JP3061740B2 - Method for producing conductive carbon black-containing polyphenylene ether-based resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyphenylene ether resin comprising a polyphenylene ether resin and a polystyrene resin and a specific carbon black, having a heat resistance of not less than 100.degree. The present invention relates to a method for producing a polyphenylene ether-based resin composition with a low content without scattering of carbon black and with high productivity.

[0002]

2. Description of the Related Art A conductive resin provided with conductivity by blending carbon black with a thermoplastic resin is used for applications such as prevention of static electricity and shielding of electromagnetic waves in electronic parts, computers, and home appliances. In recent years, conductive resin has been used for conductive IC trays used in IC drying processes.
Applications for use at a high temperature of 00 ° C. or more are increasing, and the demand for conductive polyphenylene ether resins having heat resistance is increasing (JP-A-62-1005553, JP-A-2-180958, JP-A-4-30
0956). As a method for producing such a conductive resin, a method using a continuous twin-screw extruder has been conventionally used. In a manufacturing method using a continuous twin-screw extruder, as a method of feeding to an extruder, a method of previously blending carbon black and a resin with a Henschel mixer or a tumbler mixer, and then feeding them with various feeders, using a quantitative feeder Generally, a method of quantitatively supplying the resin and the carbon black, respectively, is used. However, the resin and carbon black have different true specific gravities, bulk densities, shapes, etc., regardless of the method of supply, so they are classified after being supplied to the blending stage or extruder, and as a result, the concentration of carbon black in the composition In some cases, a conductive resin having stable conductivity with little variation in conductivity is not obtained, and may not be practically used.

[0003] In general, polyphenylene ether resin is in a powder form, and since the bulk density of carbon black is very low, both resin and carbon black contain a large amount of air. During the step of dispersing in the resin, a large amount of air escapes and this air rises from the material supply port, so that carbon black scatters with the rise of this air. As a result, a concentration difference of carbon black in the composition occurs,
Various problems have been pointed out, such as that the working environment is deteriorated due to the scattering of carbon black, and floating carbon black fine particles adhere to the inside of precision machines and destroy electronic components inside. Since the blow-up of the carbon black has a correlation with the supply amount of the carbon black, when the carbon black scatters, the supply amount must be reduced, and thus the productivity is reduced. As a manufacturing method applicable when the raw material is a fine powder, an opening is provided downstream of the material supply port, and a screw configuration between the material supply unit and the opening does not compress the material and performs only melting or kneading. A manufacturing method by adopting a configuration is proposed (Japanese Unexamined Patent Publication No.
8-29644), however, when the resin composition of the present invention was produced, no improvement was possible even by using this method.

[0004]

SUMMARY OF THE INVENTION The present invention relates to a polyphenylene ether-based resin composition having a heat resistance of a heat distortion temperature of 100 ° C. or higher and having a small variation in conductivity, without scattering of carbon black, and An object is to provide a method for manufacturing with high productivity.

[0005]

According to the present invention, a specific carbon black is used, a polyphenylene ether resin and a styrene resin are used at a specific ratio, and a continuous type co-rotating twin screw extruder is used. Has been made based on the finding that the above-mentioned object can be achieved by the production method described above.
That is, the present invention relates to a polyphenylene ether resin of 30 to 90% by weight, a polystyrene resin of 70 to 10% by weight, and a polyphenylene ether resin of 80 to 97 parts by weight based on 100 parts by weight of the total amount of the polyphenylene ether resin and the styrene resin. Parts by weight and 20 to 3 parts by weight of conductive carbon black having a heat distortion temperature of 100
A method for producing a polyphenylene ether-based resin composition having a heat resistance of not less than 0 ° C., wherein carbon black having a specific surface area of 700 to 1500 m ² / g is used as the conductive carbon black, and continuous co-rotating twin screw extrusion is performed. After feeding the polyphenylene ether resin to the machine and gelling, the side feeder is used to forcibly supply conductive carbon black into the barrel of the continuous co-rotating twin screw extruder, and the conductive carbon black is converted to polyphenylene ether. Before completely dispersing in the system resin, after degassing at normal pressure from the degassing holes provided in the continuous co-rotating twin screw extruder, kneading is continued, and the polyphenylene ether resin and conductive carbon black are discharged from the die. A method for producing a conductive carbon black-containing polyphenylene ether-based resin composition, characterized by obtaining a mixture of Subjected to.

As the polyphenylene ether resin used in the present invention, those having strength, heat resistance and moldability corresponding to the use of the conductive resin composition of the present invention are used, and are represented by the following general formula. It has a unit structure.

[0007]

Embedded image

Wherein R ₁ , R ₂ , R ₃ and R ₄ are hydrogen, halogen, hydrocarbon, substituted hydrocarbon, cyano, phenoxy, nitro, amino or sulfo. Specifically, for example, poly-2,6-dimethyl-
1,4-phenylene ether, poly-2,6-diethyl-1,4-phenylene ether, poly-2,6-dipropyl-1,4-phenylene ether, poly-2-methyl-6-isopropyl-1,4 -Phenylene ether, poly-2,6-dimethoxy-1,4-phenylene ether, poly-2,6-dichloromethyl-1,4-phenylene ether, poly-2,6-diphenyl-1,4-phenylene ether, poly -2,6-dinitrile-1,4-
Phenylene ether, poly-2,6-dichloro-1,4
Phenylene ether, poly-2,5-dimethyl-1,
4-phenylene ether and the like.

The polystyrene resin used in the present invention includes GP polystyrene (polystyrene homopolymer),
Examples include high impact polystyrene, styrene / butadiene copolymer, styrene / maleic anhydride copolymer, styrene / acrylonitrile copolymer, styrene / acrylonitrile / butadiene copolymer, and styrene / methyl methacrylate copolymer. Of these, GP polystyrene and high impact polystyrene are preferred. As a polystyrene resin, MI is 0.1 to 50 g / 10 min.
(200 ° C, 5kg load) is good, especially 1-25g /
10min. (200 ° C, 5kg load) is good. These polystyrene resins are 10 to 7 parts by weight based on 100 parts by weight of the total amount of the polyphenylene ether resin and the styrene resin.
It is blended at a ratio of 0% by weight. Preferably it is 20 to 50% by weight. If the amount of the polystyrene resin is less than 10% by weight, kneading by a twin-screw extruder becomes difficult, and if the amount is more than 70% by weight, heat resistance (heat deformation temperature) is undesirably low.

The carbon black used in the present invention has a bulk specific gravity of 160 g / l or less and a specific surface area of 700 to 1500 m ² / l.
g, preferably a bulk specific gravity of 150 g / l or less,
It has a specific surface area of 750 to 1300 m ² / g. Bulk specific gravity greater than 160 g / l or specific surface area of 70
It is not preferable to use carbon black having a value smaller than 0 m ² / g because it becomes difficult to impart conductivity to the obtained resin composition. The compounding amount of carbon black used in the present invention is a total amount of carbon black, polyphenylene ether resin and polystyrene resin of 10%.
3 parts by weight to 20 parts by weight, preferably 5 parts by weight with respect to 0 parts by weight
１５15 parts by weight. When the amount is less than 3 parts by weight, it is difficult to impart conductivity to the obtained resin composition, and when the amount is more than 20 parts by weight, kneading by a twin-screw extruder becomes difficult, and the resin composition is practically used. It is not preferable because it is not provided.

In the present invention, a known thermoplastic elastomer and an inorganic filler can be blended in order to impart strength according to the use of the conductive resin composition. As the thermoplastic elastomer used, "Plastic
VOL.38, No. 9 Recent Trends in High Performance of Thermoplastic Elastomers ", styrene, olefin, polyvinyl chloride, urethane, polyester, polyamide,
Fluorine-based, chlorinated polystyrene-based thermoplastic elastomers and the like are listed, and styrene-based resins having good compatibility with polyphenylene ether resin are preferable. Specific examples include styrene / butadiene / styrene block copolymer elastomers, styrene / isoprene / styrene block copolymer elastomers, styrene / ethylene / butylene / styrene block copolymer elastomers, styrene / ethylene / propylene / styrene block copolymer elastomers, and the like. It is a hydrogenated double bond of an elastomer. The blending amount of the thermoplastic elastomer is 3 to 30 parts by weight, preferably 3 to 20 parts by weight, based on 100 parts by weight of the total of the polyphenylene ether resin and the polystyrene resin. If the amount is more than 30 parts by weight, heat resistance (heat distortion temperature) is undesirably reduced.

Examples of the inorganic filler include talc, mica, calcium carbonate, magnesium carbonate, calcium silicate, zonolite, glass beads, glass fiber, asbestos fiber, and carbon fiber. Among them, talc and mica have heat resistance. It is particularly preferable because the effect of improving it is large. The amount of the inorganic filler is 5 to 30 parts by weight based on 100 parts by weight of the polyphenylene ether-based resin,
Preferably it is 5 to 20 parts by weight. If the amount is more than 30 parts by weight, kneading with a twin-screw extruder becomes difficult, which is not preferable. The composition of the present invention may contain known additives other than the above-mentioned components as long as the object of the present invention is not impaired. For example, foaming agents, lubricants, antioxidants, UV inhibitors, coupling agents, flame retardants, heat stabilizers,
Graphite.

In the production method of the present invention, when the total barrel length of the co-rotating twin-screw extruder is 100, the center of the charging port is located at 0 to 10%, preferably 0 to 7% from the motor side. It is good to set the input port. The resin may be charged into the barrel by a natural fall from a hopper or may be forcibly supplied into the barrel, but preferably by a natural fall.

In the present invention, after the polyphenylene ether-based resin supplied into the barrel is gelled by the kneading action of the screw installed in the barrel and external heating, the polyphenylene ether-based resin is forced from at least one side feeder. The conductive carbon black is supplied into the barrel to disperse the conductive carbon black in the gelled resin. Here, any side feeder can be used as long as the conductive carbon black can be forcibly supplied into the barrel. However, it is preferable to use a method in which the conductive carbon black is forcibly supplied by a screw. Specifically, TW made by Nakatani Machinery
IN FEEDER 251 and the like. The side feeder is installed in a barrel at a position where the resin is gelled.
When it is set to 0, it is appropriate to install at a position of 29 to 50%, preferably 33 to 50% from the motor side. If the side feeder is installed at a position where the resin is not gelled, the carbon black injected from the side feeder scatters from the resin inlet or deaeration hole, lowering the productivity, and polyphenylene ether based with little variation in conductivity It is not preferable because a resin cannot be obtained. Similarly, if an input port is provided in the same position instead of this feeder, and carbon black is input by natural fall from the upper part of the input port using a fixed-quantity feeder, carbon black will scatter from this input port, reducing productivity, and It is not preferable because a polyphenylene ether-based resin with little variation in conductivity cannot be obtained.

According to the present invention, before the conductive carbon black is completely dispersed in the resin, for example, the center of the deaeration hole is located on the downstream side (100 × 2/1) from the installation position of the side feeder.
2)% to 23% downstream, preferably 17% downstream The barrel is provided with one or more deaeration holes, from which deaeration is performed under normal pressure. In particular, the deaeration hole is preferably provided at the top (upper part) of the barrel. The size of the deaeration hole varies depending on the size of the extruder, but usually 1 cm ^{2 to} 80 cm ² is appropriate.
Preferably a 1cm ² ~30cm ^2. If the carbon black is introduced without providing the deaeration holes, the air contained in the carbon black escapes from the side feeder, and as a result, the carbon black cannot be introduced.

As the screw of the co-rotating twin-screw extruder used in the present invention, a well-known screw is used and has a diameter of from 20 to
The 150 mm length is generally 20 to 50 times the diameter, and a known extruder body and motor according to the size of the screw are used. Known screw parts are also used as the screw parts of the extruder, specifically,
Journal of Japan Society of Plastics Processing “Molding” VOL3, N
Element as described in O6 (1991),
There are right type (R-KD), left type (L-KD) and neutral type (N-KD) kneading disks, and these are arranged in an appropriate order according to the properties of the resin to be used and the amount of carbon black compounded. Can be used. In particular, if a neutral type kneading disk that only performs kneading without transporting or reversing capability and / or a light type kneading disk that performs transport and kneading is placed at the position where the side feeder is installed, there is no scattering of carbon black and productivity is improved. Is preferred because the

The polyphenylene ether resin and the polystyrene resin of the present invention are fed from a resin feed port provided at the above-mentioned position by using a known feeder to obtain a polyphenylene ether-based resin composition having little variation in conductivity. For the purpose, it is preferable to use a gravimetric quantitative feeder having a quantitative accuracy within ± 1%. In the case where a thermoplastic elastomer and / or an inorganic filler is used, it is preferable to add them together with the polyphenylene ether resin and the polystyrene resin from the resin inlet provided at the above-mentioned position. In this case, polyphenylene ether resin, polystyrene resin, thermoplastic elastomer and / or
Or, after the inorganic filler is previously mixed uniformly by a tumbler, Henschel mixer, ribbon blender, etc.,
It is preferable to feed the resin from the resin inlet, but it is also possible to supply the components individually using a fixed-quantity feeder without mixing the components.

The carbon black of the present invention is forcibly supplied by a side feeder after gelling the resin. In order to obtain a polyphenylene ether-based resin composition with little variation in conductivity, the screw of the side feeder is rotated in advance so that it can be charged at a speed higher than the charging speed of carbon, and the weight of the carbon black is within a quantitative accuracy of ± 1%. It is preferable to drop on the screw of the side feeder using a formula quantitative feeder, and then to forcibly feed the extruder by the side feeder. When the weight-type quantitative feeder used for charging the resin and carbon black is an interlocking type in which the input amount of the other feeder changes in accordance with the change of the input amount of one feeder, the conductivity of the obtained polyphenylene ether-based resin is improved. This is particularly preferable because the variation in properties is reduced.

The temperature of the barrel of the co-rotating twin-screw extruder used in the present invention is determined by the gelling temperature of the resin used, and is set at a temperature 30 to 150 ° C. higher than the gelling temperature of the resin. In order to obtain a polyphenylene ether-based resin composition having a small variation in the temperature, the temperature from the upstream side of the barrel where the side feeder is installed to the barrel where the deaeration hole is installed is 10%. The temperature is set to 60 ° C. to 150 ° C., preferably 70 ° C. to 150 ° C. higher than the gelling temperature of the resin, and the temperature of the barrel downstream from the position where the deaeration holes are installed is 30 ° C. ~ 70 ° C, preferably 30 ° C ~ 60
It is desirable to set the temperature higher by ℃. The rotation speed of the screw can be, for example, about 100 to 300 rpm. In the present invention, after degassing at normal pressure, the kneading is continued, and the kneaded product of the polyphenylene ether-based resin and the conductive carbon black is arbitrarily formed from a die in a form such as a sheet, a pellet, or a line. Obtainable.

[0020]

According to the present invention, the heat distortion temperature is 100 ° C.
A polyphenylene ether-based resin composition having the above heat resistance and little variation in conductivity can be obtained in a good production amount without scattering of carbon black. Therefore, the conductive resin composition obtained by the present invention can be used for various purposes, for example, other than conductive materials such as electromagnetic wave shielding materials, covering materials for high-voltage cables, ignition cords, sheet heating elements, sheet switches, and electrodes. It can be used in many fields, such as application to packaging materials for electronic devices and ICs and holding materials for tests. Further, since the production method of the present invention is suitable for obtaining a composition in which powder is filled in a resin, when filling with an inorganic filler or metal having a small bulk specific gravity, or when obtaining a plastic magnet or a high specific gravity plastic It can also be applied as a production method when a resin is highly filled with powder.

[0021]

【Example】

Example 1 Four types of schematic diagrams shown in (A) to (D) of FIG.
Continuous type co-rotating twin screw extruder (screw diameter: 57m
m, L / D: 36, 65 parts by weight of a polyphenylene ether resin (manufactured by GEM Polymer Co., Ltd., NR-II 57 mm co-rotating twin-screw vent type extruder).
Intrinsic viscosity 0.5 in chloroform at 5 ° C.) and 25 parts by weight of high impact polystyrene resin (HI Stylon 470 MI manufactured by Asahi Kasei: 15 g / 10 min), bulk specific gravity 140 g / l, carbon black 10 having a specific surface area of 810 m ² / g. Parts by weight were charged by the method shown in Table 1 to obtain a conductive resin composition at a screw rotation speed of 220 rpm. In FIG. 1, 1 to 12: barrel zone, 13: die, 14: resin inlet, 15: closed side feeder, 16: carbon black inlet, 17: deaeration hole (4 cm × 4 cm square), 18: deaeration hole (4cm x 4cm square),
19: Motor. The length of each of the barrel zones 1 to 12 is 1 when the total length of the barrel is 100.
It is half the length.

The screw configuration is such that melting, kneading and conveying are performed without compressing the material in the barrel zones 1 to 5, the kneading, compressing and conveying are performed in the barrel zones 6 and 8,
The rest was configured to perform compression and transport. The charging method of the resin and the carbon black is as follows. Charging method A: As shown in FIG. 1 (A), a mixture of polyphenylene ether resin and carbon black was dropped from a charging port provided at 14 using a quantitative feeder (Arculate 602 manufactured by Kuma Engineering). The mixture was charged into a twin-screw extruder. Deaeration holes are provided at 17 positions. Charging method B: As shown in FIG. 1 (B), a polyphenylene ether-based resin was quantitatively fed from a charging port provided at 14 (Kurama Engineering's Acurate 6).
(Type 02) and let it fall into a twin-screw extruder by allowing it to fall naturally. Also, in the figure, a screw of a side feeder (TWIN FEEDER 251 manufactured by Nakatani) set at 15 is set at a speed higher than the feeding speed of carbon black. It was rotated so that it could be charged, and carbon black was naturally dropped on the screw using a quantitative feeder (Arculate 602 type manufactured by Kuma Engineering), and was forcibly supplied into a twin-screw extruder by a side feeder.
Deaeration holes are provided at 17 positions.

Injection method C: As shown in FIG. 1 (C), the polyphenylene ether resin is allowed to fall naturally from an introduction port provided at 14 by using a quantitative feeder (Arculate 602 type manufactured by Kuma Engineering). Into a twin-screw extruder, and a side feeder (TWIN FEED manufactured by Nakatani) installed at 15 in the figure.
ER251) is rotated so that it can be charged at a higher speed than the charging speed of carbon black, and a fixed-quantity feeder (Kurama Engineering Acurate 60) is used.
(Type 2), carbon black was naturally dropped on the screw, and was forcibly supplied into a twin-screw extruder by a side feeder. Deaeration holes are provided at 18 positions. Charging method D: As shown in FIG. 1 (D), a polyphenylene ether-based resin was quantitatively fed from a charging port provided at 14 by a feeder (Kuma Engineering, Inc.
Using a fixed-quantity feeder (Arculate 602 manufactured by Kuma Engineering Co., Ltd.) through the inlet installed at 16 in the figure. The black was fed into a twin-screw extruder by gravity drop. 1 vent hole
7 is provided.

The temperature conditions of the twin-screw extruder are as follows. Temperature condition 1: barrel zone 1; cooling barrel zone 2 to 6; 320 ° C barrel zone 7 to 12; 280 ° C, die; 280 ° C Temperature condition 2: barrel zone 1; cooling barrel zone 2 to 6; 320 ° C barrel zone 7 320 ° C, die; 280 ° C Temperature condition 3: barrel zone 1; cooling barrel zone 2 to 6; 240 ° C barrel zone 7 to 12; 280 ° C, die; 280 ° C barrel zone 5 in which side feeders are installed Are as follows. 4N: 4N type kneading disk made by Nakatani machine 41: 41 type kneading disk made by Nakatani machine 3N: 3N type kneading disk made by Nakatani machine 3R: 3R type kneading disk made by Nakatani machine

Table 1 shows the method of charging polyphenylene ether resin, polystyrene resin and carbon black, the type of screw parts at the same position where the side feeder is installed, the set temperature of each barrel, and the resin at position 5 in FIG. The maximum discharge rate and discharge rate when the gelled state of the carbon black does not scatter at all is 80 kg / hr.
2 shows the scattering state of carbon black and the volume resistivity value of the obtained conductive resin composition. In addition, the gelation state of the resin is represented by ○ when the resin is gelled at the position 5 in FIG. 1 and as x when the resin is not gelled. The state of carbon black scattering is indicated by ○ when carbon black is not scattered, and × when carbon black is scattered violently.
Was evaluated. The volume resistivity was determined by press-molding the obtained thermoplastic resin composition at 300 ° C. to prepare five samples of 10 cm × 10 cm × 0.2 cm. The maximum value and the minimum value were measured according to the measurement method of SRIS2301, and the results are shown in Table 1. The heat distortion temperature is ASTM D
It was measured at a load of 18.5 kg according to 648.

[0026]

[Table 1] Table 1 ─────────────────────────────────── NO. 1 2 3 4 5 6 * 7 * 8 * 9 * と With resin Carbon Bubbles BBBBBBDACB Rack Loading Method Screw Parts 4N 41 4N 3R 3N 41 41 41 41 (Position 5) Temperature Conditions of Each Barrel 1 1 2 2 1 1 1 1 3 Gelled state of resin ○ ○ ○ ○ ○ ○ ○ ○ × (Position 15) Maximum discharge rate (kg / hr) 130 115 115 130 130 65 40 40 45 Carbon black ○ ○ ○ ○ ○ × × × × Scattering volume specific resistance Maximum value (Ω ・cm) 41 51 54 44 44 280 1200 3800 2100 Minimum value (Ω · cm) 33 35 38 37 31 41 48 43 45 Heat deformation temperature 151 152 150 153 152 149 148 149 149 ─────────── ────────────────────────

In the table, 6 * to 9 * are comparative examples. Maximum discharge rate
(kg / hr) is the maximum discharge amount when carbon black is not scattered, and the discharge amount of carbon black is 80 kg
This shows the scattering state of carbon black when set to / hr. According to the results of Table 1, according to the method of the present invention, carbon black was not scattered, and the discharge amount was 115 to 130 kg /.
hr, the productivity is good, and it can be seen that the conductive polyphenylene ether-based resin composition obtained by this method shows stable conductivity with little variation in volume resistivity. On the other hand, the comparative examples No. 6 (a method in which carbon black is injected by natural fall from the inlet at the same barrel position instead of the side feeder) and No. 7 (a natural fall from the inlet into which polyphenylene ether resin is injected) No. 8 (1)
No. 7 (method where there is no deaeration hole) and No. 9 (method where the resin is not gelled at the position where the carbon black is injected by the side feeder) is 80 kg.
/ Hr, the carbon black scatters violently, and the discharge amount is reduced by 1 / compared to the production method of the present invention to prevent the scatter.
It can be seen that the productivity has to be reduced to 2/3 and therefore the productivity is reduced. Further, even in a conductive polyphenylene ether-based resin composition manufactured with reduced productivity, the variation in conductivity is 7 to 88 times (maximum value of volume resistivity / minimum value of volume resistivity), which is not practical.

Example 2 A continuous co-rotating twin-screw extruder equipped with a resin inlet, a deaeration hole, and a side feeder shown in FIG. 1B (screw diameter: 57 mm, L / D: 36, Nakatanani Machine made N
Using a R-II 57 mm co-rotating twin-screw vented extruder), a predetermined amount of a polyphenylene ether-based resin, an inorganic filler, and a thermoplastic elastomer were charged from the inlets of 14 in the same manner as in Example 1, and a predetermined amount was also charged. Of carbon black is forcibly supplied by 15 side feeders,
A conductive polyphenylene ether-based resin composition was obtained at a screw rotation speed of 220 rpm and the temperature condition described in Example 1: 2. The screw configuration was such that melting, kneading, and conveying were performed without compressing the material in the barrel zones 1 to 5, the kneading, compressing, and conveying were performed in the barrel zones 6 and 8, and the compression and conveying were otherwise performed. The screw part at the position where the side feeder is installed was 4N described in Example 1. In addition, barrel zone 20
The length of each zone of ~ 31 is one-twelfth assuming the total length of the barrel as 100. Tables 2 and 3 show the compositions, the gelled state of the resin at the positions shown in FIGS. 1 and 5, the maximum discharge amount when carbon black is not scattered, the volume resistivity of the obtained conductive resin composition, the heat distortion temperature and IZOD
Shows impact strength. In addition, the gelation state and the volume resistivity value of the resin were evaluated by the same method as the method described in Example 1. The heat distortion temperature is 18.5 according to ASTM D648.
kg load and IZOD impact strength is AS
It was measured on a sample having a thickness of 1/8 inch and no notch according to TMD256.

The types of the thermoplastic resin, carbon black and inorganic filler used in Example 2 are shown. Thermoplastic resin: Polyphenylene ether resin: manufactured by GEM Polymer Co., Ltd., intrinsic viscosity in chloroform (PPE) at 25 ° C .: 0.5 Polystyrene resin: Asahi Kasei HI Stylon 470 MI: 1 (PS) 5 g / 10 min Thermoplastic elastomer A: Shell Chemical Carriflex TR1117 Thermoplastic Elastomer B: Shell Chemical Clayton G1652 Inorganic Filler: Talc: Hayashi Kasei MICRON WHITE # 5000S Mica: Kuraray SUZORITE MICA 200-KI Carbon Black: Carbon Black A: Bulk Specific Gravity: 140 g / l , specific surface area: 810m ² / g of mosquitoes over carbon black carbon black B: bulk density: 125 g / l, a specific surface area: 1240m ² / g of carbon black carbon black C: bulk density: 250 g / , Specific surface area: Car carbon black of 70m ² / g

[0030]

[Table 2] Table 2 Ｎｏ No. 10 11 12 13 * 14 * 15 * 16 * 17 * ─────────────────────────────────── Composition (parts by weight) PPE 45 68 67 18 86 73 53 68 PS 45 22 28 72 4 25 18 22 Carbon black A 10 10 0 10 10 2 30 0 Carbon black B 0 0 5 0 0 0 0 0 Carbon black C 0 0 0 0 0 0 0 10 ──ゲ ル Gelation state of resin ○ ○ ○ ○ ○ ○ ○ ○ (Position 24) Maximum discharge volume 130 110 135 135 30 160-* 140 (kg / hr) Volume specific resistance Maximum value (Ω · cm) 43 41 62 54 38 **-* ** Minimum value (Ω · cm) 31 29 43 37 31 **-* ** Heat deformation temperature (℃) 143 155 153 90 160 120-* 125 IZOD impact strength 30 25 34 40 15 60-* 60 (kgcm / cm) ───────── ── ─────────────────────── In the table, 13 * to 17 * are comparative examples. Maximum discharge rate (kg / hr)
Is the maximum discharge amount in a state where the carbon black is not scattered. -*: Although there was no scattering of carbon black, the torque was over and a conductive polyphenylene ether-based resin composition could not be obtained. **: 1016 or more

[0031]

[Table 3] Table 3 ─────────────────────────────────── No. 18 19 20 21 22 23 24 組成 Composition (parts by weight) PPE 59 55 68 68 56 54 56 PS 23 22 17 17 15 23 24 Elastomer A 0 0 5 0 10 5 0 Elastomer B 0 0 0 5 0 0 5 Talc 10 0 0 0 13 0 10 Mica 0 15 0 0 0 10 0 Carbon black A 8 8 10 10 6 8 0 Carbon black B 0 0 0 0 0 0 5 ゲ ル Resin gelation Status ○ ○ ○ ○ ○ ○ ○ (Position 24) Maximum discharge volume 115 110 135 135 110 115 120 (kg / hr) Volume specific resistance Maximum value (Ωcm) 25 28 52 54 31 33 54 Minimum value (Ω cm) 19 21 33 37 22 24 32 Heat deformation temperature (° C) 170 172 155 158 168 169 168 168 IZOD impact strength (kg · cm / cm) 29 25 42 40 42 41 43 ───────────────────────────────────

In the table, the maximum discharge rate (kg / hr) is the maximum discharge rate in a state where carbon black is not scattered.

[Brief description of the drawings]

FIG. 1 shows an outline of a continuous co-rotating twin-screw extruder for carrying out the present invention. In the figure, 1 to 12 are barrel zones, 13 is a die, 14 is a resin inlet, 15 is a side feeder, 16 is a carbon black inlet 17 and 18 are deaeration holes 19 is a motor.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁷ Identification code FI C08L 71:12) (72) Inventor Hideo Komatsu 1-3-7 Honjo, Sumida-ku, Tokyo Inside Lion Corporation (72) Inventor Yoshiaki Nagai 1-37, Honjo, Sumida-ku, Tokyo Inside Rion Co., Ltd. (56) References JP-A-6-172633 (JP, A) "Plastics" Vol. 42, No. 4, P114-122, 1991 (58) Fields investigated (Int. Cl. ⁷ , DB name) C08J 3/30 C08K 3/00-3/04 C08L 25 / 04,71 / 12

Claims (4)

(57) [Claims] 1. A polyphenylene ether resin having a polystyrene resin content of 30 to 90% by weight based on 100 parts by weight of a total of a polyphenylene ether resin and a styrene resin.
A polyphenylene ether-based resin composition comprising 0 to 10% by weight of a polyphenylene ether-based resin of 80 to 97 parts by weight and 20 to 3 parts by weight of a conductive carbon black and having a heat distortion temperature of 100 ° C. or more. Using a carbon black having a specific surface area of 700 to 1500 m ² / g as the conductive carbon black and supplying a polyphenylene ether resin to a continuous co-rotating twin screw extruder to form a gel. After that, conductive carbon black is forcibly supplied from the side feeder into the barrel of the continuous co-rotating twin-screw extruder, and before the conductive carbon black is completely dispersed in the polyphenylene ether-based resin, A deaeration hole provided in a co-rotating twin-screw extruder of the type, and a side barrel when the total barrel length of the extruder is 100. After deaerating hole center from the installation position of Ida was degassed at atmospheric pressure from the deaerating hole provided on the downstream side (100 × 2/12)% ~23% of the positions, to continue the kneading, polyphenylene ether from the die A method for producing a conductive carbon black-containing polyphenylene ether-based resin composition, comprising obtaining a mixture of a conductive resin and a conductive carbon black. 2. The method according to claim 1, wherein the thermoplastic elastomer is contained in an amount of 3 to 30 parts by weight based on 100 parts by weight of the polyphenylene ether resin. 3. The method according to claim 1, wherein 5 to 30 parts by weight of an inorganic filler is contained based on 100 parts by weight of the polyphenylene ether resin. 4. A neutral kneading disc and / or a carrier and a conductive carbon black forcibly supplied from a side feeder, which is provided in the barrel and has only a kneading function without carrying or back-feeding ability. 2. The method according to claim 1, wherein the kneading disk is supplied to a kneading light type kneading disk.