JP2018048227A - Method for producing thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a thermoplastic resin composition which is excellent in productivity and hardly generates foreign matter and shavings. SOLUTION: The method for producing a thermoplastic resin composition of the present invention includes a screw configuration including (a) a solid transport zone having a first supply port, (b) a right-handed kneading disk and a screw with less pressure increase. 2 has a first kneading zone having a zone length of Lz / D = 3 to 12, (c) a first melt transport zone, (d) a second kneading zone, and (e) a second melt transport zone. Using a shaft extruder, at least 80 to 98 parts by mass of a thermoplastic resin having an average particle size of 1 to 1000 μm and a block of an aromatic vinyl compound and a conjugated diene compound having an average particle size of 1 to 1000 μm are used. It is characterized in that 2 to 20 parts by mass of the hydrogenated additive of the polymer is supplied from the first supply port and melt-kneaded. [Selection diagram] Fig. 1

Description

  The present invention relates to a method for producing a thermoplastic resin composition. Specifically, using a twin screw extruder having a specific screw configuration, a block copolymer of a thermoplastic resin having an average particle diameter of 1-1000 μm and an aromatic vinyl compound / conjugated diene having an average particle diameter of 1-1000 μm. The present invention relates to a method for producing a thermoplastic resin composition that melts and kneads a coalesced hydrogenated product, has excellent productivity, and generates a small amount of foreign matter and scum.

  Good productivity as a method for producing a composition in which a powdered thermoplastic resin and a hydrogenated compound of a powdered aromatic vinyl compound / conjugated diene block copolymer are melt-kneaded using a twin screw extruder Therefore, there is a demand for a method that generates less foreign matter due to thermal degradation and less generation of scum. However, since the raw material is a powder, the conveyance capacity is lowered and the residence time is long, so that the resin is likely to be thermally deteriorated, and when heat-degraded foreign matter is generated, or in order to melt and knead with high shear, In some cases, the hydrogenated compound of the powdery aromatic vinyl compound / conjugated diene block copolymer decomposes and the physical properties deteriorate. In addition, the decomposed component may cause the occurrence of scum at the orifice exit of the strand die plate.

  In Patent Document 1, from the first supply port, 57 to 95 parts by mass of a polyphenylene ether-based resin powder, 2 to 1 of a hydrogenated compound powder of a block copolymer of an aromatic vinyl compound and a conjugated diene compound are provided. After supplying 30 parts by mass, 3-30 parts by mass of organic phosphoric acid is supplied from the second supply port using a liquid feeder, and two clockwise kneading discs (kneading discs having a phase of 45 degrees or less) are provided. (Approx. L / D = 2.1), then mixed, then clockwise kneading disc, neutral (90 ° phase kneading disc), counterclockwise kneading disc (negative phase 45 ° or less kneading disc) ) And melt kneading techniques are disclosed.

  Patent Document 2 discloses a technique of a screw configuration having a high conveyance capability of a powdered thermoplastic resin.

  Patent Document 3 discloses a technology that improves the conveying ability of a powdered thermoplastic resin if the twist angle of a clockwise kneading disk is set to 11 to 35 degrees even when a pressure screw is used.

Japanese Patent No. 2012-153832 Japanese Patent Laid-Open No. 10-024487 Japanese Patent Laid-Open No. 10-180840

  Patent Document 1 discloses a screw configuration in which only two clockwise kneading disks in the first kneading zone are used (L / D = about 2.1) and a screw configuration in which a pressure screw is used in the second kneading zone. ing. However, the screw configuration in the first kneading zone is to facilitate the melt kneading in the second kneading zone by mixing the phosphate ester with the powdered polyphenylene ether resin to lower the viscosity of the polyphenylene ether resin. . Since the first kneading zone has no melt kneading action, when the phosphate ester is not included, the powder itself blows up from the degassing vent due to insufficient kneading of the powdered polyphenylene ether resin, and production does not occur. It becomes possible.

  Patent Document 2 discloses a screw configuration that uses a screw other than the single flight screw, the double flight screw, and the pressurizing screw in order to increase the conveying capability of the powder raw material. However, there is no disclosure of melt kneading of a powdered thermoplastic resin and a powdered aromatic vinyl compound / conjugated diene block copolymerized hydrogenated compound.

  In the technique of Patent Document 3, since there is a pressurizing screw in the first kneading zone, the conveying ability decreases as the concentration of the powdered resin increases. In addition, since the pressurizing screw is used, a part of the powdered thermoplastic resin melts and adheres to the barrel at the portion of the two-flight flight screw on the upstream side of the first kneading zone. Causes foreign matter.

  Then, an object of this invention is to provide the manufacturing method of the thermoplastic resin composition which is excellent in productivity and is hard to generate | occur | produce a foreign material and a mean.

  As a result of intensive studies by the present inventors, a block copolymer of a powdery thermoplastic resin having an average particle diameter of 1-1000 μm, a powdery aromatic vinyl compound having an average particle diameter of 1-1000 μm, and a conjugated diene. The present inventors have found that the above problems can be solved by using a twin-screw extruder having a specific screw configuration when melt-kneading the hydrogenated product.

That is, the present invention is as follows.
[1]
(A) a solid conveyance zone having a first supply port;
(B) A first kneading zone (Lz is a zone length Lz / D = 3 to 12) provided with a screw configuration including a clockwise kneading disc and a screw with low pressure increase downstream of the solid conveyance zone. Zone length (mm), D represents screw diameter (mm)),
(C) a first melt transport zone downstream of the first kneading zone;
(D) a second kneading zone downstream of the first melt conveying zone;
(E) a second melt conveying zone downstream of the second kneading zone;
Using a twin screw extruder having
Hydrogenated product 2 of a block copolymer of an aromatic vinyl compound and a conjugated diene compound having an average particle size of 1 to 1000 μm and at least 80 to 98 parts by mass of a thermoplastic resin having an average particle size of 1 to 1000 μm -20 mass parts is supplied from the said 1st supply port, and it melt-kneads, The manufacturing method of the thermoplastic resin composition characterized by the above-mentioned.

[2]
The (a) is a single-flight flight screw having an overall screw length of Ls / D = 4.5 to 20, and an overall screw length of Ls / D = 1.5 to downstream of the single-flight flight screw. 20 is a solid conveyance zone having a screw configuration having a two-flight flight screw and having a zone length of Lz / D = 6.0 to 30 (Ls represents the length of the screw (mm)).
(C) is a first melt conveyance zone having a screw configuration composed of two-flight flight screws, having at least one atmospheric vent or vacuum vent, and a zone length of Lz / D = 3-20. Yes,
(D) is a second kneading zone comprising a screw configuration having at least one pressurizing screw, the zone length being Lz / D = 2-12,
(E) is a second melt transport zone having a screw configuration consisting of a two-flight flight screw, having at least one vacuum vent, and having a zone length of Lz / D = 3-20. [1] A process for producing a thermoplastic resin composition according to [1].

[3]
The pitch of the elements constituting the single flight screw in (a) is Lp / D = 1.0 to 2.0 (Lp represents the length (mm) of the pitch). A method for producing a thermoplastic resin composition.

[4]
The pitch of the elements constituting the two-flight flight screw in (a), (c), and (e) is Lp / D = 0.25 to 1.0 (Lp represents the pitch length (mm)). A method for producing a thermoplastic resin composition according to [2] or [3].

[5]
The heat according to any one of [2] to [4], wherein in (a), (c), and (e), the screw is arranged so that the pitch becomes shorter from the upstream side toward the downstream side. A method for producing a plastic resin composition.

[6]
The method for producing a thermoplastic resin composition according to any one of [1] to [5], wherein the screw with low pressure increase in (b) is a neutral kneading disk or a two-cut notched flight screw.

[7]
Any of [1] to [6], wherein the blade width of the clockwise kneading disk in (b) is Lw / D = 0.10 to 0.5 (Lw represents blade width (mm)) A process for producing the thermoplastic resin composition according to claim 1.

[8]
The method for producing a thermoplastic resin composition according to any one of [1] to [7], wherein the oxygen concentration of (a) is less than 1.0% by volume.

[9]
The method for producing a thermoplastic resin composition according to any one of [2] to [5], wherein an inert gas is supplied to the atmospheric vent or the vacuum vent of (c).

[10]
[2] to [5], wherein the pressurizing screw of (d) includes at least one selected from the group consisting of a counterclockwise kneading disk, a two-thread counterclockwise flight screw, and a single-thread counterclockwise notch screw. [9] A method for producing a thermoplastic resin composition according to any one of [9].

[11]
The method for producing a thermoplastic resin composition according to any one of [2] to [5], [9], and [10], wherein an inert gas is supplied to the vacuum vent of (e).

[12]
The thermoplastic resin according to any one of [1] to [11], wherein the thermoplastic resin is at least one selected from the group consisting of a polyphenylene ether resin, a polycarbonate resin, a polyphenylene sulfide resin, a polyamide resin, and a polyoxymethylene resin. A method for producing a thermoplastic resin composition.

[13]
The number average molecular weight of the block copolymer is 50,000 to 500,000,
The heat according to any one of [1] to [12], wherein the content of the aromatic vinyl compound in the block copolymer is 15 to 80% by mass and the content of the conjugated diene compound is 20 to 85% by mass. A method for producing a plastic resin composition.

  According to the method for producing a thermoplastic resin composition of the present invention, it is possible to produce a thermoplastic resin composition that is excellent in productivity and is less likely to generate foreign matter or scouring.

Drawing 1 is a schematic diagram showing an example of a twin screw extruder used for a manufacturing method of a thermoplastic resin composition of this embodiment. FIG. 2 is a schematic front view (a) and a schematic side view (b) showing an example of a single-flight flight screw used in the method for producing a thermoplastic resin composition of the present embodiment. FIG. 3 is a schematic front view (a) and a schematic side view (b) showing an example of a two-flight flight screw used in the method for producing a thermoplastic resin composition of the present embodiment. FIG. 4 is a schematic front view (a) and a schematic side view (b) showing an example of a clockwise kneading disk used in the method for producing a thermoplastic resin composition of the present embodiment. FIG. 5 is a schematic front view (a) and a schematic side view (b) showing an example of a two-notch flight screw used in the method for producing a thermoplastic resin composition of the present embodiment. FIG. 6: is the schematic front view (a) and schematic side view (b) which show an example of the 1 piece left-handed notch flight screw used for the manufacturing method of the thermoplastic resin composition of this embodiment. FIG. 7: is the schematic front view (a) and schematic side view (b) which show an example of the counterclockwise kneading disk used for the manufacturing method of the thermoplastic resin composition of this embodiment. FIG. 8 is a schematic front view (a) and a schematic side view (b) showing an example of a two-handed counterclockwise flight screw used in the method for producing a thermoplastic resin composition of the present embodiment.

  Hereinafter, a mode for carrying out the present invention (hereinafter also referred to as “the present embodiment”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

The method for producing the thermoplastic resin composition of the present invention comprises:
(A) a solid conveyance zone having a first supply port;
(B) A first kneading zone (Lz is a zone length Lz / D = 3 to 12) provided with a screw configuration including a clockwise kneading disc and a screw with low pressure increase downstream of the solid conveyance zone. Zone length (mm), D represents screw diameter (mm)),
(C) a first melt transport zone downstream of the first kneading zone;
(D) a second kneading zone downstream of the first melt conveying zone;
(E) a second melt conveying zone downstream of the second kneading zone;
Using a twin screw extruder having
Hydrogenated product 2 of a block copolymer of an aromatic vinyl compound and a conjugated diene compound having an average particle size of 1 to 1000 μm and at least 80 to 98 parts by mass of a thermoplastic resin having an average particle size of 1 to 1000 μm ~ 20 parts by mass are supplied from the first supply port and melt-kneaded.
In the present specification, the method for producing the thermoplastic resin composition of the present embodiment may be simply referred to as “the production method of the present embodiment”.
In the present specification, a hydrogenated product of a block copolymer of an aromatic vinyl compound and a conjugated diene compound may be referred to as “hydrogenated product of an aromatic vinyl conjugated diene copolymer”.
In the present specification, the upstream side and the downstream side refer to the upstream side of the flow of the molten resin and the downstream side as the downstream side in the twin-screw extruder used in the method for producing the thermoplastic resin composition of the present embodiment. To do. That is, the first supply port side is the upstream side and the die part side is the downstream side.
Moreover, in this specification, a screw diameter means the major axis of a screw.

(Twin screw extruder)
Hereinafter, the twin-screw extruder used with the manufacturing method of this embodiment is demonstrated using FIG.
The twin-screw extruder (1) used in the production method of the present embodiment is preferably a complete meshing type co-rotating twin-screw extruder. As specific examples of the twin screw extruder (1), ZSK series (MC, MC +, Mc18, etc.) manufactured by Coperion, Germany, TEM series (SS, SX, etc.) manufactured by Toshiba Machine, Nippon Steel Works Examples thereof include TEX series (α, α2, α3, etc.) manufactured by the Company.
The screw rotation speed of the twin-screw extruder (1) is preferably 300 to 1200 rpm from the viewpoint that the powder can be conveyed at high speed. Further, the extrusion torque of the twin screw extruder (1) is preferably 30 to 80%, and a high torque twin screw extruder (for example, ZSK-MC having a torque density of 11.0 N · m / cm ³ or more, It is preferable to use TEM-SS, more preferably Mc18 or TEM-SX having a torque density of 18.4 N · m / cm ³ .
The twin screw extruder preferably has a screw diameter D of 40 to 160 mm, and the length of the extruder is preferably 30 to 60 times the screw diameter D of the screw used in the extruder. Moreover, it is preferable that the number of barrels of a twin-screw extruder (1) is 7-18, and the length of 1 barrel is 3-10 times the screw diameter D of the screw used for a barrel. preferable.

  The motor used in the twin-screw extruder (1) is preferably a direct current motor or an inverter motor that has a constant torque even when the screw rotation speed is changed. The cooling of the motor is preferably air-cooled or water-cooled, and the air-cooled method may diffuse small dust in the air, so the water-cooled method is more preferable.

Here, the screw pitch (the length of the pitch) refers to the distance between adjacent screw threads. In the case of a single thread screw, the distance traveled when the screw rotates 360 °, and in the case of a two thread screw, This is the distance traveled when the screw is rotated 180 °.
The screw lead (lead length) refers to the distance traveled when the screw is rotated 360 ° (one rotation). Here, in the case of a single thread screw, the screw pitch is equal to the screw lead, and in the case of a two thread screw, the screw lead is twice the screw pitch.
Moreover, the length of a screw means the full length of a screw, for example, when a screw is comprised only from a screw element, it means the total length of all the screw elements.
Further, the zone length Lz / D refers to a portion having a screw configuration in the zone.

The meaning of dispersion mixing and distribution mixing of flight screw and kneading disc will be explained.
Dispersive mixing refers to mixing by shear rate generated in a screw. Distributive mixing refers to mixing by the generation of a diversion generated in a screw and the union of the diversion. “Mixing” in melt kneading represents distributed mixing, and “kneading” represents dispersive mixing.

The twin-screw extruder (1) used in the production method of the present embodiment includes a solid conveyance zone (2), a first kneading zone (3), a first melt conveyance zone (4), and a second kneading zone (5). The second melt conveying zone (6) is provided, and if necessary, the second melt conveying zone, the third melt conveying zone, and the like may be further included.
In the twin screw extruder (1), the raw material is supplied from the first supply port hopper (8) to the first supply barrel (7) using, for example, the first raw material supply device (12) and the second raw material supply device (13). ). In addition, you may further provide another raw material supply port downstream from the 1st supply port barrel.
The first melt transport zone (4) preferably has a vent (9). Examples of the vent (9) include an air vent and a vacuum vent.
The second melt conveying zone (6) preferably has a vent (10). Examples of the vent (10) include a vacuum vent.
The die part (11) is provided in the most downstream part of the twin-screw extruder (1).
Hereinafter, each zone will be described.

-Solid conveyance zone-
Solid conveyance zone (2) has the 1st supply port hopper (8) which supplies a raw material.
The screw configuration in the solid conveyance zone (2) preferably has a single flight screw and a double flight screw, and the single screw flight screw having an overall screw length of Ls / D = 4.5-20, It is more preferable to have a two-flight flight screw having an overall screw length of Ls / D = 1.5 to 20 on the downstream side of the single flight screw, and a screw length of Ls / D = 4.5 to 20 More preferably, it consists only of a certain one-flight flight screw and a two-flight flight screw having a screw length Ls / D = 1.5 to 20 on the downstream side of the one-flight flight screw. Ls is the length (mm) of the screw.
In addition, Ls / D of screw length means the total value of Le / D (Le is the length (mm) of a screw element) of each screw element which comprises the screw. The screw configuration in the solid conveyance zone (2) is that the two-flight flight screw element is located downstream of the screw including the one-flight flight screw element in which the total Le / D value of the single-flight flight screw element is 4.5 to 20. It is more preferable to have a screw including a two-flight flight screw element in which the total value of Le / D is 1.5 to 20.
Moreover, in this specification, zone length Lz / D means the total value of Le / D of each screw element which comprises the screw in a zone.

It is preferable that the pitch of the elements constituting the single flight screw in the solid transport zone (2) is Lp / D = 1.0 to 2.0 (Lp is the pitch length (mm)). The screw element length is Le / D = 1. It is preferable that it is -2.0.
It is preferable that the pitch of the elements constituting the two-flight flight screw in the solid transport zone (2) is Lp / D = 0.25 to 1.1.0. The screw element length is preferably Le / D = 0.50 to 2.0.
Further, when using screw elements having different screw pitches in the solid conveyance zone (2), the screw pitch is arranged from the long pitch to the short pitch from the upstream side, that is, the screw pitch is shortened from the upstream side to the downstream side. Thus, it is preferable to arrange the screw elements.

  In the solid transport zone (2), supply inert gas to the powder feeder (feeder) and the first supply port hopper to prevent the powder from sticking to the screw element surface and barrel surface and causing thermal degradation. No. The oxygen concentration in the first supply port hopper (8) of one barrel is preferably less than 1.0% by volume, more preferably less than 0.5%, and even more preferably less than 0.1% by volume. .

  The length of the solid transport zone (2) is preferably Lz / D = 6.0-30.

-First kneading zone-
The first kneading zone (3) is provided on the downstream side of the solid conveyance zone (2).
The first kneading zone (3) is composed of a clockwise kneading disk and a screw with little pressure increase from the viewpoint that the resin temperature at the outlet of the orifice and the extrusion torque do not become excessively high, and the generation of foreign matter and mess can be suppressed. A screw structure is provided, and the zone length of the first kneading zone is Lz / D = 3-12.

The screw configuration of the first kneading zone (3) includes a clockwise kneading disk and a screw with low pressure increase.
Examples of the clockwise kneading disk include the kneading disk shown in FIG. 4, and the blade width is preferably Lw / D = 0.10 to 0.5, and Lw / D = 0.15. More preferably, it is -0.5. Lw is the blade width (mm) of the kneading disk.
Examples of the screw element with low pressure increase include a neutral kneading disk, a two-thread notched flight screw, a single blade kneading disk, etc., among which a neutral kneading disk and a two-thread notched flight screw are preferable. .
Examples of the neutral kneading disk include those having a twist angle (see FIG. 4) of 80 to 100 ° (preferably, 90 °). The blade width of the neutral kneading disk is preferably Lw / D = 0.06 to 0.3. The length of the neutral kneading disk (the distance traveled when the blade rotates 180 ° (half rotation)) is Lk / D = 0.3 to 1.5 (Lk is 180 ° of the blade of the kneading disk) The distance traveled (mm) when rotated (half rotation) is preferable.
Examples of the two-thread notched flight screw include a mixing screw (for example, a two-thread notched flight screw shown in FIG. 5) obtained by notching a screw pile. In the two-flight flight screw, the number of notches is preferably 10 to 20 per screw lead.

The overall length of the first kneading zone (3) is Lz / D = 3 to 12, and preferably Lz / D = 3 to 8. If the total length of the first kneading zone (3) is less than Lz / D = 3, kneading (distribution mixing and dispersion mixing) becomes insufficient, and if it exceeds Lz / D = 12, the powder conveying ability decreases. Is not preferable.
In addition, as long as the pressure in a 1st kneading zone does not become high too much, you may insert a 2 piece flight screw suitably.

-1st melt conveyance zone-
The first melt conveyance zone (4) is provided on the downstream side of the first kneading zone (3).
The screw configuration of the first melt conveyance zone (4) preferably includes a two-flight flight screw, and more preferably includes a two-flight flight screw.
The zone length of the first melt conveyance zone (4) is preferably Lz / D = 3-20.

The pitch of the elements constituting the two-flight flight screw in the first melt conveyance zone (4) is preferably Lp / D = 0.25 to 1.0, and Lp / D = 0.35 to 1.0. More preferably, Lp / D = 0.5 to 0.75 is more preferable from the viewpoint of increasing the conveying ability and not reducing the filling rate of the melt too much.
The screw element length of the two-flight flight screw in the first melt transport zone (4) is preferably Le / D = 0.5 to 2.0, and more preferably Le / D = 0.7 to 2.0. Le / D = 1.0 to 1.5 is more preferable.

  In order to increase the productivity of the powder in the first kneading zone, at least one atmospheric vent or vacuum vent is provided in the first melt conveying zone (4), and a large amount of gas contained in the powder can be removed. preferable. Moreover, since molten resin may adhere to the periphery of the opening of the air vent or vacuum vent, when there is a large amount of adhering molten resin, it is preferable to supply an inert gas around the opening to prevent carbonization. From the viewpoint of preventing residual monomers and volatile components from condensing in the vent, the temperature of the inert gas to be supplied is preferably heated to a set barrel temperature of −50 ° C. to + 50 ° C. Examples of the inert gas to be used include nitrogen, carbon dioxide, and the like. Among these, nitrogen is preferable from the viewpoint of cost.

  From the viewpoint of stabilizing the supply to the melt in the second kneading zone, the upstream side of the second kneading zone gradually increases the filling rate of the melt as the pitch of the two-flight flight screw is sequentially reduced. In the case of using screw elements having different screw pitches in one melt conveying zone (4), the screw pitch is arranged from the long pitch to the short pitch from the upstream side, that is, the length of the screw pitch from the upstream side to the downstream side. It is preferable to arrange the screw elements so that the length becomes shorter.

-Second kneading zone-
The second kneading zone (5) is provided on the downstream side of the first melt conveying zone (4).
The screw configuration of the second kneading zone (5) preferably has at least one booster screw, and more preferably consists of a booster screw. Examples of the pressure screw element include a counterclockwise kneading disk (FIG. 7), a two-thread counterclockwise flight screw (FIG. 8), a varistor ring, a one-thread counterclockwise notched flight screw (FIG. 6), a turbine masser, and the like. Among these, it is preferable to include at least a left-handed kneading disk, a two-way counterclockwise flight screw, or a single-handed left-handed notched screw, and more preferably a left-handed kneading disc and a two-handed left-handed flight screw.

  The screw configuration of the second kneading zone may further include a kneading disk, a neutral kneading disk, a two-thread notched flight screw, a single blade kneading disk, and the like.

The zone length of the second kneading zone (5) is preferably Lz / D = 2-12. If it is less than Lz / D = 2, kneading (distribution mixing and dispersion mixing) becomes insufficient, and if it exceeds Lz / D = 12, it is not preferable because the conveying ability of powder decreases.
In addition, a two-flight flight screw may be appropriately added as long as the pressure in the second kneading zone does not become too high.

-Second melt transfer zone-
The second melt conveying zone (6) is provided on the downstream side of the second kneading zone (5).
The screw configuration of the second melt conveyance zone (6) preferably includes a two-flight flight screw, more preferably a two-flight flight screw.
The length of the second melt conveyance zone (6) is preferably Lz / D = 3-20.

The pitch of the elements constituting the two-flight flight screw in the second melt conveyance zone (6) is preferably Lp / D = 0.25 to 1.0, and Lp / D = 0.35 to 1.0. More preferably, Lp / D = 1.0 to 1.5 is more preferable from the viewpoint of increasing the conveyance capacity and not reducing the filling rate of the melt too much.
The screw element length of the two-flight flight screw in the second melt conveyance zone (4) is preferably Le / D = 0.5 to 2.0, and more preferably Le / D = 0.7 to 2.0. Le / D = 1.0 to 1.5 is more preferable.

  The second melt transport zone (6) is provided with at least one vacuum vent in order to remove the cracked gas and residual monomer generated in the second kneading zone, and remove the residual monomer and cracked gas contained in the melt. This is preferred. Moreover, since molten resin may adhere to the periphery of the opening of the vacuum vent, when there is a large amount of molten resin adhering, it is preferable to supply an inert gas around the opening to prevent carbonization.

  Since the filling rate of the melt gradually increases, in the case where screw elements having different screw pitches are used in the second melt transport zone (6) from the viewpoint that the supply of the melt to the die portion is stabilized, The screw elements are preferably arranged from the long pitch to the short pitch, that is, the screw elements are arranged so that the length of the screw pitch decreases from the upstream side to the downstream side.

It is preferable that a die part exists in the most downstream side of the twin-screw extruder used with the manufacturing method of this embodiment.
The residence time of the molten resin in the die part is preferably within 90 seconds, more preferably within 60 seconds, and even more preferably within 30 seconds. When the residence time of the molten resin exceeds 90 seconds, the molten resin is thermally deteriorated and foreign matter increases.

A die plate may be installed at the tip of the die part.
The hole diameter of the strand of the die plate can be, for example, about 1.5 to 6.0 mm, and the number of holes can be adjusted so that the flow rate is about 10 to 40 kg / hr per hole.
In the case of the strand cut method, a scum may be generated at the outlet of the strand on the die plate. Therefore, a scouring device for blowing air may be installed. The air used at that time should be passed through a filter having a pore diameter of about 5 μm. The cooling water of the strand bath should be passed through a filter having a pore diameter of about 10 μm.
Further, instead of the strand cut method, a hot cut method or an underwater cut method may be adopted. The pellet obtained by the strand cut method is cylindrical. On the other hand, pellets obtained by the hot cut method and the underwater cut method are spherical or elliptical.
The average size of the obtained pellets is preferably 1 to 6 mm, more preferably 2 to 5 mm, and further preferably 2.5 to 3.5 mm. You may fully knead | mix the obtained pellet with a molding machine screw or an extruder screw.

Next, the screw element used for the twin-screw extruder used with the manufacturing method of this embodiment is demonstrated.
It is preferable that the pitch length of the elements constituting the single flight screw (FIG. 2) is Lp / D = 1.0 to 2.0. When the pitch length is less than Lp / D = 1.0, the conveyance capacity may be reduced, and when Lp / D = 2 is exceeded, the biting of the powder from the first supply port of the first barrel may be reduced.
Moreover, it is preferable that the length of the said 1-flight flight screw is 0.5-2 times the length of the pitch of the element which comprises a 1-flight flight screw. If the length of the screw is less than 0.5 times, the conveying ability may be reduced, and if it is more than 2 times, the biting of the powder from the first supply port of the first barrel may be reduced.
The total length of the single-flight flight screw is preferably Ls / D = 4.5-20. If the screw length is less than Ls / D = 4.5, the powder supply capacity may decrease. If the screw length exceeds Ls / D = 20, the powder enters the gap between the flight portion of the single screw and the barrel. In some cases, heat degradation products increase.

The element constituting the two-flight flight screw (FIG. 3) preferably has a pitch length of Lp / D = 0.25 to 3.0, and Lp / D from the viewpoint of more stable supply of powder. It is more preferable that it is = 0.25-1.0, and Lp / D = 0.5-3.0 may be sufficient. If the pitch length is less than Lp / D = 0.25, the carrying capacity may be reduced. If the pitch length is more than 3.0, the carrying capacity may be too large and the powder supply may not be stable. is there.
Moreover, it is preferable that the length of the screw of the two-flight flight screw is 0.5 to 2 times the length of the pitch.
The total length of the two-flight flight screw is preferably Ls / D = 1.5 to 20, and more preferably Ls / D = 3.0 to 20. If the screw length is less than Ls / D = 1.5, the powder conveying ability may be reduced, and if it exceeds Ls / D = 20, the powder supply may become unstable.
In the case where the two-flight flight screw is provided on the downstream side of the one-flight flight screw, between the one-flight flight screw and the two-flight flight screw, the connection flight screws of the first and second flights (for example, the first to second flights). A conversion screw or the like may be used.

The clockwise kneading disk (FIG. 4) preferably has a blade width of Lw / D = 0.10 to 0.5. When the blade width is less than Lw / D = 0.1, the powder conveying ability may be reduced. When Lw / D is more than 0.5, dispersion and mixing in the blade portion becomes strong, and the resin temperature rises. Deterioration of the resin may occur.
The twist angle of the clockwise kneading disk is preferably 10 to 50 °. If the twist angle is less than 10 °, the powder conveying ability may be reduced, and if it exceeds 50 °, the powder conveying ability may be reduced.
The length of the clockwise kneading disk is preferably Lk / D = 0.3 to 2.5. If the length is less than Lk / D = 0.3, the powder conveying ability may be reduced. If the length is more than Lk / D = 2.5, the dispersion mixing becomes strong, the resin temperature rises, and the resin deteriorates. It may happen.

The neutral kneading disk (for example, having a twist angle of 90 degrees in FIG. 4) preferably has a blade width of Lw / D = 0.07 to 0.3. If the blade width is less than Lw / D = 0.07, the powder conveying ability may decrease, and if it exceeds Lw / D = 0.3, the dispersion mixing in the blade portion becomes strong, the resin temperature increases, Deterioration of the resin may occur.
The twist angle of the neutral kneading disk is preferably 80 to 100 °. If the twist angle is less than 80 degrees, the distribution / mixing ability may decrease, and even if it exceeds 100 °, the distribution / mixing ability may decrease.
The kneading disc length of the neutral kneading disc is preferably Lk / D = 0.3 to 1.5. When the kneading disc length is less than Lk / D = 0.3, the distribution and mixing ability may decrease. When the kneading disk length exceeds Lk / D = 1.5, the dispersion mixing becomes strong, the resin temperature rises, and the resin deteriorates. May occur.

It is preferable that the pitch length of the elements constituting the two-notch flight screw (FIG. 5) is Lp / D = 0.2 to 0.5. If the pitch length is less than Lp / D = 0.2, the powder conveying ability may be reduced. If the pitch length exceeds Lp / D = 0.5, the conveying ability is too large and kneading becomes insufficient. There is a case.
As for the said 2 notch flight screw, it is preferable that the screw element length is Le / D = 0.4-1.0. If the screw length is less than Le / D = 0.4, the powder conveying ability may be reduced. If Le / D = 1.0, the conveying ability is too large and the kneading becomes insufficient. There is a case.
The number of notches in the two-thread notched flight screw is preferably 10 to 20 in one screw lead. If the number of notches is less than 10, distribution mixing may be insufficient, and if it exceeds 20, dispersion mixing may be insufficient.

  The single-blade kneading disk may have one blade and the same blade width and kneading disc length. The blade width is preferably Lw / D = 0.5 to 1.0.

It is preferable that the pitch length of the elements constituting the above-mentioned single left-handed notch screw (FIG. 6) is Lp / D = 0.1 to 0.5. When the screw pitch is less than Lp / D = 0.1, the flight and the width of the flight are narrowed, and the resin temperature may be too high. When Lp / D is more than 0.5, the pressure is excessively increased and the resin temperature is too high. May be higher.
It is preferable that the number of notches of the above-mentioned single left-handed notch screw is 10 to 20 in one screw lead. If the number of notches is less than 10, distribution mixing may be insufficient, and if it exceeds 20, dispersion mixing may be insufficient.

The counterclockwise kneading disk (FIG. 7) preferably has a blade width of Lw / D = 0.08 to 0.3. When the blade width is less than Lw / D = 0.08, dispersion mixing may decrease. When Lw / D = more than 0.3, dispersion mixing at the blade portion becomes strong, the resin temperature rises, and the resin deteriorates. May occur.
The kneading disc length of the counterclockwise kneading disc is preferably Lk / D = 0.4 to 1.5. When the kneading disc length is less than Lk / D = 0.4, the dispersion mixing may decrease. When the kneading disk length exceeds Lk / D = 1.5, the dispersion mixing becomes strong, the resin temperature rises, and the resin deteriorates. It may happen.
The twist angle of the counterclockwise kneading disk is preferably 10 to 50 ° in the left direction. When the twist angle is less than 10 °, the distribution mixing may decrease, and when it exceeds 50 °, the dispersion mixing may decrease.

The above-mentioned two-thread counterclockwise flight screw (FIG. 8) is also called “reverse screw”, and is a screw whose flight direction is opposite to that of FIG.
It is preferable that the element which comprises the said 2 item | clock left-handed flight screw is pitch length Lp / D = 0.25-0.5. If the pitch length is less than Lp / D = 0.25, the pressure may be too high and dispersion mixing may become too strong. If the pitch length exceeds Lp / D = 0.5, the length of the portion for dispersion mixing is long. As a result, the resin temperature may rise too much.
The length of the screw element of the above two left-handed flight screw is preferably Le / D = 0.5 to 1.0.

  The varistor ring (not shown) is also called “seal ring”, and the pressure is higher than that of the two-way counterclockwise flight screw. The screw element length of the varistor ring is preferably Le / D = 0.3 to 1.0. When the screw length is less than Le / D = 0.3, the effect of increasing the pressure is small, and when it exceeds Le / D = 1.0, the pressure increases too much and the resin temperature may become too high.

The turbine mixer (not shown) is a screw element in which a notch portion of a single left-handed notch screw is attached to a sealing screw portion of a varistor ring (seal ring). The element length of the varistor ring is preferably Le / D = 0.3 to 1.0. If the element length of the varistor ring is less than Le / D = 0.3, the effect of increasing the pressure is small, and if it exceeds Le / D = 1.0, the pressure increases too much and the resin temperature may become too high.
The number of notches in the varistor ring is preferably 10 to 20 per pitch.

(Thermoplastic resin)
Hereinafter, the raw material used for the manufacturing method of this embodiment is demonstrated.
Examples of the thermoplastic resin used in the production method of the present embodiment include polyphenylene ether resin (poly (2,6-dimethyl-1,4-phenylene ether), poly (2,6-dimethylphenylene ether-co-2). , 3,6-trimethylphenylene ether)), polyphenylene ether resin and alkenyl resin mixture, polycarbonate resin, polyolefin resin (high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene, polypropylene, ethylene・ Propylene copolymer, etc.), homopolyoxymethylene, oxymethylene copolymer, polyphenylene sulfide resin, polystyrene resin (polystyrene, high impact polystyrene, acrylonitrile / styrene copolymer, syndiotactic polymer) Styrene, acrylonitrile / butadiene / styrene copolymer, etc.), polyamide resins (polyamide 6, polyamide 6,6, polyamide 4,6, polyamide 11, polyamide 12, polyamide 6,10, polyamide 6,12, polyamide 6/6) , 6, polyamide 6 / 6,12, polyamide MXD (m-xylylenediamine), 6, polyamide 6, T, polyamide 9, T, polyamide 6, I, polyamide 6/6, T, polyamide 6/6, I , Polyamide 6,6 / 6, T, polyamide 6,6 / 6, I, polyamide 6/6, T / 6, I, polyamide 6,6 / 6, T / 6, I, polyamide 6/12/6, T, polyamide 6,6 / 12/6, T, polyamide 6/12/6, I, polyamide 6,6 / 12/6, I, etc.), polyester resin (polybutylene) Terephthalate, polyethylene terephthalate, etc.) and the like.
Among them, polyphenylene ether resin (poly (2,6-dimethyl-1,4-phenylene ether), poly (2,6-dimethylphenylene ether-co-2,3,6-trimethylphenylene ether), etc.), polycarbonate resin, At least one selected from the group consisting of polyolefin resins, polyphenylene sulfide resins, and polyamide resins is preferred.
In addition, polyphenylene ether resin (poly (2,6-dimethyl-1,4-phenylene ether), poly (2,6-dimethylphenylene ether-co-2,3,6-trimethylphenylene ether)), polycarbonate resin, At least one selected from the group consisting of a polyphenylene sulfide resin, a polyamide resin, and a polyoxymethylene resin is preferable.
More preferably, polyphenylene ether resin (poly (2,6-dimethyl-1,4-phenylene ether), poly (2,6-dimethylphenylene ether-co-2,3,6-trimethylphenylene ether), etc.), polyphenylene It is at least one selected from the group consisting of sulfide resins and polyamide resins.
The said thermoplastic resin may be used independently and may be used in combination of 2 or more type.

The average particle diameter of the thermoplastic resin is 1-1000 μm, preferably 10-1000 μm, and more preferably 100-1000 μm.
The average particle size can be measured with a call counter measuring machine, a laser diffraction particle size meter, or the like.
In the present specification, a compound having an average particle size of 1 to 1000 μm is used as a powder, and a compound having an average particle size of more than 1000 μm is used as a pellet.

The amount of the thermoplastic resin supplied from the first supply port is 80 to 98 parts by mass with respect to the total amount of the thermoplastic resin and the hydrogenated product of the aromatic vinyl conjugated diene copolymer, preferably Is 85 to 98 parts by mass, more preferably 85 to 97 parts by mass.
Moreover, it is preferable that the quantity of the said thermoplastic resin supplied from the said 1st supply port is 80-98 mass% with respect to the total amount (100 mass%) of the raw material supplied from a 1st supply port.

Hydrogenated aromatic vinyl conjugated diene copolymer is a hydrogenated product in which at least a part of a block copolymer of a polymer block containing an aromatic vinyl compound and a polymer block containing a conjugated diene compound is hydrogenated. The block copolymer is preferably a hydrogenated block copolymer obtained by hydrogenating at least part of a block copolymer of a polymer block made of an aromatic vinyl compound and a polymer block made of a conjugated diene compound. More preferably, it is a coalescence.
In the block copolymer, the aromatic vinyl compound may be uniformly distributed or tapered in the polymer block of the aromatic vinyl compound. Further, a polymer block containing an aromatic vinyl compound contained in the block copolymer (or made of an aromatic vinyl compound) and / or a polymer block containing a conjugated diene compound (or made of a conjugated diene compound). May be of the same type or different. Further, the content of the aromatic vinyl compound and / or the content of the conjugated diene compound in each polymer block may be the same or different.

The aromatic vinyl compound used for the hydrogenated product of the aromatic vinyl conjugated diene copolymer is not limited to the following, but examples thereof include styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene. And diphenylethylene. In particular, styrene is preferable as the aromatic vinyl compound.
The said aromatic vinyl compound may be used individually by 1 type, and may use 2 or more types together.

The conjugated diene compound used for the hydrogenated product of the aromatic vinyl conjugated diene copolymer is not limited to the following, and examples thereof include butadiene, isoprene, 1,3-pentadiene, and 2,3-dimethyl-1. , 3-butadiene, and combinations thereof. In particular, as the conjugated diene compound, butadiene, isoprene and a combination thereof are preferable.
The said conjugated diene compound may be used individually by 1 type, and may use 2 or more types together.

  The content of the aromatic vinyl compound in the hydrogenated product of the aromatic vinyl conjugated diene copolymer is preferably 15 to 80% by mass, and the content of the conjugated diene compound is preferably 20 to 85% by mass. By setting it as such content, impact resistance can be provided. Moreover, 30-80 mass% is more preferable, and, as for content of a vinyl aromatic compound, 50-75 mass% is further more preferable. The content of the conjugated diene compound is more preferably 20 to 70% by mass, and further preferably 25 to 50% by mass.

The microstructure which is a polymerization mode of the conjugated diene compound in the hydrogenated product of the aromatic vinyl conjugated diene copolymer can be arbitrarily selected. For example, when butadiene is used as the conjugated diene compound, the 1,2-vinyl bond content relative to the total double bonds in the polymer block composed of the conjugated diene compound is preferably 2 to 85%, more preferably 10 It is -85%, More preferably, it is 35-85%.
In isoprene, the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds is preferably 2 to 85% with respect to the full double bonds in the polymer block composed of the conjugated diene compound. More preferably, it is 3-75%, More preferably, it is 3-60%. The 1,2-vinyl bond and 3,4-vinyl bond may be uniformly distributed in the conjugated diene compound polymer block or may be distributed in a tapered shape.

  The polymer block composed of the conjugated diene compound is a polymer part having a different amount of 1,2-vinyl bond or a total amount of 1,2-vinyl bond and 3,4-vinyl bond, for example, 1,2-vinyl. There may be a polymer block portion in which the bond content or the total amount of 1,2-vinyl bond and 3,4-vinyl bond is less than 30% and polymer block of 30% or more, and further 30% In a polymer block portion of less than 30% and / or a polymer block of 30% or more, a plurality of polymer blocks having different vinyl bond amounts may coexist.

  The number average molecular weight (polystyrene conversion molecular weight by gel permeation chromatography) of the hydrogenated product of the aromatic vinyl conjugated diene copolymer is preferably 50,000 to 500,000, more preferably 55,000 to 400,000. 000, more preferably 60,000 to 400,000. When the number average molecular weight of the hydrogenated aromatic vinyl conjugated diene copolymer is in the above range, it is difficult for the molten resin to adhere to the screw, and the generation of foreign matters can be suppressed.

  The average particle diameter of the hydrogenated product of the aromatic vinyl conjugated diene copolymer is 1-1000 μm, preferably 2-800 μm. If it is less than 1 μm, liquefaction of the powder tends to occur, and if it exceeds 1000 μm, unmelted powder tends to be generated. The average particle diameter is a value measured with a call counter measuring machine, a laser diffraction particle size meter, or the like.

  In the production method of the present embodiment, pellet resins, additives, flame retardants, and the like may be used in addition to the thermoplastic resin and the hydrogenated product of the aromatic vinyl conjugated diene copolymer.

  When using a pellet-type resin, it is preferable to use 80-99 mass parts of the said thermoplastic resin with respect to the total amount of the said thermoplastic resin and the said pellet-type resin, More preferably, it is 85-99 mass parts. If the amount is less than 80 parts by mass, it is difficult to impart the performance of the powdered thermoplastic resin in the thermoplastic resin composition, and if it exceeds 99 parts by mass, it is difficult to impart the performance of a resin other than the thermoplastic resin.

As the above additives, heavy calcium carbonate, colloidal calcium carbonate, soft calcium carbonate, silica, kaolin, clay, barium sulfate, zinc oxide, alumina, magnesium hydroxide, talc, mica, glass flakes, hydrotalcite, acicular Filler (wollastonite, potassium titanate, basic magnesium sulfate, seplite, zonotolite, aluminum borate), glass beads, silica beads, alumina beads, carbon beads, glass balloons, metallic conductive filler, non-metallic conductive Fillers, carbon, magnetic fillers, piezoelectric / pyroelectric fillers, slidable fillers, fillers for encapsulants, UV absorbing fillers, damping fillers, conductive fillers (Ketjen black, acetylene black), glass fibers, carbon fibers , Reinforcement of metal fibers, etc. Oil (paraffinic, naphthenic, silicon-based), the functional groups imparting agent (maleic acid, fumaric acid, itaconic acid, maleic anhydride, malic acid, citric acid) and the like.
The addition amount of the additive is preferably 0.01 to 150 parts by mass, more preferably 100 parts by mass in total of the thermoplastic resin and the hydrogenated product of the aromatic vinyl conjugated diene copolymer. Is 0.01 to 140 parts by mass, more preferably 0.01 to 100 parts by mass. If it exceeds 150 parts by mass, the resin temperature rises and oxidation degradation products increase.

Examples of the flame retardant include triphenyl phosphate, phenyl bisdodecyl phosphate, phenyl bisneopentyl phosphate, phenyl-bis (3,5,5'-trimethyl-hexyl) phosphate, ethyl diphenyl phosphate, 2-ethylhexyl di (p-tolyl) ) Phosphate, bis (2-ethylhexyl) p-tolyl phosphate, tolyl phosphate, bis (2-ethylhexyl) phenyl phosphate, tri (nonylphenyl) phosphate, di (dodecyl) p-tolyl phosphate, tricresyl phosphate, dibutylphenyl Phosphate, 2-chloroethyldiphenyl phosphate, p-tolylbis (2,5,5'-trimethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate, 2,2 Bis- {4- [bis (phenoxy) phosphoryloxy] phenyl} propane, 2,2-bis- {4- [bis (methylphenoxy) phosphoryloxy] phenyl} propane, phosphoric acid- (3-hydroxyphenyl) diphenyl, Examples thereof include phosphate esters or diphosphinic acid salts such as resorcinol bis (diphenyl phosphate), 2-naphthyl diphenyl phosphate, 1-naphthyl diphenyl phosphate, and di (2-naphthyl) phenyl phosphate.
The amount of the flame retardant added is preferably 0 to 50 parts by weight, more preferably 0 to 40 parts by weight with respect to a total of 100 parts by weight of the thermoplastic resin and the hydrogenated product of the aromatic vinyl conjugated diene copolymer. Parts, more preferably 0 to 30 parts by mass. If it exceeds 50 parts by mass, the melt viscosity will be too low and it will be difficult to form pellets.
When the flame retardant is supplied to the solid conveyance zone, the powder raw material melts in the solid conveyance zone and deposits on the inner surface of the barrel and the screw surface, causing foreign matter. A zone where the resin added downstream is melted is preferred.

  In the production method of the present embodiment, further, plasticizers, various colorants, coloring additives (titanium oxide, etc.), ultraviolet absorbers, antistatic agents, stabilizers (zinc oxide, zinc sulfide, phosphorus-based, sulfur-based, hinders) You may add dophenol type etc.).

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

<Twin screw extruder>
The twin screw extruder used in the examples and comparative examples is as follows.
As the twin-screw co-rotating extruder, TEM58SS (12 barrels: Lt / D = 49.6 (Lt represents the length (mm) of the twin-screw extruder)) manufactured by Toshiba Machine Co., Ltd. was used.
The screw configuration and barrel configuration are as follows.
・ No. 1 barrel: 20 L / min of nitrogen gas was supplied to the solid conveyance zone (first supply port) and the hopper.
・ No. 2 to 4 barrels: solid conveyance zone 5 barrels: No. 1 kneading zone 6 barrels: 1st melt conveyance zone (atmospheric vent: nitrogen gas 5 L / min)
・ No. 7-9 barrels: 1st melt conveyance zone No. 10 barrels: No. 2 kneading zone 11 barrel: second melt conveyance zone (vacuum vent: 6579 Pa, nitrogen gas 5 L / min)
・ No. 12 barrels: second melt transfer zone

Mesh: 20 # / 40 # (aperture 415 μm) / 30 # / 20 #
・ Die head: Orifice hole diameter 4.0Φmm 15mm length 15 holes ・ Strand bath: Water temperature 40 ℃ ± 3 ℃
・ Pelletizer: Column shape 2.5 ± 0.3mm target ・ Vibrating sieve: Long pellets, continuous pellets and chips are eliminated ・ First raw material feeder: Kubota Corporation CE-W-4 (powdered thermoplastic resin ), 20 L / min of nitrogen gas was supplied to the raw material hopper.
Second raw material supply device: Kubota Corporation CE-W-4 (hydrogenated product of powdery aromatic vinyl compound / conjugated diene compound block copolymer) and a raw material hopper were supplied with 5 L / min of nitrogen gas.
In addition, the 1st raw material supply apparatus and the 2nd raw material supply apparatus are No. It connected to the 1st feed port of 1 barrel.

<Screw configuration>
The screw configuration of each zone is as follows.
In addition, the screw of each zone was described in order from the upstream side to the downstream side. Moreover, the screw showed pitch length (mm) / screw length (mm).
-Solid conveyance zone 75/75, 1-flight flight screw (Le / D = 1.29), 5 pieces (total screw length Ls / D = 6.45 of a single-thread screw)
60/60, 1 to 2 conversion screw (Le / D = 1.03), 1 75/75, 2 flight screw (Le / D = 1.29), 4 60/60, 2 flight Screw (Le / D = 1.03), 1 piece 45/45, Double flight screw (Le / D = 0.78), 1 piece (Double screw total screw length Ls / D = 8.00)
Solid conveyance zone length Lz / D = 14.45
-1st kneading zone 1st kneading zone length: Lz / D = 5.95 (a screw structure is described in Table 1)
-1st melt conveyance zone 75/75, 2 piece flight screw (Le / D = 1.29), 10 pieces 60/60, 2 piece flight screw (Le / D = 1.03), 2 pieces 1st fusion Body transport zone length Lz / D = 14.96
-Second kneading zone twist angle 45 degrees, 5 blades, clockwise kneading disc, kneading disc length 60mm
Twist angle 90 degrees, 5 blades, neutral kneading disc, kneading disc length 60mm
Twist angle 45 degrees, 5 blades, counterclockwise kneading disc, kneading disc length 30 mm
Second kneading zone length: Lz / D = 150 mm / 58 mm = 2.58
Second melt transfer zone 75/75, two-flight flight screw (Le / D = 1.29), seven 60/30, two-flight flight screw (Le / D = 0.51), one 60/60 Two-flight flight screw (Le / D = 1.03), two pieces Second melt conveyance zone length Lz / D = 11.6

Measurement methods and evaluation methods applied in Examples and Comparative Examples are shown below.
<Maximum extrusion amount>
The maximum extruding amount (kg / hr) at which the powdery raw material did not accumulate in the first supply port hopper was measured.

<Torque>
The torque was the indicated value of torque% on the extruder control panel.

<Resin temperature>
When the die plate is viewed in front, the temperature at the outlet of the third orifice from the right is measured using a handy type thermometer HD-1100 manufactured by Anritsu Keiki Co., Ltd. with a needle sensor, and the resin temperature (° C.) It was.

<Foreign matter in the pellet>
From the pellets obtained in the examples or comparative examples, a press plate having a diameter of 180 mm and a thickness of 1 mm was used to produce a flat plate by compression molding at 250 ° C. The number of black spots (pieces) having a diameter of 200 μm or more on the back surface was measured. The black spot is the number of oxidation degradation products.

<Occurrence of Meani>
The size of the sag generated at the opening of the orifice of the die plate (strand outlet) during 10 minutes after the strand began to be discharged was measured using a caliper. The determination was performed according to the following criteria.
1: Mayan having a length of 1 mm or less was generated or not being formed 2: Mayan having a length of more than 1 mm to 3 mm or less was generated 3: Mayan having a length of more than 3 mm to 5 mm or less was generated 4: More than 5 mm in length to 10 mm or less 5: Mayan with a length of more than 10mm

Example 1
A polyphenylene ether (trade name “S201A”, manufactured by Asahi Kasei Plastic Singapore) with an average particle size of 700 μm, a bulk density of 550 kg / m ³ , and a reduced viscosity of 0.51 (extreme viscosity of 0.48) is introduced into the first raw material supply apparatus. The addition amount was set to 95 parts by mass. Further, SEBS (trade name “G1651”) having a particle size of 250 μm, a number average molecular weight of 250,000, a styrene part content of 67% by mass, and a hydrogenation content of a conjugated diene compound of 33% by mass in the second raw material supply device. , Manufactured by Kraton Polymer Japan Company), and the addition amount was set to 5 parts by mass.
No. The oxygen concentration in the 1-barrel first supply port hopper was measured using a zirconia oxygen analyzer (ZR402G, manufactured by Yokogawa Electric Corporation). The oxygen concentration was 0.5% by volume.
The screw configuration of the first kneading zone was A in Table 1.
The barrel temperature is No. 1 barrel is 50 ° C. 2-No. 4 barrels at 270 ° C. 5-No. 12 barrels were set at 290 ° C, and the die temperature was set at 320 ° C.
The screw rotation speed was 300 rpm, and after measuring the maximum extrusion amount, the resin temperature and the extruder torque display were recorded.
As a result, the maximum extrusion amount was 350 kg / hr, the torque was 78%, the resin temperature (die plate orifice outlet temperature) was 351 ° C., the number of foreign matters in the pellet was one, and no scum was generated.

(Comparative Example 1)
SEBS3 of Example 1 having an average particle diameter (diameter) of 3 mm (pellet) (trade name “H-1081”, manufactured by Asahi Kasei Corporation, styrene content 60%, number average molecular weight 100,000) is used. The same procedure as in Example 1 was performed except that.
Compared to Example 1, the maximum extrusion amount was the same, but the torque and the resin temperature were high, the number of foreign matters in the pellets increased to 7, and the occurrence of scraping increased to level 3.

(Comparative Example 2)
SEBS4 of Example 1 having an average particle size (diameter) of 3 mm (pellet) (trade name “H-1272”, manufactured by Asahi Kasei Co., Ltd., styrene content 67%, number average molecular weight 200,000) was used. The same procedure as in Example 1 was performed except that.
Compared to Example 1, the maximum extrusion amount was the same, but the torque and resin temperature were high, the number of foreign matters in the pellets increased to 6, and the occurrence of scraping increased to level 3.

(Comparative Example 3)
SEBS of Example 1 was carried out in the same manner as Example 1 except that general purpose polystyrene (trade name “685”, manufactured by PS Japan Ltd.) having an average particle diameter (diameter) of 3 mm (pellet) was used.
Compared with Example 1, the maximum extrusion amount was the same, but the torque and the resin temperature were high, the number of foreign matters in the pellet increased to 23, and the occurrence of scum was increased to level 5.

(Comparative Example 4)
The SEBS of Example 1 was carried out in the same manner as in Example 1 except that high impact polystyrene (trade name “CT60”, manufactured by Petrochemical Co., Malaysia) having an average particle diameter (diameter) of 3 mm (pellet) was used. did.
Compared to Example 1, the maximum extrusion amount was the same, but the torque and the resin temperature were high, the number of foreign matters in the pellets increased to 21, and the occurrence of scraping increased to level 5.

(Comparative Example 5)
The same procedure as in Example 1 was performed except that the screw configuration of the first kneading zone was changed from A to B.
When a counterclockwise kneading disk that is a pressure screw is used, the bite of the powder in the first kneading zone becomes worse compared to Example 1, the maximum extrusion amount decreases, the resin temperature and torque also increase, Increased amount of foreign material and spears.

(Comparative Example 6)
The same procedure as in Example 1 was performed except that the screw configuration of the first kneading zone was changed from A to C.
When using a double-handed counterclockwise flight screw, which is a pressurizing screw, compared to Example 1, the bite of the powder in the first kneading zone becomes worse, the maximum extrusion amount decreases, the resin temperature and torque increase, and the pellets The amount of foreign matter and scum is increased.

(Comparative Example 7)
The same procedure as in Example 1 was performed except that the screw configuration of the first kneading zone was changed from A to D.
There was no screw with little pressure increase, and all kneading discs caused kneading failure, and powder was blown out from the air vent (vent up).

(Example 2)
The same procedure as in Example 1 was performed except that the screw configuration of the first kneading zone was changed from A to E.
Compared to Example 1, the maximum extrusion amount increased and the resin temperature and torque increased slightly. The amount of foreign matter in the pellet and the amount of scum generation were the same.

(Example 3)
The same procedure as in Example 1 was performed except that the screw configuration of the first kneading zone was changed from A to F.
Compared to Example 1, the maximum extrusion amount increased and the resin temperature and torque increased slightly. The amount of foreign matter in the pellet and the amount of scum generation were the same.

Example 4
The same procedure as in Example 1 was performed except that the screw configuration of the first kneading zone was changed from A to G.
Compared to Example 1, the maximum extrusion amount increased and the resin temperature and torque increased slightly. The amount of foreign matter in the pellet and the amount of scum generation were the same.

(Example 5)
Example SEBS of Example was used except that SEBS1 having an average particle size of 270 μm, a number average molecular weight of 280,000, a styrene part content of 70% by mass, and a hydrogenation content of a conjugated diene compound of 30% by mass was used. 1 was carried out.
Compared with Example 1, although the torque and the resin temperature increased a little because the molecular weight increased, the amount of foreign matter in the pellet and the amount of generated resin were the same.

(Example 6)
Example SEBS of Example was used except that SEBS2 having an average particle size of 270 μm, a number average molecular weight of 100,000, a styrene part content of 43% by mass, and a hydrogenation content of a conjugated diene compound of 57% by mass was used. 1 was carried out.
Compared with Example 1, the amount of molecular weight decreased, the torque and the resin temperature were slightly lowered, and the amount of foreign matter in the pellet and the amount of generated resin were the same.

(Example 7)
The same procedure as in Example 1 was performed except that the mass ratio of polyphenylene ether and G1651 was changed to 90/10.
Compared with Example 1, the maximum extrusion amount increased, the torque increased, but the resin temperature decreased. The amount of foreign matter in the pellet and the amount of scum generation were the same.

(Example 8)
The same procedure as in Example 1 was performed except that the mass ratio of polyphenylene ether and G1651 was changed to 80/20.
Compared to Example 1, the amount of maximum extrusion increased and the torque increased but the resin temperature decreased. The amount of foreign matter in the pellet and the amount of scum generation were the same.

Example 9
The same procedure as in Example 1 was performed except that the polyphenylene ether of Example 1 was changed to polyphenylene ether S202A (manufactured by Asahi Kasei Plastic Singapore) having an average particle size of 500 μm and a reduced viscosity of 0.41.
Compared with Example 1, the resin temperature and the torque were reduced, and the amount of foreign matter in the pellet and the generated amount of scum were the same.

(Example 10)
The same procedure as in Example 9 was performed except that the screw configuration of the first kneading zone was changed from A to E.
Compared to Example 9, the amount of extrusion increased and the resin temperature and torque increased slightly. The amount of foreign matter in the pellet and the amount of scum generation were the same.

(Example 11)
The same procedure as in Example 9 was performed except that the screw configuration of the first kneading zone was changed from A to F.
Compared to Example 9, the amount of extrusion increased and the resin temperature and torque increased slightly. The amount of foreign matter in the pellet and the amount of scum generation were the same.

(Example 12)
It implemented similarly to Example 9 except having changed the screw structure of the 1st kneading zone from A to G.
Compared to Example 9, the amount of extrusion increased and the resin temperature and torque increased slightly. The amount of foreign matter in the pellet and the amount of scum generation were the same.

(Example 13)
The polyphenylene ether of Example 9 was changed to polyphenylene sulfide (trade name “L4230”, manufactured by Toray Industries, Inc., average particle size 60 μm), and 0.3 parts by mass of glycidyl methacrylate as a compatibilizer was blended with G1651. The same operation as in Example 9 was carried out except that.
As in Example 9, the amount of foreign matter and spears generated in the pellets was small.

(Example 14)
The polyphenylene ether of Example 9 was changed to polycarbonate (trade name “Panlite L-1250Y”, manufactured by Teijin Ltd.) pulverized to an average particle size of 350 μm, and 0.3 part by mass of maleic anhydride as a compatibilizer was changed to G1651. The same operation as in Example 9 was performed except that a blended material was used.
As in Example 9, the amount of foreign matter and spears generated in the pellets was small.

(Example 15)
Example 9 except that the polyphenylene ether of Example 9 was changed to polyamide 66 (trade name “1300S”, manufactured by Asahi Kasei Co., Ltd.) pulverized to an average particle size of 420 μm, and 0.3 part by mass of maleic anhydride was blended with G1651. It carried out like.
As in Example 9, the amount of foreign matter and spears generated in the pellets was small.

(Example 16)
The polyphenylene ether of Example 9 was changed to freeze-ground polyoxymethylene (trade name “7520”, manufactured by Asahi Kasei Co., Ltd., average particle size 300 μm), and 0.3 part by mass of glycidyl methacrylate as a compatibilizer was blended with G1651. This was carried out in the same manner as in Example 9 except that the above was used.
As in Example 9, the amount of foreign matter and spears generated in the pellets was small.

  From the examples and comparative examples, when melt-kneading the powdered thermoplastic resin and the powdered aromatic vinyl compound / conjugated diene compound hydrogenated block copolymer, by using a specific screw configuration, It was found that a thermoplastic resin composition having good productivity and less foreign matter and scum was obtained.

  The thermoplastic resin composition obtained by the production method of the present embodiment is suitable for application fields such as pump housings and parts, medical housings and parts, electronic materials, optical materials, battery case materials, battery cell materials, films, and sheets. It is.

1: Twin screw extruder 2: Solid conveyance zone 3: First kneading zone 4: First melt conveyance zone 5: Second kneading zone 6: Second melt conveyance zone 7: First supply barrel 8: First supply Mouth hopper 9: Vent 10: Vent 11: Die unit 12: First raw material supply device 13: Second raw material supply device

Claims (13)

(A) a solid conveyance zone having a first supply port;
(B) A first kneading zone (Lz is a zone length Lz / D = 3 to 12) provided with a screw configuration including a clockwise kneading disc and a screw with low pressure increase downstream of the solid conveyance zone. Zone length (mm), D represents screw diameter (mm)),
(C) a first melt transport zone downstream of the first kneading zone;
(D) a second kneading zone downstream of the first melt conveying zone;
(E) a second melt conveying zone downstream of the second kneading zone;
Using a twin screw extruder having
Hydrogenated product 2 of a block copolymer of an aromatic vinyl compound and a conjugated diene compound having an average particle size of 1 to 1000 μm and at least 80 to 98 parts by mass of a thermoplastic resin having an average particle size of 1 to 1000 μm -20 mass parts is supplied from said 1st supply port, and it melt-kneads, The manufacturing method of the thermoplastic resin composition characterized by the above-mentioned. (A) is a single flight screw having a screw length of Ls / D = 4.5-20, and a screw length of Ls / D = 1.5-20 on the downstream side of the single flight screw. A solid conveyance zone having a screw configuration having a two-flight flight screw and a zone length of Lz / D = 6.0 to 30 (Ls represents the length of the screw (mm));
(C) is a first melt conveyance zone having a screw configuration composed of two-flight flight screws, having at least one atmospheric vent or vacuum vent, and a zone length of Lz / D = 3-20. Yes,
(D) is a second kneading zone comprising a screw configuration having at least one pressurizing screw, the zone length being Lz / D = 2-12,
(E) is a second melt transport zone having a screw configuration comprising a two-flight flight screw, having at least one vacuum vent, and having a zone length of Lz / D = 3-20.
The manufacturing method of the thermoplastic resin composition of Claim 1.   The pitch of the elements constituting the single flight screw in (a) is Lp / D = 1.0 to 2.0 (Lp represents the length of the pitch (mm)). A method for producing a thermoplastic resin composition.   The pitch of the elements constituting the two-flight flight screw in (a), (c), and (e) is Lp / D = 0.25 to 1.0 (Lp represents the pitch length (mm)). The manufacturing method of the thermoplastic resin composition of Claim 2 or 3 which exists.   The heat according to any one of claims 2 to 4, wherein in (a), (c), and (e), the screw is arranged so that the pitch becomes shorter from the upstream side toward the downstream side. A method for producing a plastic resin composition.   The method for producing a thermoplastic resin composition according to any one of claims 1 to 5, wherein the screw having a small pressure increase in (b) is a neutral kneading disk or a two-cut notched flight screw.   The blade width of the clockwise kneading disk in (b) is Lw / D = 0.10 to 0.5 (Lw represents blade width (mm)). A method for producing the thermoplastic resin composition according to Item.   The manufacturing method of the thermoplastic resin composition of any one of Claims 1-7 whose oxygen concentration of said (a) is less than 1.0 volume%.   The method for producing a thermoplastic resin composition according to any one of claims 2 to 5, wherein an inert gas is supplied to the atmospheric vent or the vacuum vent of (c).   The said pressurization screw of said (d) contains at least 1 sort (s) chosen from the group which consists of a left-handed kneading disk, a 2 piece left-handed flight screw, and a 1 piece left-handed notch screw. A method for producing the thermoplastic resin composition according to claim 1 or 9.   The method for producing a thermoplastic resin composition according to any one of claims 2 to 5, wherein an inert gas is supplied to the vacuum vent of (e).   12. The thermoplastic resin according to claim 1, wherein the thermoplastic resin is at least one selected from the group consisting of a polyphenylene ether resin, a polycarbonate resin, a polyphenylene sulfide resin, a polyamide resin, and a polyoxymethylene resin. A method for producing a thermoplastic resin composition. The number average molecular weight of the block copolymer is 50,000 to 500,000,
The heat according to any one of claims 1 to 12, wherein the content of the aromatic vinyl compound in the block copolymer is 15 to 80% by mass, and the content of the conjugated diene compound is 20 to 85% by mass. A method for producing a plastic resin composition.

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