JPH1143690A - Detergent composition for automatic dishwasher - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a detergent without a phosphate which provides an excellent cleaning capability by blending a surfactant, an amino polycarboxylic acid type org. builder and an enzyme in a specific ratio. SOLUTION: A surfactant in an amt. of 0.5 to 15 wt.%, 1 to 50 wt.% of an amino polycarboxylic acid type org. builder represented by formula I [wherein R is -(CH2 )n -B (B is OH or COOH; and n is 0-3); A is H or OH; and M is H, Na, K or NH4 ) and an enzyme are blended. As an amino polycarboxylic acid type org. builder, comps. having formulae II, III, IV or V can be combined for use. As an enzyme enumerated are an amylase, a protease, a lipase, etc. A pref. amylase is α-amylase. Further a bleaching agent, an alkaline agent and a calcium ion scavenging component except those having formulae II-V can be blended.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a detergent composition for an automatic dishwasher which does not contain a phosphate which causes eutrophication of the sea, lakes and the like and has an excellent detergency.

[0002]

2. Description of the Related Art Automatic dishwashing machines have rapidly spread and are being used not only for business purposes but also for general households. Cleaning agents suitable for machines have also been developed. Conventionally, as a detergent for automatic dishwashers, α- is used to remove starchy stains such as boiled rice and dye stains such as tea ash, which are strongly adhered to dishes.
A phosphorus-containing detergent containing a starch-degrading enzyme such as amylase and a chlorine bleach such as dichloroisocyanurate is mainly used. On the other hand, since enzymes, fragrances, dyes, and the like are unstable with respect to chlorine bleach, phosphorus-containing detergents using oxygen bleach instead of chlorine bleach have also been provided (JP-A-60-1985). No. 60198).

[0003] However, at present, the mainstream of detergents is phosphorus-free detergents, and it is not preferable to use phosphate-containing detergents that cause eutrophication in terms of environmental problems. Therefore, with the spread of automatic dishwashers, there is a strong demand for a technique for eliminating the use of a detergent used in the dishwasher without reducing the detergency against various stains.

Accordingly, an object of the present invention is to provide a detergent composition for an automatic dishwasher which does not contain a phosphate and has an excellent detergency.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve such an object, and as a result, by combining an enzyme and a specific aminopolycarboxylic acid type organic builder, the same cleaning as a phosphorus-based detergent has been achieved. The present inventors have found that the enzyme has high performance and that the stability of the enzyme is higher than that of a phosphorus-based detergent, and thus completed the present invention.

That is, the present invention relates to (a) a surfactant of 0.5 to 0.5;
15% by weight, (b) the following general formula (I):

[0007]

Embedded image

Wherein R is-(CH ₂ ) _n -B (where
B represents OH or COOH, and n represents a number of 0 to 3)
A represents H or OH, and M represents H, Na, K or NH ₄ ], wherein 1 to 50% by weight of an aminopolycarboxylic acid type organic builder represented by An object of the present invention is to provide a cleaning composition for an automatic dishwasher.

[0009]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS As the surfactant of the component (a) used in the present invention, general surfactants can be widely used, but in the present invention, nonionic surfactants are preferable. The nonionic surfactant is not particularly limited, but includes polyoxyethylene alkyl or alkenyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxypropylene alkyl or alkenyl ethers, polyoxybutylene alkyl or alkenyl ethers, alkylene oxide Addition alkyl or alkenyl group-containing nonionic surfactant mixture, sucrose fatty acid esters, aliphatic alkanolamides, fatty acid glycerin monoesters, amine oxides, ethylene oxide condensed surfactants and alkyl glycosides One or more selected ones are preferable. More specifically, such nonionic surfactants are described in the following (1) to (1).
(11) can be mentioned.

(1) Polyoxyethylene alkyl or alkenyl ethers having an alkyl group or alkenyl group having an average carbon number of 10 to 20 and an ethylene oxide addition mole number of 1 to 30 mole on average.

(2) Polyoxyethylene alkyl phenyl ethers, wherein the average carbon number of the alkyl group is 6 to
12, and the number of moles of ethylene oxide added is 1 on average.
~ 25 mol.

(3) Polyoxypropylene alkyl or alkenyl ethers having an alkyl group or alkenyl group having an average carbon number of 10 to 20 and a propylene oxide addition mole number of 1 to 20 mole on average.

(4) Polyoxybutylene alkyl or alkenyl ethers having an alkyl group or alkenyl group having an average carbon number of 10 to 20 and an average number of moles of butylene oxide added of 1 to 20 mol.

(5) Having an alkyl group or an alkenyl group, ethylene oxide and propylene oxide (molar ratio: 0.1 / 9.9 to 9.9 / 0.1) or ethylene oxide and butylene oxide (molar ratio: 0.1 / 9.9 to 9.9)
/0.1), wherein the average number of carbon atoms of the alkyl group or alkenyl group is 10 to 20, and the number of moles of alkylene oxide added per molecule is 1 to 30 on average. What is a mole.

(6) Higher fatty acid alkanolamides represented by the following general formula (II) or alkylene oxide adducts thereof.

[0016]

Embedded image

Wherein R ³ represents an alkyl or alkenyl group having 10 to 20 carbon atoms, R ⁴ and R ⁵ represent the same or different H or CH ₃ , p represents a number of 1 to 3, and q represents 0 to 3].

(7) Sucrose fatty acid esters whose fatty acid moiety has an average carbon number of 10 to 20.

(8) Fatty acid glycerin monoesters having a fatty acid moiety having an average carbon number of 10 to 20.

(9) Amine oxides. Examples thereof include an alkyl or alkenylamine oxide having a linear or branched alkyl or alkenyl group having 1 to 24 carbon atoms. More preferred amine oxides include alkylamine oxides represented by the following general formula (III).

[0021]

Embedded image

[Wherein, R ⁶ represents an alkyl group or alkenyl group having 8 to 24 carbon atoms, R ⁷ and R ⁸ represent the same or different alkyl groups having 1 to 3 carbon atoms, and D represents —NHC (=
O)-or -C (= O) NH-, E represents an alkylene group having 1 to 5 carbon atoms, a and b are a = 0 and b
= 0 or a = 1 and b = 1] In the general formula (III), R ⁶ is an alkyl group or an alkenyl group having 8 to 24 carbon atoms, and particularly preferably has 12 to 24 carbon atoms.
Preferred are 18 alkyl groups. R ⁷ and R ⁸ have 1 to 3 carbon atoms
And particularly preferably a methyl group having 1 carbon atom.

(10) A nonionic surfactant having a trade name of "Pluronic" (Asahi Denka Co., Ltd.) obtained by condensing ethylene oxide and propylene oxide.

(11) Alkyl polysaccharides. For example, an alkyl polysaccharide represented by the following general formula (IV). R ⁹ (OR ¹⁰ ) _x G _y (IV) wherein R ⁹ represents a linear or branched alkyl group, alkenyl group or alkylphenyl group having 8 to 18 carbon atoms, and R ¹⁰ represents a carbon number 2 to 4 alkylene groups, G represents a residue derived from a reducing sugar having 5 to 6 carbon atoms, x
(Average value) represents 0 to 5, and y (average value) represents 1 to 5].

In the formula, x has an average value of 0 to 5,
By changing this value, the water solubility and crystallinity of the cleaning composition can be adjusted. In other words, the larger the value of x,
Water solubility tends to increase and crystallinity tends to decrease.
A preferred value of x is 0 to 2, and particularly preferably 0.

When the average value of y in the formula is greater than 1, that is, when a sugar group of two or more saccharides is used as a hydrophilic group, the binding mode of the sugar chain is 1-2, 1-3, 1-4. , 1-6 linkages, as well as any mixture having α-, β-pyranoside bonds or furanoside bonds and their mixed modes of attachment. Further, y in the general formula (IV)
Has an average value of 1 to 5, preferably 1 to 1.5, more preferably 1.1 to 1.4. The measured value of y is based on the proton NMR method.

R ⁹ in the formula is preferably an alkyl group having 10 to 14 carbon atoms from the viewpoint of solubility and detergency. R ¹⁰ is
An alkylene group having 2 to 3 carbon atoms is preferable from the viewpoint of water solubility.

The structure of G in the formula is determined by a raw material of monosaccharide or disaccharide or more. Examples of the raw material of G include glucose, fructose, galactose, xylose, mannose, lyxose, arabinose and monosaccharides. And disaccharides, maltose, xylobiose, isomaltose, cellobiose, gentibiose, lactose, sucrose, nigerose, turanose, raffinose, gentianose, melezitose, and mixtures thereof. Among these, preferred raw materials are glucose and fructose for monosaccharides, and maltose and sucrose for disaccharides or more, in view of their availability and cost. Of these, glucose is particularly preferred in terms of availability.

Further, a 1 mol adduct of pentaerythritol / isostearyl glycidyl ether, a 1 mol adduct of sorbitol / isostearyl glycidyl ether, a 1 mol adduct of mannitol / 2-octyldodecyl glycidyl ether, methyl glucoside / isostearyl glycidyl 1 mol adduct of ether, 1 mol adduct of diglycerin / isostearyl glycidyl ether,
A nonionic surfactant having at least one long-chain branched alkyl group or alkenyl group and at least three hydroxyl groups in one molecule such as phytantriol can be used.

Among these nonionic surfactants, the nonionic surfactants (1), (6), (9) and (11) are preferable, and the nonionic surfactants (9) and (11) are preferable. Particularly preferred.

The content of the surfactant in the detergent composition for an automatic dishwasher is 0.5 to 15% by weight in order to give a sufficient washing effect while taking into account the mixing of other components. Preferably it is 1.5 to 5% by weight, particularly preferably 2 to 3% by weight.

The component (b) used in the present invention has the general formula (I)
In the aminopolycarboxylic acid type organic builder represented by, H, Na or K is preferable as M (counter ion). In this case, M is partially neutralized (part of M is H
) Has the highest sequestering ability and a large effect of improving the detergency, but the completely neutralized one also shows a sufficient improvement in the detergency.

The aminopolycarboxylic acid type organic builder of the component (b) includes the following general formulas (I) -1 to (I) -4:

[0034]

Embedded image

[Wherein M represents H, Na, K or NH ₄ ] may be used alone or in combination of two or more. The amino polycarboxylic acid type organic builder of the component (b) has a Ca chelate stability constant of 6.
It is preferably 0 or more.

The content of the component (b) in the detergent composition for an automatic dishwasher can be determined without impairing the activity of the enzyme.
In order to provide sufficient detergency, it is 1 to 50% by weight,
It is preferably from 10 to 30% by weight, particularly preferably 1 to 30% by weight.
0 to 20% by weight.

As the enzyme of the component (c) used in the present invention, amylase, protease or lipase can be exemplified.

As the amylase, those generally used as detergent enzymes can be used. Preferred examples of the amylase include Bacillus licheniformis and Bacillus
Examples thereof include α-amylase obtained from Subtilis, and specifically, Termamyl (registered trademark) sold by Novo Industry and Maxamyl (registered trademark) sold by Gist. And the like.

When using amylase as the enzyme,
The amount of amylase used per 1 g of the detergent composition is 0.05 in order to give sufficient washing effect to starch stains within a usual washing time while considering economy.
It is preferably from 500 to 500 units, and particularly preferably from 100 to 500 units. One unit of amylase is a value determined by measurement under the following conditions.

0.9 ml of a substrate solution in which soluble starch is dissolved in various buffers (final concentration in the reaction system is 0.5%)
0.1 ml of the enzyme solution is added thereto, and the mixture is reacted at 50 ° C. for 15 minutes. After the reaction, the reducing sugar is quantified by the DNS method. That is, 1.0 ml of the DNS reagent is added to 1.0 ml of the reaction solution, and the mixture is heated and colored at 100 ° C. for 5 minutes. The enzyme titer is defined as 1 unit (IU) of the amount of the enzyme produced in the reducing sugar corresponding to 1 μmol of glucose per minute.

As the protease, those generally used as detergent enzymes can be used. Suitable proteases include Bacillus licheniformis and
Subtilisins obtained from Bacillus Subtilis can be mentioned, for example, Maxatase (registered trademark) sold by Gist, Alcalase (registered trademark) sold by Novo Industries, and Esperase (registered trademark). ), Savinase (registered trademark) and the like.

When a protease is used as the enzyme, the amount of the protease used per 1 kg of the detergent composition is not limited in consideration of economy, and in order to provide a sufficient washing effect on protein stains within a usual washing time. It is preferably from 0.05 to 100 Anson units, and particularly preferably from 1 to 60 Anson units.

The quantification of protease activity is carried out by a modified Anson-hemoglobin method, ie, by denaturing denatured hemoglobin with a protease under standard conditions. Undegraded hemoglobin is precipitated with trichloroacetic acid and the amount of trichloroacetic acid soluble product is colorimetrically determined at 750 nm with a Folin Thiocarteau phenol reagent. One anson unit (AU) refers to a trichloroacetic acid-soluble component in which the initial rate of hemoglobin hydrolysis under standard conditions per minute equals 1 m equivalent of tyrosine shows the same color degree as that of a phenol reagent. [MLAnson, Journal of General Physiology, 2
2 (1939), P79-89].

When lipase is used as the enzyme, the amount of the protease per 1 kg of the detergent composition is not limited to 10,000 to 1,1,0 because the economical efficiency is taken into consideration and the sufficient washing effect on fat stains is imparted. Preferably, it is in the form of 1,000,000 lipase units (LU).

One unit (1 LU) of lipase activity refers to an enzyme activity that releases 1 μM fatty acid per minute from olive oil used as a substrate. The details are as follows. First, 4 ml of an olive oil emulsion and 4 ml of a 0.1 M phosphate buffer (pH 7.0) are accurately placed in a 50-ml Erlenmeyer flask with a stopper, mixed well, and placed in a 37 ° C water bath.
Preheat for 0 minutes. 1 ml of the sample solution is accurately added thereto, mixed well, and after exactly 20 minutes, an acetone / ethanol mixed solution is added. Thereafter, titration is performed with a 0.05N sodium hydroxide reagent using 5 drops of the phenolphthalein solution as an indicator. Separately, 5 ml of olive oil emulsion and 4 ml of 0.1 M phosphate buffer (pH 7.0) are accurately placed in a 50 ml Erlenmeyer flask with a stopper, heated at 37 ° C. for 30 minutes, and then poured with 20 ml of an acetone / ethanol mixture. Next, 1 ml of the sample solution is accurately added, and titrated with a 0.05N sodium hydroxide reagent using 5 drops of a phenolphthalein solution as an indicator to obtain a control solution. The lipase activity is determined from the following equation.

[0046]

(Equation 1)

In the present invention, in addition to the above enzymes, bacteria of the genus Klebsiella, bacteria of the genus Bacillus, Aspergillus
s genus, pullulanase exhibiting amylopectin-6-glucanohydrase activity obtained from Pseudomonas genus fungi, etc.
Starch branching enzymes such as isopululase and isoamylase can be used.

The detergent composition for an automatic dishwasher according to the present invention further comprises a bleaching agent, an alkali agent or calcium other than those represented by the general formulas (I) and (I) -1 to (I) -4. An ion-trapping component can be included.

Examples of the bleaching agent include an enzyme bleaching agent. Examples of the oxygen-based bleaching agent include organic hydrochloric acid such as magnesium monoperoxyphthalate or a salt thereof, alkali metal perborate (monohydrate or tetrahydrate), percarbonate and persilicate. A peroxide that generates hydrogen peroxide in an aqueous solution can be used. Among these hydrogen peroxide adducts, preferred are sodium perborate and sodium percarbonate. A peroxide that generates hydrogen peroxide in an aqueous solution is preferably used in combination with an activator. Examples of the activator include tetraacetylethylenediamine (TAED), tetraacetylglycoluril (TAGU), glucose pentaacetic acid (GPA), and xylosetetraacetic acid (XTA). The peroxide / activator is 8/1 to 1 by weight.
It can be used in the range of 1/1.

The content of the bleaching agent in the detergent composition for an automatic dishwashing machine is preferably 0.1 to provide a sufficient bleaching effect without inhibiting other components such as enzymes.
-20% by weight, particularly preferably 1-10% by weight.

Examples of the alkaline agent include sodium hydrogen carbonate, sodium carbonate, borax, sodium silicate and the like. Since sodium silicate has a metal corrosion inhibiting action, it is desirable to use it in combination with another alkali agent. In particular, sodium bicarbonate and sodium silicate (SiO ₂ / NaO ratio is 1/1 to 4/1, preferably 2/1 to 1
2.5 / 1) in a weight ratio 35 / 1-2 / 1 or sodium and sodium silicate carbonate (SiO ₂ / Na ₂ O ratio of 1 / 1-4 / 1,
Preferably 2/1 to 2.5 / 1) is 35/1 to 2/1 by weight.
It is preferable to use together.

The content of the alkaline agent in the detergent composition for automatic dishwashers is preferably 0.1 to 30% by weight.
In this range, the blending amount is adjusted such that the pH of the detergent solution having a concentration of 0.05 to 1% by weight becomes 9.0 to 11.0.

Examples of the calcium ion scavenger include oxalic acid, malonic acid, succinic acid, citric acid, malic acid, glutaric acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, tripolyphosphoric acid, hexametaphosphoric acid, aminotri (methylenesulfonic acid), One or more selected from -hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), polyacrylic acid and a polymer of acrylic acid and maleic acid, or an alkali metal salt thereof or ethylenediaminetetraacetic acid Alkaline earth metal salts and the like can be mentioned.

The content of the calcium ion scavenger in the detergent composition for an automatic dishwasher is preferably 0.1 to 20 in order to maintain necessary enzyme activity and impart a sufficient calcium ion scavenging effect. %, Particularly preferably 1 to 10% by weight.

The detergent composition for an automatic dishwasher of the present invention may further contain an oxygen bleach stabilizer, a copper corrosion inhibitor and the like. Examples of the stabilizer include ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) and water-soluble salts thereof, and complexes thereof with calcium, magnesium, aluminum or zinc. These can be added as they are. However, it is particularly preferable to use a calcium complex. As a copper corrosion inhibitor, a hydrocarbon chain length of about 8 to
Adding 0.1 to 5% by weight of a fatty acid having 18;
Furthermore, benzotriazole etc. can be mentioned.

The detergent composition for automatic dishwashers of the present invention can generally be in the form of a dry, granular product. This can be produced by dry mixing the powdery or granular components and then spraying a liquid component (such as a non-ionic surfactant) onto the mixture according to conventional manufacturing techniques. In addition, the detergent composition for automatic dishwashers of the present invention,
As described above, by using a surfactant as an essential component without using a strong alkali, it has sufficient detergency, and is mainly used for automatic dishwashers for home use where it is difficult to use a strong alkali. It becomes suitable for it.

[0057]

Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the following examples, “%” represents “% by weight”.

Synthesis Example 1 A reaction vessel was charged with 314.0 g of L-aspartic acid, 350.0 g of a 40% aqueous sodium hydroxide solution and 200.0 g of water, and the temperature was raised to 90 ° C. Prussic acid 11 in the reaction mixture
0.8 g, 405.4 g of 30% formalin and 450.0 g of a 40% aqueous sodium hydroxide solution were added, and the mixture was stirred at 105 ° C. for 2 hours. After completion of the reaction, 10% formalin 30.
0 g was added to decompose the remaining hydrocyanic acid, and 1000.0 g of a 40% aqueous sulfuric acid solution was added for acid precipitation, and the precipitated crystals were separated by filtration to obtain 441.8 g of crude crystals of N, N-bis (carboxymethyl) glutamic acid. I got The crude crystals were recrystallized from water-methanol to obtain 411.9 g of purified N, N-bis (carboxymethyl) glutamic acid (yield 75.5).
%). This is neutralized with 40% sodium hydroxide, and the formula
The sodium salt of the compound represented by (I) -1 was obtained.

Synthesis Example 2 The procedure of Synthesis Example 1 was repeated, except that 2-amino-3-hydroxybutanedioic acid was used instead of L-aspartic acid.
The sodium salt of the compound represented by (I) -2 was obtained.

Synthesis Example 3 A sodium salt of the compound represented by the formula (I) -3 was obtained in the same manner as in Synthesis Example 1 except that serine was used instead of L-aspartic acid.

Synthesis Example 4 A sodium salt of the compound represented by the formula (I) -4 was obtained in the same manner as in Synthesis Example 1 except that glutamic acid was used instead of L-aspartic acid.

Examples 1 to 6 and Comparative Examples 1 to 5 The compositions shown in Table 1 below were prepared and subjected to a detergency test under the following conditions. In Table 1, "Pluronic L"
"92" is a nonionic surfactant manufactured by Asahi Denka Co., Ltd. Table 1 shows the results.

<Washing Conditions> Washing machine used: Matsushita Electric Co., Ltd. fully automatic dishwasher (model
NP-600) A type in which a cleaning composition aqueous solution is sprayed from a rotary nozzle, and the dishes set on the upper surface of the spray track are washed. Washing temperature; temperature gradually rises from 5 ° C to 55 ° C Washing water; hardness 3.5% DH water Detergent concentration; 0.2% Washing time; washing 20 minutes-rinsing 20 minutes Circulating water volume during washing; about 2.5 liters.

<< Evaluation of Detergency >> [Measurement Method of Rice Dirt Detergency] (Preparation of Contaminated Dish) Soft cooked rice was left at room temperature for 30 minutes, and 3 g was spread on a porcelain dish having a diameter of 25 cm and applied. Then, six air-dried one day and night at room temperature were subjected to washing. (Evaluation method for cleaning power of rice soil) The area of the blue portion generated by the color reaction of iodine (P)
Was measured by photographic judgment, and the washing rate of each dish was determined from the initial contaminated area (S) by the following equation. Further, the washing rates of the six dishes were averaged to obtain an average washing rate. Washing rate of one dish (%) = [(SP) / S] × 100 Average washing rate (%) = sum of washing rates of each dish / 6 [Composite soil washing power measurement method] (Preparation of contaminated dishes) ) White sauce (Heinz canned) 100g in margarine (Yukizai Neosoft)
10 g was added, and the mixture was heated to 60 ° C. and mixed well to obtain a composite soil. 5 g of the above-described composite soil is applied per porcelain dish having a diameter of 25 cm and baked at 120 ° C. for 15 minutes.
This was left for one day and then washed. (Washing Test and Detergency Evaluation Method) Five contaminated dishes were placed in a washing machine and washed under the above washing conditions. The washed dishes were judged one by one according to the following criteria, and the washing evaluation points were calculated by the following equation. Thoroughly washed. 5 points There is a slight residue of dirt, but within the allowable range. 4 points A small amount of dirt remains. 3 points Stain remains on about 1/4 of the dish. 2 points Approximately の of the dish has residual stains. 1 point Not washed at all. 0 points Cleaning evaluation point = [sum of evaluation points of each contaminated dish] x 4

[0065]

[Table 1]

[0066]

The detergent composition for automatic dishwashers according to the present invention is excellent in preventing ordinary dish stains despite the absence of phosphate due to the action of the aminopolycarboxylic acid type organic builder. Has detergency. Further, in the detergent composition for an automatic dishwasher of the present invention, since the stability of the enzyme is high, the ability to sufficiently exhibit the resolution for the dirt component also contributes to the improvement of the detergency.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C11D 3/395 C11D 3/395

Claims (7)

[Claims] (1) 0.5 to 15% by weight of a surfactant,
(B) the following general formula (I): [Wherein, R represents-(CH ₂ ) _n -B (where B represents OH or COOH, n represents a number from 0 to 3), A represents H or OH, and M represents H , Na, K or NH ₄ ]
Aminopolycarboxylic acid type organic builders 1 to 5
A detergent composition for an automatic dishwasher, comprising 0% by weight and (c) an enzyme. 2. The aminopolycarboxylic acid type organic builder of the component (b) is represented by the following general formulas (I) -1 to (I) -4.
The detergent composition for an automatic dishwasher according to claim 1, comprising at least one compound. Embedded image [Wherein, M represents H, Na, K or NH ₄ ] 3. The detergent composition for an automatic dishwasher according to claim 1, wherein the enzyme is amylase, protease or lipase. 4. The detergent composition for an automatic dishwasher according to claim 3, wherein the amylase is α-amylase. 5. The cleaning composition according to claim 1, further comprising 0.1 to 20% by weight of a bleaching agent. 6. The method further comprises 0.1 to 30% by weight of an alkali agent.
The detergent composition for an automatic dishwasher according to any one of claims 1 to 4, which contains the detergent composition. 7. A calcium ion-trapping component other than those represented by the general formulas (I) and (I) -1 to (I) -4 of 0.1 to 2
The cleaning composition for an automatic dishwasher according to any one of claims 1 to 4, which contains 0% by weight.