JP3076447B2 - Magnesium compound coated particles and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a magnesium compound-coated particle, a method for producing the same, and a resin molded product, paint or ink containing the particle. More specifically, the present invention relates to a resin molded product, film or paint or ink. The present invention relates to a magnesium compound-coated particle which is suitably used as a compounding agent or filler for paper, etc., and is also suitable as a catcher for a polymerization catalyst, a method for producing the same, and resin molded articles, paints and inks containing the particles.

[0002]

2. Description of the Related Art Resin molded products, films, paints, inks,
Inorganic fine powder is generally used as a compounding agent or filler compounded in paper or the like, and fine powder particles such as silica and silica-alumina are also often used.

[0003] Many of these inorganic fine powder fillers and compounding agents have been subjected to various processings and treatments so as to have various characteristics depending on the purpose of use and application thereof, and many proposals have been made on them. It has been implemented.

[0004] For example, as a silica-based filler,
JP-A-3-60103 proposes silica fine particles having a specified particle size, particle shape and specific surface area in order to improve the fluidity and dispersibility of the particles in a resin.
JP-A-256512 discloses a specific aluminosilicate spherical inorganic filler which is inert to resins and other compounding agents, and JP-A-58-213031 discloses a resin which prevents coloring and deterioration and has an antiblocking property. Specific alumino-silica-based resin compounding agents which improve the above are disclosed.

[0005]

These compounds, in particular, silica-based compounds or silica-alumina-based compounds have advantages such as good dispersibility in resin and good transparency. All of them have high Mohs hardness and are abrasive, so when these powder particles are blended with film or other resin for molded products, these particles are present in the state of protruding on the surface of molded products, especially films, etc. However, due to the abrasiveness of the particles, there were disadvantages such as damage and abrasion of other contacting film surfaces, molded product surfaces and the like.

[0006] Such inconveniences also occur when the above-mentioned filler is applied to paints, inks, papers and the like.

[0007] An object of the present invention is to avoid the above-mentioned inconveniences when blended into resin films, paints, inks, papers, resin molded products, etc. and to have an affinity for oily substances such as inks and paints. It is an object of the present invention to provide coated fine particles which have good properties and are suitable as a filler or a compounding agent for providing a film surface or a paper surface with good compatibility with these.

Another object of the present invention is to provide coated fine particles which are excellent in transparency and can remarkably improve the slip property and anti-blocking property of the film, particularly when applied to a resin film.

Another object of the present invention is that when it is blended into a film, it is excellent in transparency, has a large far-infrared radiation effect, and is therefore excellent in heat retention properties.
In particular, it is an object of the present invention to provide coated fine particles suitable as agricultural film compounding agents.

It is still another object of the present invention to provide coated fine particles having good fluidity of particle aggregates, low dusting, and good handling workability, and a polymerization catalyst utilizing these characteristics. The purpose of the present invention is to provide shaped particles for catchers.

It is still another object of the present invention to provide a method for producing the above-mentioned coated fine particles. Another object of the present invention is to provide a resin molded article containing the above-mentioned magnesium-coated particles. Still another object of the present invention is to provide a resin molded product, a paint, and an ink containing the coated particles.

[0012]

According to the present invention, the individual particles independently have a well-defined cubic or spherical primary particle shape and 0.3 to 20 μm primary particles measured by electron microscopy. Shaped core particles comprising at least one of amorphous silica, amorphous silica-alumina or amorphous aluminosilicate having a diameter, and silanol groups on the surface of the shaped core particles
Or a magnesium compound reactively bonded to an Al (OH) group
And a magnesium compound coated particle characterized by comprising:

According to the invention, it is also preferred that the individual particles have an independently defined cubic or spherical primary particle shape and an amorphous particle having a primary particle size of 0.3 to 20 μm as measured by electron microscopy. At least one magnesium compound of magnesium hydroxide, magnesium acetate, and magnesium nitrate in an aqueous slurry having a pH of 10 or less having shaped core particles of at least one of porous silica, amorphous silica-alumina or amorphous aluminosilicate. And heat-treated at normal pressure or under pressure to obtain silanol on the surface of the shaped particles.
Group or Al (OH) group reacts with the magnesium compound
Forming a bonded magnesium compound coating layer;
Includes fixed particles with a coating layer of calcium compound as a dispersed phase
The present invention provides a method for producing magnesium compound-coated particles, characterized by filtering or drying an aqueous dispersion, and pulverizing or baking the obtained solid content at a temperature of 300 ° C to 800 ° C as required.

According to the present invention, there are also provided resin molded articles, paints and inks containing the magnesium compound-coated particles.

The magnesium compound-coated particles of the present invention
That each particle independently has a distinct cubic or spherical primary particle shape; that the primary particles have a particle size in the range of 0.3 to 20 μm; Groups present on the surface of shaped core particles such as porous silica
Or the magnesium compound reacts with AlOH group
More magnesium silicate or aluminosilicate
The magnesium compound coating layer in the form of magnesium is
It is a structural feature that it is formed on the surface of the shaped particles .

Since the particles of the present invention have the above-mentioned shape and uniform size, the specific coated particles of the present invention do not agglomerate with the primary particles to form secondary particles. The specific coated particles are less likely to form secondary particles by aggregating the primary particles, and even when the particles of the present invention are blended in a resin, paint, ink, etc., the primary particles remain in the resin and the like. Distributed. Therefore, the dispersion in the resin is kept in a uniformly good state, and the filling effect is maximized.

In the magnesium-coated particles of the present invention, the core particles are composed of amorphous silica, amorphous silica-alumina or amorphous aluminosilicate, which are compared with the corresponding crystalline silica. Because of its low density and relatively low Mohs hardness, it is relatively soft, light in weight, and combined with the action of the magnesium compound coating layer described below, it also has a polishing action even when blended in film resin etc. Does not damage the film surface.

The most important feature of the present invention is that the shaped core particles have a silanol group or Al (O
Magnesium compounds such as magnesium hydroxide are added to the H) group.
Has a coating layer formed by reacting
That is. Magnesium reactively bonded to the surface of shaped nuclear particles
The fine particles of the present invention having a coating layer of a rubber compound are uniformly present as lip-shaped or spherical particles having a uniform particle size on the surface of a resin molded product or film, paint, ink, paper, or the like. The magnesium coating layer is softer than amorphous silica or the like forming an inner core, and forms a smooth surface. Therefore, even when the film surfaces and the like come into contact with each other, they do not damage those surfaces. Moreover, since such smooth fine particles having a smooth surface are uniformly present on the surface of a film or the like, an effect of significantly improving the anti-blocking property and the slip property of the film or the like is exerted.

The coated particles of the present invention are an aggregate of primary particles having a smooth surface and uniform particles, and therefore have good fluidity, and are easy to handle due to little dusting, and are excellent in handling workability. ing.

Further, since the core particles are formed of a material such as amorphous silica or silica-alumina, the refractive index thereof is close to that of the resin or the like to be compounded. The resulting resin molded product, film, and the like have excellent transparency. Another advantage of the resin compounding agent is that since the particle nucleus is amorphous, it is lighter in weight than the compounding agent of crystalline particles.

In the present invention, the above-mentioned coating layer is formed.
Magnesium compound used for
Reacts with silanol groups and Al (OH) groups on the surface of
Magnesium silicate, aluminosilicic acid reactively bonded to the surface
A coating layer of magnesium or a mixture of these
Use any magnesium compound as long as it can form
Can be used, but in general, magnesium hydroxide
, Magnesium acetate and magnesium nitrate are preferably used
Is done.

That is, the coated particles of the present invention having the coating layer made of the above-mentioned compound have not only the above-mentioned properties but also more appropriate water repellency and low hygroscopicity. The surface of the compounded product such as a film becomes lipophilic, the affinity with an oily substance, for example, an oily ink, a paint, or the like is remarkably improved, and the printing property of the surface of the formed product is excellent.

The above magnesium compound-coated particles are
Since it has a large far-infrared radiation effect and has a refractive index close to that of many plastic film resins, it exhibits an excellent heat-retaining effect especially as a resin compounding agent for agricultural films.

Among such coated particles of magnesium silicate and the like, those obtained by forming a coating layer on the core particles of the present invention by the method for producing coated particles of the present invention, which will be described later, are excellent in the above-mentioned various properties. Since the specific surface area of the surface is small, the hygroscopicity is small, and the water repellency is excellent, so that the affinity for oily substances is remarkably excellent.

That is, for example, a compound such as magnesium hydroxide is added to a slurry of the shaped core particles of the present invention having a pH of 10 or less, and the mixture is pulverized with stirring to dissolve at least a part of the magnesium compound in a dispersion medium. The mixture treated with stirring under normal pressure or under pressure to form a coating layer of a magnesium compound was subjected to the diffraction of the added Mg (OH) ₂ as apparent from the X-ray diffraction pattern in FIG. The pattern almost disappeared, and an amorphous magnesium fluorosilicate peak appeared instead.

That is, it is understood that this coating layer is substantially made of magnesium silicate.

Such a coating layer can be formed similarly when the material of the core particles is made of silica alumina or aluminosilicate. In this case, magnesium aluminosilicate is partially mixed in addition to the above magnesium silicate. A coating layer having a predetermined shape is formed.

The coating layer of the particles formed by the method of the present invention has strong adhesion because the silanol groups of the core particles are directly bonded to magnesium, and the coating layer is formed densely. It is a suitable resin compounding compound blending particle which has little delamination or the like and is particularly excellent in the above-mentioned various properties. Among the coated particles obtained by the method of the present invention, those obtained by forming a coating layer under pressure, in particular, have markedly excellent hydrophobicity of the coated particles.

[0029]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Shaped core particles The shaped core particles of the present invention have a cubic or spherical primary particle shape and a particle size of 0.3 to 20 μm.
When the core particles are cubic, resin molded products, paper, paint,
From the viewpoints of abrasiveness and anti-blocking properties when blended in ink or the like, those having rounded corners are preferred.

As the material of the core particles, amorphous silica,
It is selected from one or more of amorphous silica / alumina or amorphous aluminosilicate.
Further, from the viewpoint of transparency when blended in a resin or the like, the refractive index is 1.
Those in the range of 47 to 1.550 are preferred.

The method for producing the shaped core particles of the present invention is not particularly limited, but the known silica-alumina, zeolite or the like having the above-mentioned shape and particle diameter is subjected to an acid treatment or other methods. Amorphized while retaining its particle shape, for example,
Those prepared by a method as described in 7163 are preferred.

As a preferred example of the amorphous silica shaped core particles of the present invention, for example, an acrylamide polymer is added to an aqueous solution of an alkali silicate, and the alkali silicate is partially neutralized with an acid. Spherical amorphous silica particles prepared by aggregating and growing into particles by aging and standing at around room temperature, p-
AMT-silica particles prepared by treating a zeolite with an acid can be exemplified.

As a preferred example of the amorphous silica-alumina shaped core particles, the molar ratio of Al ₂ O ₃ : SiO ₂ is in the range of 1: 1.8 to 1: 5.0 and the particle size is An aqueous slurry of a synthetic zeolite having a uniform pH is made to be amorphous by acid treatment under a condition of pH 5 or more, or to be calcined.

As the amorphous aluminosilicate particles, ion-exchanged zeolites, for example, zeolite A, zeolite X, zeolite Y, zeolite P, analcyme, monodenite, faujasite, etc., which have been made amorphous by acid treatment, or Can be exemplified.

In particular, amorphous aluminosilicate particles prepared by the formulation and method described in Example 1 below are preferred. Note that the fired particles are used as shaped core particles.
In this case, as shown in Example 7 described below,
After treatment with an acid such as sulfuric acid, the magnesium compound
Coating with an object. In baked products, present on the particle surface
Silanol and Al (OH) groups disappear,
Since the reaction with the nesium compound will not occur,
Restore these groups to the particle surface by acid treatment
Is necessary.

It is an essential requirement that the shaped core particles of the present invention be amorphous, and crystalline core particles have a high density and a high hardness. However, it is not suitable because it has disadvantages such as the inconvenience of damaging the resin, the reaction of forming the coating is slow, and the dispersion in the resin is difficult to be homogenized.

When the particle size is larger than the particle size specified in the present invention, not only is it difficult to uniformly disperse when blended in a resin and the like, but also the transparency and appearance are unfavorable. Particles having a large particle size, a non-uniform shape and many corners are liable to damage the surface of a film or the like, and also have an adverse effect on antiblocking properties. On the other hand, when the particle size is smaller than the specification of the present invention, handling is inconvenient and troubles such as dusting cannot be avoided.

Magnesium compounds Magnesium compounds used for coating the shaped core particles of the present invention include MgF ₂ , MgCl ₂ , and KMg.
Magnesium halides such as Cl ₃ and MgBY ₂ , M
gO, Mg _{(OH) 2} and magnesium oxides or hydroxides _{of, MgSO 4, MgSO 4 · 6H} 2 O, Mg (NO
_{3) 2, Mg (NO 3} ) 2 · 6H 2 O, Mg (PO 4)
₂ , magnesium oxyacid salts such as MgHPO ₄ and Mg (C
H ₃ COO) ₂ , Mg (CH ₃ CH ₂ COO) ₂ , and other magnesium organic acid salts can be exemplified .

Particularly, magnesium silicate, magnesium aluminosilicate, and the like formed by reacting magnesium oxide, hydroxide, and salt such as magnesium hydroxide, magnesium oxide, magnesium acetate, and magnesium nitrate on the surface of the shaped core particles are used as starting materials. Is most preferred as the coating layer.

Magnesium Compound-Coated Particles The magnesium compound-coated particles of the present invention are prepared by coating the above-mentioned shaped core particles with a magnesium compound. The amount of the magnesium compound coated on the shaped particles is preferably 2 to 30% by weight in terms of MgO per shaped core particle.

If the coating amount is less than the above lower limit, a uniform coating is not formed on the entire surface of the particles, or even if coated, the function and effect of the present invention cannot be sufficiently achieved. On the other hand, if it is more than the upper limit, the adhesion of the coating becomes poor, and the coating layer peels off, and aggregation and desorption of the particles are likely to occur and the cause is still not fully understood. The adverse effects such as increase in water repellency are also caused.

With respect to the method of coating the magnesium compound, a coating method known per se can be employed and is not particularly limited, but coated particles coated by the method described below are most preferred.

Method for Producing Magnesium Compound-Coated Particles In the present invention, the amorphous shaped particles are converted into an aqueous slurry under the condition that the pH is 10 or less.

To this aqueous slurry, at least one or more of magnesium oxide, hydroxide and magnesium salt such as magnesium hydroxide, magnesium oxide, magnesium acetate and magnesium nitrate are added, and the mixture is stirred and crushed by a mixer or the like, A dispersion is prepared in which the affiliated core particles have at least a part of the dispersed phase, the added magnesium salt or the hydroxide dissolved therein in the solution phase.

This dispersion is subjected to a heat treatment under normal pressure or under pressure to cause the core particles to react with the above-mentioned magnesium salt or hydroxide to form a coating layer on the particle surfaces.

After completion of the reaction, the solid content of the particles is filtered, washed with water, dried, and calcined at 300 to 800 ° C. to produce particles coated with a magnesium compound.

In the method for producing the magnesium compound-coated particles of the present invention, the surface of the core particles present as a slurry dispersed phase and the added magnesium compound such as Mg
It is a remarkable feature that a coating layer in a form in which (OH) ₂ is bonded by reaction is formed.

Although the mechanism of the reaction between the surface of the core particles and Mg (OH) ₂ or magnesium acetate or magnesium nitrate has not been clearly elucidated yet, it is probably that silanol groups existing mainly on the surface portion of the core particles,- Al (O
H) a relatively reactive group or moiety such as a group
It is presumed that (OH) _{2 and the} like react to form a bond. As is clear from the X-ray diffraction diagram of FIG. 5 attached thereto, the diffraction diagram of the particles after the completion of the reaction shows the added Mg.
This is supported by the fact that the diffraction pattern of (OH) ₂ almost disappeared, and instead, the peak of magnesium fluorosilicate appeared.

In the method of the present invention, the solid content of the aqueous slurry is not particularly critical, but usually the solid content is 2%.
To 50% by weight, preferably 5 to 3% by weight.
0% by weight.

In the present invention, the pH of the slurry is 10
It is kept below. If the pH exceeds 10, deposition of Mg (OH) ₂ or the like dissolved in the dispersion medium on the surface of the particles is not sufficiently performed, and a good coating layer cannot be formed. When the pH of the slurry exceeds 10, the pH is adjusted to 10 or less by adding an acid or the like.

The form of magnesium hydroxide, magnesium oxide, magnesium acetate, magnesium nitrate, etc. to be added is not particularly limited, but it is usually in the form of powder or a solution containing a small amount of a solvent or water which is convenient for dissolution. A suspension is convenient because it is easy to use.

The amount of magnesium hydroxide or the like varies depending on the concentration of the aqueous slurry used, but is usually 1 to 50% by weight in terms of MgO based on the solid content of the shaped core particles.
Is added.

To obtain the particularly preferred coated particles of the present invention, 2 to 30% by weight in terms of MgO is used based on the solid content of the shaped core particles.

In the method of the present invention, the coating forming reaction
It can be carried out under normal pressure or under pressure, but in the case of carrying out under normal pressure, magnesium hydroxide is added to the slurry, and then the dispersion is stirred and crushed by a mixer or the like. Let it mature for a while.

Thereafter, the dispersion was stirred at 50 ° C. to 200 ° C.
The temperature is raised to a temperature of ° C. to carry out the reaction. Although the reaction time depends on the temperature and other conditions, it is usually completed in 1 to 10 hours.

As a method for judging the completion of the reaction, for example, a sample of the pH of the dispersion and the slurry particles is taken at regular time intervals, and after drying, an X-ray diffraction diagram of the sample is taken. ₂ ) The end point is determined from the point in time at which the peak appearing at 37.8 ° substantially disappears and the rate of decrease in the pH of the dispersion. It is easy for those skilled in the art to determine an appropriate reaction end time in consideration of various conditions such as conditions. After completion of the reaction, the coated particle slurry thus obtained is taken out, filtered, washed with water, dried, and fired in the above-mentioned temperature range to obtain final coated particles.

When the reaction is carried out under pressure, the temperature is raised to about 150 ° C. in an autoclave or the like to terminate the reaction. Usually, the reaction time under pressure is completed in about 0.5 to 5 hours. Thereafter, the same treatment as in the normal pressure method is performed.

In the case of the reaction under pressure, aging is not necessarily required.

Applications The magnesium compound-coated particles of the present invention can be suitably used as a compounding agent or filler for various resin molded articles, films or paints, inks, papers and the like.

The particles of the present invention are cubic or spherical in shape, have a uniform primary particle diameter, and are coated with a relatively soft magnesium compound having a smooth surface. It does not damage the surface of the film, printing paper, etc. and has excellent anti-blocking properties of the resin film.

The coating layer of the particles is lipophilic and has a low hygroscopicity, so that it can be easily applied with paints and inks. Therefore, the surface of the film or other resin molded product to be coated, coated, printed, etc. Very suitable as a compounding agent.

Further, it can be suitably used as a compounding agent for agricultural films because of its excellent transparency and large radiation effect of far infrared rays.

[0063] As the resin suitable for formulation of the coated particles of the present invention are polypropylene, polyethylene emissions, crystalline propylene - ethylene copolymer, ionically crosslinked olefin copolymer
Olefinic resins such as polyethylene terephthalate,
Thermoplastic polyesters such as polybutylene 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; polycarbonate; polysulfones; polyacetal; Thermoplastic resins such as resin, thermosetting polyester resin, phenolic resin,
Thermosetting resins such as epoxy resin, bismaleimide resin, and silicone resin can be used.

It is preferable to add a heat stabilizer to these resins together with the coated particles of the present invention from the viewpoint of heat stability. Examples of the heat stabilizer include fatty acids such as stearic acid, palmitic acid and lauric acid. Metallic soaps such as calcium, zinc, magnesium, and barium salts of fatty acids, silane-based coupling agents, aluminum-based coupling agents, titanium-based coupling agents, silconium-based coupling agents, and various waxes can be used. For example, preferred waxes include polar groups such as carboxylic acid, carboxylic anhydride, carboxylate, carboxylic acid ester, carboxylic acid amide, ketone, ether, and hydroxyl group in an amount of 0.1 to 20 mmol per gram of wax. , Especially 0.5
Waxes containing at least one long-chain alkylene chain having 10 or more carbon atoms, particularly 12 or more carbon atoms, in the molecule at a concentration of 10 to 10 mmol are exemplified. In addition to these,
What has been surface-treated with various types of unmodified or modified resins (for example, rosin, petroleum resin, etc.) with a coating agent can also be used as a stabilizer.

The amount of the fine particles varies depending on the purpose and application, but is usually in the range of 0.01 to 30 parts by weight, particularly 0.05 to 5 parts by weight, per 100 parts by weight of the resin. When mixed with various paints, inks, papers and the like, it is preferable that the content is 0.5 to 30% by weight, particularly 2 to 10% by weight, based on pulp.

[0066]

The magnesium compound-coated particles of the present invention do not damage the surface of the compounded resin film or the like by polishing, have excellent antiblocking properties, have lipophilicity, and have good transparency. Because it has many properties such as a large far-infrared radiation effect, it is used for resins and (paints,
Ink) It can be used suitably for various uses as a compounding agent for paper and an additive.

[0067]

The present invention will be described in more detail with reference to the following examples. In the following examples, the measurement of chemical composition, physical properties, and the like was performed by the following methods.

(Measurement Method) Chemical composition Measured in accordance with JIS M-8852 silica stone analysis method. 2. Apparent specific gravity Measured according to JIS K-6220.6.8. 3. Oil absorption The oil absorption was measured according to JIS K-5101.19. 4. Specific surface area Carlotomba's Sorptometic Series
It was measured by the BET method using s 1800. 5. Whiteness AUTOMATIC REFLECT manufactured by Tokyo Denshoku Co., Ltd.
It was measured by O METER Model TR-600. 6. Aperture tube 20 μm by Coulter counter (TA-II type manufactured by Coulter Electronics),
It measured using 50 micrometers. 7. Particle Size by SEM Representative particles were selected from a photographic image obtained by a scanning electron microscope (S-570, manufactured by Hitachi), and the diameter of the particle image was measured using a scale, and was shown as the primary particle diameter. 8. Refractive index Determined by the liquid immersion method.

9. Abrasion amount The wear amount was measured under the following conditions using a Fircon type (manufactured by Nippon Fircon Co., Ltd.) abrasion tester. Roll used Ceramic roll rotation speed 1500 rpm Contact angle 111 ° Test piece dimensions 40 × 140 mm Test piece weight Approx. 2 g Test piece material Plastic wire Weight 850 g Solid content concentration 2% Measurement time 180 minutes Result expression value Weight loss ( mg)

Example 1 Sodium silicate (SiO ₂ 27%, Na ₂ O 9%), sodium aluminate (Al ₂ O ₃ 22.5%, Na ₂ O 18.
6%) and a commercially available 49% NaOH to prepare a diluted sodium silicate solution and a diluted sodium aluminate solution such that the total amount becomes 16 kg at the following molar ratio. Na ₂ O / SiO ₂ = 1.8 SiO ₂ / Al ₂ O ₃ = 1.8 H ₂ O / Na ₂ O = 60 Next, in a stainless steel container having an inner volume of about 20 L, 8 kg of dilute sodium silicate solution was added. 8 kg of sodium aluminate solution was slowly mixed with stirring to obtain a uniform alkali aluminosilicate gel. Then, the temperature of the alkali aluminosilicate gel was increased to 90 ° C. while stirring, and crystallization was performed at that temperature for 4 hours. After crystallization is completed, the mixture is filtered and washed with water, and the solid content concentration is 50.
% 2.5% Na-A type zeolite cake was obtained.

Next, 1 kg of the above cake was sufficiently dispersed in 4 L of water in a 10 L stainless steel container, and then the Na in zeolite was dispersed.
_An equivalent amount of 10% sulfuric acid with respect to the 2O content was added over 10 hours with stirring, and when the addition was completed, the mixture was stirred for 2 hours, and then filtered and washed with water. A slurry of porous aluminosilicate particles was obtained. The pH of the slurry at this time was 4.8. (Sample 1-1) Next, the solid content of this slurry was converted to MgO to 5%.
% Of magnesium hydroxide (# 20 manufactured by Kamishima Chemical Co., Ltd.)
0) The powder was added, and after sufficiently dispersing, the temperature was raised to 95 ° C. in a water bath, and treatment was performed at that temperature for 8 hours. After the treatment, the slurry was directly placed in a constant temperature dryer at 110 ° C. and dried overnight. The dried block was pulverized by a sample mill and fired at 500 ° C. for 1 hour to obtain amorphous magnesium aluminosilicate (chemically coated) particle powder. (Sample 1-2) The X-ray diffraction pattern of this powder is shown in FIG. 1, the SEM photograph is shown in FIG. 2, and the powder properties are shown in Table 1.

Example 2 600 g of the sample 1-1 slurry obtained in Example 1
Weighed into a stainless steel beaker,
Magnesium hydroxide (# 200 manufactured by Kamishima Chemical Co., Ltd.) powder was added so as to be 10% in terms of conversion.
g / cm ² ) for 5 hours. Thereafter, drying, pulverization and baking were performed in the same manner as in Example 1 to obtain amorphous magnesium aluminosilicate-coated particle powder. Table 1 shows the properties of the powder.

Example 3 In Example 1, the synthesis molar ratio was changed to Na ₂ O / Si ₂ O = 1.8 SiO ₂ / Al ₂ O ₃ = 1.5 H ₂ O / Na ₂ O = 30 and Na-A type was used. Example 1 except that zeolite was synthesized
To obtain amorphous magnesium aluminosilicate-coated particle powder. Table 1 shows the properties of the powder.

Example 4 In Example 1, the synthesis molar ratio was changed to Na ₂ O / Si ₂ O = 1.8 SiO ₂ / Al ₂ O ₃ = 1.8 H ₂ O / Na ₂ O = 70, and the Na-A type was used. Example 1 except that zeolite was synthesized
To obtain amorphous magnesium aluminosilicate-coated particle powder. Table 1 shows the properties of the powder.

[0075]

[Table 1]

Example 5 Sodium silicate (SiO ₂ 27%, Na ₂ O 9%) Sodium aluminate (Al ₂ O 22.5%, Na ₂ O 18.6)
%), Commercially available 49% NaOH, and
A diluted sodium silicate solution and a diluted sodium aluminate solution were prepared so as to be 6 kg. Na ₂ O / SiO ₂ = 0.8 SiO ₂ / Al ₂ O ₃ = 8.0 H ₂ O / Na ₂ O = 70 Next, a stainless steel container having an inner volume of about 20 L or a diluted sodium silicate solution (8 kg) was diluted. 8 kg of sodium aluminate solution was slowly mixed with stirring to obtain a uniform alkali aluminosilicate gel. Then, the alkali aluminosilicate gel was heated to 90 ° C. with vigorous stirring, and crystallized at the same temperature for 48 hours. After completion of the crystallization, the mother liquor and the solid content were separated by suction filtration, washed sufficiently with water, and the solid content concentration of Na was 52%.
-About 1.5 kg of P-type zeolite cake was obtained. (Sample 5
1)

Next, 1 kg of the above case was sufficiently dispersed in 4 L of water in a 10 L stainless steel container, and then the Na in the zeolite was dispersed.
₂ mol of 10% sulfuric acid per ₂ O was added over 10 hours with stirring, and after the addition was completed, the mixture was stirred for 1 hour, then filtered and washed with water, and the cake was re-valved to obtain a 40% amorphous fraction having a form concentration of 40%. A porous aluminosilicate-based particle slurry was obtained. The pH of the slurry at this time was 4.1. (Sample 5-2) Next, 10% in terms of MgO with respect to the solid content of this slurry.
Magnesium Hydroxide (Kamijima Chemical # 200)
The powder was added, and after sufficiently dispersing, the temperature was raised to 95 ° C. in a warm bath and treated at that temperature for 8 hours.
It was dried overnight in a constant temperature dryer at 10 ° C. The dried block was pulverized by a sample mill and fired at 500 ° C. for 1 hour to obtain spherical crystalline magnesium aluminosilicate coated particles. (Sample 5-3) The properties of this powder are shown in Table 2.

Example 6 The solid content of Sample 5-2 obtained in Example 5 was
Magnesium oxide (# 200 manufactured by Kamishima Chemical Co., Ltd.) powder was added so as to be 25% in terms of conversion, and after sufficiently dispersing, the mixture was placed in a 1 L autoclave and heated to 180 ° C. with stirring (pressure 8 kg /
cm ² ) for 5 hours. Thereafter, drying is performed in the same manner as in Example 5,
The powder was pulverized and calcined to obtain spherical amorphous magnesium aluminosilicate-coated particle powder. The powder properties of this product are shown in Table 2.

Example 7 1 kg of the sample 5-2 slurry obtained in Example 5 was
The mixture was stirred overnight in a constant-temperature oven at a temperature of 450 ° C., and calcined at 450 ° C. for 3 hours to obtain an amorphous aluminosilicate spherical powder. Then 3
1 L of pure water was weighed and placed in a L beaker, 300 g of the calcined amorphous aluminosilicate spherical particle powder was added with stirring and sufficiently dispersed, and A in the amorphous aluminosilicate spherical particle powder was dispersed.
Sulfuric acid (prepared to 50%) which was 1.2 times the theoretical reaction amount of l ₂ O ₃ and Na ₂ O was slowly added. At the end of the addition of sulfuric acid, the temperature of the slurry rises to about 90 ° C, but the slurry was further heated and treated at 98 ° C for 2 hours. Next, the mother liquor and the solid content were separated by suction filtration, and after sufficiently washing with water, the cake was revalved to obtain a slurry of spherical silica particles having a solid content concentration of 30%. The pH of this slurry was 3.0. (Sample 7-1)

Next, MgO was added to the solid content of the slurry.
Magnesium hydroxide (# 200 manufactured by Kamishima Chemical Co., Ltd.) powder equivalent to 10% in terms of conversion was added, and after sufficiently dispersing, the temperature was raised to 95 ° C. in a warm bath, and the mixture was treated at that temperature for 8 hours. After separating the mixture, the mixture was sufficiently washed with water and dried overnight in a constant temperature dryer at 110 ° C. The dried block was pulverized with a sample mill and fired at 500 ° C. for 1 hour to obtain spherical magnesium silicate-coated particle powder. (Sample 7-2) FIG. 3 shows an X-ray diffraction pattern of this powder, and FIG.
Table 2 shows the powder properties.

Example 8 1 L of 500 g of the sample 7-1 slurry obtained in Example 7
Weighed into a stainless steel beaker,
Magnesium hydroxide (# 200 manufactured by Kamishima Chemical Co., Ltd.) powder was added so as to be 25% in terms of conversion.
g / cm ² ) for 5 hours. Thereafter, washing with water, drying, pulverization and baking were performed in the same manner as in Example 7 to obtain spherical magnesium silicate-coated particle powder. The X-ray diffraction pattern of this powder is shown in FIG. 5, where a peak of phyllosilicate was observed. Table 2 shows the powder properties.

Examples 9 to 10 Except that the synthesis molar ratio in Example 5 was changed to Na ₂ O / SiO ₂ = 0.9 SiO ₂ / Al ₂ O ₃ = 5.0 H ₂ O / Na ₂ O = 55 A Na-P type zeolite was prepared in the same manner as in Example 5, and treated with 2 mol of sulfuric acid on Na ₂ O in the zeolite. Then, Mg was added in the same manner as in the method shown in Examples 7 and 8.
Spherical magnesium silicate-coated particles containing 10% and 25% of O were obtained. Table 2 shows the properties of this powder.

[0083]

[Table 2]

Example 11 A commercially available No. 3 sodium silicate (S) was placed in a 2 L stainless steel beaker.
_{iO 2 22.3%, Na 2 O7.0} %, SiO 2 / Na
_After weighing 471 g (7% as SiO ₂ concentration in the total liquid amount) of 471 g of pure water and adding 327 ml of pure water, the mixture was placed in a thermostat controlled at 20 ° C., and stirred with a stirrer to give an aqueous acrylamide polymer solution. (About 10% aqueous solution manufactured by Wako Pure Chemical Industries, average molecular weight: 500,000) and 300 g (SiO ₂
(28% as polyacrylamide anhydride per minute). Next, 402 g of 7% sulfuric acid adjusted to 20 ° C.
Was added for about 1 minute (pH was 10.70 after completion of the addition). After completion of the addition, the stirring was stopped, and the mixture was allowed to stand for 12 hours.

After allowing to stand for 12 hours, the precipitate and the mother liquor were separated by filtration, and the obtained cake was redispersed in pure water and sufficiently dispersed.
7% sulfuric acid was added until H became 3.0, and when the pH was almost stabilized at 3.0, the mixture was stirred for 1 hour, then filtered and washed with water, and the cake was revalved to purify a 15% -concentration spherical silica particle slurry. (Sample 11-1) Next, the solid content of this slurry was 10% in terms of MgO.
Magnesium Hydroxide (Kamijima Chemical # 200)
The powder was added, and after sufficient dispersion, the temperature was raised to 95 ° C. in a warm bath, and further treated at that temperature for 8 hours. After the treatment, the mother liquor and solids were separated by suction filtration, washed sufficiently with water, and dried at 110 ° C. in a constant temperature drier. Dried overnight. The dried block was pulverized by a sample mill and fired at 500 ° C. for 1 hour to obtain spherical magnesium silicate-based composite particles. The X-ray diffraction pattern of this powder is shown in FIG. 6, the SEM photograph is shown in FIG. 7, and the powder properties are shown in Table 3.

Example 12 Spherical silica-magnesium composite particles were obtained in the same manner as in Example 11, except that the amount of MgO added was changed to 30%. Table 3 shows the properties of this powder.

Examples 13 and 14 In Example 11, the temperature of the constant temperature bath and 7% sulfuric acid to be poured was changed to 2%.
Spherical magnesium silicate-based composite particles were prepared in the same manner as in Example 11 except that the temperature was changed to 45 ° C and 45 ° C. Table 3 shows the properties of this powder.

Example 15 Sample 11-1 in Example 11 was dried overnight at 110 ° C. in a constant temperature drier, and then pulverized to prepare spherical silica powder. Next, 28.4 g of magnesium nitrate (reagent grade Mg (NO ₃ O ₂ .6H ₂ O) manufactured by Wako Pure Chemical Industries, Ltd., 28.4 g) was weighed into a 500 ml beaker, 328 g of pure water was added, and the mixture was dissolved with stirring.
43.2 g of dried spherical silica (water 6%, 10% of MgO added to silica solids) was added little by little, and after the addition was completed, the mixture was further stirred for 1 hour and dried overnight at 110 ° C. constant temperature drying. Next, the dried block-like material was pulverized by a sample mill and calcined at 500 ° C. for 3 hours to obtain spherical magnesium silicate-based composite particles. Table 3 shows the properties of this powder.

Example 16 Spherical magnesium silicate-based composite particles were obtained in the same manner as in Example 15 except that magnesium nitrate was added so that MgO was 25%. Table 3 shows the properties of this powder.

[0090] Magnesium acetate instead of magnesium nitrate in Example 17 Example 15 (produced by Wako Pure Chemical Industries, Ltd. reagent first grade _{Mg (CH 3 COO) 2 ·} 4
Except for using H ₂ O), spherical magnesium silicate-based composite particles containing 10% of MgO were obtained in the same manner as in Example 15. Table 3 shows the properties of this powder.

[0091]

[Table 3]

Application Example 1 Application to Biaxially Stretched Polypropylene Film 100 parts by weight of a polypropylene resin powder (High Ball F657P manufactured by Mitsui Petrochemical Industries) is 0.15 parts of 2,6-di-tert-butyl paracresol and 0.1 part of calcium stearate. Parts and the additives shown in Table 4 were added,
After mixing with a super mixer for 1 minute, the mixture was melt-mixed at a kneading temperature of 230 ° C. using a single screw extruder and pelletized. An original film was formed from the above-mentioned pellet by T-die molding, and then stretched 5 times in the machine direction and 10 times in the transverse direction using a biaxial stretching machine to obtain a biaxially stretched film having a thickness of 25 μm.
The following tests were performed on the obtained films, and the results are shown in Table 4.

[0093]

[Table 4]

Haze: Measured by an automatic digital haze meter NDH-20D manufactured by Nippon Denshoku Co., Ltd. based on JIS K-6714. Blocking property: Two films are stacked, 200 g / c
After a load of m ² and left at 40 ° C. for 24 hours, the film was evaluated as follows according to its ease of peeling. ◎ Peeled without resistance ○ Slightly hard to peel off △ Hard to peel off × Extremely hard to peel off Fisheye: Film 400c by optical microscope
The number was 0.1 m / m or more in m ² . Scratchability: Two films were formed 5 hours after film formation. ◎ Little scratches ○ Slight scratches △ Slight scratches × Scratch

Application Example 2 Application to Unstretched Polypropylene Film 0.15 part of 2,6-di-tert-butylparacresol, 0.1 part of calcium stearate and the additives shown in Table 5 were added to 100 parts by weight of the polypropylene resin powder. Each was added, mixed for 1 minute with a super mixer, melt-mixed at a kneading temperature of 230 ° C. using a single screw extruder, and pelletized. Using the pellets, a non-stretched film having a thickness of 25 μ was obtained by T-die molding at the same temperature. The obtained film was evaluated for film in the same manner as in Application Example 1, and the results are shown in Table 5.

[0096]

[Table 5]

Application Example 3 Application to Polyethylene Film For a mixture of a linear low-density polyethylene having an MI of 1.3 / 10 minutes and a density of 0.92 and a low-density polyethylene having an MI of 1.1 / 3 minutes and a density of 0.93. The samples shown in Table 6 were added, and the mixture was melt-mixed at a temperature of 180 ° C. with an extruder and pelletized. Next, the pellets were supplied to an extruder and formed into a film having a thickness of 30 μm by a T-die method. The obtained film was subjected to film evaluation in the same manner as in Application Example 1, and the results are shown in Table 6.

[0098]

[Table 6]

Application Example 4 Application to matting agent for paint Acrylic urethane paint (Deep Black # 4 by Sekisui Co., Ltd.)
00), the sample shown in Table 7 was added thereto, and dispersed by a high-speed homomixer (2500 rpm) for 5 minutes.
The film was applied in a thickness of 150 μm using a film applicator of No. 1, and Table 7 shows the 60 ° specular reflectance, smoothness (bubble) and scratchability. With regard to the scratching property, the state of the scratch when rubbed with a coin was observed, and was shown as follows. ○ Almost no damage △ Slightly damaged × Significantly damaged

[0100]

[Table 7]

Comparative Example 1 Amorphous aluminosilicate particles were obtained in the same manner as in Example 1 except that MgO was not added. When the amount of wear of this product was measured, it was a large numerical value of 38 mg.

Comparative Example 2 The same treatment as in Example 7 was carried out except that the amount of MgO added was 55%, to obtain magnesium silicate-based particles. FIG. 8 shows an X-ray diffraction pattern of this product, and FIG.
, But were not recognized as regular particles.

Comparative Example 3 In Example 7, magnesium hydroxide (# 200 manufactured by Kamishima Chemical Co., Ltd.) was added to Sample 7-1 so that the amount of MgO became 30%. After sufficient dispersion, the mixture was filtered without heating, dried and dried. A magnesium acid-based particle powder was obtained. The X-ray diffraction diagram of this product is shown in FIG. 10, and a clear magnesium hydroxide peak was observed.
It was a mixture of spherical silica and magnesium hydroxide.

Comparative Example 4 The same treatment as in Example 11 was carried out except that the amount of MgO added in Example 11 was changed to 55%, to obtain magnesium silicate-based particles. The SEM photograph of this product is shown in FIG. 11, but was not recognized as a regular particle.

Comparative Example 5 Competitor silica (average particle size 2.7 μm, specific surface area 700 m)
² / g), the abrasion amount was measured and found to be as large as 42 mg.

[Brief description of the drawings]

FIG. 1 is a powder X-ray diffraction diagram of a coated particle powder of the present invention.

FIG. 2 shows an electron microscope (S) showing the structure of the coated particles of the present invention.
(EM) Photograph.

FIG. 3 is a powder X-ray diffraction diagram of another coated particle powder of the present invention.

FIG. 4 is an SEM photograph showing the structure of another coated particle of the present invention.

FIG. 5 is a powder X-ray diffraction diagram of another coated particle powder of the present invention.

FIG. 6 is a powder X-ray diffraction diagram of still another coated particle powder of the present invention.

FIG. 7 is an SEM showing the structure of still another coated particle of the present invention.
It is a photograph.

FIG. 8 is a powder X-ray diffraction chart of magnesium silicate particles other than the present invention shown in Comparative Example 2.

FIG. 9 is an SEM photograph showing the structure of the powder particles of Comparative Example 2.

FIG. 10 is an X-ray diffraction diagram of the particles shown in Comparative Example 3.

FIG. 11 is an SEM photograph showing the structure of the particles shown in Comparative Example 3.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Hideyuki Nakagawa 2-245, Johari, Meto-ku, Nagoya City, Aichi Prefecture East Hills Meito 210 (56) References JP-A-2-225314 (JP, A) JP-A-4 −220447 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C09C 1/28 C09C 1/48 C09C 3/06

Claims (7)

(57) [Claims] An amorphous silica, wherein each particle independently has a distinct cubic or spherical primary particle shape and a primary particle size of 0.3 to 20 μm as measured by electron microscopy. quality silica - and shaped core particles composed of at least one of alumina or amorphous aluminosilicate, the constant type nuclei
Reactive bond to silanol group or Al (OH) group on particle surface
And a coating layer of a magnesium compound. 2. The coating layer of the magnesium compound comprises magnesium hydroxide and a silanol group or an Al (OH) group.
The magnesium compound-coated particles according to claim 1 , which are formed by the reaction of the above. 3. The method according to claim 1, wherein the magnesium compound is Mg
The magnesium compound-coated particles according to claim 1, wherein the particles are coated at a ratio of 2 to 30% by weight in terms of O. 4. The magnesium compound-coated particles according to claim 1, wherein the refractive index of the magnesium compound-coated particles is in the range of 1.47 to 1.55. 5. Amorphous silica, amorphous, wherein each particle independently has a distinct cubic or spherical primary particle shape and a primary particle size of 0.3 to 20 μm as measured by electron microscopy. Having shaped core particles comprising at least one of porous silica-alumina or amorphous aluminosilicate
Magnesium hydroxide, acetic acid
At least one magnesium compound such as magnesium or magnesium nitrate is added, and a heat treatment is performed under normal pressure or under pressure, so that silanol groups or Al (O
Magneto having the magnesium compound reactively bonded to H) group
Forming a coating layer of a calcium compound;
An aqueous dispersion containing fixed particles having a cover layer as a dispersed phase
A method for producing particles coated with a magnesium compound, characterized by filtering or drying , and crushing or baking the obtained solid content at a temperature of 300 ° C to 800 ° C as required. 6. A resin molded article containing the magnesium compound-coated particles according to claim 1. 7. A paint or ink containing the magnesium compound-coated particles according to claim 1.