JP2015021090A - Detergent for dishwasher - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a detergent for a dishwasher capable suppressing accumulation of microbial pollution.SOLUTION: There is provided a detergent for a dishwasher which comprises: a surfactant (A); at least one (B) selected from copper, manganese, nickel, cobalt, iron and zinc; an amino carboxylic acid sequestering agent (C) forming a complex with the (B) component; and a biguanide-based polymer (D).

Description

  The present invention relates to a detergent for a dishwasher.

In recent years, dishwashers have been miniaturized and water-saving performance has been improved, so that they are designed to remove more dirt with less water. In addition, there is a dishwasher equipped with a course that keeps the water temperature low during washing, such as a power-saving course. In such a course, dirt derived from foods tends to remain in the flow path in the warehouse, and a mixture of microorganisms and food-derived dirt (for example, oil) (hereinafter referred to as “microorganism dirt”) accumulates. It becomes easy to do.
The accumulated microbial contamination not only causes odor, but also clogs the flow path through which the cleaning agent flows, causing problems in the dishwasher itself and reducing cleaning efficiency.

As a detergent for a dishwasher having a high deodorizing effect at the time of washing and a low residual scent after washing, Patent Document 1 discloses a detergent composition for an automatic dishwasher containing specific fragrance particles. .
Further, as a detergent for a dishwasher having a high detergency, Patent Document 2 discloses a dishwasher containing a bleach activating component containing manganese and a chelating agent, an inorganic peroxide, and a low-foaming surfactant. Detergent compositions are disclosed.

JP 2006-45430 A JP 2009-149777 A

However, although the dishwasher cleaning agent described in Patent Document 1 has a deodorizing effect, it cannot solve the accumulation of microbial soil.
Although the detergent for dishwashers described in Patent Document 2 is excellent in detergency, it cannot solve the accumulation of microbial soil.

  This invention is made | formed in view of the said situation, and it aims at providing the washing | cleaning agent for dishwashers which can suppress accumulation | storage of microbial soil.

The present invention has the following aspects.
[1] A surfactant (A), at least one selected from copper, manganese, nickel, cobalt, iron and zinc (B), and an aminocarboxylic acid type metal ion forming a complex with the component (B) A dishwasher cleaning agent comprising a sequestering agent (C) and a biguanide polymer (D).
[2] Dishwasher washing according to [1], wherein the surfactant (A) contains an alkylamidoamine (A1) represented by the following general formula (a1) and an anionic surfactant (A2) Agent.

In the formula (a1), R ³¹ represents an alkyl group or alkenyl group having 13 to 21 carbon atoms, R ³² represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group, and R ³³ represents 1 carbon atom. Represents an alkylene group having 4 to 4, and R ³⁴ and R ³⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

  The dishwasher detergent of the present invention can suppress the accumulation of microbial soil.

The dishwasher cleaning agent of the present invention is at least one selected from surfactant (A) (hereinafter sometimes referred to as “component (A)”) and copper, manganese, nickel, cobalt, iron and zinc. Species (B) (hereinafter also referred to as “component (B)”) and aminocarboxylic acid type sequestering agent (C) (hereinafter referred to as “component (C)”) forming a complex with component (B). And biguanide polymer (D) (hereinafter also referred to as “component (D)”).
The dosage form of the dishwasher detergent of the present invention is not particularly limited as long as it contains the component (A), the component (B), the component (C), and the component (D). It may be a solid such as a liquid or a liquid.
Hereinafter, each component will be described.

<(A) component>
The component (A) is a surfactant. A dishwasher detergent contains (A) component, and exhibits high detergency. Moreover, accumulation | storage of microorganisms dirt can be suppressed by using together with the (B)-(D) component mentioned later. This is because the dishwasher cleaning agent is dispersed in the washing water (if the dishwasher cleaning agent is liquid, in the liquid dishwasher cleaning agent), the component (A) is the component (D) In addition, the aggregate takes in the complex formed by the component (B) and the component (C), so that the aggregate is adsorbed to every corner of the dishwasher, and the microbial soil It is thought to suppress the accumulation of

  Incidentally, dishwasher detergents are often required not only to have a detergency against food stains but also to have low foaming properties. If the low foaming property is insufficient, a phenomenon called “overflow”, in which bubbles overflow during operation of the dishwasher, or “air chewing” in which sufficient jetting power cannot be obtained due to bubbles entangled in the circulating water May occur, causing the dishwasher to stop abnormally or break down.

Therefore, in the present invention, it is preferable to use a low-foaming surfactant as the component (A).
Here, the “low-foaming surfactant” is a surfactant that is unlikely to cause a phenomenon such as “overflow” or “air chewing”. Specifically, it is a surfactant having an average foam height of 15 mm or less as measured by the measurement method described below.

Bubble height measurement method:
A surfactant solution is prepared by adding 0.12 g of a surfactant (total amount in the case of a mixture of two or more surfactants) to 3 L of water at 15 ° C. The detergent solution is put into a dishwasher and operated. Stop the operation 1 minute after the start of washing and open the door at the same time, and measure the foaming in the chamber after 15 seconds. In that case, three places in a store | warehouse | chamber are selected at random, the bubble height (mm) of this place is each measured, and the average value is calculated | required.

  The low-foaming surfactant may be composed of one kind of surfactant or may be composed of a mixture of two or more kinds of surfactants. Further, when the low-foaming surfactant is a mixture, if the average value of the foam height when the mixture is 15 mm, a highly foaming surfactant and a low-foaming surfactant A combination of these may be used.

  As the low-foaming surfactant, known ones can be used, for example, those described in JP-A-2006-152287 and Patent Document 1. Specific examples include polyoxyethylene polyoxypropylene alkyl ether and polyoxyethylene polyoxypropylene glycol. In addition, the low-foaming surfactant is sometimes referred to as an alkylamidoamine (A1) represented by the following general formula (a1) (hereinafter referred to as “component (A1)”) in that the effect of suppressing the accumulation of microbial soil is enhanced .).

In the formula (a1), R ³¹ represents an alkyl group or alkenyl group having 13 to 21 carbon atoms, R ³² represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group, and R ³³ represents 1 carbon atom. Represents an alkylene group having 4 to 4, and R ³⁴ and R ³⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

In formula (a1), R ³¹ represents an alkyl group having 13 to 21 carbon atoms or an alkenyl group having 13 to 21 carbon atoms. Among these, R ³¹ is preferably an alkyl group having 13 to 21 carbon atoms. The alkyl group and alkenyl group in R ³¹ may be linear or branched.
The carbon number of the alkyl group and the alkenyl group in R ³¹ is 13 to 21 respectively, and since the foam suppression effect is further increased, the carbon number is preferably 15 to 21, and more preferably the carbon number is 15 to 19. is there.

In the formula (a1), R ³² represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 1 to 4 carbon atoms. The number of hydroxy groups in the hydroxyalkyl group for R ³² may be one or two or more. Among these, as R ^32, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms is preferable, a hydrogen atom, more preferably a methyl group, a hydrogen atom is particularly preferred. The alkyl group and hydroxyalkyl group in R ³² may be linear or branched.

The carbon number of the alkylene group in R ³³ is 1 to 4, preferably 1 to 3, more preferably 2 or 3, and particularly preferably 3 carbon atoms. The alkylene group for R ³³ may be linear or branched.

The carbon number of the alkyl group in R ³⁴ and R ³⁵ is 1 to 4, preferably 1 to 3, more preferably 1 or 2, and particularly preferably 1 carbon. It is. Among these, R ³⁴ and R ³⁵ are each preferably an alkyl group having 1 to 4 carbon atoms, and preferably the same as each other. The alkyl group in R ³⁴ and R ³⁵ may be linear or branched.

  Specific examples of the component (A1) include, for example, myristic acid dimethylaminoethylamide, myristic acid diethylaminoethylamide, myristic acid dipropylaminoethylamide, myristic acid dimethylaminopropylamide, myristic acid diethylaminopropylamide, myristic acid dipropylamino. Propylamide, palmitic acid dimethylaminoethylamide, palmitic acid diethylaminoethylamide, palmitic acid dipropylaminoethylamide, palmitic acid dimethylaminopropylamide, palmitic acid diethylaminopropylamide, palmitic acid dipropylaminopropylamide, dimethylaminoethyl stearate Amides, stearic acid diethylaminoethylamide, stearic acid dipropylaminoethylamide, stearyl Acid dimethylaminopropylamide, stearic acid diethylaminopropylamide, stearic acid dipropylaminopropylamide, arachidic acid dimethylaminoethylamide, arachidic acid diethylaminoethylamide, arachidic acid dipropylaminoethylamide, arachidic acid dimethylaminopropylamide, arachidic acid Diethylaminopropylamide, arachidic acid dipropylaminopropylamide, behenic acid dimethylaminoethylamide, behenic acid diethylaminoethylamide, behenic acid dipropylaminoethylamide, behenic acid dimethylaminopropylamide, behenic acid diethylaminopropylamide, behenic acid dipropyl Aminopropylamide, Myristic acid dimethylaminoethylmethylamide, Palmitic acid dimethylamino Ethylmethylamide, stearic acid dimethylaminoethylmethylamide, arachidic acid dimethylaminoethylmethylamide, behenic acid dimethylaminoethylmethylamide, myristic acid dimethylaminopropylmethylamide, palmitic acid dimethylaminopropylmethylamide, stearic acid dimethylaminopropylmethyl Amides, arachidic acid dimethylaminopropylmethylamide, behenic acid dimethylaminopropylmethylamide and the like.

Among these, since the foam-suppressing effect is more easily obtained, the component (A1) includes myristic acid dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, stearic acid dimethylaminopropylamide, and behenic acid dimethylaminopropylamide. More preferred are palmitic acid dimethylaminopropylamide, stearic acid dimethylaminopropylamide, and behenic acid dimethylaminopropylamide, and palmitic acid dimethylaminopropylamide and stearic acid dimethylaminopropylamide are particularly preferred.
These (A1) components may be used individually by 1 type, and may use 2 or more types together.

  0.1-5 mass% is preferable and, as for content of (A1) component in 100 mass% of detergents for dishwashers, 0.5-3 mass% is more preferable. If the content of the component (A1) is less than the lower limit, the foam suppression effect may be reduced. On the other hand, if the content of the component (A1) exceeds the above upper limit, the dishwasher detergent may become non-uniform, or the cleaning power, particularly the cleaning power against oil stains, may be reduced.

The component (A) preferably contains an anionic surfactant (A2) (hereinafter also referred to as “component (A2)”) for the purpose of enhancing the detergency against oil stains.
Examples of the component (A2) include a sulfonate type, a sulfate ester salt type, a carboxylate salt type, and a phosphate ester salt type.

The sulfonate type includes alkane sulfonate, alkylbenzene sulfonate, alkyl sulfate, polyoxyalkylene sulfate, α-olefin sulfonate, α-sulfo fatty acid salt, α-sulfo fatty acid alkyl ester salt, alkyl sulfosuccinate. Acid salt, dialkylsulfosuccinate and the like.
Examples of the sulfate ester type include alkyl sulfate ester salts, alkenyl sulfate ester salts, polyoxyalkylene alkyl ether sulfate ester salts, polyoxyalkylene alkenyl ether sulfate ester salts, and the like.
Examples of the carboxylate type include alkyl ether carboxylates, amide ether carboxylates, sulfosuccinates, amino acid anionic surfactants, and the like.
Examples of the phosphoric acid ester salt type include alkyl phosphoric acid ester salts and alkyl ether phosphoric acid ester salts.

In addition, the component (A2) preferably has an alkyl group having 8 to 18 carbon atoms, or has an alkenyl group having 8 to 18 carbon atoms, and particularly has an alkyl group having 8 to 18 carbon atoms. More preferred. The alkyl group or the alkenyl group may be linear or branched.
(A2) Salts constituting the component include alkali metal salts such as sodium salt and potassium salt; alkaline earth metal salts such as magnesium salt and calcium salt; monoethanolamine salt (monoethanolammonium), diethanolamine salt (diethanolammonium salt) ), Alkanolamine salts such as triethanolamine salt (triethanolammonium); ammonium salts and the like.

Among these, since the detergency with respect to oil stains is good and it is easy to ensure low foaming properties, as the component (A2), a sulfonate type and a sulfate ester type are preferable, and a sulfonate type is particularly preferable. .
Among them, one or more selected from the group consisting of alkane sulfonates, alkylbenzene sulfonates, alkyl sulfates, polyoxyalkylene sulfates and dialkyl sulfosuccinates are preferred because the detergency against oil stains is particularly enhanced. More preferred are sulfonates, alkylbenzene sulfonates and dialkylsulfosuccinates, more preferred are alkane sulfonates and alkylbenzene sulfonates, particularly preferred are alkane sulfonates and linear alkyl benzene sulfonates, and alkane sulfonates. Most preferred.
These (A2) components may be used individually by 1 type, and may use 2 or more types together.

  The content of the component (A2) in 100% by mass of the dishwasher detergent is preferably 0.1 to 5% by mass, and more preferably 0.5 to 3% by mass. When the content of the component (A2) is less than the lower limit, the cleaning power against oil stains may be reduced. On the other hand, if the content of the component (A2) exceeds the upper limit, the foam suppression effect may be reduced.

  The component (A2) has the effect of increasing the detergency against oil stains, but the component (A2) itself is a surfactant having excellent foaming properties. Therefore, when the component (A2) is used alone as the component (A), the low foaming property is lowered. Accordingly, when the component (A2) is used, it is preferable to use a surfactant having a low foaming property. Specifically, it is preferable to use the component (A1) and the component (A2) in combination.

In the dishwasher detergent of the present invention, the mixing ratio of the component (A1) and the component (A2) is a mass ratio represented by the component (A1) / component (A2) (hereinafter referred to as “(A1) / (A2 ) "Mass ratio")) is preferably 0.1 to 10, more preferably 0.2 to 5, still more preferably 0.6 to 1.4, particularly preferably. 0.8-1.2. When the (A1) / (A2) mass ratio is at least the preferred lower limit, the detergency against oil stains increases. On the other hand, when the (A1) / (A2) mass ratio is equal to or less than the preferable upper limit value, the foam suppression effect by the component (A1) is easily exhibited.
In the present invention, “mass ratio represented by (A1) component / (A2) component” represents the ratio of the mass of component (A1) to the mass of component (A2) in the dishwasher detergent. .

  The component (A) may further contain an amphoteric surfactant, a nonionic surfactant, a semipolar surfactant, and the like. Furthermore, (A) component can contain the surfactant used for a normal cleaning agent besides these. However, it is preferable to use a combination in which the average value of the foam height is 15 mm or less when all the surfactants contained in the dishwasher detergent are mixed.

  0.1-5 mass% is preferable and, as for content of (A) component in 100 mass% of washing | cleaning agents for dishwashers, 0.5-3 mass% is more preferable. When the content of the component (A) is less than the above lower limit, the adsorptive power of the dishwasher detergent into the dishwasher cabinet decreases, or the association with the component (D) is not sufficiently formed. This is because the effect of suppressing the growth of microorganisms may be reduced, and even if the above upper limit is exceeded, the effect of suppressing the accumulation of microorganism dirt may not be further improved.

<(B) component>
The component (B) is at least one selected from copper, manganese, nickel, cobalt, iron, and zinc. When the dishwasher detergent contains the component (B), it exhibits an excellent effect of suppressing accumulation of microbial soil and an effect of suppressing the occurrence of slime. This is because the dishwasher detergent is dispersed in the washing water (in the case of the dishwasher detergent being liquid, in the liquid dishwasher detergent), the component (B) is the component (C) It is thought that this complex suppresses the growth of microorganisms in the dishwasher cabinet.

  (B) As a component, manganese, copper, or zinc is preferable, copper or zinc is more preferable, and zinc is further more preferable. By using these components (B), the effect of suppressing the accumulation of microbial soil can be further enhanced.

  (B) A component may be mix | blended as various metal compounds, and may be mix | blended as a complex with (C) component mentioned later. However, it is preferable to mix | blend (B) component as a metal compound from viewpoints, such as the beauty | look of the washing | cleaning agent for dishwashers, and production efficiency.

  Any metal compound may be used as long as it dissolves in water. Examples of salts forming the metal compound include nitrates, sulfates, chlorides, perchloric acid peroxides, ammonium chlorides, cyanides, and other inorganic salts and acetates. , Organic salts such as gluconate, tartrate, glycine salt and the like.

The manganese compound is not particularly limited as long as it releases manganese ions in water, and examples thereof include manganese nitrate, manganese sulfate, manganese chloride, manganese acetate, manganese perchlorate, and manganese acetylacetonate. Among these, manganese sulfate and manganese chloride are preferable in terms of handleability, cost, raw material supply property, and the like.
The copper compound is not particularly limited as long as it releases copper ions in water. For example, copper nitrate, copper sulfide, copper sulfate, copper chloride, copper acetate, copper cyanide, copper ammonium chloride, copper gluconate, Examples include copper tartrate and copper perchlorate. Among these, copper sulfate, copper chloride, and copper gluconate are preferable and copper sulfate is more preferable in terms of handleability, cost, raw material supply property, and the like.
The zinc compound is not particularly limited as long as it releases zinc ions in water. For example, zinc nitrate, zinc sulfide, zinc sulfate, zinc chloride, zinc acetate, zinc cyanide, ammonium zinc chloride, zinc gluconate, Examples include zinc tartrate and zinc perchlorate. Among these, zinc sulfate, zinc chloride, and gluconate are preferable, and zinc sulfate is more preferable in terms of handling property, cost, raw material supply property, and the like.

  The content of the component (B) in 100% by mass of the dishwasher detergent can be determined in consideration of the type of the component (B), and is preferably 0.05 to 1% by mass, for example, 0.1 to 0.00. 5 mass% is more preferable. If the content of the component (B) is less than the lower limit, the effect of suppressing the accumulation of microbial soil may be insufficient. On the other hand, if the content of the component (B) exceeds the upper limit, the component (B) may be separated from the dishwasher detergent, and the effect of suppressing the accumulation of microbial soil may be insufficient.

For example, when manganese is used as the component (B), the content of manganese in 100% by mass of the dishwasher detergent is preferably 0.001 to 0.5% by mass, and 0.01 to 0.3% by mass. More preferably, 0.02-0.15 mass% is further more preferable. If the manganese content is less than the lower limit, the effect of suppressing accumulation of microbial dirt may be insufficient, and even if the content exceeds the upper limit, the effect of suppressing accumulation of microbial dirt may not be improved. Because.
Or when using copper as (B) component, 0.001-0.5 mass% is preferable and, as for content of copper in 100 mass% of washing | cleaning agents for dishwashers, 0.01-0.3 mass% is More preferably, 0.02-0.15 mass% is further more preferable. If the copper content is less than the lower limit, the effect of suppressing the accumulation of microbial dirt may be insufficient, and even if the content exceeds the upper limit, the effect of suppressing the accumulation of microbial dirt may not be improved. Because.
For example, when zinc is used as the component (B), the content of zinc in 100% by mass of the dishwasher detergent is preferably 0.002 to 2% by mass, and more preferably 0.02 to 1% by mass. 0.05 to 0.5 mass% is more preferable. If the zinc content is less than the lower limit, the effect of suppressing the accumulation of microbial dirt may be insufficient, and even if the content exceeds the upper limit, the effect of suppressing the accumulation of microbial dirt may not be improved. Because.

  (B) When mix | blending a component as a complex with (C) component, a complex can be manufactured with the manufacturing method of the complex as described in international publication 09/078459, for example.

<(C) component>
Component (C) is an aminocarboxylic acid type sequestering agent that forms a complex with component (B). When the detergent for dishwashers contains (C) component, the outstanding accumulation | storage suppression effect of microbial soil and the generation | occurrence | production suppression effect of slime are exhibited.

  Examples of the component (C) include nitrilotriacetate, ethylenediaminetetraacetate, β-alanine diacetate, aspartate diacetate, methylglycine diacetate, and aminocarboxylates such as iminodisuccinate; serine diacetate, Examples thereof include hydroxyaminocarboxylates such as hydroxyiminodisuccinate, hydroxyethylethylenediamine triacetate, and dihydroxyethylglycine salt. Among them, an aminocarboxylic acid type sequestering agent having two or more carboxyl groups in the molecule is preferable, and a compound represented by the following general formula (c1) or the following general formula (c2) is more preferable. .

In the formula (c1), X ^{11 to} X ¹⁴ each independently represent a hydrogen atom, an alkali metal, an alkaline earth metal, or a cationic ammonium, R ¹¹ represents a hydrogen atom or a hydroxy group, and n1 is 0 or 1 Represents an integer.

In formula (c2), A represents an alkyl group, a carboxy group, a sulfo group, an amino group, a hydroxy group, or a hydrogen atom, and X ^{21 to} X ²³ each independently represent a hydrogen atom, an alkali metal, an alkaline earth metal, or Represents cationic ammonium, and n2 represents an integer of 0 to 5.

In formula (c1), examples of the alkali metal in X ^{11 to} X ¹⁴ include sodium and potassium. Examples of the alkaline earth metal include calcium and magnesium. In addition, when at least one of X ^{11 to} X ¹⁴ is an alkaline earth metal, it corresponds to 1/2 atom. For ^example, if ^{X 11} is calcium, -COOX ¹¹ is ^"- 1/2 (Ca) ^- COO".
Examples of the cationic ammonium include alkanolamines such as monoethanolamine and diethanolamine, and examples include those in which 1 to 3 hydrogen atoms of ammonium are substituted with alkanol groups. As for carbon number of an alkanol group, 1-3 are preferable.
Among ^them, X 11 ^{to X 14} are the alkali metal is preferable.
X ^{11 to} X ¹⁴ in the formula (c1) may be the same or different from each other.

R ¹¹ in formula (c1) may be either a hydrogen atom or a hydroxy group.
N1 in the formula (c1) is preferably 1.

  Examples of the compound represented by the formula (c1) include iminodisuccinic acid, 3-hydroxy-2,2'-iminodisuccinic acid, and salts thereof. Examples of the salt include alkali metal salts such as sodium salt and potassium salt, and alkanolamine salts such as monoethanolamine salt and diethanolamine salt. Among these, sodium salt or potassium salt is more preferable.

In formula (c2), the alkali metal, alkaline earth metal, and cationic ammonium in X ^{21 to} X ²³ are the same as the alkali metal, alkaline earth metal, and cationic ammonium in X ^{11 to} X ¹⁴ , respectively. Is mentioned. X ^{21 to} X ²³ are preferably alkali metals.
X ^{21 to} X ²³ in the formula (c2) may be the same or different from each other.

The alkyl group in A of formula (c2) may be linear or branched. 1-30 are preferable and, as for carbon number of an alkyl group, 1-18 are more preferable. In the alkyl group, a part of the hydrogen atoms may be substituted with a substituent. Examples of the substituent include a sulfo group (—SO ₃ H), an amino group (—NH ₂ ), a hydroxy group, and a nitro group (—NO ₂ ).
A may be any of an alkyl group, a carboxy group, a sulfo group, an amino group, a hydroxy group, and a hydrogen atom, and is preferably a hydrogen atom.
N2 in the formula (c2) is preferably an integer of 0 to 2, and more preferably 1.

  Examples of the compound represented by the formula (c2) include nitrilotriacetic acid, methylglycine diacetic acid, dicarboxymethyl glutamic acid, L-aspartic acid-N, N-diacetic acid, serine diacetic acid, hydroxyethyliminodiacetic acid, or their Examples include salts. Among these, nitrilotriacetic acid, methyl glycine diacetic acid, dicarboxymethyl glutamic acid, L-aspartic acid-N, N-diacetic acid or a salt thereof is preferable, and methyl glycine diacetic acid or a salt thereof is more preferable. Examples of the salt include alkali metal salts such as sodium salt and potassium salt, and alkanolamine salts such as monoethanolamine salt and diethanolamine salt. Among these, sodium salt or potassium salt is preferable.

These (C) components may be used individually by 1 type, and may use 2 or more types together.
0.1-1 mass% is preferable and, as for content of (C) component in 100 mass% of washing | cleaning agents for dishwashers, 0.3-0.7 mass% is more preferable. When the content of the component (C) is less than the lower limit, the effect of suppressing the accumulation of microbial soil may be insufficient. On the other hand, when the content of the component (C) exceeds the above upper limit, the complex formation with the component (B) becomes too strong, and the effect of suppressing accumulation of microbial soil may be insufficient.

  The mass ratio of the component (C) to the metal ion in the component (B) (hereinafter sometimes referred to as “(C) / (B) mass ratio”) is preferably 0.5 to 50. ~ 25 is more preferred. If the (C) / (B) mass ratio is less than the above lower limit value, the effect of suppressing the accumulation of microbial dirt may be insufficient, and even if the above upper limit value is exceeded, the effect of suppressing the accumulation of microbial dirt can be further improved. This is because there is a possibility that it cannot be planned.

<(D) component>
The component (D) is a biguanide polymer.
By using the component (D) and the component (A) in combination, the effect of suppressing the accumulation of microbial soil and the effect of suppressing the occurrence of slime increase. Although the reason for exhibiting an excellent effect of suppressing the accumulation of microbial soil and the effect of suppressing the occurrence of slime by using the component (A) and the component (D) in combination is not clear, it is presumed as follows.
In the washing liquid in which the dishwasher detergent is dispersed in the washing water (in the case of the dishwasher detergent being liquid, in the liquid dishwasher detergent), the components (A) and (D) are: An aggregate (hereinafter also referred to as “AD aggregate”) is formed. This AD aggregate is easily adsorbed in the dishwasher cabinet as compared to the component (D) alone. For this reason, the sterilization effect and the antibacterial effect are exhibited by the component (D) adhering to the inside of the dishwasher as an AD aggregate.
Furthermore, the AD aggregate takes in the complex formed by the component (B) and the component (C), and the synergistic effect with this complex exerts an excellent effect of suppressing the accumulation of microbial soil and the effect of suppressing the occurrence of slime. Is done.

  As the component (D), for example, a biguanide compound such as a polyalkylene biguanide compound represented by the following general formula (d1) is preferable.

In formula (d1), n5 represents the average number of repeating units represented by [(CH ₂ ) ₃ —NH—C (NH) —NH—C (NH) —NH— (CH ₂ ) ₃ ] It is the number of ~ 40, Preferably it is 2-14, More preferably, it is 11-13, More preferably, it is 12. If n5 is not less than the above lower limit, the component (D) forms an association with the component (A) incorporating the complex formed by the component (B) and the component (C), and the dishwasher warehouse It becomes easy to be absorbed inside. For this reason, the effect of inhibiting bacterial growth can be further enhanced.
If the average of n5 is below the said upper limit, the solubility to the water of (D) component will become favorable, and the liquid stability over time of the liquid dishwasher detergent will be improved.

  In the formula (d1), HY represents an organic acid or an inorganic acid, preferably hydrochloric acid, gluconic acid, or acetic acid, and more preferably hydrochloric acid.

  In formula (d1), m5 may be the same as or different from n5. Since HY partially binds to the nitrogen atom of the biguanide group to form a salt, n5 and m5 may be different.

As the component (D), a commercially available product can be used. Polyhexamethylene in which n5 of the formula (d1) is 12, HY is HCl, and an aqueous dispersion (pH 4.5) having a pure content of 20% by mass. Biguanide hydrochloride (manufactured by Arch Chemicals Japan, “Proxel IB (registered trademark)”) and the like.
These (D) components may be used individually by 1 type, and may use 2 or more types together.

  0.1-5 mass% is preferable and, as for content of (D) component in 100 mass% of washing | cleaning agents for dishwashers, 0.5-3 mass% is more preferable. If the content of the component (D) is less than the lower limit, the sterilization effect and the antibacterial effect may be reduced, and the accumulation suppression effect of microbial soil may be insufficient. On the other hand, when the content of the component (D) exceeds the upper limit, the component (D) may remain in the tableware.

  In addition, the mass ratio between the component (D) and the sum of the metal ions in the components (C) and (B) (hereinafter referred to as “(D) / ((B) + (C)) mass ratio”) Is preferably 0.1 to 10, and more preferably 1 to 6. If the (D) / ((B) + (C)) mass ratio is less than the above lower limit value, the effect of suppressing the accumulation of microbial soil may be insufficient. This is because the suppression effect may not be further improved.

<Optional component>
In addition to the components (A) to (D), the dishwasher detergent may further contain ordinary additives used for detergents for dishwashers, etc., as long as the effects of the present invention are not impaired. You may contain.
Examples of additives include hydrotropes, chelating agents (excluding component (C)), enzymes, pH adjusters, viscosity adjusters, thickeners, surface modifiers, antioxidants, ultraviolet absorbers. , Solubilizers, polymer compounds, preservatives, antibacterial agents, dispersants and the like.

(Hydrotrope agent)
Examples of the hydrotrope include monohydric alcohol having 2 to 4 carbon atoms, polyhydric alcohol having 2 to 4 carbon atoms, glycol ether, glyceryl ether having 4 to 10 carbon atoms, toluene sulfonic acid, toluene sulfonate, cumene sulfone. Acid, cumene sulfonate, benzoic acid, benzoate and the like.
Examples of the monohydric alcohol having 2 to 4 carbon atoms include ethanol, n-propanol, isopropanol, normal butanol, secondary butanol, and tertiary butanol.
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, and diethylene glycol monobutyl ether.

Among these, ethanol and propylene glycol are preferable in that they are excellent in dissolution effect and usability of the components (A) to (D) in the dishwasher detergent.
These hydrotropes may be used alone or in combination of two or more.
1-30 mass% is preferable and, as for content of the hydrotrope agent in 100 mass% of washing | cleaning agents for dishwashers, 3-15 mass% is more preferable.

(Chelating agent)
Examples of chelating agents (excluding the component (C)) include organic carboxylic acids, phosphonic acids, phosphonocarboxylic acids, phosphoric acids, and the like.
Examples of organic carboxylic acids include acetic acid, adipic acid, monochloroacetic acid, oxalic acid, succinic acid, oxydisuccinic acid, carboxymethyl succinic acid, carboxymethyloxysuccinic acid, etc., and glycolic acid, diglycolic acid, lactic acid, tartaric acid, carboxymethyl Examples thereof include hydroxycarboxylic acid substances such as tartaric acid, citric acid, malic acid and gluconic acid.
Examples of phosphonic acids include ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid and derivatives thereof, 1-hydroxyethane-1,1, Examples include 2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, and aminotrimethylenephosphonic acid.
Examples of phosphonocarboxylic acids include 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, and α-methylphosphonosuccinic acid.
Examples of the phosphoric acids include orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, metaphosphoric acid, hexametaphosphoric acid, condensed phosphoric acid such as phytic acid, and the like.

These chelating agents can be used in the acid form, and salts with basic substances such as salts with alkali metals such as potassium and sodium, salts with alkanolamines such as monoethanolamine, diethanolamine and triethanolamine. It is also possible to use in the form.
These chelating agents may be used alone or in combination of two or more.

(enzyme)
Examples of the enzyme include cellulase, α-amylase, pullulanase, lipase, hemicellulase, β-glycosidase, glucose oxidase, cholesterol oxidase, and protease.
Among these, β-glycosidase, glucose oxidase, and protease are preferable in terms of increasing detergency.
These enzymes may be used individually by 1 type, and may use 2 or more types together.

<Manufacturing method>
It does not restrict | limit especially as a manufacturing method of the washing | cleaning agent for dishwashers. For example, as a manufacturing method of the liquid dishwasher cleaning agent, it manufactures by mixing (A)-(D) component, a solvent, and an arbitrary component as needed.
As the solvent, water is preferable.

The pH (25 ° C.) of the liquid dishwasher detergent is preferably 6 or more from the viewpoint of corrosiveness to the dishwasher, and preferably 8 or less from the viewpoint of low foamability.
In this invention, pH (25 degreeC) of the washing | cleaning agent for dishwashers shows the value measured by the method based on JISZ8802: 1984 "pH measuring method".
For adjusting the pH of the dishwasher detergent, a pH adjuster such as an inorganic alkali agent or an organic alkali agent is preferably used. Examples of the inorganic alkaline agent include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like. Among them, the storage stability of the cleaning agent is easily improved. Things are preferred. Examples of the organic alkali agent include monoethanolamine, diethanolamine, triethanolamine, N-methylpropanol, 2-amino-2-methyl-1-propanol, N- (β-aminoethyl) ethanolamine, diethylenetriamine, morpholine, N- Examples thereof include amine compounds such as ethylmorpholine. Among them, monoethanolamine is preferable because the storage stability of the cleaning agent is easily improved. In addition, when pH is too high, it adjusts, for example using inorganic acids, such as hydrochloric acid and a sulfuric acid; Acids, such as carboxylic acids, such as an acetic acid and a citric acid.

As a method for producing a solid dishwasher detergent, for example, in the case of a granular 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 . This 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 (I), and let this be an average particle diameter of a sample.

<How to use>
The dishwasher cleaning agent of the present invention may be used in various amounts depending on the type of dishwasher and the degree of dirt on the dishwasher.
Examples of a method for washing an object to be washed by a dishwasher using a detergent for a dishwasher include methods having both washing and rinsing steps.
As a preferred washing method, for example, a washing liquid prepared by introducing tap water at room temperature (preferably about 5 to 30 ° C.) into the dishwasher cabinet, preferably 2 to 3 ° C./min up to 35 to 60 ° C. The step of cleaning the object to be cleaned while raising the temperature (hereinafter referred to as “cleaning step”) and the step of rinsing the object to be cleaned after washing with normal temperature tap water (hereinafter referred to as “rinsing (1) step”). Then, while raising the temperature of normal temperature tap water to preferably 50 to 80 ° C. at 2 to 3 ° C./min, further rinsing the object to be cleaned after the rinsing (1) step (hereinafter referred to as “rinsing (2) step”. And the like)).
In the washing step, it is preferable that the amount of the dishwasher cleaning agent used be 3 to 9 g with respect to about 3 L of tap water.
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.

<Effect>
According to the dishwasher cleaning agent of the present invention described above, accumulation of microbial soil can be suppressed by the interaction of the components (A) to (D).
The reason why the dishwasher detergent of the present invention is excellent in suppressing the accumulation of microbial soil is not clear, but is presumed as follows.
In the washing liquid in which the dishwasher detergent is dispersed in the washing water (in the case of the dishwasher detergent being liquid, in the liquid dishwasher detergent), the component (B) and the component (C) are complexed ( Hereinafter, it may be referred to as a “metal complex”. This metal complex inactivates microorganisms adhering to the dishwasher cabinet, suppresses the growth of microorganisms, and suppresses the accumulation of microorganism stains. As a result, odor and slime are reduced.
In addition, since this metal complex has lower water solubility than the component (B) and the component (C), the metal complex is easily incorporated into the AD aggregate. The metal complex taken into the aggregate is easily and firmly adsorbed and remains in the dishwasher cabinet as compared with the metal complex alone. The metal complex adsorbed in the dishwasher cabinet suppresses the growth of microorganisms adhering to the dishwasher cabinet and suppresses the accumulation of microbial soil.
In addition, around the component (B) of the metal complex adsorbed in the dishwasher cabinet, the ligand (C) component and the water coordinated with the component (B) are replaced with other substances. It is thought that it is in the state where it is easy to be done. For this reason, in the metal complex adsorbed in the dishwasher cabinet, an odor that tends to be positively charged is substituted with the component (B) and combined with the component (C) in the metal complex, and an odor that tends to be negatively charged is present. It is considered that it is substituted with water or the component (C) to bind to the component (B) in the metal complex. Thus, it is estimated that a metal complex captures an odor component well.
Furthermore, the effect that the odor component is captured by the metal complex is continuously exhibited. Therefore, the growth of bacteria and the generation of odor can be suppressed for a long time.

  In particular, if the component (A) is a low-foaming surfactant, a dishwasher detergent excellent in low-foaming properties can be obtained. Among them, in particular, when the component (A) includes the components (A1) and (A2) described above, the detergency against oil stains is also increased.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated in detail, this invention is not limited by the following description. In addition, the compounding quantity of the component used in each example is a pure conversion value unless there is particular notice.

"Raw material"
As the component (A), the following compounds were used. The following (A1-1) to (A1-2) correspond to the (A1) component, and (A2-1) to (A2-3) correspond to the (A2) component.
-(A1-1): C18 dimethylaminopropylamide (manufactured by Toho Chemical Co., Ltd., “Catinal MPAS”), a molecule in which R ³¹ in the general formula (a1) is a linear alkyl group having 15 carbon atoms ( A mixture of C16: C18 = 3: 7 in terms of mass ratio between C16) and a molecule (C18) in which R ^{31 is} a linear alkyl group having 17 carbon atoms. R ³² = hydrogen atom, R ³³ = propylene group ((CH ₂ ) ₃ ), R ³⁴ = methyl group, R ³⁵ = methyl group)
(A1-2): C14 dimethylaminopropylamide (R ³¹ in the general formula (a1) = linear alkyl group having 13 carbon atoms, R ³² = hydrogen atom, R ³³ = propylene group ((CH ₂ ) ₃ ), R ³⁴ = methyl group, R ³⁵ = methyl group)
(A2-1): Secondary Alkanesulfonate Sodium (SAS) having 14 to 17 carbon atoms (manufactured by Clariant Japan Co., Ltd., “HOSTAPUR SAS30A”)
-(A2-2): C10-14 alkylbenzene sulfonate sodium (Taika Co., Ltd., "Taika Power L121") neutralized with sodium hydroxide.
(A2-3): Sodium polyoxyethylene alkyl ether sulfate (AES) (average ethylene repeating number: 1, carbon number of alkyl group (linear): 12, 14)
(A3-1): Polyoxyethylene polyoxypropylene alkyl ether (manufactured by Lion Corporation, “NNAEP-3030”, average number of ethylene repeats: 3, average number of propylene repeats: 3, alkyl group (linear) Carbon number: 12, 13, average value of bubble height: 3 mm)

Synthesis method of (A1-2):
In a 3 L four-necked flask, 907.0 g (3.97 mol) of methyl myristate (molecular weight 228.4) and 121.6 g (1.19 mol) of dimethylaminopropylamine (DMAPA, molecular weight 102.2) were placed. After charging and substituting the inside of the reaction vessel with nitrogen twice under reduced pressure, the temperature was raised to 185 ° C. After aging for 1.5 hours at the start of the reaction when reaching 180 ° C., 405.7 g (3.97 mol) of DMAPA (molecular weight 102.2) was added dropwise over 4 hours. After completion of the dropwise addition, aging was performed for 7 hours, and then the temperature was raised to 195 ° C., and excess DMAPA was removed under reduced pressure (treatment for 1 hr after reaching 2.4 kPa), whereby myristic acid (C14) dimethylaminopropylamide (A1- 2) 1183 g was obtained.

Synthesis method of (A2-3):
A 4L autoclave was charged with 400 g of P & G brand name CO1270 alcohol (C12 / C14 = 75% / 25%, mass ratio) as raw material alcohol and 0.8 g of a potassium hydroxide catalyst as a reaction catalyst, and nitrogen was added to the autoclave. The temperature was raised with stirring. Subsequently, while maintaining the temperature at 180 ° C. and the pressure at 0.3 MPa or less, 91 g of ethylene oxide was introduced and reacted to obtain polyoxyethylene alkyl ether. The obtained polyoxyethylene alkyl ether had an average ethylene oxide addition mole number of 1.
Next, 237 g of the obtained polyoxyethylene alkyl ether was placed in a 500 mL flask equipped with a stirrer, and after nitrogen substitution, 96 g of liquid sulfuric anhydride (sulfan) was slowly added dropwise while maintaining the reaction temperature at 40 ° C. After completion of dropping, stirring was continued for 1 hour (sulfation reaction) to obtain polyoxyethylene alkyl ether sulfuric acid. Next, this was neutralized with an aqueous sodium hydroxide solution to obtain sodium polyoxyethylene alkyl ether sulfate (A2-3).

As the component (B), the following compounds were used.
-(B-1): Zinc sulfate heptahydrate (manufactured by Kanto Chemical Co., Inc.)
-(B-2): Copper sulfate pentahydrate (manufactured by Kanto Chemical Co., Inc.)
-(B-3): Manganese sulfate monohydrate (manufactured by Kanto Chemical Co., Inc.)

As the component (C) and the substitute for the component (C) (component (C ′)), the following compounds were used.
(C-1): trisodium methylglycine diacetate (MGDA) (manufactured by BASF, “Trilon M Compactate”)
(C-2): Trisodium nitrilotriacetate (NTA) (manufactured by BASF, “Trilon A92R”)
-(C'-1): Sodium polyacrylate (manufactured by BASF, "Sokalan PA80S")

The following compounds were used as the component (D) and an alternative to the component (D) (component (D ′)).
(D-1): Polyhexamethylene biguanide hydrochloride (manufactured by Arch Chemicals Japan, “Proxel IB”)
-(D'-1): Benzalkonium chloride (manufactured by Kanto Chemical Co., Inc.)

The following compounds were used as optional components.
-Na citrate (chelating agent): manufactured by Showa Chemical Company, "Trisodium citrate dihydrate"
Protease (enzyme): “Sabinase Ultra 16XL” manufactured by Novozymes Japan K.K.
・ Propylene glycol (hydrotrope): ADEKA Corporation, “Propylene glycol for cosmetics”
・ P-TS (hydrotrope agent): “Paratoluenesulfonic acid” manufactured by Kyowa Hakko Chemical Co., Ltd.
・ Ethanol (hydrotrope agent): manufactured by Kanto Chemical Co., Ltd. ・ Water: distilled water

"Example 1"
<Preparation of dishwasher detergent>
1000 g of the dishwasher detergent having the composition shown in Table 1 was prepared by the following procedure.
The component (A2), ethanol, and propylene glycol were placed in a 1 L beaker, and the mixture was sufficiently stirred with a magnetic stirrer (Fine, “F-606N”). Subsequently, (A1) component, (B) component, (C) component, (D) component and optional components are added, and after mixing is completed, the pH at 25 ° C. is required to be 7. Then, after adding an appropriate amount of a pH adjuster (sodium hydroxide, sulfuric acid), distilled water was added so that the total amount became 100% by mass, and the mixture was further stirred to obtain a liquid dishwasher detergent.
The pH of the dishwasher detergent (25 ° C.) is adjusted to 25 ° C. using a glass electrode pH meter (“HM-30G” manufactured by Toa DKK Corporation). It was immersed directly in a dishwasher detergent and the pH indicated after 1 minute was measured. The measuring method was performed according to JIS Z 8802: 1984 “pH measuring method”.

The obtained dishwasher detergent was evaluated as follows. The results are shown in Table 1.
In addition, the unit of the compounding quantity in Table 1 is mass%, and shows the pure amount conversion amount. Further, the balance amount of water is water whose blending amount is adjusted so that the total amount (overall amount) of the dishwasher detergent as the final product is 100% by mass.

<Evaluation of dishwasher detergent>
An automatic dishwasher (manufactured by Panasonic Corporation, “NP-40SX2”) was used as the dishwasher. In each evaluation, the washing process was performed by operating in a standard course (power saving mode or normal mode) set in the automatic dishwasher. In the power saving mode, the water temperature in the cleaning process is set to be 15 ° C. lower than that in the normal mode. The contents of the standard course (power saving mode) are shown below.

Standard course (power saving mode):
After putting 6 g of dishwasher detergent (relative to 3 L of tap water) into the automatic dishwasher, a cleaning solution prepared by introducing tap water of about 5 ° C. into the cabinet is kept at 2-3 ° C./40° C. Washing is performed for 20 minutes while raising the temperature at min, and the washing solution is drained. Next, new tap water is introduced, and rinsing (2 minutes / times) and draining are repeated three times. After draining, tap water is introduced and rinsed once (final rinse) for 20 minutes while raising the temperature to 70 ° C at 2-3 ° C / min. After draining, the dishes are dried while circulating hot air. To do.
The standard course (normal mode) is the same as the standard course (power saving mode). The standard course (power saving mode) is the same as the standard course (power saving mode). It is the same.

(Evaluation of cleaning power)
As oil stains, mixed oil of beef tallow / lard / butter / salad oil = 3/3/3/1 (mass ratio) and retort curry (bon curry gold 21 dry) were used.
A polypropylene lunch box (110 mm long, 170 mm wide, 35 mm high) contaminated by adhering 3 g of the mixed oil and 6 g of the retort curry was loaded into the automatic dishwasher and 6 g of dishwasher detergent. Was put into the standard course (power saving mode) and washed.
After the cleaning treatment, the finish of the polypropylene lunch box was observed, and the cleaning power against oil stains was evaluated based on the following evaluation criteria. ◎ and ○ were accepted.
(Evaluation criteria)
A: Oil stains are removed and there is no null.
○: Oil stains cannot be visually confirmed, but there are some nulls.
(Triangle | delta): Oil stains can be confirmed visually.
X: Oil stains remain sticky.

(Evaluation of low foam properties)
6 g of dishwasher detergent was put into the automatic dishwasher, and operation was performed on the standard course (normal mode) using 5 ° C. water.
The operation was stopped 1 minute after the start of washing, and the door was opened at the same time. After 15 seconds, the foaming condition in the cabinet was visually confirmed, and the low foaming property was evaluated based on the following evaluation criteria. ◎ and ○ were accepted.
(Evaluation criteria)
A: Less than 40% of the bottom of the automatic dishwasher is occupied by foam.
○: 40% or more and less than 80% of the bottom surface of the automatic dishwasher is occupied by foam.
Δ: 80% or more of the bottom surface of the automatic dishwasher is occupied by foam.
×: Air biting occurred and stopped abnormally.

(Evaluation of accumulation suppression of microbial dirt 1)
Prior to the evaluation, the propeller part of the automatic dishwasher was removed, the inside of the cabinet was washed with a chlorinated mold remover, and it was visually confirmed that there was no microbial contamination. Then, the propeller part was attached.
In accordance with the Better Living Association accredited standard performance test method (enforced on November 6, 1995: dishwasher), tomatoes for tableware such as chopsticks, glass cups, hot drinks, dishes (large, medium, small), soup bowls, etc. Dirt tableware was prepared by adhering juice, milk, miso soup, green tea, cooked rice, raw eggs, curry, commercial tonkatsu sauce, ham egg, and the like.
Next, the soiled dishes were stored in an automatic dishwasher after washing with a chlorinated mold remover, 6 g of dishwasher detergent was added, and washing was performed in a standard course (power saving mode).
This operation (preparation of dirt tableware, washing treatment) was repeated three times a day (running at an interval of 1 hour or more between 8:30 am and 5 pm) for 5 days.
After the washing process is completed, the automatic dishwasher is left in the room (approximately 20 ° C) for 3 days, then the propeller is removed and the inside of the cabinet is visually observed. Evaluated. ◎◎, ◎, ○ were accepted.
(Evaluation criteria)
◎◎: No microbial contamination is observed, and there is no null.
A: When carefully observed, microbial stains were observed only slightly, but no stain was observed on the soiled portions.
○: Slight microbial contamination was observed, but no stain was observed on the soiled portion.
(Triangle | delta): Microorganism stain | pollution | contamination was recognized and a slight null was recognized by the dirt part.
X: Microbial stain was clearly recognized, and a null was observed on the soiled portion.

(Evaluation of microbial dirt accumulation suppression 2)
Cleaning treatment was performed in the same manner as in Evaluation 1 for suppressing accumulation of microbial soil.
After the washing process is completed, leave the automatic dishwasher in the room (about 20 ° C) for 3 days, and then wipe the flow path in the cabinet with a sterilized cotton swab (Eiken Chemical Co., Ltd., “Wipe Wipe Check II”). Wipe area: 100 cm ² (10 cm × 10 cm)), bacteria were extracted. A 10-fold dilution series dilution was prepared using this bacterial extract.
1.0 mL of each diluted solution was dispensed into a sterile petri dish, and 15 to 20 mL of SCD agar medium at 45 to 48 ° C. was added and stirred well. The petri dish was covered and allowed to stand at room temperature. After the medium had hardened, the petri dish was inverted and cultured at a temperature of 37 ± 1 ° C. for 40 to 48 hours. After culturing, the number of colonies in the petri dish of dilution series in which 30 to 300 colonies appeared was measured, and the number of viable bacteria (N) was determined from the following formula (II).
Viable count (cfu / test piece) = number of colonies × 10 ^M × 10 (II)
In the formula (II), “M” is the number of dilutions of the dilution series diluted solution dispensed to the adopted petri dish.

Separately, a sterilized 0.05 mass / volume% (w / v%) Tween 80 aqueous solution (manufactured by Kanto Chemical Co., Ltd., “Polysorbate 80”) is used as the target cleaning agent, and the same as Evaluation 1 for suppressing accumulation of microorganism stain Washing was performed, bacteria were extracted to prepare a 10-fold dilution series dilution, the number of colonies was measured, and the number of viable bacteria (N) was determined.
The activity value is calculated from the following formula (III) from the viable count when treated with the dishwasher detergent and the viable count when treated with the target detergent, and based on the following evaluation criteria: The accumulation suppression of microbial soil was evaluated. ◎◎, ◎, ○ were accepted.
Activity value = log ₁₀ N (viable cell count when treated with target detergent) -log ₁₀ N (viable cell count when treated with detergent for dishwasher) (III)
(Evaluation criteria)
A: Activity value is 4 or more.
A: Activity value is 3 or more and less than 4.
○: The activity value is 2 or more and less than 3.
Δ: Activity value is 1 or more and less than 2.
X: Activity value is less than 1.

"Examples 2 to 24, Comparative Examples 1 to 6"
Except having changed the compounding quantity of each component as shown to Tables 1-4, the washing | cleaning agent for dishwashers of each example was prepared like Example 1, and various measurement and evaluation were performed. The results are shown in Tables 1-4.
In Example 20, (A3-1), ethanol and propylene glycol were mixed first, then the remaining components were added and further mixed, and then the pH was adjusted.

As is apparent from Tables 1 to 3, the dishwasher detergent obtained in each example had low foaming properties and could suppress the accumulation of microbial soil.
In particular, the detergents for dishwashers of Examples 1 to 19 and 21 to 24 using the components (A1) and (A2) as the component (A) were excellent in cleaning power against oil stains.

On the other hand, none of the detergents for dishwashers of Comparative Examples 1 to 4 that did not contain any of the components (A) to (D) could suppress the accumulation of microbial soil. In particular, the dishwasher detergent of Comparative Example 1 containing no component (A) was inferior in detergency.
(C) Dishwasher cleaning agent of Comparative Example 5 using sodium polyacrylate instead of component, (D) Dishwasher cleaning agent of Comparative Example 6 using benzalkonium chloride instead of component, Even the accumulation of microbial soil could not be suppressed.

Claims (2)

Surfactant (A),
At least one selected from copper, manganese, nickel, cobalt, iron and zinc (B);
An aminocarboxylic acid type sequestering agent (C) that forms a complex with the component (B);
A detergent for dishwashers comprising a biguanide polymer (D). The detergent for dishwashers of Claim 1 in which the said surfactant (A) contains the alkylamidoamine (A1) represented by the following general formula (a1), and an anionic surfactant (A2).

(In formula (a1), R ³¹ represents an alkyl group or alkenyl group having 13 to 21 carbon atoms, R ³² represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group, and R ³³ represents carbon number. Represents an alkylene group having 1 to 4 and R ³⁴ and R ³⁵ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)