JPH04362011A - Amorphous aluminosilicate and its production - Google Patents

Abstract

PURPOSE:To improve the cation exchangeability, oil absorptivity and cleaning performance by allowing an alumina source soln. to react with a silica source soln. in the presence of an alkaline earth metal. CONSTITUTION:The soln. of an alumina source such as sodium aluminate, the soln. of a silica source such as water glass and an alkaline earth metal such as Ca are mixed to obtain a composition in which the molar ratio of M2O (M is an alkali metal) is controlled to 1X10<-3>-1X10<0> and the molar ratio of MeO to H2O (Me is an alkaline earth metal) to 1m10<-7>-1X10<-1>. The composition is then heated and subjected to a reaction to produce an amorphous aluminosilicate as a compd. shown by the formula (a=0.001-0.100, b=0.200-2.00 and c=0.500-5.000) in which the cation exchange capacity is controlled to >=150 meg/100 g, oil adsorption to >=150 ml/100 g and the Al ion solubility in water at >=pH 3 to <=3mg/g.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an amorphous aluminosilicate and a method for producing the same.

0002

[Prior Art/Problems to be Solved by the Invention] Amorphous aluminosilicates have a cation exchange ability comparable to that of crystalline aluminosilicates and have high oil absorption performance, so they are used as detergent builders. It is widely used as a filler for paper manufacturing, and various attempts have been made to improve its properties. That is, many improvements have been made to aluminosilicates that give priority only to cation exchange ability and oil absorption performance.
No. 6 discloses an amorphous silicate having a high cation exchange ability. Further, JP-A-61-17411 discloses a method for obtaining an amorphous aluminosilicate with a large oil absorption amount by limiting the alkalinity during the reaction. Furthermore, JP-A-61-111911 discloses that calcium is
．． Calcium silicate containing 10 to 720 moles has been disclosed and is reported to have a high oil absorption rate.

[0003] However, all of these reports aim only at improving cation exchange ability and oil absorption performance, and do not take into account the cleaning performance of detergent compositions. When considering the cleaning performance of a detergent composition, it is also required to have the property of not eluting polyvalent metal ions. That is, when an aluminosilicate is used as a detergent composition, in addition to improving the cation exchange ability and oil absorption performance described above, it is required to prevent the elution of Al ions from the composition from the viewpoint of reducing the cleaning ability. . This is due to the elution of Al ions, causing fatty acids and Al in human sebum stains.
This is because the ions react and become a binder for dirt, reducing the cleaning ability. Furthermore, the dispersibility of mud in the washing liquid becomes worse, resulting in re-contamination. However, the reality is that no aluminosilicate has been found that has both such oil absorption performance and cleaning performance.

[0004] Accordingly, an object of the present invention is to provide an amorphous aluminosilicate having both oil absorbing performance and cleaning performance. Another object of the present invention is to provide a method for producing such amorphous aluminosilicate.

[0005]

[Means for Solving the Problems] As a result of intensive studies to solve the above problems, the present inventors found that amorphous aluminosilicate with a specific composition has excellent oil absorption performance and cleaning performance. The present inventors have discovered that the present invention is useful as a detergent composition, and have completed the present invention. That is, the gist of the present invention is (1
) aMeO・bM2 O・Al2 O3 ・cSiO2
Amorphous aluminosilicate represented by (where Me is an alkaline earth metal, M is an alkali metal, and a=0.0
01~0.100, b=0.200~2.000, c=
0.500 to 5.000), and (2) M2 O/H2 as a charging composition when reacting an alumina source solution and a silica source solution in the presence of an alkaline earth metal.
The molar ratio of O (where M represents an alkali metal) is 1×
10−3 to 1×100 and the molar ratio of MeO/H2O (where Me represents an alkaline earth metal) to 1×10
The present invention relates to a method for producing an amorphous aluminosilicate, characterized in that the aluminosilicate is -7 to 1×10 −1 .

[0006] In the amorphous aluminosilicate of the present invention,
The alkaline earth metal represented by Me is not particularly limited, but calcium and magnesium are usually used because they are inexpensive and easy to obtain industrially. The composition ratio is a=0.001 to 0.100, and the present invention is particularly characterized in that it contains an alkaline earth metal oxide and has the above composition ratio. That is, in those that do not contain alkaline earth metal oxides, the Al ion solubility is 3 mg/1 g or more, and even if it does, it is 0.00
If it is less than 1 mol, the effect of reducing Al ion solubility is small;
If the content exceeds 0.100 mol, the oil absorption capacity and cation exchange capacity will decrease, which is not preferable.

The alkali metal represented by M is not particularly limited, but sodium and potassium are usually preferably used from the viewpoint of detergent formulations. The composition ratio is b
=0.200 to 2.000. Further, the composition ratio of SiO2 is c=0.500 to 5.000.

The aluminosilicate of the present invention is amorphous and has a cation exchange capacity of usually 150 meq/100 g.
Above, preferably 200meq/100g or above,
and the oil absorption amount is 150ml/100g or more, preferably 2
00ml/100g or more. Here, the cation exchange capacity refers to the amount of Ca in the filtrate obtained by adding a sample to a calcium chloride solution, stirring it at 25°C for 15 minutes, and then performing suction filtration using a type 5 C filter paper. It is determined by titration. In addition, oil absorption refers to the amount measured by crushing a sample and using the oil absorption measurement method of JIS K 6220.

[0009] Furthermore, the amorphous aluminosilicate of the present invention is
Al ion solubility in water with pH 3 or higher is usually 3 m
g/1g or less, preferably 2mg/1g or less. Here, Al ion solubility is an index of cleaning performance, and this is determined by suspending the sample in ion-exchanged water (pH 7) and stirring it at 25°C for 1 hour.
The concentration of Al ions in the filtrate was determined by plasma emission spectrometry after suction filtration using a membrane filter.

The amorphous aluminosilicate of the present invention can be easily prepared by reacting an alumina source solution and a silica source solution in the presence of an alkaline earth metal. As the alumina source solution, an alkali metal aluminate solution is usually used, and for example, sodium aluminate, potassium aluminate, etc. are preferably used from the viewpoint of being inexpensive and easy to obtain industrially. These are adjusted to appropriate molar ratios and concentrations using caustic alkali and water as needed. For example, a sodium aluminate solution can be prepared by mixing aluminum hydroxide and sodium hydroxide in water, heating and dissolving the mixture, and adding this solution to water with stirring to obtain an alumina source solution. Further, such adjustment of the molar ratio and concentration can also be carried out by introducing water into the reaction tank in advance and adding a highly concentrated alkali metal aluminate solution and caustic alkali to the water.

Water glass is usually used as the silica source solution, and can be dissolved in water to form the silica source solution. Examples of the alkaline earth metal include calcium, magnesium, etc., and for example, calcium chloride, magnesium chloride, etc. are preferably used. These alkaline earth metal compounds may be mixed with a sodium aluminate solution and included in the alumina source solution, or may be dissolved in water together with water glass and included in the silica source solution. Further, the alkaline earth metal compound may be used alone by being dissolved in water.

[0012] In order to react the alumina source solution and the silica source solution in the presence of an alkaline earth metal, the silica source solution may be added dropwise to the alumina source solution while the alumina source solution is being stirred. The alumina source solution and the silica source solution may be simultaneously added dropwise into the solution to react. In particular, when the alkaline earth metal compound is used alone dissolved in water, the alumina source solution and the silica source solution may be added dropwise at the same time while the solution is being stirred to react.

In order to obtain the amorphous aluminosilicate having the above composition of the present invention, MeO/A is used as the feed composition.
The molar ratio of l2O3 is usually 0.001 to 0.100,
Preferably 0.005 to 0.095, M2O/Al2
The molar ratio of O3 is usually 0.2 to 5.0, preferably 0.
．． 5 to 4.0, the molar ratio of SiO2/Al2O3 is usually 0.5 to 10, preferably 1.0 to 8.0, M2
The molar ratio of O/H2O is usually 1 x 10-3 to 1 x 100
, preferably 2 x 10-3 to 2 x 10-1, MeO/H
The molar ratio of 2O is adjusted to be 1 x 10-7 to 1 x 10-1, preferably 5 x 10-7 to 5 x 10-2.

The reaction temperature is usually 10 to 100°C, preferably 20 to 100°C, and the reaction time is usually 0 to 120 minutes, preferably 1 to 60 minutes, although it varies depending on the reaction temperature. After the reaction is completed, the product can be obtained by processing in a conventional manner. For example, the aluminosilicate powder of the present invention can be obtained by heating and aging for usually 1 to 300 minutes, separating the precipitate from the mixture by filtration or centrifugation, washing and drying, and then pulverizing. . The aluminosilicate powder of the present invention thus obtained can be used by being incorporated into a detergent composition.

[0015]

[Examples] The present invention will be explained in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples in any way. Incidentally, the measured values in the present examples and comparative examples were measured by the method shown below.

(1) Accurately weigh 0.1 g of the cation exchange capacity sample in terms of anhydride, and add 100 ml of calcium chloride solution (500 ppm as CaCO3).
After stirring at 25° C. for 15 minutes, suction filtration is performed using Type 5 No. C filter paper. 50 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 that value.

(2) Oil absorption A sample was crushed in a mortar and measured by the oil absorption measurement method of JIS K 6220.

(3) Al ion solubility 1 g of the sample is suspended in 50 ml of ion-exchanged water (pH 7), stirred at 25° C. for 1 hour, and then suction filtered using a membrane filter with a pore size of 0.2 μm. Measuring the Al ion concentration in the filtrate by plasma emission spectrometry,
The Al ion solubility was determined from the value.

Example 1 100 parts by weight of aluminum hydroxide and 59 parts by weight of sodium hydroxide were mixed in 60 parts by weight of ion-exchanged water and then heated and dissolved to obtain 20.3% by weight of Na2O, Al2O3.
28.2% by weight, Al2O3/Na2O=0.8
A sodium aluminate solution of 47 (molar ratio) is prepared in advance. Add 384g of this solution to 6600g of ion-exchanged water.
was added to the solution while stirring and kept at 30°C to obtain an alumina source solution. In addition, No. 3 water glass (Na2O 9.5% by weight
, SiO2 29.0% by weight, SiO2 /Na2O
= 3.15 (molar ratio) ) and 1.56 g of calcium chloride dihydrate are dissolved in 660 g of ion-exchanged water to prepare a silica source solution. While the alumina source solution was being stirred at a rotation speed of 5000 rpm using a homomixer, the silica source solution was added dropwise over 20 minutes. After the dropwise addition, stirring was continued for 10 minutes, followed by heat aging at 100° C. for 10 minutes, followed by filtration and washing. The resulting wet cake was heated to 100°C.
After drying for 11 hours, the powder was crushed to obtain the aluminosilicate powder of the present invention. The composition of the obtained powder was found to be CaO/Al2O3 as a result of atomic absorption spectrometry and plasma emission spectrometry.
=0.009 Na2O/Al2O3
=0.95SiO2/Al2O3 =3.59. Also, cation exchange capacity is 323meq/100g
The oil absorption amount was 308 ml/100 g, and the Al ion solubility was 0.4 mg/g.

Example 2 A sodium aluminate solution was prepared in the same manner as in Example 1, and 192 g of this solution and 7.8 g of calcium chloride dihydrate were added to 10,300 g of ion-exchanged water to obtain an alumina source solution. Additionally, 440 g of No. 3 water glass was added to 1030 g of ion-exchanged water to obtain a silica source solution. The silica source solution was added dropwise over 15 minutes while the alumina source solution was kept at 30° C. and stirred at a rotation speed of 5000 rpm using a homomixer. After the dropwise addition, stirring was continued for 10 minutes, followed by heating and aging at 100°C for 10 minutes, and the same operation as in Example 1 was carried out.
Aluminosilicate powder was obtained. The composition of the obtained powder is C
aO/Al2 O3 =0.047 Na2
O/Al2 O3 = 0.47SiO2 /Al2
O3 = 1.07. Also, the cation exchange capacity is 2
61meq/100g, oil absorption 298ml/100g
, the Al ion solubility was 0.9 mg/g.

Example 3 A sodium aluminate solution was prepared in the same manner as in Example 1, and 384 g of this solution was added to 110 g of ion-exchanged water to obtain an alumina source solution. In addition, No. 3 water glass 440
g and 4.7 g of calcium chloride dihydrate with 6 g of ion-exchanged water.
Dissolve in 5 g to obtain a silica source solution. Ion exchange water 283
While keeping 0g at 40℃, mix it with a homomixer for 5 minutes.
While stirring at a rotation speed of 1,000 rpm, the alumina source solution and silica source solution were simultaneously added dropwise over 20 minutes using a microtube pump. After continuing to stir for 10 minutes after dropping, heat aging was performed at 100 ° C. for 20 minutes.
The same operation as in Example 1 was performed to obtain aluminosilicate powder. The composition of the obtained powder is CaO/Al2O3
=0.015 Na2O/Al2O3
=0.87SiO2/Al2O3 =2.27. In addition, the cation exchange capacity is 312meq/100
g, oil absorption was 338 ml/100 g, and Al ion solubility was 1.8 mg/g.

Example 4 A sodium aluminate solution was prepared in the same manner as in Example 1, and 384 g of this solution was added to 110 g of ion-exchanged water to obtain an alumina source solution. In addition, No. 3 water glass 440
g to 65 g of ion-exchanged water to prepare a silica source solution. Magnesium chloride hexahydrate 21 to 1670 g of ion-exchanged water
．． The alumina source solution and the silica source solution were simultaneously added dropwise over 20 minutes while the magnesium chloride solution in which 5 g of magnesium chloride was dissolved was kept at 40° C. and stirred at a rotation speed of 5000 rpm using a homomixer. After the dropwise addition, the mixture was stirred for 20 minutes, heated and aged for 10 minutes, and the same operations as in Example 1 were carried out to obtain aluminosilicate powder. The composition of the obtained powder is CaO/Al
2 O3 =0.054 Na2 O/Al2
O3 = 1.00SiO2 /Al2 O3 =
It was 1.80. Also, the cation exchange capacity is 302me
q/100g, oil absorption was 286ml/100g, and Al ion solubility was 0.8mg/g.

Examples 5 to 15 Aluminosilicate powders were produced in the same manner as in Examples 1 to 4 from compositions having the proportions shown in Table 1. The composition, cation exchange capacity, oil absorption, and Al ion solubility of the obtained powder were examined, and the results are shown in Table 1.

[0024]

[Table 1]

Comparative Example 1 A sodium aluminate solution was prepared in the same manner as in Example 1, and 384 g of this solution was added to 6,600 g of ion-exchanged water to obtain an alumina source solution. Further, 440 g of No. 3 water glass was added to 660 g of ion-exchanged water, and this was used as a silica source solution. 40% alumina source solution
While maintaining the temperature at 5000 rpm using a homo mixer.
While stirring at a rotational speed of , the silica source solution was added dropwise over 20 minutes using a micro tube pump. After completion of the dropwise addition, stirring was continued for 10 minutes, followed by heat aging at 100° C. for 10 minutes, followed by filtration and drying in the same manner as in Example 1 to obtain an aluminosilicate. The cation exchange capacity and oil absorption capacity of this powder are 333 meq/100, respectively.
g, 290 ml/100 g, but the Al ion solubility was 3.6 mg/g, and Al ions were eluted compared to the aluminosilicate of the present invention containing an alkaline earth metal.

Comparative Example 2 A sodium aluminate solution was prepared in the same manner as in Example 1, and 384 g of this solution and 11.9 g of potassium hydroxide were added to 2,690 g of ion-exchanged water to obtain an alumina source solution. Also, No. 3 water glass 440g
was added to 660 g of ion-exchanged water, and this was used as a silica source solution. While the alumina source solution was maintained at 30° C. and stirred at a rotational speed of 5000 rpm using a homomixer, the silica source solution was added dropwise over 20 minutes using a microtube pump. After the addition was completed, stirring was continued for 10 minutes, followed by heat aging at 100° C. for 10 minutes, followed by filtration and drying in the same manner as in Example 1 to obtain an aluminosilicate. The cation exchange capacity and oil absorption capacity of this powder are 340 meq/100g and 215ml/100, respectively.
g, but the Al ion solubility was 4.3 mg/g, and compared to the aluminosilicate of the present invention containing an alkaline earth metal, Al ions were eluted.

Comparative Example 3 A sodium aluminate solution was prepared in the same manner as in Example 1, and 384 g of this solution was added to 110 g of ion-exchanged water to obtain an alumina source solution. Further, 550 g of No. 3 water glass was dissolved in 65 g of ion-exchanged water to obtain a silica source solution. 5580g of ion-exchanged water at 50℃
5000 rpm with a homomixer while maintaining
While stirring at a rotational speed of , the alumina source solution and silica source solution were simultaneously added dropwise over 10 minutes using a microtube pump. After completion of the dropwise addition, stirring was continued for 20 minutes, followed by heat aging at 100° C. for 10 minutes, followed by filtration and drying in the same manner as in Example 1 to obtain an aluminosilicate. The cation exchange capacity and oil absorption capacity of this powder are 270 meq/100g and 292ml/100g, respectively.
However, the Al ion solubility was 3.2 mg/g, and Al ions were eluted compared to the aluminosilicate of the present invention containing an alkaline earth metal.

Comparative Example 4 A sodium aluminate solution was prepared in the same manner as in Example 1, and 192 g of this solution and 78 g of calcium chloride dihydrate were added to 5150 g of ion-exchanged water to obtain an alumina source solution. Additionally, 440 g of No. 3 water glass was added to 330 g of ion-exchanged water to obtain a silica source solution. The silica source solution was added dropwise over 10 minutes while the alumina source solution was kept at 60° C. and stirred at a rotation speed of 5000 rpm using a homomixer. After the dropwise addition, stirring was continued for 10 minutes, and then heated and aged at 100° C. for 20 minutes, followed by filtration and drying in the same manner as in Example 1 to obtain an aluminosilicate. The composition of this powder is CaO/Al2 O3 =0.410
Na2O/Al2O3 = 0.37S
iO2/Al2O3 = 1.03, and contained a large amount of calcium. In addition, the Al ion solubility is
0.5 mg/g, but the cation exchange capacity and oil absorption amount were 84 meq/100 g and 144 ml/1, respectively.
00g, which was inferior to the aluminosilicate of the present invention.

Comparative Example 5 A sodium aluminate solution was prepared in the same manner as in Example 1, and 128 g of this solution was added to 560 g of ion-exchanged water.
In addition, it is used as an alumina source solution. Also, No. 3 water glass 5
Add 50 g to 65 g of ion-exchanged water to obtain a silica source solution. A magnesium chloride solution prepared by dissolving 71.8 g of magnesium chloride hexahydrate in 1800 g of ion-exchanged water was added to the
5000 rpm using a homo mixer while keeping at ℃
The silica source solution and the alumina source solution were simultaneously added dropwise over 10 minutes while stirring at a rotational speed of m. 20 minutes after dropping
After continued stirring for a minute, the mixture was heated and aged at 100° C. for 10 minutes, followed by filtration and drying in the same manner as in Example 1 to obtain an aluminosilicate. The composition of this powder is MgO
/Al2O3 = 0.240 Na2O
/Al2O3 = 0.46 SiO2 /Al2O3 = 3.20, and contained a large amount of magnesium. In addition, the Al ion solubility was 0.7 mg/g, but the cation exchange capacity and oil absorption were 118 meq/100 g and 132 m
l/100g, which was inferior to the aluminosilicate of the present invention. Table 2 shows the charging composition, powder composition, cation exchange capacity, oil absorption, and Al ion solubility in Comparative Examples 1 to 5.

[0030]

[Table 2]

Test Example Powder raw materials (beef tallow soap, zeolite A
(equivalent to 35% by weight), amorphous aluminosilicate, soda carbonate (average particle size 290μ), No. 2 sodium silicate, Glauber's salt, carboxymethyl cellulose, sodium polyacrylate, and fluorescent dye) using a rolling granulator ( Polyoxyethylene dodecyl ether and coconut oil diethanolamide were gradually introduced into the mixture (Ledige mixer), and then the polyethylene glycol melt was added to obtain a powder detergent dough with an average particle size of 402 μm. Enzyme, fragrance and a small amount of zeolite A (equivalent to 5% by weight) were added and mixed to obtain a final detergent product having the following composition. As the amorphous aluminosilicate, an example in which the amorphous aluminosilicate obtained in Example 1 was used was designated as Formulation Example 1, and an example in which the one obtained in Comparative Example 1 was used as Formulation Example 2.

[0032] Detergent composition: - Polyoxyethylene dodecyl ether
25wt% (average number of added moles of ethylene oxide=8, melting point 15℃,
HLB 10.14) ・Coconut oil diethanolamide
3. Beef tallow soap

2. Zeolite A (average particle size 4μ)
30・Amorphous aluminosilicate
15.Soda carbonate (average particle size 290μ)
No. 8/2 Sodium Silicate
5. Glauber's Salt

4.7 Polyethylene glycol (
Mw6000) 2.Carboxymethylcellulose
2. Sodium polyacrylate (Mw8000)
2. Enzyme

0.5・Fragrance

0.3・Fluorescent dye
0.5

0
Next, using Formulation Example 1 and Formulation Example 2, a cleaning test was conducted by the following method. Mud soil contaminated cloth (artificially contaminated cloth): Akadama soil for Kanuma gardening was dried at 120℃±5℃ for 4 hours and then ground, passed through 150Mesh (100 μm) 1
After drying for 2 hours at 20°C ± 5°C, 150g of soil is dispersed in 1000 liters of perkleen, and a #2023 gold cloth is brought into contact with the liquid and brushed to remove the dispersion liquid and remove excess dirt. -26473 Publication)
. Sebum/carbon stain contaminated cloth (artificially contaminated cloth): (Model sebum/carbon stain composition) Carbon black 15% cottonseed oil
60% cholesterol 5% oleic acid
5% palmitic acid
5% liquid paraffin
1 kg of the above 10% composition is dissolved and dispersed in 80 liters of perculen, a gold cloth #2023 cloth is dipped therein to adhere dirt, and then the perculen is removed by drying.

Washing conditions and evaluation method: Add 5 pieces each of 10 cm x 10 cm muddy soil-stained cotton cloth or sebum/carbon soil-stained cloth (artificially contaminated cloth) to 1 liter of detergent aqueous solution for evaluation, and run at 100 rpm using a tergotometer.
Washing was carried out under the following washing conditions. (Washing conditions) Washing time: 10 minutes Washing concentration: 0.133% Water hardness
4° Water Temperature: 20°C Sugi Sugi 5 minutes with tap water The detergency was determined by measuring the reflectance at 460 nm of the original fabric before contamination and the contaminated fabric before and after washing using a self-recording colorimeter (manufactured by Shimadzu Corporation), and using the following formula. The cleaning rate (%) was determined. Cleaning rate (%)
= (Reflectance after washing - Reflectance before washing) / (Reflectance of original fabric - Reflectance before washing) x 100

[0035] As a result, the cleaning rate in Formulation Example 1 was as follows:
The cleaning rate was 70% for cloth contaminated with carbon stains and 68% for cloth contaminated with mud stains.On the other hand, the cleaning rate in Formulation Example 2 was 60% for cloth contaminated with sebum/carbon stains, and 55% for cloth contaminated with mud stains. , detergent compositions containing the amorphous aluminosilicate of the present invention showed excellent results.

[0036]

Effects of the Invention The amorphous aluminosilicate of the present invention has excellent cation exchange ability and oil absorption performance, and at the same time
It has low ionic solubility and has properties that combine oil absorption and cleaning performance. Therefore, a detergent composition containing this
Compared to the conventional amorphous aluminosilicate compound,
It exhibits high cleaning performance, has a low elution amount of Al ions, and is a powder with low reactivity, so it is useful as a filler for pure polymers and as a carrier.

Claims (4)

[Claims] [Claim 1] aMeO・bM2 O・Al2 O3
・Amorphous aluminosilicate represented by cSiO2 (
However, Me represents an alkaline earth metal, M represents an alkali metal, a=0.001 to 0.100, b=0.200 to 2
．． 000, c=0.500 to 5.000). [Claim 2] Cation exchange capacity is 150 meq/1
00g or more, and the oil absorption amount is 150ml/100
The amorphous aluminosilicate according to claim 1, wherein the amorphous aluminosilicate has a molecular weight of at least 100 g. 3. The amorphous aluminosilicate according to claim 1 or 2, wherein the solubility of Al ions in water having a pH of 3 or more is 3 mg/1 g or less. 4. When reacting an alumina source solution and a silica source solution in the presence of an alkaline earth metal, the molar ratio of M2O/H2O (where M represents an alkali metal) as a charging composition is 1×. 10-3 to 1 x 100 and a molar ratio of MeO/H2O (where Me represents an alkaline earth metal) to 1 x 10-7 to 1 x 10-1. Method for producing silicates.