JPS58223207A - Semiconductive composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention]

This IF relates to semiconducting compositions, particularly semiconducting compositions suitable for use in electrical cables. Power couple, especially cross-linked poly-1-J1 non-insulating case 1
Traditionally, cloth tape coated with a semiconductive composition has been used for semiconductive bamboo waste. However, semi-conductive hook-and-loop tape does not easily absorb moisture, and also causes fluff, so it cannot be used at the interface with the insulator.
? Nf! Due to the lack of I, there is a problem that this interfacial irregularity causes water leakage and electricity generation, and in order to solve this problem, an extruded semiconductive layer was developed. There are two types of layers for the extrusion mold 21': a crosslinked semiconductive bamboo waste layer and a non-crosslinked semiconductive 111 layer. ^77 Generally, ethylene/vinyl acetate copolymer, -[
Bren・]-Til Acryl No I11. By using such a low melting point, low viscosity polymer as a hese polymer, extrusion at low temperatures is possible, and processability is excellent. However, it is necessary to perform crosslinking after molding to maintain shape at high temperatures, and it is necessary to consider the balance between the crosslinking speed of the insulator and the crosslinking speed of the semiconductive layer when manufacturing the couple. The latter is a mixture of ethylene rubber and poly(11) tyrene, and this polymer has a high melting point, so it has to be crosslinked to form a shape at high temperatures. Retention is achieved and basebolin is non-(
Because it is published separately, it has properties such as water absorption or small size. However, due to the large intermolecular size of -1-brene propylene gol, the viscosity fα of the forming part is high, and high temperature extrusion of close to 200°C is required, which poses some obstacles to the production of 111 clay. Based on the above, this book was made/1, and the molding agent at low temperature (4'1.7: non-crosslinked 111 half-9 electric wire 11 silk composition a5 and the use of this) In other words, the semiconducting f!I composition of the present invention is one
α-olefin/polyene copolymer rubber and medium-low IT-FA poly-I with a null of 1 to 1 or more
A mixture of 100 parts of Blen, conductive ("I
In the present invention, ethylene/α-Δ-ref/polyene copolymer rubber contains ethylene and a carbon atom having 4 to 4 carbon atoms. 10 α-
The density obtained by continuous polymerization of olefins and polyenes under a specific condition (i) is 0.88 to 0.91 ("il/c
I will be happy if you give me m3). That is, for example, VO(OR)nx3-n as a catalyst
(However, 1.1<(Yofatty rib hydrocarbon group, × is halogen, O≦n≦3) - is a hydrocarbon star; It is obtained by continuously polymerizing ethylene and a polyene such as an α-olefin having 4 to 10 carbon atoms at a temperature of 40 to 100°C in the presence of poly-In hydrogen in a solvent. Ratio to 75/
25 to 9515, the obtained ethylene
The α-olefin/polyene copolymer rubber is in the form of pellets, making it easier to handle later. ] If the distance between dilene is below this range, it will be difficult to form pellets from 1 to 1, and if it exceeds this range, the 1 and 1 qualities of the rubber will tend to be lost. The melt index (M I
) is 1 (y/10 minutes) or more. Here, the α-olefin has three or more carbon atoms, such as propylene, budene-1, and octene-1,4-methylpentene-1. In addition, when IVII is less than 1, the viscosity of the semiconductive composition formed in one pot becomes high, and moldability becomes poor. 4- The mixing ratio of medium and low pressure polyethylene to the ethylene/α-olefin/polyene copolymer rubber must be 20 to 50% by weight. If C is less than 20% by weight, the appearance of the extruded cloth will be poor, and if it exceeds 50% by weight, the elasticity will be lost and elongation will be poor. The present invention

[Puru conductivity] Typical 'tK' products include carbon black, such as Brennell black, furnace black, and A1? Well-known ones such as Diren Black are used. Conductive f! L (during the addition of H, it is necessary to add 40 parts by weight or more to 100 parts by weight of the above-mentioned mixture in order to obtain the desired conductivity. M2+4(1
50°C) is preferably 30 to 60; if it is less than 30, the heat deformation resistance will be poor, and if it exceeds 60, the extrusion property will be poor at low pressure. The preparation of a semiconductive composition is conventionally carried out by mixing necessary additives such as an anti-aging agent in the preparation of a composition. N.
I-1~limethyl-1,2-dihydro1]4-noline)I1 is 71-nol-based 2,2゛-methylenebis(/l
-Methyl-6-tert-butylphenol, 2.
6-tert-dityl-1-meJrufuJnor, 4
,4-diAbis(6-tert-butyl-3-methylphenol) etc. are imidazole-based 2-mercar-1
1 to penzimitazole, 2-mercap 1 to qh lead salts of benzimidazole, and other anti-aging agents used for rubber etc. 1. Thus, 14) the resulting semiconductive composition satisfies the properties of the conventional semiconductive composition based on 1-Chiresieve [-1 pyrene rubber], and also has low performance (specifically, 150 to 160°C) with excellent extrusion moldability. From this point of view, the semiconductive f4 composition of the present invention can be used for electric cables, connection parts and terminal parts of electric cables, and electrostatic shields +ATj of electronic equipment and communication cables, and in particular for the inside and outside of electric cables, 1′ conductivity f! What is the preferred layer? Examples of the present invention will be explained below by comparing them with comparative examples. The compounds shown in the upper column of Table 1 were kneaded for 10 minutes at a resin temperature of 15°C using a 6-inch rubber kneader, and then mixed into semiconductive sheets 1 to 1 mm thick. The properties of these semiconductive sheets are shown in the lower part of Table 1. Judgment was made based on the appearance of the string.A sheet-shaped molded product was used to measure the Togi-Mouni viscosity.
In addition, the extrusion string I ~ land string is a sheet-shaped molded product, one-loss pelletizer, C pellets 1 ~, 40 mm tilli.
111k by passing l:j lX, lt. For extrusion, a metering-type scrico with l-, / l) = 22 and compression ratio of 3.5 was used, the rotation speed was 20 rrlm, and the die temperature was [7-].
To measure volume resistivity, water absorption, and thermal deformation at 0°C,
180℃, 100Kg using a press molding machine
/ci, 10 minutes of forming strip f1 to press sheets of 1 mm for the first two and 3 mm for the latter 8, and serve them.1. :. Measurement of volume resistivity is 30 m+ vertically from press sea 1~
, cut out a rectangular sea 1 ~ with a width of 100 mm, and create a rectangular sea 1
Make electrodes by applying conductive paint to both ends of the
0" C was measured. The water absorption rate was measured from press sea 1 to 50 mm in length and 80 mm in width.
Cut out a rectangular sheet 1~ of mm and place it in lake water at 90℃? Soaking-C was left until the water absorption amount was saturated, and calculations were made from the change in labor before and after soaking in oil. The heating deformation rate is 120° (] in accordance with JIS-0305.
's warm If r ill! I decided. The elongation was measured in accordance with JIS-C3005 at a tensile temperature of 200 breaths/min. 8-jsu-1 I was able to explain [Do7J11 etc. clearly 41 ways,
In the present invention, the conventional l-1) rm-based extrusion part Jl cross-linked semi-electrode 1'composition's shortcoming C was low extrusion processing] IIl was carried out in Kaiura, and qiHIJ electric power Rippu 21
Receiving telephone number 171 is like a silk product. 1. Procedural amendment (voluntary) 57.! 5.21 Showa D Month 14 Director General of the Patent Office Haruki Shimada 1982 Patent Application No. 106466 2 Title of the invention Semiconducting composition 3 Person making the amendment 4 Agent 〒】00 Location 2-1-2 Marunouchi, Chiyoda-ku, Tokyo Telephone: Tokyo (21G) 1611 (main representative) 11- Detailed explanation of the invention in the specification to be amended. The entire text from page 11 of the Specification of Contents of the Amendment is deleted and the following text is corrected. The results obtained from the test are shown in Table 1. Example 1.2 is a composition in which Melt Intex MI 5.0 ethylene-α-olefin polyene copolymer comb and Melt Intex MI 1.8 medium-low pressure polyethylene are blended and subjected to the blending treatment specified in the present invention. This is an example of a thing. The extrudability at 150°C was good, and the volume resistivity, water absorption rate, and thermal deformation rate all showed excellent values as a semiconducting layer for an electric cable. Example 6.4 is a blend of Melt Intex MI 4.0 medium and low pressure polyethylene. Viscosity is reduced and extrudability is improved. Other properties are also good. Although the heating deformation rate increases slightly, this does not pose a practical problem. Examples 5 and 6 were Melt Intex MI 1 o, 0
This is an example using an ethylene/a-olefin-polyene copolymer rubber, and the viscosity is lower and the extrusion processability is improved compared to the example with ■φI5.0. Comparative Example 1.2 has a melt index M that is not specified in the present invention.
This is an example using medium-low pressure polyethylene with I.
Mouni viscosity is high and the extrusion appearance at 150°C is poor. Comparative Examples 6 and 4 are examples in which the blend ratio of medium and low pressure polyethylene was outside the scope of the present invention. When the blend amount of medium-low pressure polyethylene is small as in Comparative Example B, the extruded appearance is poor and the heat deformation rate is large, which causes practical problems. When the amount of blending is large as in Comparative Example 4, the elongation becomes small. Comparative Example 5 is a case where the amount of carbon black is outside the specification of the present invention, and the volume resistivity is high and the heating deformation is large, which causes a practical problem. Comparative Examples 6 and 7 are conventional examples in which ethylene/propylene rubber was used. The viscosity at 150'c was extremely high and extrusion processing was not possible. As is clear from the above explanation, according to the present invention, extrusion processability at low temperatures, which was a drawback of conventional GP rubber-based extrusion-type non-crosslinked semiconducting compositions, can be improved, and in particular, semiconductive compositions for electrical cables can be improved. It is an excellent conductive composition. ” d=4-146--

Claims (1)

[Claims] 11-Dylene/α-A renoin/polyene copolymer rubber with a melt index of 1 or more, and a mixing ratio of 11 (Jf process polyethylene J-rinari, medium/low pressure process poly)-tyrene is 20 ~50@i1% mixture 100w ih
1. A semiconductive composition characterized by adding 10 parts or more of conductive NJ LJ to 1 part of C. 2 - Note 2 [Small synthetic rubber containing thylnon, α-olefin, and polyethylene is composed of α-olefin and polyene having 4 to 10 carbon atoms such as 1-dylene, and J-dylene and α-olefin. - The semiconductive composition according to item 1, characterized in that the molar ratio of the olefin is 75/25 to 95/Fi. 3) The medium-low pressure poly-f-tyrene of
Renoin JL small engagement body and α-olefin 1
Special 8'1 characterized by having a large cable number of 31 meters C.
Claim 1 or Iζ is the semiconductive composition according to claim 2. 4. 1. The half-cuff 11f according to claim 1(4), 2(2) or 31(f4), characterized in that it is made of electrically conductive carbon black. ft composition.
150'C) is 30-60C.Semiconducting f No. 1 composition 3 according to the range 1, 2, 3 or 1 of the special edition request,