JPH0325451B2 - - Google Patents

Description

[Detailed description of the invention]

(Field of Application) The present invention relates to an alumina-silica resin compound and a method for producing the same. More specifically, the present invention relates to an alumina-silica resin compound having a fine particle size and a distinct particle shape, and by compounding it into a resin molded product. This invention relates to a compounding agent for imparting slip properties, anti-blocking properties, etc., and a method for producing the same. (Prior art) Resin molded products such as films and sheets tend to block each other when stacked. To prevent this and further impart slip properties, various inorganic materials are added to the resin. Combining compounding agents has been practiced for a long time. It is already known that zeolite is excellent in such properties, and for example, in Japanese Patent Publication No. 16134/1983, 0.01 to 5% by weight of zeolite powder with an average particle size of 20 microns or less is added to polypropylene.
It has been shown that the addition of these compounds improves the blocking resistance of biaxially oriented polypropylene films. Also, in Japanese Patent Application Laid-open No. 54-34356,
Thermal stability can be improved by incorporating ion-exchangeable zeolite crystalline aluminosilicates into chlorine-containing polymers in amounts of 0.01 to 10% by weight, with the added benefit of external lubricity. A significant improvement is disclosed. As mentioned above, zeolite particles are excellent in providing slip properties (external slip properties) and anti-blocking properties to resin molded products;
Zeolite contains a considerable amount of basic components such as sodium, potassium, calcium, and magnesium in the form of aluminosilicate, and the presence of these basic components makes it difficult to blend zeolite particles. There is a problem that the resin molded product becomes colored over time. Furthermore, zeolite has adsorption properties, particularly water adsorption properties, and there is also the problem that it foams when blended into a resin. On the other hand, JP-A No. 58-213031 describes Al ₂ O ₃ :
It consists of cubic primary particles with a side length of 5 microns or less having a composition in which the molar ratio of SiO ₂ is in the range of 1:1.8 to 1:5, and the particles are substantially amorphous in terms of X-ray diffraction. and has a BET specific surface area of 100 m ² /g or less. Although crystallinity virtually disappears,
It can be obtained by acid treatment under conditions that do not damage the particle shape, and the particle size is 10μ or less.
It is also described that it is preferable to have a secondary particle size distribution in which the particle size is 98% by weight or more and 70% by weight or more of the total particle size. (Problems to be Solved by the Invention) The above-mentioned amorphous alumina-silica particles produced by acid treatment of zeolite solve various problems that occur when blending zeolite particles with resin, but For example, household laptops that require
There is a problem that the particle size characteristics are too coarse for use in film substrates such as magnetic tapes, so we need a compounding agent that has finer particle size characteristics and has excellent dispersibility in resin to impart slip and anti-blocking properties. is required. However, when the zeolite particles to be subjected to acid treatment are made finer, the regular cubic shape of the primary particles of the zeolite particles is destroyed during the acid treatment and becomes irregularly shaped, and furthermore, these irregularly shaped primary particles aggregate and become coarse. This results in the disadvantage of SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an amorphous silica-alumina compound and a method for producing the same, which effectively eliminate the drawbacks of the conventional amorphous silica-alumina compound described above. Another object of the present invention is to maintain a clear primary particle shape, suppress both primary particles and secondary particles to a fine particle size range, and have good dispersibility in resin, non-foaming properties, The object of the present invention is to provide an amorphous silica-alumina resin compound having an excellent combination of slip properties and anti-blocking properties. Still another object of the present invention is to provide a method for reliably and easily producing an amorphous silica-alumina resin compound having the above characteristics. Still another object of the present invention is to provide an amorphous alumina-silica resin compound suitable for blending into thin film substrates such as household wrap magnetic tapes. (Means for Solving the Problems) The present inventors selected a synthetic zeolite with a primary particle size of less than 0.6 μm, and placed this synthetic zeolite under buffer conditions that suppressed the decrease in local pH. In addition, when acid treatment is performed under conditions that the final pH does not become lower than 5, and then heat treatment is performed, an amorphous alumina-silica resin compound with novel particle size characteristics and adsorption characteristics detailed below is used. It has been found that this formulation is suitable for the above-mentioned purpose. That is, according to the present invention, in an alumina-silica resin compound comprising amorphous particles having a molar ratio of Al ₂ O ₃ :SiO ₂ in the range of 1:1.8 to 1:5.0,
The alumina-silica particles have a distinctly cubic or spherical primary particle shape, with an average primary particle diameter of less than 0.6μ as measured by electron microscopy, and less than 1μ as measured by gravimetric sedimentation. The particle size is 77% by weight or more and the secondary particle size is measured by gravimetric sedimentation method.
having a secondary particle size distribution such that the secondary particle distribution ratio of particles of 0.5 μ or less among 1 μ or less is 55% or more, and the particles have a BET specific surface area of 50 m ² /g or less, After heating at 550℃ for 3 hours, relative humidity 75%,
Provided is an alumina-silica resin compound characterized by an amount of water adsorption of 10% by weight or less when left in an atmosphere at a temperature of 25° C. for 24 hours. In addition, the above-mentioned compound has a molar ratio of Al ₂ O ₃ :SiO ₂ in the range of 1:1.8 to 1:5.0, and fine cubic particles having an average primary particle diameter of less than 0.6μ as measured by an electron microscope. Synthesis of zeolite by preparing an aqueous slurry of zeolite and contacting the aqueous slurry with an acid in an aqueous medium containing at least 1.0 mole % alkali metal salt per acid and under conditions such that the final pH does not fall below 5. It is produced by acid-treating zeolite and firing the resulting acid-treated zeolite at a temperature of 300°C or higher. (Function) The present invention selects a synthetic zeolite with a primary particle size of less than 0.6 μm, and processes this synthetic zeolite under buffer conditions that suppress local PH reduction and in the final stage.
A remarkable feature is that the acid treatment is carried out under conditions where the pH does not fall below 5. That is, according to research conducted by the present inventors, it has been found that in the acid treatment of synthetic zeolite, the particle shape and secondary particle size of amorphous particles have a significant influence on the particle size of the original zeolite particles. For example, when zeolite particles with a primary particle size of 0.8μ or more are acid-treated, amorphous alumina-silica particles that have substantially the same cubic shape as the zeolite particles are produced regardless of the acid treatment conditions. . However, when zeolite having a primary particle diameter of less than 0.6 microns is acid-treated, the cubic shape of the zeolite particles is often lost, resulting in amorphous alumina-silica particles having irregular shapes. In general, it has been observed that in powders of inorganic compounds, especially powders of amorphous substances, the finer the primary particle size, the greater the tendency for secondary aggregation, and the tendency for the secondary particle size to increase. It will be done. The present invention provides that even if the zeolite particles are finely synthesized zeolite particles with an average primary particle size smaller than 0.6μ, when the zeolite particles are acid-treated under the above-mentioned conditions, the primary particles characteristic of the zeolite particles are This is based on the new knowledge that the particle shape is maintained in a straight shape and a fine primary particle size and secondary particle size distribution can be obtained. In the present invention, an aqueous medium containing a certain concentration of an alkali metal salt is used for the acid treatment of zeolite particles, and this is necessary to suppress local PH decrease in the acid treatment system. Another notable feature of the present invention is that it is possible to make the zeolite amorphous by acid treatment when the final pH is 5 or more, and it is possible to make the zeolite amorphous under such mild acid treatment conditions. This is also related to the fact that the primary particle size of the raw material zeolite used is fine. Under normal acid treatment conditions, i.e., under conditions where a local pH decrease occurs or where the final pH is lower than 5, the distinct primary particle shape is lost and the particles become amorphous. occurs, secondary aggregation is significant, and the dispersed particle size becomes coarse. FIG. 1 of the attached drawings is an electron micrograph showing the particle structure of the alumina-silica compound according to the present invention, and FIG. 2 is an electron micrograph showing the particle structure of the alumina-silica compound according to the present invention. - (2))) is an electron micrograph showing the particle structure of the product. From these photographs, it can be seen that the alumina-silica particles according to the present invention have an average primary particle diameter of less than 0.6 μm, especially a primary particle diameter of 0.2 to 0.5 μm, and are clearly cubic to spherical primary particles. It can be seen that it has the surprising feature that it has a similar shape, and the degree of secondary aggregation is also extremely small. Further, FIG. 3 is an X-ray diffraction diagram of the alumina-silica particles shown in FIG. 1, and FIG. 4 is an X-ray diffraction diagram of synthetic zeolite A used as the raw material. These results show that the alumina-silica particles of the present invention are completely amorphous and have the above-mentioned particle structure and particle size characteristics even though they are amorphous. Furthermore, FIG. 5 is the particle size distribution curve of the silica-alumina particles of the present invention shown in FIG. 1, and FIG. 6 is the particle size distribution curve of the silica-alumina particles outside the scope of the present invention shown in FIG. be. From these results,
In the formulation of the present invention, the secondary particle size is in an extremely fine range, that is, the particle size of particles smaller than 1 μm is 77% by weight.
or more and the secondary particle diameter is 1μ as measured by gravimetric sedimentation method.
Among the following, an important feature becomes clear that the secondary particle distribution rate of particles having a size of 0.5 μ or less is controlled within a range of 55% or more. Because of these novel particle structure and particle size characteristics, the alumina-silica particles of the present invention are
When blended into a resin for thin film, it is easily dispersed into fine particles in the resin, and it also significantly improves anti-blocking and slip properties without impairing the transparency or continuity of the film. It can be improved. The alumina-silica compound according to the present invention has the above-mentioned fine particle size and is stabilized in an amorphous state, so it is said that the water adsorption property is suppressed to a significantly lower level than that of zeolite. It also has an exceptionally low BET specific surface area for an amorphous alumina-silica.
Therefore, the compounding agent of the present invention completely eliminates the problem of foaming due to adsorbed moisture or adsorbed gas when resin is compounded. (Description of preferred embodiments of the invention) Chemical composition and other properties of the compound The alumina-silica resin compound used in the present invention has an Al ₂ O ₃ :SiO ₂ molar ratio of 1:1.8 to 1:5;
In particular, it has a composition in the range 1:2 to 1:4. If the molar ratio of Al ₂ O ₃ :SiO ₂ is outside the above range, it is difficult to form the alumina-silica into cubic or spherical particles with a clear and constant particle size, and furthermore, properties such as slip properties are not within the scope of the present invention. It becomes inferior to what is inside. The alumina-silica compound used in the present invention is
In addition to the essential components of alumina and silica, it is permissible to contain some basic components, especially alkali metal components. However, this alkali metal content is less than 50%, especially less than 30%, of the alkali metal content of zeolite whose molar ratio of Al ₂ O ₃ :SiO ₂ is within the same range, and compared to zeolite. It should be noted that the content of basic components is extremely low. This alumina-silica compound has a moisture adsorption amount (moisture, regain) of 10% by weight or less, particularly 6% by weight or less, as measured by the method described above. However, although this compound may contain more water than the above-mentioned water adsorption amount, it is generally desirable that the water content is below the above-mentioned water adsorption amount. A few examples, on a compositional weight basis, of particularly desirable alumina-silica formulations for the purposes of this invention are shown below. Type Al ₂ O ₃ 27-45% SiO ₂ 32-55% Na ₂ O 0.1-20% H ₂ O 0-25% Type Al ₂ O ₃ 38-54% SiO ₂ 32-64% Na ₂ O 0.1 ~20% H ₂ O 0-30% Type Al ₂ O ₃ 47-64% SiO ₂ 38-78% Na ₂ O 0.1-20% H ₂ O 0-30% Amorphous with the above composition In addition, the alumina-silica particles exhibit chemical properties not found in zeolites. For example, when made into an aqueous suspension with a solids content of 1%, zeolites typically have a
In contrast, the amorphous alumina-silica particles of the present invention exhibit a pH of 10 or less. In addition, zeolites, such as type A zeolites,
In differential thermal spectroscopy, the amorphous alumina-silica cubic particles of the present invention have an endothermic peak at a temperature of 780-920°C and are converted to carnegate at the above temperature, whereas the amorphous alumina-silica cubic particles of the present invention have an endothermic peak at a temperature of 780-920°C. It shows an endothermic peak in the temperature range of , and is converted to Al ₂ SiO ₅ at this temperature. Furthermore, known amorphous alumina-silica has an area of 100 m ² /
In contrast, the alumina-silica cubic particles of the present invention have a significantly smaller specific surface area, less than 50 m ² /g, especially 30 m 2 /g.
It has a BET specific surface area of m ² /g or less. In addition, this amorphous alumina-silica particle
Oil absorption according to JISK-5101 is generally 120 to 20
ml/100g, especially in the range 60 to 30ml/100g. Manufacturing method As the raw material crystalline zeolite, zeolite A, zeolite The primary particle size of the raw zeolite should be less than 0.6 μm, especially in the range 0.2 to 0.5 μm. As described in Japanese Patent Publication No. 58-51992 by the present inventors, the raw material zeolite having a fine primary particle size and uniform particle size can be obtained from active solid silicic acid, especially smectite group clay such as acid clay. It is a synthetic zeolite obtained using layered activated silicic acid or layered activated aluminosilicate obtained by acid treatment of minerals as a raw material. This type of synthetic zeolite is made amorphous by acid treatment.
It has the characteristic that it can be performed under mild conditions, such as higher pH, or for a shorter period of time. This zeolite is made into an aqueous slurry and subjected to acid treatment. The acid to be used may be an inorganic acid or an organic acid without particular limitation, but economically, acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and carbonic acid are used. These acids are used in the form of dilute aqueous solutions for the neutralization reaction with the crystalline zeolite. When an acid is added to an aqueous slurry of crystalline zeolite, the pH naturally shifts to the acidic side as the acid is added, but in the present invention, acid treatment is performed so as to satisfy the two conditions mentioned above. First, in order to suppress a sudden and local PH drop, an acid treatment medium that has PH buffering properties is used. For this purpose, acid treatment is carried out in such a manner that 1.0 mol % or more, particularly 3.0 mol % or more of an alkali metal salt coexists with respect to the acid in the medium. As the alkali metal salt, those having pH buffering properties such as sodium acetate are suitable, but when using sulfuric acid, sodium sulfate can also be used, and when using hydrochloric acid, sodium chloride can also be used suitably. . Thus, the method of adding an additional amount of acid to the mother liquor containing the alkali metal salts produced as a by-product in the process of acid treatment of zeolite and using the resulting acid-alkali salt solution in the subsequent treatment of zeolite has been proposed. Advantageously applied in processing. Furthermore, care must be taken to ensure that the pH of the medium during acid treatment does not fall below 5 even in the final stage. The obtained amorphous alumina-silica is 300%
The product is dried or fired at a temperature of ℃ or higher. In this case, it is of course possible to previously coat the surface of the particles with a metal soap, a resin acid metal soap, or another dispersant, etc., by means known per se. In this case, the dispersant is preferably used in an amount of 0.1 to 8% based on the alumina-silica particles. Applications The alumina-silica resin compound of the present invention can be used for various resins, such as olefin resins such as polypropylene, polyethylene, crystalline propylene-ethylene copolymers, and ionically crosslinked olefin copolymers; polyethylene terephthalate, polybutylene, etc. Thermoplastic polyester such as terephthalate; 6-
Polyamides such as nylon, 6,6-nylon, and 6,8-nylon; Chlorine-containing resins such as vinyl chloride resin and vinylidene chloride resin; Polycarbonate;
Polysulfones: Can be used by blending with thermoplastic resins such as polyacetal to impart slip properties or anti-blocking properties to resin molded products. Further, it can be added to a kneaded composition or a liquid composition for coating formation to impart anti-blocking properties to the coating. For such applications, the amorphous alumina-silica cubic particles of the present invention can be used in amounts per 100 parts by weight of resin.
It is used in amounts of 0.001 to 10 parts by weight, especially 0.01 to 3 parts by weight. The amorphous alumina-silica cubic particles of the present invention have a low alkali content, do not cause coloring or deterioration of resins, and are well kneaded with resins, so they can also be used as fillers for resins. - Those made of silica can also be blended with the above resins or various thermosetting resins as flame-retardant fillers for various purposes. The invention is illustrated by the following example. Comparative Example 1 The zeolite used in this comparative example is a 4A type zeolite synthesized by the following method. As the silicic acid content, a fine particle silicic acid gel obtained by acid-treating acid clay from Nakajo, Niigata Prefecture, which is a smectite group clay mineral, was selected. Acidic clay from Nakajo, Niigata Prefecture, has a moisture content of 45% in its natural state.
The main components are SiO ₂ 72.1% by weight (drying at 110°C) on a dry matter basis.
The values were Al ₂ O ₃ 14.2, Fe ₂ O ₃ 3.87, MgO 3.25, CaO 1.06, and loss on ignition 3.15. This raw material acid clay was formed into a cylinder shape with a diameter of 5 mm and a length of 5 to 20 mm, and an amount equivalent to 765 g of dry matter was collected in each conical beaker in No. 5, and 2 sulfuric acid solutions with a concentration of 50% by weight were added. After heating to 90°C and selecting a treatment time of 7 hours, the granules were treated with acid, and then the sulfate, the basic component that had reacted with the sulfuric acid, was washed and removed using a dilute sulfuric acid solution and water using the decantation method. Then, the mixture was washed with water until the sulfate roots were removed to obtain a granular acid-treated acid clay. Next, in order to produce zeolite, first, the granular acid-treated product produced above was placed in a household mixer (Hitachi Mixer, VA-853 model) in order to distribute the particle size suitable for use as a synthetic raw material.
Water was added to the mixture so that the solid content concentration was 20% by weight, and the mixture was stirred and crushed for 20 minutes.Then, the mixture was classified using a 200-mesh wire mesh and then crushed in a No. 7 ball mill for 3 hours to adjust the particle size. A clay slurry was obtained. The particle size distribution (%) was measured, and the results are shown in Table 1 below.

[Table] In addition, the chemical composition analysis (weight % based on 110°C dry matter) of the acid-treated viscosity slurry obtained here was conducted, and the results are shown below. Burning loss 3.93, SiO ₂ 94.19, Al ₂ O ₃ 1.05,
Fe ₂ O ₃ 0.15, CaO 0.49, MgO 0.10 As the production conditions for the zeolite, the following molar ratios were first selected based on oxides as the composition molar ratios. Na ₂ O / SiO ₂ = 1.2 SiO ₂ / Al ₂ O ₃ = 2.0 H ₂ O / Na ₂ O = 35 The alumina content, the alkali content necessary for the reaction, and the water necessary for the reaction were mixed with a commercially available reagent alkali aluminate solution (composition Na ₂ O 2 1.0%, Al ₂ O ₃ 18.8%) and a commercially available reagent caustic soda ( Mix NaOH) and water to achieve the desired mixing ratio above, filter this mixture to select a purified mixture, and place the slurry of the acid-treated product and the purified mixture in 10 stainless steel containers. The liquid volume of this reaction system is about 7
When the raw materials are mixed by stirring at 20° C., the mixed system temporarily passes through a gel state and is obtained as a homogeneous slurry. Then 95
When heated to ℃ and stirred for 3 hours, crystal particles of alkali aluminosilicate (zeolite) are generated. After crystal formation, the reaction product containing crystals is aged for 2 hours at the above-mentioned temperature, and then the reaction mother liquor is separated, the overcake is recovered, and the obtained reaction product overcake is then dried. The mixture was added and mixed in an amount of 4 parts by weight of ion-exchanged water to 1 part by weight, and stirred to form a homogeneous slurry. The mother liquor was again separated by filtration. The pH of the liquid at this time was 12.5. The primary particle diameter of this substance measured by scanning electron microscopy is approx.
It was 0.5μ. After dispersing 1000 g of this 4A type zeolite percake (515 g as anhydride) in dilute sulfuric acid 5 adjusted to pH 2, it was poured simultaneously with the above dilute sulfuric acid into a 200 container equipped with a high-speed stirrer. The amount of dilute sulfuric acid used was 172
The pH at the end of the injection was 5.8. Then 50℃
After heating and holding for 1 hour, the mixture was washed with water and dried.
The mixture was further calcined at 350°C for 2 hours and then pulverized using an atomizer to obtain an amorphous aluminosilicate. Table 2 shows the physical properties of this product. The test method in this example was based on the following. (1) Packing density Based on JIS-K6220. (2) Specific surface area 0.5 to 0.6 g of the material previously dried at 150°C to a constant weight is placed in a weighing bottle, dried for 1 hour in a constant temperature dryer at 150°C, and the weight is immediately accurately weighed. This sample was placed in an adsorption sample tube (2 to 5 ml), heated to 200℃, degassed until the degree of vacuum in the adsorption sample tube reached 10 ^-4 mmHg, and after being left to cool, it was adsorbed in liquid nitrogen at approximately -196℃. Insert the sample tube P _N2 /P ₀ = 0.05 to 0.30 (P _N2 : Nitrogen gas pressure, P ₀ : Atmospheric pressure at the time of measurement)
Measure the amount of _N2 gas adsorbed at 4 to 5 points between the two locations. Then, the amount of _N2 gas adsorbed after subtracting the dead volume is 0°C.
Convert it to the adsorption amount at 1 atm and substitute it into the BET formula,
Vm [ml/g] (indicating the amount of nitrogen gas adsorbed necessary to form a monomolecular layer on the sample surface) is determined. The specific surface area S is determined by the following formula. S=4.35×Vm [m ² /g] (3) Oil absorption amount Based on JIS-K-5101. (4) Whiteness According to JIS-P-8101. (5) Particle size determined by electron microscopy Take an appropriate amount of sample fine powder onto a metal sample plate, thoroughly disperse it, and use a metal coating device (Hitachi E-
101 type ion sputter) and use it as a photographic sample. Next, by changing the field of view using a scanning electron microscope (Hitachi S-570) in a conventional manner, four 10,000x electron micrograph images suitable for primary particle measurement are obtained. Six representative particles were selected from among the cubic particle images in the field of view, and the length of one side of each cubic particle image was measured using a scale, and the length was expressed as the primary particle diameter in the Examples herein. (6) Crystallinity by X-ray diffraction The sample was passed through a 2.00 mesh standard sieve in advance, and dried in an electric constant temperature dryer at 105°C for 3 hours together with a standard sample (UCC Na-A type zeolite standard sample). After cooling in a desiccator, X-ray diffraction measurement is performed, and the degree of crystallinity is calculated according to the formula below. (Equipment) Rigaku Denki Co., Ltd. X-ray diffractometer goniometer - PMG-S2 Rate meter ECP-D2 (Measurement conditions) Target Cu Filter Ni Voltage 35kV Current 20mA Count full scale 4×10 ³ C/S Time constant 1sec Chart speed 1cm/min Scanning speed 1°/min Diffraction angle 1° Slit width 0.15mm Measurement range 2θ = 20° ~ 32° Na-A zeolite crystallinity = 100 (Σ sample peak height at 21.7°, 24.0゜, 27.2゜, 300
゜/ΣPeak height of standard sample at21.7゜, 24.0゜, 27.2゜, 300゜) (7) Particle size distribution Seishin Enterprise Micron Photosizer SKN
Measurements were carried out using the -1000 model. as a dispersion medium
Use 0.2% sodium pyrophosphate aqueous solution. At the beginning of measurement, adjust the zero point and swing width of the recorder using only the dispersion medium. The amount of light transmitted through the blank should match Log1.95 of the recording paper. The sample dispersion was prepared as follows. Pour 100ml of dispersion medium into a 200ml beaker and add approximately
Add 15mg and disperse for about 2 minutes using SKDisperser (ultrasonic disperser). At this time, stir occasionally with a stirrer. After the dispersion is completed, the liquid is cooled or heated until the liquid temperature reaches a predetermined temperature. This dispersion liquid is poured into the glass cell up to the marked line while maintaining a uniformly dispersed state. When the cell is set in the cell holder and the light source lamp is turned on, if the recorder pen is between Log 1.3 and Log 1.4, the concentration of the dispersion liquid is appropriate.
If it is less than Log1.3, it is too thick, and if it is more than Log1.4, it is too thin, so re-adjust it. Measurement is maximum particle size
This is done under the conditions that the thickness is 30μ. Comparative Example 2 Same 4A type zeolite filter cake as Comparative Example 1
After dispersing 200 g (103 g of anhydride) in dilute sulfuric acid 2 adjusted to pH 2, it was vacuum filtered using a Buchner funnel. During the process, before the cake is exposed, add 2 ml of dilute sulfuric acid with a pH of 3, and then add industrial water (PH
5.8) Add 5 and end the pass. The pH of the liquid near the end was 6.6. After that, finishing was carried out in the same manner as in Comparative Example 1. Table 2 shows the physical properties of this product. Example 1 4A type zeolite filter cake same as Comparative Example 1
100 g (51.5 g anhydrous) of a pre-prepared buffer solution (250 ml of 1M sodium acetate, 75 ml of 1N hydrochloric acid, 1000 g of water)
ml, PH4.9) was added under stirring, heated to 50°C and held for 3 hours. The pH at that time was 5.6. After that, finishing was carried out in the same manner as in Comparative Example 1. However, firing
It was carried out at 500℃. Table 2 shows the physical properties of this product.

[Table] Comparative Examples 3 to 6 Zeolite with a primary particle size of about 0.5μ used in Comparative Example 1 (Comparative Example 3-1), zeolite for detergents with a primary particle size of about 0.8μ (Silton B manufactured by Mizusawa Chemical Industry Co., Ltd.) , Comparative Example 4),
Detergent zeolite manufactured by Company D (Comparative Example 5) with a primary particle size of approximately 2.0μ was used, and 0.5N hydrochloric acid was added dropwise to 500ml of a 3% zeolite slurry under stirring at room temperature using a biuret so that the pH reached 4 in approximately 30 minutes. . After that, adjust the pH with 0.5N hydrochloric acid every hour until the pH stabilizes.
The pH was adjusted to about 4, and the test was completed in about 10 hours. Thereafter, it was filtered, washed with water, and dried to obtain an amorphous aluminosilicate. Regarding the zeolite of Comparative Example 3-1, except that the stable pH of the slurry was set to about 5,
An amorphous aluminosilicate was obtained in the same manner as above (Comparative Example 3-2). Furthermore, an amorphous aluminosilicate was obtained in exactly the same manner as in Example 1 of JP-A-58-213031 (Comparative Example 6). Table 3 shows the physical properties of these amorphous aluminosilicates. From the results in Table 3, it is understood that there are very few particles smaller than 1μ.

[Table] Application example A polypropylene film was created using the amorphous aluminosilicate obtained in Example 1 and the amorphous aluminosilicate obtained in Comparative Examples 3-1, 3-2, and 6, and its transparency (haze ), and the anti-blocking properties were evaluated. The evaluation results are shown in Table-3. The method for preparing the polypropylene film and the evaluation method for transparency and anti-blocking properties are as follows. Preparation of polypropylene film; Polypropylene resin [F-5962 manufactured by Chitsuso Co., Ltd.]
and the above amorphous aluminosilicate, respectively.
1000ppm was mixed, extruded using a T-die extruder, and then subjected to stretching treatment of 5 times the length and 9 times the width, followed by corona discharge treatment of 60W/m ² /min.
A polypropylene film with a thickness of 25 μm was obtained. Measurement of haze; 50mm of the polypropylene film obtained above
Cut into 50mm size and according to JIS K6758.
Pretreatment was carried out for 1.5 hours at a temperature of 20±5° C. and a humidity of 65±20% RH. Then JIS K 6714 and JIS
Haze was measured using a digital haze meter NDH-20D manufactured by Nippon Denshoku Kogyo in accordance with the K6718 test method, and was used as a transparency evaluation standard. Measurement of anti-blocking property: After pre-treating a 50 mm x 50 mm polypropylene film in the same manner as above, it was processed using a 60 mm x 60 mm holding plate according to the measurement conditions below, and then manually The anti-blocking property was evaluated using the following criteria while peeling the film. Measurement conditions (1) After separating the two films, place them between the holding plates with the sides to be measured aligned. (2) Place a 2Kg weight on it. (3) Leave at 40±1℃ and 70±2%RH for 24 hours. Judgment criteria: Grade 1: Peels off without resistance. Grade 2: Some resistance. Grade 3: There is considerable resistance, but it can be peeled off. Grade 4: Does not peel off, can be removed later by hand. Grade 5: Will not peel off, and will not slip when removed by hand later. The above operation is performed by holding the sample between the thumb, index finger, and middle finger and shifting the fingers.

【table】 [Brief explanation of drawings]

FIG. 1 is an electron micrograph showing the particle structure of the alumina-silica compound according to the present invention;
The figure is an electron micrograph showing the alumina-silica particle structure outside the scope of the present invention, FIG. 3 is an X-ray diffraction diagram of the alumina-silica particle in FIG. Fig. 5 is an X-ray diffraction diagram of synthetic zeolite A used as a raw material, Fig. 5 is a particle size distribution curve of the alumina-silica particles shown in Fig. 1, and Fig. 6 is a particle size distribution curve of the alumina-silica particles shown in Fig. 2. This is the particle size distribution curve.

Claims (1)

[Claims] 1 Al ₂ O ₃ :SiO ₂ molar ratio is 1:1.8 to 1:5.0
In an alumina-silica resin compound consisting of amorphous particles in the range of The average primary particle diameter and the secondary particle size of particles whose particle size is 77% by weight or more of particles smaller than 1μ as measured by gravimetric sedimentation method and 0.5μ or less among those whose secondary particle diameter is 1μ or less as measured by gravimetric sedimentation method. and a secondary particle size distribution such that the particle distribution ratio is 55% or more, and the particles have a BET specific surface area of 50 m ² /g or less,
After heating at 550℃ for 3 hours, relative humidity 75%, 25℃
An alumina-silica resin compound characterized by an amount of water adsorption of 10% by weight or less when left in an atmosphere at a temperature of 24 hours. 2 Al ₂ O ₃ :SiO ₂ molar ratio is 1:1.8 to 1:5.0
an aqueous slurry of fine cubic particle synthetic zeolite having an average primary particle size of less than 0.6 microns as measured by electron microscopy, and combining the aqueous slurry with an acid in an amount of at least 1.0 mole percent alkali per acid. in an aqueous medium containing metal salts and the final
Contact under conditions where the pH does not fall below 5,
Synthetic zeolite is acid-treated and the resulting acid-treated zeolite is calcined at a temperature of 300°C or higher to produce cubic or spherical primary particles with an average primary particle size of less than 0.6μ when measured with an electron microscope. Secondary particle distribution of particles whose particle size is 77% by weight or more of particles smaller than 1μ as measured by gravimetric sedimentation method and whose secondary particle diameter is 0.5μ or less as measured by gravimetric sedimentation method It has a secondary particle size distribution such that the ratio is 55% or more and a BET specific surface area of 50 m ² /g or less, and after heating at 550°C for 3 hours, the relative humidity is 75%,
A method for producing an alumina-silica resin compound whose water adsorption amount is 10% by weight or less when left in an atmosphere at a temperature of 25°C for 24 hours.