TW201711826A - Extruder and method for manufacturing thermoplastic resin composition using the same solving the problem occurred when melt-kneading a thermoplastic resin with a low melting point additive - Google Patents

Abstract

An object of the present invention is to solve the problem occurred when melt-kneading a thermoplastic resin with a low melting point additive. The present invention provides an extruder capable of manufacturing a thermoplastic resin composition having uniform physical properties with higher stability and higher productivity, and a method for manufacturing the thermoplastic resin composition using the extruder. The extruder of the present invention is characterized in having a raw material supplying port to which a raw material supplying line is connected, wherein the raw material supplying line has a cooling gas supplying line communicated with at least a part thereof. In addition, the method for manufacturing the thermoplastic resin composition of the present invention is characterized in using the extruder.

Description

Extruder and method of manufacturing thermoplastic resin composition using same

The present invention relates to an extruder having a cooling gas supply line and a method of producing a thermoplastic resin composition using the same.

In the production of a thermoplastic resin composition produced industrially, a low-melting-point additive (for example, an additive having a melting point of 40 to 200 ° C) is added, and the thermoplastic resin is supplied to the extruder through a raw material supply line, and these are supplied. Melt and knead.

At this time, there is a case where the temperature of the low melting point additive reaches a temperature exceeding the melting point. Therefore, the low melting point additive is melted inside the raw material supply line, and the low melting point additive functions as an adhesive for the other raw materials. In this case, there is a case where the raw material becomes a large block and the inner wall of the feeder screw, the supply pipe, and the hopper are clogged.

For example, Patent Document 1 discloses a technique of raising a mixture of a vinyl chloride resin and a plurality of additives to a temperature exceeding a softening point of a vinyl chloride resin, fusing various additives to the surface of the resin, and preventing the inorganic filler from sticking. The mixture is cooled to below the softening point of the low melting point additive on the surface of the resin, and then an inorganic compound filler is added to the cooled mixture to prevent the mixture from forming a bridge in the hopper of the extruder (larger block) .

Further, Patent Document 2 discloses a technique of reducing the temperature of a cylinder of a side feeder to 15 to 100 ° C, and supplying an additive to an extruder via a side feeder.

Further, Patent Document 3 discloses a technique in which the melting point is 40 to 200 ° C. When the phosphorus-based flame retardant is supplied to the supply port of the extruder, the gas is intermittently blown at or near the supply port to remove the block.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 8-302026

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2003-285317

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2014-074094

However, in the technique of Patent Document 1, there is a problem that even if the mixture of the low melting point additive and the thermoplastic resin is cooled to 50 ° C or lower, the inside of the raw material supply line of the mixture containing the low melting point additive is not sufficiently cooled. Therefore, the inside of the raw material supply line still becomes a high temperature, and adhesion occurs inside the raw material supply line.

Further, in the technique of Patent Document 2, the material of the side feeder is cooled by water, but the cooling is not sufficiently considered, and the raw material supply line is still at a high temperature, and adhesion occurs inside the raw material supply line. .

Further, in the technique of Patent Document 3, the gas is intermittently blown, but since the inside of the raw material supply line is not sufficiently cooled, the low-melting-point additive is melted and adheres to the wall, and the deposit is further solidified and removed. Gradually become difficult.

An object of the present invention is to solve the above problems in the case of melt-kneading a thermoplastic resin and a low-melting-point additive, and to provide an extruder capable of producing a thermoplastic resin composition having uniform physical properties with high stability and high productivity. And a method of producing a thermoplastic resin composition using the extruder.

The inventors have conducted diligent research and found that by using a raw material supply line having at least one cooling gas supply device connected thereto and supplying the above-mentioned raw material supply line with The above-described problems can be advantageously solved by the extruder in which the first supply port is connected and the method of producing the thermoplastic resin composition using the same, and the present invention has been completed.

The gist of the present invention is as follows.

[1] An extruder comprising a raw material supply port to which a raw material supply line is connected, wherein the raw material supply line is provided with a cooling gas supply line that communicates with at least a part thereof.

[2] The extruder according to [1], wherein the cooling gas supply line is provided with a cooler.

[3] The extruder according to [2], wherein the cooler is a vortex cooler.

[4] The extruder according to any one of [1] to [3] comprising a plurality of the cooling gas supply lines.

[5] The extruder according to any one of [1] to [4] comprising a plurality of the raw material supply ports.

[6] The extruder according to any one of [1], wherein the raw material supply line sequentially includes a raw material storage tank, a raw material cutting device, a raw material supply device, and a raw material supply toward the raw material supply port. The piping and the raw material supply hopper, and the cooling gas supply line is in communication with the raw material supply hopper.

[7] The extruder according to any one of [1] to [6] further comprising a heat insulating material covering at least a part of an outer surface of the extruder.

[8] The extruder according to any one of [1] to [7] wherein the cooling gas supply line extends in a direction orthogonal to an axial direction of the extruder.

[9] The extruder according to any one of [1] to [8] wherein the cooling gas supply line is disposed at a distance from the axis of the extruder to a diameter D of the cylinder D of 1 to 500 times. The area of the location.

[10] The extruder according to any one of [1] to [9] wherein the raw material supply device is a weight type feeder.

[11] The extruder according to any one of [1] to [10] wherein the above extruder is a single shaft extruder or a twin shaft extruder.

[12] A method for producing a thermoplastic resin composition, characterized in that the thermoplastic resin and the additive having a melting point of 40 to 200 ° C are melt-kneaded by using the extruder according to any one of [1] to [11]. .

[13] The method for producing a thermoplastic resin composition according to [12], wherein the thermoplastic resin is a polyphenylene ether resin or a polycarbonate resin, and the additive having a melting point of 40 to 200 ° C is a phosphorus flame retardant. Agent.

[14] The method for producing a thermoplastic resin composition according to [13], wherein the phosphorus-based flame retardant is a phosphate compound or a phosphazene compound.

[15] The method for producing a thermoplastic resin composition according to [14], wherein the phosphazene compound is a phenoxyphosphazene compound.

[16] The method for producing a thermoplastic resin composition according to [14] or [15] wherein the phosphate compound is triphenyl phosphate.

The method for producing a thermoplastic resin composition according to any one of the above aspects, wherein the thermoplastic resin and the above-mentioned additive having a melting point of 40 to 200 ° C further comprise a liquid additive and a filler. Melt and knead.

[18] The method for producing a polyphenylene ether-based resin composition according to the invention of claim 12, wherein the polyphenylene is produced by using the extruder according to any one of [1] to [11] In the method of the ether resin composition, the total mass of the polyphenylene ether, the styrene resin, the fibrous filler, and the triphenyl phosphate is 90% by mass or more, and the total mass is 100% by mass and the polyphenylene is contained. The raw materials of 25 to 85% by mass of ether, 0 to 30% by mass of styrene resin, 10 to 50% by mass of fibrous filler, and 5 to 20% by mass of triphenyl phosphate are melted and kneaded.

[19] The method for producing a polyphenylene ether resin composition according to [18], wherein the cooling gas supply line includes a vortex cooler, and the cooling gas is nitrogen.

[20] The method for producing a polyphenylene ether-based resin composition according to [18] or [19] wherein the extruder is a twin-screw extruder.

The method for producing a polyphenylene ether-based resin composition according to any one of the aspects of the present invention, wherein the fibrous filler comprises glass fibers.

The method for producing a polyphenylene ether-based resin composition according to any one of the aspects of the present invention, wherein the fibrous filler comprises carbon fibers.

According to the present invention, a thermoplastic resin composition having uniform physical properties can be produced with high stability and high productivity.

1‧‧‧Extrusion machine

2‧‧‧Material supply pipeline

2-1‧‧‧1st raw material supply pipeline

2-2‧‧‧Second raw material supply pipeline

3‧‧‧Cooling gas supply line

3-1‧‧‧1st cooling gas supply line

3-1A‧‧‧1A cooling gas supply line

3-1B‧‧‧1B cooling gas supply line

3-2‧‧‧2nd cooling gas supply line

3-2A‧‧‧2A cooling gas supply line

3-2B‧‧‧2B cooling gas supply line

4‧‧‧Insulation

10‧‧‧Bowl

10a‧‧‧1st barrel

10l‧‧‧12th barrel

11‧‧‧Material supply port

11-1‧‧‧1st raw material supply port

11-2‧‧‧2nd material supply port

12‧‧‧ venting holes

12-1‧‧‧1st vent

12-2‧‧‧2nd exhaust hole

13‧‧‧Mold head

20‧‧‧Material supply hopper

21‧‧‧Material storage tanks

22‧‧‧Material cutting device

23‧‧‧Material supply device

24‧‧‧Material supply piping

31‧‧‧ chiller

201‧‧‧1st raw material supply hopper

202‧‧‧Second raw material supply hopper

211‧‧‧1st raw material storage tank

211A‧‧‧1A raw material storage tank

211B‧‧‧1B raw material storage tank

211C‧‧‧1C raw material storage tank

212‧‧‧Second raw material storage tank

221‧‧‧1st raw material cutting device

221A‧‧‧1A raw material cutting device

221B‧‧‧1B raw material cutting device

221C‧‧‧1C raw material cutting device

222‧‧‧Second raw material cutting device

231‧‧‧1st raw material supply device

231A‧‧‧1A raw material supply device

231B‧‧‧1B raw material supply device

231C‧‧‧1C raw material supply device

232‧‧‧2nd material supply device

241‧‧‧1st raw material supply piping

241A‧‧‧1A raw material supply piping

241B‧‧‧1B raw material supply piping

241C‧‧‧1C raw material supply piping

242‧‧‧Second raw material supply piping

311‧‧‧1st cooler

311A‧‧‧1A cooler

311a‧‧‧Normal temperature gas supply port

311B‧‧‧1B cooler

311b‧‧‧low temperature gas discharge

311c‧‧‧High temperature gas discharge

312‧‧‧2nd cooler

312A‧‧‧2A cooler

312B‧‧‧2B cooler

D‧‧‧Barrel diameter

Gc‧‧‧Cooling gas

Gr‧‧‧ Countercurrent high temperature gas from extruder

L‧‧‧ Effective length of barrel

RH‧‧‧ Radiation heat from the barrel of the extruder

X‧‧‧Axis of extruder

Fig. 1 is a side view showing an outline of an extruder of the embodiment.

Fig. 2 is a side elevational view showing the cooling gas supply line provided in the extruder of the embodiment shown in Fig. 1 and its periphery.

Hereinafter, the form for carrying out the present invention (hereinafter, simply referred to as "this embodiment") will be described in detail with reference to the drawings as needed. The following examples are intended to illustrate the invention and are not intended to limit the invention. Further, the present invention can be carried out with appropriate modifications within the scope of the gist of the invention. In the drawings, positional relationships such as up, down, left, and right are assumed to be based on the positional relationship shown in the drawings unless otherwise specified.

(extruder)

In Fig. 1, an outline of an extruder of this embodiment is shown in a side view.

The extruder 1 of the present embodiment is not particularly limited, and may be a single-axis extruder, a two-way kneader type extruder, a multi-axis extruder such as a twin-screw extruder, or the like, for example, as shown in FIG. The raw material supply port 11 (the first raw material supply port 11-1 and the second raw material supply port 11-2 in Fig. 1) and the cartridge 10 (12th to 12th in Fig. 1) are provided. Die head 13 and the like.

Here, in the extruder 1 of the present embodiment, the raw material supply line 11 (the first raw material supply port 11-1 and the second raw material supply port 11-2 in Fig. 1) is connected to the raw material supply line 2 ( In FIG. 1, the first raw material supply line 2-1 and the second raw material supply line 2-2), and at least a part of the raw material supply line 2 (the raw material supply hopper 20 and the raw material supply pipe 24 in FIG. 1) The cooling gas supply line 3 is in communication.

As a result of intensive studies, the inventors have found that the reason for the melting and adhesion of the low melting point additive in the extruder 1 is the high temperature which flows back from the cylinder 10 of the extruder 1 to the raw material supply line 2. The temperature of the raw material supply line 2 caused by the gas Gr (see Fig. 2) is increased.

According to the extruder 1 of the present embodiment, the high-temperature gas Gr flowing back from the cylinder 10 of the extruder 1 to the raw material supply line 2 is mixed with the cooling gas Gc, and the raw material supply line 2 can be efficiently cooled. With this, it is possible to greatly suppress the increase in the temperature of the raw material supply line 2 caused by the high-temperature gas Gr, which is caused by the reverse flow, and to reduce the melting of the low-melting-point additive inside the constituent members of the raw material supply line 2 such as the raw material supply hopper 20. Attached.

In this aspect, in particular, the refrigerant flows through the outer wall of the constituent members of the raw material supply line 2, and the extruder 1 of the present embodiment is internally self-contained as compared with the method of cooling the raw material supply line 2 from the outside. The constituent members of the raw material supply line 2 are cooled. Thereby, the effect of reducing the melting and adhesion of the above-mentioned low melting point additive is extremely high.

The effects of the extruder 1 of the example shown in Fig. 1 will be described below.

A low melting point additive is introduced into the first raw material storage tank 211A. The low melting point additive is supplied to the first raw material supply hopper 201 via the first raw material cutting device 221A, the first A raw material supply device 231A, and the first A raw material supply pipe 241A.

On the other hand, a thermoplastic resin is introduced into the first raw material storage tank 211B. The thermoplastic resin is supplied to the first raw material supply hopper 201 via the first raw material cutting device 221B, the first B raw material supply device 231B, and the first B raw material supply pipe 241B.

At this time, the first B cooling gas supply line provided in the first A raw material supply pipe 241A 3-1B supplies a cooling gas Gc of -50 to 20 ° C, and the cooling gas Gc is cooled by the low melting point additive of the pipe 241A.

Further, the first A cooling gas supply line 3-1A provided in the first raw material supply hopper 201 supplies a cooling gas Gc of -50 to 20 ° C, and the cooling gas Gc is heated at a high temperature of 70 to 350 ° C from the extruder 1 . The gas Gr is cooled, and the low melting point additive supplied to the hopper 201 and the thermoplastic resin are cooled.

By the cooling effect described above, the melting and adhesion of the low melting point additive are reduced in the first raw material supply hopper 201.

More specifically, the effects of the case of using a raw material containing a polyphenylene ether, a styrene resin, a fibrous filler, and triphenyl phosphate are described.

Triphenyl phosphate was introduced into the 1A raw material storage tank 211. The triphenyl phosphate is supplied to the first raw material supply hopper 201 via the first raw material cutting device 221A, the first A raw material supply device 231A, and the first A raw material supply pipe 241A.

On the other hand, polyphenylene ether and styrene resin are respectively introduced into the first B raw material storage tank 211B and the first C raw material storage tank 211C. The polyphenylene ether is supplied to the first raw material supply hopper 201 via the first raw material cutting device 221B, the first raw material supply device 231B, and the first raw material supply pipe 231B, and the styrene resin is passed through the first C raw material cutting device 221C. The 1C raw material supply device 231C and the first C raw material supply pipe are supplied to the first raw material supply hopper 201.

At this time, the first A cooling material supply line 3-1B of the first A raw material supply pipe 241A supplies the cooling gas Gc of -40 to 25 ° C, and the cooling gas Gc is cooled by the triphenyl phosphate of the pipe 241A.

Further, the first B cooling gas supply line 3-1A provided in the first raw material supply hopper 201 supplies a cooling gas Gc of -40 to 25 ° C, and the cooling gas Gc is heated at a high temperature of 55 to 100 ° C from the extruder 1 . The gas Gr is cooled, and the triphenyl phosphate supplied to the hopper 201 and the polyphenylene ether and the styrene resin are cooled.

By the above-described cooling effect, in the first raw material supply hopper 201, the melting and adhesion of triphenyl phosphate are reduced.

At this time, in particular, the temperature of the cylinder 10 having the raw material supply port 11, the temperature of the cylinder 10 forming the solid transfer zone, the temperature of the cylinder 10 forming the kneading zone, and the low melting point additive are set by sequentially increasing the height. It is sufficiently mixed with the thermoplastic resin and then melted, so that the physical properties of the thermoplastic resin composition become more uniform (described below).

The second raw material supply line 2-2 also exhibits the same operational effects as those of the first raw material supply line 2-1.

- Raw material supply pipeline -

The raw material supply line 2 used in the present embodiment is not particularly limited as long as it can supply a thermoplastic resin and a low melting point additive. Further, the details of the raw material supply line 2 will be described below.

In the extruder 1 shown in FIG. 1, the raw material supply line 2 is provided with a raw material storage tank 21, a raw material cutting device 22, a raw material supply device 23, a raw material supply pipe 24, and a raw material supply hopper 20 in order to the raw material supply port 11.

Specifically, the first raw material supply pipe 2-1 shown in FIG. 1 includes the first raw material supply hopper 201 and the three raw material supply pipes 24 (the first A raw material supply pipe 241A, the first B raw material supply pipe 241B, and the first C raw material supply). Pipe 241C), three raw material supply devices 23 (first A raw material supply device 231A, first B raw material supply device 231B, first C raw material supply device 231C), and three raw material cutting devices 22 (first A raw material cutting device 221A, first B raw material) The cutting device 221B, the first C material cutting device 221C), and the three material storage tanks 21 (the first A material storage tank 211A, the first B material storage tank 211B, and the first C material storage tank 211C).

In addition, the second raw material supply pipe 2-2 shown in FIG. 1 includes the second raw material supply hopper 202, one raw material supply pipe 24 (second raw material supply pipe 242), and one raw material supply device 23 (second raw material supply device) 232), one material cutting device 22 (second material cutting device 222), and one material storage tank 21 (second material storage tank 212).

-Cooling gas supply line -

The cooling gas supply line 3 used in the present embodiment is not particularly limited as long as it can supply a gas lower than the temperature at which the internal temperature of the cylinder 10 to which the raw material supply port 11 of the raw material supply line 2 is connected is supplied. Further, the details of the cooling gas supply line 3 will be described below.

In the extruder 1 of the example shown in Fig. 1, in order to cool the raw material supply line 2 and the cylinder 10 connected thereto, the cooling gas supply line 3 is provided with a cooler 31, more specifically, a vortex cooler.

Hereinafter, the arrangement of the cooling gas supply line 3 in the extruder 1 of the present embodiment will be described in detail.

In the extruder 1 of the present embodiment, as for the example shown in FIG. 1, it is preferable to provide a plurality of cooling gas supply lines 3 for one raw material supply line 2. According to this configuration, the cooling efficiency of the raw material supply line 2 can be improved.

In the extruder 1 of the example shown in FIG. 1, the first raw material supply line 2-1 includes two of the first A cooling gas supply line 3-1A and the first B cooling gas supply line 3-1B, and the second raw material supply line 2-2 includes two of the second A cooling gas supply line 3-2A and the second B cooling gas supply line 3-2B.

In the extruder 1 of the present embodiment, as shown in FIG. 1, it is preferable to provide a plurality of raw material supply ports 11 to which a raw material supply line 2 including a cooling gas supply line 3 is connected. According to this configuration, the low melting point additive can be supplied in plural times, and the physical properties of the thermoplastic resin composition can be improved.

Further, in the extruder 1 of the present embodiment, the cooling gas supply line 3 may be connected to at least a part of the raw material supply line 2, but the cooling gas supply line 3 is preferably in communication with the raw material supply hopper 20 (refer to FIG. 1). Then, it is preferable to communicate with the raw material supply pipe through which the gas Gr flowing backflow flows, and further, it is preferable to communicate with the conveying portion of the raw material supply device 23 in the case where heat is easily generated. According to this configuration, it can be cooled coldly But low melting point additives.

In the example shown in FIG. 1, in the first raw material supply line 2-1, the first A cooling gas supply line 3-1A communicates with the first raw material supply hopper 201 at the lid thereof, and the first B cooling gas supply line. 3-1B is in communication with the first A-material supply pipe 241A. Further, in the second raw material supply line 2-2, the second A cooling gas supply line 3-2A communicates with the second raw material supply hopper 202 at the lid thereof, and the second B cooling gas supply line 3-2B and the second raw material The supply pipe 242 is in communication.

In the extruder 1 of the present embodiment, the direction in which the cooling gas supply line 3 extends is not particularly limited. As shown in FIG. 1, the cooling gas supply line 3 is preferably along the axis X direction of the extruder. Orthogonal direction extends. According to this configuration, in the case of the top feeding and the side feeding, the high-temperature gas Gr and the cooling gas Gc which are countercurrently flowed from the cylinder 10 to the raw material supply line 2 are efficiently mixed, and may have The raw material supply line 2 is efficiently cooled.

In the example shown in FIG. 1, the first A cooling gas supply line 3-1A of the first raw material supply line 2-1 is perpendicular to the direction of the axis X of the extruder (perpendicular to the first raw material supply hopper 201). The cover) extends downward in the direction of gravity, and the second A-cooling gas supply line 3-2A of the second raw material supply line 2-2 is perpendicular to the direction of the axis X of the extruder (perpendicular to the second raw material supply hopper) Cover of 202), extending downward in the direction of gravity.

In the extruder 1 of the present embodiment, the cooling gas supply line 3 is preferably disposed from the axis X of the extruder (the line connecting the center of the cross section of the cylinder 10) to the inner diameter D of the cylinder 1 to 500 times. The area of the location of the distance. According to this configuration, it is possible to prevent the low-melting-point additive from being exposed to the high-temperature gas Gr flowing back from the cylinder 10 to the raw material supply line 2 for a long period of time, so that the melting and adhesion of the low-melting-point additive can be reduced.

In order to enhance the above effect, the cooling gas supply line 3 is further preferably a region from the axis X of the extruder to a distance of 1 to 50 times the inner diameter D of the cylinder.

More specifically, the use of polyphenylene ether, styrene resin, fibrous filling In the case of the material and the raw material of triphenyl phosphate, in the extruder 1, the cooling gas supply line 3 is preferably disposed on the axis X of the extruder (the line connecting the center of the section of the cylinder 10) to the material. The area at the position where the inner diameter D of the cylinder is 2 to 300 times.

According to this configuration, since the low-melting-point additive such as triphenyl phosphate (D) can be prevented from being exposed to the high-temperature gas Gr flowing back from the cylinder 10 to the raw material supply line 2 for a long period of time, triphenyl phosphate can be reduced ( D) Melting and adhesion of a low melting point additive. If it is less than 2 times, it is difficult to supply to the extruder 1 of the raw material, and if it exceeds 300 times, it is difficult to sufficiently cool the raw material supply line 2 and the raw material supply hopper 20.

In order to enhance the above effect, the cooling gas supply line 3 is further preferably a region from the axis X of the extruder to a distance of 5 to 250 times the inner diameter D of the cylinder.

Further, as a further feature of the present embodiment, the extruder 1 of the present embodiment further includes a heat insulating material 4 that covers at least a part of the outer surface of the extruder 1.

According to the study by the inventors and the like, it is also known that the melting and adhesion of the low melting point additive in the extruder 1 is also released from the cylinder 10 of the extruder 1 in particular in the cylinder 10 forming the kneading zone. The temperature of the raw material supply line 2 caused by the radiant heat RH (see FIG. 2) outside the extruder 1 is increased.

By providing the heat insulating material in the extruder 1 of the present embodiment, the radiant heat RH can be blocked, and the melting and adhesion of the low melting point additive can be reduced, and the physical properties of the thermoplastic resin composition can be made uniform.

Further, in the case where the cartridge cover is provided on the cartridge 10, the heat insulating material 4 may be provided on the outer side and/or the inner side of the cartridge cover.

Further, in order to improve the above effect, in the extruder 1 of the present embodiment, the heat insulating material 4 preferably covers the outer surface of the cylinder 10 forming the kneading zone.

The extruder 1 of the example shown in Fig. 1 further includes a second cylinder 10b covering the cylinder 10 adjacent to the first cylinder 10a provided with the material supply port 11 to the fifth cylinder 10e forming the kneading zone. Insulation material 4 on the outer surface.

According to this configuration, it is possible to greatly suppress the high temperature of the raw material supply line 2 caused by the radiant heat RH released from the cylinder 10 of the extruder 1 to the outside of the extruder 1 in the cylinder 10 of the kneading zone. The melting and adhesion of the low-melting-point additive inside the constituent members of the raw material supply line 2 such as the raw material supply hopper 20 are reduced.

Further, in the extruder 1 of the present embodiment, at least a part of the outer surface of the wall of the raw material supply hopper 20 may be covered by the heat insulating material 4.

The details of each element of the raw material supply line 2 will be described below.

The raw material supply hopper 20 is located at the end of the raw material supply line 2, and is connected to the raw material supply port 11 in the extruder 1.

In order to make the raw materials difficult to bridge, the angle of the hopper wall of the raw material supply hopper 20 is preferably from vertical (90°) to 60°.

In order to prevent oxidative degradation of the raw material from occurring, the raw material supply hopper 20 may be replaced with an inert gas. Further, in order to prevent the fine raw material from adhering to the inner wall, a shaker or a vibrator can be appropriately attached to the hopper 20.

The raw material storage tank 21 is a tank for temporarily storing raw materials. In the case where the raw material is a powdery flammable resin, the inside of the storage tank 21 may be replaced with an inert gas, or when a raw material is easily bridged, a bridge breaker or the like may be installed as needed.

The material cutting device 22 is a device that supplies the raw material supply device 23 and supplies the raw material when the raw material supply hopper 20 becomes empty. When the hopper 20 becomes empty, a signal is sent to the cutting device 22 (when the cutting device 22 is a gate valve), the gate valve is opened, and the raw material is supplied from the raw material storage tank 21 to the raw material supply device 23 in a short time (10 to 120 seconds). supply. If the hopper 20 is full, the above signal will not be sent and the cutting valve will be closed. Furthermore, the cutting device 22 can be in the form of a gate valve or in the form of a screw.

The raw material supply device 23 can generally suitably use a weight type feeder, and includes a hopper portion for storing the raw material and a conveying portion for quantitatively transferring the raw material. The transfer unit may be of a screw type, a belt type, a vibrating type or the like, and may be any type.

In particular, in the case of using a screw type, in order to prevent the low melting point additive from being melted in order to prevent heat generation in the conveying portion, it is preferable to use a screw having a large pitch and a screw such as a coil type which is less likely to cause heat generation. The belt type and the vibrating type are preferable because they are less likely to cause heat generation.

Preferably, in the supply device 23, a load cell is attached in order to improve the supply accuracy, and the supply amount is controlled based on the weight reduction of the raw material.

The raw material supply pipe 24 supplies the raw material supplied from the conveying unit of the raw material supply device 23 to the piping of the raw material supply hopper 20 . The mounting angle of the raw material supply pipe 24 is preferably (90 degrees) to 45 degrees in order to make the raw materials difficult to bridge.

The raw material supply line 2 used in the present embodiment does not require all of the above elements. For example, in the case of a uniaxial extruder, the raw material supply line 2 may be provided with only the raw material supply hopper 20, and the raw material supply hopper 20 may be attached with a screw for press-fitting.

The details of the cooling gas supply line 3 will be described below.

In Fig. 2, the cooling gas supply line provided in the extruder of the present embodiment and its periphery are enlarged and shown in a side view.

The cooler 31 (see FIG. 1) is not particularly limited as long as it is a device that can generate a cooling gas having a temperature lower than the temperature of the normal temperature gas by 15 to 75 °C.

The vortex cooler included in the extruder 1 shown in Fig. 1 includes a casing, a generator, a normal temperature gas supply port 311a, a low temperature gas discharge port 311b, and a high temperature gas discharge port 311c.

In the cooler 31, first, a gas having a specific pressure (0.1 to 1.0 MPa) and a specific temperature (10 to 50 ° C) is supplied from the normal temperature gas supply port 311a, and then generated by pressure in the machine of the cooler 31. The high-speed eddy current of about 1 million rpm is separated into a low-temperature gas and a high-temperature gas, and then the low-temperature gas is discharged as a cooling gas from the low-temperature gas discharge port 311b (that is, one is supplied to the inside of the raw material supply line 2), and the high-temperature gas is supplied. The high-temperature gas discharge port 311c is discharged to the outside of the raw material supply line 2.

Specific examples of the vortex cooler include a vortex tube manufactured by Rainbow Technology Co., Ltd., a manual cleaning system, a cold air gun, a panel protection cooler, etc.; a jet cooler manufactured by Newera Co., Ltd.; Air coolers manufactured by the company.

The details of the extruder 1 are described below.

The extruder 1 of the present embodiment is not particularly limited, and examples thereof include a uniaxial extruder, a two-way kneader type extruder, a multi-axis extruder such as a twin-screw extruder, and the like, in particular, a fiber. From the viewpoint of sufficient melt kneading of the filler (C), a biaxial extruder is preferred.

As the uniaxial extruder, for example, a uniaxial extruder provided with a kneading screw or the like can be cited.

Examples of the extruder of the two-way kneading machine type include a two-way kneader manufactured by Buss Corporation.

As the twin-screw extruder, for example, a non-intermeshing counter-rotating twin-screw extruder, an intermeshing counter-rotating twin-screw extruder, and a co-rotating twin-screw extruder (for example, ZSK MEGAcompounder manufactured by Coperion Co., Ltd.) Series, MEGAVolume PLUS series, MC18 series; TEM BS series, SS series, SX series manufactured by Toshiba Machine Co., Ltd.; TEXα series, α2 series, α3 series, etc. manufactured by Nippon Steel Works Co., Ltd.). More specifically, a ZSK40MC twin-screw extruder (manufactured by Coperion Co., Ltd., number of cylinders 13, screw diameter 40 mm, L/D = 50; and kneading disc L (Left-handed): two, Kneading disc R (Right-handed): 6 and kneading disc N (Neutral): 4 screw styles, which can be used at a cylinder temperature of 270-330 ° C and a screw revolution of 150 Melt kneading was carried out under conditions of ~450 rpm and an extrusion rate of 40 to 220 kg/h. In addition, as a twin-axis extruder, the TEM58SS twin-axis extruder (The Toshiba Machine Co., Ltd., the number of cylinders 13, the screw diameter of 58 mm, L/D=53, and the kneading disk L: two, kneading disk are mentioned. R: 14 and kneading disc N: 2 screw styles), can also be used in the cylinder temperature 270~ Melt kneading was carried out under the conditions of 330 ° C, screw rotation number 150 to 500 rpm, and extrusion speed of 200 to 600 kg / h.

The standard or size of the extruder 1 is not particularly limited, and the inner diameter (diameter) D of the cylinder is preferably 40 to 200 mm. If the inner diameter D of the cylinder is less than 40 mm, the productivity is low. If the inner diameter D of the cylinder exceeds 200 mm, it is difficult to suppress heat generation during melt kneading. The effective length L of the cylinder is not particularly limited, and is preferably 12 to 60 times the inner diameter D of the cylinder. If the effective length L of the cylinder is less than 12 times the inner diameter D of the cylinder, it is difficult to sufficiently knead the raw material. If the effective length L of the cylinder exceeds 60 times the inner diameter D of the cylinder, the vibration of the screw shaft increases. The mixing of raw materials has become awkward.

The motor of the extruder 1 is not particularly limited and may be a variable frequency motor or a direct current motor. A cooling device can be provided on the motor as needed. Examples of the cooling device for the motor include an air-cooling type and a circulating water-cooling type. However, from the viewpoint of dispersing foreign matter in the air, a circulating water-cooling type is preferable.

The cylinder structure of the extruder 1 is exemplified by a cylinder comprising: a cylinder 10 having at least one raw material supply port, at least a solid transport zone (before melting) and/or a melt transport zone. One cylinder 10, at least one cylinder 10 forming a kneading zone, and a cylinder 10 having at least one venting hole 12. Here, the vent hole 12 may be an atmospheric vent hole or a vacuum vent hole. Further, the supply of the raw material may be set to the top feed or may be set to the side feed.

In the example shown in Fig. 1, there are 12 barrels 10 (10a to 10l (L)) having the first to twelfth barrels, and the first barrel (10a) and the seventh barrel (10g) have raw materials. The cartridge 10 of the supply port, the second to fourth cylinders (10b to 10d) form the cylinder 10 of the solid transfer zone, and the 9th, 10th, and 12th cylinders (10i, 10j, 10l (L)) Forming the cylinder 10 of the melt transfer zone, the fifth and eighth cylinders (10e, 10h) form the cylinder 10 of the kneading zone, and the sixth cylinder (10f) is the cylinder 10 having the atmospheric vent hole, The 11 cylinder (10k) is a cylinder 10 having a vacuum vent.

In particular, in the extruder 1 of the present embodiment, the number of the cartridges 10 forming the solid transfer zone is preferably 1 to 8 times the number of the cartridges 10 having the raw material supply ports 11 corresponding thereto. Good for 2 to 5 times.

In the example shown in Fig. 1, the number of the cartridges 10 (10b to 10d) forming the solid transfer zone is three times the number of the cartridges 10 (10a) having the first raw material supply port 11-1.

As the screw element used in the cartridge 10, for example, two or three kneading segments (right-hand rotation, left-hand rotation, neutral, reverse feed), two or three screw screws (right-hand rotation) can be cited. , left-hand rotation), one, two or three slit screws or cutting screws, seal rings, etc., may be used in combination as needed.

The diameter of the screw is preferably set to 25 to 90 mm, more preferably 40 to 70 mm.

The mold head 13 of the extruder 1 of the present embodiment can be provided with a foreign matter removing plate for mounting a metal mesh for removing foreign matter contained in the molten thermoplastic resin (mesh is #10~#300) Screen).

Moreover, the template head 13 can be mounted with a template having a plurality of apertures. In this case, the inner diameter of the aperture can be set to 2 to 6 mm, the length of the aperture can be set to 6 to 20 mm, and the aperture can be set to 1 to 20 mm. The amount of extrusion can be set to 10~40kg/hr. Further, a resin deposit removing device may be further provided which can remove the resin deposit generated in the opening by blowing a gas or applying microvibration to the opening of the orifice of the template.

Further, in the case of producing a thermoplastic resin composition containing a filler, it is preferred that the above-mentioned metal mesh is not used in the die head 13 from the viewpoint of avoiding clogging.

Further, the resin composition produced can be discharged from the die attached to the die head 13 in the form of a strand of strands having a diameter of about 3 mm, and thereafter, moderately in a strand groove filled with water of a suitable temperature. Ground cooling. The cut temperature of the strand is preferably 100 to 200 ° C, preferably by cutting the appropriately cooled strand into a length of 3 mm before and after using a granulator to form a cylindrical particle of a suitable length. 120 to 170 ° C, and more preferably 140 to 160 ° C. From the viewpoint of suppressing generation of chips at the time of cutting, it is preferably 100 ° C or more, and is preferably 200 ° C or less from the viewpoint of preventing thermal deterioration of particles. The pellets cut by the granulator can then be cooled by a particle cooler. Also, The slender or continuous granules and the powder produced by the cutting are removed by sieving the granules by means of a vibrating sieve.

(Method for Producing Thermoplastic Resin Composition)

The method for producing the thermoplastic resin composition of the present embodiment uses the extruder 1 and includes the following steps: a raw material supply step of supplying a raw material (thermoplastic resin (A), low melting point additive (B), etc.) to the raw material supply line 2; a cooling gas supply step of supplying a gas having a temperature lower than an internal temperature of the extruder 1 to the raw material supply line 2; A mixing step that melts and kneads the raw materials.

Further, in the present embodiment, as described below, it is necessary to use the extruder 1 of the above-described embodiment.

Hereinafter, each component used in the method for producing a thermoplastic resin composition of the present embodiment will be described.

The thermoplastic resin composition produced by the method for producing a thermoplastic resin composition of the present embodiment is not particularly limited, and may contain a thermoplastic resin (A), an additive having a melting point of 40 to 200 ° C (low melting point additive) (B), and a filler. (C), liquid additives, other additives.

The thermoplastic resin (A) used in the method for producing a thermoplastic resin composition of the present embodiment is not particularly limited, and examples thereof include polyphenylene ether resins (polyphenylene ether, polyphenylene ether, and (hereinafter) polycondensation). a blend of a styrene resin), a polystyrene resin (general polystyrene, impact-resistant polystyrene, acrylonitrile/styrene copolymer, acrylonitrile/butadiene/styrene copolymer, etc.), Polycarbonate resin, polyolefin resin (polypropylene resin, polyethylene resin, etc.), homopolymer type polyoxymethylene, copolymer type polyoxymethylene, polyphenylene sulfide, polyamine resin, polyamine醯imine, polyarylate, polyaryl fluorene, polyether oxime, polyether oximine, polytetrafluoroethylene, polyether ketone, etc., especially polyphenylene ether resin, polycarbonate resin, polyfluorene Amine resin, homopolymer type polyoxymethylene, copolymer type polyoxymethylene, acrylonitrile/butyl A diene/styrene copolymer or the like.

These thermoplastic resins (A) may be used alone or in combination of two or more.

Hereinafter, the above polyphenylene ether will be described in detail.

The polyphenylene ether has a repeating unit of the following formula (1) and/or (2), and preferably the constituent unit comprises a homopolymer of the formula (1) or (2), or a formula (1) Or a copolymer of (2) a constituent unit.

(In the above formulae (1) and (2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently an alkyl group having 1 to 4 carbon atoms and a carbon number of 6 to 12 a group, another monovalent group, for example, selected from the group consisting of halogen, hydrogen, etc., except where R ⁵ and R ⁶ are both hydrogen)

Further, as the other monovalent group, hydrogen is preferred. Further, the hydrogen atom of the above alkyl group and the above aryl group may be substituted by a halogen, a hydroxyl group or an alkoxy group. Further, a preferred carbon number of the above alkyl group is 1 to 3, and a preferred carbon number of the above aryl group is 6 to 8.

In addition, the number of the repeating units in the above formulas (1) and (2) can be various depending on the molecular weight distribution of the polyphenylene ether, and is not particularly limited.

Among the polyphenylene ethers, the homopolymer is not limited to the following, and examples thereof include poly(2,6-dimethyl-1,4-phenylene) ether and poly(2-methyl-6-). Ethyl-1,4-phenylene ether, poly(2,6-diethyl-1,4-phenylene) ether, poly(2-ethyl-6-n-propyl-1,4- Phenyl)ether, poly(2,6-di - n-propyl-1,4-phenylene ether, poly(2-methyl-6-n-butyl-1,4-phenylene) ether, poly(2-ethyl-6-isopropyl) -1,4-phenylene ether, poly(2-methyl-6-chloroethyl-1,4-phenylene)ether, poly(2-methyl-6-hydroxyethyl-1,4 -phenylene)ether and poly(2-methyl-6-chloroethyl-1,4-phenylene)ether, etc., especially in terms of ease of obtaining raw materials and processability, preferably poly (2,6-Dimethyl-1,4-phenylene)ether.

Among the polyphenylene ethers, the copolymer is not limited to the following, and examples thereof include a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, and 2,6-dimethyl group. A copolymer of phenol and o-cresol, and a copolymer of 2,3,6-trimethylphenol and o-cresol, etc., have a polyphenylene ether structure as a main component, in particular, from the viewpoints of ease of raw material acquisition and processability. In other words, a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol is preferred, and 2,6-dimethylphenol and 2 are more preferable from the viewpoint of physical property improvement. a copolymer of 3,6-trimethylphenol (especially comprising 90 to 70% by mass of the 2,6-dimethylphenol moiety and 10 to 30% by mass of the 2,3,6-trimethylphenol moiety).

The above various polyphenylene ethers may be used alone or in combination of two or more.

The polyphenylene ether may contain a polyphenylene ether having a partial structure including various other phenyl ether units other than the above formulas (1) and (2) as long as the heat resistance of the resin composition is not excessively lowered.

The phenyl ether unit is not limited to the following, and examples thereof include a 2-(dialkylaminomethyl group) described in JP-A-H01-297428, and JP-A-63-301222. a -6-methylphenyl ether unit or a 2-(N-alkyl-N-phenylaminomethyl)-6-methylphenyl ether unit.

Regarding polyphenylene ether, biphenyl hydrazine or the like may be bonded to the main chain of polyphenylene ether.

Further, the polyphenylene ether may have a part or all of a polyphenylene ether and a mercapto group-containing functional group, and may be selected from the group consisting of a carboxylic acid, an acid anhydride, a guanamine, a quinone imine, an amine, an orthoester, a hydroxyl group, and an ammonium carboxylate. The functionalizing agent of one or more functional groups of the group consisting of a salt is reacted (modified) to be substituted with a functionalized polyphenylene ether.

The ratio of the weight average molecular weight Mw of the polyphenylene ether to the number average molecular weight Mn (Mw/Mn value) is preferably 2.0 or more, more preferably 2.5 or more, and furthermore, from the viewpoint of moldability of the resin composition. Further, it is preferably 3.0 or more, and is preferably 5.5 or less, and more preferably 4.5 or less from the viewpoint of mechanical properties of the resin composition. Further, the weight average molecular weight Mw and the number average molecular weight Mn can be obtained by measuring the molecular weight in terms of polystyrene obtained by GPC (Gel Permeation Chromatography).

The reduction viscosity of the polyphenylene ether is preferably 0.25 dl/g or more, more preferably 0.30 dl/g or more, and still more preferably 0.33 dl/g or more, from the viewpoint of sufficient mechanical properties. From the viewpoint of workability, it is preferably 0.65 dl/g or less, more preferably 0.55 dl/g or less, still more preferably 0.42 dl/g or less. Further, the reducing viscosity can be measured using a Ubbelohde viscometer using a chloroform solvent, a solution of 30 ° C, and a 0.5 g/dl solution.

Hereinafter, the above polystyrene resin will be described in detail.

The polystyrene resin is added to the resin composition of the present embodiment from the viewpoint of improving the molding fluidity.

In the resin composition of the present embodiment, the polystyrene resin is a polymer obtained by polymerizing a styrene compound in the presence or absence of a rubber polymer, or a styrene compound and the like. A copolymer obtained by copolymerizing a compound in which a styrene compound is copolymerized in the presence or absence of a rubbery polymer.

The styrene-based compound refers to a compound in which one or a plurality of hydrogen atoms of styrene are substituted with a monovalent group.

The styrene-based compound is not limited to the following, and examples thereof include styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene, and the like. From the viewpoint of easy availability of a stable quality raw material and balance of characteristics of the composition, tributylstyrene, ethylstyrene, and the like are preferably styrene.

The compound which can be copolymerized with the above styrene-based compound is not limited to Examples thereof include methacrylates such as methyl methacrylate and ethyl methacrylate; unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile; and unsaturated acid anhydrides such as maleic anhydride.

Further, among the above polystyrene resins, a polymer or a copolymer obtained by polymerizing or copolymerizing in the presence of a rubbery polymer is referred to as a rubber-reinforced polystyrene resin, and is polymerized in a rubbery state. The polymer or copolymer obtained by carrying out polymerization or copolymerization in the absence of a substance is referred to as a non-rubber-reinforced polystyrene-based resin.

The polystyrene-based resin in the present invention is preferably a polystyrene-based resin which is not rubber-reinforced from the viewpoint of mechanical properties of the molded article.

Examples of the additive (low melting point additive) (B) having a melting point of 40 to 200 ° C used in the method for producing a thermoplastic resin composition of the present embodiment include a phosphorus-based flame retardant, a higher fatty acid derivative, and a dicarboxylic acid. Acid, petroleum resin, etc.

These additives (low melting point additives) (B) having a melting point of 40 to 200 ° C may be used alone or in combination of two or more.

When the melting point of the additive is less than 40, the additive has a tendency to be easily liquefied, and when the melting point exceeds 200 ° C, the additive causes poor melting and is not sufficiently dispersed in the resin composition. Hey.

In the present embodiment, from the viewpoint of obtaining the effect of the present invention more efficiently, the melting point of the additive may be 40 to 200 ° C, preferably 40 to 190 ° C, and more preferably 40 to 180 ° C.

Examples of the phosphorus-based flame retardant include a phosphate compound, a phosphoric acid condensed ester, a cyclic and/or chain phosphazene compound, and the like.

The phosphate compound and the phosphoric acid ester are not particularly limited, and examples thereof include triphenyl phosphate, tricresyl phosphate, tris(xylylene) phosphate (TXP), tolyl diphenyl phosphate, and 2-ethyl phosphate. Dihexyl diphenyl ester, t-butylphenyl diphenyl phosphate, bis-(t-butylphenyl)phenyl phosphate, tris-(t-butylphenyl) phosphate, isopropyl phosphate Phenyldiphenyl ester, bis-(isopropylphenyl)diphenyl phosphate, tris-(isopropylphenyl)resorcinol bis-(diphenyl phosphate), resorcinol bis-(phosphoric acid) Di(xylylene) ester), bisphenol A bis-(diphenyl phosphate), biphenyl bis-(diphenyl phosphate), etc., particularly preferably triphenyl phosphate.

These may be used alone or in combination of two or more.

Examples of the cyclic and/or chain phosphazene compound include (poly)toluene phosphorus such as phenoxyphosphazene, o-tolyloxyphosphazene, m-tolyloxyphosphazene, and p-tolylphosphoronitrile. Nitrile, o-, m-xylylene phosphazene, o-p-xylylene phosphazene, m-p-xyloxyphosphazene, etc. (poly)xyloxyphosphazene, o-, m-, p-trimethyl Phenoxyphosphazene, phenoxy-o-tolyloxyphosphazene, phenoxy-tolyloxyphosphazene, phenoxy-p-toluoxyphosphazene, etc. (poly)phenoxytoluenephosphazene, phenoxy Phenyloxy-p-methoxyphosphazene, phenoxy- ortho-p-xyloxyphosphazene, phenoxy-p-p-methoxy-p-methoxyphosphazene, etc. Phosphazene, phenoxy ortho, m-p-trimethoxyphenoxyphosphazene, etc., particularly preferably cyclic and/or chain phenoxyphosphazene.

These may be used alone or in combination of two or more.

Examples of the higher fatty acid derivatives include fatty decylamines such as stearylamine, oleic acid amine, and sucrose decylamine; alkyl decylamines such as methylenebisstearylamine and ethylbisstearylamine. a fatty acid salt such as calcium stearate, zinc stearate or magnesium stearate.

Examples of the dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, maleic anhydride, malic acid, and citric acid.

Examples of the petroleum resin include a hydrocarbon compound having a molecular weight of 3,000 or less, an aliphatic compound having a carbon number of 5, and/or a petroleum fraction of an aromatic compound having a carbon number of 9, and the like.

The filler (C) used in the method for producing the thermoplastic resin composition of the present embodiment is not particularly limited, and may be a fibrous filler, and examples thereof include glass fiber, carbon fiber, metal fiber, and potassium titanate. Crystal, magnesium sulfate whisker, aluminum borate whisker, calcium carbonate whisker, carbonized whisker crystal, zinc oxide whisker, calcium silicate (silver), mica, slip Stone, glass shards, calcium carbonate, clay, kaolin, barium sulfate, cerium oxide, aluminum oxide, magnesium oxide, magnesium sulfate, copper iodide, potassium iodide, etc., especially glass fiber, carbon fiber, calcium silicate, mica, talc Glass shards, calcium carbonate, kaolin, cerium oxide, copper iodide, and potassium iodide are particularly preferably glass fibers and carbon fibers from the viewpoint of imparting sufficient rigidity.

As the type of the glass fiber, a known one can be used, and examples thereof include E glass, C glass, S glass, and A glass. Glass fiber refers to a fiber in the shape of a fiber, which is distinguished from a block of glass or glass powder.

The average fiber diameter of the glass fiber is preferably from the viewpoint of reduction in rigidity, heat resistance, impact resistance, durability, and the like of the molded body due to breakage of the fiber during extrusion or molding, or production stability. 5 μm or more, and more preferably 7 μm or more, it is preferably 15 μm or less, and more preferably 13 μm or less from the viewpoint of imparting sufficient mechanical properties or maintaining the surface appearance of the molded article.

The average length of the glass fibers is preferably 0.5 mm or more, more preferably 1 mm or more, still more preferably 10 mm or less, and still more preferably 6 mm or less from the viewpoint of handleability.

In addition, the average L/D ratio (ratio of length to fiber diameter) of the glass fiber is preferably 70 or more, and more preferably 100, from the viewpoint of balance between rigidity, durability, moldability, and molded appearance. The above is preferably 200 or more, and more preferably 1200 or less, more preferably 1,000 or less, and most preferably 800 or less.

The glass fiber used in the present embodiment may be subjected to surface treatment using a surface treatment agent such as a decane compound. The decane compound used in the surface treatment is usually used in the case of surface treatment of a glass filler or a mineral filler. Specific examples of the decane compound include vinyl decane compounds such as vinyl trichloromethane, vinyl triethoxy decane, and γ-methyl propylene methoxy propyl trimethoxy decane; γ-glycidyloxy group; Epoxy decane compound such as propyltrimethoxydecane; bis-(3-triethoxy fluorene) a sulfur-based decane compound such as an alkylpropyl)tetrasulfide; a mercaptodecane compound such as γ-mercaptopropyltrimethoxydecane; γ-aminopropyltriethoxydecane, γ-ureidopropyltriethoxy An amino decane compound such as decane or the like is preferably an amino decane compound from the viewpoint of achieving the object of the present invention.

These decane compounds may be used alone or in combination of two or more. Further, the decane compound may be previously mixed with an astringent such as an epoxy-based or urethane-based compound, and subjected to surface treatment using the mixture.

The carbon fiber used in the present embodiment can be appropriately selected from known ones, and can be selected, for example, from PAN (Polyacrylonitrile) carbon fiber, pitch-based carbon fiber, lanthanum-based carbon fiber, lanthanide-based carbon fiber, and vapor-grown carbon fiber. Wait. Further, in terms of handleability, it is preferable to use an astringent such as an urethane-based or an epoxy-based astringent to converge the original yarn in a range of 3 to 6 mm in the range of 10 to 20 k. Cut stocks. The fiber diameter is preferably from 0.5 to 15 μm, particularly preferably from 5 to 10 μm.

The preferred average number of fiber lengths of the fibrous filler used in the embodiment in the resin composition is preferably in the range of from 100 to 700 μm, more preferably in the range of from 200 to 500 μm. From the viewpoint of imparting sufficient mechanical strength, it is preferably 100 μm or more, and is preferably 700 μm or less from the viewpoint of maintaining the surface appearance, moldability, and flame retardancy of the molded article.

The liquid additive used in the method for producing the thermoplastic resin composition of the present embodiment is not particularly limited, and examples thereof include polyethylene glycol having a molecular weight of 300 to 20,000 and alkane oil having a carbon number of 4 to 155 (for example, K-350 (99.9995% liquid paraffin) manufactured by Kaneda Co., Ltd., PW-90 (normal paraffin-based processing oil) manufactured by Idemitsu Kosan Co., Ltd., Neochiozoru manufactured by Sanko Chemical Industry Co., Ltd.; cyclopentane (C ₅ H ₁₀ ), cyclohexane (C ₆ H ₁₂ ), fettlite (C ₁₉ H ₃₄ ), oleanane (C ₃₀ H ₅₂ ), and mixtures thereof An anthracane-based oil (for example, Diana Process Oil NS90S manufactured by Idemitsu Kosan Co., Ltd., Diana Process Oil NS100 manufactured by Idemitsu Kosan Co., Ltd., etc.).

The other additives used in the method for producing the thermoplastic resin composition of the present embodiment are not particularly limited, and examples thereof include an elastomer, various coloring agents, a coloring agent (such as titanium oxide), and an ultraviolet absorber. A light-resistant agent, a stabilizer (zinc oxide, zinc sulfide, phosphorus-based, sulfur-based, hindered phenol-based, etc.).

More specifically, the thermoplastic resin composition produced in the method for producing a thermoplastic resin composition of the present embodiment preferably contains a polyphenylene ether as a thermoplastic resin (A) and a polystyrene resin. Polyphenylene ether-based resin composition of a low-melting-point additive (B) and a fibrous filler as a filler (C) (hereinafter also referred to as "PPE (polyphenylene ether) resin combination) ")").

Here, in the polyphenylene ether-based resin composition, the total mass of the polyphenylene ether, the polystyrene resin, the triphenyl phosphate, and the fibrous filler is preferably 90% by mass or more.

In particular, it is more preferable that the total mass of the polyphenylene ether, the polystyrene resin, the triphenyl phosphate, and the fibrous filler is 100% by mass, and the polyphenylene ether is 25 to 85% by mass. The polystyrene resin is 0 to 30% by mass, the triphenyl phosphate is 5 to 20% by mass, and the fibrous filler is 10 to 50% by mass. As the fibrous filler, glass fibers and/or carbon fibers are more preferable.

In the PPE-based resin composition, the content of the polyphenylene ether in 100% by mass of the total mass of the polyphenylene ether, the polystyrene resin, the triphenyl phosphate, and the fibrous filler is sufficient to impart heat resistance. From the viewpoint of flame retardancy, it is 25% by mass or more, preferably 35% by mass or more, more preferably 40% by mass or more, and it is preferably 85% by mass or less from the viewpoint of moldability. 70% by mass or less, more preferably 60% by mass or less.

In the PPE-based resin composition, the content of the polystyrene resin in a total mass of 100% by mass of the polyphenylene ether, the polystyrene resin, the triphenyl phosphate, and the fibrous filler is sufficient to impart sufficient heat resistance. From the viewpoint of the properties and flame retardancy, it is 30% by mass or less, preferably 20% by mass or less.

In the PPE-based resin composition, the content of the triphenyl phosphate in the total mass of 100% by mass of the polyphenylene ether, the polystyrene resin, the triphenyl phosphate, and the fibrous filler is the resin combination of the present invention. In view of the fact that the resin composition is sufficiently flame-retardant, it is preferably 5% by mass or more, preferably 7% by mass or more, and is preferably 20% by mass or less from the viewpoint of maintaining sufficient heat resistance of the resin composition. It is 15% by mass or less.

In the PPE-based resin composition, the content of the fibrous filler in the total mass of 100% by mass of the polyphenylene ether, the polystyrene resin, the triphenyl phosphate, and the fibrous filler is improved by the resin composition. From the viewpoint of the mechanical properties, it is 10% by mass or more, preferably 20% by mass or more, and is 50% by mass or less from the viewpoint of not impairing the flame retardancy and the molded appearance of the resin composition. Preferably, it is 45 mass% or less.

In particular, the PPE-based resin composition may contain stabilizers such as antioxidants, ultraviolet absorbers, and heat stabilizers, colorants, and the like insofar as the mechanical properties, the flame retardancy, and the surface appearance of the molded article are not significantly lowered. A release agent or the like is used as another material.

When the total mass of the polyphenylene ether, the polystyrene resin, the triphenyl phosphate, and the fibrous filler is 100 mass, the content of the antioxidant or the like is sufficient. The viewpoint of the effect of the addition is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, still more preferably 0.2% by mass or more, and further, from the viewpoint of maintaining the physical properties of the resin composition of the present embodiment, It is preferably 3% by mass or less, more preferably 2% by mass or less, and still more preferably 1% by mass or less.

In the PPE resin composition, an inorganic filler other than the fibrous filler may be contained in a range that does not significantly lower mechanical properties, impact resistance, and flame retardancy.

The inorganic filler other than the fibrous filler is not limited to the following, and examples thereof include mica, talc, glass cullet, and glass ground fiber (when the glass fiber is ground to obtain a powder), and chlorite. Wait.

The total mass of the polyphenylene ether, the polystyrene resin, the triphenyl phosphate, and the fibrous filler is set to the content of the inorganic filler other than the fibrous filler. In the case of 100% by mass, from the viewpoint of imparting rigidity and durability, it is preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 10% by mass or less, and more preferably 8% by mass. the following.

Hereinafter, a method for producing the thermoplastic resin composition of the present embodiment using the extruder 1 of the present embodiment will be described in detail.

The method for producing a thermoplastic resin composition of the present embodiment requires the use of the extruder 1 of the above-described embodiment, and includes the following steps: a step of supplying a raw material (a thermoplastic resin (A), a low melting point additive (B), etc.) from the raw material supply port 11 to the extruder 1 through a raw material supply line 2 (a raw material supply step); a step of supplying a gas (cooling gas) having a temperature lower than an internal temperature of the extruder 1 to the raw material supply line 2 through a cooling gas supply line 3 communicating with at least a part of the raw material supply line 2 (cooling gas supply step); In the extruder 1, a step of melting and kneading the supplied raw material (melt kneading step).

As described above, the inventors of the present invention have made an effort to study the results of the method for producing a thermoplastic resin composition using the extruder 1 in which the melting and adhesion of the low-melting-point additive in the extruder 1 is caused. The temperature of the raw material supply line 2 caused by the high-temperature gas Gr flowing back from the cylinder 10 of the extruder 1 to the raw material supply line 2 is increased.

According to the method for producing a thermoplastic resin composition of the present embodiment using the extruder 1 of the present embodiment, the high-temperature gas Gr and the cooling gas Gc which flow back from the cylinder 10 of the extruder 1 to the raw material supply line 2 are used. By mixing, the raw material supply line 2 can be efficiently cooled. With this, it is possible to greatly suppress the increase in the temperature of the raw material supply line 2 caused by the high-temperature gas Gr, which is caused by the reverse flow, and to reduce the melting of the low-melting-point additive inside the constituent members of the raw material supply line 2 such as the raw material supply hopper 20. Attached.

In this regard, in particular, the method of cooling the raw material supply line 2 from the outside by externally flowing the refrigerant through the outer wall of the constituent members of the raw material supply line 2 is In the method for producing a thermoplastic resin composition, the constituent members of the raw material supply line 2 are cooled from the inside. Therefore, the effect of reducing the melting and adhesion of the above-mentioned low melting point additive is extremely high.

The effects of the method for producing the thermoplastic resin composition of the present embodiment using the extruder 1 of the example shown in Fig. 1 will be described below.

The low melting point additive (B) is introduced into the first raw material storage tank 211. The low-melting-point additive (B) is supplied to the first raw material supply hopper 201 via the first raw material cutting device 221A, the first A raw material supply device 231A, and the first A raw material supply pipe 241A.

On the other hand, the thermoplastic resin (A) is introduced into the first raw material storage tank 211B. The thermoplastic resin (A) is supplied to the first raw material supply hopper 201 via the first raw material cutting device 221B, the first B raw material supply device 231B, and the first B raw material supply pipe 241B.

At this time, the first B cooling gas supply line 3-1B provided in the first A raw material supply pipe 241A supplies the cooling gas Gc at -50 to 20 ° C, and the cooling gas Gc is cooled by the low melting point additive (B) of the pipe 241A.

Further, the first A cooling gas supply line 3-1A provided in the first raw material supply hopper 201 supplies a cooling gas Gc of -50 to 20 ° C, and the cooling gas Gc is heated at a high temperature of 70 to 350 ° C from the extruder 1 . The gas Gr is cooled, and the low melting point additive (B) and the thermoplastic resin (A) supplied to the hopper 201 are cooled.

By the cooling effect described above, the melting and adhesion of the low melting point additive (B) are reduced in the first raw material supply hopper 201.

In the following, more specifically, the effects of the production method of the polyphenylene ether-based resin composition containing a raw material containing a polyphenylene ether, a styrene resin, a fibrous filler, and a triphenyl phosphate are described.

Triphenyl phosphate is introduced into the first raw material storage tank 211. The triphenyl phosphate is supplied to the first raw material supply hopper 201 via the first raw material cutting device 221A, the first A raw material supply device 231A, and the first A raw material supply pipe 241A.

On the other hand, polyphenylene ether and styrene resin are respectively introduced into the first B raw material storage tank 211B and the first C raw material storage tank 211C. The polyphenylene ether is supplied to the first raw material supply hopper 201 via the first raw material cutting device 221B, the first raw material supply device 231B, and the first raw material supply pipe 241B, and the styrene resin is passed through the first C raw material cutting device 221C. The 1st C raw material supply apparatus 231C and the 1st C raw material supply piping are supplied to the 1st raw material supply hopper 201.

At this time, the first A cooling material supply line 3-1A of the first A raw material supply pipe 241A supplies the cooling gas Gc at -40 to 25 ° C, and the cooling gas Gc is cooled by the triphenyl phosphate of the pipe 241A.

Further, the first B cooling gas supply line 3-1B provided in the first raw material supply hopper 201 supplies a cooling gas Gc of -40 to 25 ° C,

The cooling gas Gc cools the high-temperature gas Gr of 55 to 100 ° C which is returned from the extruder 1 , and cools the triphenyl phosphate supplied to the hopper 201 and the polyphenylene ether and the styrene resin.

By the above-described cooling effect, in the first raw material supply hopper 201, the melting and adhesion of triphenyl phosphate are reduced.

The second raw material supply line 2-2 also exhibits the same operational effects as those in the first raw material supply line 2-1.

In particular, by setting the temperature of the cylinder 10 having the raw material supply port, the temperature of the cylinder 10 forming the solid transfer zone, and the temperature of the cylinder 10 forming the kneading zone in a sequential manner, the low melting point additive and the thermoplastic resin are sufficient. After mixing, it melts, and the physical properties of the thermoplastic resin composition become more uniform (described below).

In particular, in the raw material supply step in the method for producing a polyphenylene ether resin composition, polyphenylene ether, styrene resin, and triphenyl phosphate are preferable from the viewpoint of imparting heat resistance and mechanical properties to the raw material. It is supplied from the raw material supply port (top feed) at the most upstream part of the extruder, and the fibrous filler is supplied from the raw material supply port (side feed) in the middle of the extruder. give.

Here, in the cooling gas supply step in the method for producing a thermoplastic resin composition of the present embodiment, the temperature of the cooling gas Gc is not particularly limited.

In particular, in the cooling gas supply step in the method for producing a polyphenylene ether resin composition, the temperature of the cooling gas Gc is preferably set to a temperature lower by 90 to 25 ° C than the melting point of triphenyl phosphate, more preferably It is a temperature of 70 to 35 ° C lower, and further preferably a temperature of 70 to 40 ° C lower.

Further, specifically, the temperature of the cooling gas Gc is preferably -40 to 25 ° C, more preferably -20 to 15 ° C, still more preferably -20 to 10 ° C.

Regarding the cooling gas line 3 in the cooling gas supply step, the ratio of the flow rate (NL (standard liter) / hr) of the cooling gas Gc to the supply amount (kg / hr) of the raw material supplied from the raw material supply line 2 is preferably It is set to 1 to 1000 (NL/kg), more preferably 5 to 500 (NL/kg), and further preferably 5 to 250 (NL/kg). The ratio of the high-temperature gas Gr to the cooling gas Gc which is countercurrent is preferably from 0.01 to 0.3, more preferably from 0.03 to 0.2, still more preferably from 0.03 to 0.15.

In the case where a plurality of cooling gas lines 3 are provided in one raw material supply line 2, the flow rate of the cooling gas Gc in the cooling gas line 3 means the total flow rate of each cooling gas line 3.

Examples of the cooling gas Gc in the cooling gas supply step include nitrogen gas, carbon dioxide (CO ₂ ), argon gas, air, helium gas, and the like.

When using the extruder 1 having the vortex cooler as shown in FIG. 1, The temperature of the normal temperature gas is preferably from 10 to 50 ° C, more preferably from 10 to 40 ° C, and still more preferably from 15 to 40 ° C. In particular, in the method for producing a PPE resin composition, the temperature of the normal temperature gas is preferably from 10 to 50 ° C, more preferably from 10 to 30 ° C, still more preferably from 10 to 20 ° C.

The pressure of the normal temperature gas can be set to 0.1 to 2.0 MPa, preferably 0.15 to 0.8 MPa, and more preferably 0.3 to 0.8 MPa. When the pressure is less than 0.1 MPa, since there is no The eddy current is strong, so the temperature of the cooling gas Gc does not decrease. When the pressure exceeds 1.0, it exceeds the range that the body of the cooler 31 can withstand. In particular, in the method for producing a PPE resin composition, the pressure of the normal temperature gas may be 0.1 to 1.0 MPa, preferably 0.15 to 0.8 MPa, and more preferably 0.3 to 0.8 MPa. When the pressure is less than 0.1 MPa, since the strong eddy current does not occur, the temperature of the cooling gas Gc does not decrease. When the pressure exceeds 1.0, it exceeds the range that the body of the cooler 31 can withstand.

The humidity of the normal temperature gas is preferably less than 0.1%, and the normal temperature gas of the humidity is preferably adjusted by a filter for removing foreign matter, and the foreign matter having a size of 5 μm or less is less than 0.1% by mass.

When using a vortex cooler, The temperature of the cooling gas Gc is preferably 15 to 75 ° C lower than the temperature of the supplied normal temperature gas, more preferably 20 to 75 ° C lower. In particular, in the method for producing the PPE resin composition, the temperature of the cooling gas Gc is preferably 15 to 75 ° C lower than the temperature of the supplied normal temperature gas, and more preferably 20 to 55 ° C lower.

The temperature of the high temperature gas is preferably 5 to 110 ° C higher than the temperature of the supplied normal temperature gas, more preferably 30 to 75 ° C lower. In particular, in the method for producing a PPE resin composition, the temperature of the high temperature gas is preferably 5 to 110 ° C higher than the temperature of the supplied normal temperature gas, more preferably 25 to 45 ° C lower.

The rate of generation of the cooling gas Gc from the normal temperature gas is expressed by the ratio of the discharged cooling gas Gc to the supplied normal temperature gas, and can be 20 to 80%, preferably 30 to 70%, and more preferably 40 to 40. 70%. If it is less than 20%, the economic loss is large, and if it exceeds 80%, the temperature of the generated cooling gas Gc is not sufficiently lowered.

In the melt-kneading step, When the cartridge 10 having the raw material supply port 11, the cartridge 10 forming the solid transfer zone, and the extruder 1 forming the cartridge 10 of the kneading zone are used as shown in FIG. Setting of the cartridge 10 (the first cartridge 10a in Fig. 1) having the raw material supply port 11 Specifically, the temperature is preferably 50 ° C or lower, more preferably 45 ° C or lower, and still more preferably 40 ° C or lower. If the cylinder temperature exceeds 50 ° C, the temperature of the high-temperature gas Gr which rises countercurrent rises, which is not preferable.

The set temperature of the cylinder 10 (the second to fourth cylinders (10b to 10d) in FIG. 1) for forming the solid transfer zone is preferably 50 to 300 ° C, more preferably 50. It is preferably -250 ° C or lower, more preferably 60 to 250 ° C or lower. When the temperature of the cylinder 10 forming the solid transfer zone exceeds 300 ° C, the cylinder 10 forming the solid transfer zone and the cylinder 10 having the raw material supply port adjacent to each other via the gasket are not sufficiently cooled, and the countercurrent is high. The temperature of the gas Gr is substantially increased, which is not preferable.

The setting temperature of the cylinder 10 (the fifth cylinder 10e in FIG. 1) which forms the kneading zone is the thermoplastic resin (A) (the resin which is the most supplied when the thermoplastic resin is two or more types) In the case of a crystalline resin, it is preferably a temperature of 0 to 100 ° C higher than the melting point, and more preferably a temperature of 10 to 50 ° C higher. When the thermoplastic resin (A) is an amorphous resin, it is preferably at a temperature of 50 to 150 ° C higher than the glass transition temperature, and more preferably at a temperature of 70 to 120 ° C.

In particular, in the melt-kneading step in the method for producing a polyphenylene ether-based resin composition, When the cartridge 10 having the raw material supply port 11, the cartridge 10 forming the solid transfer zone, and the extruder 1 forming the cartridge 10 of the kneading zone are used as shown in FIG. The set temperature of the cylinder 10 having the raw material supply port 11 (the first cylinder 10a in Fig. 1) is preferably set to a temperature lower by 0 to 50 ° C than the melting point of triphenyl phosphate (D). More preferably, it is a temperature lower by 10 to 40 ° C, and further preferably a temperature lower by 5 to 30 ° C. More specifically, it is preferably 50 ° C or lower, more preferably 45 ° C or lower, and still more preferably 40 ° C or lower. If the cylinder temperature exceeds 50 ° C, the temperature of the countercurrent high-temperature gas Gr rises, which is not preferable.

The set temperature of the cylinder 10 (the second to the fourth cylinders (10b to 10d) in Fig. 1) forming the solid transfer zone is preferably set to be lower than the melting point of the triphenyl phosphate (D). -250~0 The temperature of °C is more preferably a temperature of -150 to -20 ° C, and further preferably a temperature of -50 to -20 ° C. More specifically, it is preferably 300 ° C or lower, more preferably 200 ° C or lower, and still more preferably 100 ° C or lower. When the temperature of the cylinder 10 forming the solid transfer zone exceeds 300 ° C, the cylinder 10 forming the solid transfer zone and the cylinder 10 having the raw material supply port adjacent to each other via the gasket are not sufficiently cooled, and the countercurrent is high. The temperature of the gas Gr is substantially increased, which is not preferable.

The set temperature of the cylinder 10 (the fifth cylinder 10e in Fig. 1) forming the kneading zone is preferably set to a temperature 30 to 130 ° C higher than the melting point of the polyphenylene ether (A), more preferably It is set to a temperature of 50 to 110 °C. More specifically, it is preferably 245 to 345 ° C, more preferably 265 to 325 ° C, still more preferably 270 to 320 ° C.

In the melt-kneading step, the gear box of the extruder 1 has a torque density Td of 6 to 25 N·m/cm ³ , preferably 8 to 24 N·m/cm ³ , and more preferably 14 to 23 N·m/cm. ³ . When the torque density Td is in the range of 6 or more and 25 or less, the productivity of the resin composition and the stability of the quality can be excellent.

In addition, the torque density Td (N‧ m/cm ³ ) of the gear case is obtained by the following formula (1).

Torque density Td (N‧m/cm ³ ) = maximum motor power (kw) × 1000 / (2 × 3.14 × maximum number of revolutions) / ((screw diameter d (cm) / 10) ³ ) (1)

For example, when a TEM58SS manufactured by Toshiba Machine Co., Ltd. is used for a motor having a maximum number of revolutions of 10 rps and 181 kw, the torque density Td is 14.8 N‧ m/cm ³ .

The thermoplastic resin composition produced by the method for producing a thermoplastic resin composition of the present embodiment can be suitably used for OA (Office Automation) materials (printers, photocopiers, etc.), electronic materials, optical materials, and battery cans. Server fans such as bulk materials, battery cell materials, films, sheets, appliances, or computers.

The extruder of the present invention and the thermoplastic of the same using the same according to the drawings The embodiment of the method for producing the resin composition is exemplified, but the above embodiment can be appropriately modified, and the present invention is not limited to the above-described embodiment.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples, but the invention should not be construed as limited.

The extruder of the examples and the comparative examples and the method for producing the thermoplastic resin composition using the same are described below.

- Raw material supply pipeline -

--The first raw material supply pipeline --

The first raw material supply hopper (conical type, hopper wall angle of 60 degrees)

---The 1A series (for low melting point additives) ---

1A raw material storage tank (200L)

1A material cutting device (sliding door valve)

1A raw material supply device (weight feeder A: CE-W-2 manufactured by Kubota)

1A raw material supply piping (4 inch piping, inclined 45 degree piping)

---The 1B series (for thermoplastic resin) ---

1B raw material storage tank (500L)

1B material cutting device (sliding door valve)

1B raw material supply device (weight feeder B: CE-W-4 manufactured by Kubota Co., Ltd.)

1B raw material supply piping (4 inch piping, inclined 45 degree piping)

---The 1C series (for thermoplastic resin) ---

1C raw material storage tank (500L)

1C raw material cutting device (sliding door valve)

1C raw material supply device (weight feeder B: CE-W-4 manufactured by Kubota)

1C raw material supply piping (4 inch piping, inclined 45 degree piping)

--The second raw material supply pipeline --

2nd raw material storage tank (200L)

Second material cutting device (sliding door valve)

Second raw material supply device (weight feeder C: CE-W-2 manufactured by Kubota)

The second raw material supply pipe (4 inch piping, inclined 90 degree piping)

The second raw material supply hopper (conical type, hopper wall angle of 60 degrees)

-Cooling gas supply line -

Two panel protection coolers (760J, manufactured by Rainbow Technology Co., Ltd.) were used as the cooler. These are arranged as described in Table 1.

-Extruder -

A twin-shaft co-rotating extruder (TEM58SS (12 barrel extruder length 48D) manufactured by Toshiba Machine Co., Ltd.) was used as an extruder.

The barrel configuration is as follows.

1st barrel: first supply port (top feed barrel, weight feeders A, B, C)

2nd barrel: solid transfer area

3rd barrel: solid transfer area

4th barrel: solid transfer area

5th barrel: the first mixing area

6th barrel: atmospheric vent

7th barrel: second supply port (side feed barrel, weight feeder D)

8th barrel: second mixing area

9th barrel: melt transfer area

10th barrel: melt transfer area

11th barrel: vacuum vent

12th barrel: melt transfer area

Mold head: template (hole diameter 4mm , the number of holes is 20 holes)

-Insulation -

Superwool mat (manufactured by ASUKA Co., Ltd.) (thickness 50mm)

-other devices-

Strand trough: water temperature 40±3°C

Granulator: particle length 2.5 ± 0.3mm, particle shape: cylindrical shape

(Method for Producing Thermoplastic Resin Composition)

- thermoplastic resin (A) -

(A-1) Polyphenylene ether resin (manufactured by Asahi Kasei Chemicals Co., Ltd., S201A) (glass transition temperature: 220 ° C)

(A-2) Reducing viscosity (measured at 30 ° C using a chloroform solvent) 0.40 dl / g of poly(2,6-dimethyl-1,4-phenylene) ether

(A-3) General Polystyrene 685 (manufactured by PS Japan)

(A-4) General-purpose polystyrene (trade name: Styron 660 (registered trademark), manufactured by Dow Chemical Co., Ltd.)

(A-5) Polycarbonate (manufactured by Mitsubishi Engineering-Plastics Co., Ltd., Iupilon S3000F (registered trademark)) (glass transition temperature: 150 ° C)

(A-6) Nylon 66 (manufactured by Asahi Kasei Chemical Co., Ltd., Leona 1300S (registered trademark)) (melting point 265 ° C)

- low melting point additive (B) -

(B-1) Triphenyl phosphate (manufactured by Daiba Chemical Co., Ltd., TPP (registered trademark)) (melting point 50 ° C)

(B-2) Citric acid (melting point 153 ° C)

(B-3) Phosphazene (Rapidle FP110 (registered trademark) manufactured by Fushimi Pharmaceutical Co., Ltd.) (melting point 100 ° C)

-Filler (C)-

(C-1) Glass fiber (manufactured by Nippon Electric Glass Co., Ltd., ECS03T-249 (registered trademark), diameter 13 μm)

(C-2) GF: Glass fiber having a fiber diameter of 10 μm and a fiber-cut length of 3 mm by surface treatment with an amino decane compound (trade name: EC10 3MM 910 (registered trademark), manufactured by NSG Vetrotex Co., Ltd.)

- Masterbatch -

Including talc (manufactured by FUJI TALC INDUSTRIAL, RGE-250, average particle diameter: 2 μm), 85 parts by mass, and ethyl bis-stearylamine (manufactured by Kao Co., Ltd., KAO WAX EB-FF, melting point: 142 ° C), 10 parts by mass , polyethylene glycol (Linzhi Pharmaceutical Co., Ltd., PEG400, melting point -12 ° C) 5 parts by mass of about 2 mm spherical masterbatch (the melting point of the masterbatch is 75 ° C)

(test methods)

(1) The internal temperature of the raw material supply hopper

A portable thermometer (HD-1100, manufactured by Anritsu Co., Ltd., HD-1100, for the air) is placed at a position 20 cm below the cover of the material supply hopper (the middle height of the hopper) and at the center of the horizontal direction of the raw material supply hopper. AT-40 type) and measure the temperature (°C). The results are shown in Table 1.

(2) Internal temperature of raw material supply piping

The material supply pipe has a length of 120 cm and is disposed in the vertical direction along the extending direction.

The raw material supply piping was placed at a position of 110 cm from the side end of the cylinder (a model manufactured by Anritsu Co., Ltd., HD-1100, and the sensor was used for the surface type A-2), and the temperature (° C.) was measured. The results are shown in Table 1.

(3) The temperature of the outer wall surface of the screw cylinder of the weight feeder of the raw material supply device

A portable thermometer (HD-1100, manufactured by Anritsu Co., Ltd., HD-1100, sensor type A-2) is placed on the upper side of the cylinder on the screw outlet side of the weight feeder of the raw material supply device, and the temperature is measured. (°C). The results are shown in Table 1.

(evaluation method)

(4) Stability of the strand

The strands ejected from the head of the die of the extruder were visually evaluated for the presence or absence of fluctuations (corrugations) and the presence or absence of strand breakage. Then, the stability of the strand is determined based on the following criteria.

<Judgment criterion (expressed by "decision point: state of strand")>

1: No fluctuations. No strand breaks.

2: No fluctuations. No strand breaks. However, the vibration of the strand is greater than one.

3: No fluctuations initially, resulting from more than 30 minutes. No strand breaks.

4: No fluctuations initially, resulting from more than 30 minutes. There is a strand break.

5: Fluctuations have occurred since the beginning. Strand breaks often occur.

(5) The extent to which the raw materials are supplied to the inside of the hopper

The degree of the deposit inside the raw material supply hopper was evaluated by visual observation, and the determination was made based on the following criteria.

<Criteria for judgment (expressed by "decision point: degree of deposit")>

1: Not at all.

2: There is accumulation in the raw material supply port, but there is no accumulation on the wall surface.

3: The accumulation of the raw material supply port is about 1/4 of the area of the supply port, and there is no accumulation on the wall surface.

4: The accumulation of the raw material supply port is about 1/4 to 1/2 of the area of the supply port, or there is a small accumulation on the wall surface of the raw material supply hopper.

5: The accumulation of the raw material supply port is 1/2 or more of the area of the supply port, or there is a large accumulation on the wall surface of the raw material supply hopper.

(6) The extent to which the raw material is supplied to the raw material block inside the hopper

The degree of supply of the raw material to the inside of the hopper after extrusion was visually evaluated to the extent that the flow of the raw material supply line was maintained in a good state or blocked.

(7) The degree of foreign matter in the strand

The strands ejected from the head of the die of the extruder were made into pellets having a thickness of 3 mm and a length of 3 mm by means of a granulator, and the pellets were pressurized by a press molding machine (temperature: 250 ° C, pressure: 5 to 10 MPa). Thus, a flat plate having a thickness of 1 mm and a bottom surface of 254 cm ^{2 was} produced. Then, the flat plate was observed with a magnifying glass of 10 times, and the size (maximum diameter) of the foreign matter point mainly containing the oxide observed on the back surface and the front surface of the flat plate was evaluated, and each foreign matter point was evaluated according to the following criteria. The total evaluation points for all the foreign matter observed are shown in Table 1.

<Evaluation criteria (expressed by "evaluation point: size of foreign matter point")>

1: Less than 200 μm.

2: 200~400μm.

4:400~800μm.

8: More than 800 μm.

(8) Melt flow rate (MFR)

The measurement of MFR was carried out in accordance with ISO 1133, and the pellets were sampled every 10 minutes at the outlet of the self-made granulator, and each pellet was subjected to 6 times. For the measurement, in Examples 1 to 13 and Comparative Examples 1 to 6, the cylinder temperature was set to 300 ° C, and the pellets were heated for 3 minutes, and a load of 5 kg was applied thereto, and the measurement was carried out for 10 minutes. (In the case of polycarbonate, the load is 1.2 kg). In Examples 14 to 18 and Comparative Examples 7 to 9, the cylinder temperature was set to 250 ° C, and a load of 10 kg was applied and measured.

(9) UL (Underwriters Laboratories, American Underwriters Laboratories) Combustion Test

The pellets were sampled every 10 minutes at the outlet of the self-made granulator, and the pellets were supplied to an injection molding machine equipped with a die (IS80EPN, manufactured by Toshiba Machine Co., Ltd.) at a cylinder temperature of 320 ° C, a die temperature of 90 ° C, and an injection pressure of 120 MPa. The molding was carried out under the conditions of an injection speed of 90% (panel display), injection time/cooling time = 10 sec/30 sec, and a short-length molded piece having a thickness of 0.8 mm was produced. The UL-94 test piece was used to perform a UL burning test using the 0.8 mm thick strip forming piece.

(Example 1)

Into the 1A raw material storage tank which is located upstream of the weight feeder A of the raw material supply line, triphenyl phosphate (TPP) (manufactured by the eighth chemical company) having a melting point of 50 ° C as a phosphorus-based flame retardant is introduced. The 1B raw material storage tank located upstream of the weight type feeder B was charged with polyphenylene ether resin (S201A, manufactured by Asahi Kasei Chemicals Co., Ltd.) (glass transition temperature: 220 ° C), and was placed at the first CC upstream of the weight type feeder C. In the raw material storage tank, general-purpose polystyrene 685 (manufactured by PS Japan Co., Ltd.) was charged.

The supply amount in the weight feeder A/weight feeder B/weight feeder C was set to 20 parts by mass/55 parts by mass/25 parts by mass, and the extrusion amount was set to 400 kg/hr, and the number of revolutions of the screw was Set to 400 rpm.

The panel protection cooler 760J, which is a cooler attached to the cooling gas supply line, is set as follows: a filter of 1 μm is supplied at 5400 NL/hr and the humidity is less than 0.001%, the nitrogen concentration is 99.99%, the pressure is 0.6 MPa, and the temperature is 40 °C. Nitrogen gas; a cooling gas of -4 ° C was discharged at 3120 NL / hr, and a high temperature gas of 103 ° C was discharged at 2280 NL / hr.

One of the panel protection coolers is disposed below the lid of the first A material supply hopper in the direction of gravity, and the other cover of the first A material storage tank is disposed downward in the direction of gravity, and in detail, it is placed in Table 1- The position shown in 1.

No insulation is used.

The conditions of the extruder are as follows.

The cylinder temperature was set to 1st barrel: 35 ° C, 2nd barrel: 50 ° C, 3rd barrel: 100 ° C, 4th barrel: 250 ° C, 5th to 12th barrel: 280 ° C.

The set temperature of the die head was set to 280 °C.

Other conditions in the manufacture are set as shown in Table 1-1.

After the start of production, the MFR was measured every 10 minutes, and after 1 hour, the extruder was stopped, and the inside of the raw material supply hopper was inspected. The temperature of each location is up to 41 °C. After 1 hour, the extruder was stopped, and the deposit was confirmed, and as a result, there was no deposit at all. The operation is also stable, MFR is also stable.

The measurement results and evaluation results of Example 1 are shown in Table 1-1.

(Comparative Example 1)

The same procedure as in Example 1 was carried out except that the cooling gas supply line was not used.

The temperature of the raw material supply line reaches a temperature exceeding the melting point of triphenyl phosphate. After 1 hour, the extruder was stopped, and the inside of the raw material supply hopper was inspected, and as a result, a large block was observed on the wall surface, and 3/4 or more of the area of the raw material supply port of the extruder was blocked. MFR also decreases with time. The measurement results and evaluation results of Comparative Example 1 are shown in Table 1-1.

(Comparative Example 2)

The same procedure as in Example 1 was carried out except that the panel-protected cooler of the cooling gas supply line was stopped and supplied with uncooled nitrogen gas at 5,400 NL/hr.

The results in Comparative Example 2 were substantially the same as in Comparative Example 1. The measurement results and evaluation results of Comparative Example 2 are shown in Table 1-1.

(Example 2)

The same procedure as in Example 1 was carried out except that the cooling gas supply line was placed only in the first raw material supply hopper.

The temperature of the raw material supply hopper, the raw material supply pipe, and the screw cylinder is higher than the temperature of the first embodiment, but the temperature in the entire first raw material supply line is lower than the melting point of triphenyl phosphate. In the same manner as in the first embodiment, no block or the like was generated inside the raw material supply hopper. MFR is also stable. The results of Example 2 are shown in Table 1-1.

(Examples 3 to 5)

One of the cooling gas supply lines is connected to the first A raw material supply hopper, and the other of the cooling gas supply lines is connected to the first A raw material cutting device (Example 3), the first A raw material supply device (Example 4), and the first A. The raw material supply piping (Example 5) was connected, and the same procedure as in Example 1 was carried out.

The results in Examples 3 to 5 were almost the same as those in Example 1, and the productivity was good. The measurement results and evaluation results of Examples 3 to 5 are shown in Table 1-1.

(Example 6)

The temperature of the second and third cylinders was set to 280 ° C, and the heat insulating material was placed on the upper surfaces of the second to fifth cylinders, and the same procedure as in the first embodiment was carried out.

The results of Example 6 were substantially the same as those of Example 1, and the productivity was good.

The measurement results and evaluation results of Example 6 are shown in Table 1-1.

(Example 7)

The same procedure as in Example 1 was carried out except that the gas supplied to the panel-protected cooler was set to be compressed air of 0.6 MPa of the air compressor instead of nitrogen.

In Example 7, as in Example 1, productivity was good, but since air was used instead of nitrogen, foreign matter increased.

The measurement results and evaluation results of Example 7 are shown in Table 1-1.

(Example 8)

The same procedure as in Example 1 was carried out except that the second raw material supply line was used instead of the first raw material supply line to supply the TPP. In this case, one of the panel protection coolers is disposed below the lid of the second material supply hopper, and the other of the panel protection coolers is connected to the first A material supply hopper, and is disposed in detail. The location shown in Table 1.

The measurement results and evaluation results of Example 8 are shown in Table 1-1.

(Example 9)

Further, 0.8 parts by mass of citric acid was supplied from the first raw material supply port using the weight type feeder A, and glass fiber (ECS03T-249, manufactured by Nippon Electric Glass Co., Ltd., diameter: 13 μm) was supplied from the second raw material supply port using the weight type feeder D. Except that the amount was 20 parts by mass, the same procedure as in Example 1 was carried out.

In Example 9, productivity was good in the same manner as in Example 1.

The measurement results and evaluation results of Example 9 are shown in Table 1-1.

(Embodiment 10)

S201A was set to 65 parts by mass from 55 parts by mass, and was set to Rabitle FP110 (10 parts by mass) instead of TPP (20 parts by mass), and the temperature of the second and third barrels was adjusted in order to improve the kneadability of FP110. The procedure was carried out in the same manner as in Example 1 except that the temperature was 280 °C.

In the tenth embodiment, the internal temperature of the raw material supply hopper was increased in accordance with the increase in the temperature of the second and third cylinders, but the productivity was stabilized in the same manner as in the first embodiment.

The measurement results and evaluation results of Example 10 are shown in Table 1-2.

(Comparative Example 3)

The same procedure as in Example 10 was carried out except that the cooling gas supply line was not used.

In Comparative Example 3, the internal temperature of the raw material supply hopper exceeded 100 ° C, and a block was generated inside the raw material supply hopper, and there were also many foreign matters.

The measurement results and evaluation results of Comparative Example 3 are shown in Table 1-2.

(Example 11)

The same procedure as in Example 10 was carried out, except that 90 parts by mass of polycarbonate (glass transition temperature: 150 ° C) was used instead of S201A and GP685.

In Example 11, productivity was stabilized in the same manner as in Example 9.

The measurement results and evaluation results of Example 11 are shown in Table 1-2.

(Embodiment 12)

The same procedure as in Example 1 was carried out, except that 20 parts by mass of the master batch was used in place of 20 parts by mass of the TPP, and the temperature of the second and third cylinders was set to 280 ° C in order to improve the dispersibility of the talc.

In Example 12, productivity was stabilized in the same manner as in Example 1.

The measurement results and evaluation results of Example 12 are shown in Table 1-2.

(Comparative Example 4)

The same as in the example 12 except that the cooling gas supply line was not used. Shi.

In Comparative Example 4, the amount of adhesion to the inner wall of the raw material supply hopper increased in accordance with the temperature increase in the raw material supply hopper.

The measurement results and evaluation results of Comparative Example 4 are shown in Table 1-2.

(Example 13)

80% by mass (melting point 265 ° C) was used instead of S201A and GP685, and the gas supplied to the panel protection cooler was set to 0.6 MPa of compressed air of the air compressor instead of nitrogen gas, and Example 12 was used. Implemented in the same way.

In Example 13, productivity was good.

The measurement results and evaluation results of Example 13 are shown in Table 1-2.

(Comparative Example 5)

The same procedure as in Example 13 was carried out except that the cooling gas supply line was not used.

In Comparative Example 5, the amount of adhesion to the inner wall of the raw material supply hopper increased in accordance with the temperature increase in the raw material supply hopper.

The measurement results and evaluation results of Comparative Example 5 are shown in Table 1-2.

(Comparative Example 6)

The cooling gas supply line was not used, and the outer wall of the first raw material supply hopper was set to two layers, and the cooling water was passed through the inside of the first raw material supply hopper, and the raw material supply hopper was cooled, and the same as in the first embodiment. Implementation. Specifically, in Comparative Example 6, a flow path was provided between the outer walls so as to flow spirally from the bottom of the raw material supply hopper to the lid portion. Here, a free cooling chiller (ORION machine) was used. Co., Ltd. manufactured), supplying -4 ° C cooling water.

The temperature of the raw material supply line reaches a temperature exceeding the melting point of triphenyl phosphate. After 1 hour, the extruder was stopped, and the inside of the raw material supply hopper was inspected. As a result, the condensate of the organic matter was observed on the wall surface, and a larger block was visible thereon, and 3/4 of the area of the raw material supply port of the extruder occurred. Blocked. MFR also decreases with time. The result of Comparative Example 6 is shown In Table 1.

The measurement results and evaluation results of Comparative Example 6 are shown in Table 1-2.

(Example 14)

The TPP is put into the 1A raw material storage tank (200L) located upstream of the weight feeder A of the raw material supply line, and the PPE is put into the 1B raw material storage tank (500L) located upstream of the weighted feeder B. The GPPS is charged into the feeder C, and the GF is fed into the weight feeder D.

The supply amount in the weight feeder A/weight feeder B/weight feeder C/weight feeder D is set to 15 parts by mass / 52 parts by mass / 3 parts by mass / 30 parts by mass, and the discharge amount is set. At 400 kg/hr, the number of revolutions of the screw was set to 400 rpm.

The panel protection cooler 760J which is a cooler attached to the cooling gas supply line is set as follows: a filter of 1 μm is supplied at 90 N-L/min, and the humidity is less than 0.001%, the nitrogen concentration is 99.99%, the pressure is 0.6 MPa, and the temperature is set. Nitrogen gas at 40 ° C; a cooling gas of -4 ° C was discharged at 54 N-L/min, and a high-temperature gas of 103 ° C was discharged at 36 N-L/min.

One of the panel protection coolers is disposed below the first raw material supply hopper in the direction of gravity, and the other is placed in the first A material storage tank, and in detail, it is placed at the position shown in Table 1.

No insulation is used.

The conditions of the extruder are as follows.

The cylinder temperature was set to 1st barrel: 35 ° C, 2nd barrel: 50 ° C, 3rd barrel: 100 ° C, 4th barrel: 250 ° C, 5th to 12th barrel: 280 ° C.

The set temperature of the die head was set to 280 °C.

Other conditions in the manufacture are set as shown in Table 1.

After the start of production, the pellets were sampled every 10 minutes and the degree of flame retardancy of MFR and UL was determined. After 1 hour, the extruder was stopped and the inside of the raw material supply hopper was inspected. After 1 hour, the extruder was stopped, and the raw material block was confirmed. As a result, there was no raw material block at all. Running from the beginning At the end of the day, the MFR and UL flame retardancy of the particles sampled every 10 minutes were also stable, and no problem was observed.

The measurement results and evaluation results of Example 14 are shown in Table 1-3.

(Comparative Example 7)

The same procedure as in Example 1 was carried out except that the cooling gas supply line was not used.

The temperature of the raw material supply line reaches a temperature exceeding the melting point of triphenyl phosphate. The strand take-up property was unstable from the start of the squeezing operation, and the operation was stopped due to an increase in the screw torque after about 37 minutes passed. When the extruder was stopped and the inside of the raw material supply hopper was inspected, it was confirmed that the raw material block caused by the molten TPP was generated on the wall surface, and the supply port of the extruder was completely blocked. Further, regarding the degree of flame retardancy of MFR and UL, the particles sampled after 30 minutes were also seen to be reduced. Since the extrusion was stopped, the sampling after 30 minutes and the measurement of the MFR and UL flame retardancy were not performed.

The measurement results and evaluation results of Comparative Example 7 are shown in Table 1-3.

(Comparative Example 8)

The same procedure as in Example 1 was carried out except that the panel-protected cooler of the cooling gas supply line was stopped and the uncooled nitrogen gas was directly supplied at 90 N-L/min.

The results in Comparative Example 2 were substantially the same as in Comparative Example 1. The temperature of the raw material supply line reaches a temperature exceeding the melting point of triphenyl phosphate. When the elapse of about 53 minutes from the start of the squeezing operation, the operation was stopped due to an increase in the screw torque. When the extruder was stopped and the inside of the raw material supply hopper was inspected, it was confirmed that the raw material block caused by the molten TPP was generated on the wall surface, and the supply port of the extruder was completely blocked. Further, regarding the degree of flame retardancy of MFR and UL, the particles sampled after 30 minutes were also found to be uneven.

The measurement results and evaluation results of Comparative Example 8 are shown in Table 1-3.

(Example 15)

The same procedure as in Example 1 was carried out except that the cooling gas supply line was placed only in the first raw material supply hopper.

The temperature of the raw material supply pipe and the screw cylinder was higher than that of the first embodiment, but the temperature of the raw material supply hopper was the same as that of the first embodiment. In the same manner as in the first embodiment, no block or the like was generated inside the raw material supply hopper. The flame retardancy of MFR and UL is also stable.

The measurement results and evaluation results of Example 15 are shown in Table 1-3.

(Embodiment 16)

The same procedure as in Example 1 was carried out except that the cooling gas supply line was placed only in the 1A raw material storage tank.

The temperature of the raw material supply hopper, the raw material supply pipe, and the screw cylinder may be slightly higher than the temperature of the first embodiment, but both are lower than the melting point of the TPP. In the same manner as in the first embodiment, no block or the like was generated inside the raw material supply hopper. The flame retardancy of MFR and UL is also stable.

The measurement results and evaluation results of Example 16 are shown in Table 1-3.

(Example 17)

The supply amount in the weight feeder A/weight feeder B/weight feeder C/weight feeder D is set to 15 parts by mass/40 parts by mass/0 parts by mass/45 parts by mass, in addition to It was carried out in the same manner as in Example 1. The squeezing operation was stable from start to finish and no special problems were observed. After 1 hour, the extruder was stopped, and the inside of the raw material supply hopper was inspected, and as a result, there was no raw material block at all. The MFR and UL flame retardancy of the particles sampled every 10 minutes were also stable, and no particular problem was observed.

The measurement results and evaluation results of Example 17 are shown in Table 1-3.

(Comparative Example 9)

A cooling water supply line was not used, and a cooling water water jacket was attached to the outer wall of the first raw material supply hopper, and the cooling water was supplied to the casing to cool the raw material supply hopper, and the same as in the first embodiment. Implementation.

The results of Comparative Example 9 were substantially the same as those of Comparative Example 7.

The measurement results and evaluation results of Comparative Example 9 are shown in Table 1-3.

(Embodiment 18)

The gas supplied to the panel protection cooler is set to be vaporized liquid nitrogen instead of nitrogen, and the gas is dried, and then the cooling gas is supplied at 54 N-L/min by a supply pipe which is cooled by a heat insulating material (glass wool). Supply lines 1, 2 are supplied.

The results of Example 18 were substantially the same as in Example 14.

The measurement results and evaluation results of Example 18 are shown in Table 1-3.

[Industrial availability]

According to the present invention, a thermoplastic resin composition having uniform physical properties can be produced with high stability and high productivity.

The thermoplastic resin composition obtained by the extruder of the present invention and the production method using the same can be suitably used for a master batch, a concentrate of an intermediate material, an OA material, an electronic material, an optical material, a battery case material, a battery unit. Materials, films, sheets, etc.

1‧‧‧Extrusion machine

2‧‧‧Material supply pipeline

2-1‧‧‧1st raw material supply pipeline

2-2‧‧‧Second raw material supply pipeline

3‧‧‧Cooling gas supply line

3-1A‧‧‧1A cooling gas supply line

3-1B‧‧‧1B cooling gas supply line

3-2A‧‧‧2A cooling gas supply line

3-2B‧‧‧2B cooling gas supply line

4‧‧‧Insulation

10‧‧‧Bowl

10a‧‧‧1st barrel

10l‧‧‧12th barrel

11‧‧‧Material supply port

11-1‧‧‧1st raw material supply port

11-2‧‧‧2nd material supply port

12‧‧‧ venting holes

12-1‧‧‧1st vent

12-2‧‧‧2nd exhaust hole

13‧‧‧Mold head

20‧‧‧Material supply hopper

21‧‧‧Material storage tanks

22‧‧‧Material cutting device

23‧‧‧Material supply device

24‧‧‧Material supply piping

31‧‧‧ chiller

201‧‧‧1st raw material supply hopper

202‧‧‧Second raw material supply hopper

211A‧‧‧1A raw material storage tank

211B‧‧‧1B raw material storage tank

211C‧‧‧1C raw material storage tank

212‧‧‧Second raw material storage tank

221A‧‧‧1A raw material cutting device

221B‧‧‧1B raw material cutting device

221C‧‧‧1C raw material cutting device

222‧‧‧Second raw material cutting device

231A‧‧‧1A raw material supply device

231B‧‧‧1B raw material supply device

231C‧‧‧1C raw material supply device

232‧‧‧2nd material supply device

241A‧‧‧1A raw material supply piping

241B‧‧‧1B raw material supply piping

241C‧‧‧1C raw material supply piping

242‧‧‧Second raw material supply piping

311A‧‧‧1A cooler

311B‧‧‧1B cooler

312A‧‧‧2A cooler

312B‧‧‧2B cooler

D‧‧‧Barrel diameter

L‧‧‧ Effective length of barrel

X‧‧‧Axis of extruder

Claims (22)

An extruder comprising a raw material supply port to which a raw material supply line is connected, and a raw material supply line having a cooling gas supply line communicating with at least a part thereof. The extruder of claim 1, wherein the cooling gas supply line is provided with a cooling machine. The extruder of claim 2, wherein the cooler is a vortex cooler. An extruder according to any one of claims 1 to 3, which is provided with a plurality of the above-mentioned cooling gas supply lines. The extruder according to any one of claims 1 to 4, which is provided with a plurality of the above-mentioned raw material supply ports. The extruder according to any one of claims 1 to 5, wherein the raw material supply line sequentially includes a raw material storage tank, a raw material cutting device, a raw material supply device, a raw material supply pipe, and a raw material supply hopper, toward the raw material supply port, and The cooling gas supply line is in communication with the raw material supply hopper. The extruder of any one of claims 1 to 6, further comprising a heat insulating material covering at least a portion of an outer surface of the extruder. The extruder according to any one of claims 1 to 7, wherein the cooling gas supply line extends in a direction orthogonal to an axial direction of the extruder. The extruder according to any one of claims 1 to 8, wherein the cooling gas supply line is provided in a region from the axis of the extruder to a distance of from 1 to 500 times the diameter D of the cylinder. The extruder of any one of claims 1 to 9, wherein the raw material supply device is a weight type feeder. The extruder of any one of claims 1 to 10, wherein the extruder is a single shaft extruder or a twin shaft extruder. A method for producing a thermoplastic resin composition, characterized in that a thermoplastic resin is melt-kneaded with an additive having a melting point of 40 to 200 ° C using an extruder according to any one of claims 1 to 11. The method for producing a thermoplastic resin composition according to claim 12, wherein the thermoplastic resin is a polyphenylene ether resin or a polycarbonate resin, and the additive having a melting point of 40 to 200 ° C is a phosphorus-based flame retardant. The method for producing a thermoplastic resin composition according to claim 13, wherein the phosphorus-based flame retardant is a phosphate compound or a phosphazene compound. The method for producing a thermoplastic resin composition according to claim 14, wherein the phosphazene compound is a phenoxyphosphazene compound. The method for producing a thermoplastic resin composition according to claim 14 or 15, wherein the phosphate compound is triphenyl phosphate. The method for producing a thermoplastic resin composition according to any one of claims 12 to 16, wherein the liquid additive and the filler are melt-kneaded in addition to the thermoplastic resin and the additive having a melting point of 40 to 200 °C. A method for producing a polyphenylene ether-based resin composition, which is a method for producing a polyphenylene ether-based resin composition by using the extruder according to any one of claims 1 to 11, and a polyphenylene ether, The total mass of the styrene resin, the fibrous filler, and the triphenyl phosphate is 90% by mass or more, and the total mass is 100% by mass, and the polyphenylene ether is 25 to 85% by mass, and the styrene resin is 0 to 0. 30% by mass, 10 to 50% by mass of the fibrous filler, and 5 to 20% by mass of the triphenyl phosphate are melted and kneaded. The method for producing a polyphenylene ether-based resin composition according to claim 18, wherein the cooling gas supply line includes a vortex cooler, and the cooling gas is nitrogen. The method for producing a polyphenylene ether-based resin composition according to claim 18 or 19, wherein the above extruder is a twin-screw extruder. The method for producing a polyphenylene ether-based resin composition according to any one of claims 18 to 20, wherein the fibrous filler comprises glass fibers. The method for producing a polyphenylene ether-based resin composition according to any one of claims 18 to 21, wherein the fibrous filler contains carbon fibers.