JP2759243B2 - Inorganic builder - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

This invention relates to inorganic builders.
More specifically, the present invention relates to an inorganic builder and a hydrate thereof useful as a water softener and an alkali adjuster used in detergents.

[0002]

2. Description of the Related Art Sodium silicate has an ion exchange ability higher than that of zeolite, but since it is completely dissolved in water, its ion exchange rate is small and its use is limited. As a means for solving the problem, Japanese Unexamined Patent Publication No. Sho 60-239320 discloses a method in which sodium silicate is heated, dehydrated and calcined to obtain a powder. The methods are disclosed in JP-A-3-93649, but all have insufficient water resistance, low ion exchange capacity, and low ion exchange rate. Further, a crystalline calcium silicate alkali hydrate obtained by hydrothermal synthesis is disclosed in Japanese Patent Publication No. 61-59245, but has sufficient water resistance but low ion exchange capacity, and is substantially used for detergents. Not suitable as a builder. Furthermore, the dispersibility in water is poor because the particle shape is coarse long fiber or mica,
Substantial ion exchange capacity is further reduced. DD-2
Although 79234A1 discloses a crystalline magnesium-containing silicate obtained by hydrothermal synthesis, it is pointed out that the ion-exchange ability is extremely low and cannot be applied practically as a detergent builder. In particular, when used as a water softener for detergents, it is necessary to perform ion exchange within a limited time, and a large initial cation exchange rate is required. That is, it is necessary to sufficiently capture Ca, Mg ions and the like within 5 minutes, preferably within 3 minutes.

Accordingly, an object of the present invention is to provide a novel inorganic builder having excellent water resistance, high ion exchange capacity and a high initial cation exchange rate, and a hydrate thereof.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, have found a novel inorganic builder having a specific composition and a hydrate thereof, thereby completing the present invention. Reached. That is, the gist of the present invention is:
(1) An anhydride having the general formula SiO ₂ .aNa ₂ O.bK ₂
O.cCaO.dMgO (however, a + b = 0.5-2.
0, b / a = 0.005-8.0, c + d = 0.005
-1.0, d / c = 0.01 to 100), (2) an initial cation exchange rate of 60 CaCO ₃ mg / g · min or more and a cation exchange capacity of 200 to 500CaCO ₃ mg / g in which the (1), wherein the inorganic builder, (3) the having alkalizing ability is buffering action to acids (1) or (2) above, wherein the inorganic builder, (4) the (1), The present invention relates to a hydrate of the inorganic builder according to (2) or (3), and (5) a detergent composition containing the inorganic builder according to any one of (1) to (4).

The composition of the inorganic builder of the present invention in the form of an anhydride is represented by the general formula: SiO ₂ .aNa ₂ O.bK ₂ O.cCaO
-It is represented by dMgO. Here, a + b is usually 0.5 to 2.0, preferably 0.6 to 1.5.
It is. That is, a + b is preferably 0.5 or more to increase the cation exchange capacity and alkali capacity, and is preferably 2.0 or less to increase the cation exchange rate. b / a is usually 0.005 to 8.0 from the viewpoint of increasing the cation exchange rate, and preferably 0.01 to 6.0.
0. c + d is usually 0.005 to 1.0, preferably 0.02 to 0.6. That is, c + d is preferably 0.005 or more to increase the cation exchange rate, and 1.0 or less to increase the cation exchange capacity and alkalinity. d / c is usually 0.01 to 100 from the viewpoint of increasing the cation exchange capacity,
Preferably it is 0.2-5.0. The inorganic builder of the present invention may be a hydrate. In this case, the hydration amount is usually 0 to 20 mol% in terms of a molar amount of H ₂ O.

The inorganic builder according to the present invention comprises SiO ₂ , Na ₂ O, K ₂ O, CaO, MgO
Of each component. Therefore, in order to produce the inorganic builder 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, Na ₂ O component, K ₂ O
As the component, CaO component, and MgO component, oxides, hydroxides, salts, and minerals containing the element can be used alone or in combination. Specifically, for example, Na ₂
Raw materials for the O component and the K ₂ O component include NaOH, KO
H, Na ₂ CO ₃ , K ₂ CO ₃ , Na ₂ SO _{4 and the} like. As the CaO component, CaCO ₃ , Ca (O
H) ₂ , CaCl ₂ , dolomite and other MgO components include MgCO ₃ , Mg (OH) ₂ , Mg (NO ₃ ) ₂ ,
Dolomite or the like is used. As the SiO ₂ component, silica stone, silica sand, kaolin, talc, fused silica, sodium silicate and the like are used.

In the present invention, these raw materials are mixed at a predetermined ratio such that the desired inorganic builder is 1: a: b: c: d, and is usually 300 to 1500 ° C., preferably 500 to 1500 ° C. 1000 ° C, more preferably 600 to
Examples include a method of firing at 900 ° C. for crystallization and a method of vitrifying and melting the raw material components before firing, further adding water or water-vitrifying, and then firing. In this case, if the heating temperature is lower than 300 ° C., crystallization is insufficient and the water resistance is poor. If the heating temperature is higher than 1500 ° C., coarse particles are formed and the ion exchange ability is reduced. Heating time is usually 0.1 to 2
4 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 if necessary to prepare a predetermined particle size. As the pulverizer, for example, a ball mill, a roller mill or the like is used.
Although the pulverized particle size is not particularly limited, the pulverized particle size is set to 0.1 from the viewpoint of dispersibility.
A range of 1 to 50 μm is preferred. The hydrate of the inorganic builder of the present invention can be easily prepared by a known method, and is not particularly limited. For example, there is a method in which the anhydride of the inorganic builder obtained as described above is suspended in ion-exchanged water, hydrated, dried, and powdered.

The thus obtained inorganic builder or hydrate of the present invention has an initial cation exchange rate of preferably 60 CaCO ₃ mg / g · min or more, more preferably 70 CaCO ₃ mg / g · min. It has the above. The inorganic builder or hydrate thereof of the present invention has a cation exchange capacity of 200 to 500 CaC.
O ₃ mg / g is preferred, and more preferably 2 mg / g.
50-500 CaCO ₃ mg / g. Further, the inorganic builder or its hydrate of the present invention has an alkaline ability as a buffering action against an acid. Here, the alkaline ability means that the pH of the suspension is maintained at 9.0 or more by a buffering action when a predetermined amount of hydrochloric acid having a constant concentration is dropped while a sample is suspended in a fixed amount of ion-exchanged water and stirred. Ability.

The inorganic builder of the present invention is widely used as a constituent of detergents for clothing, tableware, metal, teeth, body, etc., and has superior cation-capturing ability and alkalinity control of Ca, Mg, etc. as compared with conventional ones. And a buffering effect.
As a result, the cleaning composition of the present invention containing the above-mentioned inorganic builder has excellent cleaning performance. Those having controlled powder shapes are useful as oil-absorbing carriers.

[0010] The detergent composition of the present invention contains the above-mentioned inorganic builder, and its compounding amount is usually 0.1 to 90%, preferably 0.5 to 80%, more preferably. Is 1 to 75%. If it is less than 0.1%, sufficient cleaning performance will not be exhibited, and if it exceeds 90%, dispersibility will be poor. In particular, the amount of the inorganic builder of the present invention as a detergent for clothing is usually 0.5 to 70%, preferably 1 to 70%.
-60%, more preferably 2-55%. Also,
Two or more inorganic builders of the present invention may be used in combination, and may be used in combination with other builders such as zeolite, sodium citrate, sodium carbonate, sodium tripolyphosphate, and sodium metaphosphate.

The detergent composition of the present invention can further contain various additives (components) which are usually added to the detergent. Such additives are not particularly limited, and include, for example, various surfactants such as nonionic, anionic and cationic types, enzymes such as protease, lipase, cellulase and amylase, and various electrolytes. It is appropriately blended. The method for producing the cleaning composition is not particularly limited, and a generally known method can be used.

Although the cleaning composition of the present invention is not particularly limited, it is used for various uses such as a detergent for clothing, a softener, a dishwashing detergent, a toothpaste, a body cleaning agent, and a metal cleaning agent. Is done.

[0013]

The present invention will be described in more detail with reference to the following Examples, Comparative Examples and Test Examples, but the present invention is not limited to these Examples. In addition, the measured value in this example and a comparative example was measured by the following method. (1) Initial cation exchange rate 0.1 g of a sample is precisely weighed, and a calcium chloride solution (concentration is C
(500 ppm as aCO ₃ )
After stirring at 5 ° C. for 30 seconds, 60 seconds, 120 seconds and 180 seconds, a membrane filter having a pore size of 0.2 μm for each (Advantech, manufactured by Nitrocellulose)
, And 10 ml of the filtrate was taken, and the amount of Ca in the filtrate was measured by EDTA titration. From that value, the calcium ion exchange capacity (cation exchange capacity) of the sample
Was determined, and the value obtained by averaging the cation exchange rates at each time was defined as the initial cation exchange rate. (2) Cation exchange capacity In the above method, after the sample solution was stirred for 60 minutes,
Similarly, the amount of Ca in the filtrate was measured by EDTA titration, and the calcium ion exchange capacity of the sample was determined. (3) Alkaline capacity 1 g of a sample was precisely weighed, suspended in 1000 ml of ion-exchanged water, and stirred while 10 ml of 0.25 N hydrochloric acid was added dropwise. Those shown were judged to have good alkalinity, and when the pH was less than 9.0, they were judged to be insufficient in alkalinity. If the pH exceeds 12.0, the alkalinity is too high and the storage stability is poor, so it was determined to be unsuitable as a detergent formulation.

Example 1 No. 1 water glass (SiO ₂ / Na ₂ O = 2.14, H ₂ O)
200 g) and sodium hydroxide (NaO).
H) 2.28 g and potassium hydroxide (KOH) 1.39
g, Ca (OH) ₂ 3.64 g, Mg (OH) ₂ 1.4
3 g was mixed using a homomixer. An appropriate amount of the mixture was placed in a nickel crucible, fired in air at 700 ° C. for 1 hour, quenched, and then the fired body was pulverized to obtain inorganic builder 1 of the present invention. The initial cation exchange rate of this powder was 86 CaCO ₃ mg / g · min, and the cation exchange capacity was 286 CaCO ₃ mg / g. Further, the powder X-ray (CuKα) diffraction pattern of the obtained fired body showed a diffraction pattern different from that of the mixture before firing, and was a substance showing a novel crystal structure. After one week in a constant temperature and humidity chamber of 30 ° C. and 80 ° HD, no caking phenomenon was observed, and the water resistance was sufficient. The pH in the test for alkalinity was 1
1.1, and the alkali ability was good.

Examples 2 to 8 In Example 1, KOH, NaOH, Ca (OH) ₂ ,
Inorganic builders 2 to 8 were obtained in the same manner as in Example 1, except that the composition shown in Table 1 was obtained by changing the amount of Mg (OH) ₂ added. The obtained powder was measured for initial cation exchange rate, cation exchange capacity, and pH value by an alkalinity test, and the results are shown in Table 1.
As shown in Table 1, both of the initial cation exchange rate and the cation exchange capacity were excellent, and the alkali ability was also good. Also, the powder X-ray (Cu
Each of the Kα) diffraction patterns showed a diffraction pattern different from that of the mixture before firing, indicating a novel crystal structure. In addition, a 30 ° C., 80 ° HD
After standing for a week, no caking phenomenon was exhibited, and the water resistance was sufficient.

[0016]

[Table 1]

Comparative Examples 1 to 5 Similar to Example 1, they were mixed so as to have the composition shown in Table 1, and an appropriate amount of this was placed in a nickel crucible and fired at 700 ° C. in air for 1 hour. After quenching, crush and compare builder 1
~ 5. The obtained comparison builder is comparison builder 4
Except for Comparative Builder 2, the initial cation exchange rate was low, and the alkali capacity was insufficient or excessive except for Comparative Builder 2. All were unsuitable as detergent formulations.

Preparation Example of Detergent Composition Detergents having the compositions shown in Table 2 (formulations A and B are those containing the inorganic builder of the present invention and formulation C is a comparative product not containing) are prepared by the following method. Manufactured.

That is, the powdery raw materials (sodium silicate, sodium carbonate, sodium sulfate, amorphous silica, inorganic builders 2 and 5) are charged into a stirring type tumbling granulator (Ladyge mixer), and polyoxyethylene dodecyl ether and polyethylene are mixed. Glycol was added to obtain a powder detergent having an average particle size of 368 to 412 µm.

[0020]

[Table 2]

Similarly, a detergent having the composition shown in Table 3 was prepared (formulations D and E contain the inorganic builders 2 and 5 of the present invention, and formulation F contains the comparative builder 1). did. Here, an aqueous slurry of components other than the inorganic builder was prepared at 60 ° C., and was made into a dry powder by a spray dryer. This was put in a centrifugal tumbling granulator (high speed mixer), and granulated by adding a little water to obtain an average particle diameter of 39.
A powder cleaner of 6 to 418 μm was obtained. Similarly, a cleaning agent having the composition shown in Table 4 (formulations G and H contain the inorganic builders 2 and 3 of the present invention, and formulations I and J use 4A zeolite and tri-Na citrate as comparative builders). Containing).

[0022]

[Table 3]

[0023]

[Table 4]

Test Examples Formulations A to J obtained by the above-mentioned preparation examples of the detergent composition
, A cleaning test was performed by the following method. (1) Mud stained cloth (artificially stained cloth): Akatama soil for Kanuma horticulture was dried at 120 ° C. ± 5 ° C. for 4 hours, pulverized, and 150 mesh (100 μm)
m) After drying the pass at 120 ° C. ± 5 ° C. for 2 hours, soil 15
Disperse 0g in 1000 liters of PARKUREN and use gold width # 2023
A cloth is contacted with this liquid and brushed to remove the dispersion and to remove excess adhered dirt (Japanese Patent Laid-Open No. 55-26473). (2) Sebum / carbon stained cloth (artificial stained cloth): (model sebum / carbon stain composition) carbon black 15% cottonseed oil 60% cholesterol 5% oleic acid 5% palmitic acid 5% liquid paraffin 10% 1 kg of the above composition After dissolving and dispersing in 80 liters of perclene, dipping a # 2023 cloth to attach dirt, the perclene is dried and removed.

(3) Washing conditions: Five pieces of 10 cm × 10 cm cotton soiled soiled cloth or sebum / carbon soiled cloth (artificial soiled cloth) are put in each liter of the detergent aqueous solution for evaluation, and 100 rpm using a tergotometer. And washed under the following washing conditions. (Washing conditions) Washing time: 10 minutes Washing concentration: 0.133% Water hardness: 4 ° Water temperature: 20 ° C Sugi: 5 minutes in tap water (4) Washing test evaluation method: Washing power: original fabric before contamination and contamination before and after cleaning The reflectance of the cloth at 460 nm was measured using a self-recording colorimeter (manufactured by Shimadzu Corporation), and the cleaning rate (%) was determined by the following equation. Cleaning rate (%) = (Reflectance after cleaning−Reflectance before cleaning) /
(Reflectance of original cloth−Reflectance before washing) × 100 The obtained results are shown in the lower columns of Tables 2 to 4, and excellent cleaning performance was recognized by using the cleaning composition of the present invention. Was done. Further, since the inorganic builder of the present invention has an alkali ability in addition to high cation exchange properties, even if the use of sodium carbonate or the like as a conventional alkali adjuster is greatly reduced, as shown in Table 4, Shows high cleaning performance.

[0026]

The inorganic builder of the present invention is excellent in cation exchange ability, initial cation exchange rate, alkali ability and water resistance, and thus is useful as, for example, a water softener or an alkali conditioner used in detergents. It is. Further, it is also useful as an oil-absorbing carrier.

────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Masaki Tsumatori 6-23 Saikazaki, Wakayama City, Wakayama Prefecture (58) Fields investigated (Int. Cl. ⁶ , DB name) C11D 3/08 C01B 33/32 CA (STN ) REGISTRY (STN)

Claims (5)

(57) [Claims] 1. An anhydride having a general formula: SiO ₂ .aNa ₂ O
BK ₂ O.cCaO.dMgO (however, a + b = 0.
5 to 2.0, b / a = 0.005 to 8.0, c + d =
0.005 to 1.0, d / c = 0.01 to 100). 2. An initial cation exchange rate of 60 CaCO ₃
mg / g · min or more, and the cation exchange capacity is 20 mg / g · min.
0~500CaCO ₃ mg / g inorganic builder according to claim 1, wherein a. 3. The inorganic builder according to claim 1, which has an alkaline ability as a buffering action against an acid. 4. A hydrate of the inorganic builder according to claim 1, 2 or 3. 5. A cleaning composition comprising the inorganic builder according to claim 1.