JP2002003892A - Detergent composition for automatic dishwashers - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a detergent for an automatic dishwasher which has excellent detergency against various stains on tableware and has no scale adhesion. SOLUTION: The present invention provides, as a component (A), 0.5 to 30% by weight of potassium hydrogen persulfate; and as a component (B), 0.1 to 15% by weight of a surfactant; and (C) It is a detergent composition for an automatic dishwasher, characterized by containing 0.1 to 50% by weight of a silicate as a component. Further, those containing a carbonate as the component (D) and a hydroxy polycarboxylic acid or a salt thereof as the component (E) are more preferable. Further, the ratio of component (A) / component (C) is 1/3 to 1
/ 10 is more preferable. It has excellent detergency against various stains on tableware and has little adhesion of scale.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cleaning agent for automatic dishwashers, which is used for washing dishes, containers, such as metal, glass, and ceramics, with automatic dishwashers.

[0002]

2. Description of the Related Art Conventionally, in kitchens such as hotels, restaurants, and catering centers, automatic dishwashers have been used for automatic and mechanized washing of dishes and cooking utensils. The use of automatic dishwashers has also become widespread at home. With the spread of such automatic dishwashers, various detergents have been conventionally proposed as detergents suitable for these automatic dishwashers. Examples of such a cleaning agent include, for example, a cleaning agent containing caustic alkali, sodium tripolyphosphate, silicate, and a high-molecular substance (JP-A-63-3788), caustic alkali and 2-hydroxyethyliminodidiamine. Cleaning agent containing acetate (Japanese Patent Publication No. 2-27397), cleaning agent containing caustic alkali, polyacrylate, and specific water (Japanese Patent Application Laid-Open No. 4-15299), bleaching using enzymes and bleaching A detergent containing a hydroxy polycarboxylic acid, a polymer chelating agent, a phosphorus-free alkali agent, an amylase, and an oxygen-based bleach as a detergent having an action (Japanese Patent Laid-Open No. 1-1)
98699) and the like.

[0003]

These detergents have a detergency against oil, protein, and starch stains, which are typical stains on tableware, but they have the same effect as tea stains and tea astringents. It is difficult to easily remove sticky stains or stains that have been denatured over time. Also, when washed with water having high hardness, adhesion of calcium components and the like on the tableware surface after washing, so-called scale adhesion is observed, and particularly in a transparent glass tableware etc., a transparent and clean appearance cannot be obtained. There were also problems.

[0004] The present inventors have conducted intensive studies to obtain a detergent which solves the problems of the conventional automatic dishwashing detergent, and as a result, completed the present invention. Therefore, an object of the present invention is that when dishes are washed with an automatic dishwasher, there is no scale adherence even when washed with water having high hardness, and the washing power of dishes for general dirt is reduced. An object of the present invention is to provide a cleaning agent for an automatic dishwasher which has excellent detergency especially for stains of tea and stains of tea astringent without causing the stain.

[0005]

That is, the present invention is a detergent composition for an automatic dishwasher, comprising the following components (A) to (C) as essential components. (A) 0.5-30% by weight of potassium monopersulfate, (B) 0.1-15% by weight of a surfactant, and (C) 0.1-50% by weight of a silicate. Further, the present invention is a detergent composition for an automatic dishwasher, which contains up to 5% by weight of a carbonate as a component (D) in addition to the above components (A) to (C). Further, the present invention provides a detergent composition for an automatic dishwasher, which contains, in addition to the above components (A) to (D), up to 20% by weight of a hydroxy polycarboxylic acid or a salt thereof as a component (E). It is. Further, the present invention is a detergent composition for an automatic dishwasher, wherein the ratio of the above components (A) to (C) is preferably in the range of 1: 3 to 1:10 by weight.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The component (A) potassium monoperoxide of the present invention is an acidic peroxygen compound having a strong oxidizing power represented by the chemical formula of KHSO ₅ and has a composition requiring an odorless oxidizing agent. And oxidizing agents in organic reactions, and is generally used as potassium hydrogen persulfate (KHS
It can be used as a double salt of potassium monohydroperoxide in the form of a triple salt consisting of 2 mol of O ₅ ), 1 mol of potassium hydrogen sulfate (KHSO ₄ ) and 1 mol of potassium sulfate (K ₂ SO ₄ ). Commercially, it is sold by Dupont under the trade name Oxon and can be obtained. In the cleaning composition of the present invention, the use of the component (A) potassium monohydroperoxide in combination with the other components (B) and (C) eliminates scale adhesion. Demonstrates excellent detergency against stuck and deteriorated stains such as tea stains and tea astringency. The potassium monohydroperoxide is contained in the detergent composition in an amount of 0.5 to 30% by weight, preferably 1.0 to 20% by weight, more preferably 1.5 to 30% by weight.
Used at a rate of 10% by weight. When using a potassium monohydroperoxide double salt, it is used in an amount as described above as an effective component of potassium monopersulfate hydrogen in the double salt. If it exceeds 30% by weight, the obtained effect cannot be improved, and it is uneconomical.

The surfactant used as the component (B) in the present invention is an anionic surfactant, a nonionic surfactant, or an amphoteric surfactant. The anionic surfactant is not particularly limited, and a commonly used anionic surfactant can be used. Preferred anionic surfactants include sodium lauryl sulfate, sodium oleyl sulfate, and sodium coconut alkyl sulfate. Alkyl sulfates of several tens to 20; alkyl ether sulfates of 10 to 20 carbon atoms such as sodium polyoxyethylene lauryl sulfate and sodium polyoxyethylene stearyl sulfate; sodium stearate, sodium myristate, coconut fatty acid sodium and the like Examples thereof include fatty acid alkali metal salts having 10 to 20 carbon atoms. The nonionic surfactant is not particularly limited, and a commonly used nonionic surfactant can be used. However, polyoxyalkylene obtained by adding an alkylene oxide such as ethylene oxide or propylene oxide to an aliphatic alcohol having 10 to 20 carbon atoms can be used. Examples thereof include alkylene alkyl ethers and those in which their terminals are blocked with an alkyl group, and a low-foaming nonionic surfactant is particularly preferred. Specific examples include various nonionic surfactants available under trade names such as SOFTANOL series (Nippon Shokubai Kagaku Kogyo Co., Ltd.), PULLAFAX series (BASF Corporation), and Lionol series (Lion Corporation). Can be The amphoteric surfactant is not particularly limited, and a commonly used amphoteric surfactant can be used. Preferred amphoteric surfactants include alkyl acetate betaines having 10 to 20 carbon atoms in the alkyl group and alkyl sulfobetaines. And the like. The surfactant is present in the composition in an amount of 0.1 to 15% by weight, preferably 1 to 10% by weight, more preferably 3 to 5% by weight.
Used in percentages by weight. If the amount exceeds 15% by weight, no further improvement in the effect can be seen and the cost increases.
If the content is less than 0.1% by weight, a sufficient cleaning action is not exhibited, which is not preferable.

The silicate used as the component (C) in the present invention is used in combination with the component (A), potassium hydrogen hydrogen persulfate, to saponify and neutralize organic dirt having a carboxyl group and to neutralize water. It is used to improve the dispersibility of soil by increasing the negative surface potential of the substrate surface with respect to the soil dispersed in water. This silicate is typically represented by nM ₂ O · mSiO ₂ (M is an alkali metal) and has a m / n ratio of 1/1 to 4/1, preferably 2/1 to 3/1. belongs to. M is preferably sodium. Specifically, in the case of a sodium salt, examples thereof include sodium metasilicate, sodium disilicate, sodium tetrasilicate, sodium orthosilicate, and a mixture thereof. These silicates may be crystalline or amorphous, and include amorphous powdery sodium silicate, crystalline sodium silicate, layered sodium silicate, and the like. So-called water glasses can also be used in the present invention in mixtures of these silicates.

Of these, Na ₂ O · mSi
O ₂ . xH ₂ O (m = 1.9 to 2.0), and since layered sodium silicate having a layered crystal structure has a binding ability with calcium and magnesium when used in combination with potassium hydrogen monopersulfate, In particular, it suppresses the formation of water-insoluble salts even when used in water with high hardness, exhibits excellent dirt dispersing ability and anti-redeposition ability, and reduces the adhesion of rough dirt on the surface of tableware etc. It has the effect of suppressing the fogging of glass tableware. Calcium and magnesium ions form water-insoluble compounds, especially with anionic surfactants such as those contained in detergents, which reduce the detergency and adversely affect the cleaning effect. Further, the above-mentioned water-insoluble compounds such as calcium accumulate in the fiber fabric, and impair both the comfort and the life of the fabric. By lowering or removing the amount of calcium and magnesium ion ions in such a washing solution, the washing power and rinsing effect can be substantially improved, but soft water of layered sodium silicate having a layered crystal structure can be obtained. The chemical action is
It is based on its layered molecular structure and also on the inherent pH value of the hydrogen silicate, whereby the deposition or precipitation (softening of water) of the ions of alkaline earth metals such as calcium and magnesium contained in the water is reduced. Occurs.

The silicate is present in the composition in an amount of 0.1 to 50% by weight, preferably 1 to 20% by weight, more preferably 3 to 50% by weight.
It is used in a proportion of 10% by weight. If the amount exceeds 50% by weight, no further improvement in the effect can be seen and the cost is increased. If the amount is less than 0.1% by weight, a sufficient cleaning effect is not exhibited, which is not preferable.

The carbonate used as the component (D) of the present invention is used to increase the detergency by making the system of the detergent composition of the present invention alkaline, and is preferably sodium carbonate. The carbonate may be of commercially available purity and is not particularly limited. This carbonate is used in the composition in a proportion of up to 5% by weight, preferably 0.1 to 3% by weight, more preferably 0.5 to 2% by weight. 5
If the amount exceeds% by weight, not only the effect is not further improved but also if washed with water having high hardness, water-insoluble calcium carbonate is generated, which is not preferable because it causes scale adhesion.

The carbonate used as the component (E) in the present invention is a hydroxy polycarboxylic acid or a salt thereof, which is a compound represented by the following general formula or a water-soluble salt thereof.

[0013]

Embedded image

Wherein X is H, —CH ₃ , —CH ₂ COO
H or —CH (OH) COOH, where Y is H or O
H Among them, citric acid, malic acid, tartaric acid and salts thereof are preferable. Examples of the salt include a sodium salt, a potassium salt, a monoethanolamine salt, a diethanolamine salt, and a triethanolamine salt. The hydroxy polycarboxylic acid or a salt thereof, when used in combination with the above-mentioned components (A) to (D), causes black tea stains or tea astringent sticking.
Alternatively, the cleaning power for the deteriorated dirt is increased. The hydroxy polycarboxylic acid or salt thereof is used in the composition in a proportion of up to 20% by weight, preferably 5 to 15% by weight, more preferably 8 to 12% by weight. If the amount exceeds 20% by weight, no further improvement in the effect can be seen, and if it is less than 1% by weight, a sufficient cleaning effect is not exhibited.

The components (A) and (C) of the present invention are preferably blended in the composition at a weight ratio of 1: 3 to 1:10. Even if the ratio is higher or lower, potassium hydrogen persulfate is stably present in the cleaning solution,
Sufficient washing and bleaching action cannot be obtained.

The detergent composition for an automatic dishwasher according to the present invention includes various known enzymes such as amylase, protease, lipase and cellulase; organic chelating agents such as ethylenediaminetetraacetate; sodium percarbonate and sodium perborate. Bleach components such as sodium persilicate, sodium hypochlorite, sodium dichloroisocyanurate and the like can be used. Further, if necessary, various alkali agents, inorganic salts, fragrances, dyes and the like can be added and used.

The detergent composition for an automatic dishwasher of the present invention can be formed into any shape such as liquid, powder, granule, and solid depending on the form and conditions of the washer used. .

[0018]

Next, the present invention will be described with reference to examples, but the present invention is not limited to these examples. In the examples, parts and% are parts by weight and% by weight, respectively.

1) Preparation of Cleaning Composition The cleaning composition of the present invention of Example 1 having the composition shown in Table 1 was prepared as follows. First, 5 parts of sodium carbonate powder (heavy ash), 10 parts of No. 2 powder sodium silicate, and 60.5 parts of sodium sulfate powder are charged into a tabletop powder mixer, Kenmix Iko (manufactured by Aikosha Seisakusho), and mixed for 1 minute. . Here, 3 parts of nonionic surfactant B (trade name: Emulmin FL-100, Sanyo Chemical Co., Ltd.) is charged and mixed for 3 minutes. Then, silica powder (trade name: Nipsil N)
1.5 parts of SK, manufactured by Nippon Silica Industry Co., Ltd.)
Mix for 3 minutes. Subsequently, 5 parts of trisodium citrate and 2 parts of EDTA (trade name: Crewat S2, manufactured by Teikoku Chemical Industry Co., Ltd.) were charged and mixed for 2 minutes, and then potassium monohydroperoxide double salt (trade names: Oxone, 10 parts (manufactured by Mitsubishi Gas Chemical Co., Ltd.) (5 parts as potassium monohydrogen oxyacid effective component) are charged and mixed for another 2 minutes. Finally, a protease is used as an enzyme (trade name: Everase 8T, Novo
(Nordisk Bio-Industry Co., Ltd.) 0.5
And 2.5 parts of Amylase (trade name: Duamyl 60T, manufactured by Novo Nordisk Bioindustry Co., Ltd.) were added and mixed for 30 seconds to prepare a powdery detergent composition of Example 1. Examples 2 to 18 and Comparative Examples 1 to 6
, A detergent composition was prepared in the same manner as in Example 1 using the components and the mixing ratios shown in Tables 1 and 2, respectively.

2) Scale adhesion test Under the following washing conditions, various dishes shown below were washed with an automatic dishwasher, and a scale adhesion test during washing was performed. That is, before each step of pre-washing, washing, and rinsing of the automatic dishwasher, washing was performed in a standard course while adjusting the hardness of the washing liquid to 300 ppm by adding water whose hardness was adjusted. After the washing, the degree of adhesion between the dishes and the scale in the washing machine was evaluated by visual observation and feel by touch according to the following criteria.

<Tableware used for one wash>-Porcelain products: 4 large plates, 3 small plates, 3 small bowls, 3 bowls
Individual, 3 cups,-Glassware: 3 glasses,-Plastic products: 3 plastic arms,-Stainless steel products: 3 spoons, 3 forks,

<Washing conditions>-Washing machine used: NP-5800M automatic dishwasher (Matsushita Electric Co., Ltd.)-Washing course: Standard course (1 minute pre-washing → 28 minutes washing → 3 minutes rinsing × 2 times) →・ Detergent concentration: 7.5 g / 5 liter ・ Washing water hardness: 300 ppm (Adjust to 300 ppm by adding hardness adjusting water to tap water.)

<Evaluation Criteria> A: No adherence of white scale was observed in the washing machine, and there was no rough hand to the tableware. B: A white scale is partially adhered to a lid or the like in the washing machine, and each dish has a partially rough feel to the hands. C: A white scale adheres to about half the area in the washing machine, and a rough hand feels to about half the area of each dish. D: White scale adheres to the entire surface of the washing machine, and all the dishes have a rough hand feeling.

3) Detergency test A washing test was carried out under the following washing conditions using an automatic dishwasher using dishes contaminated with various stains prepared by the following method. That is, the contaminated dishes are washed in a standard course of automatic dishwasher prewashing, washing, and rinsing, and the degree of dirt removal of the dishes after washing is visually determined according to the following evaluation criteria, and the formula for calculating the cleaning power score is as follows. Was used to calculate the evaluation score. The corn starch stain and the porridge stain were visually determined after coloring with an iodine solution.

<Preparation of Contaminated Tableware> (i) Corn Starch Dirt 12 g of corn starch (sold by Shimoda Corporation) is distilled water 6
The mixture was heated and dissolved in 00 mL. Apply 10 g of the dissolved corn starch solution to each porcelain platter,
After drying for 20 minutes, it was left overnight in a room at a constant temperature and humidity of 22 ° C. and 50% RH, and then subjected to a washing test.

(Ii) Porridge dirt Five minutes each of 5 g of porridge is applied to a porcelain platter, a tea bowl, and a plastic bowl, and dried at 80 ° C. for 30 minutes.
After leaving it to stand overnight in a room at a constant temperature and humidity of 50 ° C. and 50% RH, it was subjected to a cleaning test.

(Iii) Soil of eggs The chicken eggs are boiled in boiling water for 5 minutes, cooled with cold water, and only the yolk portion is taken out. 3 g of the yolk taken out is applied to a small porcelain dish, a small bowl and a cup of tea, respectively, at 22 ° C. and 50%
It was left overnight in a room of constant temperature and humidity of RH. Immersed in boiling water for 15 seconds immediately before the post-wash test was used for the test.

(Iv) Tea Astringent Stain 1 in a commercially available coffee cup (white) with a capacity of 150 mL
00 mL of boiling water was poured, a commercially available black tea bag (manufactured by Nittocha Co., Ltd.) was immersed, and left as it was at room temperature for one week. After that, the contents were discarded, and the coffee cup lightly washed with water was subjected to a detergency test.

<Contaminated Tableware Used in One Washing Test and Number of Contaminated Tableware> ・ Plate (2 each for corn starch stains and porridge stains)
・ Tea bowl, bowl (three each for porridge stains), ・ small bowl, small plate, cup (three for egg stains each), ・ Coffee cup (four for tea astringent stains),

<Washing conditions>-Washing machine used: NP-5800M automatic dishwasher (manufactured by Matsushita Electric Co., Ltd.)-Washing course: standard course (1 minute prewashing → 28 minutes washing → 3 minutes rinsing × 2 times) →・ Rinse concentration: 7.5 g / 5 liter

<Evaluation Criteria> Stain removal 0% or more to less than 40% 1 point 40% to less than 60% 2 points 60% to less than 80% 3 points 80% or more to less than 100% 4 points 100% 5 point

[0032]

(Equation 1)

Tables 1 and 2 show the test results of the scale adhesion on the inside of the washing machine and the degree of scale adhesion of each tableware, and the cleaning power on the degree of removal of each stain.

[0034]

[Table 1]

[0035]

[Table 2]

The components used in the table were as follows: Potassium hydrogen monopersulfate double salt Trade name: Oxone (manufactured by Mitsubishi Gas Chemical) Anion activator A Sodium alkyl sulfate derived from coconut oil alcohol Anion activator B Coconut fatty acid sodium Nonionic activator A aliphatic alcohol alkoxylate (trade name: Plurafac LF431, manufactured by BASF) Nonionic activator B aliphatic alcohol alkoxylate (trade name: Emulmin FL-100, manufactured by Sanyo Chemical Co., Ltd.) Powdered silicate No. 2 powdered sodium silicate layered silicate Product name: SKS-6 (manufactured by Clariant) Carbonate sodium carbonate (heavy ash) EDTA Product name: Crewat S2 (manufactured by Teikoku Chemical Industry) Silica Product name: Nipsil NS-K (Nippon Silica) Industrial) Protease Product Name: EVALASE 8T (Novo Nordisque Bio Industries) Amylase Product name: Duamill 60T (Novo Nordisk Bio-Industries)

[0037]

According to the automatic dishwashing detergent composition of the present invention, compared with the conventional automatic dishwashing detergent as shown in the comparative example, there is no adherence of scale to dishes, and at the same time, various types of dishwashing are possible. With excellent detergency against dirt.

 ──────────────────────────────────────────────────続 き Continued on front page F-term (reference) 4H003 AB03 AB27 AC08 BA01 BA09 BA12 DA19 EA12 EA15 EA16 EA25 EB08 EB16 EC01 EC02 EE05 FA06

Claims (6)

[Claims] 1. Component (A) is 0.5 to 30% by weight of potassium hydrogen persulfate; (B) component is 0.1 to 15% by weight of a surfactant; and (C) component is A detergent composition for an automatic dishwasher, comprising 0.1 to 50% by weight of a silicate. 2. The cleaning composition for an automatic dishwasher according to claim 1, wherein the component (B) is a nonionic surfactant. 3. The cleaning composition for an automatic dishwasher according to claim 1, wherein the component (C) is layered sodium silicate. 4. The cleaning composition for an automatic dishwasher according to claim 1, further comprising up to 5% by weight of a carbonate as a component (D). 5. The detergent composition for an automatic dishwasher according to claim 1, further comprising as component (E) up to 20% by weight of a hydroxy polycarboxylic acid or a salt thereof. object. 6. The automatic method according to claim 1, wherein the ratio of the component (A) to the component (C) in the composition is in the range of 1: 3 to 1:10 by weight. A detergent composition for a dishwasher.