the component (A) is 8.5 or more and less than 12.0, the detergency against oil / scale composite dirt is enhanced, and re-contamination such as oil dirt on the object to be cleaned is also suppressed.
In particular, when the HLB of the component (A) 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 (A) is less than 12.0, low foamability during cleaning can be ensured.
In addition, when using 2 or more types of (A) component, the HLB of these mixtures requires that the weighted average value of HLB of each (A) component is in the range of 8.5 or more and less than 12.0. Shall.

The melting point of the component (A) is preferably 35 to 70 ° C, more preferably 40 to 65 ° C.
If the melting point of the component (A) is equal to or more 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 (A) 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, “melting point of component (A)” is a mixture of component (A) with a mixing ratio of (A) component / purified water = 9/1 (mass ratio) and purified water in a mortar. Is taken as a sample, 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 rate of temperature increase of 3 K / min is shown. Let it be temperature.

The component (A) 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 (a-1) or the compound represented by general formula (a-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 (a-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 9 to 17 carbon atoms, more preferably 11 to 15 carbon atoms, from the viewpoint of detergency against oil / scale composite soil. It is.

［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 (a-2), examples of R ² include the same as R ¹ in the formula (a-1).
In the formula (a-2), n is an average number of repetitions, and is preferably a number of 3 or less, more preferably 2 or less, from the viewpoint of the detergency against oil / scale composite dirt and the effect of suppressing recontamination. More preferably, the number is 1 or less, and particularly preferably 1.
In addition, the compound represented by general formula (a-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 (A) 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 bromide and the like.
Among these, fatty acid monoalkanolamides are preferable from the viewpoints of detergency against oil / scale composite stains and the effect of suppressing recontamination of oil stains such as plastic containers, particularly hydrophobic dishes. Oil fatty acid monoethanolamide, lauric acid monoethanolamide, and lauric acid monoisopropanolamide are more preferred, and coconut oil fatty acid monoethanolamide is particularly preferred.
Among the polyoxyethylene fatty acid monoalkanolamides, polyoxyethylene myristic acid is used in terms of its detergency against oil / scale composite stains and the effect of suppressing recontamination of oil stains on hydrophobic dishes such as plastic containers. Monoethanolamide is preferred, and an oxyethylene group having an average repeating number of 1 is particularly preferred.

(A) 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 (A), 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 (A) 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 (A) is equal to or more than the preferable lower limit value, the cleaning power against the oil / scale composite dirt increases, and the re-contamination of the oil dirt and the like on the object to be cleaned is easily suppressed. On the other hand, if the content of the component (A) is equal to or less than the preferable upper limit, foaming at the time of washing is easily suppressed.

  Among the components (A), 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.

<(B) component: chelating agent>
Component (B) is a chelating agent.
(B) It does not specifically limit as a component, The common chelating agent used for the washing | cleaning agent for dishwashers until now is mentioned, Either a high molecular chelating agent or a low molecular chelating agent can be used.
Specific examples of the polymer chelating agent include a copolymer of maleic acid and acrylic acid (hereinafter referred to as “maleic acid / acrylic acid copolymer”) or a salt thereof.
The maleic acid / acrylic acid copolymer or salt thereof preferably has a maleic acid / acrylic acid molar ratio of 70/30 to 30/70.
The maleic acid / acrylic acid copolymer or salt thereof preferably has a weight average molecular weight of 1000 or more as measured by gel permeation chromatography using sodium acrylate as a standard substance, and ranges from 1500 to 200000. More preferred are those in the range of 2000 to 100,000, particularly preferred are those in the range of 10,000 to 100,000, and most preferred are those in the range of 40,000 to 60,000. When the weight average molecular weight is 1000 or more, the effect of preventing reattachment of soap scum is improved. On the other hand, when the weight average molecular weight is 200,000 or less, the caking resistance is improved when a solid dosage form such as a powder is formed.
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, hydroxyethanediphosphonic acid, nitrilotriacetic acid, glutamic acid diacetic acid, methylglycine diacetic acid, and salts thereof.

(B) 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 (B), it is preferable to use at least one selected from the group consisting of a maleic acid / acrylic acid copolymer, glutamic acid diacetic acid, methylglycine diacetic acid, citric acid, and salts thereof.
In the dishwasher detergent, the content of the component (B) is preferably 4 to 20% by mass, more preferably 8 to 16% by mass, and still more preferably 8 to 13% by mass with respect to the total mass of the detergent. 10 to 12.5% by mass is particularly preferable.
When the content of the component (B) is equal to or more than the preferable lower limit, the cleaning power against oil / scale composite dirt is increased. Especially, the detergency against scale dirt increases. On the other hand, if the content of the component (B) is equal to or less than the preferable upper limit value, the caking resistance is improved when a solid dosage form such as a granular form is obtained. In addition, when a liquid dosage form is used, it becomes easy to maintain a uniform dispersion state of the cleaning agent.

  As the component (B), one synthesized by a known method may be used, or one commercially available may be used. Examples of commercially available sodium salts of maleic acid / acrylic acid copolymers include AQUALIC TL400 (weight average molecular weight 50000) manufactured by Nippon Shokubai Co., Ltd., Socaran CP7, CP5 or CP12S manufactured by BASF. (Weight average molecular weight CP7 = 50000, CP5 = 70000, CP12S = 3000). For glutamic acid diacetic acid sodium salt, examples include Dissolvine GL47-S or GL-PDS manufactured by Akzo Nobel. For methylglycine diacetic acid sodium salt, examples include Trilon M manufactured by BASF, and citric acid. Or if it is sodium citrate, Fuso Chemical Co., Ltd. citric acid or sodium citrate may be used.

In the present invention, “mass ratio represented by (B) component / (A) component” represents the ratio of the mass of component (B) to the mass of component (A) in the dishwasher detergent. .
In the dishwasher detergent of the present invention, the mixing ratio of the component (A) and the component (B) is a mass ratio represented by the component (B) / component (A) (hereinafter also referred to as “B / A ratio”). .) Is 1 to 50, preferably 3 to 25, and more preferably 5 to 20.
By setting the B / A ratio in the above range, the detergency against oil / scale composite dirt increases.
In addition, if the B / A ratio is less than 1, the detergency against oil / scale composite dirt tends to decrease. This is thought to be due to the reduction in the ratio of component (B), in which scale dirt cannot be removed, scale dirt tends to remain on tableware, etc., and oil dirt also tends to remain on the remaining scale dirt. It is done. Furthermore, the foaming property derived from the component (A) 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 B / A ratio exceeds 50, the detergency against oil / scale composite dirt tends to decrease. This is presumed that if the ratio of component (B) increases, the cleaning power against scale dirt is simply increased. However, if the ratio of component (A) decreases, the scale dirt dispersed in the cleaning liquid is lost in dishes, etc. This is probably because oil stains further adhere to the re-deposited scale soiled portion.

<Optional component>
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.
As an arbitrary component, it is not specifically limited, What has been used for the washing | cleaning agent for dishwashers until now is mentioned. For example, surfactants other than the component (A), bleach, bleach activator, alkaline agent, enzyme (protease, amylase, etc.), plant extract, fragrance, oil absorbent, antifoaming agent, dish protection agent, thickening agent Agents, colorants, preservatives, pH adjusters, powdering agents (such as anhydrous silicic acid), process agents (such as sodium sulfate, potassium sulfate, and sodium chloride) can be used.
However, in a dishwasher, it is necessary to suppress foaming during washing. For this reason, it is preferable that the total content of the component (A) and the other surfactant in the dishwasher detergent is 11% by mass or less based on the total mass of the detergent. The content is more preferably 2 to 11% by mass, further preferably 0.3 to 5% by mass, and particularly preferably 0.5 to 3% by mass.
In addition, the content of the component (A) in the total surfactant is preferably 25% by mass or more, more preferably 50% by mass or more, and further preferably based on the total mass of all the surfactants. Is 70 mass% or more, and may be 100 mass%. When the content of the component (A) is equal to or more than the preferred lower limit, foaming is kept low when performing dishwashing and the like washing with a dishwasher. In addition, the detergency against oil stains and the like is enhanced, and recontamination of oil stains and the like on the object to be cleaned (particularly hydrophobic tableware) is easily suppressed.

(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, (B) component, and an arbitrary component as needed. Especially, since a uniform solution is easy to be obtained, the method of preparing (A) component solution and (B) component solution beforehand, respectively, and mixing (A) component solution and (B) component solution is preferable.
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 or more, more preferably 7 to 10, and even more preferably 7 to 8.
If this pH (25 degreeC) is more than a preferable lower limit, the detergency with respect to oil / scale composite dirt will increase. In addition, recontamination such as oil stains on the object to be cleaned is easily suppressed.
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)
The method of using the dishwasher cleaning agent of the present invention varies depending on the type of dishwasher and the degree of contamination of the dishwasher. For example, the amount of the dishwasher cleaning agent used is about 3 liters of tap water. It is preferable to set it as 3-9g with respect to it.
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 the component (A) in the cleaning liquid within the above range, the cleaning power against oil / scale composite dirt is increased. In addition, re-contamination such as oil stains on hydrophobic tableware such as plastic containers can be easily suppressed. If the concentration of component (A) in the cleaning liquid is less than 2 ppm (mass basis), the cleaning power may be insufficient. On the other hand, if it exceeds 300 ppm (mass basis), foaming tends to be excessive during washing. It is not preferable.

As described above, the dishwasher detergent composition of the present invention has an excellent detergency against oil / scale composite dirt by using the component (A) and the component (B) in combination. In addition, the adoption of the component (A) makes it difficult for oil stains to reattach to tableware and the like during rinsing, and recontamination such as oil stains on hydrophobic tableware is greatly suppressed. Furthermore, since the mass ratio represented by the component (B) / component (A) is 1 to 50, the detergency against the oil / scale composite soil is synergistically increased, so that the soil removal effect and the recontamination prevention effect are achieved. In addition, foaming is suppressed and low foaming is ensured.
According to the detergent composition for a dishwasher of the present invention, even when the dishwasher is subjected to a washing treatment without prewashing, the oil / scale composite stain is secured while ensuring low foaming properties. Excellent cleaning effect under severe conditions. In addition, recontamination of oil stains on tableware (plastic containers, etc.) using a hydrophobic material such as polypropylene is suppressed.
According to such a detergent composition for a dishwasher, tea astringent stains can be satisfactorily removed in addition to the cloudy stains of glass tableware.

  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 blending composition shown in Tables 1 to 4, the cleaning agents of each example were prepared by the production method described later (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 (ion-exchanged water or sodium sulfate) is blended so that the total blending amount (mass%) of all the blending ingredients contained in the cleaning agent of each example is 100% by mass. means.
"B / A ratio" is synonymous with the mass ratio represented by (B) component / (A) component, and represents the ratio of the content mass of (B) component to the mass content of (A) component in the cleaning agent. means.
Below, the component shown in the table | surface is demonstrated.

-(A) component A-1: Palm oil fatty acid monoethanolamide (made by Kawaken Fine Chemicals, Amizole CME), HLB10.3, melting | fusing point 43.7 degreeC.
A-2: Lauric acid monoethanolamide (synthetic product), HLB 10.7, melting point 61.2 ° C.
A-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.
A-4: Lauric acid monoisopropanolamide (manufactured by Kawaken Fine Chemicals, Amizole PLME-A), HLB10.3, melting point 50.6 ° C.
A-5: Polyoxyethylene lauric acid monoethanolamide (ethylene oxide average 1-mole adduct of lauric acid monoethanolamide, synthetic product), HLB 10.0, melting point 51.3 ° C.

-Component (A) comparative component [hereinafter referred to as "(A ') component". ]
A′-1: Decanoic acid monoethanolamide (synthetic product), HLB 12.5, melting point 53.2 ° C.
A′-2: stearic acid monoethanolamide (synthetic product), HLB 7.5, melting point 94 ° C.
A′-3: Palm oil fatty acid diethanolamide (manufactured by Kawaken Fine Chemicals, Amizole CDE), HLB 12.0, melting point 5.0 ° C.
A′-4: C12,13 polyoxyalkylene alkyl ether (a mixture of an alcohol having 12 carbon atoms and an alcohol having 13 carbon atoms added with an average of 3 mol of ethylene oxide and an average of 3 mol of propylene oxide) (manufactured by Lion Chemical) NNAEP-3030), HLB4.5.
A′-5: polyoxyethylene (5) lauryl ether, ethylene oxide average 5 mol adduct (Nippon Emulsion, Emalex 705), HLB 9.5, melting point 8.4 ° C.
A′-6: lauric acid diethanolamide (manufactured by Kawaken Fine Chemicals, Amizole LDE), HLB 12.5, melting point 41 ° C.

[Method for synthesizing synthetic product in component (A) or component (A ′)]
Synthesis example of A-2, A′-1, A′-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 monoethanolamide A-2, A'-1, and A'-2 were obtained by carrying out the pressure reduction to 1.3 kPa and ageing | curing | ripening for 4 hours after completion | finish of dripping, respectively.
As such fatty acid methyl ester, lauric acid methyl ester is used when A-2 is synthesized, decanoic acid methyl ester is used when A'-1 is synthesized, and stearic acid methyl ester is used when A'-2 is synthesized. It was.

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

-(B) component B-1: Sodium salt of maleic acid / acrylic acid copolymer (Nippon Shokubai Co., Ltd., Aqualic TL400), weight average molecular weight 50000, active ingredient 40 mass%.
B-2: Sodium salt of glutamic acid diacetic acid (Diszoline GL47-S, manufactured by Akzo Nobel) 47% by mass of active ingredient.
B-3: Sodium salt of methylglycine diacetic acid (BASF, Trilon M) active ingredient 40% by mass.
B-4: Sodium salt of maleic acid / acrylic acid copolymer (manufactured by BASF, Socaran CP7), weight average molecular weight 50,000.
B-5: Sodium citrate (manufactured by Fuso Chemical).

-Optional component Silicic anhydride (manufactured by Tokuyama, 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 1-19, Comparative Examples 1-10)
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 capacity beaker, the component (B) was dissolved in ion-exchanged water, and an aqueous chelating agent solution was prepared so that the total amount thereof was 50% by mass of the entire composition.
Separately, in a 1 L beaker, the ion exchange water adjusted to 75 ° C. and the component (A) or the component (A ′) are mixed, and the interface is such that the total amount thereof is 40% by mass of the entire composition. An activator solution was prepared.
Next, the whole amount of the surfactant solution adjusted to 75 ° C. is added to the aqueous chelating agent solution heated to 75 ° C. while stirring at 6000 rpm, and then stirred for 30 seconds to prepare the component (A) or (A A liquid mixture containing the component ') and the component (B) was obtained.
After cooling this mixed liquid to 25 ° C., the pH of the composition (25 ° C.) is adjusted to 9.5 using 1N sulfuric acid or 1N sodium hydroxide so that the whole composition becomes 100% by mass. The remaining ion exchange water was added to and stirred to obtain a liquid detergent.
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.

(Powder cleaning agent: Examples 20 to 22)
According to the composition of Table 4, 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. . Subsequently, (A) component and (B) component were added, and the granular cleaning agent was obtained by mixing for 10 minutes at 25 rpm.

<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 1-4.
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:
After putting 6g of cleaning agent (relative to 3L of tap water) into the automatic dishwasher, tap water is introduced into the cabinet to prepare a cleaning solution, and the temperature is raised from room temperature to 55 ° C at 2-3 ° C / min. While being washed for 20 minutes, it is drained. After that, new tap water is introduced, rinse with normal temperature tap water (2 minutes / times) and drainage are repeated three times, and then new tap water is introduced, and from normal temperature to 70 ° C. Rinsing is performed once (final rinsing) for 20 minutes while raising the temperature at 3 ° C./min, and after drainage, the tableware and the like are dried while circulating warm air.

[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 detergency against oil / scale composite dirt]
Glass cups (upper diameter 63 mm, lower diameter 53 mm, height 100 mm) are stored in the automatic dishwasher, 1.2 g of sodium carbonate is placed in the cabinet, and operation is performed on the standard course using 30 degree hard water. Cloudy dirt (scale dirt) was adhered to the glass cup.
Next, 8 g of beef tallow was applied to the inner surface of the glass cup to which the scale dirt had adhered, and the glass cup to which this oil / scale composite dirt had adhered was used as the object to be cleaned.
Next, eight objects to be cleaned were stored in one automatic dishwasher and operated on the standard course to perform a cleaning process.
The appearance of the glass cup after the washing treatment (after drying) was visually observed, and the detergency against the oil / scale composite soil was evaluated based on the following evaluation criteria.
The evaluation points of 8 glass cups were averaged, and if the average value was 3.0 points or more, it was regarded as acceptable.
(Evaluation criteria)
4 points: Both oil stains and scale stains are clearly removed from the glass cup, and no water droplet traces are observed.
3 points: Oil stains and scale stains are removed from the glass cup, but traces of water droplets are observed.
2 points: Oil glass and scale residue remained slightly on the glass cup, and traces of water droplets were also observed.
1 point: Residual oil stains and scale stains are clearly observed in the glass cup.

[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.

  From the results shown in Tables 1 to 4, the cleaning agents of Examples 1 to 22 to which the present invention is applied have excellent cleaning power against oil / scale composite dirt while ensuring low foaming properties. It can be seen that recontamination of the object to be cleaned, such as oil stains, is suppressed.

Claims (1)

(A) 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 or more and less than 12.0;
(B) component: containing a chelating agent,
(B) Dishwasher washing | cleaning agent characterized by the mass ratio represented by a component / (A) component being 1-50.