Electroconductive resin composition

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an electroconductive resin composition exhibiting a high and stable electroconductivity which contains a small filling amount of a specific carbon black and graphite combination as the electroconductive filler which is used to fill a thermoplastic resin and/or a thermosetting resin.
2. Description of the Related Art
Remarkable developments have and are occurring in the field of electronic machines such as computers, VTR, acoustic instruments, home appliances, word processors, etc. In these electronic instruments, due to the high integration density of electronic circuits and devices thereof, microcurrents are used, and thus a problem arises in that an erroneous actuation, etc., may be caused by electromagnetic waves from an external source.
Plastic moldings are frequently used as casings of these electronic instruments to cope with the demands for a lightweight, low cost, mass-produced article, etc., but these plastic moldings do not have a shielding effect against electromagnetic waves, and thus cannot solve the above problem.
In the prior art, as a method for imparting an electromagnetic wave shielding property to plastic moldings, an electroconductive resin has been proposed comprising an electroconductive filler which is filled and dispersed in a resin. As the electroconductive filler, a metal type filler and a carbon type filler are generally employed.
A metal type filler is suitable for imparting a high electroconductivity, but has drawbacks in that the specific gravity thereof is high, the electroconductivity is reduced the losses occurring due to filler cutting during molding, and the metal type filler causes abrasion of the extrusion screws and molds.
A carbon type filler such as carbon black or graphite will not substantially abrade extrusion screws or molds, but it is not suitable for uses in which a high electroconductivity with a volume resistivity value of 1 .OMEGA..multidot.cm or less is required, such as electromagnetic shielding materials, electrodes, etc. Among electroconductive carbon blacks, a small amount of Ketjen Black EC (produced by Ketjen Black International) can provide a satisfactory electroconductivity, but the mechanical strength of the composition is remarkably worsened and the resultant material is very brittle and easily destroyed. Graphite itself has a good electro-conductivity, but when dispersed in a resin, a high electroconductivity can not be obtained unless a large filling hereof is used, and further, a problem arises in that the resistance value has a great amplitude of 10.sup.1 to 10.sup.-1 .OMEGA..multidot.cm, and a stable electroconductivity cannot be obtained (Japanese Unexamined Patent Publication (Kokai) No. 60-118744). Further, when carbon black and graphite are used in combination, although a high electroconductivity can be obtained from a low filling amount, the mechanical strength of the composition is lowered and the moldability reduced. Therefore, when a highly electroconductive resin composition is obtained by using the carbon black and graphite of the prior art, molding becomes difficult and the resin composition obtained has a lowered mechanical strength, particularly a lowered impact strength, and since carbon black and graphite are more expensive and have a higher specific gravity than the resin, a composition obtained by using these fillers is disadvantageous both in terms of having a high cost and in that it is heavy. To improve the moldability, a method has been proposed in which a propylene-ethylene copolymer with a high binder efficiency is formulated (Japanese Unexamined Patent Publication (Kokai) No. 51-17937), and a method in which a resin-coated carbon black and a resin-coated graphite are employed (Japanese Unexamined Patent Publication (Kokai) No. 61-218648), etc. However, these methods do not provide a reduction of the filling amount of carbon black and graphite, and thus did not provide a solution to the above problems. Accordingly, it is desirable that a carbon black and graphite which is capable of exhibiting a high electroconductivity even at a low filling amount, be produced.
SUMMARY OF THE INVENTION
Accordingly, the objects of the present invention are to eliminate the above-mentioned disadvantages of the prior art and to provide an electroconductive resin composition having a stable and high electroconductivity when a small filling amount of an electroconductive filler is formulated therein, and which has an excellent mechanical strength, kneadability, and moldability properties.
Other objects and advantages of the present invention will be apparent from the following description.
In accordance with the present invention, there is provided an electroconductive resin composition comprising (i) 100 parts by weight of at least one resin selected from the group consisting of thermoplastic resins and thermosetting resins and (ii) 15 to 150 parts by weight of (a) carbon black having a DBP oil absorption amount of 400 ml/100 g or more and (b) expanded graphite having an average particle size of 40 .mu.m or more, wherein the expanded graphite content is 40 to 90% by weight of the total amount of the carbon black and the expanded graphite.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present inventors previously proposed a composition having a high electroconductivity even at a filling amount of about 80%, compared with a carbon black of the prior art, for example, Ketjen Black EC (DBP oil absorption amount: 325 ml/100 g) by using a specific carbon black with a DBP oil absorption amount of 400 ml/100 g or more (Japanese Unexamined Patent Publication (Kokai) No. 60-8335). As a result of further investigations, to accomplish the present invention, a special graphite was used in combination with the special carbon black, to obtain an electroconductive resin composition having a high electroconductivity at a filling amount of about 60%, compared with the carbon black and graphite of the prior art, and consequently, having a lower cost and an improved specific gravity, and having excellent kneadability and mechanical strength properties.
The carbon black usable in the present invention has a DBP oil absorption amount of 400 ml/100 g or more. When the oil absorption amount is less, a larger amount of carbon black must be formulated to obtain a resin composition with a high electroconductivity, and thus the mechanical strength is impaired.
On the other hand, although the upper limit value of the DBP oil absorption amount is not particularly limited, when this amount is more than 700 ml/100 g, the dispersibility of carbon black in the resin is reduced, and therefore, preferably the DBP oil absorption amount is in the range of 400 to 600 ml/100 g. The term "DBP oil absorption amount" used in the present specification means the oil absorption amount defined according to ASTM D2414-79.
The expanded graphite usable in the present invention can be prepared by treating natural or artificial graphite with, for example, an inorganic acid such as sulfuric acid, nitric acid, etc., to form graphite interlayer compounds, washing the compounds with water followed by dehydration, abruptly heating and expanding the compounds, and compressing the resultant expanded graphite into a sheet or mass followed by mechanical pulverization thereof, by means of a Henschel mixer, hammer mill, ball mill, etc., to a particle size of 40 .mu.m or more.
The upper limit value of the particle size of the expanded graphite is not particularly limited, but if the size is 5 cm or larger, kneading becomes undesirably difficult, and therefore, in the present invention, the range of the particle size is preferably from 40 to 20,000 .mu.m.
The amounts of carbon black and expanded graphite used with the present invention are 15 to 150 parts by weight, preferably 20 to 130 parts by weight, based on 100 parts by weight of the thermoplastic and/or thermosetting region. At an amount lower, a high conductivity of 1.times.10.degree. .OMEGA..multidot.cm or lower can not be exhibited, and at an amount higher, kneading becomes impossible.
The ratio of the carbon black to the graphite to be used in the represent invention may be 40 to 90% by wight, preferably 45 to 85% by weight, for the graphite based on 100% by weight of the total amount of the carbon black, and the graphite. When the graphite content excess 90% by weight, the electroconductivity is lowered, and at a content lower than 40% by weight, although the electroconductivity is good, the mechanical strength is lowered, and thus the object of the present invention tends to be difficult to be achieved.
The thermoplastic resins and thermosetting regions usable in the present invention include various types known in the art and are not particularly limited. Specific examples may include thermoplastic resins such as low, medium and high density polyethylenes, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, acrylonitrile-butadiene-styrene ternary copolymer, polystyrene, acrylonitrile-styrene copolymer, nitrile rubber, butadiene rubber, styrene-butadiene rubber, ethylene-propylene-diene rubber, silicone rubber, thermoplastic polyurethane resin, polyamide resin, polyester resin, polycarbonate, polyvinyl chloride, polyacetal resin, polyphenylene sulfite, polyphenylene oxide, etc. Examples of the thermosetting resins may include thermosetting acrylic resins, phenol resins, unsaturated polyester resins, epoxy resins, urethane resins, alkyd resins, etc.
The electroconductive resin composition of the present invention may further contain additives such as antioxidants, heat-resistant stabilizers, lubricants, flame retardants, pigments, plasticizers, cross-linking agents, UV-ray absorbers, reinforcing agents, etc., which are conventionally used in thermoplastic resins.
The composition of the present invention can be prepared according to any known method, but preferably is molded into pellets by mixing and kneading uniformly in a conventional manner by a suitable blender such as a kneader, Banbury mixer, mixing rolls, pressure kneader, etc., and these pellets are molded into a desired product by press molding, extrusion molding, injection molding, sheeting, blow molding, etc.
According to the present invention, a resin composition with a stable and high electroconductivity can be obtained at a low filling amount of carbon black and graphite, and therefore, is highly electroconductive compared with the resin composition of the prior art, and has excellent mechanical strength and moldability properties with a lower specific gravity. Accordingly, the electroconductive resin composition of the present invention can be applied to various fields, and can be utilized not only in electromagnetic wave shielding materials, but also, for example, as an electroconductive material for high voltage cables, ignition cables, plane heat-generating members, plane switches, electrodes, etc., or for applications such as electronic instruments or IC package materials, as a material for molded video discs, and as a permanent antistatic material, etc.

EXAMPLES
The present invention will now be further illustrated by, but is by no means limited to, the following Examples. The electroconductivity in the Examples was evaluated in terms of the volume resistivity value according to the measuring method of SRIS 2301 of the Rubber Society of Japan, the electromagnetic shielding effect was measured by both a TR-4172 and a shielding box produced by Advantest K. K., and the shielding was evaluated at a shielding of 300 MHz in the electrical field. The mechanical strength of the composition was evaluated by the Izod impact strength value obtained by the method of JIS-K-7110, and the specific gravity of the composition was measured according to the method of JIS-K-7112.
EXAMPLE 1
A polypropylene resin (produced by Idemitsu Sekiyu Kagaku, trade name: J-465H), carbon black and/or the various graphites as shown in Table-1 were formulated in the respective predetermined amounts, kneaded by a Laboplastomill at a temperature of 200.degree. C., and then press molded into a plate 15 cm square with a thickness of 2 mm. The volume resistivity value (hereinafter abbreviated as VR) and the shielding effect of the obtained molded product were measured, and the results thereof are as shown in Table 1, in relation to each electroconductive resin composition.
When graphite alone was used (see Experiments No. 14-16), even when filled in an amount of 60 parts by weight based on 100 parts by weight of the total amount of the resin and the graphite, the VR and shielding effect were poor, and the amplitude of the measured value was great. Also, even when the graphite of the present invention was used alone, only a VR and shielding effect substantially equal to that obtained when employing a graphite other than that of the present invention were exhibited. On the other hand, as understood from Table 1, when the carbon black and the graphite of the present invention were used in combination (see Experiments No. 1-8), the VR is about 5.times.10.sup.-2 .OMEGA..multidot.cm and the shielding effect was good at about 70 dB and stable with little amplitude of the value, thus having a superior shielding effect by about 15 dB and an about 4-fold VR, compared with the use of a carbon black and graphite other than those of the present invention (see Experiments No. 9-13), even at the same filling amount.
TABLE 1__________________________________________________________________________ Present InventionExperiment No. 1 2 3 4 5 6 7 8__________________________________________________________________________Electroconductive resincomposition (wt. parts)Polypropylene resin 57 57 57 57 57 57 57 57DBP oil absorption amount480 ml/100 g carbon black 13 13 13 13 13 0 0 0420 ml/100 g carbon black 0 0 0 0 0 13 13 0400 ml/100 g carbon black 0 0 0 0 0 0 0 13325 ml/100 g carbon black*.sup.1 0 0 0 0 0 0 0 0Graphite powder (average particle size)Expanded graphite (2.8 .mu.m) 0 0 0 0 0 0 0 0Expanded graphite (4.2 .mu.m) 0 0 0 0 0 0 0 0Expanded graphite (40 .mu.m) 30 0 0 0 0 0 0 0Expanded graphite (70 .mu.m) 0 30 0 0 0 30 0 0Expanded graphite (500 .mu.m) 0 0 30 0 0 0 0 0Expanded graphite (5 mm) 0 0 0 30 0 0 30 30Expanded graphite (10 mm) 0 0 0 0 30 0 0 0Vein graphite (40 .mu.m) 0 0 0 0 0 0 0 0Artificial graphite (80 .mu.m) 0 0 0 0 0 0 0 0Volume resistivity value (.OMEGA. .multidot. cm)*.sup.2 6.3 .times. 4.1 .times. 3.8 .times. 3.7 .times. 3.8 .times. 5.1 .times. 4.7 .times. 5.0 .times. 10.sup.-2 10.sup.-2 10.sup.-2 10.sup.-2 10.sup.-2 10.sup.-2 10.sup.-2 10.sup.-2 6.7 .times. 4.3 .times. 3.9 .times. 3.9 .times. 3.9 .times. 5.2 .times. 4.9 .times. 5.1 .times. 10.sup.-2 10.sup.-2 10.sup.-2 10.sup.-2 10.sup.-2 10.sup.-2 10.sup.-2 10.sup.-2Shielding effect in electrical field 67.2 70.1 70.3 70.4 71.2 69.9 70.2 68.8of 300 MHz (dB)*.sup.2 68.5 72.1 72.2 72.3 72.3 70.8 71.0 69.8__________________________________________________________________________ ComparativeExperiment No. 9 10 11 12 13 14 15 16__________________________________________________________________________Electroconductive resincomposition (wt. parts)Polypropylene resin 57 57 57 57 57 40 40 40DBP oil absorption amount480 ml/100 g carbon black 13 13 13 13 0 0 0 0420 ml/100 g carbon black 0 0 0 0 0 0 0 0400 ml/100 g carbon black 0 0 0 0 0 0 0 0325 ml/100 g carbon black*.sup.1 0 0 0 0 13 0 0 0Graphite powder (average particle size)Expanded graphite (2.8 .mu.m) 30 0 0 0 0 0 0 0Expanded graphite (4.2 .mu.m) 0 30 0 0 0 0 0 0Expanded graphite (40 .mu.m) 0 0 0 0 30 60 0 0Expanded graphite (70 .mu.m) 0 0 0 0 0 0 60 0Expanded graphite (500 .mu.m) 0 0 0 0 0 0 0 0Expanded graphite (5 mm) 0 0 0 0 0 0 0 0Expanded graphite (10 mm) 0 0 0 0 0 0 0 0Vein graphite (40 .mu.m) 0 0 30 0 0 0 0 60Artificial graphite (80 .mu.m) 0 0 0 30 0 0 0 0Volume resistivity value (.OMEGA. .multidot. cm)*.sup.2 1.8 .times. 1.4 .times. 1.8 .times. 2.3 .times. 1.0 .times. 2.8 .times. 1.9 .times. 3.0 .times. 10.sup.-1 10.sup.-1 10.sup.-1 10.sup.-1 10.sup.-1 10.sup.0 10.sup.0 10.sup.0 2.0 .times. 1.6 .times. 2.5 .times. 2.8 .times. 1.2 .times. 8.2 .times. 6.3 .times. 8.0 .times. 10.sup.-1 10.sup.-1 10.sup.-1 10.sup.-1 10.sup.-1 10.sup.0 10.sup.0 10.sup.0Shielding effect in electrical field 51.3 53.2 49.1 46.2 56.0 6.2 9.5 6.3of 300 MHz (dB)*.sup.2 52.4 55.5 52.3 49.3 59.0 19.3 23.7 18.2__________________________________________________________________________ *.sup.1 Carbon black with DBP oil absorption amount of 325 ml/100 g is Ketjen Black EC *.sup.2 Volume resistivity value and shielding effect at electrical field of 300 MHz was measured with 3 samples prepared with the same composition and the upper limit value and the lower limit value measured are shown.
EXAMPLE 2
A polypropylene resin (produced by Idemitsu Sekiyu Kagaku, trade name: J-465H) was formulated with the carbon black and various types of graphite shown in Table 2 so that the molded plate exhibited a VR of about 1.times.10.sup.-1 .OMEGA..multidot.cm, and kneaded and molded according to the same method as described in Example 1. The VR, Izod impact strength and specific gravity of the molded plate obtained were measured, and the results are shown in Table 2 in relation to each electroconductive resin composition.
From Table 2 it can be seen that, by using the carbon black and graphite of the present invention, when a VR of about 1.times.10.sup.-1 is exhibited, the filling amount may be about 60% by weight, compared with that when employing a carbon black and graphite other than that of the present invention, whereby the Izod impact strength can be improved and the specific gravity reduced.
TABLE 2__________________________________________________________________________ Present Invention ComparativeExperiment No. 17 18 19 20 21 22 23__________________________________________________________________________Electroconductive resincomposition (wt. parts)Polypropylene resin 65 67 71 70 52.4 53.3 58.7Oil absorption amount 10.5 9.9 8.7 9.0 14.3 14.0 0480 ml/100 g carbon blackOil absorption amount 0 0 0 0 0 0 12.4325 ml/100 g carbon blackGraphite powder (particle size)Expanded graphite (4.2 .mu.m) 0 0 0 0 33.3 0 0Expanded graphite (40 .mu.m) 24.5 0 0 0 0 0 28.9Expanded graphite (70 .mu.m) 0 23.1 0 0 0 0 0Expanded graphite (500 .mu.m) 0 0 20.3 0 0 0 0Expanded graphite (5 mm) 0 0 0 21.0 0 0 0Scale graphite (40 .mu.m) 0 0 0 0 0 32.7 0Volume resistivity value (.OMEGA. .multidot. cm) 9.1 .times. 10.sup.-2 9.7 .times. 10.sup.-2 9.8 .times. 10.sup.-2 9.9 .times. 10.sup.-2 9.5 .times. 10.sup.-2 9.7 .times. 10.sup.-2 1.1 .times. 10.sup.-1Izod impact strength (kg .multidot. cm/cm) 3.0 3.3 4.2 4.2 0.2 0.1 1.1Specific gravity 1.14 1.12 1.10 1.09 1.25 1.25 1.20Total amount of carbon black and 53.8 49.3 40.8 42.9 90.8 87.6 70.2graphite based on 100 parts by weightof polypropylene__________________________________________________________________________
EXAMPLE 3
A 100 parts by weight amount of a high density polyethylene resin (produced by Idemitsu Sekiyu Kagaku, trade name: 520 (B) was formulated respectively with predetermined amounts of a carbon black with a DBP oil absorption amount of 480 ml/100 g and an expanded graphite with an average particle size of 500 .mu.m, kneaded by a Laboplastomill at a temperature of 180.degree. C., and press molded according to the same method as in Example 1. The VR, the shielding effect, and the Izod impact strength of the molded plate obtained were measured, and the results are shown in Table 3 in relation to each electroconductive resin composition.
TABLE 3__________________________________________________________________________ Present Invention ComparativeExperiment No. 24 25 26 27 28 29 30 31__________________________________________________________________________Electroconductive resincomposition (wt. parts)High density polyethylene resin 100 100 100 100 100 100 100 100DBP oil absorption amount 12.0 10.8 15 13 14.7 7.8 7.5 16480 ml/100 g carbon black (A)Expanded graphite 8.0 7.2 135 117 6.3 5.2 142.5 144(average particle size 500 .mu.m) (B)Carbon black A/Expanded graphite 60/40 60/40 10/90 10/90 70/30 60/40 5/95 10/90(500 .mu.m) BVolume resistivity value (.OMEGA. .multidot. cm) 2.0 .times. 10.sup.-1 9.0 .times. 10.sup.-1 3.5 .times. 10.sup.-2 4.2 .times. 10.sup.-2 2.3 .times. 10.sup.-1 8.0 .times. 10.sup.0 6.3 --*mes. 10.sup.Shielding effect in electrical field 50.6 31.1 72.2 71.4 49.9 5.9 9.5 --*of 300 MHz (dB)Izod impact strength (kg .multidot. cm/cm) 3.0 8.2 1.5 2.0 0.2 10.5 1.0 --*__________________________________________________________________________ *No sample preparation possible because kneading was impossible.
EXAMPLE 4
Different types of resins (70 parts by weight), 9 parts by weight of a carbon black with a DBP oil absorption amount of 480 ml/100 g and 21 parts by weight of an expanded graphite with an average particle size of 500 .mu.m were kneaded and press molded at a temperature shown in Table 4, to obtain a plate 15 cm square having a thickness of 2 mm. The VR and the shielding effect of the molded plate were measured, and the types of resins, kneading, and molding temperatures employed, and the measurement results, are shown in Table 4.
TABLE 4__________________________________________________________________________ Volume Shielding effect Kneading Molding resistivity in electricalExperi- Resin temperature temperature value field of 300 MHzment No (kind) (.degree.C.) (.degree.C.) (.OMEGA. .multidot. cm) (dB)__________________________________________________________________________32 ABS 200 220 2.3 .times. 10.sup.-1 48.9 (Mitsubishi Monsanto Kasei, trade name: Tuflex 710)33 Polystyrene 200 220 9.2 .times. 10.sup.-2 60.0 (produced by Idemitsu Sekiyu Kagaku, trade name: SEHI 110)34 Polybutyleneterephthalate 230 260 2.2 .times. 10.sup.-1 49.4 (Toray, trade name: PBT-1400L)35 Polyphenylene oxide 200 220 2.4 .times. 10.sup.-1 48.4 (Produced by Engineering Plastic trade name: Noryl 731J-802)36 Nylon 250 270 2.0 .times. 10.sup.1 50.1 (Produced by Du Pont, trade name: Zaitel ST801)37 Low density polyethylene 120 150 9.5 .times. 10.sup.-2 59.6 (Produced by Mitsubishi Yuka, trade name: Yukalon 2F-30)__________________________________________________________________________
EXAMPLE 5
A 70 parts by weight amount of a polypropylene resin (produced by Idemitsu Sekiyu Kagaku, trade name: J-465H), 9 parts by weight of a carbon black with a DBP oil absorption amount of 480 ml/100 g and 21 parts by weight of an expanded graphite with an average particle size of 500 .mu.m were added with additives for resins such as antioxidants for resins, UV-ray absorbers, flame retardants, reinforcing agents, lubricants, etc., shown in Table 5, and kneaded and molded according to the same method as in Example 1. The VR and the shielding effect of the molded products obtained were measured, and the types and amounts of the additives for resins employed, and the measurement results, are shown in Table 5.
TABLE 5__________________________________________________________________________Experiment No. 38 39 40 41 42 43 44Additives for resins Amount added (wt. parts)__________________________________________________________________________Pentaerythrityl-tetrakis 3-(3,5-di- 2.0 2.0 2.0 2.0 2.0 2.0 2.0tert-butyl-4-hydroxyphenyl)propiolatePhenylsalicylate 0.1 0 0 0.1 0 0.1 02-Hydroxy-4-n-octoxybenzophenone 0.1 0.2 0 0 0 0 0Trichloroethyl phosphate 0 0 0.1 0.1 0 0 0Antimony trioxide 5.0 0 0 5.0 0 0 0Decabromodiphenyl oxide 0 0 5.0 5.0 0 0 0Zinc stearate 0.5 0.5 0 0 2.0 0 2.0Ethylene bisstearoamide 0 0 0.5 0 0 0.5 0Glass fiber 0 15 0 0 15 15 0Volume resistivity value (.OMEGA. .multidot. cm) 9.9 .times. 10.sup.-2 1.3 .times. 10.sup.-1 9.9 .times. 10.sup.-2 1.2 .times. 10.sup.-1 1.3 .times. 10.sup.-1 1.2 .times. 10.sup.-1 9.6 .times. 10.sup.-2Shielding effect in electrical field 59.1 55.7 59.2 56.8 55.8 56.8 59.5of 300 MHz (dB)__________________________________________________________________________
EXAMPLE 6
A thermoplastic resin, carbon black having a DBP oil absorption amount of 480 ml/100 g, expanded graphite, antioxidants for resins, flame retardants, reinforcing agents, lubricants, and plasticizers listed in Tables 6 and 7 were formulated in an amount shown in Tables 6 and 7. The mixture was kneaded and molded in the same manner as in Example 1. The VR and the shielding effect of the molded products obtained were measured. The results are shown in Tables 6 and 7 in relation to the composition of the electroconductive resin.
TABLE 6__________________________________________________________________________Experiment No. 45 46 47 48 49 50 51 52__________________________________________________________________________Composition of electrocon-ductive resin (wt. parts)Polypropylene resin A*.sup.1 72.5 0 0 0 0 0 0 0Polypropylene resin B*.sup.2 0 72.5 0 0 0 0 0 0Polypropylene resin C*.sup.3 0 0 48 0 0 0 0 48Polypropylene resin D*.sup.4 0 0 0 48 48 36 36 0Polypropylene resin E*.sup.5 0 0 0 0 0 12 12 0Ethylene-propylene 0 0 10 10 0 10 0 0rubber A*.sup.6Ethylene-propylene 0 0 0 0 10 0 10 10rubber B*.sup.7Carbon black having DBP oil 11 11 11 11 11 11 11 9absorption amount of480 ml/100 gExpanded graphite having 16.5 16.5 16.5 16.5 16.5 16.5 16.5 21particle size 5 mmTalc 0 0 14.5 14.5 14.5 0 0 0Glass fiber 0 0 0 0 0 14.5 0 14.5Calcium carbonate 0 0 0 0 0 0 14.5 0Antioxidant for resin A*.sup. 8 1 1 0 0 0 0 0 0Antioxidant for resin B*.sup.9 0 0 1 1 1 1 1 1Ethylenebis hydrogenated 1 1 1 1 1 1 1 1tallow acid amideVolume resistivity value 1.1 .times. 10.sup.-1 1.0 .times. 10.sup.-1 1.2 .times. 10.sup.-1 1.2 .times. 10.sup.-1 1.0 .times. 10.sup.-1 1.2 .times. 10.sup.-1 1.2 .times. 10.sup.-1 1.0 .times. 10.sup.-1(.OMEGA. .multidot. cm)Shielding effect in electrical 57.3 58.8 56.4 56.0 57.5 56.2 56.1 57.3field of 300 MHz (dB)__________________________________________________________________________ *.sup.1 Karupu Kogyo K. K. 4200G *.sup.2 Karupu Kogyo K. K. 4560GF *.sup.3 Idemitsu Petrochemical Co. J5050H *.sup.4 Idemitsu Petrochemical Co. J465H *.sup.5 Idemitsu Petrochemical Co. J3066H *.sup.6 Japan Synthetic Rubber Co. EP07P *.sup.7 Japan Synthetic Rubber Co. EP912P *.sup.8 Pentaerythtyltetrakis 3(3,5-di-t-butyl-4-hydroxyphenyl)propiolate *.sup.9 Pentaerythtyltetrakis 3(3,5-di-t-butyl-4-hydroxyphenyl)propionate/Tris(2,4-di-t-butylphenyl)phophite = 50/50
TABLE 7__________________________________________________________________________Experiment No. 53 54 55 56 57 58 59 60 61 62__________________________________________________________________________Composition of Electroconductiveresin (wt. parts)6-Nylon resin A*.sup.1 47 0 0 45 0 0 0 0 0 06-Nylon resin B*.sup.2 0 47 30 0 0 0 0 0 0 06-Nylon resin C*.sup.3 0 0 20 0 0 0 0 0 0 0High-density polyethylene resin*.sup.4 0 0 0 0 64 48 0 0 0 0ABS resin*.sup.5 0 0 0 0 0 0 75 72.5 0 0PBT resin*.sup.6 0 0 0 0 0 0 0 0 47 50Carbon black having DBP oil absorption 6.9 6.9 7.5 10 10.8 11 10 8.25 6.9 10amount of 480 ml/100 gExpanded graphite having average 16.1 16.1 17.5 15 25.2 16.5 15 19.25 16.1 15particle size of 5 mm of 5 mmButyl benzyl phthalate 0 0 0 0 0 0 5 0 0 0Antioxidant for resin A*.sup.7 0 0 0 1 0 0 0 0 1 1Antioxidant for resin B*.sup.8 0 0 0 0 1 1 1 1 0 0Cuprous iodide 1 1 1 0 0 0 0 0 0 0Ethylene-propylene rubber A*.sup.9 0 0 0 0 0 10 0 0 0 0Ethylene-propylene rubber B*.sup.10 0 0 0 5 0 0 0 0 0 10Antimony trioxide 3.75 3.75 2.5 3.75 0 0 0 0 3.75 0Decabromo diphenyl ether 11.25 11.25 7.5 11.25 0 0 0 0 11.25 0Glass fiber 15 15 15 10 0 0 0 0 15 15Talc 0 0 0 0 0 14.5 0 0 0 0Ethylenebis hydrogenated tallow acid 1 1 1 0 1 1 1 1 1 1amideBenzene sulfonic acid butyl amide 0 0 0 1 0 0 0 0 0 0Volume resistivity value (.OMEGA. .multidot. cm) 1.2 .times. 1.2 .times. 1.0 .times. 1.0 .times. 8.3 .times. 1.3 .times. 1.0 .times. 1.0 .times. 1.1 1.3 .times. 10.sup.-1 10.sup.-1 10.sup.- 1 10.sup.-1 10.sup.-2 10.sup.-1 10.sup.-1 10.sup.-1 10.sup.-1 10.sup.-1Shielding effect in electrical field 56.0 56.5 58.3 58.1 61.3 54.0 57.3 57.5 57.1 54.3of 300 MHz (dB)__________________________________________________________________________ *.sup.1 Mitsubishi Chemical Co., 1007J (pellet) *.sup.2 Mitsubishi Chemical Co., 1007J (Crushed powder having a size of 100-200 .mu.m) *.sup.3 Mitsubishi Chemical Co., ST145 *.sup.4 Idemitsu Petrochemical Co., 110J *.sup.5 Japan Synthetic Rubber Co., JSR ABS 35 *.sup.6 Toray Co., PBT1400L *.sup.7 N,NHexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamide)/tris(2,4-di--butyl-phenyl)phosphite = 50/50 *.sup.8 Pentaerythtyltetrakis 3(3,5-di-t-butyl-4-hydroxyphenyl)propiolate *.sup.9 Japan Synthetic Rubber Co., EP07P *.sup.10 Japan Synthetic Rubber Co., T7741P

Number	Date	Country
0109824	May 1984	EPX
0129193	Dec 1984	EPX
51-17937	Feb 1976	JPX
60-8335	Jan 1985	JPX
60-118744	Jun 1985	JPX
61-218648	Sep 1986	JPX

Electroconductive resin composition

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