JPH0643515B2 - New filler and its manufacturing method - Google Patents

Description

The present invention relates to an amorphous silica or silica / alumina-based filler having a unique particle shape and structure and excellent in non-abrasiveness, and its production. Regarding the method.

(Prior Art) Resin molded products such as films and sheets tend to block each other when they are stacked, and in order to prevent this, it is possible to mix various kinds of inorganic compounding agents into the resin. It has been done since ancient times.

In addition, increasing the amount of paper for various printing paper, recording paper, etc.
In order to improve printability and recording characteristics, various inorganic compounding agents have been incorporated into paper and recording layers thereon.

As such an inorganic compounding agent, many inorganic fillers such as amorphous silica, various clays and zeolites are known.

Japanese Unexamined Patent Publication No. 58-213031 (Japanese Patent Publication No. 61-36866) discloses that the length of one side having a composition in which the molar ratio of Al ₂ O ₃ : SiO ₂ is 1: 1.8 to 1: 5. Alumina / silica-based resin compounding agent comprising cubic primary particles having a size of 5 microns or less, the particles being substantially amorphous by X-ray diffraction and having a BET specific surface area of 100 m ² / g or less. Is listed. It is also described that this product can be obtained by subjecting a crystalline zeolite having a cubic particle shape to an acid treatment under conditions in which the crystallinity disappears but the particle shape is not impaired.

Further, in JP-A-59-213616, in the slurry of the acid-treated product of zeolite as described above, a small amount of an aqueous solution of sodium silicate is added, and then an aqueous solution of sodium silicate and sulfuric acid are simultaneously added, It is described that the amorphous silica is densely deposited on the surface of the acid-treated product.

(Problems to be Solved by the Invention) The above-mentioned prior art provides a silica / alumina-based filler that is amorphous but has a cubic particle shape and a uniform particle size and a uniform particle size. Although significant, this filler is a regular particle, but on the other hand, it has a relatively small oil absorption and is not yet sufficiently satisfactory as an inorganic filler requiring an oil absorption.

In addition, conventionally used silica-based or silica-alumina-based fillers are used in various molding machines when blending with resin or paper.
It has a drawback that it is easy to wear a papermaking screen or a cutter by polishing them.

The present inventors have found that when the zeolite is subjected to a specific treatment described in detail below, it has a regular particle shape, is extremely porous inside, and has a large oil absorption amount and a relatively low water density. However, it has been found that a silica or silica-alumina-based filler excellent in non-abrasiveness can be obtained.

That is, an object of the present invention is that while having a regular particle shape and a uniform and fine particle diameter, the inside is remarkably porous, has a large oil absorption amount and a relatively low water density, and is excellent in non-abrasiveness. Another object is to provide a silica or silica-alumina-based filler and a method for producing the same.

(Means for Solving the Problems) According to the present invention, it is composed of a porous amorphous silica or silica-alumina core and a porous shell of amorphous silica, and has a cubic or spherical regular shape as a whole. 85 to 2 consisting of particles having a particle-like shape and a porous shell structure.
Provided is a filler characterized by having an oil absorption of 00 cc / 100 g, a bulk specific gravity of 0.1 to 0.6 g / cc, and a volume-based median diameter of 0.5 to 10 μm.

According to the present invention, the SiO ₂ of the zeolites and zeolite with respect to producing an aqueous slurry containing alkali silicate equivalent to SiO ₂ of 2 to 40 wt%, the acid in this slurry was added Producing coated particles in which porous silica shells are bonded to the zeolite core and continuing to add acid to the slurry of coated particles to elute at least a part of the alkaline component or further aluminum content in the zeolite. Then, a method for producing a silica or silica-alumina-based filler is provided, which comprises converting the core zeolite into amorphous silica or silica-alumina.

(Operation) The present invention will be described from the manufacturing method thereof so that the invention can be easily understood.

According to the invention, firstly the zeolite and SiO _{2 in the} zeolite are
2-40% by weight, especially 5-25% by weight
An aqueous slurry containing an alkali silicate corresponding to SiO ₂ is produced, and an acid is added to the slurry to produce coated particles in which a shell of amorphous silica is bonded to a zeolite core. That is, when the zeolite particles are dispersed and an acid is added to the slurry in which the alkali silicate is dissolved, the alkali silicate is first neutralized to form silica sol, and this silica sol is in the form of amorphous silica. Deposited as Ciel around. The zeolite / alkali silicate generally has a pH of 11 to 13, but the formation of amorphous silica from the alkali silicate generally occurs at a pH of 10.5 to 8, whereas the elution of the alkali content in the zeolite is generally Since it occurs at a pH of 8 to 5, it is an important point that it is possible to form a silica coating with this as a core without substantially changing the chemical structure of the zeolite. In addition, the shell of amorphous silica produced by neutralization from the alkali side is not a dense form like silica produced by simultaneous injection of alkali silicate and acid, but is very porous and scanning type. Under the observation with an electron microscope, it has a rough or snow-like appearance.

Next, the acid is continued to be added to the aqueous slurry of the coated particles thus formed to elute at least a part of the alkali component or further the aluminum content in the zeolite, and the core zeolite is converted to amorphous silica or silica. -It is converted to alumina. That is, by adding an acid subsequently to the slurry of coated particles, the pH in the system is lowered to the above pH range, and moreover, the shell of amorphous silica existing around the zeolite core is porous. The zeolite is converted to amorphous silica or silica-alumina by elution of at least part of the alkali content or the aluminum content from the zeolite.

In this case, it is also an important point that the zeolite core is converted into amorphous silica or silica-alumina in a state where the shell of the amorphous silica is bonded. In general, when zeolite is acid-treated, the acid-treated product naturally has a reduced particle size due to the elution of the constituent components of the zeolite even if the particle-shaped features of the zeolite remain. On the other hand, when the acid treatment means is applied, elution of alkali components and aluminum components constituting zeolite in a state where the outer surface of the zeolite core is fixed with amorphous silica occurs, so that the particle size does not decrease. Moreover, the core is porous and has a significantly large pore volume.

Thus, the amorphous silica-based or silica.
The alumina-based filler is composed of a porous amorphous silica or silica-alumina core and an amorphous shell, and has a cubic or spherical regular particle shape and a porous shell structure as a whole. It is characterized by having. The regular particle shape is a concern to be compared with the irregular particle shape that a normal amorphous silica or the like has, and a constant particle shape in which substantially all particles are fixed, in this case, a cube, It means that it takes the form of a slightly rounded cube, regular polyhedron, sphere, or the like.

FIG. 1 is a scanning electron micrograph of the amorphous silica-alumina filler particles according to the present invention, and FIG. 2 is a scanning electron micrograph of the amorphous silica filler particles according to the present invention. . Further, FIG. 3 is a scanning electron micrograph of the raw material zeolite particles used in the production of the filler particles shown in FIGS. 1 and 2.

From these electron micrographs, the filler particles according to the present invention have a certain fixed particle shape corresponding to the original zeolite particle shape, and the surface thereof has a porous shell structure (see FIGS. 1 and 2). In the figure, it can be seen that it has a rough snow shape.

The fact that the core in the filler according to the invention consists of porous, amorphous silica or silica-alumina and the shell consists of amorphous sili It is confirmed by subjecting the filler particles to a grinding treatment, separating the shell component and the core component, and then performing physical property measurement and chemical analysis for each of them. For example, when the filler is strongly ground, the silica of the shell is removed from the core and separated into a shell component and a core component. Chemical analysis and pore volume measurements on this core component confirm the fact that the core component consists of porous, amorphous silica or silica-alumina. In addition, when the pore volume of the whole filler particle is measured, the pore volume of the whole particle is remarkably increased as compared with the arithmetic mean value of the pore volume of amorphous silica and the pore volume of ordinary acid-treated zeolite. It can be seen from the fact that the porosity of the core is increased.

Due to the above-mentioned particle structure, the filler of the present invention is 85 to 200 cc / 100 g, particularly 90 to 150 cc / 100 g.
large oil absorption of 0.1 to 0.6g / cc, especially 0.2
It has a relatively low bulk specific gravity of 0.5 to 0.5 g / cc. The volume-based median diameter of the filler is 0.5 to 10 μm, particularly 0.8 to 5 μm. Also,
The pore volume of this product is silica or silica.
Depending on whether it is alumina, in the former case,
0.3 to 1.2cc / g, especially 0.5 to 1.0cc / g, in the latter case
It is on the order of 0.2 to 0.8 cc / g, especially 0.3 to 0.6 cc / g.

Moreover, since the porous amorphous silica that exists as a shell in the present invention has a very soft structure, even when this filler is compounded with resin or paper, it has a polishing effect on various devices. It does not exhibit and is particularly excellent as a filler.

(Preferable Embodiment) As the raw material zeolite, synthetic zeolites having various crystal structures are used because the particle shape and the particle diameter are constant and the content of impurities is small. Examples thereof include zeolite A, zeolite X, zeolite Y, zeolite P, analcime, sodalite, etc., but A and X are suitable in terms of cost. A and X have a cubic or rounded-cornered cubic particle shape, while P has a spherical particle shape, and anal sim has a regular icosahedron particle shape. Representative chemical compositions of various zeolites are shown below.

The zeolite used is determined so that the treated particles have the above-mentioned particle size. This can be easily determined by investigating beforehand the relationship between the particle size of zeolite before treatment and the increase in particle size due to the amount of silica deposited.

As the alkali silicate, a water-soluble alkali silicate is used. Generally, in the formula M ₂ O · nSiO ₂ (1), M is an alkali metal, especially sodium, and n is a number from 1 to 3.5, especially 2 It is a number from 3.5 to 3.5.

Those having the composition of are used.

The zeolite slurry and the alkali silicate aqueous solution are mixed in the above-mentioned quantitative ratio to form an aqueous slurry. From the viewpoint of workability and productivity, it is preferable that the solid content concentration of zeolite in the aqueous slurry is generally in the range of 5 to 30% by weight, particularly 10 to 20% by weight.

The acid used may be an inorganic acid or an organic acid without particular limitation, but economically, mineral acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid are advantageously used. These acids, in the form of dilute aqueous solutions, are used to neutralize the zeolite-alkali silicate slurry.

In the present invention, in order to attach the porous amorphous silica to the surface of the zeolite, it is important to add an acid to the slurry of zeolite / alkali silicate. That is, in the method of simultaneously pouring an alkali silicate and an acid into an aqueous slurry of zeolite, a dense and acid-resistant amorphous silica film is formed around the zeolite, so that the zeolite is made amorphous. Difficult to do. In addition, zeolite
A non-porous amorphous silica coating also tends to be formed when the reaction between the alkali silicate slurry and the acid is carried out at high temperature. From this point of view, the reaction between the slurry and the acid is generally performed at a temperature of 0 to 50 ° C., and particularly preferably at room temperature.

The addition of acid to the slurry promotes the formation of amorphous silica shell and subsequently the amorphous core zeolite.
This acid treatment step may be performed in a plurality of different apparatuses, may be intermittently performed in the same apparatus, and may be performed continuously or batchwise. If the acid treatment is continuously carried out, the treatment can be carried out in a single reaction tank, which is advantageous in terms of operation and facility costs.

In the amorphization of the latter-stage core zeolite, it is preferable to elute and remove 50% or more, particularly 70% or more of the alkali content in the zeolite. When this alkali content is removed, part of the aluminum content may also be eluted. When an amorphous silica filler is produced by removing substantially all of the aluminum component, it is preferable that the pH of the reaction system be 3 or less, particularly 1 or less.

The acid-treated amorphous silica or silica-alumina particles are filtered, washed, dried or further calcined and crushed to obtain a filler. In addition, since the filler has a porous body in both the inner core portion and the surface shell portion, a plasticizer,
A lubricant, an antistatic agent, an antifogging agent, an ultraviolet absorber, an antioxidant, an insect repellent, an insect repellent, an antibacterial agent, a fragrance, a coloring agent, an organic component such as a medicinally active ingredient may be supported and used.
Furthermore, this filler also includes various metal soaps, waxes, resins, including the above-mentioned fillers supporting various organic components.
It is also possible to pre-treat the surface with a surfactant, various coupling agents and the like.

The filler of the present invention utilizes various properties described above, for example, various resins, for example, olefin resins such as polypropylene, polyethylene, crystalline propylene-ethylene copolymer, and ion-crosslinked olefin copolymer; polyethylene terephthalate, poly Thermoplastic polyesters such as butylene terephthalate; polyamides such as 6-nylon, 6,6-nylon and 6,8-nylon; chlorine-containing resins such as vinyl chloride resin and vinylidene chloride resin; polycarbonates; polysulfones; heat such as polyacetal It can be used by adding it to a plastic resin so as to impart slip properties or anti-blocking properties to a resin molded product formed. Further, it can be added to a kneading composition or a liquid composition for forming a coating to impart antiblocking property to the coating.

For such use, the filler according to the present invention may be added in an amount of 0.01 to 10 parts by weight, particularly 0.05 to 2 parts by weight, per 100 parts by weight of the resin.
It is recommended to use in an amount of parts by weight.

Further, the filler of the present invention can be used as an internal addition filler for various papers, as a recording layer filler for various recording papers, and as a coating agent filler for various coated papers. For example,
This filler is useful as a filler for preventing the generation of dust on the thermal recording paper and as a coating layer filler for holding the ink of the inkjet recording paper. For such applications, the filler is 1 to 30 g / m ^{2 on} paper,
In particular, it is preferable that the coating amount is 3 to 20 g / m ² .

Further, this filler can be blended in various paints and used for semi-blanking application. For such use, 2 to 30 parts by weight, particularly 5 to 10 parts by weight per 100 parts by weight of the solid content of the paint are used. It can be used in an amount of parts by weight.

(Effects of the Invention) According to the present invention, zeolite-alkali silicate slurry is acid-treated to once produce zeolite particles having a porous silica shell, and the acid treatment is continued to form an amorphous zeolite core. By qualification, it consists of porous amorphous silica or silica-alumina core and amorphous silica porous shell, and has a cubic or spherical regular particle shape and porous shell structure as a whole. The filler is obtained from particles having a uniform particle size and a uniform fine particle size, but the inside is extremely porous, has a large oil absorption amount and a relatively low bulk density, and is non-abrasive. It has the advantage of being excellent.

Example 1 A synthetic A-type zeolite was used as a starting material for core particles to prepare a novel filler according to the present invention by the following method, and its physical properties are shown in Table 1.

Preparation of Synthetic Type A Zeolite Aqueous slurry of activated silicic acid gel, which is an acid treatment product of acid clay from Nakajo, Niigata prefecture, with 25% aqueous slurry and commercial sodium aluminate (Al ₂ O ₃ : 22.5%, Na ₂ O: 17.6%) ) And caustic soda were used to prepare a silicic acid slurry (A slurry) and a dilute sodium aluminate solution (B solution).

Next, in a stainless steel container having an internal volume of 100, 45 kg of A slurry and 55 kg of B were prepared so that the following molar ratio was obtained.
The liquids were mixed with stirring to form a uniform aluminosilicate alkali gel slurry.

Na ₂ O / SiO ₂ = 1.2 SiO ₂ / Al ₂ O ₃ = 2.0 H ₂ O / Na ₂ O = 48 Then, this gel is gradually heated under stirring and crystallized at 90 ° C. for 2 hours to form an A-type zeolite. An alkaline slurry was obtained.

Thereafter, the mother liquor and the solid content were separated by suction filtration and washed sufficiently with water to obtain a water-containing cake of A-type zeolite having a solid content concentration of 48%.

A sample of this cake partially dried at 110 ° C
It is shown in Table 1 as No. A-0.

Next, 1 kg of this cake was adjusted to a slurry having a solid content concentration of 20%, put into a ball mill having an internal volume of 15 and crushed for 1 hour to obtain C of synthetic type A zeolite having a median diameter of 2.55 μm.
A slurry was prepared.

In the present invention, the percentage display means% by weight unless otherwise specified.

Preparation of New Filler Next, 4.5 kg of C slurry, which is a raw material for the core of the new filler particles according to the present invention, was placed in 10 stainless steel containers, and SiO ₂ was added to the silica content of the zeolite particles with stirring.
As a 10% sodium silicate solution (SiO ₂ 22.5
%, Na ₂ O 7.1%) 144 g and thoroughly mixed with stirring (first step).

Then, at room temperature (25 ° C), 10% dilute sulfuric acid 2,10
0 ml was added using a microtube pump over 2 hours (2nd step).

The slurry pH at the end of pouring was 4.6. After completion of the pouring, the mixture is stirred for about 1 hour as it is, and thereafter filtered and washed with water by a conventional method, and the surface of the X-ray amorphous and sufficiently porous core particles is dry and porous and amorphous. A water-containing cake of filler particles according to the present invention, which was coated with fine silica as a shell layer, was obtained.

Next, after drying the above cake at 110 ° C., it was crushed by a sample mill and baked at 450 ° C. for 2 hours to obtain a silica / alumina-based filler (Sample No. 1-1) of the present invention. Shown in the table.

In order to clarify the characteristics of the particles of the present invention, Sample No. 1-
The following experiment was carried out using Sample No. 1 and the result was sample No. 1
It is shown in Table 1 as -2, No. 1-3.

Crushing treatment In order to crush and separate the shell layer and the core particles forming the particles of the present invention, sample No. 1-1 was put into a ball mill and 2
After dry crushing for 4 hours, classify with a small wind classifier manufactured by Yasukawa Electric, classify into fine powder fraction sample No. 1-2 and coarse powder fraction sample No. 1-3, and check its properties. The results are shown in Table 1.

Sample No.A-0, Sample No.1-1, No.1 shown in Table 1
-2 and No. 1-3 bulk density, oil absorption, specific surface area and X
When the filler particles according to the present invention are compared and evaluated by line diffraction, the silica-alumina core particles (core) in which zeolite is made amorphous and the coating layer of porous amorphous silica with a high dryness (see ) Is well understood. In the present invention, the following physical property tests were performed on the filler particles.

(1) Bulk density Measured according to JIS K 6220.6.8.

(2) Specific surface area Using Sorptomatic Series 1800 manufactured by Carlo Erba,
It was measured by the BET method.

(3) Whiteness Measured according to JIS P 8123.

(4) pH of 5% suspension measured according to JIS K 5101 / 24A
pH value.

(5) Particle size by electron microscope An appropriate amount of sample fine powder is placed on a metal sample plate, sufficiently dispersed, and metal coated with a metal coating device (Hitachi E-101 type ion sputter) to obtain a projection sample. Then, the field of view is changed with a scanning electron microscope (Hitachi S-570) by a conventional method to obtain several electron micrographs. Representative particles were selected from the spherical particle image in the visual field, the diameter of the spherical particle image was measured using a scale, and displayed as the primary particle diameter.

(6) Oil absorption (ml / 100g) Measured according to the JIS K 5101 pigment test method. Sample is 0.5g
And

(7) Moisture absorption amount Approximately 1 g of sample is put in a weighing bottle of 40 × 40 mm, the weight of which has been measured in advance, and dried in a desiccator for 3 hours in an electric constant temperature oven at 150 ° C., but the weight of the sample is then accurately weighed. Then, the sample was placed in a desiccator whose relative humidity was adjusted to 90% with sulfuric acid in advance, and the weight increase after 48 hours was measured and taken as the moisture absorption amount.

(8) Average particle size 1 g of a sample is weighed in a 200 ml beaker, 150 ml of deionized water is added thereto, and the mixture is ultrasonically dispersed for 2 minutes while stirring. This dispersion is measured using a Coulter Counter (TAII type) aperture tube 50 μ. Obtain the average particle size from the cumulative distribution chart.

(9) Refractive index Using Abbe's refractometer, a solvent with a known refractive index (α-
Bromnaphthalene, kerosene). Then Lars
According to en oil immersion method, a few mg of sample powder was taken on a slide glass, 1 drop of a solvent with a known refractive index was added, a cover glass was placed, and the solvent was sufficiently immersed, and then the Becke line was moved with an optical microscope. Observe and ask.

Larsen's oil immersion method When the powder is dipped in a liquid and the transmitted light is observed with an optical microscope, the boundary line between the powder and the liquid appears bright. This is called the Becke line (Backe). At this time, if the tube of the microscope is moved up and down, this Becke line moves. When the tube is lowered, the bright line moves to the inside of the particle and the particle looks bright, and when the tube is raised, the bright line moves to the outside and the particle looks dark, when the liquid has a higher refractive index than the powder. . The opposite phenomenon is seen when the powder has a higher refractive index. By measuring with a suitable liquid and selecting one having a refractive index larger than that of the powder and one having a smaller refractive index than the powder, the refractive index of the powder can be obtained as an intermediate value between the refractive indexes of these two types of liquids.

(10) Pore volume Measured using a surface area adsorption device by the BET method. This is based on the adsorption of nitrogen gas at the liquid nitrogen temperature (-196 ° C). Using the adsorption amount when the relative pressure P / PO of the adsorption isotherm is 1, all pores with a pore diameter of 300 Å or less are used. This is a method of obtaining the volume.

Example 2 According to the present invention in the same manner as in Example 1 except that a sodium silicate solution was added so that the coating amount of silica for shell was 5% and 20% as SiO _{2 with} respect to the silica content of zeolite of the core particles. A silica / alumina-based filler was prepared, and its physical properties are shown in Table 1 as Sample Nos. 2-1 and 2-2, respectively.

Example 3 After the zeolite core particles were coated with a shell layer in the same manner as in Example 1, 100 g of each slurry was placed in a beaker of 1 and 400 cc of water was added and sufficiently stirred. Grade 36%) 153g
(0.6 mol amount relative to Al ₂ O ₃ , Na ₂ O) and 306 g (Al ₂ O ₃ , N
a ₂ O to 1.2 molar amount) of the raised gradually increased added each 95
Treated for 2 hours at ° C.

Then, it is filtered, washed with water, dried and crushed to obtain sample No. 3-1.3.
-2, the silica-alumina type filler according to the present invention was obtained, and its physical properties are shown in Table 2.

Comparative Example 1 4.5 kg of the C slurry obtained in Example 1 was used as the internal volume of 10
Put it in the stainless steel container of 10% sulfuric acid 1960 ml under stirring without adding sodium silicate as silica source for shell.
The same treatment as in Example 1 was performed with (amount excluding the neutralized portion of sodium silicate) to obtain an amorphous acid-treated product of zeolite without a shell coating layer (Sample No. H-1), and its physical properties. Is shown in Table 3.

Comparative Example 2 Each of the zeolite cakes obtained in Example 1 was placed in a beaker of 500 ml, water was added to adjust the slurry concentration to 20%, and the mixture was heated to 60 ° C. with stirring, and then the zeolite in this slurry was added. Silica sol (manufactured by Nissan Kagaku; Snowtex) was added to the silica content of the particles so that they would be 26% and 52%, respectively, based on silica, and the mixture was stirred and concentrated as it was until it became a pace, then dried at 110 ° C. did.

Then, crushed with a Sanopul mill and baked at 450 ° C. for 2 hours. Sample Nos. H-21 and H-22
The physical properties are shown in Table 3.

Comparative Example 3 50 g of acid-treated dried zeolite obtained in Comparative Example 1
Add each to a 500 ml beaker, add water and add 20%.
250 g of concentrated slurry was prepared.

Next, 5% sodium silicate aqueous solution was added to adjust the pH to 9.8, and then the temperature was kept at 90 ° C. and 4% sulfuric acid and 5% sodium silicate aqueous solution were added to the slurry in an amount of 26.8% as SiO _{2 with} respect to SiO ₂ content. A silica coating treatment was carried out by gradually adding them simultaneously so as to obtain 48.2.

Then, after adjusting to pH 6.5 with sulfuric acid, it is separated by filtration, washed with water, dried, pulverized and calcined at 450 ° C. for 2 hours by a conventional method,
The silica-coated amorphous aluminosilicates of Sample Nos. H-31 and H-32 were obtained, and the physical properties thereof are shown in Table 3.

Comparative Example 4 The acid-treated dried zeolite product obtained in Comparative Example 1 was slurried in the same manner as in Comparative Example 3 and then heated to 90 ° C. with stirring to obtain a 6% sodium silicate aqueous solution as SiO _2. 4% Sulfuric acid was gradually added simultaneously to coat the zeolite particles with silica.

Then, the above coated product was washed with water, dried, pulverized and calcined at 450 ° C. for 2 hours by a conventional method to obtain a silica-coated amorphous aluminosilicate of sample No. H-4.

Example 4 In the same manner as in Example 1, except that the active A silica gel, commercially available sodium aluminate and caustic soda were used as the preparation conditions for the synthetic A-type zeolite in the same manner as in Example 1 except that the molar ratios were as follows. An alkaline slurry of A-type zeolite was prepared.

Na ₂ O / SiO ₂ = 1.4 SiO ₂ / Al ₂ O ₃ = 2.0 H ₂ O / Na ₂ O = 30 Next, add water to the A-type zeolite cake with a solid content concentration of 45% obtained by filtering and washing with water After making 20% slurry,
Similarly, crush with a ball mill to obtain a median diameter of 0.91μ
A m-thick synthetic A-type zeolite slurry was obtained.

Then, the slurry is treated in the same manner as in Example 1 so that the coating amount of the shell layer is 5, 10 and 16% based on the silica based on the silica content of the core particles to form the shell layer. Sample Nos. 4-1, 4-2, and 4-3 of the silica-alumina-based filler according to the present invention were prepared, and the physical properties thereof are shown in Table 2.

Example 5 Using a synthetic X-type zeolite as a starting material for core particles, a novel filler according to the present invention was prepared in the same manner as in Example 1,
The physical properties are shown in Table 2.

Preparation of Synthetic X-Type Zeolite From the aqueous slurry of active silicic acid used in Example 1 and commercially available sodium aluminate and caustic soda, the silicic acid slurry and dilute sodium aluminate solution were mixed so that the total amount would be 100 kg at the following molar ratio. Prepared.

Na ₂ O / SiO ₂ = 1.2 SiO ₂ / Al ₂ O ₃ = 3.3 H ₂ O / Na ₂ O = 45 Next, 45 kg of silicic acid slurry and 55 kg of dilute sodium aluminate solution were placed in a stainless steel container having an internal volume of about 100. The mixture was slowly mixed with stirring to obtain a uniform aluminosilicate alkaligen.

Next, this gel was gradually heated and crystallized at 90 ° C. for 5 hours to give an alkali slurry of X-type zeolite, which was then suction-filtered and washed with water to obtain an X-type zeolite cake having a solid content concentration of 43%.

A sample of this cake partially dried at 110 ° C
It is shown in Table 2 as No. X-0.

Next, water is added to this cake to make a slurry having a concentration of 20%, and 5 is put into a ball mill having an internal volume of 15
After time grinding, to SiO ₂ minutes to core particles in the same manner as in Example 1, silica-alumina-based filler samples No.5-1 of the present invention is coated with 10% SiO ₂ basis as shell layer Was obtained and its physical properties are shown in Table 1.

Example 6 250 g of the powder of Sample No. 1-1 prepared in Example 1 was placed in a beaker of Example 1, 580 cc of water was added, and the silane coupling agent (γ-aminopropyltriethoxysilane) was added under stirring.
After slowly adding 22.5 g of a solution prepared by diluting 3 times with water,
The mixture was concentrated on a water bath under stirring to form a paste, and dried at 110 ° C for 6 hours. Then, the dried product was crushed and subjected to silane coupling treatment, Sample No. SC1.
-1 was obtained.

Similarly, sample N obtained in Examples 3 and 4 and Comparative Example 3
o.3-2, 4-2 and H-32 which were subjected to silane coupling treatment were sample Nos. C3-2 and SC4, respectively.
-2 and SCH-32.

Further, 37.5 g of PE emulsion (Permarin PN Sanyo Kasei) was added to the slurry of Sample No. 1-1 powder in the same manner as in the above method, followed by concentration in the same manner as in the above method and drying in an oven at 80 ° C. for 36 hours. Then, the powder was pulverized to obtain a wax-coated silica-alumina-based filler of Sample No. PW1-1.

Similarly, sample Nos. 3-2, 4-2 and H-32 were treated with wax to obtain sample No. PW3-
2, PW4-2 and PWH-32.

Next, in order to evaluate the characteristics of the bulky particles of the present invention using the above-mentioned surface-treated sample, sedimentation stability in various solutions was examined by the following method, and the results are shown in Table 4 (10). % Slurry) and Table 5 (30% slurry)
It was shown to.

In addition, in order to clarify the effect of the present invention, the sample No.SCH
-32, PWH-32, H-32 and commercially available synthetic silica (sideroid ^# 244) were evaluated as comparative examples. All synthetic silicas used in the present invention are Syloid ^#
244 was used.

Sedimentation stability test 20g of the sample and 180g of each of the following solvents (in the case of 10% slurry) and 140g of each of the following solvents (in the case of 30% slurry) were placed in a 200ml beaker and stirred for 3 hours with a magnetic stirrer. After 100
Transferred to a ml colorimetric tube and a 100 ml beaker and examined for sedimentation stability. As the solvent, 30% lactam aqueous solution and ethylene glycol were used.

Evaluation method Supernatant 5 No supernatant 4 At least 2 vol% of supernatant 3 At about 10 vol% of supernatant 2 At about 30 vol% of supernatant 1 At about 50 vol% Liquids Sediment A No sediment at the bottom B Sediment of trace level C Sediment of about 2 m / m D Sediment of 5 vol% or more Example 7 In order to evaluate the non-wearing property and hardness of the novel filler according to the present invention, sample Nos. 1-1, 4-2 and 4 according to the present invention are used.
-3 and SC1-1, the wear amount and the relative Mohs hardness were measured by the methods described below, and the results are shown in Table 6.

In addition, in order to clarify the effect of the present invention, the sample No.
0.8 μm spherical silica obtained by hydrolyzing H-1, H-31, A-0 and organic silane was evaluated as a comparative example.

Abrasion test The amount of abrasion was measured using the Filcon abrasion tester under the following conditions.

Test conditions ・ Slurry concentration 2% ・ Flow rate 0.65 / min ・ Roll material ceramic ・ Roll diameter φ60mm ・ Roll speed 1500 times / min ・ Contact angle Plastic: 111 ° ・ Weight 850g ・ Wire type Plastic: OS-60 ・ Wire -Dimension 40 × 140 mm ・ Test time 180 minutes ・ Result expression value Weight loss (mg) Relative Mohs hardness test 11 × 17 × 40 mm square eraser with a 5 mmφ hole in the center, and the hole is filled with sample powder. The center of the eraser was pressed with a finger on the metal plate described below and reciprocated 50 times, and the presence or absence of scratches was observed with a magnifying glass to determine the relative Mohs hardness.

Mohs hardness Lead plate 1.5 Vinyl chloride plate 2.0 Zinc plate 2.5 Copper plate 3.0 Iron plate 4.5 As is clear from Table 6, the novel filler according to the present invention has a core particle coated with a bulky shell layer. It is understood that the wear resistance is excellent and the hardness is also reduced as a relative value.

Example 8 To a linear low-density polyethylene having a melt flow rate of 1.0 g / 10 minutes and a density of 0.920 g / cm ³ , erucamide and the sample shown in Table 7 were added and melted at a temperature of 190 ° C. in an extruder. Pelletized after kneading. The pellets were supplied to an extruder and inflation-formed into a film having a thickness of 40 μm under the conditions of a melting section of 210 ° C. and a die of 220 ° C.

The following physical properties of the obtained film were measured and are shown in Table 7.

Haze: Compliant with ASTM-D-1003 Blocking property: Two film surfaces are overlaid, a load of 200 g / cm ² is applied, and the film is left at 40 ° C for 24 hours.
The film was evaluated for its ease of peeling.

Peel without resistance ◎ Somewhat difficult to peel ○ Hard to peel △ Very hard to peel × Luminous; extremely glossy ◎ Good gloss ○ Somewhat poor gloss △ Poor gloss × Table 7 As is clear from the results, the filler according to the present invention has anti-blocking properties, glossiness and haze.
Since the cores of the particles are of a fixed shape and the particle shapes are the same, it is understood that the filler is excellent in dispersibility and compatibility.

Example 9 An inflation film was formed in the same manner as in Example 8 except that the powder samples shown in Table 8 were added to polypropylene resin powder.

The obtained film was evaluated in the same manner as in Example 8.

The fish eye is film 500 by an optical microscope.
It is shown by the number of 0.1 mm or more in cm ² .

Example 10 Sample Nos. 2-2 and 4-3 silica according to the present invention
Alumina-based filler, various organic media, and synthetic silica were mixed in a supermixer at the composition and temperature shown in Table 9,
A composition containing a spherical organic medium of 40 to 100 mesh, which was supplied at a rate of about 1 kg / min into a kneader heated to a predetermined temperature, and the melt was dropped on a disk rotating at 3,000 rpm with a diameter of 12 cm. Got The organic medium used is as follows.

(1) Calcium stearate SC (manufactured by NOF Corporation) (2) Erucamide amide Alfuro P-10 (manufactured by NOF CORPORATION) (3) Polyglycerin monostearate GS-106 (manufactured by NOF CORPORATION) (4) Sorbitan fatty acid ester MP61 ℃ (5) Electrostripper-TS (manufactured by Kao Atlas) (6) Terpene resin chloralon P-75 (manufactured by Yasuhara Yushi) (7) BHT Example 11 To low density polyethylene having a melt flow rate of 1.5 g / 10 min and a density of 0.920 g / cc, the samples obtained in Experiment Nos. 31 to 36 shown in Table 9 were added, and the mixture was extruded at 150 with an extruder. The mixture was melt-kneaded at a temperature of ° C and pelletized.

The pellets were supplied to an extruder and inflation-formed into a film having a thickness of 50 μm under the conditions of a melting section of 160 ° C. and a die of 170 ° C.

The following physical properties of the obtained film were measured. Tenth
The results are shown in the table.

(11) Anti-fogging property 300 ml of hot water at 50 ° C is put in a beaker of 500 ml, covered with a film, put in a thermostatic chamber at 50 ° C, and the temperature is stabilized.
After the film was transferred to a constant temperature of 0 ° C. for 6 hours, the state of the film was observed and evaluated as antifogging property.

◎ Transparent and no fog ○ Slight water droplets △ Large water droplets are opaque × Fine water droplets are opaque on the entire surface (12) Surface resistance measurement According to JIS K-6723, Hewlett-Packard Company Made by Res
Using an instance meter, the volume resistivity after 3 days at RH 50% and a temperature of 25 ° C. was measured.

The test piece used was a T-die molded to a thickness of 0.7 to 0.8 m / m.

Example 12 Sample Nos. 2-2, 4-2 and 4-3 according to the present invention were used as a filler to prepare a thermosensitive recording layer forming liquid having the following composition, and an undercoat paper was coated with a No. 8 bar coater. A coating amount of 7 g / cm ² was applied, and after air-drying, it was calendered at 5 kg / cm ² to prepare a thermal paper.

Dye Slurry 10 parts Developer Slurry 20 parts Sensitizer Slurry 20 parts Binder 15 parts Test Material 20 parts Next, using NTT FAX-510T, the thermosensitive paper is colored by copying the IEICE Test Chart No. 1, Color density of DENSITOMETER FSD-103 (Fuji Photo Film)
Was measured using.

Similarly, the non-colored portion was also measured and displayed as background stain.

Furthermore, in the dust adhesion test, the ink ribbon of the NEC PC-PR1O1TL Japanese color thermal transfer printer was removed, and the adhesion state of dust on the thermal head when printing solid black on the thermal paper for examination was observed and evaluated as follows. It is shown in Table 11.

◎ None at all ○ Slightly present △ Slightly adhered × Severe adhesion Experiment Nos. 34H to 37H show comparative examples. Example 13 Sample Nos. 1-1, 2-1 and 4-3 according to the present invention were used as a filler to make an inner filler paper, and the following tests were conducted. The results are shown in Table 12.

Experiment Nos. 41H to 43H show comparative examples.

(13) Abrasion Degree The loss of the plastic wire was measured with a Filcon abrasion tester.

(14) Papermaking yield Using a raw pulp and sulfuric acid band of 80 parts LBKP and 20 parts KBKP, JIS P
45 g / m ² paper was prepared according to -8209, and the yield was measured according to JIS P-8128.

The yield of talc according to this method was 35%.

(15) Paper opacity Paper was prepared under the same conditions as in (14) and measured according to JIS-P8113.

(16) Printed matter Opaqueness A paper is made under the same conditions as in (14), and the wire side of the paper is solidly printed with a RI (Rotary Ink) tester, and JIS P-8
After drying for 24 hours under the condition of 111, the whiteness of the non-printed surface (the surface opposite to the wire surface) of this paper was measured.
Ratio of the whiteness of the opposite surface of the wire surface before printing to this whiteness, that is, (whiteness after printing / whiteness before printing) × 100
(%) Was used as the print opacity. The printing condition is that the ink used is Web-King ink (manufactured by Toyo Ink) and the ink supply is 0.5m.
l, printing speed 30 rpm. Printing was also performed under JIS P-8111 environmental conditions.

Example 13 Sample Nos. 1-1, 2-1 and 4-1 powders according to the present invention were used to prepare an acid-curable aminoalkyd resin paint, and the matting effect, coating smoothness and storage stability of the paint were measured. The results are shown in Table 13.

The above sample was added to 100 parts of commercially available acid-curing aminoalkyd resin.
A predetermined number of parts of No. 1 and No. 2 fine powders were mixed and dispersed for 15 minutes with a disper type dispersion machine (1500 rpm manufactured by Tokushu Kika Kogyo). This is applied to a glass plate with a film applicator of 5M: 1 at a film thickness of 150 μ, and 140 ° C. × 2
60 ° specular reflectance and smoothness of coating film after baking for 0 minutes
Was measured. Further, the prepared coating material was adjusted to a viscosity KU value of 60, stored at room temperature for two months, and the state of the sedimentation cake was observed. The results are shown in Table 13.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a scanning electron micrograph showing the particle structure of the amorphous silica-alumina filler according to Example 1. FIG. 2 is a scanning electron micrograph showing the particle structure of the amorphous silica filler according to Example 3. FIG. 3 is a scanning electron micrograph showing the particle structure of the raw material zeolite particles. 4, 5, 6 and 7 are sample Nos. H-22, H-31 and H-32 obtained by the comparative examples, respectively.
3 is a scanning electron micrograph showing the particle structures of H-4 and H-4.

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Claims (5)

[Claims] 1. A porous or amorphous silica or silica-alumina core and an amorphous silica porous shell, which have a cubic or spherical regular particle shape and a porous shell structure as a whole. Comprised of particles having 85 to 20
A filler having an oil absorption of 0 cc / 100 g, a bulk specific gravity of 0.1 to 0.6 g / cc, and a volume-based median diameter of 0.5 to 10.0 μm. 2. A zeolite and SiO ₂ in the zeolite with respect to the manufacture of an aqueous slurry containing alkali silicate equivalent to SiO ₂ of 2 to 40 wt%, zeolite by adding an acid to the slurry To produce coated particles in which a porous shell of amorphous silica is bonded to the core of, and to continue adding an acid to the slurry of the coated particles to elute at least a part of the alkaline component in the zeolite or further the aluminum content. , Core zeolite with amorphous silica or silica
A method for producing silica or a silica / alumina-based filler, which comprises converting to alumina. 3. A resin molded body containing 0.01 to 10 parts by weight of the silica or silica-alumina-based filler according to claim 1 per 100 parts by weight of the resin. 4. A paper containing the silica or the silica-alumina-based filler according to claim 1 in an amount of ^{2 to} 40 g / m ² with respect to the paper. 5. A coating material using the silica or silica-alumina-based filler according to claim 1 as an extender pigment.