JPH1153943A - Cable part - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cable part having superior electrical and magnetic properties in electric field decentralization, electrical stress reduction, corona discharge prevention, and electromagnetic wave sealing properties and their superiority in heat resistance, flame-retardan, water resistance, air tightness, and rigidity. SOLUTION: This cable part comprises a polyarylenesulphide resin composition containing (A) 49 to 90 wt.% of polyarylenesulphide of 25 Pa.s or more in molten viscosity measured at 310 deg.C and at a shear speed of 1200/sec, (B) 3 to 6 wt.% of a conductive carbon black, (C) 2 to 10 wt.% of graphite of 60 μm or less in average particle size, and (D) 5 to 35 wt.% of an α-olefinic copolymer containing an epoxy group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a cable component, and more particularly, to a cable component obtained by using a polyarylene sulfide resin composition having a controlled volume resistivity. The cable component of the present invention has excellent electrical and magnetic properties such as electric field concentration mitigation, electric stress mitigation, corona discharge prevention, antistatic and electromagnetic wave sealing properties, as well as heat resistance, weather resistance, and flame retardancy. ,Waterproof,
The present invention relates to a cable component having excellent airtightness and toughness.

[0002]

2. Description of the Related Art Various types of cables such as power cables (electric cables) and power lines (electric wires) include, for example, electric wire clamps, electric wire spacers, connectors, connecting parts, connecting part reinforcements, connecting part protectors, and stress cones. Many components are used, such as spiral rods, electric field relaxation tubes, sleeves, and sleeve covers. In addition to the shape and function required for each component, these cable components include, for example, electric field concentration relief, electrical stress relief,
It is often required to have electrical and magnetic properties such as corona discharge prevention, antistatic and electromagnetic wave sealing properties.
In addition, since cable parts are often used outdoors, they are required to have various properties such as heat resistance, weather resistance, flame retardancy, waterproofness, and airtightness.

[0003] Conventionally, in addition to insulators (hard porcelain) and metals, polymer materials such as synthetic rubbers, epoxy resins, cross-linked polyethylene resins, and fluororesins have been used alone or as materials for various cable parts. Used in combination with various materials. For example, JP-A-8-2271
No. 6 proposes using a high dielectric constant insulating rubber composition obtained by blending furnace carbon black with ethylene propylene rubber or ethylene propylene diene rubber for a stress cone forming an intermediate connection portion or a terminal connection portion of a power cable. Have been. Japanese Patent Application Laid-Open No. 8-149675 describes that a bushing for protecting an electrical connection portion of a terminal of a high-voltage cable with a device or the like is formed by molding an epoxy resin. JP 8
Japanese Patent Publication No. 223763 discloses a connection portion of a power cable having an outer semiconductive layer and an inner semiconductive layer made of a crosslinked or uncrosslinked conductive rubber, and an insulating layer made of a crosslinked or uncrosslinked insulating rubber / plastic. A stiffener is disclosed.

Japanese Patent Application Laid-Open No. Hei 8-275366 proposes that a connection point between a high-voltage cable terminal and an insulated wire be covered with a protective member made of fluororesin. JP-A-8-2
No. 80128 discloses that a sleeve attached to a connection portion of an overhead electric wire is covered with a linear sleeve cover made of polyethylene resin colored black. JP-A-9-9472 and JP-A-9-103023 disclose an electric wire spacer having a structure in which a reinforced plastic core is covered with synthetic rubber. JP-A-9-23
Japanese Patent Application Publication No. 562 proposes that an electric field relaxation tube used for a tube-shaped terminal connection portion of a power cable is formed of a high dielectric silicon rubber tube having a semiconductive layer formed on an inner surface. JP-A-9-111089 discloses that an outer semiconductive layer of a crosslinked polyethylene insulated power cable is made of a semiconductive composition obtained by blending oil furnace carbon black and an antioxidant with a styrene-modified ethylene-vinyl acetate copolymer. It has been proposed to form. Japanese Patent Application Laid-Open No. 9-168223 proposes a joint end portion of a spiral rod. In this publication, a spiral rod that is wound around an overhead electric wire to prevent wind noise and snow accumulation is made of a metal material, nylon, or the like. It is disclosed to be formed of a synthetic resin or a composite material in which a metal material is wrapped with a synthetic resin.

However, conventional polymer materials used in the field of cable parts do not sufficiently satisfy various properties such as heat resistance, weather resistance and flame retardancy. In addition, cable parts must have intermediate conductivity (called semi-conductivity) between metal and polymer materials from the viewpoint of antistatic properties, electromagnetic wave sealing properties, corona discharge preventing properties, etc. However, it is difficult to stably obtain a desired semiconductivity with a conventional polymer material. On the other hand, polyarylene sulfide (hereinafter abbreviated as PAS) represented by polyphenylene sulfide (hereinafter abbreviated as PPS)
Is an engineering plastic excellent in heat resistance, flame retardancy, chemical resistance, dimensional stability, mechanical properties, and the like, and is widely used as electric / electronic parts, precision equipment parts, automobile parts, and the like. However, a resin composition in which conductive particles are blended with PAS has a large variation in electric resistance (volume resistivity) in a semiconductive region, and mechanical properties are also reduced. When the electric resistance is made lower, the variation of the electric resistance is reduced, but the deterioration of the mechanical properties is further increased.

Conventionally, in order to solve these problems, for example, a PPS resin composition (JP-B-5-86982) in which (1) PPS is blended with conductive carbon black, natural scale graphite, and an inorganic filler. Publication), (2) PA
S, preferably an electrically conductive composition (JP-A-1-272665) in which conductive carbon black, graphite, and a filler are blended with PPS. (3) PPS and carbon black are dispersed in a polymer binder resin. (4) A conductive resin composition comprising (4) a thermoplastic resin such as PPS mixed with a conductive carbon rack, graphite, and polytetrafluoroethylene which can be fibrillated (Japanese Patent Application Laid-Open No. 3-91556). , (5) a conductive resin masterbatch pellet in which conductive carbon black and artificial graphite are blended in a thermoplastic resin such as PPS, and a conductive thermoplastic resin product in which this is blended in a thermoplastic resin (Japanese Patent Laid-Open No. 7-286103) and the like.

[0007] By blending conductive carbon black and graphite in PAS, the electrical resistance can be reduced. However, conventional conductive PAS resin compositions generally have low toughness typified by tensile elongation at break (tensile elongation at break) and cannot be used in fields requiring high toughness. In addition, conventional conductive PAS
The resin composition has a large variation in volume resistivity, and it has been difficult to obtain a resin composition having a desired volume resistivity with good reproducibility. As described above, the PAS resin is excellent in various properties such as heat resistance, weather resistance, and flame retardancy, and has good electrical properties. There are many points to be improved such as having toughness and stably achieving a desired volume resistivity.

[0008]

An object of the present invention is to provide a PA
Using a resin composition containing an S resin, electric field concentration relaxation,
In addition to excellent electrical and magnetic properties such as electrical stress relaxation, corona discharge prevention, antistatic, electromagnetic wave sealing,
An object of the present invention is to provide a cable component excellent in heat resistance, weather resistance, flame retardancy, waterproofness, airtightness, toughness, and the like. The present inventors have conducted intensive studies to overcome the problems of the prior art. As a result, PAS having a specific melt viscosity was added to conductive carbon black, graphite having an average particle size of 60 μm or less, and α- By blending the olefin-based copolymer at a specific ratio, the volume resistivity is 10 ³ to 10 ¹³ Ωcm.
Can be controlled with good reproducibility at any point in the range, and the tensile elongation at break is 10% or more, and the toughness is excellent.
It has been found that a resin composition that can be injection molded or extruded can be obtained. Using this resin composition, cable parts such as electric wire clamps, electric wire spacers, connectors, connection parts, connection part reinforcements, connection part protectors, stress cones, spiral rods, electric field relaxation tubes, sleeves, and sleeve covers. As a result, it was found that they exhibited excellent electrical and magnetic properties and were excellent in heat resistance, weather resistance, flame retardancy, waterproofness, airtightness, toughness and the like. The present invention has been completed based on these findings.

[0009]

According to the present invention, (A)
Polyarylene sulfide having a melt viscosity of 25 Pa · s or more measured at 310 ° C. and a shear rate of 1200 / sec.
0% by weight, (B) 3 to 6% by weight of conductive carbon black, (C) 2 to 10% by weight of graphite having an average particle size of 60 μm or less, and (D) an epoxy group-containing α-olefin copolymer 5-35. Provided is a cable component comprising a polyarylene sulfide resin composition containing 0.1% by weight. Hereinafter, the present invention will be described in detail.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Polyarylene sulfide (PAS) The PAS used in the present invention is an arylene sulfide represented by the formula [-Ar-S-] (where -Ar- is an arylene group). An aromatic polymer having a repeating unit as a main component. When [-Ar-S-] is defined as 1 mol (basic mol), the PAS used in the present invention is
Is a polymer containing this repeating unit in an amount of usually at least 50 mol%, preferably at least 70 mol%, more preferably at least 90 mol%. As an arylene group, for example,
p-phenylene group, m-phenylene group, substituted phenylene group (the substituent is preferably an alkyl group having 1 to 6 carbon atoms,
Or a phenyl group. ), P, p'-diphenylenesulfone group, p, p'-biphenylene group, p, p'-diphenylenecarbonyl group, naphthylene group and the like. As the PAS, a polymer having mainly the same arylene group can be preferably used, but from the viewpoint of processability and heat resistance, a copolymer containing two or more arylene groups can also be used.

Among these PASs, PPS having a repeating unit of p-phenylene sulfide as a main constituent element
However, it is particularly preferable because it has excellent workability and is easily available industrially. In addition, polyarylene ketone sulfide, polyarylene ketone ketone sulfide, and the like can be used. Specific examples of the copolymer include a random or block copolymer having a repeating unit of p-phenylene sulfide and m-phenylene sulfide, a random or block copolymer having a repeating unit of phenylene sulfide and a repeating unit of arylene ketone sulfide, phenylene sulfide And a random or block copolymer having a repeating unit of arylene ketone ketone sulfide and a repeating unit of phenylene sulfide and arylene sulfone sulfide. These PASs are preferably crystalline polymers. PAS is preferably a linear polymer from the viewpoint of toughness and strength.

Such a PAS is prepared by a known method (for example, JP-B-63-3377) in which a polymerization reaction of an alkali metal sulfide and a dihalogen-substituted aromatic compound is carried out in a polar solvent.
No. 5). Examples of the alkali metal sulfide include lithium sulfide, sodium sulfide,
Examples thereof include potassium sulfide, rubidium sulfide, and cesium sulfide. Sodium sulfide or the like generated by reacting NaSH and NaOH in the reaction system can also be used. Examples of the dihalogen-substituted aromatic compound include, for example, p-dichlorobenzene, m-dichlorobenzene, 2,5-dichlorotoluene, p-dibromobenzene, 2,6-dichloronaphthalene, 1-methoxy-
2,5-dichlorobenzene, 4,4'-dichlorobiphenyl, 3,5-dichlorobenzoic acid, p, p'-dichlorodiphenylether, 4,4'-dichlorodiphenylsulfone, 4,4'-dichlorodiphenylsulfoxide,
4,4'-dichlorodiphenyl ketone and the like can be mentioned. These can be used alone or in combination of two or more.

A small amount of a polyhalogen-substituted aromatic compound having three or more halogen substituents per molecule can be used in order to introduce a slight branched or cross-linked structure into the PAS. Preferred examples of the polyhalogen-substituted aromatic compound include 1,2,3-trichlorobenzene,
1,2,3-tribromobenzene, 1,2,4-trichlorobenzene, 1,2,4-tribromobenzene, 1,
Examples thereof include trihalogen-substituted aromatic compounds such as 3,5-trichlorobenzene, 1,3,5-tribromobenzene, and 1,3-dichloro-5-bromobenzene, and alkyl-substituted products thereof. These can be used alone or in combination of two or more. Among these, 1,2,4-trichlorobenzene, 1,3,3
5-Trichlorobenzene and 1,2,3-trichlorobenzene are more preferred. Examples of the polar solvent include N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) and the like.
Aprotic organic amide solvents typified by alkylpyrrolidone, 1,3-dialkyl-2-imidazolidinone, tetraalkylurea, hexaalkylphosphoric triamide, etc., have a high stability of the reaction system and are easy to obtain a high molecular weight polymer. preferable.

The melt viscosity of the PAS used in the present invention (31)
0 ° C., shear rate 1200 / sec) is 25 Pa · s or more,
Preferably at least 50 Pa · s, more preferably 80 Pa
-It is s or more. If the melt viscosity of PAS is too small, it is difficult to increase the tensile elongation at break, and other mechanical properties may be insufficient. The melt viscosity of PAS is
Usually 25 to 600 Pa · s, preferably 50 to 400
Pa · s, more preferably 80 to 300 Pa · s. The mixing ratio of PAS is 49 to 90 based on the total amount of the composition.
%, Preferably 55 to 85% by weight, more preferably 60 to 80% by weight. If the blending ratio of PAS is too small, the mechanical strength is reduced, and it is difficult to exhibit various PAS intrinsic properties such as heat resistance, flame retardancy, and chemical resistance. If the proportion of PAS is too large, it is difficult to reduce the volume resistivity to a desired level.

Conductive Carbon Black In the present invention, conductive carbon black is blended in order to control the volume resistivity of the PAS resin within a desired range.
The conductive carbon black has a DBP oil absorption of 36.
It is preferably 0 ml / 100 g or more. The DBP oil absorption of the conductive carbon black is measured by a method specified in ASTM D2414. That is, the measuring device (Ab
A carbon black is placed in a sorpometer chamber, and DBP (n-dibutyl phthalate) is added at a constant rate into the chamber. DBP
As it absorbs, the viscosity of the carbon black increases,
From the amount of DBP absorbed by the time it reaches a certain
Calculate the P oil absorption. The viscosity is detected by a torque sensor. If the DBP oil absorption of the conductive carbon black is too small, it is necessary to incorporate a large amount of the conductive carbon black in order to reduce the electrical resistance of the PAS resin composition to a desired level. It is not preferable because the physical properties are impaired. The upper limit of the DBP oil absorption of the conductive carbon black is not particularly limited, but is usually 750 ml / 100 g or less for convenience in production. The DBP oil absorption is more preferably from 400 to 60.
It is 0 ml / 100 g.

The mixing ratio of the conductive carbon black is 3 to 6% by weight, preferably 4 to 5% by weight based on the total amount of the composition.
It is. By adjusting the compounding ratio of the conductive carbon black within a limited range, the balance between physical properties such as volume resistivity, strength, and elongation is improved. When the conductive carbon black is added in a large proportion, the resin composition causes a rapid decrease in electric resistance, and it is difficult to control the conductive carbon black alone to a desired volume resistivity with good reproducibility. It is. In addition, it is particularly difficult to reproduce sufficient elongation in the region where the volume resistivity is 10 ⁵ Ωcm or less by using the conductive carbon black alone.

Graphite In the present invention, the average particle size is 60 μm or less, preferably 30 μm.
m or less, more preferably 15 μm or less. If the average particle size of graphite is too large, the electrical resistance tends to decrease, but the tensile elongation at break decreases. As the graphite, natural graphite such as artificial graphite, flake graphite, scale graphite, and earth graphite obtained by graphitizing coke, tar, pitch and the like at a high temperature can be used. The compounding ratio of graphite is 2 to 10% by weight, preferably 2 to 6% by weight based on the total amount of the composition. By using graphite in combination with the conductive carbon black in this range, the volume resistivity of the resin composition can be easily and stably reduced to a desired level.

Epoxy Group-Containing α-Olefin Copolymer The epoxy group-containing α-olefin copolymer used in the present invention comprises at least a repeating unit derived from α-olefin (that is, α-olefin unit) and a glycidyl group. Repeating units derived from the unsaturated monomer containing (ie,
(Glycidyl group-containing unsaturated monomer unit). Representative examples of the epoxy group-containing α-olefin copolymer include (1) a copolymer of an α-olefin and a glycidyl group-containing unsaturated monomer, and (2) a copolymer of an α-olefin and a glycidyl group-containing unsaturated monomer. A graft precursor obtained by polymerizing at least one vinyl monomer and a radical (co) polymerizable organic peroxide in the presence of a copolymer with a monomer can be exemplified. The grafting precursor may be grafted at the time of melt-kneading with other components, or may be melt-kneaded and grafted before blending with other components.

As the copolymer of an α-olefin and a glycidyl group-containing unsaturated monomer, besides a binary copolymer of both, an α-olefin, a glycidyl group-containing unsaturated monomer and another unsaturated monomer are used. A ternary or more multi-component copolymer with a monomer unit is also included. The α-olefin unit in the copolymer is usually 50 units.
-99.5% by weight, preferably 60-99% by weight, more preferably 70-98% by weight. The content of the glycidyl group-containing unsaturated monomer unit is usually 0.5 to 50% by weight, preferably 1 to 40% by weight, more preferably 2 to 30% by weight. Other unsaturated monomer units are usually 0 to 40% by weight,
Preferably it is 0 to 30% by weight, more preferably 0 to 20% by weight. The polymerization form of the epoxy group-containing α-olefin copolymer may be any of a random copolymer, a block copolymer, a graft copolymer, and the like.

Examples of the α-olefin monomer include ethylene, propylene, 1-butene, 1-hexene, 1-octene and 4-methyl-1-pentene. Of these, ethylene is particularly preferably used. Can be As the glycidyl group-containing unsaturated monomer, for example, glycidyl acrylate, glycidyl methacrylate, monoglycidyl itaconate, monoglycidyl butenetricarboxylate, diglycidyl butenetricarboxylate, triglycidyl butenetricarboxylate, maleic acid Glycidyl esters such as monoglycidyl ester, crotonic acid monoglycidyl ester and fumaric acid monoglycidyl ester; glycidyl ethers such as vinyl glycidyl ether, allyl glycidyl ether, glycidyloxyethyl vinyl ether, styrene-p-glycidyl ether; p-glycidyl styrene And the like. Among these, α, β-
It is a glycidyl ester of an unsaturated acid.

Other unsaturated monomers include, for example, vinyl ester monomers such as vinyl acetate and vinyl propionate, vinyl ether monomers, and vinyl aromatic monomers such as (meth) acrylonitrile, styrene and α-methylstyrene. Monomers, carbon monoxide and the like can be mentioned. Specific examples of the copolymer of an α-olefin and a glycidyl group-containing unsaturated monomer include ethylene / glycidyl methacrylate copolymer, ethylene / vinyl acetate / glycidyl methacrylate copolymer, ethylene / ethyl acrylate / Glycidyl methacrylate copolymer, ethylene / glycidyl acrylate copolymer, ethylene / vinyl acetate / glycidyl acrylate copolymer and the like can be mentioned. Preferred among these are ethylene / glycidyl methacrylate copolymer, ethylene / ethyl acrylate / glycidyl methacrylate copolymer, and ethylene / vinyl acetate / glycidyl methacrylate copolymer. These copolymers can be used alone or in combination of two or more.

The copolymer of the above-mentioned α-olefin and the glycidyl group-containing unsaturated monomer is composed of 50 to 9 α-olefins.
9.5% by weight, glycidyl group-containing unsaturated monomer 0.5 to 0.5%
50% by weight and a monomer mixture containing 0-40% by weight of other unsaturated monomers, the presence of 0.0001-1% by weight, based on the total weight of all monomers, of a radical polymerization initiator It can be obtained by high-pressure polymerization under the following conditions. The polymerization pressure is usually 5 to 40 kPa, preferably 10 to 35 kPa
It is. The reaction temperature is usually 50 to 400C, preferably 100 to 350C. Under these reaction pressure and reaction temperature conditions, in the presence of a chain transfer agent and, if necessary, an auxiliary,
A polymerization reaction is carried out by a method of contacting and polymerizing the monomer mixture simultaneously or stepwise.

Examples of the radical polymerization initiator include general-purpose initiators such as peroxides, hydroperoxides, azo compounds, amine oxide compounds, and oxygen. As the chain transfer agent, methane, ethane, butane, isobutane, n
-Saturated aliphatic hydrocarbons such as hexane, n-heptane and chloroform, and halogen-substituted hydrocarbons thereof; saturated aliphatic alcohols such as methanol, ethanol, propanol and isopropanol; saturated aliphatic carbonyl compounds such as acetone and methyl ethyl ketone; Aromatic compounds such as diethylbenzene and xylene; and hydrogen. When the α-olefin is not propylene or 1-butene, these can also be used in combination as a chain transfer agent.

It is obtained by polymerizing at least one vinyl monomer and a radical (co) polymerizable organic peroxide in the presence of a copolymer of an α-olefin and a glycidyl group-containing unsaturated monomer. The grafting precursor is described in, for example,
No. 131220, JP-A-1-138214,
It is a known one disclosed in Japanese Patent Application Laid-Open No. 2-129245. The grafting precursor is 100 to 3
It is easily grafted by heating to 00 ° C. Grafting refers to a copolymer of an α-olefin and a glycidyl group-containing unsaturated monomer, in which a polymer of a vinyl monomer is subjected to a grafting reaction, a crosslinking reaction, and a mixed reaction of these.
It means chemically bonding. The fact that they are chemically bonded can be revealed, for example, by the fact that two (co) polymers cannot be separated by a solvent that dissolves one (co) polymer. The copolymer of the α-olefin and the glycidyl group-containing unsaturated monomer also includes a terpolymer or higher copolymer obtained by copolymerizing another unsaturated monomer, as described above.

The proportion of the copolymer of the α-olefin and the glycidyl group-containing unsaturated monomer in the grafting precursor is usually 5 to 95% by weight, preferably 20 to 90% by weight. If the proportion of this copolymer is too small, the compatibility with PAS becomes insufficient, while if it is too large, the heat resistance and dimensional stability of the resin composition may be reduced. The proportion of the glycidyl group-containing unsaturated monomer unit in the copolymer is usually 0.5 to 50% by weight, preferably 1 to 40% by weight, more preferably 2 to 30% by weight. When the glycidyl group-containing unsaturated monomer unit is contained in the polymer of the vinyl monomer, the ratio of the glycidyl group-containing unsaturated monomer unit in the copolymer is determined according to the copolymerization ratio. Can be reduced.

The vinyl monomer used for producing the grafting precursor includes, for example, vinyl aromatic monomers such as styrene, α-methylstyrene, chlorostyrene, etc .; (Meth) acrylic ester monomers such as alkyl esters of 7; glycidyl ester monomers of α, β-unsaturated acids; unsaturated nitrile monomers such as (meth) acrylonitrile; vinyl esters such as vinyl acetate And the like. Among these,
It is preferable that the main component be any of a glycidyl ester monomer of an α, β-unsaturated acid, a vinyl aromatic monomer, and an unsaturated nitrile monomer. In addition, (meth) acrylic acid represents acrylic acid or methacrylic acid.

A copolymer of an α-olefin and a glycidyl group-containing unsaturated monomer is polymerized with a vinyl monomer polymer by a grafting reaction, a cross-linking reaction, or a mixture of these, and contains an epoxy group-containing epoxy group. The α-olefin-based copolymer can be obtained by copolymerization by a chain transfer method, an ionizing radiation irradiation method, or the like. Most preferably, however, the grafting precursor is a radical (co) polymerized such as t-butyl peroxymethacryloyloxyethyl carbonate in the presence of a copolymer of an α-olefin and a glycidyl group-containing unsaturated monomer. It can be obtained by (co) polymerizing at least one kind of vinyl monomer using a volatile organic peroxide.

More specifically, in order to produce the grafting precursor, an aqueous suspension obtained by suspending 100 parts by mass of a copolymer of an α-olefin and a glycidyl group-containing unsaturated monomer in water is used. Prepare. On the other hand, at least one kind of radical (co) is added to 5 to 400 parts by weight of at least one kind of vinyl monomer.
0.1 to 10 parts by weight of a polymerizable organic peroxide with respect to 100 parts by weight of a vinyl monomer, and a radical polymerization initiator having a decomposition temperature of 40 to 90 ° C. for obtaining a half-life of 10 hours. A solution is prepared by dissolving 0.01 to 5 parts by weight with respect to a total of 100 parts by weight of the monomer and the radical (co) polymerizable organic peroxide. The solution is added to the aqueous suspension, and the mixture is heated under a condition that decomposition of the radical polymerization initiator does not substantially occur, and a vinyl monomer, a radical (co) polymerizable organic peroxide, and a radical polymerization initiator are added. Is impregnated with a copolymer of an α-olefin and a glycidyl group-containing unsaturated monomer, and then the temperature of the aqueous suspension is increased to obtain a vinyl monomer and a radical (co) polymerizable organic peroxide. Are copolymerized in the copolymer to produce a grafted precursor.

The grafting precursor is 100 to 300
When kneaded under melting at a temperature of ℃ C, an epoxy group-containing α-olefin copolymer having a structure in which a copolymer of an α-olefin and a glycidyl group-containing unsaturated monomer and a polymer of a vinyl monomer are chemically bonded. A polymer can be obtained. The grafting precursor may be grafted when melt-kneaded with PAS and other components. Preferably, an epoxy group-containing α-olefin copolymer having a structure in which a copolymer of an α-olefin and a glycidyl group-containing unsaturated monomer and a polymer of a vinyl monomer are chemically bonded in advance is prepared. And this is PA
Melt and knead with S and other components. Examples of the radical (co) polymerizable organic peroxide used in the production of the grafting precursor include a compound represented by the following formula (1).

[0030]

Embedded image [Wherein, R ₁ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R ₂ is a hydrogen atom or a methyl group, R ₃ and R
₄ is an alkyl group having 1 to 4 carbon atoms, R ₅ is an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkyl-substituted phenyl group, or a cycloalkyl group having 3 to 12 carbon atoms, and m is 1 or 2. ] The compound represented by this can be mentioned. Another example of the radical (co) polymerizable organic peroxide is a compound represented by the following formula (2).

[0031]

Embedded image Wherein R ₆ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₇ is a hydrogen atom or a methyl group, R ₈ and R
₉ is an alkyl group having 1 to 4 carbon atoms, R ₁₀ is an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkyl-substituted phenyl group, or a cycloalkyl group having 3 to 12 carbon atoms, and n is 1 or 2. ]

Examples of the radical (co) polymerizable organic peroxide represented by the above formula (1) include t-butylperoxy (meth) acryloyloxy (ethoxy) ethyl carbonate and t-amylperoxy (meth) allylloyxy (ethoxy). Ethyl carbonate, t-hexylperoxy (meth) acryloyloxy (ethoxy) ethyl carbonate, cumylperoxy (meth) acryloyloxy (ethoxy) ethyl carbonate, p-isopropylperoxy (meth) acryloyloxy (ethoxy) ethyl carbonate and the like can be exemplified. . As the radical (co) polymerizable organic peroxide represented by the formula (2),
Examples thereof include t-butyl peroxy (meth) allyl carbonate, cumyl peroxy (meth) allyl carbonate, t-butyl peroxy (meth) allyloxyethyl carbonate, and the like.

Of these, preferred are t-butyl peroxyacryloyloxyethyl carbonate, t-butyl
-Butyl peroxymethacryloyloxyethyl carbonate, t-butyl peroxyallyl carbonate, t-
Butyl peroxyallyl carbonate and t-butyl peroxymethacrylic carbonate. The mixing ratio of the epoxy group-containing α-olefin copolymer is 5 to 35% by weight, preferably 9 to 34% by weight, based on the total amount of the composition.
More preferably, it is 14 to 20% by weight. If the compounding ratio is too small, the tensile elongation at break becomes insufficient and brittle fracture easily occurs. If this compounding ratio is too large, in addition to the processability at the time of extrusion being reduced, the epoxy-containing α-olefin-based copolymer forms a continuous layer in the resin composition, and the PAS resin inherently has a feature. May be damaged.

Other Components Various fillers can be added to the resin composition of the present invention, if desired, as long as the object of the present invention is not impaired. Specific examples of the filler include, for example, glass fiber, carbon fiber, asbestos fiber, silica fiber, alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber,
Inorganic fibrous materials such as boron fiber and potassium titanate fiber; metal fibrous materials such as stainless steel, aluminum, titanium, copper, and brass; high-melting organic fibrous materials such as polyamide, fluororesin, polyester resin, and acrylic resin; Fibrous filler. As the filler, for example, mica, silica, talc, alumina, kaolin,
Granular or powdery fillers such as calcium sulfate, calcium carbonate, titanium oxide, ferrite, clay, glass powder, zinc oxide, nickel carbonate, iron oxide, quartz powder, magnesium carbonate, barium sulfate and the like can be mentioned.

These fillers can be used alone or in combination of two or more. Further, the filler may be treated with a sizing agent or a surface treatment agent as necessary. Examples of the sizing agent or surface treatment agent include functional compounds such as epoxy compounds, isocyanate compounds, silane compounds, and titanate compounds. These compounds may be used after subjecting the filler to a surface treatment or a sizing treatment, or may be added at the same time when the composition is prepared.

Other additives include, for example, a resin modifier such as ethylene glycidyl methacrylate;
A lubricant such as pentaerythritol tetrastearate, a thermosetting resin, an antioxidant, an ultraviolet absorber, a nucleating agent such as boron nitride, a flame retardant, and a coloring agent such as a dye or a pigment can be appropriately added. . The PAS resin composition of the present invention can be prepared by equipment and a method generally used for preparing a synthetic resin composition. That is, each raw material component is mixed, kneaded using a single-screw or twin-screw extruder, and extruded into a pellet for molding. A method of mixing some of the necessary components as a masterbatch and then mixing with the remaining components.Also, in order to enhance the dispersibility of each component, some of the raw materials used are pulverized, mixed with a uniform particle size, and melt-extruded. It is also possible.

Cable Parts The PAS resin composition of the present invention can be formed into sheets, films, tubes, and other molded products by general melt molding methods such as injection molding and extrusion molding. The PAS resin composition of the present invention can control the volume resistivity within a desired range, and retains various characteristics inherent in the PAS resin, and has good toughness. Molded articles obtained from the PAS resin composition of the present invention are excellent in heat resistance, weather resistance, flame retardancy, waterproofness, airtightness, toughness, etc., and furthermore, since they have an appropriate volume resistivity, Electric field concentration relief, electrical stress relief, corona discharge prevention, antistatic,
It has excellent electrical and magnetic properties such as electromagnetic wave sealing. The PAS resin composition of the present invention has a suitably high dielectric constant. The PAS resin composition of the present invention can prevent corona noise,
It is also suitable for parts intended for wind noise prevention, icing (ice pillar) prevention, electromagnetic radiation countermeasures, and the like. Therefore, in the present invention, the PAS resin composition is molded into a cable part by utilizing these various properties. The cable component may be a composite of a member made of the PAS resin composition and a member made of another material.

As the cable component, (1) a member (for example, an outer semiconductive layer, a sheath,
(2) components used for erection of cables (for example, clamps for attaching components to cables, clamps for retaining cables, and distances between parallel conductors). Spacers for holding, devices for removing ice and snow from cables,
Devices for damping mechanical vibrations of cables),
(3) Cable accessories (for example, cable terminal parts, cable connection parts, etc.) and the like. Specific examples of the cable component include, for example, a cable covering member, a wire clamp, a spacer, a spiral rod, a stress cone, a sign attachment component, a ground wire lead-out portion cover, a fastening band, a connection component, a connection portion reinforcement, and a sleeve. , Sleeve cover, bushing, protective equipment, cable terminal,
Examples thereof include a cable joint, an electric field relaxation tube, a connector, a closure, an electric field relaxation tape, a part for an arrester, a part for an insulator device, a part for a transmission line support device, a cable detention device, and a binding device for a wire harness. The shape and function of the cable component are arbitrary such as a heat-shrinkable tube, a heat-recoverable component, a pipe, a tape, and a sheet.

[0039]

The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples. In addition, the measuring method of a physical property is as showing below. (1) Tensile properties (tensile strength, tensile elongation) Tensile strength and tensile elongation (tensile elongation at break) of the resin composition
Was measured in accordance with ASTM D638 at a measurement temperature of 23 ° C., a distance between gauge points of 50 mm, and a crosshead speed of 5 mm / min. (2) Volume resistivity Measured according to JIS K6911.

[Synthesis Example 1] (Synthesis of Polymer A) 720 kg of N-methylpyrrolidone (NMP) was placed in a polymerization vessel.
And 420 kg of sodium sulfide pentahydrate containing 46.21% by weight of sodium sulfide (Na ₂ S), and after replacing with nitrogen gas, the temperature was gradually raised to 200 ° C. while stirring, and 160 kg of water was distilled. Let out. At this time, 62
Mole of H ₂ S was stripped off. After the dehydration step, p
-364 kg of dichlorobenzene (pDCB) and NMP
250 kg was added and reacted at 220 ° C. for 4.5 hours with stirring. Thereafter, 59 kg of water was injected while stirring was continued, the temperature was raised to 255 ° C., and the reaction was performed for 5 hours. After the completion of the reaction, the content was cooled to around room temperature, the content was passed through a 100-mesh screen, and the granular polymer was sieved, washed twice with acetone and further three times with water to obtain a washed polymer. Further, the washed polymer was washed with a 3% aqueous solution of ammonium chloride and then washed with water. After dehydration, the recovered granular polymer was dried at 105 ° C. for 3 hours. The yield of the polymer (A) thus obtained was 89%, and the melt viscosity was 140 Pa · s.

Synthesis Example 2 (Synthesis of Polymer B) Sodium sulfide pentahydrate 42 containing 720 kg of NMP and 46.21% by weight of sodium sulfide (Na ₂ S) in a polymerization vessel
After 0 kg was charged and replaced with nitrogen gas, the temperature was gradually raised to 200 ° C. while stirring to distill 158 kg of water.
At this time, 62 mol of H ₂ S volatilized at the same time. next,
371 kg of pDCB and 189 kg of NMP were added and reacted at 220 ° C. for 4.5 hours with stirring. Thereafter, 49 kg of water was injected while stirring was continued, the temperature was raised to 255 ° C., and the reaction was performed for 5 hours. After completion of the reaction, the produced polymer was treated in the same manner as in Synthesis Example 1. The polymer (B) thus obtained has a yield of 92% and a melt viscosity of 55%.
Pa · s.

Synthesis Example 3 (Synthesis of Polymer C) Sodium sulfide pentahydrate 39 containing 800 kg of NMP and 46.40% by weight of sodium sulfide (Na ₂ S) in a polymerization vessel.
After 0 kg was charged and replaced with nitrogen gas, the temperature was gradually raised to 200 ° C. while stirring to distill 147 kg of water.
At this time, 57 mol of H ₂ S was volatilized at the same time. next,
339 kg of pDCB, 218 kg of NMP and 9.2 k of water
g was added and reacted at 220 ° C. for 4.5 hours with stirring. Thereafter, 70 kg of water was injected while stirring was continued.
After raising the temperature to 55 ° C. and reacting for 3 hours, the reaction was continued at 245 ° C. for 8 hours. After the completion of the reaction, the same treatment as in Synthesis Example 1 was performed to collect a granular polymer. Recovered polymer (C)
Was 90% and the melt viscosity was 236 Pa · s.

[Examples 1 to 7, Comparative Examples 1 to 6] Each of the polymer components shown in Table 1 was uniformly dry-blended with a Henschel mixer and supplied to a 45 mmφ twin-screw kneading extruder (CM-45, manufactured by Ikegai Iron & Steel Co., Ltd.) And cylinder temperature 260-330
The mixture was kneaded at ℃ to obtain a pellet. After the obtained pellets were dried at 150 ° C. for 6 hours, the mold temperature was 135 by an injection molding machine (IS-75 manufactured by Toshiba Machine Co., Ltd.).
The tensile test piece was produced at 300C and a cylinder temperature of 300 to 320C. Table 1 shows the results.

[0044]

[Table 1]

(Footnotes) (1) Epoxy group-containing α-olefin copolymer: Modiper A4400 (manufactured by NOF CORPORATION, graft precursor) (2) Carbon black (DBP oil absorption 500 ml / 1)
00g): Ketjen Black EC600JD (manufactured by Lion Corporation) (3) Carbon black (DBP oil absorption 100ml / 1)
00g): MA100 (manufactured by Mitsubishi Chemical Corporation) (4) Graphite (average particle size 6 μm): artificial graphite HAG-15
(Manufactured by Nippon Graphite Industries)

Example 8 The resin composition obtained in Example 1 was coated (2 mm thick) on an insulating rod (reinforced plastic; 2 cmφ) by extrusion to produce a rod-shaped spacer. This rod-shaped spacer prototype is excellent in weather resistance, waterproofness, and the like, and has a stable volume resistivity, so that a change in insulation resistance due to water (rainwater) is small.

Example 9 The resin composition obtained in Example 7 was supplied to a 45 mmφ single screw extruder equipped with a nozzle having a diameter of 3 mm and three nozzles, and was heated at a cylinder temperature of 220 to 330 ° C. Extruded. The fibrous material emerging from the nozzle was cooled with warm water of 80 ° C.,
The film was stretched by one step, and then subjected to relaxation heat treatment at 240 ° C. for 30 seconds to obtain a monofilament having a diameter of 1.5 mm. As shown in FIG. 1, this monofilament was wound around an overhead electric wire 1 as a spiral rod 2 and its characteristics were evaluated. As a result, not only the heat resistance and weather resistance, but also the wind noise, corona noise and corona discharge characteristics were excellent. I was

[0048]

According to the present invention, 10 ³ to 10 ¹³ Ωcm
Can be obtained with good reproducibility, and the obtained PAS resin composition has a tensile elongation at break of 10% or more and is excellent in toughness. It can be formed into various molded products by molding, extrusion molding and the like. This PAS resin composition combines electrical and magnetic properties such as semi-conductivity, antistatic properties and electromagnetic wave sealing properties with PAS's inherent properties such as heat resistance, weather resistance, and flame retardancy, and has toughness. Therefore, it is particularly suitable as a cable component. That is, the cable component of the present invention can reduce electric field concentration, electric stress,
In addition to excellent electrical and magnetic properties such as corona discharge prevention, antistatic, and electromagnetic wave sealing properties, it has excellent heat resistance, weather resistance, flame retardancy, waterproofness, airtightness, and toughness.

[Brief description of the drawings]

FIG. 1 is a schematic view of an overhead electric wire wound with a spiral rod.

[Explanation of symbols]

 1: overhead wire 2: spiral rod

Claims (2)

[Claims] (A) 49 to 90% by weight of a polyarylene sulfide having a melt viscosity of 25 Pa · s or more measured at 310 ° C. and a shear rate of 1200 / sec; (B) 3 to 6% by weight of a conductive carbon black; C) A cable component comprising a polyarylene sulfide resin composition containing 2 to 10% by weight of graphite having an average particle size of 60 μm or less and (D) 5 to 35% by weight of an epoxy group-containing α-olefin copolymer. 2. The cable component according to claim 1, wherein the volume resistivity of the polyarylene sulfide resin composition is in the range of 10 ³ to 10 ¹³ Ωcm.