JPH05239377A - Production of surface-treated inorganic filler - Google Patents

Abstract

PURPOSE:To obtain the subject filler used for improving the physical properties of thermoplastic resins by grinding and classifying the mixture of an inorganic filler with a surface-treating agent using a vertical roll mill having a classification machine therein to perform the grinding and surface treatment of the inorganic filler. CONSTITUTION:The raw material mixture of a preliminarily coarsely ground inorganic filler with a surface-treating agent is charged into the raw material-charging port 9, fed on a rotated grinding table 4 disposed in the mill casing 2 of a vertical roll mill 1 and subsequently ground by the actions of the grinding table 4 and the grinding roller 5 loaded thereon. The ground product is upward carried with air charged from a ventilation route 12, and the particles passed through the space between the blades 6 of a rotated classification machine 7 is further carried up and subsequently discharged from the discharging port 14 together with the air. The discharged particles are separated from the air with a powder-separating machine 15 and then taken out from a product-discharging port 16 to provide the objective surface-treated inorganic filler. It is because the surfaces of the particles of the inorganic filler are treated with the coexisting surface-treating agent during the grinding of the inorganic filler.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a surface-treated inorganic filler, and in particular, it 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 Patent Laid-Open No. 62-87237 discloses a surface-treated powder in which a jet airflow type pulverizer is used to mechanochemically treat the powder with a surface treatment agent using the impact force of a jet airflow. Is disclosed. Further, JP-A-62-235350 discloses that ethylene.
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 treatment agent using a jet stream type pulverizer such as a fluidized bed jet pulverizer. The thing is disclosed. Further, in Japanese Patent Laid-Open No. 63-120758, a filler obtained by surface-treating talc with a titanium-based or aluminum-based coupling agent using a jet crusher at the time of crushing is blended with a thermoplastic resin. It is disclosed.

The surface-treated inorganic fillers described in these publications are produced by a so-called mechanochemical means in which the surface treatment is carried out while pulverizing the inorganic filler together with the surface treatment agent. Is also made using a jet stream crusher.

However, the method of pulverizing the inorganic filler by using the jet stream type pulverizer is not suitable for large-scale treatment of the filler, because of a large noise at the time of pulverization, a large amount of energy required per unit amount of treatment of the filler, and a large amount of energy. There are problems such as.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a surface-treated inorganic filler which has improved surface properties and can be blended with various thermoplastic resins to improve its physical properties. It is an object of the present invention to provide a method capable of being manufactured without causing the problems of the above-mentioned conventional techniques.

[0007]

According to the present invention, a mixture of an inorganic filler and a surface treatment agent is pulverized and classified by using a vertical roller mill having a classifier, thereby pulverizing the inorganic filler. A method for producing a surface-treated inorganic filler, characterized in that the surface treatment and the surface treatment are simultaneously performed.

Preferred aspects 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 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, wherein the surface-treating agent is a substance selected from the group consisting of stearic acid, rosin, a silane coupling agent, and a titanate coupling agent. Manufacturing method.

(3) The surface-treated inorganic material characterized in that the surface treatment agent is contained in an amount of 0.01 to 10 parts by weight relative to 100 parts by weight of the inorganic filler. A method for manufacturing a filler.

(4) The vertical roller mill includes a crushing means which is composed of a crushing table which rotates in the main body and a crushing roller which is rotated by being pressed by the upper surface of the crushing table, and a rotation which is provided above the crushing means. A method for producing the surface-treated inorganic filler as described above, which is a mill having a classifier for

(5) The method for producing a surface-treated inorganic filler as described above, which comprises pulverizing the inorganic filler until a powder having an average particle size of 5 μm or less is obtained.

(6) A method for producing a surface-treated inorganic filler, which comprises classifying the surface-treated inorganic filler produced by the above-mentioned production method to produce a powder having a maximum particle size 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 comprises a pulverizing table which rotates in the main body and a pulverizing roller which is driven to rotate while being pressed by the upper surface of the pulverizing table, and pulverizing means for pulverizing an object to be crushed under pressure.
And a mill having a rotating classifier provided above the crushing means

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

In FIG. 1, a vertical roller mill 1 has a crushing means in a mill casing 2 which comprises a crushing table 4 rotated by a motor 3 and a crushing roller 5 which is driven by the upper surface of the crushing table 4 and is driven to rotate. 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 air stove 11 to the inside of the mill, and below the mill casing 2 is a transport machine for circulating uncrushed materials. 13 are provided. A discharge port 14 for discharging the crushed material together with air is provided on the upper portion of the mill casing 2. The discharge port 14 is connected to a powder separator 15 (for example, a bag filter) and an exhaust fan 17.

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

A raw material mixture of an inorganic filler and a surface-treating agent, which has been roughly crushed in advance, is placed in the raw material charging port 9, and a supply chute 10 is provided.
To 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 its own weight and the action of springs, hydraulic cylinders, etc. It's spinning. Therefore, the raw material mixture supplied to the upper surface of the crushing table 4 is crushed by the action of the crushing table 4 and the crushing roller 5 and gradually moves in the outer peripheral direction of the crushing table 4. During the pulverization of the inorganic filler, the surface of the particles of the inorganic filler is treated by the coexisting surface treatment agent, and the surface treatment agent is firmly bound to the surface of the particles of the inorganic filler by the mechanochemical effect.

Small particles (surface-treated inorganic filler particles) of the pulverized product are carried upward by the air from the ventilation passage 12, and particles passing between the blades 6 of the rotating classifier 7 are Further, it is carried to the upper side and is discharged together with air from the discharge port 14. The particles discharged from the discharge port 14 are
It 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 caused by the rotation of the blade 6 and the coarse particles that have not reached the blade 6 fall on the crushing table 4 and are crushed again.

Large particles of the crushed material from the crushing table 4 fall inside the ventilation path 12 against the air from the ventilation path 12, are circulated to the supply chute 10 through the transportation machine 13, and are again crushed by the crushing table 4. Is supplied to the upper surface of and subjected to a crushing process.

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

If desired, hot air heated to a desired temperature may be sent from the hot air oven 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, magnesium carbonate. , Calcium silicate, magnesium silicate, calcium sulfate, barium sulfate, calcium sulfite, talc, mica, clay, dolomite, basic magnesium carbonate, glass and the like. Particularly, heavy calcium carbonate (limestone is pulverized by dry or wet method, washed with water and then dried) and talc are preferable. The above-mentioned inorganic filler is preliminarily 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 are 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 thereof include γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-chloropropyltrimethoxysilane.

Examples of titanate coupling agents include isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditrityl). Decylphosphite) titanate, tetra (2,2-
Diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl iso Stearoyl diacrylic titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, isopropyl tri (N-amidoethyl aminoethyl) titanate, dicumyl phenyloxyacetate titanate, diisostearoyl ethylene titanate, etc. can be mentioned. ..

The amount ratio of the surface treatment agent to the inorganic filler varies depending on the kind of the surface treatment agent and the use of the treated inorganic filler, but generally 0.01 to 10 parts by weight of the surface treatment agent to 100 parts by weight of the inorganic filler. It is preferably 0.5 part by weight, especially 0.5 to 5 parts by weight. When the amount of the surface treatment agent is larger than the above range, the raw material tends to slip during the crushing and is not caught between the crushing table 4 and the crushing roller 5, and the crushing ability tends to be lowered, and when the amount is less than the above range. ,
The surface cannot be uniformly treated, and the impact strength of the added resin is not improved so much.

The pulverization of the inorganic filler in the present invention is 5 μm.
It is preferable to carry out until a powder having an average particle diameter of m or less is obtained. The average particle size of the obtained powder can be easily controlled by controlling the pulverization conditions as described above.

The surface-treated inorganic filler produced by the production method of the present invention is subjected to an appropriate 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 by using. It is preferred to use a classifier to produce a surface-treated inorganic filler powder having a maximum particle size of 8 μm or less, especially 5 μm or less. The powder having a larger particle size obtained by a classifier can be used as a raw material in the production method of the present invention and further pulverized.

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

Examples of the above-mentioned thermoplastic resins include polyolefins such as polyethylene, polypropylene and ethylene-α-olefin copolymers, polyamides such as 6-nylon, 66-nylon and 12-nylon, polyethylene terephthalate and polyethylene naphthalate. Such as polyester, polyacetal, and the like.

The mixing ratio of the surface-treated inorganic filler to the thermoplastic resin is 3 with respect to 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]

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

[Embodiment 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 vertical roller mill was rotated at a rotation speed of 50 rpm of the crushing table 4 and a rotation speed of 1000 rpm of the classifier 7.
Coarse pulverized product of high-purity heavy calcium carbonate (55.8% as CaO) (passing through a sieve with 40 mm openings) while operating at a flow rate of 50 m ³ / min. Then, a mixture of 100 parts by weight of an average particle size of 15 mm) and 3 parts by weight of stearic acid was charged into the vertical roller mill from the raw material charging port 9 at a rate of 100 kg / hour.

From the product outlet 16, a surface-treated ground calcium carbonate powder 1A having the properties shown in Table 1 is obtained.
Got

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

[Example 2] Ground calcium carbonate was crushed 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, and from the product outlet 16,
A surface-treated ground calcium carbonate powder 2A having the properties shown in Table 1 was obtained.

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

[Example 3] Heavy calcium carbonate was carried out 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 (Plainact KR-TTS manufactured by Ajinomoto Co., Inc.). Was ground and the surface-treated heavy calcium carbonate taken out from the product take-out port 16 was classified using the same dry classifier as used in Example 1 to obtain a powder having the properties shown in Table 1. 3C
Got

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

This powder 4A was classified using the same dry classifier 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 are 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: Laser diffraction type particle size analyzer (manufactured by Nikkiso Co., Ltd .: Microtrack). Apparent specific gravity: JIS K6223 (calcium carbonate for rubber) DOP Absorption: Conforms to JIS K6223 (calcium carbonate for rubber) Whiteness: Hunter whiteness (Nippon Denshoku SZ-Σ80)

Next, reference examples in which the surface-treated heavy calcium carbonate obtained in the examples is blended in a thermoplastic resin, and comparative reference examples in which the control powder or the conventional additives are blended in 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 powder of the surface-treated heavy calcium carbonate obtained in the example were dry-blended, and the resulting mixture was mixed using a Ube Industries, Ltd. twin-screw kneader 2.UCM. Melt kneading was performed at 220 ° C. to prepare chips, and each test piece was molded from the chips.

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

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

[0049]

[Table 2]

Reference Example 2 60 parts by weight of chip-like 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 was melt-kneaded using a twin-screw kneader (PCM-45 manufactured by Ikegai Tekko Co., Ltd.) at an outlet temperature of about 270 ° C. (calcium carbonate was added from the middle of the kneader), and then a pelletizer. Were pelletized, and each test piece was molded from this pellet.

The physical properties of the nylon composition containing the above-mentioned heavy calcium carbonate were evaluated. The measurement results of each physical property are shown in Table 3.

COMPARATIVE REFERENCE EXAMPLE 2 Reference Example 1 except that the same amount of control powder or wollastonite shown in Table 1 was used in place of the surface-treated ground calcium carbonate powder obtained in the example. In the same manner as in, to produce a nylon composition,
Physical properties were evaluated in the same manner as in Reference Example 2. The measurement results of each physical property are shown in Table 3.

[0053]

[Table 3]

From the results shown in Tables 2 and 3, the surface-treated heavy calcium carbonate produced according to the present invention, when blended with the thermoplastic resin, has a remarkable impact strength without sacrificing other physical properties. It is obvious to improve.

[0055]

The method for producing a surface-treated inorganic filler according to the present invention has improved surface characteristics and can be incorporated into various thermoplastic resins to improve its physical properties. The material is remarkably excellent in that it can be easily and efficiently manufactured.

[Brief description of drawings]

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

[Explanation of Codes] 1 vertical roller mill, 2 mill casing, 3 motor, 4 grinding table, 5 grinding roller, 6 blades, 7 classifier,
8 motor, 9 raw material charging port, 10 supply chute, 11 hot air stove, 12 ventilation passage, 13 transport machine, 14 discharge port, 15 powder separator, 1
6 material outlet, 17 exhaust fan.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Kenichiro Matsuda, 8-4 Goi Minamikaigan, Ichihara-shi, Chiba Stock Company Calceed (72) Inventor Kazuhiro Segawa 8-4 Goiminamikaigan, Ichihara-shi, Chiba Stock Association In the company Calceed (72) Inventor Naohiko Sasaki 8-4 Goi Minamikaigan, Ichihara, Chiba Stock Company Calceed (72) Inventor Tetsuzo Hironaga 8-4 Goi Minamikaigan, Ichihara, Chiba Stock Company Calcied

Claims (1)

[Claims] 1. A mixture of an inorganic filler and a surface treatment agent,
A method for producing a surface-treated inorganic filler, which comprises pulverizing and classifying an inorganic filler at the same time by pulverizing and classifying using a vertical roller mill having a classifier.