WO1991015860A1 - Semiconductive resin composition and rubber/plastic insulated power cable produced by using the same - Google Patents
Semiconductive resin composition and rubber/plastic insulated power cable produced by using the same Download PDFInfo
- Publication number
- WO1991015860A1 WO1991015860A1 PCT/JP1991/000441 JP9100441W WO9115860A1 WO 1991015860 A1 WO1991015860 A1 WO 1991015860A1 JP 9100441 W JP9100441 W JP 9100441W WO 9115860 A1 WO9115860 A1 WO 9115860A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- melting point
- less
- power cable
- resin composition
- crystal melting
- Prior art date
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B9/00—Power cables
- H01B9/02—Power cables with screens or conductive layers, e.g. for avoiding large potential gradients
- H01B9/027—Power cables with screens or conductive layers, e.g. for avoiding large potential gradients composed of semi-conducting layers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
Definitions
- the present invention relates to a semiconductive resin composition and a rubber-plastic insulated power cable using the same, and more particularly, to a material for an inner semiconductive layer and / or an outer semiconductive layer of a high-pressure rubber-plastic insulated power cable.
- the present invention relates to a semiconductive resin composition useful as a material and a rubber / plastic insulated power cable using the same.
- Rubber / plastic insulated power cables are usually cable cores with an inner semiconductive layer and insulator layer around the conductor, or inner semiconductive layer, insulator layer and outer It has a cable core provided with a semiconductive layer.
- the inner semiconductive layer and the outer semiconductive layer described above are generally formed of a resin composition obtained by mixing a desired amount of conductive carbon black with an olefin resin or a crosslinked body thereof. is there.
- a resin composition obtained by mixing a desired amount of conductive carbon black with an olefin resin or a crosslinked body thereof. is there.
- Japanese Unexamined Patent Publication Nos. Sho 56-79685, Sho 62-06855, and Sho 124-677 disclose a cable half.
- a conductive resin composition a mixture of an ethylene-vinyl acetate copolymer and polyethylene is used as a base resin, and carbon black is added thereto.
- a composition incorporating the compound is disclosed.
- compositions have been developed for the purpose of preventing thermal deformation, improving adhesion to an insulator, or improving extrusion workability, and all of them are base resins essential for achieving the object of the present invention described later. No reference is made to the crystal melting point or crystallinity.
- Japanese Patent Application Laid-Open No. 55-111110 discloses a semiconductive composition in which a specific carbon black such as Ketjen black is blended in combination with acetylene black to stabilize conductivity. A resin composition is disclosed.
- Ketchen Black has poor dispersibility and has a large amount of foreign substances, and therefore has a drawback in that the extruded product has a difficulty in surface smoothness and easily generates electric birds.
- Japanese Patent Application Laid-Open No. 59-56441 discloses a crystalline melting point of 90 to 120.
- a semiconductive resin composition using, as a base resin, a mixture of an ethylene-based polymer of C and an ethylene / polyolefin / polyene copolymer rubber is disclosed.
- rubber when rubber is used as the base resin, pelletization is difficult and handling becomes difficult, so foreign matter is likely to be mixed.
- the melt viscosity is high and molding processability is poor, the surface smoothness of the extruded product is reduced. It may cause damage.
- the compounded conductive resin black exists as a network in an olefin-based resin which is a matrix, and as a result, a desired conductive resin is obtained.
- the above-described network of conductive carbon black means that the distance between adjacent carbon black particles is short, and that the carbon black particles are densely packed in the resin as a whole. This refers to the state of distribution in a three-dimensional structure.
- the above-mentioned resin composition constituting the inner and outer semiconductive layers in the power cable is heated at about 90 ° C, which is the temperature at the time of use of the power cable, due to the softening or melting of the resin composition. It is known that the network of the conductive carbon black collapses due to expansion, and as a result, the rate of increase in volume resistivity increases.
- the conductivity of the inner and outer semiconductive layers becomes unstable, and the tan S rises, thereby increasing the loss of power transmission energy. As a result, the performance of the power cable is reduced.
- the present invention solves the above-mentioned problems, and has a small increase in volume resistivity even at the operating temperature of a power cable, and thus has a stable conductivity. It is intended to provide a conductive resin composition and a rubber-plastic insulated power cable using the same. Disclosure of the invention
- an off-line polymer having a crystal melting point of less than 86 ° C or an off-line polymer having a crystal melting point of 100 ° C. or more with the above-mentioned off-line polymer having a crystal melting point of less than 86 ° C.
- a resin composition is provided.
- the inner semiconductive layer and the Z or outer semiconductive layer are provided.
- the present invention provides a rubber-plastic insulated power cable characterized by being formed from the semiconductive resin composition or a crosslinked body thereof.
- the semiconductive resin composition of the present invention is composed of the above-described base resin and conductive bobb black as essential components.
- the base resin is a mixture of one or two or more olefin polymers. It is necessary to have substantially no crystal melting point in the range of 86 ° C. or more and less than 100 ° C. and to have a crystallinity of 20 to 35%.
- Both the crystalline melting point and the crystallinity in the present invention are differential.
- the sample to be measured is now heated at a heating rate of 10 ° C./min to draw a differential calorimetric curve, and to give an endothermic peak of the curve that appears as the crystal component in the sample melts.
- the temperature is the crystal melting point (° C).
- the degree of crystallinity (%) is defined as the value obtained by substituting into XA.
- the crystallinity of the base resin is less than 20%
- the target resin composition is prepared by blending the conductive carbon black described below with the base resin
- the conductivity in the resin composition is reduced. Since a network of carbon black is not sufficiently formed, a resin composition having satisfactory conductivity cannot be obtained.
- the crystallinity exceeds 35%, the extrudability of the prepared resin composition is reduced. For example, when the resin composition is extrusion-coated on the outer periphery of a conductor to form a semiconductive layer. would be inconvenient.
- the preferred crystallinity of the base resin is 25 to 30%.
- This base resin has a crystal melting point of 86 ° C or higher.
- Examples of the polymer having a crystal melting point of less than 86 ° C include ethylene-vinyl acetate copolymer having a density of 0.940 g / ml or more, and ethylene-ethyl acrylate having an ethyl acrylate content of 17% by weight or more.
- Polymer ethylene-methyl acrylate copolymer with a methyl acrylate content of 25% by weight or more, ethylene-methacrylic acid copolymer with a density of 0.940 g / m 1 or more, ethylene with a density of 0.940 g / ml or more Methyl methacrylate copolymer, preferably ethylene monoacetic acid having a density of 0.994 to 0.945 g / ml Examples thereof include vinyl copolymers, which may be used alone or in combination of two or more.
- Examples of the polymer having a crystalline melting point of 100 ° C. or higher include, for example, low-density polyethylene, ultra-low-density polyethylene, linear low-density polyethylene having a density of 0.940 g / ml or less, High-density polymerization low-density polyethylene having a density of 92 g / ml or less and ultra-low-density polyethylene having a density of 0.90 g / ml or less can be used alone or in combination of two or more. May be used.
- the base resin may be an off-line polymer having a crystal melting point of less than 86 ° C alone or an off-line polymer having a crystal melting point of less than 86 ° C and an off-line polymer having a crystal melting point of 100 ° C or more. It is possible to use any of the admixtures with the base polymer, but the use of the admixture makes it easy to adjust the crystallinity of the base resin, moldability, and simplifies the construction of the Ripbon black network. It is preferable because the composition becomes balanced.
- the compounding amount thereof is set to 200 parts by weight based on 100 parts by weight of the base resin. If limited to parts by weight or less, it may be blended. This If the amount of these copolymers is less than 20 parts by weight, the crystal melting point peak in the DSC chart of the obtained base resin is not less than 86 ° C and less than 100 ° C. This is because it is not substantially shown in the range.
- the semiconductive resin composition of the present invention can be obtained.
- any one of acetylene black and furnace black or a mixture thereof can be used.
- the amount of the conductive carbon black is set to 40 to 80 parts by weight based on 100 parts by weight of the base resin.
- the crystal melting point peak in the DSC chart of the obtained semiconductive resin composition slightly shifts to a lower temperature side, depending on the blending amount. I do.
- the amount When the amount is less than 40 parts by weight, the conductivity of the obtained resin composition becomes too low. When the amount exceeds 80 parts by weight, the viscosity at the time of melting becomes high, and the molding processability and carbohydrate are increased. This is because the dispersibility of the black is remarkably reduced, and any of them becomes unsuitable as a material for the semiconductive layer.
- the preferred amount is 50 to 70 parts by weight based on 100 parts by weight of the base resin.
- the resin composition of the present invention contains the above-mentioned components as essential components.
- Various fillers such as lubricants and lubricants can be added.
- the cross-linking agent include 1,3-bis (t-butyl-peroxy-i-propyl) benzene, t-butyl -.- cumylperoxide, dicumylperoxide, 2,4-diphenyl-4-methyl-1-pentene.
- antioxidant for example, 4,4'-bis (3-methyl-1-6-t-butylphenol), bis [2-methyl-41- (3-n-alkylthiopropionyloxy) 1,5_t-butylphenyl] sulfide, 2,5—di-t-butylhydroquinone, 2,6—di-t-butyl—P—cresole, 2,2'-thiomethylenebis- [3 — (3,5—di-tert-butyl-14-hydroxyphenyl) propionate], dilaurylthiodiprobionate, distearylthiodipropionate .
- the lubricant examples include zinc stearate, magnesium stearate, stearate, oxy fatty acid, amide oleate, amide esylate, ethylene glycol monostearate, and cetyl alcohol. , Stearinole alcohol, silicon halide.
- the inner semiconductive layer or the outer semiconductive layer is composed of the above semiconductive resin composition or a crosslinked body thereof.
- These semiconductive layers press the resin composition on the outer periphery of the conductor. It is formed by out-coating and, if necessary, subsequent crosslinking treatment.
- the tape may be formed by molding a tape with the above resin composition, winding the tape around the conductor, and thereafter subjecting the tape to a crosslinking treatment as necessary.
- the resin composition After the crosslinking treatment, the resin composition has a crystal melting point of less than 81 ° C or 95 ° C or more, and a crystallinity of 18 to 32%.
- the final object of the present invention is to stabilize the performance of a power cable, and the object can be sufficiently achieved if the semiconductive layer has the above crystal melting point and crystallinity in a cable state.
- FIG. 1 is a chart showing a differential calorimetric curve of the base resin of Example 4.
- FIG. 2 is a cross-sectional view showing the cross-sectional structure of the power cable
- FIG. 3 is a graph showing the tan 5 characteristics of the power cable.
- FIG. 1 shows the differential calorific value curve of the base resin of Example 4.
- the conductor 11 has a cross-sectional area of 150 mm 2
- the inner semiconductive layer 12 formed on the outer periphery thereof is a cross-linked body of each resin composition having a thickness of 1 mm
- the insulator layer 13 has a thickness of 6 mm.
- outer semi-conductive layer 14 is made of a cross-linked body of each of the above resin compositions with a thickness of 1 mm
- semi-conductive cloth tape 15 around the outer circumference
- metal The shielding layer 16, the holding tape 17 and the sheath layer 18 are sequentially formed.
- the inner semiconductive layer composed of a crosslinked body of the resin composition containing the above crosslinking agent was used in Examples 1, 3, and 4 and Comparative Examples 3 and 7, and its crystal melting point and crystallinity were measured. It was determined based on the DSC method. Table 2 shows the results. Table 2
- the crystalline melting point of the semiconductive resin composition of the present invention is out of the vicinity of the temperature when the power cable is used, the inner and outer semiconductive layers formed with the resin composition when the power cable is used. There is no decrease in conductivity, and a stable state is maintained. Moreover, the extrudability is good. Further, when the crystallinity is 20 to 35%, the network of the compounded conductive carbon black can be well constructed, and proper conductivity can be exhibited.
- the power cable formed with an electrical layer or an external semiconductive layer has stable volume performance without increasing the volume resistivity of these semiconductive layers even in actual use. Functions as a power cable
- the power cable of the present invention is particularly useful as a high-voltage power cable.
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Conductive Materials (AREA)
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1019910701750A KR920701991A (ko) | 1990-04-03 | 1991-04-02 | 반도전성 수지 조성물 및 그것을 사용한 고무 · 플라스틱 절연전력 케이블 |
FI915679A FI915679A0 (fi) | 1990-04-03 | 1991-12-02 | Halvledande hartskomposition och en gummi- eller plastisolerad starkstroemskabel daer denna anvaends. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8939690 | 1990-04-03 | ||
JP2/89396 | 1990-04-03 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1991015860A1 true WO1991015860A1 (en) | 1991-10-17 |
Family
ID=13969491
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1991/000441 WO1991015860A1 (en) | 1990-04-03 | 1991-04-02 | Semiconductive resin composition and rubber/plastic insulated power cable produced by using the same |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0480056A4 (ja) |
KR (1) | KR920701991A (ja) |
BR (1) | BR9105675A (ja) |
FI (1) | FI915679A0 (ja) |
WO (1) | WO1991015860A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102134348A (zh) * | 2010-12-14 | 2011-07-27 | 江苏德威新材料股份有限公司 | 用于≤20kv硅烷交联架空电缆的聚烯烃半导电复合物 |
CN112521885A (zh) * | 2020-11-18 | 2021-03-19 | 科建高分子材料(上海)股份有限公司 | 一种高从形性通讯电缆用半导电自粘带 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2331870A (en) * | 1997-11-28 | 1999-06-02 | Asea Brown Boveri | Connection to outer semiconductor of HV cable |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS54115798A (en) * | 1978-03-01 | 1979-09-08 | Fujikura Ltd | Semiconductive composition for power cable |
JPS57158907A (en) * | 1981-03-26 | 1982-09-30 | Fujikura Ltd | Power cable |
JPS59168051A (ja) * | 1983-03-16 | 1984-09-21 | Tokyo Ink Kk | 導電性樹脂組成物 |
JPS62256847A (ja) * | 1986-05-01 | 1987-11-09 | Furukawa Electric Co Ltd:The | 導電性組成物 |
JPH01243305A (ja) * | 1987-11-20 | 1989-09-28 | Sumitomo Electric Ind Ltd | 電気絶縁ケーブル |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DK452584A (da) * | 1983-09-22 | 1985-03-23 | Raychem Corp | Ledende polymer |
JPH0638322B2 (ja) * | 1988-02-24 | 1994-05-18 | 住友電気工業株式会社 | 走水防止電力用電線、ケーブル |
-
1991
- 1991-04-02 EP EP19910906857 patent/EP0480056A4/en not_active Ceased
- 1991-04-02 BR BR919105675A patent/BR9105675A/pt not_active Application Discontinuation
- 1991-04-02 KR KR1019910701750A patent/KR920701991A/ko not_active Application Discontinuation
- 1991-04-02 WO PCT/JP1991/000441 patent/WO1991015860A1/ja not_active Application Discontinuation
- 1991-12-02 FI FI915679A patent/FI915679A0/fi not_active Application Discontinuation
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS54115798A (en) * | 1978-03-01 | 1979-09-08 | Fujikura Ltd | Semiconductive composition for power cable |
JPS57158907A (en) * | 1981-03-26 | 1982-09-30 | Fujikura Ltd | Power cable |
JPS59168051A (ja) * | 1983-03-16 | 1984-09-21 | Tokyo Ink Kk | 導電性樹脂組成物 |
JPS62256847A (ja) * | 1986-05-01 | 1987-11-09 | Furukawa Electric Co Ltd:The | 導電性組成物 |
JPH01243305A (ja) * | 1987-11-20 | 1989-09-28 | Sumitomo Electric Ind Ltd | 電気絶縁ケーブル |
Non-Patent Citations (1)
Title |
---|
See also references of EP0480056A4 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102134348A (zh) * | 2010-12-14 | 2011-07-27 | 江苏德威新材料股份有限公司 | 用于≤20kv硅烷交联架空电缆的聚烯烃半导电复合物 |
CN112521885A (zh) * | 2020-11-18 | 2021-03-19 | 科建高分子材料(上海)股份有限公司 | 一种高从形性通讯电缆用半导电自粘带 |
Also Published As
Publication number | Publication date |
---|---|
EP0480056A1 (en) | 1992-04-15 |
EP0480056A4 (en) | 1992-09-16 |
KR920701991A (ko) | 1992-08-12 |
FI915679A0 (fi) | 1991-12-02 |
BR9105675A (pt) | 1992-05-19 |
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