JP2909519B2 - Method for producing surface-treated inorganic filler - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a surface-treated inorganic filler, and more particularly, to a method for producing a surface-treated inorganic filler which has improved surface properties and can be incorporated into various thermoplastic resins to improve its physical properties. The present invention relates to a method for producing a surface-treated inorganic filler.

[0002]

2. Description of the Related Art Conventionally, it has been proposed to add a surface-treated inorganic filler to a thermoplastic resin for the purpose of increasing the physical properties of the thermoplastic resin, particularly the impact strength.

For example, Japanese Unexamined Patent Publication (Kokai) No. 62-87237 discloses a surface-treated powder in which a powder is mechanochemically treated with a surface-treating agent by using an impact force of a jet airflow using a jet airflow type pulverizer. Is disclosed. Japanese Patent Application Laid-Open No. Sho 62-235350 discloses that ethylene
A composition in which a blend of a propylene block copolymer and an ethylene / propylene copolymer rubber is blended with an inorganic filler pulverized together with a surface treating agent using a jet stream type pulverizer such as a fluidized bed type pulverizer. Is disclosed. Japanese Unexamined Patent Publication (Kokai) No. 63-120758 discloses that a filler obtained by surface-treating talc with a titanium-based or aluminum-based coupling agent at the time of pulverization using a jet pulverizer is mixed with a thermoplastic resin. It has been disclosed.

[0004] The surface-treated inorganic fillers described in these publications are made by so-called mechanochemical means for performing a surface treatment while pulverizing the inorganic filler together with a surface treating agent. Was also made using a jet stream crusher.

[0005] However, the method of pulverizing the inorganic filler using a jet stream type pulverizer has a large noise at the time of pulverization, requires a large amount of energy per unit processing amount of the filler, and is not suitable for mass processing of the filler. There are problems such as.

[0006]

The object of the present invention is to provide a surface-treated inorganic filler which has improved surface properties and can be incorporated into various thermoplastic resins to improve its physical properties. It is an object of the present invention to provide a method that can be manufactured without causing the problems of the related art as described above.

[0007]

According to the present invention, an inorganic filler and a surface treating agent are introduced on a pulverizing table in a vertical roller mill having a classifier therein, and the introduced inorganic filler is introduced on the pulverizing table. By crushing the filler in the presence of the surface treatment agent, the inorganic filler is crushed and the crushed material is subjected to a surface treatment with the surface treatment agent. The surface-treated fine pulverized material is separated and recovered by this contact, while the coarsely pulverized material with insufficient surface treatment is returned to the pulverization table, and the pulverization and the surface treatment are performed again. And producing a surface-treated inorganic filler.

[0008] Preferred embodiments of the present invention are as follows. (1) The inorganic filler is heavy calcium carbonate, light calcium carbonate, calcium oxide, magnesium oxide, silicon oxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, magnesium carbonate, calcium silicate, magnesium silicate, A method for producing the above-mentioned surface-treated inorganic filler, which is calcium sulfate, barium sulfate, calcium sulfite, talc, mica, clay, dolomite, basic magnesium carbonate, or glass.

(2) The surface-treated inorganic filler as described above, wherein the surface-treating agent is a substance selected from the group consisting of stearic acid, rosin, silane-based coupling agents, and titanate-based coupling agents. Manufacturing method.

(3) The surface-treated inorganic material, wherein the amount ratio of the surface-treating agent to the inorganic filler is 0.01 to 10 parts by weight based on 100 parts by weight of the inorganic filler. Manufacturing method of filler.

(4) The vertical roller mill has a crushing means comprising a crushing table rotating in the main body, and a crushing roller which is driven and rotated while being pressed against the upper surface of the crushing table, and a rotation provided above the crushing means. A method for producing a surface-treated inorganic filler, comprising: a mill having a classifier.

(5) The method for producing a surface-treated inorganic filler as described above, wherein the pulverization of the inorganic filler is performed until a powder having an average particle diameter of 5 μm or less is obtained.

(6) A method for producing a surface-treated inorganic filler characterized by classifying the surface-treated inorganic filler produced by the above-mentioned production method to produce a powder having a maximum particle diameter of 8 μm or less.

A vertical roller mill used in the present invention will be described with reference to the accompanying drawings. The vertical roller mill used in the present invention is a crushing means for pinching and crushing an object to be crushed, comprising a crushing table rotating in a main body and a crushing roller driven and rotated while being pressed against the upper surface of the crushing table,
And a mill having a rotating classifier provided above the grinding means.

FIG. 1 is a schematic sectional view showing an example of a vertical roller mill used in the present invention.

Referring to FIG. 1, a vertical roller mill 1 has a milling means comprising a milling table 4 rotated by a motor 3 and a milling roller 5 driven and rotated while being pressed against the upper surface of the milling table 4 in a mill casing 2. A classifier 7 having a blade 6 is provided above the crushing means so as to be rotatable by a motor 8. A supply chute 10 for supplying the raw material from the raw material charging port 9 onto the crushing table 4 is provided so as to open above the crushing table 4. An air passage 12 is provided between the crushing table 4 and the mill casing 2 for sending air from the hot blast stove 11 to the inside of the mill, and a transport machine for circulating uncrushed material is provided below the mill casing 2. 13 are provided. A discharge port 14 for discharging the pulverized material together with air is provided at an upper portion of the mill casing 2. The outlet 14 is connected to a powder separator 15 (for example, a bag filter) and further to an exhaust fan 17.

Using a vertical roller mill 1 shown in FIG.
A method for producing a surface-treated inorganic filler according to the present invention will be described.

A raw material mixture of an inorganic filler and a surface treatment agent, which have been coarsely pulverized in advance, is put into a raw material charging inlet 9 and a supply chute 10
From the crushing table 4. The crushing table 4 is rotating, and the crushing roller 5 placed on the crushing table 4 is pressed against the upper surface of the crushing table 4 by the action of its own weight and the action of a spring, a hydraulic cylinder, and the like. It is spinning. Therefore, the raw material mixture supplied to the upper surface of the pulverizing table 4 is pulverized by the action of the pulverizing table 4 and the pulverizing roller 5 and gradually moves toward the outer periphery of the pulverizing table 4. During the pulverization of the inorganic filler, the surface of the particles of the inorganic filler is treated by the coexisting surface treating agent, and the surface treating agent is strongly bonded to the surface of the particles of the inorganic filler by a mechanochemical effect.

Small particles (powder-treated inorganic filler particles) of the pulverized material are carried upward by the air from the ventilation passage 12, and the particles passing between the rotating blades 6 of the classifier 7 It is further carried upward, and is discharged together with air from the outlet 14. The particles discharged from the outlet 14 are
The powder is separated from the air by the powder separator 15 and taken out from the product outlet 16 as a product of the surface-treated inorganic filler. The coarse particles classified by the swirling airflow generated by the rotation of the blade 6 and the coarse particles that have not reached the blade 6 fall onto the crushing table 4 and are crushed again.

The large particles of the pulverized material from the pulverizing table 4 fall in the ventilation path 12 against the air from the ventilation path 12, are circulated to the supply chute 10 through the transport device 13, and are again crushed. Is supplied to the upper surface of the substrate and undergoes a pulverization process.

The size of the particles from the product outlet 16 depends on the charged amount of the raw material mixture, the pressing force of the crushing roller 5, the rotation speed of the crushing table 4, the amount of ventilation from the ventilation passage 12, the blade 6.
By controlling crushing conditions such as the length, mounting radius and number, and the rotation speed of the classifier 7, it can be appropriately changed.

If necessary, hot air heated to a desired temperature may be sent from the hot blast stove 11.

Examples of the inorganic filler used as a raw material in the present invention include heavy calcium carbonate, light calcium carbonate, calcium oxide, magnesium oxide, silicon oxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, and magnesium carbonate. , Calcium silicate, magnesium silicate, calcium sulfate, barium sulfate, calcium sulfite, talc, mica, clay, dolomite, basic magnesium carbonate, glass and the like. In particular, heavy calcium carbonate (which is obtained by pulverizing limestone by a dry or wet method, washing with water, and then drying) and talc are preferable. The above-mentioned inorganic filler is supplied after being coarsely pulverized to a particle size suitable for the model number (size) of the vertical roller mill.

The surface treating agent used in the present invention is preferably a substance selected from the group consisting of stearic acid, rosin, silane coupling agents, and titanate coupling agents.

Examples of silane coupling agents include vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, β- (3,4 -Epoxycyclohexyl)
Ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl)
Examples include γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-chloropropyltrimethoxysilane.

Examples of titanate-based coupling agents include isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, and tetraoctyl bis (ditrityl). (Decyl phosphite) titanate, tetra (2,2-
Diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropyliso Stearoyl diacryl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, isopropyl tri (N-amidoethyl aminoethyl) titanate, dicumyl phenyloxy acetate titanate, diisostearoyl ethylene titanate, and the like can be given. .

The amount ratio of the surface treating agent to the inorganic filler varies depending on the type of the surface treating agent and the use of the treated inorganic filler. Generally, 0.01 to 10 parts by weight of the surface treating agent per 100 parts by weight of the inorganic filler. It is preferable that the amount be 0.5 parts by weight, especially 0.5 to 5 parts by weight. When the amount of the surface treating agent is larger than the above range, the raw material slips during the pulverization, so that the raw material does not bite between the pulverizing table 4 and the pulverizing roller 5 and the pulverizing ability tends to decrease. ,
The surface cannot be uniformly treated, and the impact strength of the added resin is not significantly improved.

In the present invention, the pulverization of the inorganic filler is 5 μm.
It is preferably carried out until a powder having an average particle size of not more than m is obtained. The average particle size of the obtained powder can be easily controlled by controlling the above-mentioned pulverization conditions.

[0029] The surface-treated inorganic filler produced by the production method of the present invention is subjected to a suitable classification device, for example, a dry classification device using a fixed blade (or blade) or a rotating blade (or blade) and an air flow. It is preferable to further classify using. It is preferred to produce a powder of a surface-treated inorganic filler having a maximum particle size of 8 μm or less, particularly 5 μm or less using a classifier. The powder having a larger particle size obtained by the classifier can be used as a raw material in the production method of the present invention and further pulverized.

The surface-treated inorganic filler prepared according to the present invention can be blended with various thermoplastic resins to significantly increase the physical properties of the resin, particularly the impact strength.

Examples of the thermoplastic resin include polyolefins such as polyethylene, polypropylene and ethylene-α-olefin copolymer, polyamides such as 6-nylon, 66-nylon and 12-nylon, polyethylene terephthalate and polyethylene naphthalate. And polyester, polyacetal, and the like.

The mixing ratio of the surface-treated inorganic filler to the thermoplastic resin is 3 parts per 100 parts by weight of the thermoplastic resin.
It is preferably from 100 to 100 parts by weight, particularly preferably from 10 to 90 parts by weight.

[0033]

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples.

[Example 1] As a pulverizer, a vertical roller mill as shown in FIG.
m, blade: effective length 450 mm, width 50 mm, effective mounting radius 400 mm, 24 sheets) were used.

The above-mentioned vertical roller mill was rotated at a rotation speed of the grinding table 4 of 50 rpm and a classifier 7 of 1000 rpm.
m., while operating at an air flow rate of 50 m ³ / min from the ventilation passage 12, coarsely ground high-purity heavy calcium carbonate (55.8% as CaO) (passed through a 40 mm sieve). Then, a mixture of 100 parts by weight of average particle size (15 mm) and 3 parts by weight of stearic acid was charged into the vertical roller mill from the raw material charging inlet 9 at a rate of 100 kg / hour.

From the product outlet 16, surface-treated heavy calcium carbonate powder 1 A having the properties shown in Table 1
I got

The powder 1A was classified using a dry classifier (UFC-200 manufactured by Ube Industries, Ltd.),
Powder 1B and powder 1C having the properties shown in the table were obtained.

Example 2 Heavy calcium carbonate was pulverized in the same manner as in Example 1 except that 3 parts by weight of stearic acid was changed to 5 parts by weight of rosin.
A surface-treated heavy calcium carbonate powder 2A having the properties shown in Table 1 was obtained.

This powder 2A was classified using the same dry classification apparatus as used in Example 1 to obtain powder 2B having the properties shown in Table 1.

Example 3 Heavy calcium carbonate was prepared in the same manner as in Example 1, except that 3 parts by weight of stearic acid was changed to 1 part by weight of a titanate coupling agent (manufactured by Ajinomoto Co., Inc .: Plenact KR-TTS). Is ground, and the surface-treated heavy calcium carbonate taken out from the product outlet 16 is classified using the same dry classifier as used in Example 1 to obtain powder having the properties shown in Table 1. 3C
I got

Example 4 3 parts by weight of stearic acid were combined with a silane coupling agent (KPN, manufactured by Shin-Etsu Chemical Co., Ltd.).
-3504) The heavy calcium carbonate is pulverized in the same manner as in Example 1 except that the weight is changed to 1 part by weight, and the surface-treated heavy carbonic acid having the properties shown in Table 1 is obtained from the product outlet 16. Calcium powder 4A was obtained.

This powder 4A was classified using the same dry classification device as used in Example 1 to obtain powder 4B having the properties shown in Table 1.

[0043]

[Table 1]

The properties shown in Table 1 were measured by the following methods. Specific surface area: Blaine specific surface area according to JIS R5201 (physical test method for cement) Maximum particle size and average particle size: Measured by a laser diffraction particle size analyzer (Nikkiso Co., Ltd .: Microtrac). Apparent specific gravity: JIS K6223 (calcium carbonate for rubber) DOP absorption: Complies with JIS K6223 (calcium carbonate for rubber) Whiteness: Hunter whiteness (color difference meter SZ- # 80 manufactured by Nippon Denshoku Co., Ltd.)

Next, a reference example in which the surface-treated heavy calcium carbonate obtained in the examples was blended with a thermoplastic resin, and a comparative reference example in which the control powder or the conventional additive was blended with the same thermoplastic resin are shown. .

Reference Example 1 Granular polypropylene (manufactured by Ube Industries, Ltd .: J709HK: physical properties are shown in Table 2)
80 parts by weight and 20 parts by weight of the surface-treated heavy calcium carbonate powder obtained in the examples were dry-blended, and the obtained mixture was mixed with a Uaxial Kosan Co., Ltd. twin-screw kneader 2.UCM. Chips were prepared by melt kneading at 220 ° C., and each test piece was formed from the chips.

The properties of the polypropylene composition containing the above-mentioned heavy calcium carbonate were evaluated. Table 2 shows the measurement results of each physical property.

Comparative Reference Example 1 Instead of the surface-treated heavy calcium carbonate powder obtained in the example, the same amount of the control powder shown in Table 1 or a commercially available colloidal calcium carbonate for filling polypropylene was used. Otherwise, a polypropylene composition was produced in the same manner as in Reference Example 1, and
The physical properties were evaluated in the same manner as in the above. Table 2 shows the measurement results of each physical property.

[0049]

[Table 2]

[Reference Example 2] 60 parts by weight of chip-shaped nylon (UBE Nylon 1013B manufactured by Ube Industries, Ltd .; physical properties are shown in Table 3) and the surface-treated heavy calcium carbonate powder obtained in Example 4 40 parts by weight were melt-kneaded using a twin-screw kneader (PCM-45, manufactured by Ikegai Iron Works Co., Ltd.) at an outlet temperature of about 270 ° C. (calcium carbonate was added from the middle of the kneader) and then a pelletizer. , And each test piece was formed from the pellet.

The properties of the nylon composition containing the above calcium carbonate were evaluated. Table 3 shows the measurement results of each physical property.

Comparative Reference Example 2 Reference Example 1 was repeated except that the same amount of control powder or wollastonite shown in Table 1 was used in place of the surface-treated heavy calcium carbonate powder obtained in the example. Producing a nylon composition in the same manner as in
Physical properties were evaluated in the same manner as in Reference Example 2. Table 3 shows the measurement results of each physical property.

[0053]

[Table 3]

From the results in Tables 2 and 3, it can be seen that the surface-treated heavy calcium carbonate produced according to the present invention, when blended with a thermoplastic resin, has a remarkable impact strength without sacrificing other physical properties. It is clear that it improves.

[0055]

The method for producing a surface-treated inorganic filler according to the present invention has improved surface properties and can be blended with various thermoplastic resins to improve the physical properties thereof. The material has a remarkably excellent effect that the material can be easily and efficiently manufactured.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing an example of a vertical roller mill used in the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Vertical roller mill 2 Mill casing 3 Motor 4 Grinding table 5 Grinding roller 6 Blade 7 Classifier 8 Motor 9 Raw material loading port 10 Supply chute 11 Hot blast stove 12 Ventilation path 13 Transporter 14 Discharge port 15 Powder separator 16 Product outlet 17 Exhaust fan

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kenichiro Matsuda 8-4 Goi-minamikaigan, Ichihara-shi, Chiba Prefecture Within Calced Co., Ltd. (72) Inventor Kazuhiro Segawa 8-4 Goi-minamikaigan, Ichihara-shi, Chiba Prefecture Calcedo Co., Ltd. (72) Inventor Naohiko Sasaki 8-4 Goi-Minamikaigan, Ichihara-shi, Chiba Prefecture Inside Calcedo Co., Ltd. (72) Inventor Tetsuzo Hironaga 8-4 Goi-minamikaigan, Ichihara-shi, Chiba Prefecture Co., Ltd. (56) Reference Reference JP-A-52-119482 (JP, A) JP-A-61-141767 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C09C 1/00-3/12 B02C 4 / 00

Claims (1)

(57) [Claims] An inorganic filler and a surface treating agent are introduced onto a pulverizing table in a vertical roller mill having a classifier therein,
On the pulverizing table, the introduced inorganic filler is pulverized in the presence of a surface treating agent, whereby the inorganic filler is pulverized and the pulverized material is subjected to a surface treatment with a surface treating agent. Is placed in an air stream and brought into contact with a classifier equipped with a rotating blade to separate and collect surface-treated fine pulverized matter, while the coarse pulverized matter with insufficient surface treatment is placed on a pulverizing table. A method for producing a surface-treated inorganic filler, which is returned and the pulverization and the surface treatment are performed again.