JP2000007321A - Production of makatite type sodium silicate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a makatite type sodium silicate having a high calcium ion exchange capacity in high yield with a high productoivity. SOLUTION: A seed crystal of makatite and a water-miscible or a water-soluble nonionic or anionic organic crystallizing agent are added to an aqueous solution or dispersion of sodium silicate and the resultant mixed composition is then heated to produce a makatite type sodium silicate. A water-miscible organic solvent, especially an organic solvent having >=60 deg.C boiling point is used as the organic crystallizing agent and a polyhydric alcohol or its ether derivative, a nonionic surfactant or an anionic surfactant, a nonionic water-soluble polymer or an anionic water-soluble polymer can be used as the preferred one.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing macatite-type sodium silicate, and more particularly, to a method for producing macatite-type sodium silicate excellent in calcium ion exchange capacity with high yield and high productivity. It relates to a method of manufacturing.

[0002]

BACKGROUND OF THE INVENTION It has long been known that polysilicates are useful as detergent builders. For example, Shoko 2
JP-A-3-3328 discloses that acid clay or similar clay is treated with a mineral acid to elute and remove components other than silicic acid to obtain active silicic acid, which is then treated with alkali to produce an alkali polysilicate. There is described a method for producing a soap, characterized in that the soap is blended with a fatty acid soap or a resin soap.

Japanese Patent Application Laid-Open No. 1-192718 discloses a sheet-like structure and a SiO ₂ / Na ₂ O molar ratio of 1.
X-ray crystalline sodium silicate having a ratio of 9: 1 to 3.5: 1 is dissolved in water and the solution is brought to a temperature of 20-445 ° C.
Sheet-like structure characterized by being evaporated with
X with a ₂ / Na ₂ O molar ratio of 1.9: 1 to 3.5: 1
A method for producing linear crystalline sodium silicate is described.

Further, Japanese Patent Application Laid-Open No. 6-183724 discloses a layer structure and 1.9 to 20: 1, preferably 3.5.
To 4.5: The method of manufacturing a sodium silicate having a first SiO ₂ / Na ₂ O molar ratio, substantially [delta]-N
A process for producing the above-mentioned crystalline sodium silicate, which comprises reacting sodium silicate comprising a ₂ Si ₂ O ₅ with at least one kind of acid in a pH range of 9 to 13 under stirring, is described.

[0005] Known sodium silicates, including natural or synthetic ones, include disilicate Na ₂
Si ₂ O ₅ ), macatite (Makatite Na ₂ Si ₄ O)
₉ · 5H ₂ O), Magadeiaito (Magadiite Na ₂
Si ₁₄ O ₂₉ xH ₂ O), Kenyaite N
a ₂ Si ₂₀ O.xH ₂ O) and the like are known.

Japanese Unexamined Patent Application Publication No. 10-815 proposed by the present applicant
No. 09 discloses a formula (1) Na ₂ O.nSiO ₂ .mH ₂ O (1) where n is a number of 3 to 5, especially 4 to 5, and m is 0.
Having a chemical composition represented by the number of from 10 to 10, especially from 4.0 to 7.0, more preferably from 5.0 to 7.0,
In the following formula (2), R _I = I ₀₃₁ / I ₂₀₀ ‥‥ (2) where I ₀₃₁ is the relative intensity of the X-ray diffraction peak of the plane index (031), and I ₂₀₀ is the X of the plane index (200). The X-ray diffraction intensity ratio defined by the relative intensity of the X-ray diffraction peak is 0.
In the range of 2 to 1.20 and the plane index (031)
The crystallite size determined from the half width of the diffraction peak of
Sodium silicate characterized by being in the range of Å or less, and Na ₂ O: Si
The molar ratio of O ₂ of 1.0: 2.8 to 1.0: the aqueous solution of sodium silicate in the range of 3.8, the following formula _{(3) Na 2 O · nSiO} 2 · mH 2 O ‥‥ (3 In the formula, n is a number of 3 or more, m is 0 or any positive number, and a solid sodium silicate having a crystallite size of 500 Å or less is seeded. And concentrate the composition under normal pressure,
There is described a method for producing sodium silicate, which comprises crushing and washing the obtained solid reaction product with water.

[0007]

Among these sodium silicates, disilicate has theoretically the highest calcium ion exchange capacity, but has a very high pH when added to washing water, and has an extremely high pH. There is a tendency to decompose the activator or damage the fiber, and in a humid environment such as in Japan, this deliquesces, causing the detergent to condense and thereby reduce the fluidity. Did not.

On the other hand, although there is no clear description of macatite,
As is clear from the molecular formula, it is predicted that the pH at the time of dispersing in water is not so high and the tendency to deliquesce under high humidity is less than that of disilicate, but almost no synthesis examples are known. It is reported that the synthesis is carried out slightly from silica and sodium (see [L. Muculloch, J.
our.Amer.Chem.Soc., 74, 2453 (1952)]), and details of the synthesis conditions are unknown.

Japanese Patent Application Laid-Open No. 10-815 proposed by the present applicant
Sodium silicate described in JP-A-09-0909 is one of macatite.
It is considered to be a kind of deformation and deserves evaluation because it has excellent calcium ion exchange capacity.However, it is still difficult to stably produce a product having high calcium ion exchange capacity. There are problems that the production operation is complicated, the productivity is low, and the yield is still low, for example, it is necessary to concentrate the product, pulverize the solid reaction product, and wash with water.

[0010] Accordingly, an object of the present invention is to provide a method capable of producing macatite-type sodium silicate having a high calcium ion exchange capacity in a high yield and a high productivity.

[0011]

According to the present invention, a seed crystal of macatite and a water-miscible or water-soluble nonionic or anionic organic crystallizing agent are added to an aqueous solution or dispersion of sodium silicate. The present invention further provides a process for producing a macatite-type sodium silicate, which comprises heating the mixed composition. In the production method of the present invention, 1 to 50 parts by weight, particularly 5 to 3 parts by weight of a seed crystal of macatite per 100 parts by weight of SiO _{2 in} sodium silicate
1. 0 parts by weight, 5 to 300 parts by weight, especially 10 to 200 parts by weight of organic crystallization agent per 100 parts by weight of SiO _{2 in} sodium silicate
2. adding in parts by weight; 3. further adding a water-soluble inorganic salt to the aqueous solution or dispersion of sodium silicate; 4. Addition of 5 to 300 parts by weight, especially 10 to 200 parts by weight, of a crystallization promoting aid consisting of a water-soluble inorganic salt per 100 parts by weight of SiO _{2 in} sodium silicate; The mixed composition is heated at 60 to 150 ° C., particularly 80 to 12
It is preferable to generate crystals while maintaining the temperature at 0 ° C. As the organic crystallization agent, a water-miscible organic solvent, particularly, having a boiling point of 6
An organic solvent having a temperature of 0 ° C. or higher is used, and preferable examples thereof include polyhydric alcohols and ether derivatives thereof. Further, as the organic crystallization agent, a nonionic surfactant or an anionic surfactant is suitably used, and further, a nonionic water-soluble polymer or an anionic water-soluble polymer is also used.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS [Action] To an aqueous solution or dispersion of sodium silicate, a seed crystal of macatite and a water-miscible or water-soluble nonionic or anionic organic crystallization promoter are added. By heating the product, it is possible to produce a macatite-type sodium silicate having a high calcium ion exchange ability in a high yield and with high productivity.

In the production method of the present invention, an aqueous solution or dispersion of sodium silicate is used as a raw material. It is essential to add a macatite seed crystal to the raw material. In this case, it is difficult to crystallize the sodium of the macatite type.

In the present invention, it is important to add a water-miscible or water-soluble, nonionic or anionic organic crystallization accelerator to a sodium silicate solution or the like containing the seed crystal. In addition, it is possible to produce macatite-type sodium silicate with high yield and high productivity. Moreover, the obtained macatite-type sodium silicate has a high calcium ion exchange ability and also has excellent stability over time of the ion exchange ability.

See the example below. That is, when the synthesis of macatite-type sodium silicate was carried out in the same manner as in the present invention except that the organic crystallization accelerator was not added (see Comparative Example 1), the silica (SiO ₂ ) in the raw material sodium silicate was completely converted to that of macatite. The yield of macatite-type sodium silicate with 100% (theoretical amount) when used for the production is at most 10% (when reacted for 40 hours). On the other hand, when an organic crystallization promoter is added to a solution of sodium silicate containing a seed crystal and the like to synthesize a macatite-type sodium silicate, the yield of the macatite-type sodium silicate (relative to the theoretical amount) is obtained. ) Is improved to 30% or more, which is an unexpected effect according to the present invention.

According to the study of the present inventors, removal of water from the reaction system to the outside of the reaction system was indispensable for crystallization of the macatite-type sodium silicate from the sodium silicate solution. The removal of water from the system has a problem that the reaction system has a remarkably thickened state that is difficult to handle, and the thickened state also makes it difficult to crystallize the macatite-type sodium silicate. On the other hand, if an organic crystallization accelerator is added to the sodium silicate solution, it becomes possible to crystallize the macatite-type sodium silicate without the need to drive out water out of the reaction system. The crystallization accelerator is readily soluble or miscible in an aqueous solution or dispersion of sodium silicate as a raw material because it is water-miscible or water-soluble and is nonionic or anionic. It is recognized that the crystallization of macatite-type sodium silicate is promoted by depriving the sodium silicate of water by holding the water itself or by holding a hydrated layer around it.

[Production method] Raw material sodium silicate In the present invention, an aqueous solution or dispersion of sodium silicate is used as a raw material. This raw material solution may be a transparent solution of sodium silicate such as so-called water glass, may be solid sodium silicate, or may be a combination thereof. The raw material sodium silicate used has a molar ratio of Na ₂ O: SiO ₂ of 1.0: 2.5 to 1.0: 3.5, particularly 1.0: 2.
Those in the range of 8 to 1.0: 3.2 are preferred.
If the amount ratio of Na ₂ O is larger than the above range, the amount of the required organic crystallization accelerator is disadvantageously increased, while SiO ₂ is disadvantageous.
If the amount ratio is larger than the above range, it is disadvantageous because the reactivity is lowered and the calcium ion exchange capacity of the produced sodium macatite silicate is lowered.

The amount of water in the aqueous solution or dispersion of the raw material sodium silicate also has a certain preferable range, and the amount of water is in the range of 4 to 40, particularly 5 to 30 in terms of molar ratio (SiO ₂ / H ₂ O). Preferably it is. That is, when the amount of water is more than the above range, the amount of the organic crystallization accelerator tends to be large, and when the amount of water is less than the above range, the calcium ion exchange capacity of the generated macatite-type sodium silicate is reduced. In addition to the tendency to decrease, the viscosity of the reaction mixture tends to be too high and the productivity tends to decrease.

2. Seed Crystal In the present invention, a seed crystal of macatite-type sodium silicate is added to the above sodium silicate. The seed crystal, the following formula _{(3) Na 2 O · nSiO} 2 · mH 2 O ‥‥ (3) wherein, n is the number of 3 or more, m is 0 or any positive number, in the table Solid sodium silicate having a chemical composition and a macatite-type crystal structure, and having a crystallite size of 600 angstroms or less is particularly suitable.

It is preferable to add 1 to 50 parts by weight, particularly 5 to 30 parts by weight, of a seed crystal of macatite per 100 parts by weight of SiO _{2 in} sodium silicate. The yield of sodium silicate is inadequate, while using it in amounts greater than the above ranges has no particular advantage and is economically disadvantageous.

3. Organic crystallization accelerator As an organic crystallization agent, a water-miscible organic solvent, particularly, having a boiling point of 6
An organic solvent having a temperature of 0 ° C. or higher is used, and preferable examples thereof include polyhydric alcohols and ether derivatives thereof. Further, as the organic crystallization agent, a nonionic surfactant or an anionic surfactant is suitably used, and further, a nonionic water-soluble polymer or an anionic water-soluble polymer is also used. Of course, these can be used alone or in combination of two or more.

As the water-miscible organic solvent, known organic solvents which are miscible with water are used, for example, alcohol solvents such as methanol, ethanol, isopropanol and butanol; ethylene glycol, propylene glycol, butanediol and glycerin. Polyhydric alcohols such as trimethylolpropane, neopentyl glycol, diethylene glycol, triethylene glycol and polyethylene glycol, ethylene glycol dimethyl ether, cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, diglyme Ether solvents such as dioxane, tetrahydrofuran and ethyl methyl ether: acetone, methyl ether Ketone solvents such as ketone; dimethylformamide, amide solvents such as dimethylacetamide; acid methyl, ester solvents such as ethyl acetate; dimethyl sulfoxide and the like.

Among these water-miscible organic solvents, organic solvents having a boiling point of 60 ° C. or more, particularly organic solvents having a boiling point of 90 ° C. or more, are mixed with sodium silicate and stabilize the crystallization of macatite-type sodium silicate. It is desirable to perform. Particularly preferred organic solvents are polyhydric alcohols or their ether derivatives.

As the nonionic surfactant, any known nonionic surfactant can be used.
Polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene fatty acid amide ether, polyhydric alcohol fatty acid ester, polyoxyethylene polyhydric alcohol, fatty acid ester, fatty acid sucrose ester, alkylolamide , Polyoxyalkylene block copolymers and the like are used. For example, in these nonionic surfactants, generally, when the content of polyoxyethylene units increases, the hydration layer increases, so that by adjusting the number of moles of ethylene oxide added, a desired crystallization promoting effect is obtained. be able to.

The anionic surfactants include, for example, primary higher alcohol sulfates, secondary higher alcohol sulfates, primary higher alkyl sulfonates, secondary higher alkyl sulfonates, and the like. Higher alkyl disulfonate, sulfonated higher fatty acid salt, higher fatty acid sulfate, higher fatty acid ester sulfonate, higher alcohol ether sulfate, higher alcohol ether sulfonate, higher fatty acid amide alkylolated sulfate Any anionic surfactants such as salts, alkyl benzene sulfonates, alkyl phenol sulfonates, alkyl naphthalene sulfonates, and alkylbenzimidazole sulfonates may be used. More specific compound names of these surfactants are described, for example, in "Synthetic Surfactants" by Hiroshi Horiguchi (Showa 41)
Sankyo Publishing).

Further, as the nonionic or anionic water-soluble polymer, any known polymer can be used. Examples of the anionic polymer include sodium polyacrylate, or a copolymer of sodium polyacrylate and polyacrylamide, polysodium methacrylate, sodium alginate, ammonium alginate, carboxymethyl starch, carboxymethyl cellulose, acrylamide-acrylic acid Copolymers, maleic anhydride-vinyl ether copolymer, chitosan, sodium styrenesulfonate copolymer and the like are used. On the other hand, as nonionic polymers, polyacrylamide,
Examples include polyvinyl alcohol (PVA), starch, cyanated starch, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, veegum, gelatin, polyethylene glycol and the like. These water-soluble polymers are
Although they can be used alone or in combination of two or more, it is generally preferable to use them in combination with another organic crystallization promoter.

The organic crystallization accelerator may be used alone or
More than one combination may be used. It is also possible to use the organic crystallization promoter in combination with an inorganic crystallization promoter, for example, a water-soluble inorganic salt. Organic crystallization accelerators (surfactants) of Examples 3 and 4 to be described below, which can be produced with high productivity even if the yield is, of course, reduced even if the addition amount of the organic crystallization accelerator is reduced. In the case of single addition, the yield was 30 to 40%, whereas in Example 1
In Examples 2 and 13, the yield can be increased to 60% or more by further adding sodium carbonate. Examples of the inorganic crystallization promoting aid include water-soluble alkali metal salts such as sodium sulfate, potassium sulfate, sodium chloride, potassium chloride, sodium nitrate, potassium nitrate, sodium phosphate, potassium phosphate, sodium carbonate, potassium carbonate, and bicarbonate. Sodium, potassium bicarbonate, sodium borate, potassium borate, sodium percarbonate, sodium perborate, and the like; and citric acid, tartaric acid, acetic acid, hydrogen bromide, hydrogen iodide, thiocyanic acid, chloric acid, and the like. Alkali salts are preferred, but if they are water-soluble,
It is not limited to this example. Among them, the sodium salt is preferred.

In the present invention, the organic crystallization accelerator is used in an amount of 5 to 3 per 100 parts by weight of SiO _{2 in} sodium silicate.
It is preferably added in an amount of 00 parts by weight, especially 10 to 200 parts by weight. When the amount of the organic crystallization accelerator is below the above range, there is no sufficient effect to crystallize the macatite-type sodium silicate as compared to the case where the amount is in the above range, and the viscosity of the reaction mixture is too high, On the other hand, if it exceeds the above range, there is no particular effect in terms of promoting crystallization, and it is disadvantageous economically.

On the other hand, when an inorganic crystallization promoting auxiliary is used together with the organic crystallization promoting agent, the auxiliary is used in an amount of 5 to 300 parts by weight per 100 parts by weight of silica (SiO ₂ ) in the raw material sodium silicate. Parts, especially 10 to 200 parts by weight.

[Crystallization of Macatite Type Sodium Silicate]
In the present invention, a mixed composition containing sodium silicate, a seed crystal and an organic crystallization promoter is treated at a temperature of 60 to 150 ° C., particularly 8 ° C.
The crystallization is performed while maintaining the temperature at 0 to 120 ° C. Generally, it is preferable to carry out the crystallization under normal pressure. The time for crystallization varies depending on the composition of the alkali silicate, the type and amount of the organic crystallization accelerator, the amount of the seed crystal, and the temperature, but generally, 5 to 72 hours, Especially 1
It is about 0 to 40 hours.

This mixed composition may be formed by one-sided or simultaneous pouring, for example, by pouring an organic crystallization accelerator or an aqueous solution thereof into an aqueous solution of alkali silicate, or by adding silicate to an aqueous medium. A method of simultaneously adding an organic crystallization accelerator or an aqueous solution thereof to an alkali or an aqueous solution thereof may be employed.

The crystallization of the macatite type sodium silicate is as follows:
The reaction may be carried out with stirring or without stirring. However, when the stirring is carried out without stirring, the crystallization speed tends to be higher and the yield tends to be improved. The crystallization reaction can be carried out continuously or batchwise. In the former case, for example, a moving bed type crystallization operation by a piston flow or the like using a pipe-like (static mixer or the like) reaction vessel or the like is desirable. Alternatively, the reaction mixture may be poured into a gutter formed by a conveyor belt or the like to perform crystallization while moving. The mixed composition of the present invention has a considerably high viscosity, the effect of interdiffusion between the front and rear mixtures is almost negligible, and the crystallization reaction proceeds smoothly.

According to the production method of the present invention, the sodium (silicate) of the macatite type is converted to silica (SiO 2) in the raw material alkali silicate.
₂ ) It can be synthesized in a yield of 30% or more, especially 50% or more on the basis. Further, the obtained macatite-type sodium silicate has an advantage that it has a high calcium ion exchange ability itself and that the decrease in the calcium ion exchange ability with time is small.

The reaction product containing the crystallized macatite-type sodium silicate is converted into a slurry as it is,
Alternatively, it can be dried and supplied like a detergent builder. This reaction composition naturally contains an organic crystallization promoter or a further inorganic crystallization promoter in addition to the macatite-type sodium silicate. Is itself a compounding component for detergents, which can be effectively used for detergent applications, and these components suppress the decrease in calcium ion exchange capacity of macatite-type sodium silicate over time, and furthermore, the detergent composition It also has a suitable effect of promoting the dispersion of the macatite-type sodium silicate particles in the material.

Of course, it is also possible to isolate the crystallized sodium sodium silicate from the reaction mixture according to the invention in the form of a wet slurry or a dry powder, for example by dispersing the reaction mixture in water. As a result, the macatite-type sodium silicate is easily dispersed in water to form an aqueous slurry. Therefore, this is separated into solid and liquid by filtration or the like to obtain a wet cake, or to dry it to obtain a dry powder, respectively. Can be.

[Macatite-type sodium silicate] The macatite-type sodium silicate according to the present invention has the following formula (1): Na ₂ O · nSiO ₂ · mH ₂ O ₂ (1) where n is a number of 3 to 5 , Especially 4 to 5, and m is 0
Having a chemical composition represented by the number of from 10 to 10, especially from 4.0 to 7.0, more preferably from 5.0 to 7.0,
Further, it has a crystal structure of a macatite type.

FIG. 1 shows an X-ray diffraction image of a macatite-type sodium silicate according to the present invention (Example 8). Known macatite-type sodium silicate has the following X-ray diffraction image according to the ASTM card. Surface spacing d (A) Relative intensity I / I Surface index (hkl) 5.09 100 031 2.99 55 142 9.04 55 020

The macatite-type sodium silicate according to the present invention may have any X-ray diffraction image as long as it is of the macatite type, but preferably has substantially the same X-ray diffraction image as FIG. It is. When the macatite-type sodium silicate of FIG. 1 is compared with the macatite-type sodium silicate described in the above-mentioned ASTM card, the two are almost coincident at the diffraction peak position. Sodium silicate of macatite type: Surface distance d (A) Relative strength I / I Surface index (hkl) 3.71 100 200 5.09 62 031 3.42 64 220 Sodium silicate of ASTM card: Surface distance d (A ) Relative intensity I / I surface index (hkl) 5.09 100 031 9.04 55 020 2.99 55 142

The macatite-type sodium silicate according to the present invention has the following formula (2): R _I = I ₀₃₁ / I ₂₀₀ ‥‥ (2) where I ₀₃₁ is the X-ray diffraction peak of the plane index (031). The relative intensity is defined as I ₂₀₀ is the relative intensity of the X-ray diffraction peak of plane index (200).
Within the range of 4 to 1.20 and the plane index (031)
The crystallite size determined from the half width of the diffraction peak of
Those in the range of angstrom or less are preferred.

In the X-ray diffraction of the crystal, the following Bragg equation (4) nλ = 2dhkl Sinθ ‥‥ (4) In the equation, n is the order, λ is the X-ray wavelength, and dhkl
Is the (hkl) plane spacing of the crystal, and θ is the diffraction angle. It is known that an intensity peak appears in the interference, and the difference between the sharpness of the interference peak and the crystal size is known. Also, the following Scherrer equation (5) In the formula, Lhkl is a dimension in a direction perpendicular to the (hkl) plane of the crystal, K is a constant of about 0.9, H is the half width (radian) of the interference peak, and λ and θ are the same as in the above formula (1). Where there is a relationship represented by

FIG. 2 shows the diffraction obtained by lowering the scanning speed to obtain the half width of the diffraction peak of the plane index (031) for each sodium silicate used in the measurement of the X-ray diffraction image of FIG. The peak is shown. From this half width, the size of the crystallite can be calculated by the equation (5).

By setting the X-ray diffraction intensity ratio (R _I ) within the above range and suppressing the crystallite size of the plane index (031) within the above range, the calcium ion exchange capacity of the macatite-type sodium silicate can be reduced to 100 mg CaCO _3. / G or more, especially 150 mgCaCO ₃ / g or more.

FIG. 3 is a plot of the relationship between the crystallite size of the plane index (031) and the calcium ion exchange capacity. From this result, it is possible to reduce the crystallite size of the plane index (031). It is extremely effective in increasing the calcium ion exchange capacity of sodium silicate.

FIG. 4 shows the relationship between the diffraction peak position of the plane index (031) and the calcium ion exchange capacity. According to this result, the shift of this diffraction peak to the lower angle side
Again, the fact that calcium ion exchange capacity is increasing becomes apparent.

In the present invention, as described above, the growth or arrangement of crystals in the direction of the plane index (031) of the macatite-type sodium silicate is suppressed, whereby the calcium ion-exchange ability of the macatite-type sodium silicate is remarkably improved. However, the difference in the X-ray diffraction images makes the particle structure quite unique.

That is, FIG. 5 is a scanning electron micrograph (× 3000) showing the particle structure of the macatite-type sodium silicate having the X-ray diffraction image of FIG. The macatite-type sodium silicate according to the present invention is often in the form of plate-like or needle-like crystals, and generally has an average particle size in the range of 5 to 30 μm in the case of a plate-like form. The obtained primary particles generally have a minor axis of 0.05 to 1.0 μm, a major axis of 1.0 to 15 μm, particularly a minor axis of 0.1 to 0.5 μm, and a major axis of 2.0 to 10.0 μm.
Rod-shaped crystals having an aspect ratio in the range of 1 to 300, and these rod-shaped crystals may aggregate to form ball-shaped secondary particles.

As the powder characteristics of the macatite-type sodium silicate, the oil absorption according to JIS K 5101-21 is at least 60 ml / 100 g, preferably in the range of 80 to 150 ml / 100 g.

Further, the pH (25 ° C.) of the aqueous suspension of 5 g / 100 ml of the macatite-type sodium silicate according to the present invention is in the range of 10.5 to 11.5, and the pH of the disilicate is 12.9. Is in a much lower range than.

The surface of the macatite-type sodium silicate according to the present invention can be coated with various modifiers in order to improve its dissolution characteristics and storage stability. For example, metal oxides, hydroxides, carbonates, and high molecular compounds or organosilicon compounds having a hydroxyl-reactive functional group, specifically IIa, III
a, IVa, Va, VIa, VIIa, VIIIa, Ib, II
b, IIIb or IVb group, especially silica, silicon, alumina, aluminum hydroxide and the like are preferable, and as the polymer compound, polystyrene, polymethyl methacrylate, urea resin, polyethylene, polycarbonate, polypropylene, polyvinyl chloride, nylon, ABS resin, silicone resin and the like can be mentioned.

As the organosilicon compound, alkylalkoxysilane, fluoroalkylsilane, alkylchlorosilane, alkyldisilazane, fluorodisilazane, 2,
Examples include cyclic siloxanes such as 4,6,8-tetramethylcyclotetrasiloxane and silane coupling agents generally used.

The macatite-type sodium silicate and its composition according to the present invention have cation exchange properties and can be used as various ion exchangers, and are particularly useful as builders for detergents. The macatite-type sodium silicate and the composition thereof according to the present invention are excellent in detergency, solubilizing power, synergistic increase in surface activity, pH buffering action, sequestering action, prevention of redeposition of dirt, and the like. .
The macatite-type sodium silicate and the composition thereof according to the present invention may be used as various cleaning agents, such as powdery or liquid detergents for clothes or kitchens, detergents or antifouling agents for toilets, kitchen cleansers, as cleaning aids. Fabric softener, metal, automobile, floor, porcelain or glass cleaner, floor polish, shampoo, bath agent, soap,
It can be incorporated into a facial wash emulsion or cream, toothpaste and the like. The amount of the cleaning aid varies depending on the application and the dosage form, but generally ranges from 0.01 to 20% by weight, particularly from 0.1 to 5% by weight, so that the above-mentioned effect can be obtained. It is better to determine the amount. The cleaning aid of the present invention exhibits particularly excellent cleaning action in combination with various anionic surfactants and nonionic surfactants.

Further, other additives can be used in combination to the extent that the performance of the present invention is not impaired. For example, various inorganic fine particles and carboxymethylcellulose to prevent the particles from reattaching, an adhesion inhibitor of methylcellulose type, an anti-adhesion forming agent of acrylic acid-maleic anhydride copolymer type polymer type or a porous material is used. Amorphous silica and amorphous aluminosilicate can be used as the hydrophobic oil absorber.

It is also possible to use other builders in combination. Other builders include phosphates or tripolyphosphates such as sodium carbonate, sodium sulfate, sodium borate, sodium perborate, sodium metasilicate, trisodium phosphate and sodium tripolyphosphate, disilicic acid (Na ₂ Si ₂ O
₅₎ As the crystalline alkali metal silicate, kanemite _{(NaHSi 2 O 5 · 3H 2} O), Ayler Ait (N
a ₂ Si ₈ O _17), magadiite (Na ₂ Si ₁₄ 0 ₂₉ ·
10H ₂ O), Kenyaite (Na ₂ Si ₂₀ O ₄₁ · 10H)
₂ O), nitriloacetic acid, citric acid, tartaric acid, sodium sulfate, pentasodium triphosphate, sodium nitrilo-trisulfonate, and various zeolites are used. For example, the mixing ratio with zeolite or sodium disilicate (SKS-6 or the like: manufactured by Hoechst) is such that the inventive macatite-type sodium silicate: zeolite or sodium disilicate is 99: 1 to 1:99, preferably 99: 5 to Used in a ratio of 50:50.

[0054]

The present invention will be described with reference to the following examples. In the following examples, the measurement was performed by the following method.

(1) X-ray Diffraction Measurement was performed with Cu-Kα using a Geigerflex RAD-1B system manufactured by Rigaku Corporation. Target Cu filter Ni Tube voltage 40 kV Tube current 20 mA Count full scale 10 kcps Scanning speed 4 deg / min Time constant 0.5 sec Slit DS (SS) 1 deg RS 0.15
mm

(2) X-Ray Diffraction Conditions at the Time of Crystallite Size Measurement Using a Geigerflex RAD-1B system manufactured by Rigaku Denki Co., Ltd., the measurement was performed with Cu-Kα. Target Cu filter Ni Tube voltage 40 kV Tube current 20 mA Count full scale 4 kcps Scanning speed 0.25 deg / min Time constant 0.5 sec Slit DS (SS) 0.5 deg RS
15mm

(3) CEC measurement method A 0.65 g sample is precisely weighed and put into a 500 ml beaker. Next, 500 ml of hard water (ammonium alkaline CaCl2 aqueous solution, 300 mg CaO / l) is added and stirred with a magnetic stirrer for 10 minutes. Immediately after stirring, the solution is suction-filtered with a No. 6 filter paper, and exactly 10 ml of the filtrate is collected.
Then add an appropriate amount of deionized water and pipette NH4OH-NH4C
1 to 2 ml of 1 buffer solution (pH = 10) was added, and titration was carried out with 1/100 M EDTA using Black T as an indicator. Ca binding capacity (CaCO3mg / g) = ｛(C2-C1) × f × 50000｝ / ｛(100−
I) × W｝ C2: Blank (concentration M) C1: Filtrate (concentration M) W: Sample weight (g) I: Loss on ignition of sample at 860 ° C. (%) f: EDTA titer

(4) Oil absorption The oil absorption was measured according to JIS K-5101-21.

(5) Yield Assuming that the amount of silica (SiO ₂ ) in the raw material sodium silicate is completely reacted and synthesized into macatite is 100% (theoretical amount), the yield is calculated from the amount of macatite obtained. calculate.

Example 1 Powder No. 3 sodium silicate (SiO ₂ 58.4%, SiO ₂ / Na ₂ O molar ratio =
3.19), the silica of the sodium silicate (SiO
₂ ) 165 parts by weight of water and 15 parts by weight of macatite seed crystal were added to the standard, and mixed well with a stirrer. Glycerin in an amount of 171% by weight based on the silica (SiO ₂ ) of the sodium silicate was added thereto to obtain a gel-like substance.
It was reacted at 95 ° C. under normal pressure for 48 hours. The obtained gel-like substance was filtered, washed with water, and dried to obtain a powdered macatite-type sodium silicate. Table 1 shows the preparation conditions for this reaction and the properties of the obtained powder. Regarding washing with water after filtration, washing with filtered water was performed twice using the same amount of water as the reaction solution. (The same applies to the following examples)

Example 2 JIS No. 3 sodium silicate aqueous solution (SiO ₂ 28.2%, SiO ₂ / Na ₂ O molar ratio = 3.09) was added to silica (Si
O ₂ ) 15 parts by weight of the macatite seed crystal with respect to the standard were added and mixed well with a stirrer. 185 parts by weight of ethylene glycol was added to the sodium silicate based on silica (SiO ₂ ) to obtain a gel-like substance. It was reacted at 95 ° C. under normal pressure for 40 hours. The obtained gel-like substance was filtered, washed with water, and dried to obtain a powdered macatite-type sodium silicate. Table 1 shows the preparation conditions for this reaction and the properties of the obtained powder.

Example 3 JIS No. 3 sodium silicate aqueous solution (SiO ₂ 28.2%, SiO ₂ / Na ₂ O molar ratio = 3.09) was mixed with silica (Si
O ₂ ) 15 parts by weight of the macatite seed crystal with respect to the standard were added and mixed well with a stirrer. Then, 71 parts by weight of a nonionic surfactant (polyoxyethylene derivative) based on silica (SiO ₂ ) of the sodium silicate was added to obtain a gel-like substance. It was reacted at 95 ° C. under normal pressure for 20 hours. The obtained gel substance was filtered, washed with water, dried,
Powdered macatite-type sodium silicate was obtained. Table 1 shows the preparation conditions for this reaction and the properties of the obtained powder.

Example 4 JIS No. 3 sodium silicate aqueous solution (SiO ₂ 28.2%, SiO ₂ / Na ₂ O molar ratio = 3.09) was mixed with silica (Si
O ₂ ) 15 parts by weight of the macatite seed crystal with respect to the standard were added and mixed well with a stirrer. Then, 100 parts by weight of an anionic surfactant (sodium dialkyl succinate, pure content: 70%) based on the silica (SiO ₂ ) of the sodium silicate was added to obtain a gel-like substance. It was reacted at 95 ° C. under normal pressure for 20 hours. The obtained gel-like substance was filtered, washed with water, and dried to obtain a powdered macatite-type sodium silicate. Table 1 shows the preparation conditions for this reaction and the properties of the obtained powder.

Example 5 JIS No. 3 sodium silicate aqueous solution (SiO ₂ 28.2%, SiO ₂ / Na ₂ O molar ratio = 3.09) was mixed with silica (Si
O ₂ ) 15 parts by weight of the macatite seed crystal and 44 parts by weight of ion-exchanged water with respect to the standard were added and thoroughly mixed with a stirrer. And the sodium silicate silica (SiO ₂ )
100 parts by weight of polyethylene glycol (molecular weight: 200) was added to the standard to obtain a gel-like substance. It was reacted at 95 ° C. under normal pressure for 20 hours. The obtained gel-like substance was filtered, washed with water, and dried to obtain a powdered macatite-type sodium silicate. Table 1 shows the preparation conditions for this reaction and the properties of the obtained powder.

Example 6 JIS No. 3 sodium silicate aqueous solution (SiO ₂ 28.2%, SiO ₂ / Na ₂ O molar ratio = 3.09) was mixed with silica (Si)
O ₂ ) 15 parts by weight of the macatite seed crystal and 44 parts by weight of ion-exchanged water with respect to the standard were added and thoroughly mixed with a stirrer. And the sodium silicate silica (SiO ₂ )
150 parts by weight of polyethylene glycol (molecular weight: 600) was added to the standard to obtain a slurry-like substance. It was reacted at 95 ° C. under normal pressure for 20 hours. The obtained gel-like substance was filtered, washed with water, and dried to obtain a powdered macatite-type sodium silicate. Table 1 shows the preparation conditions for this reaction and the properties of the obtained powder.

Example 7 JIS No. 3 sodium silicate aqueous solution (SiO ₂ 28.2%, SiO ₂ / Na ₂ O molar ratio = 3.09) was added to the sodium silicate silica (Si
O ₂ ) 15 parts by weight of the macatite seed crystal with respect to the standard were added and mixed well with a stirrer. 10 parts by weight of carboxymethylcellulose was added to the sodium silicate based on silica (SiO ₂ ) to obtain a gel-like substance.
It was reacted at 95 ° C. under normal pressure for 20 hours. The obtained gel-like substance was filtered, washed with water, and dried to obtain a powdered macatite-type sodium silicate. Table 1 shows the preparation conditions for this reaction and the properties of the obtained powder.

Example 8 JIS No. 3 sodium silicate aqueous solution (SiO ₂ 28.2%, SiO ₂ / Na ₂ O molar ratio = 3.09) was added to silica (Si)
O ₂ ) 15 parts by weight of the macatite seed crystal and 44 parts by weight of ion-exchanged water with respect to the standard were added and thoroughly mixed with a stirrer. And the sodium silicate silica (SiO ₂ )
80 parts by weight of sodium carbonate and 47 parts by weight of polyethylene glycol were added to the standard to obtain a slurry. It was reacted at 95 ° C. under normal pressure for 20 hours. The obtained gel-like substance was filtered, washed with water, and dried to obtain a powdered macatite-type sodium silicate. Table 1 shows the preparation conditions for this reaction and the properties of the obtained powder.

Example 9 JIS No. 3 sodium silicate aqueous solution (SiO ₂ 28.2%, SiO ₂ / Na ₂ O molar ratio = 3.09) was added to the sodium silicate silica (Si
O ₂ ) 15 parts by weight of the macatite seed crystal with respect to the standard were added and mixed well with a stirrer. Then, 80 parts by weight of sodium sulfate and 47 parts by weight of polyethylene glycol were added to the sodium silicate based on silica (SiO ₂ ) to obtain a slurry-like substance. It was reacted at 95 ° C. under normal pressure for 20 hours. The obtained gel substance is filtered, washed with water,
It was dried to obtain a powdered macatite-type sodium silicate.
Table 1 shows the preparation conditions for this reaction and the properties of the obtained powder.

Example 10 JIS No. 3 sodium silicate aqueous solution (SiO ₂ 28.2%, SiO ₂ / Na ₂ O molar ratio = 3.09) was mixed with silica (S
15 parts by weight of a macatite seed crystal with respect to the iO ₂ ) standard was added and mixed well with a stirrer. 35 parts by weight of sodium chloride and 35 parts by weight of polyethylene glycol were added to the sodium silicate based on silica (SiO ₂ ) to obtain a gel-like substance. 20 at 95 ° C under normal pressure
Reacted for hours. The obtained gel-like substance was filtered, washed with water, and dried to obtain a powdered macatite-type sodium silicate. Table 1 shows the preparation conditions of this reaction and the properties of the obtained powder.
It was shown to.

(Example 11) JIS No. 3 sodium silicate aqueous solution (SiO ₂ 28.2%, SiO ₂ / Na ₂ O molar ratio = 3.09) was mixed with silica (S
15 parts by weight of a macatite seed crystal with respect to the iO ₂ ) standard was added and mixed well with a stirrer. Then, 80 parts by weight of sodium carbonate and 150 parts by weight of glycerin were added to the sodium silicate based on silica (SiO ₂ ) to obtain a slurry. It was reacted at 95 ° C. under normal pressure for 40 hours. The obtained gel-like substance was filtered, washed with water, and dried to obtain a powdered macatite-type sodium silicate. Table 1 shows the preparation conditions for this reaction and the properties of the obtained powder.

Example 12 JIS No. 3 sodium silicate aqueous solution (SiO ₂ 28.2%, SiO ₂ / Na ₂ O molar ratio = 3.09) was mixed with silica (S
15 parts by weight of a macatite seed crystal with respect to the iO ₂ ) standard was added and mixed well with a stirrer. Then, 80 parts by weight of sodium carbonate and 71 parts by weight of a nonionic surfactant were added to the silica (SiO ₂ ) of the sodium silicate to obtain a gel-like substance. It was reacted at 95 ° C. under normal pressure for 20 hours. The obtained gel-like substance was filtered, washed with water, and dried to obtain a powdered macatite-type sodium silicate. Table 1 shows the preparation conditions of this reaction and the properties of the obtained powder.
It was shown to.

Example 13 JIS No. 3 sodium silicate aqueous solution (SiO ₂ 28.2%, SiO ₂ / Na ₂ O molar ratio = 3.09) was mixed with silica (S
15 parts by weight of a macatite seed crystal with respect to the iO ₂ ) standard was added and mixed well with a stirrer. Then, 80 parts by weight of sodium carbonate and 71 parts by weight of an anionic surfactant were added to the sodium silicate based on silica (SiO ₂ ) to obtain a gel-like substance. It was reacted at 95 ° C. under normal pressure for 20 hours. The obtained gel-like substance was filtered, washed with water, and dried to obtain a powdered macatite-type sodium silicate. Table 1 shows the preparation conditions of this reaction and the properties of the obtained powder.
It was shown to.

Comparative Example 1 Powder No. 3 sodium silicate (SiO ₂ 58.4%, SiO ₂ / Na ₂ O molar ratio =
3.19), the silica of the sodium silicate (SiO
₂ ) 165 parts by weight of water and 15 parts by weight of macatite seed crystal were added to the standard, and mixed well with a stirrer. It was reacted for 96 hours at 95 ° C. under normal pressure. The obtained gel-like substance was filtered, washed with water, and dried to obtain a powdered macatite-type sodium silicate. Table 1 shows the preparation conditions for this reaction and the properties of the obtained powder.

Comparative Example 2 JIS No. 3 sodium silicate aqueous solution (SiO ₂ 28.2%, SiO ₂ / Na ₂ O molar ratio = 3.09) was mixed with silica (Si
O ₂ ) 80 parts by weight of sodium carbonate and 47
A part by weight of polyethylene glycol was added to obtain a gel-like substance. It was reacted at normal pressure at 95 ° C. for 800 hours. All the obtained gel-like substances were dissolved in the process of filtration and washing with water.

Comparative Example 3 JIS No. 3 sodium silicate aqueous solution (SiO ₂ 28.2%, SiO ₂ / Na ₂ O molar ratio = 3.09) was added to silica (Si)
O ₂ ) 15 parts by weight of the macatite seed crystal with respect to the standard were added and mixed well with a stirrer. Further, 3 parts by weight of sodium carbonate and 3 parts by weight of polyethylene glycol were added to obtain a slurry substance. It was reacted at 95 ° C. under normal pressure for 20 hours. The obtained slurry-like substance was filtered and washed with water. Table 1 shows the preparation conditions for this reaction and the properties of the obtained powder. When the yield was measured, only the seed crystal previously added was obtained.

[0076]

[Table 1]

[0077]

[Table 2]

[0078]

[Table 3]

[0079]

According to the present invention, a seed crystal of macatite and a water-miscible or water-soluble nonionic or anionic organic crystallization accelerator are added to an aqueous solution or dispersion of sodium silicate. By heating the mixed composition,
Macatite-type sodium silicate having high calcium ion exchange capacity can be produced with high yield and high productivity. The obtained macatite-type sodium silicate has a high calcium ion exchange ability and also has excellent stability over time in the ion exchange ability. Furthermore,
The resulting macatite-type sodium silicate and the resulting composition containing it have good dispersibility and are particularly useful as builders for detergents and the like.

[Brief description of the drawings]

FIG. 1 is an X-ray diffraction image of a macatite-type sodium silicate of Example 8 of the present invention.

FIG. 2 shows the diffraction peak obtained by lowering the scanning speed in order to determine the half-value width of the diffraction peak of the plane index (031) for the macatite-type sodium silicate used in the measurement of the X-ray diffraction image of FIG. Show.

FIG. 3 is a graph in which the relationship between the crystallite size of the plane index (031) and the calcium ion exchange capacity is plotted.

FIG. 4 is a graph showing the relationship between the diffraction peak position of the plane index (031) and the calcium ion exchange capacity.

FIG. 5 is a scanning electron micrograph (× 3000) showing the particle structure of sodium silicate having the X-ray diffraction image of FIG. 1;

Claims (13)

[Claims] 1. An aqueous solution or dispersion of sodium silicate is added with a macatite seed crystal and a water-miscible or water-soluble nonionic or anionic organic crystallization promoter, and the mixed composition is heated. A method for producing macatite-type sodium silicate, characterized in that: 2. The process according to claim 1, wherein 1 to 50 parts by weight of a macatite seed crystal is added per 100 parts by weight of SiO ₂ in the sodium silicate. 3. The method according to claim 1, wherein 5 to 300 parts by weight of a water-miscible, water-soluble, nonionic or anionic organic crystallization accelerator is added per 100 parts by weight of SiO _{2 in} sodium silicate. . 4. The method according to claim 1, wherein the organic crystallization accelerator is a water-miscible organic solvent. 5. The method according to claim 4, wherein the water-miscible organic solvent is an organic solvent having a boiling point of 60 ° C. or higher. 6. The method according to claim 4, wherein the water-miscible organic solvent is a polyhydric alcohol or an ether thereof. 7. The method according to claim 1, wherein the organic crystallization accelerator is a nonionic surfactant. 8. The method according to claim 1, wherein the organic crystallization accelerator is an anionic surfactant. 9. The method according to claim 1, wherein the organic crystallization accelerator is a nonionic water-soluble polymer. 10. The method according to claim 1, wherein the organic crystallization accelerator is an anionic water-soluble polymer. 11. The process according to claim 1, wherein a crystallization promoting aid comprising a water-soluble inorganic salt is further added to the aqueous solution or dispersion of sodium silicate. 12. SiO ₂ 100 in sodium silicate
The method according to claim 11, wherein the water-soluble inorganic salt is added in an amount of 5 to 300 parts by weight per part by weight. 13. The method according to claim 1, wherein the crystallization is carried out while maintaining the temperature of the mixed composition at 60 to 150 ° C.