JP6129025B2 - Silica-alumina shaped particles - Google Patents

Description

  The present invention relates to a silica-alumina-based regular particle in which individual particles exist independently and has a spherical shape or a shape close to a spherical shape.

Spherical silica-alumina-based particles are widely used in various polymer films and other fillers for resins or rubbers, fillers for cosmetics, support carriers for fragrances and chemicals, and fillers for chromatography. Yes.
The silica alumina spherical particles can be produced by spraying silica-alumina sol or colliding the spray with an air stream, hydrolyzing an organometallic compound, or crystalline zeolite having a cubic or spherical particle form. A method is known in which the alkali metal content in the zeolite is removed by neutralization with an acid under conditions where the crystal structure is destroyed but the particle morphology is not substantially impaired.

  By the way, the silica-alumina-based spherical particles produced using silica-alumina sol have a disadvantage that the primary particle size is relatively coarse, and the particle size distribution is wide. It has a problem that foaming occurs when it is blended with a resin and thermoformed. On the other hand, silica-alumina-based spherical particles produced using zeolite are excellent in dispersibility with respect to the resin, but have a problem that the refractive index of the particles is greatly different from that of the resin and the hygroscopicity is also large. ing.

  As silica-alumina-based spherical particles in which the above drawbacks have been solved, Patent Document 1 discloses that an X-ray diffraction image peculiar to P-type zeolite and individual particles as a whole have a clear spherical shape and a jagged surface. There has been proposed a zeolite particle obtained by calcination at 200 ° C. to 700 ° C. after ion exchange of the zeolite particles with calcium ions or the like.

  The silica-alumina-based spherical particles of Patent Document 1 are substantially amorphous in terms of X-ray diffraction, and each particle has a clear spherical shape and a jagged surface as a whole, and RH 90%, room temperature and It has a moisture absorption of 13% or less and a refractive index of 1.48 to 1.61 at 48 hours. Such particles have good dispersibility with respect to the resin and low moisture absorption, so that the problem of foaming is effectively solved, and the refractive index is close to the refractive index of various resin films. In addition, since the particles have a jagged surface, the properties as an anti-blocking agent are excellent, and when blended in a resin film, the transparency of the film is maintained while maintaining transparency. Adhesion can be prevented.

  However, the amorphous silica-alumina spherical particles of Patent Document 1 also have insufficient properties as an anti-blocking agent. For example, in order to ensure good anti-blocking properties, a considerable amount of particles are added to the resin film. In addition, since the particles are dense and hard and the particle diameter is large, there is also a disadvantage that the surface is damaged when the films are rubbed together.

  On the other hand, Patent Document 2 discloses silica-alumina-based agglomerated particles that are excellent in anti-blocking properties and excellent in scratch resistance against resin films. The silica-alumina-based aggregated particles are amorphous in terms of X-ray diffraction, and have a form in which fine primary particles are aggregated to form secondary particles having an appropriate size. In other words, there are voids in the particles and the bulk density is small. Therefore, compared to the amorphous silica-alumina spherical particles disclosed in the above-mentioned Patent Document 1, more protrusions can be formed when blended in the same weight in the resin, and it has an excellent anti-blocking characteristic. ing. Further, since the primary particles are small and behave in the form of an aggregate in which small primary particles are aggregated, scratch resistance (scratch resistance) is also good.

  Patent Documents 1 and 2 are both proposed by the present applicant, and the silica-alumina aggregated particles of Patent Document 2 can certainly exhibit excellent antiblocking properties. However, the silica-alumina aggregated particles of Patent Document 2 need to control the aggregated state very precisely in order to exhibit excellent antiblocking properties. When the particles are in an inappropriately aggregated state, fine powders are generated due to the collapse of the aggregated particles when blended in a film, and there is often a disadvantage that the antiblocking property and scratch resistance are insufficient.

  Further, Patent Document 3 discloses that the zeolite slurry is spray-granulated, but even if the particles are formed into a spherical shape by spray granulation, the anti-blocking property and scratch resistance can be improved. Can not.

No. 6-17217 JP 2012-91940 A JP 59-137314 A

  Accordingly, an object of the present invention is to provide silica-alumina particles that are excellent in antiblocking properties and scratch resistance, and that these properties are not varied and can be stably exhibited.

  As a result of conducting many experiments on the anti-blocking properties and scratch resistance of the silica-alumina aggregated particles described above, the present inventors have exchanged Ca particles for the P-type zeolite crystal particles produced by a known method. After thoroughly wet-grinding, the particles are shaped by spray granulation, and the amorphous shaped particles obtained by firing the particles exhibit stable anti-blocking and scratch resistance when blended with resin. As a result, the present inventors have completed the present invention.

According to the present invention, on an anhydride basis, the following formula (1);
_{mCaO · nNa 2 O · pSiO 2} · Al 2 O 3 (1)
Where
m and n are positive numbers;
m + n is 0.9 to 1.1, m / n is 0.05 / 0.95 to 0.9 / 0.1
In the range of
p is a number from 2.3 to 15,
X-ray diffraction-amorphous, a volume-based median diameter (D ₅₀ ) measured by laser diffraction scattering method is in the range of 3 to 20 μm, and 1. The particle size distribution is such that the content of fine particles of 3 μm or less is 8% or less, the bulk density is in the range of 0.40 to 0.65 g / ml, and the pore radius is measured by mercury porosimetry. The pore volume at 1.8 to 25 nm is in the range of 0.15 to 0.40 ml / g, and the following formula (2);
Mesopore volume ratio (%) = (mesopore volume / total pore volume) × 100 (2)
In the formula, the mesopore volume is a pore volume having a pore radius of 1.8 to 110 nm,
The total pore volume is the cumulative pore volume with a pore radius of 1.8 to 10800 nm.
There is provided a silica-alumina-based shaped particle characterized in that the mesopore volume ratio defined by the above is in the range of 30% or more.

According to the present invention, there is also provided an antiblocking agent comprising the silica alumina based regular particles.
According to the present invention, there is further provided a resin composition comprising 0.01 to 5 parts by weight of the antiblocking agent per 100 parts by weight of a thermoplastic resin.

The silica-alumina-based regular particles of the present invention have a volume-based median diameter (D ₅₀ ) in the fine range of 3 to 20 μm, and at the same time, the fine particle content of 1.3 μm or less is 8% or less, Very low content of fine powder. Furthermore, it has many intraparticle voids and a low bulk density (0.40 to 0.65 g / ml). Therefore, compared to the amorphous silica alumina spherical particles disclosed in Patent Document 1 described above, this regular particle can form more protrusions when blended in the same weight in the resin, and has excellent antiblocking properties. And scratch resistance.

  As in the present invention, the silica-alumina aggregated particles disclosed in Patent Document 2 have many intraparticle voids and a low bulk density. However, voids larger than the pore radius of 110 nm are large in proportion, and the mesopore volume ratio shown in the above formula (2) is small. When blended with the resin, the molten resin easily enters the pores having a large diameter, and the aggregated particles may be collapsed by applying a large shearing force thereto. As a result, the fine powder generated in the resin forms only small protrusions that do not contribute to the antiblocking property, and the antiblocking property and scratch resistance may be lowered. On the other hand, in the present invention, the mesopore volume ratio represented by the formula (2) is as extremely large as 30% or more. That is, there are relatively few voids in the particle having a pore radius of 110 nm or more that are easily penetrated by the molten resin, and particle collapse hardly occurs. Therefore, the amount of fine powder generated in the resin is extremely small, and protrusions can be formed effectively. This is a factor in which excellent anti-blocking properties and scratch resistance are stably and evenly expressed.

The X-ray-diffraction image of the P-type zeolite used as a manufacturing raw material of the silica alumina type regular particle (Example 1) of this invention. The X-ray-diffraction image of the silica alumina type regular particle (Example 1) of this invention. The electron micrograph (5000-times multiplication factor) which shows the silica alumina type regular particle (Example 1) of this invention. The electron micrograph of Example 8 (magnification 5000 times). Electron micrograph (magnification 5000 times) of silica-alumina aggregated particles (Comparative Example 1) obtained by immediately firing without performing thorough pulverization and spray granulation after making P-type zeolite crystal particles amorphous. ). The pore distribution measured by the mercury intrusion method of Example 1 and Comparative Examples 1, 2, and 4 (vertical axis: cumulative pore volume). The pore distribution measured by the mercury intrusion method of Example 1 and Comparative Examples 1, 2, and 4 (vertical axis: dV / dR pore volume). The pore distribution measured by the mercury intrusion method of Examples 7 to 9 (vertical axis: cumulative pore volume). The pore distribution measured by the mercury intrusion method of Examples 7 to 9 (vertical axis: dV / dR pore volume).

<Manufacture of silica-alumina shaped particles>
The silica-alumina shaped particles of the present invention are produced by exchanging P-type zeolite crystal particles with Ca and then firing, as in the case of silica-alumina-based aggregated particles disclosed in Patent Document 2, for example. Is that the Ca-exchanged particles are thoroughly pulverized under wet conditions prior to firing, and then the particles are shaped by spray granulation. That is, after carrying out thorough pulverization and spray granulation under wet conditions, the silica-alumina-based regular particles of the present invention having the characteristics described later can be obtained by firing.
Hereinafter, each process etc. are demonstrated in detail.

1. Raw material P-type zeolite;
The P-type zeolite used as a raw material in the present invention is Na-type. Specifically, sodium silicate or activated silicate gel, silica sol, metakaolin, sodium aluminate, alumina sol, and sodium hydroxide satisfy the following conditions. Made from sodium aluminosilicate gel mixed with
Compounding conditions (molar ratio)
Na ₂ O / SiO ₂ : 0.2 to 8 (preferably 0.5 to 1.0)
_{SiO 2 / Al 2 O 3:} 3~20 ( preferably 3.5-6)
H ₂ O / Na ₂ O: 20 to 200 (preferably 30 to 120)

  When producing a gel of sodium aluminosilicate having the above blending conditions, P-type zeolite can be added as a seed crystal. The seed crystals of the P-type zeolite to be added can be added in the form of a powder or in the form of an aqueous slurry, but in general, the seed crystals are preferably added in the form of an aqueous slurry. Further, this seed crystal can be adjusted to a particle size of about 0.1 to 2 μm by wet pulverization, so that coarse secondary particles (aggregates) are not generated and a P-type zeolite having a sharp particle size distribution. It is suitable for obtaining. This particle size can be confirmed by, for example, a Coulter counter method.

The amount of seed crystals added is preferably about 1 to 20% by weight per sodium aluminosilicate produced by the reaction.
Also, when mixing the seed crystals in the form of an aqueous slurry, the water concentration of the mixed system should be such that it does not deviate from the above conditions. Generally, in the form of an aqueous slurry having a concentration of 1 to 30% by weight. It is better to mix.

  The gel is formed by aging while maintaining the above mixed system at a temperature of about 10 to 80 ° C. for about 0.1 to 20 hours with stirring.

  After the formation of the gel, it can be crystallized at a temperature of 80 to 200 ° C. under normal pressure or hydrothermal conditions, and the gel can be eliminated to obtain the desired P-type zeolite particles.

2. Ca exchange treatment;
The crystal particles of P-type zeolite obtained as described above are subjected to ion exchange treatment with Ca ions after filtration and washing with water. By this treatment and the firing treatment described later, the zeolite becomes substantially amorphous.
Such Ca exchange treatment is performed by using an aqueous solution of a water-soluble Ca salt, for example, chloride, nitrate, acetate, etc., and bringing these aqueous solutions into contact with P-type zeolite particles. For this contact, a method of stirring the Ca salt aqueous solution and the P-type zeolite in an aqueous slurry state or a method of contacting the P-type zeolite with the Ca salt aqueous solution in a fixed bed or a fluidized bed is adopted. Or it can carry out by a multistage type, and can carry out by any of a continuous type and a batch type.

Although a part of Na is ion-exchanged with Ca by the above Ca exchange treatment, this treatment condition is, for example, at least 10 mol% or more, particularly 30 mol% or more of Na ₂ O in P-type zeolite. The conditions may be replaced with Specifically, the Ca salt aqueous solution is used in such an amount that the amount of Ca is 0.5 mol times or more, particularly 1.0 mol times or more per Na ₂ O content in the P-type zeolite. It is preferable to contact with 10 to 50% by weight, especially 20 to 40% by weight of Ca salt aqueous solution. The temperature at the time of contact is in the range of 20 to 100 ° C., particularly 30 to 70 ° C. As a matter of course, the exchange treatment is shortened at higher temperatures. The contact time varies depending on the temperature and the exchange rate, but is in the range of 0.5 to 3 hours.

3. Thorough grinding and spray granulation;
In order to obtain the silica-alumina shaped particles of the present invention, prior to the firing treatment described later, the slurry containing the Ca-exchanged P-type zeolite particles obtained as described above is solid-liquid separated by filtration, washed with water, It is also important that the filter cake is thoroughly crushed and then spray granulated.

This thorough pulverization process must be performed until there are no unpulverized particles of P-type zeolite. Specifically, when the particle size of Ca-exchanged P-type zeolite particles is less than the median diameter of 0.5 μm or less under wet conditions, It is necessary to carry out until the particle size distribution becomes the same. As a result, the intra-particle voids are increased, and the mesopore pore volume ratio of the finally obtained silica-alumina-based regular particles can be increased to a predetermined range. As a result, the surface of the shaped particle is in a dense state as shown in FIGS. For example, even if this wet pulverization is not performed, or even if wet pulverization processing is performed, if the median diameter has not been thoroughly performed until it reaches 0.5 μm or less, the mesopore pore volume ratio is set to It cannot be larger than a predetermined range. In other words, the final silica-alumina shaped particles that are obtained are only aggregates of unmilled particles, and have many interparticle voids that are easily intruded by the molten resin. It becomes impossible to avoid generation of fine powder.
Whether or not the median diameter has been pulverized to 0.5 μm or less can be confirmed by a laser diffraction scattering method.

The above-described thorough pulverization treatment under wet conditions is performed in the form of a slurry in which Ca-exchanged P-type zeolite particles are mixed with an aqueous medium (usually water). In order to raise, it is usually set to about 5 to 25% by weight. Further, at this time, SiO ₂ / Al ₂ O ₃ (molar ratio) is in a range not exceeding 15, more preferably in an amount of 5 to 20% by weight per Ca-exchanged P-type zeolite particles, and fine particles such as colloidal silica. Silica particles can also be added as a binder. By adding such a binder, the pore distribution is shifted in the direction of decreasing the mesopore diameter, and the particle strength can be further increased and the generation of fine powder can be suppressed.
It is necessary to use such a high-level pulverizable apparatus as the pulverizing apparatus used for the pulverization treatment. Generally, a high-hardness ball having a Vickers hardness of 13 GPa or more and a ball system of 5 mm or less (for example, Alumina balls) are used, and for example, pulverization by a ball mill can be mentioned.

After the above-described thorough pulverization under wet conditions, spray granulation is performed, whereby the particles are shaped, and for example, shaped particles having a spherical shape or a shape close to a spherical shape can be obtained.
Note that spray granulation of zeolite slurry is known as described in, for example, Patent Document 3 described above. However, as far as the present inventors know, the means for thoroughly pulverizing the zeolite slurry prior to such spray granulation has not been adopted so far. Incidentally, in this patent document 3, the pulverization before spray granulation is at a level where the median diameter is about 1 μm.

In the present invention, such spray granulation is usually performed by adjusting the solid content concentration of the aqueous slurry to about 5 to 25% by weight and using a two-fluid nozzle at an injection pressure of about 1 to 5 kgf / cm ^2. Thus, regular particles granulated into a spherical shape or a shape close to a spherical shape can be obtained.

4). Baking treatment;
The shaped particles of Ca-exchanged zeolite obtained by spray granulation as described above are subjected to a firing treatment.
The firing conditions vary depending on the Ca exchange rate, but are generally in the range of 300 to 850 ° C, particularly 600 to 800 ° C.
Moreover, the calcination can be performed in a fixed bed, a moving bed or a fluidized bed, and the treatment time is sufficient in the range of 0.5 to 5 hours. By calcination in addition to the Ca exchange described above, the P-type zeolite is It is completely amorphized, and physical properties suitable as a resin compounding agent are obtained. For example, if the baking temperature is too high, the refractive index becomes considerably higher than that of the resin, and there is a possibility that inconveniences such as loss of transparency when blended in the resin may occur. In addition, when the firing temperature is low and firing is insufficient, amorphization becomes insufficient, and it exhibits hygroscopicity derived from the crystal structure of the remaining Ca-exchanged zeolite. There is a risk of foaming.
The fired product is appropriately crushed or pulverized, and classified as necessary to obtain the silica-alumina shaped particles of the present invention.

<Silica alumina based particles>
Since the silica-alumina shaped particles of the present invention obtained as described above have been modified to amorphous by Ca exchange and firing, for example, as shown in the X-ray diffraction image of FIG. The crystal peak derived from the crystal structure has completely disappeared, and the chemical composition in terms of anhydride is the above formula (1), that is,
_{mCaO · nNa 2 O · pSiO 2} · Al 2 O 3 (1)
Where
m and n are positive numbers;
m + n is 0.9 to 1.1, m / n is 0.05 / 0.95 to 0.9 / 0.1
In the range of
p is a number from 2.3 to 15,
The thermal loss (110 ° C.) is about 0.1 to 5% by weight.

In addition, since thorough pulverization and spray granulation are performed after Ca exchange, as shown in the micrograph of FIG. 3, it has a regular particle structure in which individual particles exist independently, The jagged surface peculiar to P-type zeolite has also disappeared into spherical or nearly spherical shaped particles.
For example, the shaped particles typically have the following formula:
A = (r ₁ · r ₂ ) ^1/2 / r ₁
Where r ₁ is the circumscribed radius of the particle observed in the electron micrograph of the particle,
r ₂ is the inscribed circle radius of the particle observed in the electron micrograph of the particle,
Is in the range above 0.70.

Furthermore, since it has the particle structure as described above, the volume-based median diameter (D ₅₀ ) measured by the laser diffraction scattering method is in the range of 3 to 20 μm, particularly 3 to 12 μm, and is extremely fine. In addition, the content of fine particles of 1.3 μm or less is 8% or less, particularly 6.5% or less, has a very sharp particle size distribution, and the bulk density is 0.40 to 0.65 g / ml. It is in a remarkably small range.

In addition to the particle structure described above, the silica-alumina-based regular particles of the present invention have a pore volume of 0.15 to 0.40 ml / g at a pore radius of 1.8 to 25 nm as measured by mercury porosimetry. By the above-described thorough wet grinding, the following formula (2);
Mesopore volume ratio (%) = (mesopore volume / total pore volume) × 100 (2)
In the formula, the mesopore volume is a pore volume having a pore radius of 1.8 to 110 nm,
The total pore volume is the cumulative pore volume with a pore radius of 1.8 to 10800 nm,
The mesopore volume ratio defined by is considerably large as 30% or more. That is, in comparison with a case where thorough pulverization is not performed, the intra-particle voids into which the molten resin easily intrudes are narrowed.

  The silica alumina type regular particles of the present invention having such a particle structure are excellent in scratch resistance when blended with a resin, and in addition to being fine and having a sharp particle size distribution, the bulk density is considerably small. Therefore, the number of particles when a predetermined weight is blended with the resin can be considerably large and uniformly dispersed, and excellent anti-blocking properties are exhibited.

  Further, as described above, the silica-alumina shaped particles of the present invention have a large mesopore volume ratio as described above, and the voids in the particles where the molten resin easily enters are considerably narrowed. The strength is high, and when the compound is added to the resin or when a shearing force is applied in the resin by subsequent processing or the like, particle collapse is suppressed, and generation of fine powder in the resin is effectively prevented. In other words, the particle size distribution is sharp and not only contains very fine particles, but also the generation of fine powder in the resin is prevented, so that the above-mentioned scratch resistance and anti-blocking properties are stable and uniform in the resin. Demonstrated in

  Furthermore, since the silica-alumina-based regular particles of the present invention are obtained using P-type zeolite as a raw material, the refractive index approximates the refractive index of various resins. It is in the range of about 49 to 1.53. Therefore, when blended in a resin film, a decrease in transparency due to scattering at the interface between the resin and particles can be greatly suppressed. Convex portions derived from the blended particles are generated on the film surface, and this convex portion exhibits anti-blocking properties and at the same time causes a decrease in transparency. If this convex part is not large enough, antiblocking property will not be expressed, but it will only reduce transparency. That is, in the case of particles containing a large amount of fine powder, the transparency thereof is lowered when blended in a resin film. However, in this invention, since generation | occurrence | production of such a fine powder can be suppressed effectively, the fall of transparency can also be avoided effectively.

  In addition, the silica-alumina shaped particles of the present invention have a small amount of moisture absorption because the crystal structure of the zeolite has disappeared, and can effectively prevent foaming when mixed with a resin and thermoformed. Moreover, the whiteness by Hunter reflection method is 90% or more, and it is excellent in whiteness.

<Application>
As understood from the above description, the silica-alumina-based regular particles of the present invention are extremely useful as an anti-blocking agent, have good scratch resistance, and when blended into a film or the like, due to rubbing between films. The film surface is not damaged. Therefore, this regular particle is made of various resins such as polypropylene, polyethylene, linear low density polyethylene, crystalline polypropylene-ethylene copolymer, ion-crosslinked olefin copolymer, ethylene-vinyl acetate copolymer and the like. Resins; Thermoplastic polyesters such as polyethylene terephthalate and polybutylene terephthalate; Polyamides such as 6-nylon and 6,6-nylon; Chlorine-containing resins such as vinyl chloride resin and vinylidene chloride resin; Polycarbonates; Polysulfones; Thermoplastics such as polyacetal It can mix | blend with resin and can use it suitably for the objective of providing antiblocking property to a resin molded product, for example, a biaxially stretched film.

In addition to the low fine powder content, the silica-alumina shaped particles of the present invention have mesopores in the shaped particles, which reduces the bulk density. As described above, excellent antiblocking properties can be ensured even with a small amount.
For example, in order to develop anti-blocking properties, the present invention is used as an anti-blocking agent in an amount of 0.01 to 5 parts by weight, particularly 0.10 to 0.6 parts by weight per 100 parts by weight of the thermoplastic resin described above. What is necessary is just to mix | blend the silica alumina type regular particle of this. At this time, as described above, the transparency is not lowered and foaming during film forming is effectively prevented.

  In the present invention, the surface of the silica-alumina shaped particles is coated with an inorganic oxide such as titanium oxide, silicon oxide, zirconium oxide, zinc oxide, barium oxide, magnesium oxide, calcium oxide, silane, titanium or zirconium. It can also be coated with various coupling agents, fatty acids, resin acids, various soaps, amides, esters and other derivatives, or surface-treated and blended with various resins.

  Furthermore, in addition to the above, the silica-alumina-based regular particles of the present invention can be used for fillers or reinforcing agents for molding thermosetting resins and coating-forming coatings, and further for use as ceramic substrates, Fillers for various papers, coating fillers for papers, powder foundations, liquid (paste) foundations, various cosmetic bases such as baby powders and creams, abrasives, toothpaste bases, pharmaceuticals, agricultural chemicals, fragrances, fragrances It is also useful as a carrier for supporting an agent and the like, and can be supplied for use as a carrier for various chromatographies.

  The excellent effect of the present invention will be described in the following experimental example. Various physical properties of the silica-alumina shaped particles were measured by the following methods.

(1) chemical composition;
For elemental analysis, Rigaku RIX 2100 manufactured by Rigaku Corporation was used, the target was Rh, the analytical line was K _α , and the detector was PC under the following conditions. The sample is based on a product dried at 150 ° C. for 2 hours.
From the obtained analysis data, the chemical composition values of Al ₂ O ₃ , CaO, Na ₂ O, and SiO ₂ were determined, and the values of the molar ratios m, n, and p with respect to Al ₂ O ₃ were calculated.

(2) X-ray diffraction (XRD);
X-ray diffraction was performed using RINT-Ultima IV manufactured by Rigaku under the following conditions.
Target: Cu
Voltage: 40 kV
Current: 40 mA
Step size: 0.02 °
Scanning speed (step): 2 ° / min
Slit: DS2 / 3 ° RS0.3mm SS2 / 3 °

(3) Median diameter (D ₅₀ );
Using a Masterizer 3000 manufactured by Malvern, the median diameter (D ₅₀ ) on a volume basis was measured by a laser diffraction scattering method using water as a solvent.

(4) Bulk density;
JIS. K. Measurement was performed according to 6220-1 7.7: 2001.

(5) Pore volume by mercury intrusion method;
The pore volume and pore distribution were measured by mercury porosimetry using an Autopore IV9500 manufactured by Micromeritics. Measured to a pore radius of 10800-1.8 nm, and the cumulative pore volume was defined as the total pore volume. Of these, the pore radius of 110-1.8 nm was defined as mesopores, and the pore volume in this section was defined as mesopores. Volume. Moreover, following formula (2);
Mesopore volume ratio (%) = (mesopore volume / total pore volume) × 100
In the formula, the mesopore volume is a pore volume having a pore radius of 1.8 to 110 nm,
The total pore volume is the cumulative pore volume with a pore radius of 1.8 to 10800 nm.
The ratio calculated in (1) was defined as the mesopore volume ratio. The pore volume at a pore radius of 1.8 to 25 nm and the pore volume at 5 to 10 nm were also measured.
The notation of the vertical axis of the pore distribution indicates the cumulative pore volume when judging the presence or absence of mesopores and comparing the pore volume size, and dV / dR fine when comparing the mesopore radius. The pore volume was used.

(Preparation of raw material P-type zeolite 1)
No. 3 sodium silicate _{(SiO 2: 22.6mass%, Na} 2 O: 7.31mass%), sodium aluminate _{(Al 2 O 3: 24.1mass%} , Na 2 O: 19.3mass%), 49% Using sodium hydroxide and water, a dilute sodium silicate solution (A solution) and a dilute sodium aluminate solution (B solution) were prepared so that the total molar ratio was 2630 g. The caustic soda was adjusted to the B side, and the water was adjusted so that the liquids A and B had the same volume.
Compounding conditions (molar ratio)
Na ₂ O / SiO ₂ = 0.85
SiO ₂ / Al ₂ O ₃ = 4.0
H ₂ O / Na ₂ O = 70
The above solution A was put in a 3 L stainless steel container and the solution B was slowly mixed while heating to 60 ° C. to obtain a uniform aluminosilicate alkali gel. After aging for 1 hour, this alkali aluminosilicate gel was heated to 95 ° C. with stirring and reacted for 15 hours for crystallization. Subsequently, filtration and washing were carried out to obtain a cake of Na-P type zeolite spherical particles having a median diameter (D ₅₀ ) = 3.3 μm. The solid content was 35 mass%, and 223 g of Na-P zeolite cake (S-1) was recovered in terms of solid content.

(Preparation of raw material P-type zeolite 2)
Using zeolite cake (S-1) as a seed crystal, P-type zeolite was prepared as follows. The S-1 cake was diluted with water to a solid content of 10 mass%, and placed in a magnetic pot mill with an internal capacity of 6.3 L together with 3.19 kg of 3 mmφ alumina balls. Wet grinding was performed for 10 hours to obtain a seed crystal slurry having a median diameter (D ₅₀ ) = 0.38 μm. Next, the above-mentioned alkali aluminosilicate gel was adjusted so as to be 2630 g as a whole in the following molar ratio, and 5 mass% of seed crystal slurry was added to the expected yield.
Compounding conditions (molar ratio)
Na ₂ O / SiO ₂ = 0.75
SiO ₂ / Al ₂ O ₃ = 4.5
H ₂ O / Na ₂ O = 60
After aging for 1 hour, this alkali aluminosilicate gel was heated to 95 ° C. while stirring, and reacted for 36 hours while maintaining 95 ° C. for crystallization. Next, filtration and washing were performed to obtain a Na-P zeolite cake (S-2) having a fine aggregate structure. In particular, when superheated steam is directly applied to the aluminosilicate gel as a condition for heating to 95 ° C., a Na-P zeolite cake (S-3) in which aggregates are disintegrated is obtained.

(Ca exchange process)
When diluting Na-P type zeolite (S-1, S-2 or S-3) into a slurry of 20 mass% and then using S-1 or S-3 with respect to Na ₂ O in the zeolite, 1. A CaCl ₂ aqueous solution of 0 mol was added to a 0.75 mol of CaCl ₂ aqueous solution when using S-2, and each was stirred at 60 ° C. for 1 hour for ion exchange. Next, filtration, washing with water, S-1 to Ca-P type zeolite cake (S-4), S-2 to Ca-P type zeolite cake (S-5), S-3 to Ca-P type zeolite cake (S-6) obtained.

Example 1
The Ca-P type zeolite cake (S-5) was diluted with water to a solid content of 10 mass%, and placed in a magnetic pot mill with an internal capacity of 6.3 L together with 4.19 kg of 3 mmφ alumina balls. Thorough wet grinding was performed over 4 hours to obtain a slurry having a median diameter (D ₅₀ ) = 0.30 μm. This slurry was added to an anhydro spray dryer Lab. No. 1 was sprayed from a two-fluid nozzle into a dry atmosphere at 150 ° C. with a liquid amount of 1 L / h and a spray pressure of 3.0 kgf / cm ² to obtain regular particles of Ca—P type zeolite. The shaped particles were put in a crucible and fired at 750 ° C. for 1 hour in a small electric furnace to obtain silica alumina based shaped particles. The production conditions and physical properties are shown in Table 2. FIG. 2 shows an X-ray diffraction image of the silica-alumina shaped particles of the present invention, FIG. 3 shows an electron micrograph, and FIG. 6 shows the pore distribution measured by mercury porosimetry (vertical axis: cumulative pore volume) and FIG. 7 (vertical axis: dV / dR pore volume) shows.

(Example 2)
A slurry having a median diameter (D ₅₀ ) = 0.41 μm obtained by changing the Ca—P type zeolite cake to a spherical Ca—P type zeolite cake (S-4) and carrying out thorough wet grinding for 16 hours. Except for spraying, silica-alumina shaped particles were obtained under the same conditions as in Example 1. The production conditions and physical properties are shown in Table 2.

(Examples 3 to 6)
Silica-alumina shaped particles were obtained under the same conditions as in Example 1 except that the solid content concentration of the zeolite that was thoroughly wet pulverized or the spray drying conditions were changed as shown in Table 2. Table 2 shows the production conditions and physical properties.

(Example 7)
A slurry obtained by mixing 5 mass% of colloidal silica having a zeolite solid content of the slurry having a median diameter (D ₅₀ ) = 0.30 μm obtained by thorough wet grinding in Example 1 under the same conditions as in Example 1 was spray-dried. And firing to obtain silica alumina type regular particles. The production conditions and physical properties are shown in Table 2.

(Examples 8 to 9)
Silica alumina shaped particles were obtained under the same conditions as in Example 7 except that the weight ratio conditions of the colloidal silica to be mixed were changed as shown in Table 2. Table 2 shows the production conditions and physical properties. Moreover, the electron micrograph of Example 8 is shown in FIG. 4, and the pore distribution measured by the mercury intrusion method of Examples 7 to 9 is shown in FIG. 8 (vertical axis: cumulative pore volume) and FIG. 9 (vertical axis: dV / dR pore volume).

(Comparative Example 1)
Spherical Ca—P type zeolite cake (S-4) was put in a crucible and baked at 750 ° C. for 1 hour in a small electric furnace to obtain silica alumina type regular particles. The production conditions and physical properties are shown in Table 2. FIG. 5 shows an electron micrograph, and FIG. 6 (vertical axis: cumulative pore volume) and FIG. 7 (vertical axis: dV / dR pore volume) show pore distributions measured by mercury porosimetry.

(Comparative Example 2)
Silica alumina-based regular particles were obtained under the same conditions as in Comparative Example 2, except that the zeolite to be calcined was changed to Ca-P type zeolite cake (S-5). The production conditions and physical properties are shown in Table 2. Moreover, the pore distribution measured by the mercury intrusion method is shown in FIG. 6 (vertical axis: cumulative pore volume) and FIG. 7 (vertical axis: dV / dR pore volume).

(Comparative Example 3)
Silica-alumina shaped particles were obtained under the same conditions as in Comparative Example 2, except that the calcined zeolite was changed to Ca-P type zeolite cake (S-6). The production conditions and physical properties are shown in Table 2.

(Comparative Example 4)
The Ca-P type zeolite cake (S-5) was wet-ground for 1 hour to obtain a slurry having a median diameter (D50) = 0.92 μm. This slurry was spray-dried and fired under the same conditions as in Example 1 to obtain silica-alumina shaped particles. The production conditions and physical properties are shown in Table 2. Moreover, the pore distribution measured by the mercury intrusion method is shown in FIG. 6 (vertical axis: cumulative pore volume) and FIG. 7 (vertical axis: dV / dR pore volume).

(Comparative Example 5)
The spherical Ca—P-type zeolite cake (S-4) was wet crushed over 6 hours to obtain a slurry having a median diameter (D ₅₀ ) = 0.95 μm. This slurry was spray-dried and fired under the same conditions as in Example 1 to obtain silica-alumina shaped particles. The production conditions and physical properties are shown in Table 2.

Claims (3)

On the anhydride basis, the following formula (1);
_{mCaO · nNa 2 O · pSiO 2} · Al 2 O 3 (1)
Where
m and n are positive numbers;
m + n is 0.9 to 1.1, m / n is 0.05 / 0.95 to 0.9 / 0.1
In the range of
p is a number from 2.3 to 15,
X-ray diffractometrically amorphous, volume-based median diameter (D ₅₀ ) measured by laser diffraction scattering method is in the range of 3 to 20 μm and 1.3 μm The following fine particle content has a particle size distribution of 8% or less, the bulk density is in the range of 0.40 to 0.65 g / ml, and the pore radius is 1 as measured by mercury porosimetry. The pore volume at 8-25 nm is in the range of 0.15-0.40 ml / g, and the following formula (2):
Mesopore volume ratio (%) = (mesopore volume / total pore volume) × 100 (2)
In the formula, the mesopore volume is a pore volume having a pore radius of 1.8 to 110 nm,
The total pore volume is the cumulative pore volume with a pore radius of 1.8 to 10800 nm.
A silica-alumina-based regular particle characterized in that the mesopore volume ratio defined by is in the range of 30% or more.   An antiblocking agent comprising the silica-alumina-based regular particles according to claim 1.   A resin composition containing the antiblocking agent according to claim 2 in an amount of 0.01 to 5 parts by weight per 100 parts by weight of a thermoplastic resin.