JPH03255143A - Semiconductive composition - Google Patents
Semiconductive compositionInfo
- Publication number
- JPH03255143A JPH03255143A JP5179490A JP5179490A JPH03255143A JP H03255143 A JPH03255143 A JP H03255143A JP 5179490 A JP5179490 A JP 5179490A JP 5179490 A JP5179490 A JP 5179490A JP H03255143 A JPH03255143 A JP H03255143A
- Authority
- JP
- Japan
- Prior art keywords
- ethylene
- alkyl acrylate
- copolymer
- acrylate copolymer
- carbon black
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims description 16
- 229920000800 acrylic rubber Polymers 0.000 claims abstract description 20
- 239000004711 α-olefin Substances 0.000 claims abstract description 19
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000006229 carbon black Substances 0.000 claims abstract description 11
- 239000006230 acetylene black Substances 0.000 claims abstract description 8
- 239000000155 melt Substances 0.000 claims abstract description 4
- 229920000642 polymer Polymers 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000007787 solid Substances 0.000 abstract description 3
- 238000009413 insulation Methods 0.000 abstract 3
- 238000013329 compounding Methods 0.000 abstract 2
- 239000000758 substrate Substances 0.000 abstract 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 10
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 9
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- 239000005977 Ethylene Substances 0.000 description 8
- 239000005042 ethylene-ethyl acrylate Substances 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 150000001451 organic peroxides Chemical class 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 3
- 229920003020 cross-linked polyethylene Polymers 0.000 description 3
- 239000004703 cross-linked polyethylene Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- -1 hexene-1 Chemical compound 0.000 description 3
- 239000012212 insulator Substances 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- BHIIOLWIZLICII-UHFFFAOYSA-N 2-butyl-5-methylphenol Chemical compound CCCCC1=CC=C(C)C=C1O BHIIOLWIZLICII-UHFFFAOYSA-N 0.000 description 1
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 description 1
- BXAAQNFGSQKPDZ-UHFFFAOYSA-N 3-[1,2,2-tris(prop-2-enoxy)ethoxy]prop-1-ene Chemical compound C=CCOC(OCC=C)C(OCC=C)OCC=C BXAAQNFGSQKPDZ-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000010913 used oil Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、架橋ポリエチレンなどを絶縁体とする固体絶
縁ケーブルの内部半導電層及び外部半導電層として好適
な半導電性組成物に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a semiconducting composition suitable as an inner semiconducting layer and an outer semiconducting layer of a solid insulated cable whose insulator is crosslinked polyethylene or the like.
（従来の技術）
架橋ポリエチレンなどを絶縁体とする、いわゆるＣｖケ
ーブルに用いられる内部及び外部半導電層は、高分子基
材にカーボンブラックを配合したものが一般に用いられ
る。この時に、高分子基材としては、カーボンブラ・７
りを高濃度に充填する必要から、エチレン−酢酸ビニル
共重合体（以下、ＥＶＡという）が最も多くの場合に用
いられており、その他に、エチレン−エチルアクリレー
ト共重合体（以下、ＥＥＡという）などが用いられてい
る（特開昭６３−２０５３４０号公報）。(Prior Art) The inner and outer semiconducting layers used in so-called Cv cables that use crosslinked polyethylene or the like as an insulator are generally made of a polymer base material mixed with carbon black. At this time, carbon bra 7 is used as the polymer base material.
Ethylene-vinyl acetate copolymer (hereinafter referred to as EVA) is most often used because of the need to fill it with a high concentration of resin, and ethylene-ethyl acrylate copolymer (hereinafter referred to as EEA) etc. are used (Japanese Unexamined Patent Publication No. 63-205340).
（発明が解決しようとする課題〉
従来、この種の半導電性組成物は、高分子基材としての
ＥＶＡないしＥＥＡがその重合時に生しる非常に高分子
量化した成分（ポリマーゲル）を含むこと、及びＥＶＡ
ないしＥＥＡとカーボンブラックを混合する時に、カン
ボンブラックの分散不良が生しることの２つの理由によ
り、ケーブルに被覆した時に、絶縁層と半導電層との界
面に小さい突起が生しるという問題があった。(Problem to be Solved by the Invention) Conventionally, this type of semiconductive composition contains a component (polymer gel) with a very high molecular weight produced when EVA or EEA as a polymer base material is polymerized. Koto, and EVA
Also, when mixing EEA and carbon black, there are two reasons for poor dispersion of Cambon black, which causes small protrusions to form at the interface between the insulating layer and the semiconducting layer when the cable is coated. was there.
（課題を解決するための手段）
本発明者らは、上記課題について鋭意検討した結果、半
導電層を構成する高分子基材として、密度が０．９ｇ／
ｃ＋＋！以下のエチレン−炭素数４以上のα−オレフィ
ン系共重合体（以下、エチレンα−オレフィン系共重合
体と称する）にエチレンアクリル酸アルキル系共重合体
を混合した特定のオレフィン系重合体ブレンドを用いる
ことにより、絶縁層と半導を層との界面に小さい突起が
生しないことを見出し、本発明を完成するに至った。(Means for Solving the Problem) As a result of intensive study on the above-mentioned problem, the present inventors found that the density of the polymer base material constituting the semiconducting layer is 0.9 g/
c++! The following specific olefin polymer blend is prepared by mixing the following ethylene-α-olefin copolymer having 4 or more carbon atoms (hereinafter referred to as ethylene α-olefin copolymer) with an ethylene alkyl acrylate copolymer. It was discovered that by using this method, small protrusions do not form at the interface between the insulating layer and the semiconductor layer, and the present invention was completed.
すなわち、本発明は：
■ 密度が０．９ｇ／ｃｍ２以下のエチレン−炭素数４
以上のα−オレフィン系共重合体５〜８０重量部とエチ
レン−アクリル酸アルキル系共重合体９５〜２０重量部
とを含む高分子基材に、カーボンブラックを配合してな
る、半導電性組成物を提供するものであり、また
■ カーボンブラックが、アセチレンブラックである点
にも特徴があり、さらに
■ エチレン−アクリル酸アルキル系共重合体のメルト
フローレートが、３０ｇ／１０分以下である点にも特徴
がある。That is, the present invention: ■ Ethylene with a density of 0.9 g/cm2 or less - carbon number 4
A semiconductive composition made by blending carbon black into a polymeric base material containing 5 to 80 parts by weight of the above α-olefin copolymer and 95 to 20 parts by weight of the ethylene-alkyl acrylate copolymer. It also has the following characteristics: ■ The carbon black is acetylene black, and ■ The melt flow rate of the ethylene-alkyl acrylate copolymer is 30 g/10 minutes or less. It also has its own characteristics.
さらに、本発明を具体的に説明する。Furthermore, the present invention will be specifically explained.
本発明に使用するエチレン−α−オレフィン系共重合体
としては、密度が０．９ｇ／ｃｍ２！以下であって、か
つエチレンと、ブテン−１，ヘキセン１．４−メチルペ
ンテン−１などの炭素数４以上のα−オレフィンとの共
重合体が挙げられが、エチレンとブテン−】との共重合
体が好ましく使用される。The ethylene-α-olefin copolymer used in the present invention has a density of 0.9 g/cm2! Examples include copolymers of ethylene and α-olefins having 4 or more carbon atoms such as butene-1, hexene-1,4-methylpentene-1, and copolymers of ethylene and butene-] Polymers are preferably used.
また、上記二元共重合体の他に、上記共重合体の機能を
損なわない範囲の少量で１，４−へキサジエン、ジシク
ロペンタジェンなどのジエン類や塩化ビニル、スチレン
などの他のオレフィン系化合物をコモノマーとして共重
合した共重合体も使用可能である。In addition to the above binary copolymer, dienes such as 1,4-hexadiene and dicyclopentadiene, and other olefins such as vinyl chloride and styrene may be used in small amounts within a range that does not impair the functions of the above copolymer. A copolymer obtained by copolymerizing a system compound as a comonomer can also be used.
該共重合体の密度が０．９ｇ／ｃｍ２以上では、その重
合時にポリマーゲルの生成が多くなり、小突起の形成が
出来易くなる。If the density of the copolymer is 0.9 g/cm2 or more, a large amount of polymer gel is produced during polymerization, and small protrusions are likely to be formed.
本発明に使用するエチレン−アクリル酸アルキル系共重
合体としては、該共重合体中のアクリル酸アルキル単位
の含有量が１〜３５重量％、好ましくは２〜２５重量％
の範囲のものであり、かつエチレン−アクリル酸アルキ
ル共重合体、並びにその機能を損なわない範囲の少量で
該共重合成分に他の第３のオレフィン系化合物（例えば
、塩化ビニル、酢酸ビニル、アクリル酸、マレイン酸、
無水マレイン酸など）を共重合したものも含まれる。The ethylene-alkyl acrylate copolymer used in the present invention has an alkyl acrylate unit content of 1 to 35% by weight, preferably 2 to 25% by weight.
and ethylene-alkyl acrylate copolymer, as well as other third olefinic compounds (e.g., vinyl chloride, vinyl acetate, acrylic acid, maleic acid,
It also includes copolymers of maleic anhydride, etc.).
また、共重合成分である該アクリル酸アルキルとして、
アクリル酸メチル、エチル、イソプロピル、ヘキシルな
どを挙げることができ、特にエチレン−アクリル酸エチ
ル共重合体が好ましく使用できる。In addition, as the alkyl acrylate which is a copolymerization component,
Examples include methyl acrylate, ethyl, isopropyl, hexyl and the like, with ethylene-ethyl acrylate copolymer being particularly preferred.
さらに、上記エチレン−アクリル酸アルキル系共重合体
は、そのメルトフローレート（以下、ＭＦＲという）が
１９０’Ｃで荷重２，１６０ｇ下で３０ ｇ ／ １０
分以下のものが望ましく、特に好ましくは０． ５〜２
５ ｇ ／ Ｉ Ｏ分程度である。Furthermore, the ethylene-alkyl acrylate copolymer has a melt flow rate (hereinafter referred to as MFR) of 30 g/10 at 190'C and under a load of 2,160 g.
It is desirable that the value is less than 0.0 min. 5-2
It is about 5 g/IO min.
そのＭＦＲが、３０ｇ／１０分を越えると、小突起が出
来易くなる。When the MFR exceeds 30 g/10 minutes, small protrusions are likely to form.
半導電層を構成する高分子基材の構成化としては、エチ
レン−α−オレフィン系共重合体５〜８０重量部、好ま
しくは１０〜７０重量部とエチレン−アクリル酸アルキ
ル系共重合体９５〜２０重量部、好ましくは９０〜３０
重量部とを主体とするブレンドが望ましい。The polymer base material constituting the semiconductive layer is composed of 5 to 80 parts by weight, preferably 10 to 70 parts by weight of an ethylene-α-olefin copolymer and 95 to 95 parts by weight of an ethylene-alkyl acrylate copolymer. 20 parts by weight, preferably 90-30 parts by weight
A blend consisting mainly of parts by weight is desirable.
エチレン−α−オレフィン系共重合体の混合量が５重量
部未満では、ブレンドするエチレン−アクリル酸アルキ
ル系共重合体から生ずるポリマーゲルが多くなり、半導
電層に突起を形成するようになり、またカーボンの分散
性も悪くなる。If the amount of the ethylene-α-olefin copolymer mixed is less than 5 parts by weight, a large amount of polymer gel will be produced from the ethylene-alkyl acrylate copolymer to be blended, and protrusions will be formed on the semiconductive layer. Furthermore, the dispersibility of carbon also deteriorates.
また、エチレン−α−オレフィン系共重合体の混合量が
８０重量部を越えると、半導電層が粘着性の高いものと
なって取り扱い難いものとなる。Furthermore, if the amount of the ethylene-α-olefin copolymer mixed exceeds 80 parts by weight, the semiconductive layer becomes highly sticky and difficult to handle.
半導電層を構成する上記高分子基材には、前記エチレン
−α−オレフィン系共重合体とエチレンアクリル酸アル
キル系共重合体との他に、これらの機能を損なわない範
囲の少量で他のポリオレフィン系材料、例えばポリエチ
レン、エチレン酢酸ビニル系共重合体などを含ませても
よい。In addition to the ethylene-α-olefin copolymer and the ethylene alkyl acrylate copolymer, the polymer base material constituting the semiconductive layer may contain other substances in small amounts within a range that does not impair these functions. Polyolefin materials such as polyethylene, ethylene vinyl acetate copolymers, etc. may also be included.
このような高分子基材に半導電性を付与するためには、
カーボンブラック、例えば導電性カーボンブラックを配
合する必要がある。In order to impart semiconductivity to such polymer base materials,
It is necessary to incorporate carbon black, for example conductive carbon black.
このカーボンブラックとしては、前述の小突起の低減の
ためには、アセチレンブラックが特に好ましく使用でき
る。As this carbon black, acetylene black is particularly preferably used to reduce the aforementioned small protrusions.
このカーボンブラックの配合量は、半導電層に要求され
るｉｔ性を考慮して決定されるが、一般には上記高分子
基材１００重量部当たり３０〜９０重量部が用いられる
。The amount of carbon black to be blended is determined in consideration of the IT property required of the semiconductive layer, but generally 30 to 90 parts by weight is used per 100 parts by weight of the polymer base material.
本発明の半導電性＆ｌｌ威物酸物、必要に応じて滑剤、
酸化防止剤、充填剤、架橋剤、架橋助剤などの種々の添
加剤を配合することができる。The semiconducting &llacid acid of the present invention, a lubricant if necessary,
Various additives such as antioxidants, fillers, crosslinking agents, and crosslinking aids can be blended.
特に、滑剤としては、例えばステアリン酸、ステアリン
酸亜鉛などを；酸化防止剤としては、例えば４．４゛−
チオビス（６−１−ブチル−３メチルフエノール）など
を；充填剤としては、炭酸カルシウム、クレー、マグネ
シア、酸化亜鉛などを；架橋剤としては、ジク耐ルバー
オキサイド、２．５−ジメチル−２５−ジ（ｔ−ブチル
パーオキシ）ヘキシン−３などの有機過酸化物系架橋剤
を；架橋助剤としては、トリアリルイソシアヌレート、
トリアリルシアヌレート、テトラアリルオキシエタン、
ｍ−フェニレンビスマレイミドなどが好ましく使用でき
る。In particular, as a lubricant, for example, stearic acid, zinc stearate, etc.; as an antioxidant, for example, 4.4゛-
Thiobis (6-1-butyl-3-methylphenol), etc.; Fillers include calcium carbonate, clay, magnesia, zinc oxide, etc.; An organic peroxide crosslinking agent such as di(t-butylperoxy)hexyne-3; as a crosslinking aid, triallyl isocyanurate,
triallyl cyanurate, tetraallyloxyethane,
m-phenylene bismaleimide and the like can be preferably used.
そして、このような組成の本発明の半導電性組成物を用
いて半導電層を形成するには、例えば押出被覆法などを
適用して行うことができる。A semiconductive layer can be formed using the semiconductive composition of the present invention having such a composition by applying, for example, an extrusion coating method.
この際に、上記有機過酸化物などを用いる化学架橋で架
橋させても、あるいは場合により電離性放射線による架
橋を行ってもよい。At this time, crosslinking may be carried out by chemical crosslinking using the above-mentioned organic peroxide or the like, or crosslinking by ionizing radiation may be carried out depending on the case.
（作用）
■ 本発明において、密度が０．９ｇ／ｃＪ以下のエチ
レン−炭素数４以上のα−オレフィン系共重合体を用い
たので、ポリマーゲルの形成が従来（７）ＥＶＡ、 Ｅ
ＥＡ等と比べて少なく、かつカーボンの配合時にカーボ
ンの分散不良が生じにくい。(Function) ■ In the present invention, since an ethylene-α-olefin copolymer having 4 or more carbon atoms with a density of 0.9 g/cJ or less is used, the formation of a polymer gel is different from conventional (7) EVA, E
The amount is less than that of EA, etc., and poor carbon dispersion is less likely to occur when carbon is blended.
■ 一方、エチレン−アクリル酸アルキル系共重合体を
用いたので、エチレン−α−オレフィン系共重合体のみ
を用いたのでは、得られた半導電性組成物で半導電層を
形成した場合に、非常に粘着性が高くなり実用上取り扱
いにくい問題点が回避される。■ On the other hand, since an ethylene-alkyl acrylate copolymer was used, it would be difficult to use only an ethylene-α-olefin copolymer when forming a semiconductive layer with the obtained semiconductive composition. This avoids the problem of extremely high stickiness and difficulty in handling in practice.
また、ＥＶＡを用いずに、エチレン−アクリル酸アルキ
ル系共重合体を選択したので、ＥＶＡとエチレン−α−
オレフィン系共重合体とを混合した場合に小突起の個数
が増加するのに比較して、そのような現象が生しない。In addition, since we selected an ethylene-alkyl acrylate copolymer without using EVA, we used EVA and ethylene-α-
Compared to the case where the number of small protrusions increases when mixed with an olefin copolymer, such a phenomenon does not occur.
その機構は、未だ判っていないが、ＥＶＡ又はエチレン
−アクリル酸アルキル系共重合体と、エチレン−α−オ
レフィン系共重合体との相溶性の差に起因するものと考
えられる。Although the mechanism is not yet clear, it is thought to be due to the difference in compatibility between EVA or ethylene-alkyl acrylate copolymer and ethylene-α-olefin copolymer.
■ 本発明において、使用するカーボンブラックとして
は、アセチレンブラックであることが望ましい。(2) In the present invention, the carbon black used is preferably acetylene black.
その理由は、最も汎用のオイルを原料とするファーネス
ブランクは、原料中に不純物が多いことから、高分子基
材中に配合した場合に分散不良となり易い成分が多く、
かつ小突起が出来易いためである。The reason for this is that furnace blanks, which are made from the most commonly used oil, have many impurities in their raw materials, so they contain many components that tend to cause poor dispersion when blended into polymeric base materials.
This is also because small protrusions are easily formed.
■ エチレン−アクリル酸アルキル系共重合体のＶＦＲ
は、３０以下、好ましくは０． ５〜２５のイ直が望ま
しい。■ VFR of ethylene-alkyl acrylate copolymer
is 30 or less, preferably 0. A straightness of 5 to 25 is desirable.
このＭＦＲが３０を越え、ＭＦＲが大きくなると（すな
わち、分子量が低くなると）、小突起が出来やすい。When this MFR exceeds 30 and the MFR becomes large (that is, when the molecular weight becomes low), small protrusions are likely to be formed.
この理由は、混合時にエチレン−α−オレフィン系共重
合体とエチレン−アクリル酸アルキル系共重合体との粘
度が違いすぎるために両者の分散が悪くなるとか、ある
いはエチレン−アクリル酸アルキル系共重合体の分子量
が低くいために、その重合時にポリマーゲルが生し易（
なるためと考えられる。The reason for this is that the viscosity of the ethylene-α-olefin copolymer and the ethylene-alkyl acrylate copolymer is too different during mixing, resulting in poor dispersion of the two, or that the ethylene-alkyl acrylate copolymer Because the molecular weight of the polymer is low, a polymer gel is likely to form during polymerization (
It is thought that this is because
（実施例）
本発明を以下の実施例により詳細に説明するが、これら
は本発明の範囲を制限しない。(Examples) The present invention will be explained in detail by the following examples, but these do not limit the scope of the present invention.
１４ｍａ＋”の撚り線導体上に１ｍｎ厚の内部半導電層
、３ｍｍ厚のＸＬＰＥ （低密度ポリエチレン）絶縁層
、及びＩＩＩＩＩｇ−の第１表に示す配合の外部半導電
層を順次押出被覆し、赤外線ヒーターで１４０°Ｃで加
熱し、モデルケーブルを作製した。A 14 mA+” stranded wire conductor is coated with a 1 mm thick inner semiconducting layer, a 3 mm thick XLPE (low density polyethylene) insulating layer, and an outer semiconducting layer having the composition shown in Table 1 of IIIg− in order, and is coated with infrared rays. A model cable was produced by heating at 140°C with a heater.
これらのモデルケーブルからＩＩＩＩｌ厚のスライス片
を切り出し、光学顕微鏡で絶縁層と外部導電層の界面を
観察した。Slices with a thickness of III1 were cut from these model cables, and the interface between the insulating layer and the external conductive layer was observed using an optical microscope.
その結果、見つかった高さ１０μｍ以上の小突起を、比
較例１を１とした相対数で第１表に示す。As a result, the small protrusions found with a height of 10 μm or more are shown in Table 1 in relative numbers with Comparative Example 1 set as 1.
また、出来上がったケーブル表面の粘着性を触感で調べ
、同様に第１表に示した。In addition, the tackiness of the surface of the finished cable was examined by touch and is also shown in Table 1.
なお、実施例で使用した各材料は以下の通りである。The materials used in the examples are as follows.
ＥＶＡ：三井・デュポンポリケミカル製、エバフレック
スＥＶ４５０ （ＭＦＲ１５）ＥＥＡ−１：三井・デュ
ポンポリケミカル製、エバフレックスＡ−７０７（ＭＦ
Ｒ２５）ＥＥＡ−２：三井・デュポンポリケミカル製、
エバフレックスＡ−７０１（ＭＦＲ５）ＥＥＡ−３：三
井・デュポンポリケミカル製、エバフレックスＡ−７０
４（ＭＦＲ２７５）共重合体−１：エチレンとブテン−
１との共重合物 （密度０．９００ｇ／ｃｆｆｌ、 Ｍ
ＦＲＯ，８）共重合体−２：エチレンとブテン−１との
共重合物 （密度０．９０７ｇ／ｃｍ２、 ＭＦＲ０，
９）アセチレンブラック：１！Ｘ気化学■製、デンカブ
ラック、
ファーネスブラック：東海カーボン■製、ジーストＳ○
、
酸化防止剤：住友化学■製、スミライザーＷｘ−Ｒ。EVA: Manufactured by Mitsui DuPont Polychemicals, Evaflex EV450 (MFR15) EEA-1: Manufactured by Mitsui DuPont Polychemicals, Evaflex A-707 (MF
R25) EEA-2: Manufactured by Mitsui DuPont Polychemicals,
Evaflex A-701 (MFR5) EEA-3: Manufactured by Mitsui DuPont Polychemicals, Evaflex A-70
4 (MFR275) copolymer-1: ethylene and butene-
Copolymer with 1 (density 0.900g/cffl, M
FRO, 8) Copolymer-2: Copolymer of ethylene and butene-1 (density 0.907 g/cm2, MFR0,
9) Acetylene black: 1! Manufactured by Xki Kagaku ■, Denka Black, Furnace Black: Manufactured by Tokai Carbon ■, Geast S○
, Antioxidant: Sumilizer Wx-R, manufactured by Sumitomo Chemical ■.
滑剤： ステアリン酸亜鉛、有機過酸化物
二日本油脂■製、ジクミルパーオキサイド。Lubricant: Zinc stearate, organic peroxide manufactured by Nippon Oil & Fats, dicumyl peroxide.
比較例１〜２と実施例１とを比較すると、ＥＶＡ、ある
いはＥＥＡ単独使用と比べて、ＥＥＡとエチレン−炭素
数４以上のα−オレフィンの共重合体で密度０．９ｇ／
ｃｍ２以下とのブレンドを高分子基材として用いると、
絶縁層と半導電層との界面の小突起数が非常に少なくな
るのが判る。Comparing Comparative Examples 1 and 2 with Example 1, the density of EEA and ethylene-α-olefin having 4 or more carbon atoms was 0.9 g/min compared to using EVA or EEA alone.
When a blend with cm2 or less is used as a polymer base material,
It can be seen that the number of small protrusions at the interface between the insulating layer and the semiconducting layer is extremely reduced.
しかし、比較例４のように、ＥＥＡに混合するエチレン
−α−オレフィン共重合体の量が少ないブレンドでは、
上記の効果が殆どないことが判る。However, in a blend such as Comparative Example 4 in which the amount of ethylene-α-olefin copolymer mixed with EEA is small,
It can be seen that the above effect is almost absent.
次に、比較例７と実施例１とを比較すると、アセチレン
ブラックを配合する実施例１が界面の小突起数が非常に
少なくて、アセチレンブラックの使用が望ましいことが
判る。Next, when Comparative Example 7 and Example 1 are compared, it can be seen that Example 1, which contains acetylene black, has a very small number of small protrusions at the interface, indicating that it is desirable to use acetylene black.
また、実施例１．３と比較例６とを比較すると、使用す
るＥＥＡのＭＦＲ値は２５以下程度に低いことが望まし
いことが判る。Furthermore, a comparison between Example 1.3 and Comparative Example 6 shows that it is desirable that the MFR value of the EEA used be as low as about 25 or less.
さらに、実施例４の結果を他の実施例と比べると、有機
過酸化物による架橋を施してもその効果に変わりがない
ことが判る。Furthermore, when the results of Example 4 are compared with other examples, it can be seen that there is no difference in the effect even if crosslinking is performed using an organic peroxide.
さらに、実施例１と比較例８とを比較すると、エチレン
−α−オレフィン共重合体の密度は、０゜９ｇ／ｃｍ２
以下が良いことが判る。Furthermore, when comparing Example 1 and Comparative Example 8, the density of the ethylene-α-olefin copolymer was 0°9 g/cm2.
It turns out that the following is good.
（発明の効果）
以上説明したように、本発明の半導電性組成物では、Ｃ
Ｖケーブルの絶縁体と半導電層との間に存在する小突起
数を減らすことが出来る。(Effects of the Invention) As explained above, in the semiconductive composition of the present invention, C
The number of small protrusions existing between the insulator and the semiconducting layer of the V cable can be reduced.
従って、特に、超高圧ＣＶケーブルの分野において、そ
の半導電層用に用いれば初期及び長期のケーブル性能を
向上できる。Therefore, especially in the field of ultra-high voltage CV cables, the initial and long-term performance of the cable can be improved if used for the semiconducting layer thereof.
３９７397
Claims (3)
数４以上のα−オレフィン系共重合体５〜８０重量部と
エチレン−アクリル酸アルキル系共重合体９５〜２０重
量部とを含む高分子基材に、カーボンブラックを配合し
てなることを特徴とする、半導電性組成物。(1) 5 to 80 parts by weight of an ethylene-α-olefin copolymer having 4 or more carbon atoms with a density of 0.9 g/cm^2 or less and 95 to 20 parts by weight of an ethylene-alkyl acrylate copolymer. 1. A semiconductive composition comprising a polymer base material containing carbon black.
ことを特徴とする、請求項（１）記載の半導電性組成物
。(2) The semiconductive composition according to claim (1), wherein the carbon black is acetylene black.
トフローレートが、３０ｇ／１０分以下であることを特
徴とする、請求項（１）ないし（２）記載の半導電性組
成物。(3) The semiconductive composition according to any one of claims (1) and (2), wherein the ethylene-alkyl acrylate copolymer has a melt flow rate of 30 g/10 minutes or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5179490A JPH03255143A (en) | 1990-03-05 | 1990-03-05 | Semiconductive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5179490A JPH03255143A (en) | 1990-03-05 | 1990-03-05 | Semiconductive composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03255143A true JPH03255143A (en) | 1991-11-14 |
Family
ID=12896846
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5179490A Pending JPH03255143A (en) | 1990-03-05 | 1990-03-05 | Semiconductive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03255143A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5556697A (en) * | 1994-03-24 | 1996-09-17 | Bicc Cables Corporation | Semiconductive power cable shield |
| JP2019527249A (en) * | 2016-06-30 | 2019-09-26 | ダウ グローバル テクノロジーズ エルエルシー | Semiconductor shield without weld lines and protrusions |
-
1990
- 1990-03-05 JP JP5179490A patent/JPH03255143A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5556697A (en) * | 1994-03-24 | 1996-09-17 | Bicc Cables Corporation | Semiconductive power cable shield |
| JP2019527249A (en) * | 2016-06-30 | 2019-09-26 | ダウ グローバル テクノロジーズ エルエルシー | Semiconductor shield without weld lines and protrusions |
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