JP6865317B2 - Extruder and method for producing a thermoplastic resin composition using the extruder - Google Patents

Description

The present invention relates to an extruder provided with a cooling gas supply line and a method for producing a thermoplastic resin composition using the extruder.

In the production of industrially produced thermoplastic resin compositions, a thermoplastic resin is extruded through a raw material supply line while adding a low melting point additive (for example, an additive having a melting point of 40 to 200 ° C.). And these are melt-kneaded.

At this time, the temperature of the low melting point additive may reach a temperature above the melting point, so that the low melting point additive melts inside the raw material supply line and the low melting point additive adheres to other raw materials. May work as an agent. In this case, the raw material may become a large lump and cause blockage in the feeder screw, the supply pipe, and the inner wall of the hopper.

For example, in Patent Document 1, a mixture of a vinyl chloride resin and a plurality of kinds of additives is heated to exceed the softening point temperature of the vinyl chloride resin, and various additives are fused to the resin surface. In order to prevent the inorganic filler from sticking to the resin surface, the mixture is cooled below the softening point of the low melting point additive, and then the inorganic compound filler is added to the cooled mixture to obtain the mixture. Techniques have been disclosed that prevent the hopper of an extruder from forming a bridge (large mass).
Further, Patent Document 2 discloses a technique of lowering the temperature of the cylinder of the side feeder to 15 to 100 ° C. and supplying the additive to the extruder through the side feeder.
Further, Patent Document 3 describes a technique for removing lumps by intermittently spraying gas at or near the supply port when supplying a phosphorus-based flame retardant having a melting point of 40 to 200 ° C. to the supply port of the extruder. Is disclosed.

Japanese Unexamined Patent Publication No. 8-203026 Japanese Unexamined Patent Publication No. 2003-285317 Japanese Unexamined Patent Publication No. 2014-074094

However, in the technique of Patent Document 1, 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 low melting point additive-containing mixture is not sufficiently cooled. There is a problem that the temperature inside the raw material supply line becomes high and blocking occurs inside the raw material supply line.
Further, even in the technique of Patent Document 2, the cylinder of the side feeder is cooled by water, but the cooling is not sufficient, the raw material supply line becomes hot, and blocking occurs inside the raw material supply line. There was a problem.
Further, in the technique of Patent Document 3, although the gas is sprayed intermittently, the inside of the raw material supply line is not sufficiently cooled, so that the low melting point additive melts and adheres to the wall, and such deposits. There was a problem that it became more solidified and gradually became difficult to remove.

The present invention solves the above-mentioned problems in melt-kneading a thermoplastic resin and a low melting point additive to produce a thermoplastic resin composition having high stability, high productivity, and uniform physical properties. It is an object of the present invention to provide an extruder capable of making it possible, and a method for producing a thermoplastic resin composition using the extruder.

As a result of diligent studies, the present inventor used an extruder having a raw material supply line connected to at least one cooling gas supply device and connecting the raw material supply line to the first supply port. We have found that the above problems can be advantageously solved by using a method for producing a thermoplastic resin composition, and have completed the present invention.

The gist of the present invention is as follows.
[1] A raw material supply port to which a raw material supply line is connected is provided.
The raw material supply line includes a raw material stock tank, a raw material cutting device, a raw material supply device, a raw material supply pipe, and a raw material supply hopper in this order toward the raw material supply port, and is cooled so as to communicate with the raw material supply hopper. A gas supply line and a cooling gas supply line communicating with at least one of the raw material stock tank, the raw material cutting device, the raw material supply device, and the raw material supply pipe are provided .
The cooling gas supply line is equipped with a chiller.
An extruder characterized in that the cooler is a vortex type cooler.
[2] comprises a plurality of pre-Symbol raw material supply port, an extruder according to [1].
[ 3 ] The extruder according to [1] or [2] , further comprising a heat insulating material that covers at least a part of the outer surface of the extruder.
[ 4 ] The extruder according to any one of [1] to [3 ], wherein the cooling gas supply line extends in a direction orthogonal to the axial direction of the extruder.
[ 5 ] The method according to any one of [1] to [4 ], wherein the cooling gas supply line is provided in a region from the shaft of the extruder to a position at a distance of 1 to 500 times the barrel diameter D. Extruder.
[ 6 ] The extruder according to any one of [1] to [5 ], wherein the raw material supply device is a heavy-duty feeder.
[ 7 ] The extruder according to any one of [1] to [6 ], wherein the extruder is a single-screw extruder or a twin-screw extruder.
[ 8 ] A thermoplastic resin, which comprises melt-kneading a thermoplastic resin and an additive having a melting point of 40 to 200 ° C. using the extruder according to any one of [1] to [ 7]. Method for producing the composition.
[9] wherein the thermoplastic resin is a polyphenylene ether resin or polycarbonate resin, the additive of the melting point of 40 to 200 ° C. is a phosphorus-based flame retardant thermoplastic resin composition according to [8] Manufacturing method.
[ 10 ] The method for producing a thermoplastic resin composition according to [9 ], wherein the phosphorus-based flame retardant is a phosphoric acid ester compound or a phosphazene compound.
[ 11 ] The method for producing a thermoplastic resin composition according to [10 ], wherein the phosphazene compound is a phenoxyphosphazene compound.
[ 12 ] The method for producing a thermoplastic resin composition according to [10 ] or [ 11 ], wherein the phosphoric acid ester compound is triphenyl phosphate.
[ 13 ] The thermoplastic resin composition according to any one of [8 ] to [ 12 ], wherein the liquid additive and the filler are further melt-kneaded in addition to the thermoplastic resin and the additive having a melting point of 40 to 200 ° C. Manufacturing method of things.

According to the present invention, it is possible to produce a thermoplastic resin composition having uniform physical properties with high stability and high productivity.

It is a side view which shows the outline of the extruder of this embodiment. FIG. 5 is an enlarged side view showing a cooling gas supply line included in the extruder of the present embodiment shown in FIG. 1 and its periphery thereof.

Hereinafter, embodiments for carrying out the present invention (hereinafter, simply referred to as “the present embodiment”) will be described in detail with reference to the drawings as necessary. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be appropriately modified and implemented within the scope of the gist thereof. In the drawings, the positional relationships such as up, down, left, and right shall be based on the positional relationships shown in the drawings unless otherwise specified.

(Extruder)
FIG. 1 shows an outline of the extruder of the present embodiment in a side view.
The extruder 1 of the present embodiment is not particularly limited, and may be a single-screw extruder, a conider type extruder, a multi-screw extruder such as a twin-screw extruder, or the like, and is shown in FIG. 1, for example. As described above, the raw material supply port 11 (in FIG. 1, the first raw material supply port 11-1 and the second raw material supply port 11-2), the barrel 10 (12 pieces of the first to twelfth in FIG. 1), and the die portion. 13 etc. are provided.

Here, in the extruder 1 of the present embodiment, 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) is connected to the raw material supply port 11. The cooling gas supply line 3 communicates with 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).

As a result of diligent studies by the inventors, it is the high-temperature gas Gr that flows back from the barrel 10 of the extruder 1 to the raw material supply line 2 that causes the melting and adhesion of the low melting point additive in the extruder 1 (see FIG. 2). ), It was found that the cause was the high temperature of the raw material supply line 2.

According to the extruder 1 of the present embodiment, the high-temperature gas Gr flowing back from the barrel 10 of the extruder 1 to the raw material supply line 2 and the cooling gas Gc are mixed to efficiently use the raw material supply line 2. It becomes possible to cool. This makes it possible to significantly suppress the temperature rise of the raw material supply line 2 due to the high-temperature gas Gr flowing back, and the low melting point additive inside the constituent members of the raw material supply line 2 such as the raw material supply hopper 20. It is possible to reduce melting and adhesion.
In this respect, in particular, in the extruder 1 of the present embodiment, the raw material supply line is compared with the method of cooling the raw material supply line 2 from the outside by flowing a refrigerant through the outer wall of the constituent members of the raw material supply line 2. The constituent members of 2 are cooled from the inside. As a result, the effect of reducing the melting and adhesion of the above-mentioned low melting point additive is extremely high.

Hereinafter, the effects of the extruder 1 of the example shown in FIG. 1 will be described.
The low melting point additive is charged into the first raw material stock tank 211A. The low melting point additive is supplied to the first raw material supply hopper 201 via the first A 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 is put into the first B raw material stock tank 211B. The thermoplastic resin is supplied to the first raw material supply hopper 201 via the first B 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 passes through the pipe 241A. To cool.
Further, the first A cooling gas supply line 3-1A provided in the first raw material supply hopper 201 supplies the cooling gas Gc at −50 to 20 ° C., and the cooling gas Gc flows back from the extruder 1 70. The gas Gr having a high temperature of ~ 350 ° C. is cooled, and the low melting point additive and the thermoplastic resin supplied to the hopper 201 are cooled.
Due to the cooling effect, the melting / adhesion of the low melting point additive is reduced in the first raw material supply hopper 201.

At this time, in particular, the temperature of the barrel 10 having the raw material supply port 11, the temperature of the barrel 10 forming the solid transport zone, and the temperature of the barrel 10 forming the kneading zone are set to be higher in this order. Since the low melting point additive is well mixed with the thermoplastic resin and then melted, the physical properties of the thermoplastic resin composition become more uniform (described later).

The second raw material supply line 2-2 also has the same effect as that of the first raw material supply line 2-1 described above.

-Raw material supply line-
The raw material supply line 2 used in the present embodiment is not particularly limited as long as the thermoplastic resin and the low melting point additive can be supplied. The details of the raw material supply line 2 will be described later.

In the extruder 1 shown in FIG. 1, the raw material supply line 2 brings the raw material stock tank 21, the raw material cutting device 22, the raw material supply device 23, the raw material supply pipe 24, and the raw material supply hopper 20 toward the raw material supply port 11. Prepared in order.

Specifically, the first raw material supply line 2-1 shown in FIG. 1 includes a first raw material supply hopper 201, three raw material supply pipes 24 (first A raw material supply pipe 241A, first B raw material supply pipe 241B, first C raw material supply). Piping 241C), three raw material supply devices 23 (1A raw material supply device 231A, 1B raw material supply device 231B, 1C raw material supply device 231C), 3 raw material cutting devices 22 (1A raw material cutting device 221A, 1st It is provided with a 1B raw material cutting device 221B, a first C raw material cutting device 221C), and three raw material stock tanks 21 (1A raw material stock tank 211A, 1B raw material stock tank 211B, 1C raw material stock tank 211C).
Further, the second raw material supply line 2-2 shown in FIG. 1 includes a 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 raw material cutting device 22 (second raw material cutting device 222), and one raw material stock tank 21 (second raw material stock tank 212) are provided.

-Cooling gas supply line-
The cooling gas supply line 3 used in the present embodiment can supply gas having a temperature lower than the internal temperature of the barrel 10 provided with the raw material supply port 11 to which the raw material supply line 2 is connected. There is no particular limitation. The details of the cooling gas supply line 3 will be described later.

In the extruder 1 of the example shown in FIG. 1, in order to cool the raw material supply line 2 and the barrel 10 connected to the raw material supply line 2, the cooling gas supply line 3 includes a cooler 31, more specifically, a vortex type cooler. There is.

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 shown in the example shown in FIG. 1, it is preferable that one raw material supply line 2 is provided with a plurality of cooling gas supply lines 3. According to such a 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, regarding the first raw material supply line 2-1 there are two, a first A cooling gas supply line 3-1A and a first B cooling gas supply line 3-1B, and a second raw material supply line 2. Regarding -2, the second A cooling gas supply line 3-2A and the second B cooling gas supply line 3-2B are provided.

As in the example shown in FIG. 1, the extruder 1 of the present embodiment preferably includes a plurality of raw material supply ports 11 to which the raw material supply line 2 including the cooling gas supply line 3 is connected. According to such a configuration, the low melting point additive can be supplied in a plurality of times, and the physical properties of the thermoplastic resin composition can be improved.

Then, in the extruder 1 of the present embodiment, the cooling gas supply line 3 may communicate with at least a part of the raw material supply line 2, but the cooling gas supply line 3 communicates with the raw material supply hopper 20. (See FIG. 1), then the backflowing gas Gr preferably communicates with the flowing raw material supply pipe, and then communicates with the transport portion of the raw material supply device 23, which may easily generate heat. Is preferable. According to such a configuration, the low melting point additive can be efficiently cooled.
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 its lid, and also supplies the first B cooling gas. Line 3-1B communicates with the first A raw 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 its lid, and the second B cooling gas supply line 3-2B communicates with the second raw material supply hopper 202. , It communicates with the second raw material supply pipe 242.

In the extruder 1 of the present embodiment, the extending direction of the cooling gas supply line 3 is not particularly limited, but as in the example shown in FIG. 1, the cooling gas supply line 3 is in a direction orthogonal to the axis X direction of the extruder. It is preferable to extend to. According to this configuration, the high-temperature gas Gr flowing back from the barrel 10 to the raw material supply line 2 and the cooling gas Gc are efficiently mixed in both the top feed and the side feed, and the raw material supply line. 2 can be cooled efficiently.
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 orthogonal to the axis X direction of the extruder (relative to the lid of the first raw material supply hopper 201). It extends downward in the direction of gravity (vertically), and the second A cooling gas supply line 3-2A of the second raw material supply line 2-2 is orthogonal to the axis X direction of the extruder (the first). 2 (perpendicular to the lid of the raw material supply hopper 202), extending downward in the direction of gravity.

In the extruder 1 of the present embodiment, the cooling gas supply line 3 extends from the extruder shaft X (the line connecting the centers of the barrel 10 cross sections) to a position at a distance of 1 to 500 times the barrel inner diameter D. , It is preferable to be provided. 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 barrel 10 to the raw material supply line 2 for a long time, so that the low melting point additive is melted and adhered. Can be reduced.
In order to enhance the above effect, the cooling gas supply line 3 is more preferably a region from the shaft X of the extruder to a position at a distance of 1 to 50 times the inner diameter D of the barrel.

Furthermore, 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, the melting and adhesion of the low melting point additive in the extruder 1 is caused by the radiant heat RH released to the outside of the extruder 1 in the barrel 10 forming the kneading zone among the barrels 10 of the extruder 1. It was also found that the high temperature of the raw material supply line 2 due to (see 2) was also a factor.
By providing the extruder 1 of the present embodiment with a heat insulating material, the radiant heat RH can be blocked, the melting and adhesion of the low melting point additive can be reduced, and the physical characteristics of the thermoplastic resin composition can be made uniform. It becomes possible to do.

When the barrel cover is provided on the barrel 10, the heat insulating material 4 may be provided on the outside and / or inside of the barrel cover.

Then, in order to enhance the above effect, in the extruder 1 of the present embodiment, it is preferable that the heat insulating material 4 covers the outer surface of the barrel 10 forming the kneading zone.
The extruder 1 of the example shown in FIG. 1 has an outer surface from a second barrel 10b, which is a barrel 10 adjacent to a first barrel 10a provided with a raw material supply port 11, to a fifth barrel 10e forming a kneading zone. A heat insulating material 4 for covering is further provided.
According to such a configuration, it is possible to significantly suppress the temperature rise of the raw material supply line 2 due to the radiant heat RH emitted to the outside of the extruder 1 in the barrel 10 forming the kneading zone among the barrels 10 of the extruder 1. It is possible to reduce the melting and adhesion of low melting point additives inside the constituent members of the raw material supply line 2 such as the raw material supply hopper 20.

Further, the extruder 1 of the present embodiment may further cover at least a part of the outer surface of the wall of the raw material supply hopper 20 with 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 extruder 1 at the raw material supply port 11.
The angle of the hopper wall of the raw material supply hopper 20 is preferably vertical (90 °) to 60 ° so that the raw materials are difficult to bridge.
The raw material supply hopper 20 may be replaced with an inert gas in order to prevent oxidative deterioration of the raw material. Further, in order to prevent fine raw materials from adhering to the inner wall, a knocker or a vibrator may be appropriately attached to the hopper 20.

The raw material stock tank 21 is a tank for temporarily storing raw materials. When the raw material is a powder flammable resin, the inside of the stock tank 21 may be replaced with an inert gas, or when the raw material is easily bridged, a bridge breaker or the like may be attached as necessary.

The raw material cutting device 22 is a device that retains the raw materials of the raw material supply device 23 and supplies the raw materials when the raw material supply hopper 20 is empty. When the hopper 20 is emptied, a signal is sent to the cutting device 22, the sluice valve is opened (if the cutting device 22 is a sluice valve), and the raw material is supplied from the raw material stock tank 21 to the raw material supply device. It is supplied to 23 in a short time (10 to 120 seconds). When the hopper 20 is full, the above signal is not sent and the cut-out valve is closed. The cutting device 22 may be of a sluice valve type or a screw type.

The raw material supply device 23 is usually preferably a heavy-duty feeder, and includes a hopper unit for storing the raw material and a transport unit for quantitatively transporting the raw material. The transport unit includes a screw type, a belt type, a vibration type, and the like, but any type may be used.
In particular, when the screw type is used, it is preferable to use a screw having a large screw pitch or a coil type screw in which heat generation is unlikely to occur in order to prevent the transport portion from generating heat and melting the low melting point additive. The belt type and the vibration type are preferable because heat generation is unlikely to occur.
It is preferable that the supply device 23 is provided with a load cell in order to improve the supply accuracy, and the supply amount is controlled based on the reduced weight of the raw material.

The raw material supply pipe 24 is a pipe that supplies the raw material supplied from the transport section of the raw material supply device 23 to the raw material supply hopper 20. The mounting angle of the raw material supply pipe 24 is preferably vertical (90 degrees) to 45 degrees so that the raw materials are difficult to bridge.

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

The details of the cooling gas supply line 3 will be described below.
FIG. 2 shows an enlarged side view of the cooling gas supply line and its periphery included in the extruder of the present embodiment.

The chiller 31 (see FIG. 1) is not particularly limited as long as it is a device capable of generating a cooling gas having a temperature 15 to 75 ° C. lower than the temperature of the gas at room temperature.

The vortex type cooler included in the extruder 1 of the example shown in FIG. 1 includes a bushing, 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, gas at a predetermined pressure (0.1 to 1.0 MPa) and a predetermined temperature (10 to 50 ° C.) is supplied from the room temperature gas supply port 311a, and then in the cooler 31. Using pressure, a high-speed vortex of about 1 million rpm is generated, separated into low-temperature gas and high-temperature gas, and the low-temperature gas is discharged as cooling gas from the low-temperature gas discharge port 311b (that is, the raw material supply line). (While supplying to the inside of 2), the high temperature gas is discharged to the outside of the raw material supply line 2 from the high temperature gas discharge port 311c.

Specific examples of the vortex type cooler include a vortex tube manufactured by Kogi Corporation, a man cleaning system, a cold air gun, a panel guard cooler, etc.; a jet cooler manufactured by Newler Co., Ltd .; an air cooler manufactured by Nissin Sangyo Co., Ltd., etc. Can be mentioned.

The details of the extruder 1 will be described below.

The extruder 1 of the present embodiment is not particularly limited, and examples thereof include a single-screw extruder, a conider type extruder, a multi-screw extruder such as a twin-screw extruder, and the like.
Examples of the single-screw extruder include a single-screw extruder provided with a kneading type screw.
Examples of the conider type extruder include a conider manufactured by Buss.
Examples of the twin-screw extruder include a non-meshing type different-direction rotating twin-screw extruder, a meshing type different-direction rotating twin-screw extruder, and a same-direction rotating twin-screw extruder (for example, ZSK Megacon series and Megaplus series manufactured by Coperion). , MC18 series; TEM BS series, SS series, SX series manufactured by Toshiba Machine Co., Ltd .; TEXα series, α2 series, α3 series, etc. manufactured by Japan Steel Works, etc.).

The standard and size of the extruder 1 are not particularly limited, but the barrel inner diameter (diameter) D is preferably 40 to 200 mm. If the barrel inner diameter D is less than 40 mm, the productivity is low. If the barrel inner diameter D exceeds 200 mm, it is difficult to suppress heat generation during melt kneading. The effective barrel length L is not particularly limited, but is preferably 12 to 60 times the inner diameter D of the barrel. If the effective barrel length L is less than 12 times the inner diameter D of the barrel, it is difficult to knead the raw materials sufficiently, and if the effective barrel length L is more than 60 times the inner diameter D of the barrel, the vibration of the screw shaft becomes large and the raw materials are kneaded. It may be defective.

The motor of the extruder 1 is not particularly limited, and may be an inverter motor or a DC motor. The motor may be provided with a cooling device, if necessary. Examples of the motor cooling device include an air cooling type and a circulating water cooling type, but the circulating water cooling type is preferable from the viewpoint of not scattering foreign matter in the air.

The barrel configuration of the extruder 1 includes a barrel 10 having at least one raw material supply port, at least one barrel 10 forming a solid transport zone (before melting) and / or a melt transport zone, and at least forming a kneading zone. A barrel configuration comprising one barrel 10 and a barrel 10 having at least one vent 12 can be mentioned. Here, the vent 12 may be an atmospheric vent or a vacuum vent. Further, the raw material may be supplied as a top feed or a side feed.
In the example shown in FIG. 1, 12 barrels 10 (10a to 10l (el)) of the 1st to 12th barrels are provided, and the 1st barrel (10a) and the 7th barrel (10g) are raw material supply ports. The second to fourth barrels (10b to 10d) are barrels 10 forming a solid transport zone, and the ninth, tenth, and twelfth barrels (10i, 10j, 10l) are barrels 10. The barrel 10 forming the melt transport zone, the fifth and eighth barrels (10e, 10h) are the barrels 10 forming the kneading zone, and the sixth barrel (10f) is the barrel 10 having an atmospheric vent. The eleventh barrel (10k) is a barrel 10 having a vacuum vent.

In particular, in the extruder 1 of the present embodiment, the number of barrels 10 forming the solid transport zone is preferably 1 to 8 times the number of barrels 10 having the corresponding raw material supply ports 11, and is 2 to 5 times. It is more preferable that it is doubled.
In the example shown in FIG. 1, the number of barrels 10 (10b to 10d) forming the solid transport zone is three times the number of barrels 10 (10a) having the first raw material supply port 11-1.

Examples of the screw element used for the barrel 10 include a two- or three-row kneading block (right-handed, left-handed, neutral, reverse feed), a two- or three-row flight screw (right-handed, left-handed), and the like. Notch screws, cut screws, varistor rings, etc. of Article 1, Article 2, or Article 3 can be mentioned, and these can be used in combination as necessary.

A play car capable of attaching a metal mesh (mesh having openings # 10 to # 300) for removing foreign substances contained in the molten thermoplastic resin to the die portion 13 of the extruder 1 of the present embodiment. A plate may be attached.
Further, the die portion 13 may be equipped with a die plate provided with a plurality of orifices. In this case, the inner diameter of the orifice may be 2 to 6 mm, the length of the orifice may be 6 to 20 mm, and one orifice hole is used. The extrusion rate of the above may be 10 to 40 kg / hr. Further, a meshi removing device capable of removing the meshi generated in the opening by blowing gas or applying a slight vibration may be installed in the opening of the orifice of the die plate.
When producing a thermoplastic resin composition containing a filler, it is preferable not to use the metal mesh for the die portion 13 from the viewpoint of avoiding clogging.

(Manufacturing method of thermoplastic resin composition)
The method for producing the thermoplastic resin composition of the present embodiment uses an extruder 1.
A raw material supply process for supplying raw materials (thermoplastic resin (A), low melting point additive (B), etc.) to the raw material supply line 2 and
A cooling gas supply process that supplies gas at a temperature lower than the internal temperature of the extruder 1 to the raw material supply line 2 and
Includes a kneading step in which the raw materials are melt-kneaded.
In the cooling gas supply step, the cooling gas 31 provided in the extruder 1 may obtain cooling gas and supply this gas to the raw material supply line 2, but the gas is not limited to this and is cooled in advance. Gas (for example, low-temperature gas vaporized from liquid nitrogen) may be supplied to the raw material supply line 2.

In this embodiment, as will be described later, it is necessary to use the extruder 1 of the above-described embodiment.

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

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

The thermoplastic resin (A) used in the method for producing the thermoplastic resin composition of the present embodiment is not particularly limited, and is, for example, a polyphenylene ether-based resin (polyphenylene ether, polyphenylene ether, and a polystyrene-based resin (described later)). Blended with resin), polystyrene resin (general purpose polystyrene, high impact 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, polyamide resin, polyamideimide, polyarylate, polyarylsulfone, polyethersulfone, polyetherimide, polytetrafluoroethylene, poly Examples thereof include ether ketones, and in particular, polyphenylene ether-based resins, polycarbonate-based resins, polyamide-based resins, homopolymer-type polyoxymethylene, copolymer-type polyoxymethylene, acrylonitrile / butadiene / styrene copolymers, and the like are preferable.
These thermoplastic resins (A) may be used alone or in combination of two or more.

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

If the melting point of the additive is less than 40, the additive may easily liquefy, and if the melting point is more than 200 ° C., the additive causes poor melting and is contained in the resin composition. May not be sufficiently dispersed.
In the present embodiment, from the viewpoint of more efficiently obtaining the effects of the present invention, the melting point of the additive, which can be 40 to 200 ° C., is preferably 40 to 190 ° C., preferably 40 to 180 ° C. Is even more preferable.

Examples of the phosphorus-based flame retardant include a phosphoric acid ester compound, a phosphoric acid condensed ester, a cyclic and / or chain phosphazene compound, and the like.
The phosphoric acid ester compound and phosphoric acid condensation ester are not particularly limited, and for example, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate (TXP), cresyldiphenyl phosphate, 2-ethylhexyldiphenyl phosphate, tert. -Butylphenyldiphenyl phosphate, bis- (tert-butylphenyl) phenyl phosphate, tris- (tert-butylphenyl) phosphate, isopropylphenyldiphenyl phosphate, bis- (isopropylphenyl) diphenyl phosphate, tris- (isopropylphenyl) resorcinol bis- Examples thereof include diphenyl phosphate, resorcinol bis-dixylenyl phosphate, bisphenol A bis-diphenyl phosphate, biphenyl bis-diphenyl phosphate and the like, and triphenyl phosphate is particularly preferable.
These may be used individually by 1 type, and may be used in combination of 2 or more type.
Cyclic and / or chain phosphazene compounds include, for example, poly) triloxyphosphazene, o, m-xylyloxyphosphazene, such as phenoxyphosphazene, o-tolyloxyphosphazene, m-tolyloxyphosphazene, p-tolyloxyphosphazene. (Poly) xsilyloxyphosphazene such as o, p-xylyloxyphosphazene, m, p-xylyloxyphosphazene, o, m, p-trimethylphenyloxyphosphazene, phenoxy o-tolyloxyphosphazene, phenoxy m-tolyloxy (Poly) phenoxytriloxyphosphazene such as phosphazene, phenoxy p-tolyloxyphosphazene, phenoxyo, m-xysilyloxyphosphazene, phenoxyo, p-xysilyloxyphosphazene, phenoxym, p-xysilyloxyphosphazene and the like (poly) ) Phenoxytriloxyxysilyloxyphosphazene, phenoxyo, m, p-trimethylphenyloxyphosphazene and the like, with cyclic and / or chain phenoxyphosphazene being particularly preferred.
These may be used individually by 1 type, and may be used in combination of 2 or more type.

As higher fatty acid derivatives, fatty acid amides such as stearate amide, oleic acid amide, and erucic acid amide; alkylene fatty acid amides such as methylene bisstearic acid amide and ethylene bisstearic acid amide; calcium stearate, zinc stearate, magnesium stearate, etc. Examples include fatty acid salts.

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

Examples of the petroleum resin include hydrocarbon compounds having a molecular weight of 3000 or less, petroleum fractions of aliphatic compounds having 5 carbon atoms and / or aromatic compounds having 9 carbon atoms, and hydrogenated additives thereof.

The filler (C) used in the method for producing the thermoplastic resin composition of the present embodiment is not particularly limited, and is, for example, glass fiber, carbon fiber, metal fiber, potassium titanate whisker, magnesium sulfate whisker, hoe. Aluminum Acid Whisker, Calcium Carbonate Whisker, Silicon Carbide Whisker, Zinc Oxide Whisker, Calcium Silica (Wallastonite), Mica, Tarku, Glass Flake, Calcium Carbonate, Clay, Kaolin, Barium Sulfate, Silica, Alumina, Magnesium Oxide, Sulfate Examples thereof include magnesium, copper iodide and potassium iodide, and glass fiber, carbon fiber, calcium silicate, mica, talc, glass flakes, calcium carbonate, kaolin, silica, copper iodide and potassium iodide are particularly preferable.

The liquid additive used in the method for producing the thermoplastic resin composition of the present embodiment is not particularly limited, and is, for example, polyethylene glycol having a molecular weight of 300 to 20000 and a paraffinic oil having 4 to 155 carbon atoms (for example). , K-350 (liquid paraffin 99.99995%) manufactured by Kaneda Co., Ltd., PW-90 (n-paraffin-based process oil) manufactured by Idemitsu Kosan Co., Ltd., neothiozole manufactured by Sanko Chemical Industry Co., Ltd.); cyclopentane (C) ₅ H ₁₀ ), cyclohexane (C ₆ H ₁₂ ), phichterite (C ₁₉ H ₃₄ ), oleanan (C ₃₀ H ₅₂ ), and naphthenic oils such as mixtures thereof (for example, Diana process oil manufactured by Idemitsu Kosan Co., Ltd.) NS90S, Diana process oil NS100 manufactured by Idemitsu Kosan Co., Ltd., etc.) and the like.

The other additives used in the method for producing the thermoplastic resin composition of the present embodiment are not particularly limited, and are, for example, elastomers, various colorants, coloring aids (titanium oxide, etc.), ultraviolet absorbers, and electric resistance. Preventive agents, stabilizers (zinc oxide, zinc sulfide, phosphorus type, sulfur type, hindered phenol type, etc.) and the like can be mentioned.

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.
A step of supplying raw materials (thermoplastic resin (A), low melting point additive (B), etc.) from the raw material supply port 11 to the extruder 1 through the raw material supply line 2 (raw material supply process).
A step of supplying a gas (cooling gas) having a temperature lower than the 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). )When,
The extruder 1 includes a step of melt-kneading the supplied raw materials (melt-kneading step).

As described above, as a result of diligent studies by the inventors, in the method for producing a thermoplastic resin composition using the extruder 1, it is the barrel of the extruder 1 that melts and adheres the low melting point additive in the extruder 1. It was found that the cause was the increase in temperature of the raw material supply line 2 due to the high temperature gas Gr flowing back from 10 to the raw material supply line 2.

According to the method for producing a thermoplastic resin composition of the present embodiment using the extruder 1 of the present embodiment described above, the high-temperature gas Gr flowing back from the barrel 10 of the extruder 1 to the raw material supply line 2 is used. The cooling gas Gc mixes with each other, and the raw material supply line 2 can be efficiently cooled. This makes it possible to significantly suppress the temperature rise of the raw material supply line 2 due to the high-temperature gas Gr flowing back, and the low melting point additive inside the constituent members of the raw material supply line 2 such as the raw material supply hopper 20. It is possible to reduce melting and adhesion.
In this respect, in particular, as compared with the method of cooling the raw material supply line 2 from the outside by flowing a refrigerant through the outer wall of the constituent members of the raw material supply line 2, the method for producing the thermoplastic resin composition of the present embodiment. Then, the constituent members of the raw material supply line 2 are cooled from the inside. As a result, the effect of reducing the melting and adhesion of the above-mentioned low melting point additive is extremely high.

Hereinafter, 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.
The low melting point additive (B) is charged into the first raw material stock tank 211. The low melting point additive (B) is supplied to the first raw material supply hopper 201 via the first A 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 charged into the first B raw material stock tank 211B. The thermoplastic resin (A) is supplied to the first raw material supply hopper 201 via the first B 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 passes through the pipe 241A. (B) is cooled.
Further, the first A cooling gas supply line 3-1A provided in the first raw material supply hopper 201 supplies the cooling gas Gc at −50 to 20 ° C., and the cooling gas Gc flows back from the extruder 1 70. The gas Gr having a high temperature of ~ 350 ° C. is cooled, and the low melting point additive (B) and the thermoplastic resin (A) supplied to the hopper 201 are cooled.
Due to the cooling effect, the melting / adhesion of the low melting point additive (B) is reduced in the first raw material supply hopper 201.

The second raw material supply line 2-2 also has the same effect as that of the first raw material supply line 2-1 described above.

In particular, the low melting point additive is set so that the temperature of the barrel 10 having the raw material supply port, the temperature of the barrel 10 forming the solid transport zone, and the temperature of the barrel 10 forming the kneading zone are set to be higher in this order. Is mixed well with the thermoplastic resin and then melted, so that the physical properties of the thermoplastic resin composition become more uniform (described later).

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

Regarding the cooling gas line 3 in the cooling gas supply process, the ratio of the flow rate of the cooling gas Gc (NL (normal liter) / hr) to the supply amount (kg / hr) of the raw material supplied by the raw material supply line 2 is 1 to 1000. It is preferably (NL / kg), more preferably 5 to 500 (NL / kg), and even more preferably 5 to 250 (NL / kg). The ratio of the high-temperature gas Gr flowing back to the cooling gas Gc is preferably 0.01 to 0.3, more preferably 0.03 to 0.2, and further preferably 0.03 to 0. It is 15.
When 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, carbon dioxide gas, argon gas, and air.

When using an extruder 1 equipped with a vortex type cooler as shown in FIG.
The temperature of the room temperature gas is preferably 10 to 50 ° C, more preferably 10 to 40 ° C, and even more preferably 15 to 40 ° C.
The pressure of the room temperature gas may be 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, the temperature of the cooling gas Gc does not decrease because a strong eddy current cannot be formed. When the pressure is more than 1.0, it exceeds the range that the cooler 31 main body can withstand.
The humidity of the normal temperature gas is preferably less than 0.1%, and the normal temperature gas at such a humidity is further passed through a foreign matter removing filter and adjusted so that the foreign matter having a size of 5 μm or less is less than 0.1% by mass. It is preferable that the product has been used.

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 room temperature gas, and more preferably 20 to 75 ° C. lower.
The temperature of the high temperature gas is preferably 5 to 110 ° C. higher than the temperature of the room temperature gas to be supplied, and more preferably 30 to 75 ° C. lower.

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

In the melt-kneading process
When using an extruder 1 having a barrel 10 having a raw material supply port 11, a barrel 10 forming a solid transport zone, and a barrel 10 forming a kneading zone as shown in FIG.
Specifically, the set temperature of the barrel 10 having the raw material supply port 11 (the first barrel 10a in FIG. 1) is preferably 50 ° C. or lower, more preferably 45 ° C. or lower, still more preferably 40 ° C. or lower. Is. If the barrel temperature exceeds 50 ° C., the temperature of the high-temperature gas Gr that flows back rises, which is not preferable.
Specifically, the set temperature of the barrel 10 (in FIG. 1, the second to fourth barrels (10b to 10d)) forming the solid transport zone is preferably 50 to 300 ° C., more preferably 50 to 300 ° C. It is 250 ° C. or lower, more preferably 60 to 250 ° C. or lower. When the temperature of the barrel 10 forming the solid transport zone exceeds 300 ° C., the barrel 10 forming the solid transport zone and the barrel 10 having the raw material supply port adjacent to the barrel 10 forming the solid transport zone are sufficiently cooled. However, the temperature of the high-temperature gas Gr that flows backward becomes substantially high, which is not preferable.
As for the set temperature of the barrel 10 (the fifth barrel 10e in FIG. 1) forming the kneading zone, the thermoplastic resin (A) (the resin having the largest supply amount when there are two or more kinds of thermoplastic resins) is crystalline. In the case of a resin, the temperature is preferably 0 to 100 ° C. higher than the melting point, and more preferably 10 to 50 ° C. higher. When the thermoplastic resin (A) is an amorphous resin, the temperature is preferably 50 to 150 ° C. higher than the glass transition temperature, and more preferably 70 to 120 ° C. higher.

In the melt-kneading process
The torque density Td of the gearbox of the extruder 1 is 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 and quality stability of the resin composition can be made excellent.
The torque density Td (Nm / cm ³ ) of the gearbox can be obtained from the following equation (1).
Torque density Td (Nm / cm ³ ) = maximum motor power (kw) x 1000 / (2 x 3.14 x maximum rotation speed) / ((screw diameter d (cm) / 10) ³ ) ... ( 1)
For example, when TEM58SS manufactured by Toshiba Machine Co., Ltd. is used with a motor having a maximum rotation speed of 10 rps and 181 kW with a constant torque, the torque density Td is 14.8 Nm / cm ³ .

The thermoplastic resin composition produced by the method for producing a thermoplastic resin composition of the present embodiment includes OA materials (printers, copiers, etc.), electronic materials, optical materials, battery case materials, battery cell materials, films, and sheets. Etc. are preferably used.

In the above, the embodiment of the extruder of the present invention and the method for producing the thermoplastic resin composition of the present invention using the extruder has been exemplified with reference to the drawings, but the above-described embodiment can be appropriately modified. , The present invention is not limited to the above-exemplified embodiments.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

The extruders of Examples , Reference Examples, and Comparative Examples and the method for producing a thermoplastic resin composition using the extruders are described below.

-Raw material supply line-
--First raw material supply line ---
First raw material supply hopper (conical, hopper wall angle 60 °)
--- First A system (for low melting point additives) ---
1A raw material stock tank (200L)
1A raw material cutting device (slide gate valve)
1st A raw material supply device (heavy-duty feeder A: CE-W-2 manufactured by Kubota)
1A raw material supply piping (4 inch piping, 45 degree inclination piping)
--- First B system (for thermoplastic resin) ---
1st B raw material stock tank (500L)
1st B raw material cutting device (slide gate valve)
1st B raw material supply device (heavy feeder B: CE-W-4 manufactured by Kubota)
1st B raw material supply piping (4 inch piping, 45 degree inclination piping)
--- First C system (for thermoplastic resin) ---
1st C raw material stock tank (500L)
1C raw material cutting device (slide gate valve)
1st C raw material supply device (heavyweight feeder B: CE-W-4 manufactured by Kubota)
1st C raw material supply piping (4 inch piping, 45 degree inclination piping)

--Second raw material supply line ---
Second raw material stock tank (200L)
Second raw material cutting device (slide gate valve)
Second raw material supply device (heavyweight feeder C: CE-W-2 manufactured by Kubota)
Second raw material supply pipe (4 inch pipe, 90 degree inclination pipe)
Second raw material supply hopper (conical, hopper wall angle 60 °)

-Cooling gas supply line-
Two panel guard coolers (760J, manufactured by Kogi Corporation) were used as coolers. These were arranged as shown in Table 1.

-Extruder-
As an extruder, a twin-screw co-rotating extruder (TEM58SS (12 barrel extruder length 48D) manufactured by Toshiba Machine Co., Ltd.) was used.
The barrel configuration is as follows.
1st barrel: 1st supply port (top feed barrel, heavy-duty feeders A, B, C)
2nd barrel: Solid transport zone 3rd barrel: Solid transport zone 4th barrel: Solid transport zone 5th barrel: 1st kneading zone 6th barrel: Atmospheric vent 7th barrel: 2nd supply port (side feed barrel, weight type) Feeder D)
8th barrel: 2nd kneading zone 9th barrel: melt transport zone 10th barrel: melt transport zone 11th barrel: vacuum vent 12th barrel: melt transport zone Die part: die plate (orifice diameter 4 mmφ, number of orifices) 20 holes)

-Insulation material-
Super wool mat (manufactured by ASUKA Co., Ltd.) (thickness 50 mm)

-Other equipment-
Strand bath: Water temperature 40 ± 3 ° C
Pelletizer: Pellet length 2.5 ± 0.3 mm, Pellet shape: Cylindrical shape

(Manufacturing method of thermoplastic resin composition)
-Thermoplastic resin (A)-
Polyphenylene ether resin (manufactured by Asahi Kasei Chemicals, S201A) (glass transition temperature: 220 ° C)
General Purpose Polystyrene 685 (manufactured by PS Japan Corporation)
Polycarbonate (manufactured by Mitsubishi Engineering Plastics, Iupiron S3000F) (glass transition temperature: 150 ° C)
Nylon 66 (Made by Asahi Kasei Chemicals, Leona 1300S) (melting point 265 ° C)

-Low melting point additive (B)-
Triphenylphosphine (manufactured by No. 8 Chemical Co., Ltd., TPP) (melting point 50 ° C)
Citric acid (melting point 153 ° C)
Phosphazene (Ravitor FP110, manufactured by Fushimi Pharmaceutical Co., Ltd.) (melting point 100 ° C)

-Filler (C)-
Glass fiber (manufactured by NEC Glass Co., Ltd., ECS03T-249, diameter 13 μm)

-Masterbatch-
Talk (manufactured by Fuji Taruku Kogyo, RGE-250, average particle size 2 μm) 85 parts by mass, ethylene bisstearic acid amide (manufactured by Kao Corporation, Kao wax EB-FF, melting point 142 ° C) 10 parts by mass, polyethylene glycol (Hayashi) Pure Yakuhin Kogyo Co., Ltd., PEG400, melting point -12 ° C) A master batch consisting of 5 parts by mass (melting point 75 ° C as a master batch)

(Measuring method)
(1) Internal temperature of the raw material supply hopper A handy type thermometer (manufactured by Anritsu Keiki Co., Ltd.) is located 20 cm below the lid of the raw material supply hopper (intermediate height of the hopper) and at the center of the raw material supply hopper in the horizontal direction. HD-1100, the sensor is AT-40 type for air) was placed, and the temperature (° C.) was measured. The results are shown in Table 1.

(2) Internal temperature of the raw material supply pipe The raw material supply pipe has a length of 120 cm and is arranged so that its extending direction is along the vertical direction.
A handy type thermometer (manufactured by Anritsu Keiki Co., Ltd., HD-1100, sensor is A-2 type for the surface) is placed at a position 110 cm from the end of the raw material supply pipe on the barrel side to measure the temperature (° C). did. The results are shown in Table 1.

(3) Temperature of the outer wall surface of the screw cylinder of the heavy-duty feeder of the raw material supply device On the upper side of the cylinder on the screw outlet side of the heavy-duty feeder of the raw material supply device, a handy type thermometer (manufactured by Anritsu Keiki Co., Ltd., HD-1100, sensor is A-2 type) for the surface was placed and the temperature (° C.) was measured. The results are shown in Table 1.

(Evaluation method)
(4) Strand stability With respect to the strands discharged from the die portion of the extruder, the presence or absence of surging (waviness) and the presence or absence of strand breakage were visually evaluated. Then, the stability of the strand was determined according to the following criteria.
<Judgment criteria (shown in "Judgment point: Strand state")>
1: No surging. No broken strands.
2: No surging. No broken strands. However, the vibration of the strand is larger than 1.
3: Surging does not occur at first, but occurs after 30 minutes. No broken strands.
4: Surging does not occur at first, but occurs after 30 minutes. There is a broken strand.
5: Surging occurs from the beginning. Frequent broken strands.

(5) Degree of deposits inside the raw material supply hopper The degree of deposits inside the raw material supply hopper was visually evaluated and judged according to the following criteria.
<Judgment criteria (indicated by "judgment point: degree of sediment")>
1: None at all.
2: There is a pool at the raw material supply port, but there is no pool on the wall surface.
3: The pool of the raw material supply port is about 1/4 of the area of the supply port, and there is no pool on the wall surface.
4: The pool 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 pool on the wall surface of the raw material supply hopper.
5: The pool of the raw material supply port is more than 1/2 of the area of the supply port, or there is a large pool on the wall surface of the raw material supply hopper.

(6) Degree of foreign matter points in the strands The strands discharged from the die part of the extruder are pelletized with a pelletizer to a thickness of 3 mm and a length of 3 mm, and these pellets are used in a press molding machine (temperature: 250 ° C., pressure: By pressing at 5 to 10 MPa), a flat plate having a thickness of 1 mm and a bottom surface of 254 cm ^{2 was prepared.} Then, this flat plate is observed using a 10-fold loupe, and the size (maximum diameter) of foreign matter points mainly composed of oxides observed on the front and back surfaces of the flat plate is evaluated for each foreign matter point according to the following criteria. did. Table 1 shows the total evaluation points for all the observed foreign matter points.
<Evaluation criteria (indicated by "evaluation point: size of foreign matter point")>
1: Less than 200 μm.
2: 200-400 μm.
4: 400-800 μm.
8: Over 800 μm.

(7) Melt flow rate (MFR)
The MFR measurement was performed in accordance with ISO1133, pellets were sampled every 10 minutes from the pelletizer outlet, and each pellet was measured 6 times. The measurement was carried out in 10 minutes by setting the cylinder temperature to 300 ° C., heating the pellets for 3 minutes, and applying a load of 5 kg. (In the case of polycarbonate, the load is 1.2 kg)

(Example 1)
A phosphorus-based flame retardant, triphenylphosphate (TPP) (manufactured by No. 8 Chemical Co., Ltd.), which is a phosphorus-based flame retardant, is charged into the first A raw material stock tank upstream of the heavy-duty feeder A of the raw material supply line. Polyphenylene ether resin (S201A, manufactured by Asahi Kasei Chemicals Co., Ltd.) (glass transition temperature: 220 ° C.) was put into the 1st B raw material stock tank upstream of the feeder B, and into the 1st C raw material stock tank upstream of the heavy-duty feeder C. , General Purpose Polystyrene 685 (manufactured by PS Japan Corporation) was introduced.
The supply amount in the heavy-weight feeder A / heavy-weight feeder B / heavy-weight feeder C was set to 20 parts by mass / 55 parts by mass / 25 parts by mass, the extrusion amount was set to 400 kg / hr, and the screw rotation speed was set to 400 rpm.
The panel guard cooler 760J, which is a cooler installed in the cooling gas supply line, passes a filter of 1 μm, has a humidity of less than 0.001%, a nitrogen concentration of 99.99%, a pressure of 0.6 MPa, and a temperature of 40 ° C. It was set to supply at hr; cooling gas at -4 ° C was discharged at 3120 NL / hr, and hot gas at 103 ° C was discharged at 2280 NL / hr.
One of the panel guard coolers is directed downward in the direction of gravity toward the lid of the first A raw material supply hopper, and the other is directed downward in the direction of gravity toward the lid of the first A raw material stock tank. It was placed at the position shown in.
No insulation was used.
The conditions of the extruder are as follows.
The barrel temperatures were 1st barrel: 35 ° C., 2nd barrel: 50 ° C., 3rd barrel: 100 ° C., 4th barrel: 250 ° C., 5th to 12th barrels: 280 ° C.
The set temperature of the die portion was 280 ° C.
Other conditions in production are as shown in Table 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 maximum temperature at each point was 41 ° C. One hour later, the extruder was stopped and the deposits were checked and found to be none at all. The operation was stable and the MFR was stable.
Table 1 shows the measurement results and evaluation results in Example 1.

(Comparative Example 1)
It was carried out in the same manner as in Example 1 except that the cooling gas supply line was not used.
The temperatures of the raw material supply lines all exceeded the melting point of triphenylphosphine. One hour later, when the extruder was stopped and the inside of the raw material supply hopper was inspected, a large lump was found on the wall surface, and more than 3/4 of the area of the raw material supply port of the extruder was blocked. MFR also declined over time. The results of Comparative Example 1 are shown in Table 1.

(Comparative Example 2)
The same procedure as in Example 1 was carried out except that the panel guard cooler of the cooling gas supply line was stopped and uncooled nitrogen was supplied at 5400 NL / hr respectively.
The results in Comparative Example 2 were almost the same as those in Comparative Example 1. The results of Comparative Example 2 are shown in Table 1.

( Reference example 2)
The same procedure as in Example 1 was carried out except that the cooling gas supply line was arranged only in the first A raw material supply hopper.
The temperature in the raw material supply hopper, the raw material supply pipe, and the screw cylinder was higher than the temperature in Example 1, but the temperature in the entire first raw material supply line was lower than the melting point of triphenyl phosphate. No lumps or the like were generated inside the raw material supply hopper as in Example 1. The MFR was also stable. The results of Reference Example 2 are shown in Table 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) and the first A raw material supply device (Example 4), respectively. ), Except that it was connected to the first A raw material supply pipe (Example 5), it was carried out in the same manner as in Example 1.
The results in Examples 3 to 5 were almost the same as those in Example 1, and the productivity was good.

(Example 6)
The temperature of the second and third barrels was set to 280 ° C., and the same procedure as in Example 1 was carried out except that a heat insulating material was laid on the upper surfaces of the second and fifth barrels.
The results in Example 6 were almost the same as those in Example 1, and the productivity was good.

(Example 7)
The same procedure as in Example 1 was carried out except that the gas supplied to the panel guard cooler was compressed air of 0.6 MPa of the air compressor instead of nitrogen gas.
In Example 7, the productivity was good as in Example 1, but since air was used instead of nitrogen, foreign substances increased.

(Example 8)
The TPP was supplied in the same manner as in Example 1 except that the TPP was supplied using the second raw material supply line instead of the first raw material supply line. At this time, one of the panel guard coolers is directed downward in the direction of gravity toward the lid of the second raw material supply hopper, and the other panel guard cooler is directed horizontally toward the second supply pipe. It was arranged at the position shown in 1.

(Example 9)
0.8 parts by mass of citric acid using a heavy weight feeder A, 20 parts by mass of glass fiber (ECS03T-249, manufactured by NEC Glass Co., Ltd., diameter 13 μm) from the first raw material supply port, using a heavy weight feeder D The procedure was carried out in the same manner as in Example 1 except that the glass was further supplied from the second raw material supply port.
In Example 9, the productivity was good as in Example 1.

(Example 10)
The temperature of the second and third barrels was changed from 55 parts by mass to 65 parts by mass of S201A and Rabbitl FP110 (10 parts by mass) instead of TPP (20 parts by mass), and in order to improve the kneadability of FP110. The temperature was changed to 280 ° C., and the same procedure as in Example 1 was carried out.
In Example 10, the internal temperature of the raw material supply hopper increased by the amount of increasing the temperature of the second and third barrels, but the productivity was stable as in Example 1.

(Comparative Example 3)
This was carried out in the same manner as in Example 10 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., lumps were generated inside the raw material supply hopper, and there were many foreign substances.

(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, the productivity was stable as in Example 9.

(Example 12)
Same as Example 1 except that 20 parts by mass of the masterbatch was used instead of 20 parts by mass of TPP and the temperature of the second and third barrels was set to 280 ° C. in order to improve the dispersibility of talc. It was carried out in.
In Example 12, the productivity was stable as in Example 1.

(Comparative Example 4)
This was carried out in the same manner as in Example 12 except that the cooling gas supply line was not used.
In Comparative Example 4, as the temperature inside the raw material supply hopper increased, the amount of substances adhering to the inner wall of the raw material supply hopper increased.

(Example 13)
Nylon 66; 80 parts by mass (melting point 265 ° C.) was used instead of S201A and GP685, and the gas supplied to the panel guard cooler was compressed air of 0.6 MPa of the air compressor instead of nitrogen gas. Except for the above, the same procedure as in Example 12 was carried out.
In Example 13, the productivity was good.

(Comparative Example 5)
This was carried out in the same manner as in Example 13 except that the cooling gas supply line was not used.
In Comparative Example 5, as the temperature inside the raw material supply hopper increased, the amount of substances adhering to the inner wall of the raw material supply hopper increased.

(Comparative Example 6)
Except that the raw material supply hopper was cooled by making the outer wall of the first raw material supply hopper double and passing cooling water through the inside (between the outer walls) without using the cooling gas supply line, the same as in Example 1. It was carried out in the same manner. Specifically, in Comparative Example 6, a flow path is provided between the outer walls so that the raw material supply hopper flows spirally from the bottom to the lid, and a free cooling chiller (manufactured by Orion Machinery Co., Ltd.) is used here. , -4 ° C cooling water was supplied.
The temperatures of the raw material supply lines all exceeded the melting point of triphenylphosphine. One hour later, when the extruder was stopped and the inside of the raw material supply hopper was inspected, a condensed substance of organic matter was found on the wall surface, and a large lump was seen on it, which was 3/4 of the area of the raw material supply port of the extruder. The above was blocked. MFR also declined over time. The results of Comparative Example 6 are shown in Table 1.

According to the present invention, it is possible to produce a thermoplastic resin composition having uniform physical properties with high stability and high productivity.
The thermoplastic resin composition obtained by the extruder of the present invention and the manufacturing method using the same can be used as a masterbatch, a concentrate of intermediate raw materials, an OA material, an electronic material, an optical material, a battery case material, a battery cell material, and a film. , Suitable for sheets and the like.

1: Extruder 10: Barrel 11: Raw material supply port 11-1: 1st raw material supply port 11-2: 2nd raw material supply port 12: Vent 12-1: 1st vent 12-2: 2nd vent 13: Die Part 2: Raw material supply line 2-1: 1st raw material supply line 20: Raw material supply hopper 201: 1st raw material supply hopper 21: Raw material stock tank 211: 1st raw material stock tank 211A: 1st A raw material stock tank 211B: 1st B Raw material stock tank 211C: 1st C raw material stock tank 22: Raw material cutting device 221: 1st raw material cutting device 221A: 1A raw material cutting device 221B: 1st B raw material cutting device 221C: 1st C raw material cutting device 23: Raw material supply device 231: 1st raw material supply device 231A: 1st raw material supply device 231B: 1st B raw material supply device 231C: 1st C raw material supply device 24: Raw material supply pipe 241: 1st raw material supply pipe 241A: 1st A raw material supply pipe 241B: 1st B raw material supply pipe 241C: 1st C raw material supply pipe 2-2: 2nd raw material supply line 20: Raw material supply hopper 202: 2nd raw material supply hopper 21: Raw material stock tank 212: 2nd raw material stock tank 22: Raw material Cutting device 222: Second raw material cutting device 23: Raw material supply device 232: Second raw material supply device 24: Raw material supply piping 242: Second raw material supply piping 3: Cooling gas supply line 3-1: First cooling gas supply Line 3-1A: 1st A cooling gas supply line 3-1B: 1st B cooling gas supply line 31: Cooler 311: 1st cooler 311A: 1st A cooler 311B: 1st B cooler 311a: Room temperature gas supply port 311b : Low temperature gas discharge port 311c: High temperature gas discharge port 3-2: Second cooling gas supply line 3-2A: Second A cooling gas supply line 3-2B: Second B cooling gas supply line 31: Cooler 312: Second cooling Machine 312A: 2nd A cooler 312B: 2nd B cooler 4: Insulation material D: Barrel diameter L: Barrel effective length Gc: Cooling gas Gr: Backflow high temperature gas from the extruder RH: Radiant heat from the extruder barrel X: Extrusion Machine axis

Claims (13)

Equipped with a raw material supply port to which the raw material supply line is connected
The raw material supply line includes a raw material stock tank, a raw material cutting device, a raw material supply device, a raw material supply pipe, and a raw material supply hopper in this order toward the raw material supply port, and is cooled so as to communicate with the raw material supply hopper. A gas supply line and a cooling gas supply line communicating with at least one of the raw material stock tank, the raw material cutting device, the raw material supply device, and the raw material supply pipe are provided .
The cooling gas supply line is equipped with a chiller.
An extruder characterized in that the cooler is a vortex type cooler. The extruder according to claim 1, further comprising a plurality of raw material supply ports. The extruder according to claim 1 or 2 , further comprising a heat insulating material that covers at least a part of the outer surface of the extruder. The extruder according to any one of claims 1 to 3 , wherein the cooling gas supply line extends in a direction orthogonal to the axial direction of the extruder. The extruder according to any one of claims 1 to 4 , wherein the cooling gas supply line is provided in a region from the shaft of the extruder to a position at a distance of 1 to 500 times the barrel diameter D. .. The extruder according to any one of claims 1 to 5 , wherein the raw material supply device is a heavy-duty feeder. The extruder according to any one of claims 1 to 6 , wherein the extruder is a single-screw extruder or a twin-screw extruder. Using the extruder according to any one of claims 1 to 7,
A method for producing a thermoplastic resin composition, which comprises melt-kneading a thermoplastic resin and an additive having a melting point of 40 to 200 ° C. The thermoplastic resin is a polyphenylene ether-based resin or a polycarbonate-based resin.
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 8. The method for producing a thermoplastic resin composition according to claim 9 , wherein the phosphorus-based flame retardant is a phosphoric acid ester compound or a phosphazene compound. The method for producing a thermoplastic resin composition according to claim 10 , wherein the phosphazene compound is a phenoxyphosphazene compound. The method for producing a thermoplastic resin composition according to claim 10 or 11 , wherein the phosphoric acid ester compound is triphenyl phosphate. The production of the thermoplastic resin composition according to any one of claims 8 to 12 , wherein the liquid additive and the filler are further melt-kneaded in addition to the thermoplastic resin and the additive having a melting point of 40 to 200 ° C. Method.

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