JP2000169885A - Builder composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a builder composition for a detergent, having an ion- exchanging capacity of calcium of a makatite type sodium silicate, stabilized at a high level with time. SOLUTION: This builder composition includes (A) a makatite type sodium silicate having a chemical composition of the formula Na2O.nSiO2.mH2O [(n) is a number of 3-5; (m) is a number of 0-10], and 0.20-1.20 ratio of the intensities of X-ray diffraction at peaks of indexes of planes (200) and (031) of the X-ray diffraction and (B) a stabilizing component of at least one kind selected from the group comprising a substantially nonvolatile, and water-miscible or water-soluble nonionic or anionic organic substance, and a water soluble inorganic salt. The component B in an amount of 5.0 to 300 pts.wt. is preferably present based on 100 pts.wt. component A.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a builder composition excellent in calcium ion exchange capacity and its retention with time, and more particularly, to a macatite-type sodium silicate and a specific organic substance and / or The present invention relates to a builder composition containing an inorganic salt in a specific ratio.

[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 an 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 an alkali to form an alkali polysilicate. There is described a method for producing a soap, which comprises blending a fatty acid soap or a resin soap.

Further, Japanese Patent Application Laid-Open No. 1-192718 discloses a sheet-like structure and a SiO ₂ / Na ₂ O molar ratio of 1: 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 acid in a pH range of 9 to 13 with stirring is described.

[0005] Known sodium silicates, including natural and 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
Na 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 that the following formula (1) Na ₂ O.nSiO ₂ .mH ₂ O Ｏ (1) In the formula, 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,
Following formula _{(2) R I = I 031} / I 200 ‥‥ (2) _{wherein, I 031} is the relative intensity of X-ray diffraction peaks of the plane index _{(031), I 200} is X the plane index (200) The X-ray diffraction intensity ratio defined by the relative intensity of the X-ray diffraction peak is in the range of 0.2 to 1.20, and the crystallite determined from the half width of the diffraction peak having the plane index (031) A sodium silicate characterized by a size in the range of less than 500 angstroms is described, and it is further described that this sodium silicate is useful as a detergent builder.

[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.

Furthermore, according to the study of the present inventors, the macatite-type sodium silicate is not yet known,
Calcium ion exchange capacity tends to decrease over time, and its stabilization is necessary, but there is no known means for stabilizing the calcium ion exchange capacity of macatite-type sodium silicate at a high level. .

Accordingly, it is an object of the present invention to provide a detergent builder composition in which the calcium ion exchange capacity of macatite-type sodium silicate is stabilized at a high level over time.

[0012]

According to the present invention, (A)
The chemical composition represented by the following formula (1): Na ₂ O · nSiO ₂ · mH ₂ O ‥‥ (1) wherein n is a number of 3 to 5, and m is a number of 0 to 10. has the following formula _{(2) R I = I 031} / I 200 ‥‥ (2) _{wherein, I 031} is the relative intensity of X-ray diffraction peaks of the plane index _{(031), I 200} is plane index (200 ), Wherein the X-ray diffraction intensity ratio defined by the relative intensity of the X-ray diffraction peak in the range of 0.20 to 1.20 is in the range of 0.20 to 1.20; It contains at least one stabilizing component selected from the group consisting of a miscible or water-soluble nonionic or anionic organic substance and a water-soluble inorganic salt, and the component (B) per 100 parts by weight of the component (A) Is 5.0 to 300 parts by weight, especially 10.0
A builder composition is provided that is present in an amount of from about 200 parts by weight. In the builder composition of the present invention: Macatite-type sodium silicate (A) has an area index (0
31) sodium silicate having a crystallite size determined from the half width of the diffraction peak in the range of 600 Å or less; 2. the calcium ion exchange capacity of the macatite-type sodium silicate (A) is in the range of 80 mgCaCO ₃ / g or more; 3. The organic substance of the component (B) is a water-miscible organic solvent, a nonionic or anionic surfactant, or a nonionic or anionic water-soluble polymer; 4. the water-soluble sodium salt is sodium carbonate and / or sodium sulfate; This composition has the following formula (3) R = (C ₁ / C ₀ ) × 100 (3) where C ₀ is the calcium ion exchange capacity (mgCaCO ₃ / g) of the builder composition before the acceleration test. Wherein C ₁ represents the calcium ion exchange capacity (mgCaCO ₃ / g) of the builder composition after the accelerated test by standing at a temperature of 40 ° C. for 7 days. Especially 80% or more; Synthesis of macatite-type sodium silicate in which at least one component selected from the group consisting of the substantially nonvolatile water-miscible, water-soluble, nonionic or anionic organic substance and the water-soluble inorganic salt of (B) is used. It is preferred that they are blended prior to

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, as a sodium silicate for detergent builder, a macatite-type sodium silicate (A) having a chemical composition of the above formula (1) and an X-ray diffraction image of the above formula (2) is used. And at least one stabilizing component (B) selected from the group consisting of a substantially non-volatile, water-miscible, water-soluble, nonionic or anionic organic substance and a water-soluble inorganic salt. Is characterized in that the calcium ion exchange capacity of the macatite-type sodium silicate can be stabilized over time at a high level.

See the example below. That is, without the presence of the stabilizing component (B), a sodium silicate (A) is produced, and in the case of a builder composition containing the same, the calcium ion exchange capacity of the builder composition is 4 mg CaCO ₃ / After storage for 7 days at a temperature of 40 ° C., the calcium ion exchange capacity is reduced to a level of 50% immediately after production (see Comparative Example 1 for details). On the other hand, an organic stabilizing component (B1: sodium carbonate and PEG) was allowed to coexist to produce a macatite-type sodium silicate (A),
In the case of a builder composition containing it, the calcium ion exchange capacity of the resulting composition is 55 mgC immediately after production.
It is observed that the calcium ion exchange capacity is maintained at a level of 80% or more even after being stored at a temperature of 40 ° C. for 7 days while being at a high level of aCO ₃ / g (for details, see Example 1 described later). Such a stabilizing effect of the calcium ion exchange capacity is attributable to the organic stabilizing component (B1:
Instead of glycerin), an inorganic salt-based stabilizing component (B
2: sodium carbonate) is similarly expressed (for details, see Example 8 described later).

The reason why the calcium ion exchange capacity of the solid sodium silicate decreases with time and the reason that the time-dependent decrease is suppressed by the incorporation of the above-mentioned stabilizing component have not been elucidated yet. But not
It is considered as follows. The builder action by solid sodium silicate is due to the cation exchange action by the polysilicate, but the decrease in calcium ion exchange capacity over time is due to the cation exchange site of polysilicic acid disappearing due to condensation over time. It seems to be because. On the other hand, according to the present invention, when an organic and / or inorganic stabilizing component is allowed to coexist with macatite-type sodium silicate,
It is believed that the cation exchange sites of polysilicic acid are prevented from disappearing by condensation.

In the present invention, the organic and / or inorganic stabilizing component (B) is used in an amount of 5.0 to 3 based on 100 parts by weight of the macatite-type sodium silicate (A).
It is also important to formulate in an amount of 00 parts by weight, especially 10.0 to 200 parts by weight. When the compounding amount of the stabilizing component (B) is smaller than the above range, the suppression of the time-dependent decrease of the calcium ion exchange capacity is insufficient as compared with the case specified in the present invention, while it is larger than the above range. In this case, there is no particular advantage in terms of suppressing a decrease in calcium ion exchange ability over time, and the calcium ion exchange ability of the entire builder is undesirably decreased.

In the present invention, at least one type of stabilization selected from the group consisting of the substantially non-volatile, water-miscible, water-soluble, nonionic or anionic organic substances and water-soluble inorganic salts of the above (B). It is preferable that the components are blended in the reaction system prior to the synthesis of the macatite-type sodium silicate. That is, by incorporating the stabilizing component (B) into the reaction system prior to the synthesis, the stabilizing action is immediately exerted on the crystallized sodium macatite-type silicate. In such a case, there is a remarkable effect that a decrease in calcium ion exchange capacity is suppressed.

The builder composition of the present invention is characterized in that the calcium ion exchange capacity retention (R) defined by the above formula (3) is 70% or more, particularly 80% or more. In the case of the macatite-type sodium silicate containing no stabilizing component (B), the calcium ion exchange capacity retention (R) tends to be reduced to 70% or less under the accelerated test conditions described above. This reduction is effectively suppressed.

[Macatite-type sodium silicate] The macatite-type sodium silicate used in the present invention is represented by the following formula (1): Na ₂ O · nSiO ₂ · mH ₂ O (1) where n is 3 to 5 A number, especially 4 to 5, where 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 the macatite-type sodium silicate (Example 10) used in the present invention. 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 used in the present invention may have any X-ray diffraction image as long as it is of the macatite type, but those having substantially the same X-ray diffraction image as in FIG. It is suitable. When the macatite-type sodium silicate in FIG. 1 is compared with the macatite-type sodium silicate described in the ASTM card, the two are almost the same at the diffraction peak position. Sodium silicate of MacTMite type: d (A) Relative strength I / I plane index (hkl) 3.71 100 200 5.09 62 031 3.42 64 220 Sodium silicate of ASTM card: 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 used in the present invention has the following formula (2): R _I = I ₀₃₁ / I ₂₀₀ ‥‥ (2) where I ₀₃₁ is an X-ray diffraction peak having a plane index (031). And I ₂₀₀ is the relative intensity of the X-ray diffraction peak of the plane index (200), wherein the X-ray diffraction intensity ratio is in the range of 0.2 to 1.20, and It is preferable that the crystallite size determined from the half width of the diffraction peak of the index (031) is in the range of 600 Å or less, particularly 500 Å or less.

In the X-ray diffraction of the crystal, the following Bragg equation (4) nλ = 2d _hkl Sinθｉｎ (4) In the equation, n is the order, λ is the wavelength of the X-ray, and d is
It is known that when _hkl is the (hkl) plane spacing of the crystal and θ is the diffraction angle, an intensity peak appears in the interference, and the intensity peak between the interference peak and the crystal size is known. Also, the following Scherrer equation (5) In the formula, L _hkl is a dimension in a direction perpendicular to the (hkl) plane of the crystal, K is a constant of about 0.9, H is a half width (radian) of an interference peak, and λ and θ are represented by the above formula. Have a relationship.

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 is reduced to 80 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 calcium ion exchange capacity of the macatite-type sodium silicate is remarkably reduced by suppressing the growth or arrangement of the crystal in the direction of the plane index (031) of the macatite-type sodium silicate. 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 used in the present invention is often in the form of plate-like or needle-like crystals.
In the case of a needle-like shape, the primary particle diameter obtained under electron microscope observation is generally 0.05 to 1.
0 μm, major axis of 1.0 to 15 μm, especially minor axis of 0.1
A rod-shaped crystal having a diameter of 2.0 to 10.0 μm, a long diameter of 2.0 to 10.0 μm, and an aspect ratio in the range of 1 to 300. In some cases, these crystal particles aggregate to form a ball-shaped secondary particle. .

As the powder characteristics of the macatite-type sodium silicate, the oil absorption according to JIS K5101-21 is 80 ml / 100 g or more, preferably 100 ml.
/ 100 g or more.

Further, the pH (25 ° C.) of the aqueous suspension of 5 g / 100 ml of the aqueous solution of 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.

[Stabilizing Component] In the composition of the present invention, the stabilizing component (B) comprises a substantially nonvolatile water-miscible or water-soluble nonionic or anionic organic substance and a water-soluble inorganic salt. At least one selected from the group is used. That is, as the stabilizing component, the organic substance or the water-soluble inorganic salt may be used alone, or both may be used in combination.

As the organic stabilizing component, a substantially non-volatile water-miscible organic solvent, particularly an organic solvent having a boiling point of 60 ° C. or higher, is used. Preferred examples thereof include polyhydric alcohols and ether derivatives thereof. Is done. 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 non-volatile, water-miscible organic solvent, a water-miscible organic solvent known per se is used. Examples thereof include ethylene glycol, propylene glycol, butanediol, glycerin, trimethylolpropane, neopentyl glycol and diethylene glycol. , Triethylene glycol, polyhydric alcohols such as polyethylene glycol, ethylene glycol dimethyl ether, cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, polyhydric alcohol ether derivatives such as diglyme and the like. Can be

Among these, an organic solvent having a boiling point of 60 ° C. or higher, particularly an organic solvent having a boiling point of 90 ° C. or higher, is preferable in terms of stabilization continuity. Particularly suitable organic solvents are glycerin, diethylene glycol, triethylene glycol, polyethylene glycol and the like.

As the nonionic surfactant, any known nonionic surfactant can be used. In general, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene Ethylene fatty acid amide ether, polyhydric alcohol fatty acid ester, polyoxyethylene polyhydric alcohol, fatty acid ester, fatty acid sucrose ester, alkylolamide, polyoxyalkylene block copolymer and the like are used. For example, in these nonionic surfactants, in general, when the content of polyoxyethylene units increases, the hydration layer increases, so by adjusting the number of moles of ethylene oxide added,
A desired crystallization promoting action can be obtained.

Further, as the anionic surfactant, for example, primary higher alcohol sulfate, secondary higher alcohol sulfate, primary higher alkyl sulfonate, secondary higher alkyl sulfonate, 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).

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 Copolymer,
Maleic anhydride-vinyl ether copolymer, chitosan,
A sodium styrenesulfonate copolymer or the like is used. On the other hand, examples of nonionic polymers include polyacrylamide, polyvinyl alcohol (PVA), starch, cyanated starch, methylcellulose, ethylcellulose, hydroxyethylcellulose, veegum, gelatin, polyethylene glycol and the like. These water-soluble polymers can be used alone or in combination of two or more, but generally, it is desirable to use them in combination with other organic stabilizing components.

On the other hand, as the inorganic stabilizing component, any water-soluble inorganic salt can be used, but water-soluble alkali metal salts such as sodium sulfate, potassium sulfate, sodium chloride, potassium chloride and sodium nitrate can be used. , Potassium nitrate, sodium phosphate, potassium phosphate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium borate, potassium borate, sodium percarbonate, sodium perborate, and the like. However, the present invention is not limited to this example. Of these, sodium salts, particularly sodium carbonate and sodium sulfate, are preferred.

[Preparation of Builder Composition] The builder composition of the present invention can be prepared by any method. For example, a pre-synthesized macatite-type sodium silicate (A) and an organic and / or inorganic stabilizing component (B) are mixed in the above-mentioned quantitative ratio in a dry or wet manner to be stabilized. Builder composition.
However, in the present invention, as already pointed out, it is preferable to incorporate the stabilizing component into the reaction system prior to the synthesis of the macatite-type sodium silicate. It is by no means limited to cases.

In a preferred production method of the builder composition of the present invention, an aqueous solution or dispersion of sodium silicate as a raw material is added with a seed crystal of macatite and the above-mentioned organic and / or inorganic stabilizing component (B). Is added, and the mixed composition is heated to crystallize the macatite-type sodium silicate. As a result, a builder composition containing the macatite-type sodium silicate (A) and the stabilizing component (B) at a predetermined ratio is obtained. When the above-mentioned stabilizing component (B) is added to the reaction system to synthesize the macatite-type sodium silicate, an additional and very effective effect of improving the yield of the macatite-type sodium silicate is achieved. You. That is, when the synthesis of the macatite-type sodium silicate is performed only by adding the seed crystal, the yield of the macatite-type sodium silicate is at most about 10% (see Comparative Example 1 described later). When the stabilizing component (B) is added to the sodium silicate solution containing the solution to synthesize the macatite-type sodium silicate, the yield of the macatite-type sodium silicate is improved to 30% or more.

The sodium silicate used as a raw material may be an aqueous solution or a dispersion. This raw material may be a transparent solution of sodium silicate such as so-called water glass, solid sodium silicate, or 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.
Those in the range of 0: 2.8 to 1.0: 3.2 are preferred.

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 4 to 40, particularly 5 to 30% by weight in terms of a molar ratio (SiO ₂ / H ₂ O). %.

As the seed crystal, macatite-type sodium silicate is used. The seed crystal preferably has a chemical composition of the above formula (1) and an X-ray diffraction image of the above formula (2), and particularly preferably has a crystallite size of 500 Å or less.

It is preferable to add 1.0 to 50.0 parts by weight, particularly 5.0 to 30.0 parts by weight of a macatite seed crystal per 100 parts by weight of SiO _{2 in} sodium silicate.

The organic and / or inorganic stabilizing component (B) is preferably added to the reaction system in a ratio that satisfies the above-mentioned ratio with respect to the produced macatite-type sodium silicate (A).

The crystallization of the macatite-type sodium silicate is as follows:
A mixed composition containing sodium silicate, seed crystals and stabilizing component (B) at 60 to 150 ° C., especially 80 to 12 ° C.
The crystallization is carried out at a temperature of 0 ° C. Generally, it is preferable to carry out the crystallization under normal pressure. The time for crystallization is
Although it varies depending on the composition of the alkali silicate, the type or amount of the stabilizing component, the amount of the seed crystal, and the temperature, it generally ranges from 5 to 72 hours, particularly from 10 to 4 hours.
It is about 0 hours.

The mixed composition may be formed by one-sided or simultaneous pouring, for example, by pouring a stabilizing component or an aqueous solution thereof into an aqueous solution of an alkali silicate, or by adding an alkali silicate or an aqueous solution thereof in an aqueous medium. A method of simultaneously adding the aqueous solution and the stabilizing component or the aqueous solution 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-shaped 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 operation proceeds smoothly.

According to the production method of the present invention, the yield is calculated by assuming that the amount of silica (SiO ₂ ) in the raw material sodium silicate reacts and is synthesized into macatite is 100% (theoretical value). It can be synthesized in a yield of 30% or more, especially 50% or more. 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 to detergent builder applications. This reaction composition naturally contains a stabilizing component (B) in addition to the macatite-type sodium silicate (A), but the stabilizing component (B) itself is a compounding component for a detergent. While this can be effectively used for detergent applications, these components suppress the decrease in calcium ion exchange capacity of the macatite-type sodium silicate with time, and furthermore, the macatite-type sodium silicate particles in the detergent composition It has a suitable effect to promote dispersion.

The builder composition according to the present invention has cation exchange properties and is therefore particularly useful as a builder for detergents. The macatite-type sodium silicate composition according to the present invention is excellent in increasing detergency and solubilizing power, synergistically increasing surface activity, pH buffering action, sequestering action of metals, preventing redeposition of dirt, and the like. The macatite-type sodium silicate composition according to the present invention may contain, as a cleaning aid, various cleaning agents, for example, powder or liquid detergents for clothing or kitchen, detergents or antifouling agents for toilets, kitchen cleansers,
It can be incorporated in fabric softener, metal, automobile, floor, porcelain or glass cleaner, floor polish, shampoo, bath agent, soap, face 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 speaking, 0.01 to 20% by weight,
In particular, it is preferable to determine the compounding amount from the range of 0.1 to 5% by weight so that the above-mentioned effect can be obtained. 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.

Further, it can be used in combination with another builder.
Other builders are sodium carbonate and sodium sulfate
, Sodium borate, sodium perborate, sodium metasilicate
Thorium, trisodium phosphate and sodium tripolyphosphate
Phosphate or tripolyphosphate, such as sodium, disilicic acid (Na₂
Si₂O₅), Crystalline alkali metal silicates include:
Kanemite (NaHSi₂O₅・ 3H₂O), Macatai
To (Na₂Si₄O₉・ 5H₂O), Airerite
(Na₂Si₈O₁₇), Magadiite (Na₂Si
₁₄O₂₉・ 10H₂O), Kenyaite (Na₂Si
₂₀O₄₁・ 10H ₂O), nitriloacetic acid, citric acid,
Tartaric acid, sodium sulfate, pentasodium triphosphate, nitrile
Sodium trisulfonate and various zeolites are used
It is. For example, zeolite or sodium disilicate (S
KS-6 etc .: manufactured by Hoechst)
Tight type sodium silicate: zeolite or sodium disilicate
From 99: 1 to 1:99, preferably from 99: 5 to
Used in a ratio of 50:50.

[0055]

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 / CEC retention test 0.65 g of a sample is precisely weighed and put into a 500 ml beaker. Next, 500 ml of hard water (ammonium alkaline CaCl ₂ aqueous solution, 300 mg CaO / l) is added, and the mixture is stirred with a magnetic stirrer for 10 minutes. 6 immediately after stirring
Filter with suction through a No. filter paper and collect exactly 10 ml of the filtrate. Then add an appropriate amount of deionized water and pipette NH ₄ OH
2 to ₃ ml of -NH ₄ Cl buffer (pH = 10) was added, and titration was performed with 1/100 M EDTA using Black T as an indicator.
It was calculated from the following equation (6). Ca binding capacity (CaCO ₃ mg / g) = {(C2-C1) × f × 50000} / {(100−I) × W} (6) C2: blank (concentration M) C1: filtrate ( Concentration M) W: Weight of sample (g) I: Loss on ignition of sample at 860 ° C. (%) f: Titer of EDTA For CEC retention, the following formula (3) R = (C ₁ / C ₀ ) × 100 (3) In the formula, C ₀ represents the calcium ion exchange capacity (mgCaCO ₃ / g) of the builder composition before the acceleration test, and C ₁ is the builder after the acceleration test by standing at a temperature of 40 ° C. for 7 days. Calcium ion exchange capacity of the composition (mgCaCO ₃ / g)
Which is defined by

(4) Oil absorption Measured according to JIS K-5101-21.

(5) Particle Size by SEM Representative particles are selected from photographic images obtained by a scanning electron microscope (S-570, manufactured by Hitachi), and the major axis and minor axis of the particle image are measured using a scale. And expressed as a primary particle diameter.

(6) Specific surface area Measured by an automatic BET measuring apparatus (Soapmatic 1900, manufactured by Carlo Elba).

(7) Water solubility test Assumed washing system test A sample was added to tap water to which a pH 10 buffer was added so as to have a concentration of 400 ppm.
After stirring for 0 minutes, the mixture is filtered. The filter was ashed at 800 ° C. for 1 hour, weighed, and the dissolution rate in the sample was calculated. Estimated release environment test sample in tap water with a concentration of 400 ppm
And shaken lightly once a day, and the number of days that the sample was completely dissolved was visually measured.

(8) Slurry Stability Test After the slurry of the sample (2% by weight) was stirred with a constant torque, it was left for 24 hours, and the degree of re-dispersion when stirring again with the same torque was visually confirmed. . The evaluation is as follows: ：: Completely redispersible Δ: Aggregate remains at bottom ×: Redispersible

(9) Measurement of Bulk Specific Gravity The obtained builder composition (powder) was dried at 60 ° C. and measured according to the iron cylinder method.

Example 1 Powder No. 3 sodium silicate (SiO ₂ 58.4%, SiO ₂ / Na ₂ O molar ratio =
3.19), the sodium silicate silica (Si
165% by weight of water and 15% by weight of macatite seed crystals were added to the O ₂ ) standard, and mixed well with a stirrer. Glycerin of 171% by weight based on 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 to obtain a builder composition. A part thereof 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 builder composition and powder.

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 ) 15% by weight of a macatite seed crystal with respect to the standard was added and mixed well with a stirrer. 185% by weight 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 40 hours to obtain a builder composition.
A part thereof 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 builder composition and 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% by weight of a macatite seed crystal with respect to the standard was added and mixed well with a stirrer. Then, a nonionic surfactant (polyoxyethylene derivative) was added at 71% by weight based on 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 to obtain a builder composition. Part of it 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 builder composition and 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% by weight of a macatite seed crystal with respect to the standard was added and mixed well with a stirrer. And 100% by weight of the sodium silicate based on silica (SiO ₂ ).
Was added to obtain a gel-like substance (sodium dialkyl succinate; pure content: 70%). It was reacted at 95 ° C. under normal pressure for 20 hours to obtain a builder composition. A part thereof 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 builder composition and 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% by weight of a macatite seed crystal with respect to the standard was added and mixed well with a stirrer. And 100% by weight of the sodium silicate based on silica (SiO ₂ ).
Was added to obtain a gel-like substance. It was reacted at 95 ° C. under normal pressure for 20 hours to obtain a builder composition. Part of it is 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 builder composition and powder.

(Example 6) No. 3 sodium silicate aqueous solution (SiO ₂ 21.1%, SiO ₂ / Na ₂ O molar ratio =
3.07), the silica (Si) of the sodium silicate
O ₂ ) 15% by weight of a macatite seed crystal with respect to the standard was added and mixed well with a stirrer. And 150% by weight based on the silica (SiO ₂ ) of the sodium silicate.
Was added to obtain a slurry-like substance. It was reacted at 95 ° C. under normal pressure for 20 hours to obtain a builder composition. A part thereof 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 builder composition and powder.

Example 7 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% by weight of a macatite seed crystal with respect to the standard was added and mixed well with a stirrer. And 10% by weight of the sodium silicate based on silica (SiO ₂ ).
Was added to obtain a gel-like substance. It was reacted at 95 ° C. under normal pressure for 20 hours to obtain a builder composition. A part thereof 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 builder composition and 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% by weight of a macatite seed crystal with respect to the standard was added and mixed well with a stirrer. To this was added 47% by weight of sodium carbonate based on 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 to obtain a builder composition. A part thereof was filtered, washed with water, and dried to obtain a powdered macatite-type sodium silicate. Table 2 shows the preparation conditions for this reaction and the properties of the obtained builder composition and powder.

Example 9 No. 3 aqueous solution of sodium silicate (SiO ₂ 28.2%, SiO ₂ / Na ₂ O molar ratio =
3.07), the silica (Si) of the sodium silicate
O ₂ ) 15% by weight of a macatite seed crystal with respect to the standard was added and mixed well with a stirrer. And 100% by weight of the sodium silicate based on silica (SiO ₂ ).
Was added to obtain a slurry-like substance. It was reacted at 95 ° C. under normal pressure for 20 hours to obtain a builder composition.
A part thereof was filtered, washed with water, and dried to obtain a powdered macatite-type sodium silicate. Table 2 shows the preparation conditions for this reaction and the properties of the obtained builder composition and powder.

Example 10 No. 3 sodium silicate aqueous solution (SiO ₂ 21.1%, SiO ₂ / Na ₂ O molar ratio =
3.07), the silica (Si) of the sodium silicate
O ₂ ) 15% by weight of a macatite seed crystal with respect to the standard was added and mixed well with a stirrer. Then, 80% by weight of sodium carbonate and 47% by weight of polyethylene glycol 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 to obtain a builder composition. A part thereof was filtered, washed with water, and dried to obtain a powdered macatite-type sodium silicate. Table 2 shows the preparation conditions for this reaction and the properties of the obtained builder composition and powder.

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% by weight of a macatite seed crystal with respect to the iO ₂ ) standard was added, and mixed well with a stirrer. And 80% by weight based on the silica (SiO ₂ ) of the sodium silicate.
Of sodium sulfate and 47% by weight of polyethylene glycol were added to obtain a slurry-like substance. 95 ℃ under normal pressure
For 20 hours to obtain a builder composition. A part thereof was filtered, washed with water, and dried to obtain a powdered macatite-type sodium silicate. Table 2 shows the preparation conditions for this reaction and the properties of the obtained builder composition and 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% by weight of a macatite seed crystal with respect to the iO ₂ ) standard was added, and mixed well with a stirrer. And 35% by weight of the sodium silicate based on silica (SiO ₂ ).
Sodium chloride and 35% by weight of polyethylene glycol were added to obtain a gel substance. It was reacted at 95 ° C. under normal pressure for 20 hours to obtain a builder composition. A part thereof was filtered, washed with water, and dried to obtain a powdered macatite-type sodium silicate. Table 2 shows the preparation conditions for this reaction and the properties of the obtained builder composition and powder.

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% by weight of a macatite seed crystal with respect to the iO ₂ ) standard was added, and mixed well with a stirrer. And 80% by weight based on the silica (SiO ₂ ) of the sodium silicate.
Of sodium carbonate and 150% by weight of glycerin to obtain a slurry-like substance. It was reacted at 95 ° C. under normal pressure for 20 hours to obtain a builder composition. A part thereof was filtered, washed with water, and dried to obtain a powdered macatite-type sodium silicate. Table 2 shows the preparation conditions for this reaction and the properties of the obtained builder composition and powder.

Example 14 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% by weight of a macatite seed crystal with respect to the iO ₂ ) standard was added, and mixed well with a stirrer. And 80% by weight based on the silica (SiO ₂ ) of the sodium silicate.
Of sodium carbonate and 71% by weight of a nonionic surfactant (polyoxyethylene derivative) to obtain a gel-like substance. It was reacted at 95 ° C. under normal pressure for 20 hours to obtain a builder composition. A part thereof was filtered, washed with water, and dried to obtain a powdered macatite-type sodium silicate. Table 2 shows the preparation conditions for this reaction and the properties of the obtained builder composition and powder.

Example 15 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% by weight of a macatite seed crystal with respect to the iO ₂ ) standard was added, and mixed well with a stirrer. And 80% by weight based on the silica (SiO ₂ ) of the sodium silicate.
Of sodium carbonate and 100% by weight of an anionic surfactant (sodium dialkyl succinate; pure content: 70%) were added to obtain a gel-like substance. It was reacted at 95 ° C. under normal pressure for 20 hours to obtain a builder composition. A part thereof was filtered, washed with water, and dried to obtain a powdered macatite-type sodium silicate. Table 2 shows the preparation conditions for this reaction and the properties of the obtained builder composition and powder.

Example 16 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% by weight of a macatite seed crystal with respect to the iO ₂ ) standard was added, and mixed well with a stirrer. And 80% by weight based on the silica (SiO ₂ ) of the sodium silicate.
Of sodium carbonate and 71% by weight of an anionic surfactant (sodium dialkyl succinate; pure content: 70%) were added to obtain a gel-like substance. 100 parts by weight of 4-micron A-type zeolite was added to this gel-like substance, and the mixture was reacted at 95 ° C. under normal pressure for 20 hours to obtain a builder composition. A part of the gel substance was reacted at 95 ° C. under normal pressure for 20 hours, filtered, washed with water, and dried to obtain a powdered sodium macatite silicate. Table 2 shows the preparation conditions for this reaction and the properties of the obtained builder composition and powder.

Comparative Example 1 No. 3 sodium silicate aqueous solution (SiO ₂ 21.1%, SiO ₂ / Na ₂ O molar ratio =
3.07), the silica (Si) of the sodium silicate
O ₂ ) 15% by weight of a macatite seed crystal with respect to the standard was added and mixed well with a stirrer. 95 ℃ under normal pressure
For 800 hours. After the completion of the reaction, the reaction solution was filtered, washed with water, and dried to obtain a powdered sodium macatite silicate. At this time, the yield was 8%. Table 3 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 ) 15% by weight of a macatite seed crystal with respect to the standard was added and mixed well with a stirrer. 2% by weight of sodium carbonate and 2% by weight of polyethylene glycol were added thereto to obtain a gel-like substance. It was reacted at 95 ° C. under normal pressure for 72 hours to obtain a builder composition. A part thereof was filtered, washed with water, and dried to obtain a powdered macatite-type sodium silicate. Table 3 shows the preparation conditions for this reaction and the properties of the obtained powder.

Comparative 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 ) 80% by weight sodium carbonate and 47
% By weight of polyethylene glycol was added to obtain a gel-like substance. It was reacted at 95 ° C. under normal pressure for 200 hours. 200
At the end of the time, no reaction was obtained.

Comparative 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% by weight of a macatite seed crystal with respect to the standard was added and mixed well with a stirrer. And 400% by weight
Of sodium carbonate and 400% by weight of polyethylene glycol were added to obtain a gel-like substance. After a while, it solidified and could not be easily removed from the reaction vessel.

[0085]

[Table 1] However, in the table, R _i represents R _I of the above formula (2) (the same applies hereinafter).

[0086]

[Table 2]

[0087]

[Table 3]

[0088]

According to the present invention, a macatite-type sodium silicate (A) having a specific chemical composition and a specific X-ray diffraction intensity ratio is substantially non-volatile, water-miscible to water-soluble and nonionic. Alternatively, by combining at least one stabilizing component (B) selected from the group consisting of an anionic organic substance and a water-soluble inorganic salt, the calcium ion exchange capacity of the macatite-type sodium silicate can be increased at a high level over time. It is possible to stabilize it. Furthermore, this composition has good dispersibility and is particularly useful as a builder 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 10 of the present invention.

FIG. 2 is a graph showing the relationship between the half-value width of the diffraction peak of the plane index (031) and the diffraction peak obtained by lowering the scanning speed of 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;

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4G073 BA04 BB25 BD01 CA02 CB06 GA03 UA09 UB33 4H003 AB07 AC07 BA01 BA12 DA01 DA02 DA04 DA06 DA09 DA11 DA17 EA12 EA16 EA25 FA04 FA15 FA16

Claims (7)

[Claims] (A) Na ₂ O · nSiO ₂ · mH ₂ OＳｉＯ (1) where n is a number from 3 to 5, and m is a number from 0 to 10. , And 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). , I ₂₀₀ is the relative intensity of the X-ray diffraction peak of the plane index (200), wherein the X-ray diffraction intensity ratio defined in the range of 0.20 to 1.20 is in the range of 0.20 to 1.20; B) at least one stabilizing component selected from the group consisting of a substantially nonvolatile, water-miscible or water-soluble, nonionic or anionic organic substance and a water-soluble inorganic salt; A builder wherein component (B) is present in an amount of from 5.0 to 300 parts by weight per 100 parts by weight -Composition. 2. The builder composition according to claim 1, wherein the macatite-type sodium silicate is a sodium silicate having a crystallite size determined from a half width of a diffraction peak having a plane index (031) of 600 Å or less. . 3. The builder composition according to claim 1, wherein the calcium ion exchange capacity of the macatite-type sodium silicate is in the range of 80 mg CaCO ₃ / g or more. 4. The builder composition according to claim 1, wherein the organic substance is a water-miscible organic solvent, a nonionic or anionic surfactant, or a nonionic or anionic water-soluble polymer. . 5. The builder composition according to claim 1, wherein the water-soluble inorganic salt is sodium carbonate and / or sodium sulfate. 6. The following formula (3): R = (C ₁ / C ₀ ) × 100 (3) where C ₀ is the calcium ion exchange capacity (mgCaCO ₃ / g) of the builder composition before the accelerated test. Wherein C ₁ represents the calcium ion exchange capacity (mgCaCO ₃ / g) of the builder composition after the accelerated test by standing at a temperature of 40 ° C. for 7 days. The builder composition according to any one of claims 1 to 5. 7. At least one component selected from the group consisting of a substantially non-volatile, water-miscible, water-soluble, nonionic or anionic organic substance and a water-soluble inorganic salt of (B) is a macatite type. The builder composition according to any one of claims 1 to 6, which is blended prior to the synthesis of sodium silicate.