JPH10279991A - Detergent composition for automatic dishwasher - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a detergent for cleaning an automatic dishwasher having not only an excellent biodegradability, namely environmental stability, but also an excellent water solubility, cleanability and inhibitory effects on whitening of glass surface, extremely high practical value. SOLUTION: This composition comprises a polycarboxylic acid which is derived by oxidizing a polysaccharide comprising a glucose anhydride as a constituent unit or its salt and an amylase as essential components. The amount of an alkali required for the neutralization titration of the acid type polycarboxylic acid is >=435 mg calculated as sodium hydroxide based on 1 g of the poly carboxylic acid. The polycarboxylic acid has >=2000 molecular weight by weight average.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a biodegradable and highly alkaline earth metal chelating agent.
By blending a specific polycarboxylic acid or a salt thereof derived by oxidizing a polysaccharide having anhydrous glucose as a constitutional unit and amylase as essential components, high environmental safety and good water solubility, and The present invention relates to a detergent composition for an automatic dishwasher, which realizes an excellent whitening suppression effect on a glass surface and a high starch decomposition activity by a synergistic action between both components.

[0002]

2. Description of the Related Art In recent years, automatic dishwashers have rapidly become widespread, and as a result, dedicated detergents for automatic dishwashers have been actively developed. The main focus of all recently developed automatic dishwashing detergents is to enhance the cleaning effect, including the addition of special surfactants, addition of enzymes and bleaching agents, and high pH builders. The main focus was on proposals for compositions. In addition, with the advancement of such technology, scale generated by the combination of the alkaline earth metal and the alcal builder component such as carbonic acid,
The whitening phenomenon of the glass surface such as a water spot has also become a problem, and a high-performance carboxylic acid-based polymer chelating agent containing polyacrylic acid or polymaleic acid as a constitutional unit has been added.

[0003]

However, no consideration has been given to environmental stability in the course of such technical development, and specifically, the above-described high-performance carboxylic acid-based polymer chelate has been described. The agent had no biodegradability. Therefore, considering that the amount of detergent used in automatic dishwashers will further increase in the future, it is necessary to immediately consider the development of a chelating agent having good biodegradability and excellent chelating ability. . As a base material that can meet such needs, there is an oxidation product of polygluconic acid or a salt thereof as disclosed in Japanese Patent Application Laid-Open No. 8-500626, which is, in other words, an oxide of starch. Therefore, as can be easily inferred, partial oxides such as monocarboxylic acids and dicarboxylic acids have insufficient water solubility and chelating ability, and have not been put to practical use. Therefore, to solve these problems, to develop a chelating agent having sufficient water solubility and high chelating ability, and also highly biodegradable and environmentally safe, There has been a strong demand for the development of high-performance automatic dishwasher detergents.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that polycarboxylic acid derived by oxidizing a polysaccharide having a specific anhydrous glucose as a constitutional unit is obtained. By compounding an acid or a salt thereof as a chelating agent, and further by using it in combination with amylase,
It was found that high environmental safety, good water solubility, and a synergistic action between the two components resulted in an excellent dishwashing inhibitor on the glass surface and high starch-degrading activity. The invention has been completed.

That is, the present invention relates to Japanese Patent Application No. 7-1886.
No. 12, a polycarboxylic acid or a salt thereof derived by oxidizing a polysaccharide having anhydrous glucose as a structural unit, wherein an alkali required for neutralizing titration of the acid-type polycarboxylic acid is water. High environmental safety by containing, as essential components, a polycarboxylic acid or a salt thereof having a molecular weight of not less than 435 mg and a weight average of not less than 2,000 per 1 g of the polycarboxylic acid in terms of sodium oxide, and amylase. And good water solubility,
Further, the present invention provides a detergent composition for an automatic dishwasher, which realizes an excellent whitening suppression effect on a glass surface and a high starch decomposition activity.

More preferably, the polycarboxylic acid or a salt thereof contained as an essential component is a polycarboxylic acid or a salt thereof derived by oxidizing a polysaccharide having anhydrous glucose as a structural unit, The total content of a monocarboxylic acid or a salt thereof represented by the following general formula (1) and a dicarboxylic acid or a salt thereof represented by the following general formula (2) is 10 mol%. Wherein at least 50 mol%, preferably at least 70 mol%, of the compound comprises a tricarboxylic acid or a salt thereof represented by the following general formula (3) and an unoxidized polysaccharide. By doing so, it is possible to provide an environmentally friendly detergent composition for an automatic dishwasher which has remarkably improved water solubility and chelating ability, has excellent quality, and is environmentally friendly.

[0007]

Embedded image (In the formula, M ₁ represents a cation corresponding to monovalent such as a hydrogen atom or an alkali metal.)

[0008]

Embedded image (M ₂ and M ₃ in the formula represent a hydrogen atom or a monovalent cation such as an alkali metal.)

[0009]

Embedded image (M ₄ , M ₅ and M ₆ in the formula represent a hydrogen atom or a cation corresponding to monovalent such as an alkali metal.)

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION A polycarboxylic acid or a salt thereof derived by oxidizing a polysaccharide having an anhydrous glucose as a constituent unit, which is an essential component of the present invention. The alkali required for the neutralization titration is 435 mg or more per 1 g of the polycarboxylic acid in terms of sodium hydroxide, and the molecular weight thereof is 2 by weight average.
The polycarboxylic acid or salt thereof having a molecular weight of 000 or more is essentially completely different from conventionally known oxidation products of polygluconic acid. That is, conventionally, cellulose, starch, dextrin, etc., oxygen in the air,
Hydrogen peroxide, sodium hypochlorite, periodate, lead acetate, nitrogen dioxide, oxidizing using an oxidizing agent such as cerium, to produce a carboxylic acid type polysaccharide derivative,
T. P. Neverl, "Cellulose Che
mystery and Its Application
ns; Section 10: Oxidation o
f Cellulose ", John Wiley a
nd Sons, 243 (1983) and JP-A-3-21.
No. 0396, Japanese Unexamined Patent Publication No. Hei 4-233901, Japanese Unexamined Patent Publication No. Hei 5-214367, etc., which are well known, and are automatic dishwashers using such oxidized products of polygluconic acid as builders. Detergents are also available from Tokiohei 8
It has been proposed as described in US Pat. However, strictly speaking, these compounds are mainly composed of a monocarboxylic acid or a dicarboxylic acid represented by the general formula (1) or (2), and the tricarboxylic acid of the general formula (3) has a steric hindrance. Was hardly contained due to the low reactivity of the compound. In addition, when trying to obtain a tricarboxylic acid-type product by the above-described known method, the reaction must be severe due to an operation such as raising the temperature or using a large amount of an oxidizing agent. The depolymerization reaction by cleavage also proceeds at a considerable rate, and a polymer having a molecular weight substantially exceeding 2,000 cannot be obtained. As a result, a polymer having remarkably high chelating ability and water solubility has been obtained. Did not.

However, surprisingly, in the presence of a specific transition metal catalyst, when a polysaccharide having anhydrous glucose as a constitutional unit is subjected to an oxidation reaction using a hypohalite or a powder of salac, the above-mentioned general formula (I) is obtained. The monocarboxylic acid or its salt represented by 1) or (2) and the dicarboxylic acid or its salt are hardly formed, and it is found that the tricarboxylic acid of general formula (3) or its salt can be selectively obtained. Completing the present invention, we have found that the preparation of detergents for automatic dishwashers containing polycarboxylic acid results in remarkably good detergents, reflecting their excellent biodegradability, high chelating ability and water solubility. I came to.

Hereinafter, a method for producing the polycarboxylic acid or a salt thereof of the present invention will be specifically described. The polysaccharide used for obtaining the polycarboxylic acid or a salt thereof of the present invention is not particularly limited as long as it is a polysaccharide having anhydrous glucose as a constituent unit, and starch, dextrin, cellulose,
Alternatively, there may be mentioned hydrolysates thereof, or amylose or amylopectin obtained by fractionating starch, and these may be used in a mixture of two or more kinds. And the origin of these polysaccharides is not particularly limited, for example,
In the case of starch, corn starch, wheat starch, rice starch, tapioca starch and the like are used. In the case of cellulose, cellulose obtained from softwood, hardwood, cotton and the like is used. Among these polysaccharides, use of starch or cellulose is preferred from the viewpoint of availability and economy, and starch is particularly preferably used.

The polycarboxylic acid or salt thereof of the present invention can be obtained by oxidizing a polysaccharide having anhydrous glucose as a constitutional unit using a combination of a specific catalyst and an oxidizing agent. That is, it can be produced by adding an oxidizing agent to an aqueous dispersion of a polysaccharide and a metal catalyst while maintaining the pH of the solution in a certain range. The transition metal catalyst used in the present invention includes Ru, Os, Rh, Ir,
Pt, Pd and the like can be mentioned, but a ruthenium catalyst or an osmium catalyst is preferable. These metal catalysts may be in the form of a salt such as chloride, sulfide or oxide, or may be in the form of a metal. The amount of these metal catalysts used is 0.0
It is 5 mol% to 10 mol%, preferably 0.1 mol% to 7 mol%.

The oxidizing agent used in the present invention is a hypohalite (for example, a Na salt, a K salt, a Ca salt, a Mg salt, etc.) or a powdered ash, and is preferably a hypohalite.
The amount of these oxidizing agents varies depending on the content of carboxyl groups in the polycarboxylic acid to be finally obtained, but is preferably 3.5 to 12 moles, and more preferably 3.5 to 12 moles per anhydroglucose unit of the polysaccharide. It is 4 to 9 moles.
The reaction is carried out by adding these oxidizing agents to an aqueous dispersion of a polysaccharide and a transition metal catalyst. The method of adding the oxidizing agent is not particularly limited, but it is usually added continuously or dividedly. Although the reaction time is not particularly limited, it is usually 2 hours to 8 hours. Also, the reaction temperature is not particularly limited, but is usually 10 ° C to 50 ° C.

The pH of the solution during the reaction must be kept in the range of 6 to 13, preferably 7 to 12. The pH can be adjusted using an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or lithium hydroxide, or an amine such as ammonium, alkylamine or alkanolamine. Sodium or potassium hydroxide is used. Under such reaction conditions, the glucosidic bond cleavage of the main chain of the polysaccharide is relatively unlikely to occur, unlike the conventional method, and
Since the hydroxyl group of the polysaccharide is efficiently oxidized, a tricarboxylic acid having a relatively large molecular weight represented by the general formula (3) or a salt thereof, which is a main essential component of the present invention, is obtained as a main component. Therefore, sodium hydroxide required for neutralizing titration of the obtained polycarboxylic acid or its salt is incorporated into an automatic dishwashing detergent having a weight average molecular weight of 435 mg or more per 1 g of the polycarboxylic acid and a weight average molecular weight of 2,000 or more. In this case, a compound having excellent biodegradability, excellent chelating ability, and easily soluble in water can be obtained. In addition, "sodium hydroxide required for neutralization titration of polycarboxylic acid or its salt,
The expression "435 mg or more per g of polycarboxylic acid" refers to the neutralization titer in the case where any of the acid type and the salt type or a mixture thereof can be used in the present invention, and these are converted to the acid type polycarboxylic acid. That is, it is an index indicating the amount of the introduced carboxyl group.

The polycarboxylic acid or salt thereof of the present invention is preferably contained in an automatic dishwashing detergent in an amount of 0.1 to 15% by weight, more preferably 1 to 10% by weight. If the compounding amount is less than this range, a sufficient chelating effect cannot be obtained, so that the detergency is insufficient. However, it is not preferable because an economic disadvantage occurs due to an increase in cost. In addition to the polycarboxylic acid, the detergent for an automatic dishwasher of the present invention contains amylase as an essential component. Since amylase is an enzyme that degrades starch, it is a common component that is indispensable to detergents for automatic dishwashers, in many cases washing dishes with attached rice. However, surprisingly, as a result of investigation, it has been revealed that when used in combination with the polycarboxylic acid of the present invention, it exhibits a specifically high starch-degrading activity.
This is because the polycarboxylic acid of the present invention also basically has a skeleton similar to starch, and thus easily interacts with amylase, and the presence of the polycarboxylic acid and the chelating ability catalytically degrade amylase into starch. It is expected to have increased activity. Specific preferred examples of the amylase include durazyme (Novo Co., Ltd., trademark) and maxamil (IBIS, Inc.), but are not limited thereto.

The detergent for an automatic dishwasher of the present invention may optionally contain, in addition to the essential components, components usually contained in a detergent composition for an automatic dishwasher. Specific components that are suitably blended include surfactants, inorganic alkali agents, extenders, other chelating agents, pH buffers, bleaching agents, bleaching activators, enzymes, fragrances, coloring agents, and granulating agents. And the like. Hereinafter, these optional components will be described in detail. Surfactants are suitably blended for the purpose of increasing the detergency against oil stains, and are not limited by their structure or type, and include alkyl sulfate salts, alkyl ethoxy sulfate salts, α-sulfo fatty acid salts, and soaps. Any surfactant can be used as long as it is commonly used in detergents, such as alcohol ethoxylates and alkyl polyglycosides. However, since it is preferably low foam as a detergent for automatic dishwashers,
When these high foaming surfactants are used, it is necessary to add an antifoaming agent such as a silicone-based antifoaming agent or a compound type antifoaming agent. On the other hand, a low-foaming nonionic surfactant having an oxyethylene group or an oxyethylene / oxypropylene copolymer group in a hydrophilic portion does not require a combined use of an antifoaming agent, and is used in a detergent for an automatic dishwasher. Can be particularly preferably used. A preferred example of such a low-bubble nonionic activator is Soptanol E
Examples include the P series (registered trademark of Nippon Shokubai Chemical Industry Co., Ltd.) and the pull lafax series (registered trademark of BASF). The preferred amount of the surfactant in the present invention is 0.1.
The content is 1 to 10% by weight, more preferably 1% to 5% by weight. When the amount of the surfactant exceeds this range, mechanical trouble due to foaming is likely to occur. However, the cleaning power is hardly improved, and the cost is increased, which is economically disadvantageous.

In order to further enhance the detergency, it is preferable to add a bleach or an enzyme. Bleaching agents that can be preferably blended include halogen bleaching agents such as hypochlorite and halogenated isisoannulic acid, organic hydrochloric acid such as monoperoxyphthalate or a salt thereof, alkali metal perborate, percarbonate Salts, oxygen-based bleaching agents such as peroxides that generate hydrogen peroxide in aqueous solutions such as persilicates,
Of these, sodium percarbonate and sodium perborate are particularly preferred. These may be powdery or granular. Further, those subjected to a surface treatment for the purpose of stabilization are particularly preferable, and those coated with boric acid or an alkali metal salt of boric acid and silicate are particularly preferably used. To give a specific example, SPCD (Mitsubishi Gas Chemical registered trademark) or the like is very suitable. When a bleaching agent is blended, it can be blended in a range of 0.1 to 10% by weight for a halogen type and 1 to 30% by weight for an oxygen type. It is also preferable to add a bleaching activator typified by an organic peracid precursor, a metal catalyst, etc., in addition to these bleaching agents. On the other hand, the enzymes other than amylase which can be preferably blended include protease, lipase, pullulanase and the like.
It is very preferable to mix it by about 3% by weight.

Further, the detergent for an automatic dishwasher of the present invention includes a chelating agent other than the polycarboxylic acid of the present invention.
It can be suitably blended within a range that does not impair the effect. Various compounds having a relatively low molecular weight from the viewpoint of biodegradability are exemplified as compounds which can be preferably added, and specific examples thereof include citrate and succinate. In the present invention, an inorganic alkali agent can be suitably blended, and specific examples thereof include sodium carbonate and sodium silicate. These are blended for the purpose of increasing the pH of the solution at the time of cleaning in order to increase the detergency, and preferably 1 to 40% by weight. However, when the above-mentioned bleaching agent and enzyme are combined together, the solution p
If the H is too high, the effect will be low. Therefore, a pH buffer such as sodium hydrogen carbonate is blended, and the pH is adjusted to 8.5 to 10.0.
It is preferable to adjust so as to fall within the range. further,
When a granular detergent is used, an extender such as sodium sulfate or a granulating agent such as amorphous silica may be appropriately blended to obtain a desired granulated product.

The detergent for an automatic dishwasher of the present invention may contain various additives, such as inorganic additives such as sodium aluminate and organic additives such as fragrances and pigments, in addition to the above components. Thus, it is possible to appropriately mix them within a range not impairing the effects of the present invention. The detergent for an automatic dishwasher of the present invention can be manufactured by any generally known method such as stirring granulation by powder mixing, granulation method including a spray drying step, kneading, and granulation method by crushing. It is possible, and the manufacturing method is not particularly limited. However, polycarboxylic acid and amylase, which are essential components of the present invention, are a combination of compounds having strong interaction in a homogeneous solution as described above. Preferably, both components are produced as separate powders by powder mixing in order to exhibit synergistic action for the first time when melted.

[0021]

The detergent for an automatic dishwasher of the present invention thus obtained has not only good biodegradability, that is, environmental safety, but also good water solubility and cleanability, and excellent glass surface. It is an extremely high practical value detergent that has the effect of inhibiting whitening.

[0022]

Next, the present invention will be described in more detail by way of examples, which should not be construed as limiting the present invention. First, an analysis method for a polycarboxylic acid will be described. (Measurement of carboxyl group content) About 0.2 g (absolutely dry amount) of acid type polycarboxylic acid was weighed and weighed in a 200 ml conical beaker, and dissolved by adding about 50 ml of ion-exchanged water. With rain as indicator
The content of the carboxyl group is indicated as mg of sodium hydroxide required for neutralizing 1 g of the acid-form polycarboxylic acid, which is adjusted with a standard solution of / 10 N sodium hydroxide.

When it is clear that a part or all of the polycarboxylic acid whose carboxyl group content is to be measured is in the form of a salt, the polycarboxylic acid is converted into an acid-form polycarboxylic acid by the following method. Take out. That is, an aqueous solution of about 1% by weight of a polycarboxylate is prepared, passed through a column filled with a cation exchange resin (DOWEX 50W-X8), and subjected to cation exchange to be converted into an acid-type polycarboxylic acid. The cation exchange resin is used in an amount of 10 ml per 1 g of a 1% by weight aqueous solution of the polycarboxylate. The eluate is freeze-dried or dried under reduced pressure (40 ° C. or lower) to obtain an acid-type polycarboxylic acid in powder form.

(Measurement of molecular weight by GPC) About 5 mg of the same polycarboxylic acid powder as used in the neutralization titration was added to 0.1 g
It was dissolved in 5 ml of 0.1 mol / L phosphate buffer (pH 7) containing 3 mol / L NaCl, and GP was dissolved under the following conditions.
Measured by C and expressed as weight average molecular weight. Column used: Tosoh Corporation G-4000PW + G-
2500PW Eluent: 0.1 mol / L containing 0.3 mol / L NaCl
L-phosphate buffer (pH 7) Elution rate: 0.5 ml / min Column temperature: 40 ° C. Sample injection volume: 200 μl Calibration curve: Standard polyacrylic acid sodium polyacrylate
(Weight average molecular weight 2100, 5000, 20,000, 3
5000, 165300)

(Measurement of Ca ion chelating ability (CEC)) 0.1 mol / L CaCl manufactured by Orion Research Co., Ltd.
₂ CaCO ₃ by diluting the standard solution 100 times
A Ca solution corresponding to 100 ppm was prepared. On the other hand, the polycarboxylic acid to be tested was dissolved in ion-exchanged water to prepare an aqueous solution containing exactly 1% by weight of sodium polycarboxylate, and used as a test solution. Ca solution 10
0 ml was taken, 2 ml of a 4 mol / L KCl solution was added, and the pH was adjusted to 10 with 1/10 N NaOH. While stirring this aqueous solution, the initial concentration of Ca ions was measured using a Ca ion electrode. Next, 2 ml of the test solution was accurately added, and the pH was adjusted to 10 again.
The Ca ion concentration was measured using the a ion electrode. Ca
The Ca ion concentration after the addition of the test solution was subtracted from the ion initial concentration, and this amount was expressed as chelated Ca ion, and the amount of Ca ion chelated by 1 g of sodium polycarboxylate was expressed as mg of CaCO ₃ .

(Analysis of polycarboxylic acid) About 10 mg of polycarboxylic acid or a salt thereof was placed in a test tube, 5 ml of 1N hydrochloric acid was added thereto, and the mixture was sealed and allowed to stand at 100 ° C. for 16 hours to carry out hydrolysis. After evaporating the solvent and drying under reduced pressure, the residue was dissolved in 5 ml of eluent, and the amount of each organic acid and glucose produced by decomposition was measured by HPLC. The amount of each polycarboxylic acid and the amount of anhydrous glucose before hydrolysis were calculated from the measured amounts of organic acid and glucose. Column used: Shodex RSp manufactured by Shoko Tsusho Co., Ltd.
aK KC-LG + KC-811 × 2 Eluent: 3.75 mM perchloric acid aqueous solution Elution rate: 0.5 ml / min Column temperature: 40 ° C. Sample injection volume: 200 μl

The polycarboxylic acid produced by performing an oxidation reaction of a polysaccharide having anhydrous glucose as a constituent unit includes:
There are three types of monocarboxylic acid, dicarboxylic acid, and tricarboxylic acid, and the organic acids generated when these polycarboxylic acids are hydrolyzed are as shown in the following Chemical Formulas 7, 8, and 9. . That is, the monocarboxylic acid in which only the hydroxyl group at position 6 is oxidized is glucuronic acid by hydrolysis, and the dicarboxylic acid in which the hydroxyl group at position 2 and 3 is oxidized is erythronic acid and glyoxylic acid. Tartaric acid and glyoxylic acid are generated from tricarboxylic acids in which all the hydroxyl groups have been oxidized. Therefore, the content of each component unit in the polycarboxylic acid before hydrolysis can be determined by quantitative qualitative analysis of glucuronic acid, erythronic acid, and tartaric acid.

[0028]

[Monocarboxylic acid]

[0029]

Embedded image [Dicarboxylic acid]

[0030]

Embedded image [Tricarboxylic acid]

Example 1 [Production of polycarboxylic acid] Stirrer, funnel for dropping oxidizing agent,
In a 500 ml separable flask equipped with a sodium hydroxide aqueous solution dropping port, a pH electrode, and a thermometer, 10 g of corn starch in absolute dry weight and ion-exchanged water 1
00g and RuCl ₃ .nH ₂ O (Ru content 38%)
0.49 g (3 to anhydrous glucose units of starch)
Mol%). Then, the mixture was cooled in a water bath at 20 ° C., and when the internal temperature reached about 20 ° C., 230 g of a 12% by weight aqueous solution of sodium hypochlorite (6 times mol based on anhydrous glucose units of starch) was added for 3 hours. Over a period of time. During this time, a 2N aqueous sodium hydroxide solution was added using a pH stat to control the pH in the system to 9.

After completion of the addition of sodium hypochlorite, stirring was continued for another 2 hours, and the reaction mixture was slowly poured into about 1 liter of ethanol to precipitate a reaction product. The obtained precipitate was dissolved in 150 ml of ion-exchanged water, purified by diffusion dialysis with ion-exchanged water for 5 days, and then freeze-dried to obtain 7.5 g of sodium polycarboxylate powder. About the obtained sodium polycarboxylate, the carboxyl group content determined by the above-mentioned method was 521 mg, and the weight average molecular weight was 5,800. The Ca ion chelating ability (CEC) was 410 mg / g. The content of each structural unit in the polycarboxylic acid was as follows.

Using the polycarboxylic acid synthesized in this manner, the composition shown in Table 1 below was used using a ribbon mixer.
Powder mix the enzyme and solid components except sodium perborate,
Then, spray the nonionic activator, and finally the enzyme,
Produced by adding sodium perborate and fragrance, having an average particle size of about 1 mm and a bulk density of 0.95 g / ml
Of an automatic dishwasher was obtained. The following tests were performed on the detergent for an automatic dishwasher thus obtained. Table 2 shows the results. [Water solubility test] Put 1 L of water at 25 ° C. into a beaker, and stir with a magnetic stirrer to add 2 g of the detergent to be tested
Was added. At this time, the time required for complete dissolution was measured. That is, it can be said that the shorter the time, the better the water solubility. [Washing test] Washing conditions: Fully automatic dishwasher (Model NP-810) manufactured by Matsushita Electric Industrial Co., Ltd.
, Standard course washing was performed using 5 g of a detergent. Oil stain cleaning power: 5 ceramic dishes 25cm in diameter, 15c in diameter
3 m melamine dishes, box-shaped tupper container (medium size) 1
5 g of oil-red colored butter was applied to each of the pieces, and after standing for a day and night, a washing test was performed. The washing rate was calculated from the weight change according to the following equation shown in Equation 1, and the tactile sensation of the following criteria was used. It was evaluated by judgment.

[0034]

(Equation 1)

<< Tactile Judgment >> ○: Butter does not remain at all, and no slimy feeling is felt. Δ: Butter residue was not visually observed, but felt slightly slimy when touched. ×: Butter remains. Starch soil cleaning power: 5 g of retort porridge was applied to 5 ceramic bowls and 3 soup bowls, respectively, and allowed to stand for 24 hours. After that, a cleaning test was performed, and the cleaning power was evaluated according to the following criteria. ：: No rice remains. Δ: Part of rice remains. ×: Rice is clearly left.

Glass whitening: Six transparent glass cups were prepared, and three of them were coated with 0.5 g of raw eggs,
After standing for a period of time, a washing test was performed, and the glass whitening property was visually evaluated according to the following criteria. ：: No whitening such as water spots was observed in any of the cups, and the cups were transparent and beautiful. Δ: The cup without the egg applied was transparent and beautifully finished, but the egg-coated cup had some white spots. ×: Whitening was observed in all cups.

[0037]

[Table 1]Table 1: Composition table Component name Compounding amount (% by weight) Polycarboxylic acid (synthetic product) 3 Sodium citrate 12 Sodium carbonate 8 Sodium bicarbonate 10 Layered silicate (SKS-6: manufactured by Hoechst Japan) 2 Amorphous silica (Toksil N: manufactured by Tokuyama Soda) 2 Sodium aluminate 1 Low Foaming nonion (Sophanol EP90100: manufactured by Nippon Shokubai Kagaku) 4 Sodium perborate (manufactured by Mitsubishi Gas Chemical) 10 Amylase (duramil: manufactured by Novo Nordic) 0.5 Protease (durazyme: manufactured by Novo Nordic) 0.5 Perfume (Takasago) (Perfume) 0.08 Sodium sulfate balance

[0038]

[Table 2]

Example 2 [Production of polycarboxylic acid] Stirrer, funnel for dropping oxidizing agent,
In a 500 ml separable flask equipped with a sodium hydroxide aqueous solution dropping port, a pH electrode, and a thermometer, 10 g of corn starch and 5 g of ion-exchanged water in absolute dry weight.
And RuCl ₃ .nH ₂ O (Ru content 38%) 0.1
6 g (1 mol% based on the anhydrous glucose units of starch) were weighed out. Then, the mixture was cooled in a water bath at 20 ° C., and when the internal temperature reached about 20 ° C., 192 g of a 12% by weight aqueous solution of sodium hypochlorite (5 times the mol of anhydrous glucose units of starch) was added for 5 hours. Over a period of time. During this time, a 2N aqueous sodium hydroxide solution was added using a pH stat to control the pH in the system to 10.

After completion of the addition of the sodium hypochlorite, stirring was continued for another 2 hours to obtain 7.8 g of a sodium polycarboxylate powder in the same manner as in Example 1. About the obtained sodium polycarboxylate, the carboxyl group content determined by the above-mentioned method was 489 mg, and the weight average molecular weight was 8100. The Ca ion chelating ability (CEC) is 402 m
g / g. The content of each structural unit in the polycarboxylic acid was as follows. Analysis result composition Monocarboxylic acid: 1 mol% Dicarboxylic acid: 5 mol% Tricarboxylic acid: 71 mol% Non-oxide: 23 mol%

Using the polycarboxylic acid synthesized as described above, the composition shown in Table 1 was used by using a ribbon mixer.
Powder mix the enzyme and solid components except sodium perborate,
Then, spray the nonionic activator, and finally the enzyme,
Produced by the method of adding sodium perborate and fragrance, having an average particle size of about 1 mm and a bulk density of 0.90 g / ml
Of an automatic dishwasher was obtained. The above test was carried out on the detergent for an automatic dishwasher thus obtained. The results are shown in Table 3.

[0042]

[Table 3]

Comparative Example 1 [Production of polycarboxylic acid]
_The same operation was performed except that ₃ · nH ₂ O was not used.
The obtained sodium polycarboxylate was 8.3 g. About the obtained sodium polycarboxylate, the carboxyl group content determined by the above-mentioned method was 312 mg, and the weight average molecular weight was 5000. The Ca ion chelating ability (CEC) was 220 mg / g. The content of each structural unit in the polycarboxylic acid was as follows. Analysis result composition Monocarboxylic acid: 2 mol% Dicarboxylic acid: 73 mol% Tricarboxylic acid: 5 mol% Non-oxide: 20 mol%

Using the polycarboxylic acid synthesized as described above, the composition shown in Table 1 was mixed with a ribbon mixer.
Powder mix the enzyme and solid components except sodium perborate,
Then, spray the nonionic activator, and finally the enzyme,
Produced by adding sodium perborate and fragrance, having an average particle size of about 1 mm and a bulk density of 0.94 g / ml
Of an automatic dishwasher was obtained. The above test was conducted on the detergent for an automatic dishwasher thus obtained. Table 4 shows the results.

[0045]

[Table 4]

Comparative Example 2 [Procurement of polycarboxylic acid] Socaran CP-7 (trade name) which is an existing polyacrylic acid / polymaleic acid copolymer
Was obtained from BASF Japan Ltd. It is generally known that polyacrylic acid / polymaleic acid copolymer has extremely poor biodegradability. The weight average molecular weight of this socaran CP-7 determined by the method described above was 50,000. The Ca ion chelating ability (CEC) is 35
It was 0 mg / g. Using the obtained polycarboxylic acid, the composition of Table 1 was mixed with a solid component except for the enzyme and sodium perborate using a ribbon mixer, followed by spray addition of a nonionic activator, Finally, it is produced by a method of adding an enzyme, sodium perborate and a fragrance, and has an average particle size of about 1 mm and a bulk density of 0.95 g /
ml of granular detergent for automatic dishwashers were obtained. The above test was conducted on the detergent for an automatic dishwasher thus obtained. The results are as shown in Table 5.

[0047]

[Table 5]

Comparative Example 3 The same detergent as in Example 2 was produced except for removing the polycarboxylic acid. Average particle size is about 1mm, bulk density is 0.95g / ml
Of an automatic dishwasher was obtained. The above test was conducted on the detergent for an automatic dishwasher thus obtained. Table 6 shows the results.

[0049]

[Table 6]

Comparative Example 4 The same detergent as in Example 2 was produced except for the amylase.
A granular detergent for an automatic dishwasher having an average particle diameter of about 1 mm and a bulk density of 0.95 g / ml was obtained. The above test was conducted on the detergent for an automatic dishwasher thus obtained. The results are shown in Table 7.

[0051]

[Table 7]

Claims (2)

[Claims] 1. An alkali which is a polycarboxylic acid or a salt thereof derived by oxidizing a polysaccharide having an anhydrous glucose as a constitutional unit and which is required for neutralizing and titrating an acid-type polycarboxylic acid is water. In terms of sodium oxide,
A detergent composition for an automatic dishwasher, comprising, as essential components, a polycarboxylic acid or a salt thereof having an average molecular weight of at least 435 mg or more per gram of the polycarboxylic acid and an amylase. Stuff. 2. The polycarboxylic acid or a salt thereof contained as an essential component is a polycarboxylic acid or a salt thereof derived by oxidizing a polysaccharide having an anhydrous glucose as a structural unit, and is contained in the compound. Below,
The total content of a monocarboxylic acid or a salt thereof represented by the general formula (1) and a dicarboxylic acid or a salt thereof represented by the following general formula (2) is 10 mol% or less;
The compound according to claim 1, wherein at least 50 mol%, preferably at least 70 mol%, of the compound comprises a tricarboxylic acid or a salt thereof represented by the following general formula (3) and an unoxidized polysaccharide. 2. The detergent composition for an automatic dishwasher according to 1. Embedded image (In the formula, M ₁ represents a cation corresponding to monovalent such as a hydrogen atom or an alkali metal.) (In the formula, M ₂ and M ₃ represent a monovalent cation such as a hydrogen atom or an alkali metal.) (M ₄ , M ₅ and M ₆ in the formula represent a hydrogen atom or a cation corresponding to monovalent such as an alkali metal.)