JPS60106848A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To resin composition having excellent electromagnetic wave shielding properties, carbon dispersibility, and processability, comprising a thermoplastic resin containing styrene; a metal in the form of powder, etc., a carbon black treated with a titanate coupling agent and a specified lubricant. CONSTITUTION:A thermoplastic resin selected from among a polymer (1) containing styrene, a polymer (2) made by treating a polymeric material selected from among a rubbery substance and polyphenylene ether with monomers containing styrene, and a mixture (3) of the above polymeric material with a polymer containing styrene; a metal or its alloy in the form of powder, fibers and/or flakes; a conductive carbon black treated with a titanate coupling agent; and a lubricant selected from among hydroxystearic acid ethylenebisamides are compounded in the specified proportions.

Description

DETAILED DESCRIPTION OF THE INVENTION (1) Object of the Invention The present invention relates to a thermoplastic resin composition based on a thermoplastic resin containing at least styrene.

- powder, fibers and/or flakes of a single-vagum alloy, (C) electrically conductive carbon black treated with a titanate coupling agent and (D) hydroxystearate ethylene bisamide and ethylene bisamide; It relates to a thermoplastic resin composition comprising at least one lubricant selected from the group
The object of the present invention is to provide a thermoplastic resin composition which not only has excellent electromagnetic wave shielding properties but also has good dispersibility of the conductive carbon black and has excellent processability.

GD Background of the Invention The sources of electromagnetic radiation are increasing with the advancement of industry and the standard of home life. Therefore, leakage of electromagnetic waves can cause dangerous harm to the human body and damage to ICs in electronic equipment.
This has resulted in negative effects such as malfunction, and has become a serious social problem. In particular, electromagnetic waves emitted from computers and various office processing equipment are causing trouble to televisions and audio equipment.

Furthermore, in the field of automobiles, electronic devices are being used for automatic control devices for various devices including engines, as well as speedometers, tachometers, and the like. Furthermore, it has come equipped with a microcomputer. Also,
Electronic devices such as telephones, radios, and televisions are being installed inside automobiles to improve comfort. These various electronic devices are subject to problems such as malfunctions due to electromagnetic waves emitted from the engine and electromagnetic waves from outside. Currently, the biggest problem is the transient phenomenon that occurs when the current fluctuates due to the masterpiece/operation of car equipment.
These are disturbances induced by transient voltage disturbances caused by induction in the load path, capacitive coupling, inductive interference from generators, radiation from the ignition system, and electromagnetic fields generated by transmitting devices inside automobiles.

Specifically, the wiring between devices in the engine room of a car carries a high voltage, so the intensity of the radiated electromagnetic waves is strong, and the wiring between speed controllers and waste gas stations is placed in a small space.
controller, engine controller t, r tokata'
(Since there are several installations, they affect each other in a complicated manner (
ing. For these reasons, it is necessary to shield electromagnetic waves from various types of wiring such as power lines, signal lines, and control lines.

Furthermore, electromagnetic radiation is generated from electric wires, cables, etc., and sometimes causes various types of damage to various devices, either directly or through antennas. In particular, in the rapidly progressing ICs and LSIs, their operating currents are so small that they cause malfunctions. Conventionally, the sheathing of electric wires and cables has been used to carry current while minimizing power loss. Rubber-like materials filled with carbon black around an insulating layer to make it conductive are used. 1 However, these are not able to shield the electromagnetic waves emitted from the wiring. .

For these reasons, various methods have been adopted in recent years to shield electromagnetic waves.

In general, since metals have the property σ of absorbing or reflecting electromagnetic waves, they are effectively used as electromagnetic wave shielding materials for microwave ovens and various communication devices H. We also use thermal spraying, vapor deposition, painting of plastics and metals for the same purpose.
The second method of applying plating is also carried out. Furthermore, 4'A, which is obtained by mixing relatively large amounts of additives such as carbon powder and metal powder other than aluminum into plastic, has also been used.

However, the method of using metal as a material or the method of treating glass with metal such as thermal spraying has a large specific gravity, poor workability, and the processing cost is high because the processing method is not easy. There are some drawbacks in terms of navigation.

Regarding the method of mixing additives, if a small amount of this silkworm additive is mixed, the effect cannot be fully exhibited. On the other hand, if it is mixed in a large amount, it can be effective, but it has the disadvantage that the mechanical strength of the resulting molded product is significantly reduced.

Furthermore, the applicant has developed thermoplastic resins with excellent electromagnetic wave shielding properties by blending various thermoplastic resins with powdered, fibrous and/or flake materials of aluminum or aluminum alloy, and conductive carbon black. We found that a resin composition can be obtained and previously proposed (
JP-A-57-154703, etc.).

However, in these compositions, the compatibility between the carbon black and the thermoplastic resin is insufficient, so the carbon black separates from the surface of the molded product. metal powders, fibers, and/or flakes (hereinafter referred to as "metal powders, etc.") have poor adhesion to ordinary thermoplastic resins, and unsaturated materials are used to improve adhesion. Although adhesion to metal can be solved by blending a thermoplastic resin with excellent adhesiveness such as a carboxylic acid-modified thermoplastic resin, the unsaturated carboxylic acid-modified thermoplastic resin and carbon black are preferential. It is not possible to solve the problem of adhesion with metal powders because of the reaction.

As mentioned above, molded products obtained from compositions containing a large amount of metal powder and carbon black are likely to peel off from their surfaces, so the molded products can be used for the purposes described below (for example, for office equipment). When used as housing materials for computers, communication equipment, automobile instruments, etc., these materials may peel off (fall) due to external impact vibrations, damaging internal electronic circuits or causing fires. Become.

Furthermore, in the field of using compositions with excellent electromagnetic shielding properties, there is a demand for compositions with excellent moldability (fluidity) when producing large molded products or molded products with complex shapes. If stearic acid or calcium stearate, which is generally used as a lubricant in the field of thermoplastic resins used in the present invention, is used, there is little improvement in fluidity, or rather, the fluidity is reduced.

l Structure of the Invention Based on the above, the present inventors conducted various searches in order to obtain an electromagnetic wave shielding material that does not have these drawbacks and has excellent electromagnetic wave shielding performance, and as a result, -(A)( 1) A polymer containing at least styrene (2) A polymer obtained by treating a monomer containing at least styrene with a polymeric substance selected from the group consisting of a comb and polyphenylene ether (3) At least one thermoplastic resin (hereinafter referred to as "styrenic resin") selected from the group consisting of a mixture obtained by mixing the polymer substance and a polymer containing at least styrene. B) “Metal or alloy powders, fibrous materials and/or
-1 or flake-like substances” (hereinafter referred to as “metal powder-like substances, etc.”)
(C) conductive carbon black treated with a titanate coupling agent; and (D) at least one lubricant selected from the group consisting of hydroxystearate ethylene bisamide and ethylene bisamide. The content of styrene in the styrenic resin is at least 5% as a monomer unit.
The mixing ratio of the metal powder, etc. and the treated conductive carbon black in the total amount of the styrene resin, the metal powder, etc. and the treated conductive carbon black is 5 to 50 volumes each. However, the total amount of the lubricant is 10 to 60% by volume, and the blending ratio of the lubricant to the total amount of styrene resin, metal powder, etc. and the treated conductive carbon black is 100 weight MVill. The inventors have discovered that a thermoplastic resin composition containing 0.001 to 20 parts by weight not only has extremely excellent electromagnetic wave shielding performance, but also has the following effects (characteristics), and has thus arrived at the present invention.

11vl Effects of the invention That is, the electromagnetic wave shielding material obtained by the present invention not only has extremely excellent electromagnetic wave shielding performance, but also
It has the following effects (characteristics).

(1) It is lightweight.

(2) Good mechanical strength such as bending strength and spitting strength.

(3) Electromagnetic wave shielding treatment (e.g. metal spraying, painting,
This eliminates the need for secondary processing costs (such as plating, etc.), resulting in significant cost reductions.

The characteristic effects of the composition provided by the present invention are as follows.

(4) Since the blended carbon black and metal powders have excellent compatibility with the styrene resin, their dispersibility is good, so there is almost no peeling of these, and there are almost no problems as described above.

(5) Since it has excellent moldability, molded products with complex shapes and large-sized molded products can be easily molded.

Further, the resin composition of the present invention can be used as a core material in a multilayer molding method using a multilayer injection molding method or a sand etch injection molding method. When the composition of the present invention is used as a core material for multilayer molding, it not only has an electromagnetic wave shielding effect, but also (6) mechanical strength is further improved, so large molded products can be obtained; (7) the surface of the molded product is It has a beautiful finish and eliminates secondary processing such as painting.

(8) The surface of the molded product can be made insulating for the safety of the product and also for the safety of IfCId assembly and processing.

The thermoplastic resin composition obtained by the present invention not only has extremely good electromagnetic wave shielding performance but also has the above-mentioned excellent effects, so it can be used in a wide variety of fields. Typical uses are shown below.

(1) Housing materials for office equipment such as fax machines, printers, and word processing sensors; (2) Office computers and large computers.
, - housing and structural materials such as;

(3) Housing materials for electronic equipment such as televisions, videos, microwave ovens, sewing machines and other consumer electronics, electronic computers, communication equipment, various measuring instruments, and medical equipment; (4) Storage cases for automobile instruments. , (5) Housings for various control devices in automobiles, (6) Wiring covers for electric wires in automobiles, home appliances, and OA equipment (e.g., furnace tubes), (7) In the industrial field, NC machine tools, industrial robots, etc. Housing material for the controller H,; (1) Detailed Description of the Invention The styrenic resins used to produce the thermoplastic resin composition of the present invention can be broadly classified as follows.

(1) Styrene)+'L monopolymer and copolymer with other monomers containing styrene as the main component [hereinafter referred to as "styrenic resin (A month")] (2) Styrene alone or Cracking-resistant epsilon resin obtained by treating styrene and other vinyl compounds [hereinafter referred to as "styrenic resin (B)"] (3) Polymer and styrene obtained by treating polyphenylene ether with styrene A mixture (composition) consisting of a resin (A) and a polyphenylene ether (hereinafter referred to as styrene resin (C)) (4) A mixture (composition) consisting of a rubber-like material and a styrene resin (A) described below 9 [Hereinafter referred to as "styrenic resin (D)"] As the styrene resin used for the present invention, the styrene resin (A) or D) listed in -1- may be used alone, They may be combined. However, the styrene content in the total styrenic resin used is
The content is at least 5% by weight.

(Styrenic resin (A) Styrene resin used in the present invention) tri
These are styrene homopolymers and copolymers with other double bond-containing organic compounds containing at least 60% styrene by weight. Representative examples of the organic compound having double bonds include ethylene, vinyl acetate, maleic anhydride, acrylonitrile, and methyl methacrylate.

Methods for producing these styrenic polymers are widely known and used in a wide variety of fields. The molecular weight of the styrenic resin (A) is generally 1,000 to 5oo, ooo, and 1,000 to 300,000.
Preferably.

(B) Styrenic resin (B) The styrene resin (B) used in the present invention is butadiene rubber, acrylic ester rubber, : r-f
L/- Styrene alone or styrene and at least one vinyl compound selected from the group consisting of acrylonitrile and methyl methacrylate are grafted onto at least one rubber selected from the group consisting of propylene thread rubber and chlorinated polyethylene rubber. Examples include those obtained by polymerization.

(1) Butadiene-based rubber The butadiene-based rubber is a rubber whose main component is butadiene (60% by weight or more), including butadiene homopolymer rubber,
Copolymer rubber (SBR) of butadiene and a small amount of styrene or acrylonitrile.

NBR). The copolymer rubber of butadiene and styrene may be a block copolymer rubber or a random copolymer rubber.

(2) Acrylic ester rubber Also, acrylic ester rubber consists of an acrylic ester (for example, butyl acrylate) and a small amount (generally 10% by weight or less) of other monomers (for example, acrylonitrile). It is obtained by emulsion polymerization of and in the presence of a catalyst such as a persulfate, and is commonly referred to as acrylic rubber.

(3) Ethylene-propylene rubber salani, ethylene-propylene rubber toha, ethylene-propylene copolymer rubber oak obtained by copolymerizing ethylene and propylene, and ethylene-propylene copolymer rubber oak containing ethylene and propylene as main components, 1,4-pentadiene, 1 , 5-hexadiene and 3,3-dimethyl-1,5-hexadiene. Linear or branched diolefins containing i-bonds at the ends; linear or branched chains containing only one double bond at the ends, such as 1,4-hexadiene and 6-methyl-1,5-hebutadiene; obtained by copolymerizing small amounts (generally up to 10% by weight) of monomers such as diolefins or cyclic diene hydrocarbons such as bicyclo[2,2,x]-hebutene-2 and its derivatives. It is a multicomponent copolymer rubber. The weight ratio of ethylene monomer and propylene monomer units in these copolymer rubbers and multicomponent copolymer rubbers is 30/7.
0 to 70/30 is preferred. These ethylene-propylene rubbers are produced by valve-type polymerization or multicomponent copolymerization of ethylene and propylene, or ethylene, propylene, and the above monomers using a catalyst system made from a transition metal compound and an organic aluminum compound. It is something.

(4) Chlorinated polyethylene rubber Also, chlorinated polyethylene rubber refers to polyethylene powder or particles described below that are chlorinated in an aqueous suspension, or
Alternatively, it can be obtained by chlorinating polyethylene dissolved in an organic solvent (preferably, it can be obtained by chlorinating it in an aqueous suspension).In general, the chlorine content is between 20 and 50%. % by weight of amorphous or crystalline chlorinated polyethylene, especially with a salt-free content of 2
5 to 45% by weight of amorphous chlorinated polyethylene is preferred.

The polyethylene is prepared by homopolymerizing ethylene or by combining ethylene with at most 10% by weight of α-olefin (generally,
2, which can be obtained by copolymerizing carbon atoms (having at most 6 carbon atoms). Its density is generally 0.910~
It is 0.970.9/cc. Also, its molecular weight is 5
It is between 10,000 and 700,000.

In producing the styrenic resin (B) of the present invention, among these rubber-like substances, those having a Mooney viscosity of 20 to 140 are preferable, although it varies depending on the type of the rubber-like substance, and in particular, those having a Mooney viscosity of 30 to 120. is suitable. Further, these rubber-like materials are widely produced industrially and are used in a wide variety of fields. How to manufacture them, Q,'? Its properties and uses are widely known.

[For example, "Synthetic Rubber Handbook" written by Shu Kanbara (1961, published by Shokusho Shoten)].

(5) Production of styrenic resin (B) The styrenic resin (B) used in the present invention is obtained by grafting styrene alone or styrene and at least one other vinyl compound (acrylonitrile, methyl methacrylate) to the above-mentioned rubber. It is manufactured by polymerization. Graft polymerization methods include bulk polymerization, solution polymerization, emulsion polymerization, and aqueous suspension polymerization, and methods that combine these graft polymerization methods (for example, bulk polymerization followed by aqueous suspension polymerization). .

Generally, the amount of rubber material used to produce 100 parts by weight of styrenic resin CB) is 3 to 40 parts by weight, preferably 5 to 35 parts by weight, particularly 5 to 30 parts by weight. suitable. (A relatively large amount of rubber-like material is used to produce a graft polymer containing a large amount of rubber-like material, and the above-mentioned styrene, acrylonitrile,
A homopolymer resin or a copolymer resin of methyl methacrylate may be mixed, but in this case, the amount of rubber-like material used is calculated based on the mixture). Furthermore, the molecular weight of the monomers (styrene, acrylonitrile, methyl methacrylate) bonded to the rubber-like material as graft chains is usually 10.
00 to 300,000, especially 2000 to 20
0,000 is desirable. In general, complete monomer bonding to the rubber is rare, and there are grafts and homopolymers or copolymers of monomers that are not bonded to the rubber. Are these homopolymers and copolymers not separated? It is used.

(6) Typical examples of styrenic resins (FB) Typical examples of styrene resins (B) produced as described above include butadiene homopolymer rubber, block or random copolymer rubber (SBR) of styrene and butadiene, and styrene Impact-resistant styrene resin (HIPS resin) obtained by graft copolymerization of styrene and acrylonitrile, butadiene homopolymer rubber, SDR, or acrylonitrile and butadiene copolymer rubber (NBR) obtained by graft copolymerization of styrene and acrylonitrile. Acrylonitrile-butanene-styrene terpolymer resin [ABS
resin], butanene homopolymer rubber or i, J: S D
Methyl methacrylate-butadiene-styrene copolymer resin (MBS) obtained by graft copolymerizing styrene and methyl methacrylate-1 to R
resin), acrylonitrile obtained by graft copolymerizing acrylonitrile and styrene to acrylic ester rubber), lyluacrylic ester-styrene ternary copolymer resin (AAS resin), ethylene-propylene rubber, acrylonitrile and styrene, Graft co-111 polymer resin (A
ES resin] Chlorinated polyethylene rubber (CPE)K Graft copolymer resin (AC3 resin) obtained by combining styrene and acrylonitrile in a graft valve type.CPE is graft copolymerized with styrene and methyl methacrylate. An example of this is the graft copolymer resin MC8 resin.

(C) Styrenic resin (C) The styrene resin (C) used in the present invention is a polyphenylene ether (hereinafter referred to as "p P Oj") whose general formula is represented by the following formula [formula (1)] and styrene. Polymer obtained by processing] and the PP
It is a mixture consisting of O and the styrene resin (A).

(1) PPO In formula (1), Ql and Q2 are the same, but 6+, 7
It may be a species, and is an alkyl group having 1 to 4 carbon atoms, where n is a positive integer and is at least 50, and generally 100 or more.

Representative examples of the PPO include BoIJ (2,6-dimethylenylene-1,4-ether), poly(2,6-diethylphenylene-1,4-ether), poly(2-methyl-7 poly(2-methyl-6-brobylphenylene-1,4-ether) 1.I-'!J (2,6-siglopylphenylene-1, 4-ether], poly(2-methyl-6-butylphenylene-1,4-ether) and poly(2,
6-cyptylphenylene-1,4-ether).

Among them, poly(2,6-dimethylphenylene-1.4
-ether] is preferred.

(2) Treatment method By treating PPO with styrene, etc., the styrenic resin (C) can be obtained by treating PPO'vc styrene alone or with styrene and styrene having at most two alkyl groups having 1 or 2 carbon atoms, acrylonitrile, It can be obtained by graft polymerization of at least one comonomer selected from 7tY consisting of methyl methacrylate and butyl acrylate.

(3) Mixing method The styrenic resin (C) can also be obtained by mixing the styrene resin (A) and PPO. The mixing ratio id of the styrene resin (A) in the resulting mixture is 5 to 80% by weight, preferably 10 to 70% by weight.

(DJ Styrenic Resin (D)) Furthermore, the styrene resin (D) used in the present invention can be obtained by mixing the above-mentioned styrene resin (A) and a rubber-like material. The mixing ratio of styrene resin (A) is 5 to 95
The weight ratio is particularly preferably 10 to 90 weight ratio.

(E) Metal powders, etc. The types of metal powders used in the present invention include aluminum, iron, copper, nickel, zinc,
Examples include metals such as titanium and molybdenum, alloys based on these metals (for example, stainless steel and bronze), and metal coatings of these metals or alloys. Among powdery materials, the average size of the powdery material is generally 250 to 20 meshes. In addition, the diameter of the fibrous material is generally 0.0020 to 0.20 mm,
A length of 10 mm or less is preferable because it is easy to process.
Furthermore, as a flake-like material, the cross-sectional area is 0, I
Any shape such as a circle, a square, a rectangle, or a rectangle having a size of 0.1 mm to 5 x 5 tnm can be used, but it is particularly desirable to have a thickness of 0.1 mm or less. Among these, those having a rectangular shape with a cross-sectional area of about I x 1 mm and a thickness of about 0.03 mm have good dispersibility.

Metal or alloy flakes have good dispersibility in these styrene-based resins, and unlike fibrous materials, they do not get entangled with themselves to form beads. In addition, there is a strong tendency to mix the resin along the flow direction of the bottle during molding.
At the same mixing amount, not only the conductivity is good, but also the bending elastic modulus is improved.

In particular, flakes having a surface area of 1111111 x 1 mm are most preferred from the viewpoint of dispersibility. These powdery, fibrous, or flake-like materials may be used alone, but two or more of them may be used in combination. This is suitable because it allows for

(F) -4tt4i carbon black treated product Furthermore, the treated conductive carbon black used in the present invention can be obtained by treating the conductive carbon black described below with a titanate camping agent. It will be done.

(1) Conductive carbon black As the conductive carbon black used to produce the treated material, general 1fC has a specific self-sustainability of 20-18 determined by the low-temperature nitrogen absorption χ1 method and the BFT method.
00 m'/g and pore volume IJ' MIII radius, measured by mercury porosimetry in the range of 30 to 7500 A, is 15 to 4.0 cc/g, and in particular, the specific surface area is 600 m'/g.
~12007112 are valid.

Examples of the carbon black include channel black, acetylene black, and carbon black produced by the furnace black method. Regarding these carbon blacks, please refer to ``Carbon Black Handbook'' (edited by Carbon Black Association, published by Tosho Publishing Co., Ltd., 1972), 1 Handbook, edited by Rubber Digest Co., Ltd., ``Rubber/Plastic Compounded Chemicals'' (Rubber Digest Co., Ltd., published in 1972). Their manufacturing methods and physical properties are well known, such as in the above-mentioned ``Synthetic Coam Handbook'' I published by J.D. Publishing).

(2) Typical titanate coupling agents and titanate coupling agents used to produce this treated product have the following general formula [(II
Examples include a titanate coupling agent represented by the formula], a titanate coupling agent having a phosphite group and a coordinate bond, and a titanate coupling agent having a heterocycle.

In formula (■), R is an alkyl group having at most 40 carbon atoms (which may have a substituent), A and B may be the same or different, and -0COR', -0802R2
, -0PO(OH)OPO-(OR3)2 and -oR
'[However, R1, R2, R3 and R' may be the same or different and are hydrocarbon groups selected from alkyl groups, alkenyl groups, aryl groups and aralkyl groups having at most 40 carbon atoms] Choose from, X
is an integer of 1 to 3, m and n are integers of O to 3, and x −1−m 4− n is 4.

Furthermore, titanate coupling agents represented by formulas (IIl,) and (IV) can also be used.

(In formula I, R6, R7, R8 and R9 may be the same or different, and are the above-mentioned hydrocarbon groups having at most 40 carbon atoms, Rlu, R1coR, R1coR14
and R15 may be the same or different, and are a hydrogen atom or the above-mentioned hydrocarbon group.

In the measurement, RI6 is an alkylene group having at most 40 carbon atoms, a phenylene group or -c=og, and R and R may be the same or different types, and the above 10COR'
, -0SO2R2, -0PO(C)Inoopo-(OR
3) Selected from 2 and -OR'.

Among these titanate coupling agents, those in which X is 3 and m is 1 in the formula (■) are preferred.

Furthermore, in this formula (1), the carbon number of R is 11 to 2
5 [preferably 11 to 20] alkyl groups,
and A is 10COR (R is an alkyl group having 1 to 12 carbon atoms), -0502R2 (R2 is an alkyl group having at most 18 carbon atoms)
phenyl group with alkyl groups) and -0PO(
OH)OPO(OR”)2(R3 has at most 1 carbon number
2 alkyl groups) are preferred.

(3) Treatment conditions and treatment method The treated conductive carbon black of the present invention is obtained by treating the conductive carbon black with a titanate coupling agent.

In producing this treated product, the treated product may be produced in advance, or the composition of the present invention may be produced while mixing these with other composition components at 11°C.

Since the titanate-based coupling agent is a very viscous liquid at room temperature, it is common to dilute it in an organic solvent and then add conductive carbon black to it before processing.

At this time, the conductive carbon black and the titanate coupling agent may be added to the solvent and the treatment may be carried out while mixing.
It may also be treated by adding it directly to a mixer such as a ribbon preg or by spraying it.

The organic solvent used is a liquid that is inert to the titanate coupling agent and the conductive carbon black, and preferably has a melting point of 20°C or lower (preferably 0°C or lower).This solvent is used at the end of the treatment. After that, it is necessary to remove the resulting conductive carbon black from the processed material, so carbon black with a low boiling point is preferable.
~300°C (desirably 70~300°C, preferably 7
0 to b are selected from aliphatic, alicyclic and aromatic hydrocarbons, alcohols, ketones and ethers having the above melting points and boiling points. The proportion of titanate coupling agent in the treatment solution is generally 10 to 75% by weight, preferably 10 to 60% by weight, especially 15 to 60% by weight.
Heavy R% is preferred. In addition, the processing temperature is usually O~100
℃, preferably room temperature (20℃) to 100℃,
A temperature of 20 to 80°C is particularly suitable. The treatment ratio of the titanate coupling agent to 100 parts by weight of the conductive carbon blank to be treated is generally 0.1 to 15 parts by weight, preferably 02 to 15 parts by weight, particularly 05 to 10 parts by weight.
R amount parts are preferred. Further, the treatment time is usually 10 to 1 hour, and industrially generally 15 to 30 minutes. These processing conditions may vary depending on other processing conditions (e.g., type of titanate coupling agent and solvent, processing time, processing temperature, respective processing or use of titanate coupling agent, conductive carbon black, and solvent).
Ratio) varies depending on 1/C and cannot be specified as - skin, but it can be selected from the range of each processing condition mentioned above.

The treated product obtained in this way does not necessarily have to be completely dried, but it is generally used after being dried. Further, the content of the titanium-based coupling agent in the obtained treated product is usually 0.1 to 15% by weight, particularly preferably 0.5 to 10% by weight.

(G) Lubricant The lubricant used in the present invention is selected from hydroxystearate ethylene bisamide and ethylene bisamide. Stearic acid, a metal of stearic acid (
For example, the use of a calcium salt, stearic acid monoglycerol ether, is undesirable because it does not improve the flowability of the composition containing the treated conductive carbon black.

(l() Flame retardant) In the field of use of the composition of the present invention, there is a demand for a composition having flame retardancy.For this reason, the styrene resin, metal powder, etc., titanate coupling Good flame retardancy can be achieved by further blending a nitrogen-containing organic compound, antimony oxide, and a hydrous inorganic substance as a flame retardant into the composition of the present invention, which consists of conductive carbon black treated with a lubricant and a conductive carbon black treated with a lubricant. UV9
4 method, a composition with a thickness of 1/16 inch (V-0) can be obtained.

(1) Halogen-containing organic compound The halogen-containing organic compound used as a flame retardant in the present invention is widely known as a flame retardant. The halogen content of the halogen-containing organic compound is generally 20 to 90% by weight, and 30 to 90% by weight.
Preferably, those having a weight ratio of 35 to 85 K are particularly suitable. Further, those having a melting point of 200°C or less and a boiling point of 200°C or higher are suitable.

In particular, it is liquid or solid at room temperature (20 ° C.) VC,
Those having a decomposition temperature or boiling point of 300° C. or higher are preferred. Further, the molecular weight of the halogen 3' organic compound is usually 500 to 5000, particularly 500 to 710.
00 is preferred. Among the halogen-containing organic compounds of the present invention, representative examples of preferred ones include tetrachlorophthalic anhydride, λ1X paraffin, chlorinated bisphenol A, brominated bisphenol S, chlorinated phenyl, brominated Mention may be made of diphenyl, chlorinated naphthalenes, tris(β-chloroethyl)phosphate and tris(dibromobutyl)bosphate.

(2) Antimony oxide Further, the antimony oxide used in the present invention is generally used as a flame retardant aid for the halogen-containing organic compound. Representative examples include antimony trioxide and antimony pentoxide.

These halogen-containing compounds and antimony oxide are well known from the above-mentioned ``Handbook of Rubber O-Plastic Compounded Chemicals.''

(3) Water-containing inorganic material The water-containing inorganic material used in the present invention contains 10 to 80% by weight of bound water L11, and has a true specific gravity of 10 to 50. Typical examples of hydrated fH)<-like substances are hydrates of metals of Group IIA, Group IID, and Group Ill'B of the Periodic Table and salts containing these metals. The hydrated inorganic substances include magnesium hydroxide, calcium hydroxide, aluminum hydroxide (A7?, 03-nH
Compounds that have water in their composition, such as 2O), hydrated gypsum, kaholin clay, JM calcium, hydrotalcite, basic magnesium carbonate, magnesium borate, and precipitated barium sulfate, are listed. These water-containing inorganic substances are sparingly soluble in water, and their solubility in 100 cc of water is generally 1 og or less, preferably 1 g or less, especially 0.
．． 1.9 or less is suitable. Suitable hydrated inorganic substances include aluminum hydroxide, hydroxide T1 magnesium hydroxide, calcium carbonate, basic magnesium carbonate, precipitated magnesium sulfate and magnesium silicate (Mg
O-8102). Regarding these water-containing inorganic substances, see Rubber Digest Co., Ltd., 1 Handbook, Rubber-Plastic Compound Eutectics (Rubber Digest Co., Ltd.
Their manufacturing methods, physical properties, trade names, etc. are described in pages 221 to 253 of Illustrated Edition (Illustrated in 1974), and are well known.

The antimony oxide and hydrous inorganic substances used in the present invention generally have an average particle size of 01 to 100 microns, preferably 0.1 to 50 microns, and particularly preferably 0.2 to 50 microns. .

(J) Composition ratio (composition ratio) In producing the composition of the present invention, a conductive carbon blank (hereinafter referred to as "conductive carbon blank") treated with the styrene resin, metal powder, etc. and a titanate yarn coupling agent The compounding ratio (composition ratio) of metal powder, etc. in the amount (total) of the coated material (referred to as "black processed material") is 5 to 50 by volume, and 5 to 45 to q', 1.
Yōou-ke is suitable. In addition, the blending ratio of the treated conductive carbon black in the total amount is 5 to 50%.
% by volume, and preferably 10 to 45% by volume. However, the proportion of styrene resin in these total i1'fM widths is 90 to 40% by volume, especially 80 to 40% by volume.
45% BiL is suitable (i.e., the mixture of metal powder etc. and conductive carbon black treated material is 10%).
~60% by volume, especially 20-55% by volume
is preferred]. Furthermore, the volume of the metal powder and the treated conductive carbon black -XJL is 1:1~
A ratio of 1:4 is preferred, and a ratio of 35:1 to 1::i5 is particularly preferred. Especially in the high frequency range (Mn+) b, by mixing a treated conductive carbon blank that has a sound shielding effect with a metal flake-like material that has an electromagnetic wave shielding effect in the low frequency range (KHz). Not only does it exhibit a shielding effect over a wide frequency range, but even in a range where it would hardly produce an effect when used alone, it exhibits a remarkable shielding effect when both are used together.

Although the reason for this remarkable effect is not clear, it is presumed that the electromagnetic wave energy reflected or absorbed by the metal powder or the like comes into contact with the processed material of conductive carbon black. The result of all these reasons is that the conductivity of the composition of the present invention is significantly improved by using the treated conductive carbon black in combination. When the proportion of styrene resin in the total amount of styrene resin, metal powder, etc. and conductive carbon black processed material exceeds 90% by volume, the shielding effect is sufficiently exhibited, especially in the low frequency range. A composition that can be used is not obtained. On the other hand, if the volume ratio is less than 40, not only the moldability of the composition decreases, but also
A homogeneous composition may not be obtained.

Furthermore, the blending ratio of the lubricant is 0.01 to 20 parts by weight, preferably 0.05 to 20 parts by weight, based on 100 parts by weight of the total amount of styrene resin, metal powder, etc., and the treated material of conductive carbon black. , especially 01-1
A zero-layer plate portion is preferred.

If the blending ratio of the lubricant is less than 0.01 part by weight based on 100 parts by weight of the total amount of styrene resin, metal powder, etc. and conductive carbon black, a composition with excellent fluidity cannot be obtained. On the other hand, if more than 20 parts by weight of the lubricant is blended, although the fluidity is good, the heat resistance of the composition to be subjected to IJ is reduced.

When producing a composition with excellent flammability in the present invention, the total amount of styrenic resin, metal powder, etc. and conductive carbon black treated material is 100 parts by weight, ffl, and V.
The blending ratio of antimony oxide and halogen-containing organic compound to C is at least 1 part by weight, especially 221γ
f7. i: Fils or more is preferred, and 3 parts by weight or more is preferred. Further, the total amount thereof is desirably 50 parts by weight or less, particularly preferably 40 parts by weight or less. Furthermore, the blending ratio of antimony oxide to the amount of halogen element in 100 parts by weight of the halogen-containing organic compound is:
Generally, it is 100 to 600 parts by weight, and 100 to 400 parts by weight.
It is preferably 150 to 400 parts by weight in terms of flame retardancy and bleedability. The total amount is 50 parts per 100 parts of the processed material such as styrene resin, metal powder, etc. and conductive carbon black.
If antimony oxide and halogen-containing organic compounds are blended in excess of parts by weight, the moldability of the composition will be poor, and even if a molded product can be produced, the mechanical strength will not be satisfactory, so it is not preferable or not. .

In the present invention, in producing a composition with excellent f4ft flammability, the important point is that a composition with good flammability is Not obtained (UL
-94 method v-2]. Therefore, by adding a water-containing inorganic substance to these ordinary flame retardants, styrene-based At most 50 parts by weight of a water-containing inorganic substance per 100 parts by weight of the treated material such as resin, metal powder, etc. and conductive carbon black.
Parts by weight, especially less than 45 parts by weight. In addition, at least 5 parts by weight, preferably 10 parts by weight or more, preferably 111 parts by weight or more of a hydrous inorganic substance is added to 100 parts by weight of the treated conductive carbon black. , outside these ranges, a composition having good flammability, mechanical properties and moldability cannot be obtained.

In producing the composition of the present invention, styrenic resin,
(K ) Manufacture of composition, manufacture of molded article To manufacture the composition of the present invention, a Henschel mixer commonly used in the styrenic resin industry is used.
The mixture may be tri-blended using a mixer such as a Banbury mixer, a Nigoo mixer, a roll mill, and a single screw extruder. At this time, a homogeneous composition can be obtained by triblending in advance and melt-kneading the resulting composition (mixture).

In particular, it is preferable to use the styrene resin in the form of a powder because it allows for more uniform mixing.

In this case, the mixture is generally melt-kneaded, then molded into pellets, and subjected to the molding described later.

When producing the composition of the present invention, acid and heat stabilizers, metal deterioration inhibitors, plasticizers, fillers, and flame retardants commonly used in the field of styrenic resins may be further added. good.

Both melt-kneading and molding must be carried out at a temperature equal to or higher than the Europeanization point of the styrene resin used, but if carried out at a temperature of 280°C or higher,
Since a part of the styrene resin may suffer from thermal deterioration, it is a matter of course that the process must be carried out at a temperature below this temperature.

Examples of the molding method include extrusion molding, injection molding, and press molding. Furthermore, molding methods commonly used in the field of star lubricants may also be applied.

As described above, the composition of the present invention has excellent processability, so it can be molded into various shapes by the molding method described above and used in many ways.

IyD Examples and Comparative Examples The present invention will now be explained in more detail with reference to Examples.

In addition, in the Examples and Comparative Examples, the volume resistivity value is 3Qn vertically and 1c horizontally from the molded product shown in FIG.
An n+ specimen was taken out, and conductive silver paste was applied to the front and back at two locations A and B (both 1 cm wide) in Figure 1. After the paste is sufficiently dry, each paste! - Tester for resistance value between coatings [manufactured by 3-phase electric meter, 5ANWA]
, 5R-3TR). The volume resistivity value was calculated by dividing the obtained value by the thickness 1) and expressed as (Ω・mouth).Also, the electromagnetic wave shielding effect was measured using a 10×10×30α sample using a sheet with a thickness of 3 cm. A box is made, and a portal oscillator is placed inside the box at a predetermined frequency (600 kHz).
MHz). This box was installed in an anechoic chamber, and the 'C wave emitted from the transmitter inside the box was measured using a receiving antenna using a microwave power meter after passing through a detector.

The radio waves from the oscillator were measured in the same way with the box manufactured from the sheet removed, and the ratio of the electrolytic strength (μV) depending on the presence or absence of the sample box was expressed in decibels (dB) and used as the electromagnetic wave attenuation of the sample sheet.

Furthermore, the flame retardant property is rated by Underwriter Laboratories (UL).
) Measured according to the 94 method. In addition, the melt flow rate (hereinafter referred to as 1'-MFIjJ) is based on ASTM D-
According to 1238-79, the temperature is 230°C and the load is 21.6! ? Measured under the following conditions.

In addition, conductive carbon black and &I treated with a titanate yarn coupling agent, such as styrenic resin and metal powder used in Examples and Comparative Examples,
The shape, physical properties, and manufacturing method of the combustion agent are shown below.

[(A) Styrene resin (PS): As the styrene resin, styrene was suspended in water, an emulsifier and a catalyst were added, and polymerization was performed at a temperature of 90°C. As a result, melt
A styrenic resin (hereinafter referred to as "
pSj] was manufactured and used.

[(B) Styrenic resin (HIR8)] As the styrene resin, 81% styrene-butadiene lanthanum copolymer rubber [Styrene content 253%, Mooney viscosity (ML, +, ) 25 or less] 5BRj] was graft-polymerized with 92 parts by weight of styrene to produce impact-resistant polystyrene (hereinafter referred to as IPSJ) having a melt flow index of 13.0j) for 710 minutes.

((C) ABS resin) Styrene-butadiene copolymer rubber (butadiene content 80% by weight, rubber gel content 80%) 280゜0g (as solid content), 2.0.9 in a 20J? stainless steel autoclave ammonium persulfate, 80.0
．． ! 7 disproportionated sodium rosinate, 21.0. ! ? lauryl mercaptan and 8. Added 100 ml of water and stirred evenly. To this, 2520 g of styrene and 1200 g of acrylonitrile were added as monomers and stirred.
Then, the temperature was raised to 70°C while stirring. Polymerization was carried out at this temperature for 10 hours with stirring. Then,
A five-layer aqueous solution of aluminum sulfate was added to the latex-like material containing the polymer grafted as described in Section 2 above, and the grafted material prepared in step 4) was coagulated.

This coagulated material is washed with an aqueous solution of about 5.2% of IJium (about 1 part hydroxide), and an even larger amount (about 301%)
It was washed using 0°C warm water. Approximately 80% of this graft
Drying was carried out overnight at ℃ under reduced pressure. the result,
3785 g of white powdery graft material was obtained. The Izod impact strength of the resulting graft was 7.5 kg.
-cm/cm-notch, tensile strength is 468
Kg/cnr2. Moreover, the Vicat softening point U of this polymer was 101.5°C.

The content of rubbery substances in this graft product was 7.3% by weight. Hereinafter, this grafted product will be referred to as 1-ABsJ.

((D) MBS resin) Aqueous dispersion containing 1380.9 butadiene-styrene copolymer rubber (Mooney Clay 50) consisting of 76.5 weight units of butadiene and 23.5 weight units of styrene 12.
'0/' 207? was placed in a stainless steel autoclave. Dihydrate of sodium formaldehyde sulfoxylate 48 while keeping the temperature at 60°C under nitrogen stream.
09 is about 2.4j? an aqueous solution dissolved in water of 160.
Add 0.9 of cumene hydroperoxide and add 1
Stir for hours. Then, a mixed solution of 7680# methyl methacrylate and 32.0 g of cumene hydroperoxide was added to carry out polymerization. After about 7 hours, the polymerization softening rate reached 91.8%. 6880g for this reaction system
A mixed solution of 320I styrene and 320I cumene hydroperoxide was added to carry out polymerization.

After about 6 hours, the polymerization softening rate reached 933. An aqueous solution of hydrochloric acid and sodium chloride (salt) was added to this liquid to solidify it.Then, this precipitate was filtered once, thoroughly washed with hot water, and then kept under reduced pressure at a temperature of about 80°C overnight. Drying was performed. As a result, a white powdery polymer (grafted product) was obtained.
m-notch, tensile strength is 41 s Ky/an2
Met. The Vicat softening point of this graft is 97.2
It was ℃. The content of rubbery material in the obtained graft product (hereinafter referred to as "MBSJ") was 96% by weight.

C(E)AAS resin] In a 20J stainless steel autoclave, distilled water at 80C, 24.0g sodium dodecylbenzenesulfonate, 080g ammonium persulfate as a polymerization catalyst, and 784.9g butyl acrylate as a monomer. Ester and 160 g of glycidyl methacrylate were charged, and polymerization was carried out at 77° C. with stirring until the polymerization was almost completed to produce an acrylic ester rubber.

Styrene 1680.9 and acrylonitrile 720I as monomers and 160 g potassium persulfate as a polymerization catalyst were added to the polymerization system containing this acrylic ester rubber, and polymerization was carried out at 83° C. with stirring for 10 hours. As a result, an emulsion polymer (grafted product) containing almost no unreacted monomer was obtained. An aqueous solution of aluminum sulfate was added dropwise to the emulsion containing the grafted product while stirring, and the polymer (grafted product) was precipitated. Next, this water-containing polymer was dehydrated by centrifugation, and after thoroughly washing with water, it was dried at about 50° C. under reduced pressure.

The impact strength of this graft was 24.8 K.
9, cT++/CT1+ −/Tsuji, and the tensile strength was 350 to 9/c1n2. Moreover, the 1 Europeanization point was 97.6°C.

The rubber-like material content of this grafted material (hereinafter referred to as "AASJ") was 23,838% by weight.

[:(F)AES resin] 20I! 535 as a monomer in the above autoclave of
ON styrene, Mooney viscosity (ML+
+4. Ethylene-glopyrene-diene ternary copolymer rubber (non-covalent diene component: ethylidene norbornene, iodine M < value 25) having a value of 45 (100°C) and 1. OK7 n-hebutane were charged. After purging the inside of the autoclave with nitrogen, stirring was performed at 50°C for 2 hours to completely dissolve the ethylene-propylene-diene binary copolymer rubber in styrene.2150. After adding !V of acrylonitrile, sufficient stirring was performed to prepare a homogeneous solution.To this solution, 5.0.9 of terpinolene and 5.0.9 of di-tertiary-butylperoxy as a catalyst were added. Zide and 13 g of tertiary-butyl peracetate were added, and the temperature of the polymerization system was raised to 97°C. Bulk polymerization was carried out for 7 hours and 20 minutes while controlling this temperature under nitrogen pressurized conditions of IKy10n2. Polymerization completed Approximately 30 minutes earlier, 150 g of di-tertiary-butyl peroxide and 150 I of Tervirun were added to the
0.9 of styrene and added this solution. The syrup thus obtained (containing polymer) was
? 30j? water (containing 25 g of acrylic acid-acrylic acid ester copolymer as a suspending agent). The mixture was transferred to an autoclave and replaced with nitrogen. This aqueous suspension
Suspension was carried out for 2 hours at 0.degree. C. with vigorous stirring. Then, the temperature was raised to 150°C and stripping was performed for 1 hour. After thoroughly washing the polymer (graft-blend) with water, it was dried at 100°C. As a result, 928 kg of graft-blend product (hereinafter referred to as "A") was obtained.
ES) was obtained. The content of the rubbery substance in this AES was 16,060 parts by weight. The Izot impact strength of this AES (, i37.g Kg, on/cm-/
The tensile strength was 350Kg10n2.The Vicat softening point was 98.0°C.

[(G) AC8 resin] Chlorinated polyethylene with a Mooney viscosity of 76 [chlorine-containing ff140.6 weight ratio, hereinafter t] in a 201 autoclave
-c z -P E(8) J) 1600.9
, polyvinyl alcohol (saponification degree 95%) 3z.

g and 8.0 J of water (ion-exchanged water) were charged.

The mixture was then vigorously stirred at room temperature (approximately 23°C).

Styrene of 4560.9 and 1520.9% as an IP polymer were added to this dispersion while stirring at room temperature. ! 7 acrylonitrile, 320 g of liquid paraffin as a lubricant, 16.0.9 tertiary-methyl peracetate as a polymerization initiator and 160 g of tertiary-todecyl mercaptan as a chain transfer agent. After exchanging the upper part of the suspension of this reaction system with nitrogen gas for 11", the temperature was raised to 105°C. After polymerization was carried out at this temperature for 4 hours with stirring, the polymerization was further carried out at a temperature of 145°C for 2 hours. Polymerization was carried out.Then, this reaction system was allowed to cool to room temperature, and the obtained polymer (grafted product) was filtered and thoroughly washed with water.

The obtained graft material was dried under reduced pressure at 50° C. all day and night. The polymerization conversion rate (relative to the monomer used in the polymerization) was 95.4, which was 1. It was slightly powdery. In addition, this graft product [hereinafter referred to as "AC3J"]
The N content of the rubber-like material was 20.3% by weight.

[(H) Mixtures (1) and (2)] 2.6-xylenol is polycondensed by an oxidative coupling method to form poly2
,6-dimethylphenylene-1,4-ether [intrinsic viscosity (measured at 30°C, in chloroform, unit: dl/El
) 0. s 3, hereinafter referred to as "p P Oj" was produced. 100 parts by weight of PPQ, 25 parts by weight of styrene monomer, 10 parts by weight of PS produced in the above (A) and 21 parts by weight of G-tertiary. - Butyl peroxide was mixed for 10 minutes using a Henschel mixer, and then a styrene graph) PI/0 mixture [hereinafter referred to as "mixture (1)
” was manufactured.

This mixture (],) 50 nails fj'LN'? The PS50 heavy electric parts manufactured in
) was triblended in the same manner as in the preparation. Extruder (diameter 40+nm, resin temperature 2)
A mixture (hereinafter referred to as "mixture (2)") was produced while melt-kneading at a temperature of 60°C.

[(J) Mixture (3)] Acrylonitrile-styrene co-IR composite resin (acrylonitrile content 23 weight candy, hereinafter referred to as "AS") 7 each
Q,! An ethylene-butene-1 conjugate with a molecular weight of approximately 250,000 (density 0!1) is used as a rubber-like material for 1 part of fi.
31 g/on3) Water-repellent ThtJ f+'a-like f J', fuL J'l'1+ Hydrogenated polyethylene (chlorine-containing mouse) 31.
6 Weight ratio, Moony; Viscosity (MSs-+-+, ) 7
scolding) is the content GO/? Banbury kneading e: A mixture [hereinafter referred to as "mixture (3) J]" was produced by melt-kneading (resin temperature: 180 DEG C.) and melt-kneading.

[(Processed product of IO conductive carbon black) Titane!
・As a system camping agent, ingropyrtridodecylbenzenesulfonyl-f-tane-1 ・[hereinafter referred to as “compound (
a)], inglobiltris (dioctel) nogylophosphate titanate-1 [hereinafter referred to as "compound (B month)"] and isopropyltrioctadecyl titanate [hereinafter referred to as "compound (C month]"). there was.

In addition, as conductive carbon black, the average particle size is 42
Millimicron acetylene black (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name: Denka Acetylene Black, surface area: 61
m2/j), true density 1.95.9/cm3, iodine absorption; "fffi 88 mta/, 9, hereinafter gc, B
J) was used.

Each of the above titanate coupling agents shown in Table 1 was added in advance to twice the amount (by weight) of toluene, and stirred in a beaker for 3 minutes at room temperature using a magnetic cooler to form a homogeneous solution. was manufactured.

After adding each of the toluene solutions (processing ratios not shown in Table 1) prepared as above to the C0B with stirring, the mixture was stirred for 30 minutes using a 2゜l tumbler. Each treated product was manufactured. Then, it was dried for 24 hours at room temperature.

Table 1 1) 1 compound (■ indicates compound (a) and compound (b)
2 obtained by processing using 25 weight divisions of each
) Treated product (11111 is compound (a) and compound (
Those obtained by processing using 5% by weight of each of b) [
(L) Metal powder, etc.] Metal powder, etc. with a cross-sectional area of I x 1 mm
, square aluminum flakes with a thickness of 0.03fi (hereinafter referred to as "Al flakes"), particle size of 74~1
Aluminum powder of 50 microns (hereinafter referred to as "Al powder"), aluminum lia fibers with a length of approximately 6 mm and a diameter of 65 microns (hereinafter referred to as z-fibers J1f+J), and iron with an average particle size of approximately 55 microns. Powder (hereinafter referred to as "Fe powder")
Zinc powder (hereinafter referred to as "zn powder") having an average particle size of about 70 microns and brass powder (hereinafter referred to as "brass powder") having an average particle size of about 65 microns were used.

[Lubricant]

As lubricants, hydroxystearic acid ethylene bisamide [hereinafter referred to as "Lubricant (A)J"], ethylene bisamide [hereinafter referred to as F fi') agent (hereinafter referred to as B), stearic acid monoglycerin ether [hereinafter referred to as "Compound (C)"] ]
, stearic acid [hereinafter referred to as "compound (B month)"], calcium stearate [hereinafter referred to as "compound (Moe)]", and mineral oil [molecular weight approximately 350, hereinafter referred to as "compound (F)"]
] was used.

[(N) Flame retardant]

As a flame retardant, decabromodiphenyl oxide (average particle size: 3 microns, odor: about 82% by weight,
Antimony trioxide (hereinafter referred to as rsb2osJ) with an average particle size of about 0.05 microns and reduced heating, GL (4!L 0°C) of about 3
Magnesium hydroxide [average particle size
74 micron, hereinafter referred to as UMg (01()2, J) was used.

Examples 1 to 5, Comparative Examples 1 to 11 58 volumes π parts of PS as the styrene resin, 17 volumes of A/' powder as the gold 1/2 powder, etc.! ? tF? lS
, ``conductive carbon black treated product'' (hereinafter referred to as ``treated product'') -1, and untreated C1B, respectively.
5 parts by volume and f1') agent (combined amount of PS, Aj? powder and treated product or c, n) 100 weight 1ii: %
Table 2 shows the compounding amount for i'+i in advance.
Tri-blend for 3 minutes using the J tumbler 1]
:became.

Each of the obtained mixtures was melted and kneaded using a twin-screw extruder (diameter: 30 mm) at a resin temperature of 240° C. to produce pellets. ? The MFR of each IJ pellet is shown in Table 2.

Using each pellet thus printed, a sheet (test piece) with a thickness of 3 mm was made using an electric press at 230°C to measure the volume resistivity and electromagnetic wave attenuation. In addition, a flat plate (150 x 1501 mm) with a thickness of 2 squares was molded using an injection molding machine at 240 ° C, and the powdered material of decarbonized black and demetallized material (hereinafter referred to as "peel test") was molded. A test piece was manufactured for this purpose.

The volume resistivity and electromagnetic wave attenuation of each of the obtained test pieces were measured and a peel test was performed. The results are shown in Table 2. Note that the volume resistivity value was 10°Ω·m in all Examples and Comparative Examples.

The results of the peel test are expressed as follows by applying cellophane tape to the surface of a flat plate, peeling off the cellophane tape, and determining the amount of carbon black and metal powder adhering to the cellophane tape.

◎ No adhesion ○ Almost no adhesion △ Slight adhesion kl of capacity part
Powder, 25 parts by volume of the treated product (V), 5 parts by weight as a lubricant (100 parts by weight of styrene resin, Aj' powder and 100 parts by weight of the total amount of the treated product, however, Comparative Example 11
The lubricant (A) was not added in Examples 6 to 14) and was triblended and melt-kneaded under the same conditions as in Example 1 to produce pellets. To 100 parts by weight of the total amount of material M, 10 parts by weight of Mg (
OH) 2.10 parts by weight of DBP0 and 4 parts by weight of 5b
203 is further blended].

Using each of the pellets thus obtained, sheets and flat plates were manufactured as test pieces in the same manner as in Example 1. Volume resistivity value and electromagnetic wave attenuation I11 of each test piece
Measurements were made. The results are shown in Table 3. A peel test was also conducted (the display format was the same as above). The results are shown in Table 3.

Examples 17 to 25, Comparative Examples 20 to 26 The PS used in Example 1', the metal powders etc. whose types are shown in Table 4', and the treated material (V) (the blending amounts of each are shown in Table 4'). ] and these maxims 1'ij
5 parts by weight of hydroxystearate ethylene bisamide per 100 parts by weight (however, Comparative Examples 20 to 26
(not blended in Example 1) were tri-blended and melt-kneaded in the same manner as in Example 1 to produce respective pellets.

A sheet (test piece) was manufactured in the same manner as in Example 1 using each of the obtained pellets. In addition, a flat plate was manufactured in the same manner.

The volume resistivity and electromagnetic wave attenuation of each of the obtained test pieces were measured, as well as the peel test and the MFR of the pellets. The results are shown in Table 4.

From the results of the following two examples and comparative examples, it is clear that the composition according to the present invention has excellent compatibility with the carbon black, metal powder, and styrene resin that are blended. It is clear that it can be used in a wide variety of fields, since it has good properties, does not peel off, has excellent electromagnetic wave shielding properties, and has good processability.

[Brief explanation of the drawing]

FIG. 1 is a perspective view of a specimen for measuring volume resistivity. A and B [front and back] in FIG. 1 are the surfaces coated with conductive silver paste. Patent Applicant Showa Denko K.K. Agent Patent Attorney Sei Kikuchi - Figure 1 1, Display of the case Patent Application No. 63081 of 1988 2, Name of the invention Thermoplastic resin composition 3, Relationship with the amended case License applicant address: Shiba Daimon, 7-ku, Tokyo - No. 13-9, T. Name (2)
00) Showa Kata-12 Co., Ltd. Representative Nagishi Motoyasunobu 4, Agent (Postal code 105) Address Tokyo Minato 1st Shiba Daimon-cho 1 13-8-) Showa Denko Co., Ltd. Telephone: Tokyo 432-5111 No. (Major Representative) 5, Date of amendment order + J August 28, 1982 (Delivery date) 6, "Brief explanation of drawings" column and "Detailed explanation of invention" column of the specification subject to amendment 7. Contents of the amendment (1) At the end of the "Brief explanation of drawings" section of the specification (page 67, line 12), it should be added that "Figure 2 shows the injection molded product manufactured in each example and comparative example. "It is a perspective view." is added. (2) - In relation to Supplement 11 of Iz, page 44, line 4 of the specification states, ``Produce a sample box of 30cm x 10 x 30cm (perspective view: ffr, shown in Figure 2).
We will correct it.

Claims (1)

[Claims] (Al(1) a polymer containing at least styrene,
(2) Rubber-like material b: A polymer obtained by treating a polymeric substance selected from the group consisting of polyphenylene ether with a monomer containing at least styrene; and (3) a polymer containing the polymeric substance and at least styrene. (B) at least one thermoplastic resin selected from Ir"n, which is a mixture formed by mixing with a polymer; (B) a metal or alloy powder, fibrous material, and/or
or flakes, (C) electrically conductive carbon black treated with a titanate coupling agent; and (D) at least one lubricant selected from group forces consisting of ethylene bisamide droxystearate and ethylene bisamide. a composition in which the content of styrene in the thermoplastic resin is at least 5% by weight as monomer units; The amount of metal or alloy powder or fiber in the total amount of the conductive carton powder that has been treated. The blending ratio of the conductive carbon black and/or flake-like material and the treated conductive carbon black is 5 to 11, respectively.
50 volume Q%, but their total - for 10~6
0 volume, and the blending ratio of the lubricant is based on 100 parts by weight of the total amount of thermoplastic resin, metal or alloy powder, fibrous material and/or flake material, and treated conductive carbon black. A thermoplastic resin composition in an amount of 0.01 to 20 parts by weight.