JPH1046193A - Cleaning agents for automatic dishwashers - Google Patents

Abstract

(57) [Problem] To provide a detergent for an automatic dishwasher, which is free of phosphorus without deteriorating the detergency of various stains. (A) A specific aspartic acid derivative or a specific alkylglycine-N, N-diacetic acid or a salt thereof 1
A detergent for an automatic dishwasher, which comprises: 50 to 50% by weight and (b) 1 to 50% by weight of a surfactant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a phosphate-free detergent for automatic dishwashers.

[0002]

2. Description of the Related Art In recent years,
Automatic dishwashers have rapidly become widespread and have been widely used not only for business purposes but also for ordinary households.

[0003] In order to remove starchy stains such as cooked rice and dye stains such as tea ash etc., which are strongly adhered to dishes, α-amylase has been conventionally used as a detergent for automatic dishwashers. Phosphorus detergents containing starch-degrading enzymes such as chlorinated bleach such as dichloroisocyanurate have been mainly used. On the other hand, enzymes, fragrances, dyes, and the like are unstable with respect to chlorine bleaching agents, so that phosphorus-containing detergents using oxygen bleaching agents instead of chlorine bleaching agents have been provided (Japanese Patent Laid-Open Publication No. H11-163873). No. 60-60198).

[0004] However, at present, phosphorus-free detergents are the mainstream of many detergents, and phosphate-containing detergents can become a social problem from the viewpoint of environmental problems. Therefore, with the spread of automatic dishwashers, there has been a strong demand for a technology for eliminating phosphorus without reducing the cleaning power for various stains.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in order to respond to such a demand, and have found that a specific aspartic acid derivative or alkylglycine-N,
It has been found that the use of N-diacetic acid or a salt thereof has a performance equivalent to that of a phosphorus-containing detergent, and that the enzyme has better stability than a phosphorus-containing detergent, and thus completed the present invention.

That is, the present invention provides: (a) the following general formula (1)
Or 1 to 50% by weight of an alkylglycine-N, N-diacetic acid or a salt thereof represented by the following general formula (2), and (b) 1 to 50% by weight of a surfactant
The present invention provides a detergent for an automatic dishwasher, comprising:

[0007]

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(Wherein, M ^{1 to} M ⁴ represent hydrogen, an alkali metal, an alkaline earth metal, ammonium, alkylammonium or substituted alkylammonium, and R ¹ represents hydrogen or a hydroxyl group.)

[0009]

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Wherein M ^{5 to} M ⁷ represent hydrogen, an alkali metal, an alkaline earth metal, ammonium, an alkyl ammonium or a substituted alkyl ammonium, and R ² has 1 carbon atom.
~ 18 alkyl groups or alkenyl groups. )

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION As the component (a) in the present invention, an aspartic acid derivative represented by the above general formula (1) or an alkylglycine derivative represented by the above general formula (2) is used.
In N, N-diacetic acid or a salt thereof, hydrogen, sodium and potassium are generally used as M ^{1 to} M ⁷ (counter ions) in the general formulas (1) and (2). Here, the partially neutralized one has the highest sequestering ability of metal ions and has a high effect of improving the detergency, but the completely neutralized one exhibits a sufficient effect of improving the detergency. In the general formula (2), R ² is particularly preferably a linear alkyl group or an alkenyl group, and further has 1 to 18 carbon atoms, particularly 1 in terms of solubility and detergency.
~ 10 are preferred. These compounds are available, for example, as Trilon ES series manufactured by BASF or Nitto Chemical.

In the present invention, the content of the component (a) is from 1 to
It is 50% by weight, preferably 10 to 30% by weight. When the content of the component (a) is less than 1% by weight, a sufficient washing effect cannot be obtained. When the content is more than 50% by weight, the activities of enzymes and the like are impaired.

As the surfactant which is the component (b) used in the present invention, a general surfactant can be widely used, but a nonionic surfactant is preferable.

The nonionic surfactant is not particularly restricted but includes polyoxyethylene alkyl or alkenyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxypropylene alkyl or alkenyl ethers, polyoxybutylene alkyl or alkenyl ether. , Alkylene oxide-added 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 from the group is preferred. More specifically, such a nonionic surfactant is shown in the following (1)
To (11).

(1) Polyoxyethylene alkyl or alkenyl ethers having an alkyl 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 having an alkyl group having an average carbon number of 6 to 12
And the number of moles of ethylene oxide added is 1 to 1 on average.
What is 25 moles.

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

(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) a nonionic surfactant mixture to which is added, wherein the alkyl group or the alkenyl group has an average carbon number of 10 to 10;
20; the number of moles of alkylene oxide added per molecule is 1 to 30 moles on average.

(6) Higher fatty acid alkanolamides represented by the following general formula (3) or alkylene oxide adducts thereof.

[0021]

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Wherein R ³ is an alkyl or alkenyl group having 10 to 20 carbon atoms, R ⁴ and R ⁵ are the same or different and are H or CH ₃ , p is a number of 1 to 3, q Is a number from 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. For example, carbon number 1
And alkyl or alkenylamine oxides having up to 24 linear or branched alkyl or alkenyl groups. More preferred amine oxides include alkylamine oxides represented by the following general formula (4).

[0025]

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In the above general formula (4), R ⁶ has 8 carbon atoms.
It is an alkyl group or alkenyl group having from 24 to 24, preferably an alkyl group having 12 to 18 carbon atoms. R ⁷ and R ⁸ have 1 to 1 carbon atoms
Although it is an alkyl group having 3 carbon atoms, a methyl group having 1 carbon atom is particularly preferable.

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

(11) Alkyl polysaccharides. For example, an alkyl polysaccharide represented by the following general formula (5). R ⁹ (OR ¹⁰ ) _x G _y (5) wherein R ⁹ represents a linear or branched alkyl group or alkenyl group having 8 to 18 carbon atoms or an alkylphenyl group, and R ¹⁰ represents a carbon number Represents a 2 to 4 alkylene group, and G is a residue derived from a reducing sugar having 5 to 6 carbon atoms. x
(Average value) is 0 to 5, and y (average value) is 1 to 5. The alkyl glycoside represented by the general formula (5) will be further described. In the formula, x has an average value of 0 to 5, and by changing this value, the water solubility of the present detergent composition and Crystallinity can be adjusted. That is, the larger the value of x, the higher the water solubility and the lower the crystallinity. The preferred value of x is 0 to 2, and particularly preferably 0. On the other hand, when the average value of y is larger than 1, that is, when a sugar group of two or more saccharides is used as a hydrophilic group, the binding mode of sugar chains is 1-2, 1-3, 1-4, 1-6. It is possible to include any of the bonds, as well as any mixtures having α-, β-pyranoside bonds or furanoside bonds and their mixed modes of attachment. Further, y in the general formula (5)
Has an average value of 1 to 5, preferably 1 to 1.5, more preferably 1.1 to 1.4. Incidentally, the measured value of y was determined by proton NMR.
It is by law. R ⁹ in the formula is preferably an alkyl group having 10 to 14 carbon atoms from the viewpoint of solubility and detergency. Further, R ¹⁰ is preferably an alkylene group having 2 to 3 carbon atoms from the viewpoint of water solubility. Further, the structure of G 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 mixtures thereof in monosaccharides. For disaccharides or more, 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, and a 1 mol adduct of methyl glucoside / isostearyl glycidyl ether A molar adduct, a 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 is exemplified.
Among these nonionic surfactants, (1), (6), (9)
And (11) are preferred, and (9) and (11) are particularly preferred.

In the present invention, the content of the component (b) is from 1 to
50% by weight, preferably 1 to 30% by weight, more preferably 1%
~ 10% by weight. When the content of the component (b) is less than 1% by weight, a sufficient washing effect cannot be obtained, and when the content is more than 50% by weight, the degree of freedom of blending is undesirably reduced.

The amylase as the component (c) used in the present invention may be derived from bacteria. A suitable amylase is an amylase obtained from the bacterium Bacillus licheniformis, particularly preferably "Termamyl" (registered trademark) available from Novo. Amylase
0.2 to 5% by weight, whereby the saccharification activity by the DNS method was 1 × 10 ^{3 at} the actual use concentration of the detergent composition.
The amount should be at least kilo units (the amount of enzyme that produces 1 mg of glucose per minute is 100 units).

In the present invention, the content of the component (c) is 0.2
-5% by weight, preferably 1-5% by weight. When the content of the component (c) is less than 0.2% by weight, the cleaning effect is low, and when the content is more than 5% by weight, the degree of freedom of blending is reduced.

Further, in the present invention, (d) a bleaching agent,
(e) an alkaline agent and (f) a calcium ion scavenger other than an aspartic acid derivative represented by the general formula (1) or an alkylglycine-N, N-diacetate represented by the general formula (2) or a salt thereof. One or more components selected from among them may be contained.

(D) The bleaching agent includes an enzyme bleaching agent. Examples of the oxygen 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 may be used. Of 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. As an activator, tetraacetylethylenediamine (TAED), tetraacetylglycoluril (TAGU), glucose pentaacetic acid (GP
A) and xylosetetraacetic acid (XTA) are commonly used. The peroxide / activator is used in a weight ratio ranging from 8/1 to 1/1.

In the present invention, the content of the component (d) is 0.1
-20% by weight, preferably 1-10% by weight. When the content of the component (d) is less than 0.1% by weight, the bleaching effect is weak. When the content is more than 20% by weight, other components such as enzymes are inhibited.

(E) Examples of the alkali 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 2.5 /
The weight ratio of 1) is 35/1 to 2/1, or the weight ratio of sodium carbonate and sodium silicate (SiO ₂ / Na ₂ O ratio is 1/1 to 4/1, preferably 2/1 to 2.5 / 1). Is 35/1 to 2/1
Most preferably, they are used in combination.

In the present invention, the content of the component (e) is 0.1
This component is adjusted so that the pH of the detergent solution of 0.05 to 1% by weight becomes 9.0 to 11.0.

(F) As the calcium ion scavenger, oxalic acid, malonic acid, succinic acid, citric acid, malic acid, glutaric acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, tripolyphosphoric acid, hexametaphosphoric acid, aminotri (methylenesulfonic acid) ), 1-hydroxyethylidene-
One or more selected from 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 alkaline earth ethylenediaminetetraacetate Metal salts and the like.

In the present invention, the content of the component (f) is 0.1
-20% by weight, preferably 1-10% by weight. When the content of the component (f) is less than 0.1% by weight, a sufficient effect of capturing calcium ions cannot be obtained, and when the content is more than 20% by weight, the activity of the enzyme is lost.

The detergent of the present invention may further contain an oxygen bleach stabilizer, a protease, 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. It can be added in the form. It is particularly preferable to use a calcium complex.

Examples of suitable proteolytic enzymes include B. su
Subtilisins obtained from specific strains of B. bacillus and B. licheniformis. Examples of these are "Maxatase" (registered trademark) sold by Gist, "Alcalase (registered trademark)", "Esperase" (registered trademark) and "Savinase" (registered trademark) of Novo.
And so on.

It is also effective to add 0.1 to 5% by weight of a fatty acid having a hydrocarbon chain length of about 8 to 18 and to add benzotriazole or the like to prevent corrosion of copper.

The automatic dishwashing detergent of the present invention can generally be prepared in the form of a dry, granular product. That is, it can be prepared by dry mixing the powdery or granular components according to conventional manufacturing techniques and then spraying a liquid component (such as a nonionic surfactant) onto the mixture.

The cleaning agent for an automatic dishwasher of the present invention comprises:
As described above, by using a surfactant as an essential component without using a strong alkali, it has sufficient detergency. It is mainly used for automatic dishwashers for homes where it is difficult to use strong alkalis.

[0045]

As described above, the detergent for an automatic dishwasher according to the present invention has the basic properties of oil and
An automatic dishware of high practical value that has sufficient detergency against starch, is phosphorus-free, has the ability to remove pigment stains deposited on tableware, that is, has bleaching performance, and also has good enzyme stability. It is a cleaning agent for cleaning machines.

[0046]

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

Examples 1 to 4 and Comparative Examples 1 to 5 The compositions shown in Table 1 below were prepared, and washed under the following washing conditions.
The following detergency tests were performed and evaluated. Table 1 shows the results.

<< Cleaning Condition >> Washing machine used: Matsushita Electric Co., Ltd. fully automatic dishwasher (model
NP-600) A type in which a cleaning agent aqueous solution is sprayed from a rotating nozzle, and the dishes installed on the upper surface of the spray track are washed. Washing temperature; gradually increase from 5 ° C to 55 ° C. Washing water; water with a hardness of 3.5 ゜ DH 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 for Rice Dirt Detergency] (Preparation of Contaminated Dish) Soft cooked rice was allowed to stand at room temperature for 30 minutes, and 3 g was spread on a magnetic dish having a diameter of 25 cm and applied. After air-drying at room temperature for one day, six pieces were washed. (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 per dish = [(SP) / S] x 100

[0050]

(Equation 1)

[Method of Measuring Compound Soil Detergency] (Preparation of Contaminated Dish) Margarine ("Neosoft" manufactured by Snow Brand) in 100 g of white sauce (canned by Heinz)
g, and the mixture is heated to 60 ° C. and mixed well to obtain a composite soil. 5 g of the above-mentioned composite soil is applied per magnetic 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

[0052]

[Table 1]

* 1 Polyoxyethylene-polyoxypropylene condensate (Asahi Denka Kogyo Co., Ltd.) * 2 Aspartic acid-N, N-diacetate 4Na salt (in the general formula (1), M ^{1 to} M ⁴ are Na And R ¹ is hydrogen. * 3 Methylglycine-N, N-diacetate 3Na salt (in the general formula (2), a compound in which M ^{5 to} M ⁷ are Na and R ² is a methyl group) )

Claims (5)

[Claims] (A) an aspartic acid derivative represented by the following general formula (1) or an alkylglycine-N, N-diacetic acid represented by the following general formula (2) or a salt thereof of 1 to 50% by weight: %, And (b) 1 to 50% by weight of a surfactant. Embedded image (Wherein, M ^{1 to} M ⁴ represent hydrogen, an alkali metal, an alkaline earth metal, ammonium, an alkyl ammonium, or a substituted alkyl ammonium, and R ¹ represents a hydrogen or a hydroxyl group.) (Wherein, M ^{5 to} M ⁷ represent hydrogen, an alkali metal, an alkaline earth metal, ammonium, an alkyl ammonium or a substituted alkyl ammonium, and R ² represents an alkyl or alkenyl group having 1 to 18 carbon atoms.) 2. The detergent for an automatic dishwasher according to claim 1, wherein (b) the surfactant is a nonionic surfactant. 3. The method of claim 2, further comprising: (c) amylase 0.2 to 5% by weight.
The cleaning agent for an automatic dishwasher according to claim 1 or 2, comprising: 4. The detergent for an automatic dishwasher according to claim 3, wherein (c) the amylase is α-amylase. 5. A bleaching agent, (e) an alkali agent and (f) an aspartic acid derivative represented by the general formula (1) or an alkylglycine-N, N represented by the general formula (2).
-One or more components selected from calcium ion scavengers other than diacetate or a salt thereof, in the case of component (d), 0.1 to
The washing for an automatic dishwasher according to any one of claims 1 to 4, comprising 20% by weight, 0.1 to 30% by weight in the case of the component (e), and 0.1 to 20% by weight in the case of the component (f). Agent.