JP3174201B2 - Detergent composition for automatic dishwashers - Google Patents

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 containing an inorganic ion exchanger and / or a hydrate thereof. More specifically, the present invention relates to a detergent composition for an automatic dishwasher, comprising an inorganic ion exchanger having excellent ion exchange ability and alkali ability and having water resistance, and / or a hydrate thereof.

[0002]

2. Description of the Related Art Builders to be added to detergents have a large number of chelating agents to date.
Ion exchangers, precipitants, dispersants and the like have been reported. In recent years, the use of tripolyphosphate has been reduced due to concerns about eutrophication of closed water bodies such as lakes and marshes, and crystalline alumino represented by JP-A-50-12381 and JP-A-51-12805. Silicates are often used. In addition, JP-A-60-239320 and JP-A-3-93
No. 649 proposes the use of ion-exchangeable sodium silicate, and Japanese Patent Publication No. 61-59245 discloses calcium silicate alkali hydrate, DD-2792.
No. 34A1 discloses a magnesium-containing silicate. However, these builders did not have sufficient ion exchange ability because of insufficient water resistance.

[0003] In recent years, automatic dishwashers have rapidly spread, and have been actively used not only for business purposes but also for general household use. Concentration and concentration of detergents are being pursued in pursuit of the convenience of detergent users, and the builders used in detergents are single-function, such as crystalline aluminosilicates, that have only ion exchange capability. Instead, there is a need in the art for multi-functional ones suitable for concentrating detergent formulations.
Accordingly, an object of the present invention is to provide a detergent composition for an automatic dishwasher, which is excellent in ion exchange ability and alkali ability and contains a water-resistant inorganic ion exchanger, which is suitable for concentration.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, a detergent composition for an automatic dishwasher containing a novel inorganic ion exchanger having a specific composition. They found something and completed the present invention.

That is, the gist of the present invention is to provide the following components (a) to
The present invention relates to a detergent composition for an automatic dishwasher, comprising (c). (A) general _{formula, xM 2 O · ySiO 2 ·} zMe m O n ( where, M is a Group Ia element of the hydrogen or the periodic table, Me represents IIa of the periodic table, IIb, IIIa, and IVa or Group VIII element shown , Y / x = 0.5-2.0, z / x = 0.01-1.
0, n / m = 0.5 to 2.0. A crystalline silicate having a composition represented by at least 100 mg
Inorganic ion exchanger having an ion exchange capacity of CaCO ₃ / g or more and / or hydrate thereof, 0.5 to 70% by weight (b) surfactant, 0.1 to 10% by weight (c) (a) Alkaline agent other than ingredients, 1-70% by weight

In the present invention, the inorganic ion exchanger as the component (a) refers to an inorganic substance having a cation exchange ability. The inorganic ion exchanger according to the present invention has a general formula of xM ₂ O.ySiO ₂ · a ZME _m O crystalline _{silicate n} represented by. Here, M is hydrogen or I in the periodic table.
Group a element, Me is IIa, IIb, IIIa, IVa of the periodic table or
Y / x = 0.5 to 2.0, z / x =
0.01 to 1.0, n / m = 0.5 to 2.0.

Here, M is selected from hydrogen or a group Ia element of the periodic table, and examples of the group Ia element include Na and K. These may be used alone or, for example, a mixture of Na ₂ O and K ₂ O to form the M ₂ O component. Me is selected from Group IIa, IIb, IIIa, IVa or VIII elements of the periodic table, and includes, for example, Mg, Ca, Zn, Y, Ti, Zr, Fe and the like. These are not particularly limited, but are preferably Mg, Ca, F from the viewpoint of resources and safety.
e. Further, it may be mixed either alone or, for example MgO, may constitute the Me _m O _n component by mixing and CaO. The inorganic ion exchanger in the present invention may be a hydrate, and the hydration amount in this case is usually 1 to 20 in terms of a molar amount of H ₂ O.

In the general formula, y / x is 0.5 to
2.0, and preferably 1.0 to 1.8. y /
If x is less than 0.5, the water resistance is insufficient, and if it exceeds 2.0, the ion exchange capacity is reduced, and the ion exchanger is insufficient. z / x is 0.01 to 1.0, preferably 0.02 to 0.9. When z / x is less than 0.01, the water resistance is insufficient, and when it exceeds 1.0, the ion exchange capacity is lowered and the ion exchange is insufficient. x, y, and z are not particularly limited as long as they have the relationship shown in the above y / x and z / x. As described above, xM ₂ O is, for example, x′Na ₂ O · x ″
If the K ₂ O, x is the x '+ x ". This relationship is the same in the z in the case of ZME _m O _n component consists of two or more. Further, n / m =
0.5 to 2.0 indicates the number of oxygen ions coordinated to the element, and is substantially selected from values of 0.5, 1.0, 1.5, and 2.0.

The inorganic ion exchanger according to the present invention comprises M ₂ O, SiO ₂ , Me _m O as shown in the above general formula.
_{It consists} of three components, _n . Therefore, in order to produce the inorganic ion exchanger of the present invention, each component is required as a raw material. In the present invention, a known compound is appropriately used without any particular limitation. For example, M
₂ O component, the Me _m O _n component, alone or oxides of the composite of each of the elements, hydroxides, salts, the element-containing minerals is used. Specifically, for example, as a raw material of the M ₂ O component, NaOH, KOH, Na ₂ CO ₃ , K
₂ CO _3, Na ₂ SO ₄ and the like, as a material of Me _m O _{n component, CaCO 3, MgCO 3, Ca} (OH) 2, M
g (OH) ₂ , MgO, ZrO ₂ , dolomite and the like. As the SiO ₂ component, silica stone, kaolin, talc, fused silica, sodium silicate and the like are used.

In the method for preparing an inorganic ion exchanger according to the present invention, the above-mentioned raw material components are mixed at a predetermined quantitative ratio so as to obtain the desired values of x, y, and z of the inorganic ion exchanger, and usually 300 to 300. 1500 ° C, preferably 500-1000 ° C,
More preferably, a method of firing at a temperature in the range of 600 to 900 ° C. for crystallization is exemplified. In this case, the heating temperature is 3
If the temperature is lower than 00 ° C., the crystallization is insufficient and the water resistance is poor.
If the temperature is higher than 00 ° C., the particles become coarse and the ion exchange capacity decreases. The heating time is usually 0.1 to 24 hours. Such firing can be usually performed in a heating furnace such as an electric furnace or a gas furnace. After firing, the powder is crushed as necessary to adjust the particle size to a predetermined value. As the pulverizer, for example, a ball mill, a roller mill or the like is used.

The hydrate of the inorganic ion exchanger in the present invention can be easily prepared by a known method, and is not particularly limited. For example, there is a method in which an anhydride of the inorganic ion exchanger obtained as described above is suspended in ion-exchanged water, hydrated, dried, and powdered.

The inorganic ion exchanger or hydrate thereof according to the present invention thus obtained has an ion exchange capacity of at least 100 mg CaCO ₃ / g, preferably 200 to 600 mg CaCO ₃ / g. The amount of Si eluted in water is usually 1 in terms of SiO _2.
It is not more than 00 mg / g and is substantially insoluble in water. In the present invention, the term “substantially insoluble in water” means that the amount of Si eluted when 2 g of a sample is added to 100 g of ion-exchanged water and stirred at 25 ° C. for 30 minutes is usually less than 100 mg / g as SiO _2. A thing.

The inorganic ion exchanger according to the present invention has a content of 0.1 to 0.1%.
It shows a pH of 11 or more in a 1% by weight dispersion and shows excellent alkalinity. Also about the alkali buffer effect,
It is particularly excellent, and has an excellent alkali buffering effect as compared with sodium carbonate or ordinary amorphous sodium silicate. Since the inorganic ion exchanger in the present invention has excellent ion trapping ability, alkalinity adjusting ability, and a buffer effect as described above, the detergent composition for an automatic dishwasher of the present invention containing the same is excellent. It has good washing performance and is suitable for concentration.

The content of the above-mentioned inorganic ion exchanger and / or hydrate thereof is usually 0.5 to 70% by weight, preferably 2 to 60% by weight in the whole composition. 0.5% by weight
If the amount is less than the above, the performance of the inorganic ion exchanger will not be exhibited as a composition. If the amount exceeds 70% by weight, the amount of other components contained in the detergent will be restricted, and the balance of the components as the detergent will be impaired. Come.

In the present invention, the surfactant as the component (b) is blended to improve the detergency of oil and fat stains or to prevent calcium-insoluble salts from adhering.
What is used is not particularly limited, but it is preferable to use a low-foaming or non-foaming nonionic surfactant for the purpose of such compounding. Examples of this type of nonionic surfactant include block polymers of polyoxyethylene and polyoxypropylene having a molecular weight of about 1,000 to 10,000 (Pluronic series, manufactured by Asahi Denka Kogyo KK), long chain fats and the like. Polymer of aliphatic alcohol with polyoxyethylene and polyoxypropylene (Nippon Shokubai Chemical Co., Ltd.)
And a surfactant in which the terminal hydroxyl group of polyoxyethylene alkyl ether is capped with an alkyl group (BASF, Plurafac series, etc.). Further, as the surfactant as the component (b), an anionic surfactant and an amphoteric surfactant can be blended as long as the low foamability of the composition can be maintained. As anionic surfactants, potassium or sodium salts of fatty acids, alkylbenzene sulfonates, alkane sulfonates, etc., and as amphoteric surfactants, alkyldimethylamine oxide, sulfobetaine-type surfactants, carbobetaine-type surfactants Agents and the like. These can be used alone or in combination of two or more, and are blended in the detergent composition for automatic dishwashers of the present invention in an amount of 0.1 to 10% by weight, preferably 1 to 5% by weight. . If the amount is less than 0.1% by weight, a sufficient washing effect or the effect of preventing the adhesion of calcium-insoluble salts cannot be obtained. If the amount exceeds 10% by weight, the effect is saturated, so that it is economically less preferable. Absent.

In the present invention, the alkali agent other than the component (a), which is the component (c), is not particularly limited. For example, carbonates or hydrogen carbonates such as sodium carbonate, sodium hydrogen carbonate, ammonium carbonate and guanidine carbonate;
No. 1 sodium silicate, No. 2 sodium silicate, No. 3 sodium silicate, sodium silicate other than the component (a) such as sodium orthosilicate, sodium metasilicate, potassium silicate, etc., sodium borate, potassium borate, etc. Borates and the like are preferred. Furthermore, a small amount of phosphate can be used if necessary. As phosphates, potassium pyrophosphate, sodium pyrophosphate,
And sodium tripolyphosphate. They are,
They can be used alone or in combination of two or more, and are contained in the detergent composition for an automatic dishwasher of the present invention in an amount of 1 to 70% by weight, preferably 5 to 50% by weight. The amount is 1
When the amount is less than 70% by weight, the alkali buffering ability is weak, and a sufficient washing effect cannot be obtained. When the amount exceeds 70% by weight, calcium insoluble salts generated from carbonate ions and calcium ions in hard water adhere to the tableware surface. It is not preferable because it is easy to perform.

The detergent composition for an automatic dishwasher of the present invention further comprises a proton donor,
An active oxygen or active chlorine carrier, a dispersant, a filler, a stabilizer of a bleaching agent, an enzyme, a copper corrosion inhibitor and the like may be blended.

Examples of proton donors include polycarboxylic acids such as fumaric acid, adipic acid and glutaric acid; hydroxypolycarboxylic acids such as citric acid and tartaric acid; phosphonic acid derivatives such as 1-hydroxyethane-1,1
-Diphosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, aminotri- (methylenephosphonic acid),
Ethylenediaminetetra- (methylenephosphonic acid), 3
-T-alkyl-3-oxo-1-aminopropane-
1,1-diphosphonic acid, 3-t-alkyl-3-oxo-1-hydroxypropane-1,1-diphosphonic acid and ω-dimethylaminoalkane-1-hydroxy-1,1
Diphosphonic acid is suitable. Instead of these acids, their water-soluble acidic salts can also be used. Further, as a proton donor, sodium dihydrogen phosphate, potassium dihydrogen phosphate, an acidic ester of phosphoric acid, and sodium hydrogen sulfate can be used.

The active oxygen carrier may include alkali perborates, alkali persulfates, alkali percarbonates, and peroxycarboxylic acids and salts thereof, such as dodecane peroxide dicarboxylic acid or magnesium peroxyphthalate. . Further, dichloroisocyanurate can be used as the active chlorine carrier.

The dispersant, filler, stabilizer for bleaching agent, enzyme, copper corrosion inhibitor and the like are not particularly limited as long as they are generally used in detergents. For example, as a dispersant, polyacrylic acid, polymer electrolytes such as polyaconitic acid, polyethylene glycol,
Examples include non-dissociated polymers such as polyvinyl alcohol and polyvinyl pyrrolidone, polyacetal carboxylic acid polymers described in JP-A-54-52196, and carboxymethyl cellulose. Examples of the filler include an inorganic electrolyte such as a sulfate, and examples of the stabilizer for the bleaching agent include ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), water-soluble salts thereof, and calcium. , Magnesium, aluminum or a complex with zinc, which can be added as it is. It is particularly preferable to use a calcium complex. Furthermore, examples of the enzymes include amylolytic enzymes, proteolytic enzymes, and fat and oil degrading enzymes. Further, the detergent composition for an automatic dishwasher of the present invention further includes an enzyme stabilizer, a hydrotrope, as long as the effects of the present invention are not hindered.
Known conventional components such as fragrances, coloring agents, bactericides, corrosion inhibitors and the like can also be blended.

The detergent composition for an automatic dishwasher of the present invention can be easily prepared by a known method. For example, it is performed by spray drying, agitating tumbling granulation, dry mixing, and a combination of these preparation methods so that the above-mentioned components have a predetermined compounding ratio. Further, the obtained detergent composition for an automatic dishwasher of the present invention is preferably strongly alkaline from the viewpoint of detergency, and specifically, when the pH of a 0.2% by weight aqueous solution is 9.5 or more. It is particularly preferred.

[0022]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. In addition, the measured value in this example was measured by the following method.

(1) Ion exchange capacity A sample of 0.1 g was precisely weighed, and a calcium chloride solution (concentration: C
(1% as aCO ₃ )
After stirring for 5 minutes, filtration is performed using a No. 5 type C filter paper.
10 ml of the filtrate was taken, and the amount of Ca in the filtrate was measured by EDTA titration, and the calcium ion exchange capacity of the sample was determined from the value.

(2) Amount of Si elution 2 g of a sample was added to 100 g of ion-exchanged water.
Stir for 0 minutes. Thereafter, centrifugation is performed, and the supernatant is filtered using a membrane filter having a pore size of 0.2 μm. Plasma emission spectrometry (IC
P), and the elution amount of Si was calculated in terms of SiO ₂ .

Preparation Example (Inorganic ion exchanger) No. 2 sodium silicate (SiO ₂ / Na ₂ O = 2.5) 100
4.2 parts by weight of sodium hydroxide were added to parts by weight, and the mixture was stirred with a homomixer to dissolve sodium hydroxide.
To this, 10 parts by weight of finely dispersed anhydrous calcium carbonate was added and mixed using a homomixer. An appropriate amount of the mixture was placed in a nickel crucible, fired at 700 ° C. in air for 1 hour, quenched, and then the fired product was pulverized to obtain an inorganic ion exchanger powder A of the present invention. The ion exchange capacity of this powder was as high as 243 mg CaCO ₃ / g, and the amount of Si eluted was 19.7 mg SiO ₂ / g, indicating excellent water resistance. Also, the powder X-ray (Cu
Kα) The diffraction pattern showed a diffraction pattern different from that of the mixture before firing, and was a substance showing a novel crystal structure.
Similarly, inorganic ion exchanger powders B, C, and D having the compositions shown in Table 1 were obtained.

[0026]

[Table 1]

Example 1 The above-mentioned inorganic ion exchanger powder A and other components were dry-mixed to prepare a detergent composition for an automatic dishwasher having the following composition. Inorganic ion exchanger powder A 15.0% by weight Alkoxylated nonionic surfactant 5.0% by weight (Nippon Shokubai Chemical Co., Ltd., Sophanol EP7085) Sodium carbonate 40.0% by weight Sodium sulfate 37.0% by weight % Starch degrading enzyme 2.0% by weight (Novo, Termamyl) Proteolytic enzyme 1.0% by weight (Gist, Alcalase)

Example 2 The above-mentioned inorganic ion exchanger powder B and other components were dry-mixed to prepare a detergent composition for an automatic dishwasher having the following composition. Inorganic ion exchanger powder B 10.0% by weight Alkoxylated nonionic surfactant 3.0% by weight (Plurafac LF1300 manufactured by BASF Japan) 69.0% by weight of sodium carbonate 10.0% by weight of sodium percarbonate Polyacrylic Acid oligomer (average molecular weight 6,000) 5.0% by weight Starch-degrading enzyme 2.0% by weight (Novo, Teramyl) Proteolytic enzyme 1.0% by weight (Gist, Alcalase)

Example 3 The above-mentioned inorganic ion exchanger powder C and other components were dry-mixed to prepare a detergent composition for an automatic dishwasher having the following composition. Inorganic ion exchanger powder C 5.0% by weight Alkoxylated nonionic surfactant 1.0% by weight (Nippon Shokubai Chemical Co., Ltd., Sophanol EP7085) Sodium carbonate 40.0% by weight Sodium silicate No. 1 5 0.0% by weight Sodium sulfate 45.0% by weight Sodium polyacrylate (average molecular weight 2,000) 2.0% by weight Polyethylene glycol (average molecular weight 400) 2.0% by weight

Example 4 The above-mentioned inorganic ion exchanger powder D and other components were dry-mixed to prepare a detergent composition for an automatic dishwasher having the following composition. Inorganic ion exchanger powder D 10.0 wt% Alkoxylated nonionic surfactant 5.0 wt% (Nippon Shokubai Chemical Co., Ltd., Sophanol EP7085) Sodium borate 55.0 wt% Sodium citrate 30. 0% by weight

[0031]

EFFECT OF THE INVENTION The detergent composition for an automatic dishwasher of the present invention is excellent in ion exchange ability and alkali ability and contains a water-resistant inorganic ion exchanger and / or a hydrate thereof. It has excellent effects and is suitable for concentrating a detergent.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-5-184946 (JP, A) JP-A-63-55170 (JP, A) JP-A-55-42249 (JP, A) 23088 (JP, A) WO 97/3018 (WO, A2) (58) Fields investigated (Int. Cl. ⁷ , DB name) C11D 3/12 C11D 17/00 CA (STN) CAOLD (STN) REGISTRY ( STN)

Claims (3)

(57) [Claims] 1. A detergent composition for an automatic dishwasher, comprising the following components (a) to (c): (A) general _{formula, xM 2 O · ySiO 2 ·} zMe m O n ( where, M is a Group Ia element of the hydrogen or the periodic table, Me represents IIa of the periodic table, IIb, IIIa, and IVa or Group VIII element shown , Y / x = 0.5-2.0, z / x = 0.01-1.
0, n / m = 0.5 to 2.0. A crystalline silicate having a composition represented by at least 100 mg
Inorganic ion exchanger having an ion exchange capacity of CaCO ₃ / g or more and / or hydrate thereof, 0.5 to 70% by weight (b) surfactant, 0.1 to 10% by weight (c) (a) Alkaline agent other than ingredients, 1-70% by weight 2. The detergent composition for an automatic dishwasher according to claim 1, wherein the surfactant is a nonionic surfactant. 3. The automatic method according to claim 1, wherein the component (c) is one or more selected from the group consisting of carbonates, bicarbonates, silicates, borates, and phosphates. A detergent composition for a dishwasher.