JP2011046891A - Semiconductive resin composition and electric wire/cable - Google Patents
Semiconductive resin composition and electric wire/cable Download PDFInfo
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- JP2011046891A JP2011046891A JP2009198837A JP2009198837A JP2011046891A JP 2011046891 A JP2011046891 A JP 2011046891A JP 2009198837 A JP2009198837 A JP 2009198837A JP 2009198837 A JP2009198837 A JP 2009198837A JP 2011046891 A JP2011046891 A JP 2011046891A
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- ethylene
- resin composition
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- semiconductive resin
- copolymer
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- 239000011342 resin composition Substances 0.000 title claims abstract description 47
- 229920001577 copolymer Polymers 0.000 claims abstract description 47
- 239000004711 α-olefin Substances 0.000 claims abstract description 23
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000004291 polyenes Chemical class 0.000 claims abstract description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004020 conductor Substances 0.000 claims abstract description 10
- 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 claims abstract description 9
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- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000005977 Ethylene Substances 0.000 claims description 49
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 48
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000006230 acetylene black Substances 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 5
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- 229920000098 polyolefin Polymers 0.000 abstract description 7
- 230000001747 exhibiting effect Effects 0.000 abstract 1
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- 239000012212 insulator Substances 0.000 description 3
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- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
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- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
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- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
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- NHLUYCJZUXOUBX-UHFFFAOYSA-N nonadec-1-ene Chemical compound CCCCCCCCCCCCCCCCCC=C NHLUYCJZUXOUBX-UHFFFAOYSA-N 0.000 description 2
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- 229920013716 polyethylene resin Polymers 0.000 description 2
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- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- MYOQALXKVOJACM-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy pentaneperoxoate Chemical compound CCCCC(=O)OOOC(C)(C)C MYOQALXKVOJACM-UHFFFAOYSA-N 0.000 description 1
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- UBRWPVTUQDJKCC-UHFFFAOYSA-N 1,3-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC(C(C)(C)OOC(C)(C)C)=C1 UBRWPVTUQDJKCC-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- ODBCKCWTWALFKM-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhex-3-yne Chemical compound CC(C)(C)OOC(C)(C)C#CC(C)(C)OOC(C)(C)C ODBCKCWTWALFKM-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-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
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- VFBJXXJYHWLXRM-UHFFFAOYSA-N 2-[2-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]ethylsulfanyl]ethyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCSCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 VFBJXXJYHWLXRM-UHFFFAOYSA-N 0.000 description 1
- KRDXTHSSNCTAGY-UHFFFAOYSA-N 2-cyclohexylpyrrolidine Chemical compound C1CCNC1C1CCCCC1 KRDXTHSSNCTAGY-UHFFFAOYSA-N 0.000 description 1
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
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- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
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- CHIHQLCVLOXUJW-UHFFFAOYSA-N benzoic anhydride Chemical compound C=1C=CC=CC=1C(=O)OC(=O)C1=CC=CC=C1 CHIHQLCVLOXUJW-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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Abstract
Description
本発明は、電線・ケーブルの内部半導電層あるいは外部半導電層の形成に適した半導電性樹脂組成物およびこれを用いた電線・ケーブルに関する。 The present invention relates to a semiconductive resin composition suitable for forming an internal semiconductive layer or an external semiconductive layer of an electric wire / cable, and an electric wire / cable using the same.
ＣＶケーブル（架橋ポリエチレン絶縁電力ケーブル）などのゴム・プラスチック絶縁電力ケーブルにおいては、導体および絶縁体の外周に電気的ストレスの緩和やコロナ放電の防止などを目的として半導電層が設けられる。この半導電層の形成には、従来、エチレン・酢酸ビニル共重合体やエチレン・アクリル酸エチル共重合体などのエチレン系ポリマーに導電性カーボンブラックを配合した組成物が使用されている（例えば、特許文献１参照。）。 In a rubber / plastic insulated power cable such as a CV cable (crosslinked polyethylene insulated power cable), a semiconductive layer is provided on the outer periphery of a conductor and an insulator for the purpose of alleviating electrical stress and preventing corona discharge. For the formation of this semiconductive layer, a composition in which conductive carbon black is blended with an ethylene-based polymer such as an ethylene / vinyl acetate copolymer or an ethylene / ethyl acrylate copolymer has been used (for example, (See Patent Document 1).
しかし、従来の組成物は、体積抵抗率の温度依存性が大きいため、ケーブルの品質や特性が安定化しないという実用上の問題があった。 However, since the conventional composition has a large temperature dependency of the volume resistivity, there is a practical problem that the quality and characteristics of the cable are not stabilized.
すなわち、電力ケーブルは通電によって導体が発熱して温度が上昇する。通電電流は一定ではなく最大許容電流範囲内で常に変化しているため、導体の発熱温度は変化し、それに伴いケーブル温度も変化する。そして、このケーブル温度の変化に伴い半導電層の体積抵抗率も変化する（一般に、温度の上昇に伴い体積抵抗率も上昇する）が、従来の組成物は体積抵抗率の温度依存性が大きいため、半導電層の体積抵抗率は大きく変化する。その結果、電力ケーブルの品質や特性の安定性が低下するおそれがあった。 That is, in the power cable, the conductor generates heat by energization, and the temperature rises. Since the energization current is not constant but constantly changes within the maximum allowable current range, the heat generation temperature of the conductor changes, and the cable temperature also changes accordingly. As the cable temperature changes, the volume resistivity of the semiconductive layer also changes (generally, the volume resistivity increases as the temperature increases), but conventional compositions have a large temperature dependency of the volume resistivity. Therefore, the volume resistivity of the semiconductive layer varies greatly. As a result, there is a concern that the quality and stability of the power cable may be deteriorated.
このような温度変化に伴う体積抵抗率の上昇は、例えば導電性カーボンブラックの配合量を増大させることである程度対処することができるが、粘度が上昇するため、押出加工性が低下する。 Such an increase in volume resistivity due to a temperature change can be dealt with to some extent by increasing the blending amount of conductive carbon black, for example. However, since the viscosity increases, the extrusion processability decreases.
本発明はこのような従来技術の課題を解決するためになされたもので、体積抵抗率の温度依存性が小さく、かつ押出加工性に優れた半導電性樹脂組成物、およびそのような導電性樹脂組成物を用いた高信頼性の電線・ケーブルを提供することを目的とする。 The present invention has been made to solve the problems of the prior art, and has a semiconductive resin composition having a small temperature dependency of volume resistivity and excellent extrudability, and such a conductive property. An object is to provide a highly reliable electric wire / cable using a resin composition.
本発明者らは、上記の目的を達成するため鋭意研究を重ねた結果、特定のエチレン系三元共重合体を特定の割合で混合したオレフィン系ポリマーに、導電性カーボンブラックを配合することにより、体積抵抗率の温度依存性が小さく、かつ押出加工性に優れた半導電性樹脂組成物、およびこれを用いた電線・ケーブルが得られることを見出し、本発明を完成するに至った。 As a result of intensive studies to achieve the above object, the present inventors have blended conductive carbon black with an olefin polymer in which a specific ethylene terpolymer is mixed at a specific ratio. The present inventors have found that a semiconductive resin composition having a small volume resistivity temperature dependency and excellent extrudability and an electric wire / cable using the same can be obtained, and the present invention has been completed.
すなわち、上記目的を解決するため、請求項１に記載された発明は、（Ａ）下記（ｉ）〜（iii）の要件を満たすエチレン・α−オレフィン・非共役ポリエン共重合体を３０〜８０質量％含有するオレフィン系ポリマー１００質量部に対し、（Ｂ）導電性カーボンブラック４０〜９０質量部を含有することを特徴とする半導電性樹脂組成物である。
（ｉ）α−オレフィンが、１−ブテンである
（ii）非共役ポリエンが、ジシクロペンタジエン、１，４−ヘキサジエン、エチリデンノルボルネンおよびビニルノルボルネンからなる群より選ばれる少なくとも１種である
（iii）非共役ポリエン含有量が５質量％以下である
That is, in order to solve the above-mentioned object, the invention described in claim 1 is characterized in that (A) an ethylene / α-olefin / non-conjugated polyene copolymer satisfying the following requirements (i) to (iii): 30 to 80 (B) 40-90 mass parts of conductive carbon black is contained with respect to 100 mass parts of olefin-type polymers contained by mass%, It is a semiconductive resin composition characterized by the above-mentioned.
(I) The α-olefin is 1-butene (ii) The non-conjugated polyene is at least one selected from the group consisting of dicyclopentadiene, 1,4-hexadiene, ethylidene norbornene and vinyl norbornene. (Iii) Non-conjugated polyene content is 5% by mass or less
請求項２に記載された発明は、請求項１記載の半導電性樹脂組成物において、非共役ポリエンが、ジシクロペンタジエンおよび／またはエチリデンノルボルネンであることを特徴とする半導電性樹脂組成物である。 The invention described in claim 2 is the semiconductive resin composition according to claim 1, wherein the non-conjugated polyene is dicyclopentadiene and / or ethylidene norbornene. is there.
請求項３に記載された発明は、請求項１または２記載の半導電性樹脂組成物において、（Ａ）成分が、エチレン・ビニルエステル共重合体およびエチレン・（メタ）アクリル酸エステル共重合体からなる群より選ばれる少なくとも１種をさらに含むことを特徴とする半導電性樹脂組成物である。 The invention described in claim 3 is the semiconductive resin composition according to claim 1 or 2, wherein the component (A) is an ethylene / vinyl ester copolymer and an ethylene / (meth) acrylate ester copolymer. A semiconductive resin composition, further comprising at least one selected from the group consisting of:
請求項４に記載された発明は、請求項１または２記載の半導電性樹脂組成物において、（Ａ）成分が、エチレン・酢酸ビニル共重合体、エチレン・プロピオン酸ビニル共重合体、エチレン・アクリル酸エチル共重合体、エチレン・アクリル酸メチル共重合体、エチレン・メタクリル酸メチル共重合体およびエチレン・メタクリル酸エチル共重合体からなる群より選ばれる少なくとも１種をさらに含むことを特徴とする半導電性樹脂組成物である。 The invention described in claim 4 is the semiconductive resin composition according to claim 1 or 2, wherein the component (A) is an ethylene / vinyl acetate copolymer, an ethylene / vinyl propionate copolymer, It further comprises at least one selected from the group consisting of an ethyl acrylate copolymer, an ethylene / methyl acrylate copolymer, an ethylene / methyl methacrylate copolymer and an ethylene / ethyl methacrylate copolymer. It is a semiconductive resin composition.
請求項５に記載された発明は、請求項１乃至４のいずれか１項記載の半導電性樹脂組成物において、（Ｂ）成分の導電性カーボンブラックは、アセチレンブラックを含むことを特徴とする半導電性樹脂組成物である。 The invention described in claim 5 is the semiconductive resin composition according to any one of claims 1 to 4, wherein the conductive carbon black of the component (B) contains acetylene black. It is a semiconductive resin composition.
請求項６に記載された発明は、請求項１乃至５のいずれか１項記載の半導電性樹脂組成物において、１０５℃における体積抵抗率が、２３℃における体積抵抗率の１０倍以下であることを特徴とする半導電性樹脂組成物である。 The invention described in claim 6 is the semiconductive resin composition according to any one of claims 1 to 5, wherein the volume resistivity at 105 ° C. is 10 times or less of the volume resistivity at 23 ° C. This is a semiconductive resin composition.
請求項７に記載された発明は、導体外周に請求項１乃至６のいずれか１項記載の半導電性樹脂組成物からなる半導電層を有することを特徴とする電線・ケーブルである。 The invention described in claim 7 is an electric wire / cable having a semiconductive layer made of the semiconductive resin composition according to any one of claims 1 to 6 on a conductor outer periphery.
本発明によれば、体積抵抗率の温度依存性が小さく、かつ押出加工性に優れた半導電性樹脂組成物、およびそのような導電性樹脂組成物を用いた高信頼性の電線・ケーブルを得ることができる。 According to the present invention, a semiconductive resin composition having a small temperature dependency of volume resistivity and excellent extrudability, and a highly reliable electric wire / cable using such a conductive resin composition are provided. Obtainable.
以下、本発明の実施の形態について説明する。 Embodiments of the present invention will be described below.
まず、本発明の半導電性樹脂組成物について説明する。 First, the semiconductive resin composition of the present invention will be described.
本発明の半導電性樹脂組成物は、（Ａ）特定のエチレン・α−オレフィン・非共役ポリエン共重合体を含有するオレフィン系ポリマーと、（Ｂ）導電性カーボンブラックとを含有するものである。
本発明の半導電性樹脂組成物において使用される（Ａ）成分のエチレン・α−オレフィン・非共役ポリエン共重合体は、下記（ｉ）〜（iii）の要件を満たす。
（ｉ）α−オレフィンが、１−ブテンである
（ii）非共役ポリエンが、ジシクロペンタジエン、１，４−ヘキサジエン、エチリデンノルボルネンおよびビニルノルボルネンからなる群より選ばれる少なくとも１種である
（iii）非共役ポリエン含有量が５質量％以下である
The semiconductive resin composition of the present invention contains (A) an olefin polymer containing a specific ethylene / α-olefin / non-conjugated polyene copolymer, and (B) conductive carbon black. .
The ethylene / α-olefin / non-conjugated polyene copolymer (A) used in the semiconductive resin composition of the present invention satisfies the following requirements (i) to (iii).
(I) The α-olefin is 1-butene (ii) The non-conjugated polyene is at least one selected from the group consisting of dicyclopentadiene, 1,4-hexadiene, ethylidene norbornene and vinyl norbornene. (Iii) Non-conjugated polyene content is 5% by mass or less
エチレン・α−オレフィン・非共役ポリエン共重合体における非共役ポリエンとしては、なかでもジシクロペンタジエン、エチリデンノルボルネンが好ましく、特にジシクロペンタジエンが好ましい。この非共役ポリエンの含有量はエチレン・α−オレフィン・非共役ポリエン共重合体中の５質量％以下であり、５質量％を超えるとスコーチ時間が短くなり加工性が悪くなる。ただし、非共役ポリエンの含有量が少な過ぎると体積抵抗率の温度依存性が大きくなるため、含有量は２質量％以上、５質量％以下の範囲であることが好ましい。なお、エチレンおよびα−オレフィン（１−ブテン）の各単位成分については特に限定されるものではないが、好ましくはエチレン含有量は６０〜８５質量％であり、α−オレフィン含有量は１０〜２５質量％である。 As the non-conjugated polyene in the ethylene / α-olefin / non-conjugated polyene copolymer, dicyclopentadiene and ethylidene norbornene are preferable, and dicyclopentadiene is particularly preferable. The content of the non-conjugated polyene is 5% by mass or less in the ethylene / α-olefin / non-conjugated polyene copolymer, and if it exceeds 5% by mass, the scorch time is shortened and the workability is deteriorated. However, if the content of the non-conjugated polyene is too small, the temperature dependency of the volume resistivity increases, and therefore the content is preferably in the range of 2% by mass or more and 5% by mass or less. In addition, although it does not specifically limit about each unit component of ethylene and alpha-olefin (1-butene), Preferably ethylene content is 60-85 mass%, and alpha-olefin content is 10-25. % By mass.
本発明においては、上記エチレン・α−オレフィン・非共役ポリエン共重合体以外のオレフィン系ポリマーを少なくとも１種含有する。エチレン・α−オレフィン・非共役ポリエン共重合体以外のオレフィン系ポリマーとしては、例えば低密度ポリエチレン（ＬＤＰＥ）、中密度ポリエチレン（ＭＤＰＥ）、高密度ポリエチレン（ＨＤＰＥ）、超低密度ポリエチレン（ＶＬＤＰＥ）、直鎖状低密度ポリエチレン（ＬＬＤＰＥ）などのポリエチレン；ポリプロピレン（ＰＰ）；ポリイソプチレン；エチレンに、酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、パーサティック酸ビニル、ラウリン酸ビニル、ステアリン酸ビニル、安息香酸ビニル、サリチル酸ビニル、シクロヘキサンカルボン酸ビニルなどのビニルエステルを共重合させたエチレン・ビニルエステル共重合体；エチレンに、アクリル酸メチル、アクリル酸エチル、アクリル酸イソプロピル、アクリル酸イソブチル、アクリル酸ｎ−ブチル、アクリル酸イソオクチル、アクリル酸‐２‐エチルヘキシル、メタクリル酸メチル、メタクリル酸エチル、アクリル酸イソブチル、マレイン酸ジメチル、マレイン酸ジエチルなどの不飽和カルボン酸エステルを共重合させたエチレン・（メタ）アクリル酸エステル共重合体；エチレンに、アクリル酸、メタクリル酸、エタクリル酸、マレイン酸、フマル酸、イタコン酸、無水マレイン酸、無水イタコン酸、マレイン酸モノメチル、マレイン酸モノエチルなどの不飽和カルボン酸を共重合させたエチレン・不飽和カルボン酸共重合体；エチレンに、プロピレン、１−ブテン、１−ペンテン、１−ヘキセン、１−ヘプテン、１−オクテン、１−ノネン、１−デセン、１−ウンデセン、１−ドデセン、１−トリデセン、１−テトラデセン、１−ペンタデセン、１−ヘキサデセン、１−ヘプタデセン、１−ノナデセン、１−エイコセン、４−メチル−１−ペンテンなどのα−オレフィンを共重合させたエチレン・α−オレフィン共重合体；イソブチレン・イソプレン共重合体などが挙げられる。また、上述した（ｉ）〜（iii）の要件を満たすエチレン・α−オレフィン・非共役ポリエン共重合体以外のエチレン・α−オレフィン・非共役ポリエン共重合体も使用することができる。導電性カーボンを多量に添加する観点からは、なかでも、エチレン・酢酸ビニル共重合体（ＥＶＡ）、エチレン・プロピオン酸ビニル共重合体、エチレン・アクリル酸エチル共重合体（ＥＥＡ）、エチレン・アクリル酸メチル共重合体、エチレン・メタクリル酸メチル共重合体、エチレン・メタクリル酸エチル共重合体が好ましく、特に、エチレン・酢酸ビニル共重合体、エチレン・アクリル酸エチルが好ましい。 In the present invention, at least one olefin polymer other than the ethylene / α-olefin / non-conjugated polyene copolymer is contained. Examples of olefin polymers other than ethylene / α-olefin / non-conjugated polyene copolymers include low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), very low density polyethylene (VLDPE), Polyethylene such as linear low density polyethylene (LLDPE); polypropylene (PP); polyisobutylene; ethylene, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl persate, vinyl laurate, vinyl stearate, vinyl benzoate, Ethylene vinyl ester copolymer obtained by copolymerizing vinyl esters such as vinyl salicylate and vinyl cyclohexanecarboxylate; ethylene, methyl acrylate, ethyl acrylate, isopropyl acrylate, isobutyl acrylate, Ethylene / copolymerized with unsaturated carboxylic acid ester such as n-butyl crylate, isooctyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl acrylate, dimethyl maleate, diethyl maleate (Meth) acrylic acid ester copolymer; unsaturated ethylene, acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, maleic anhydride, itaconic anhydride, monomethyl maleate, monoethyl maleate, etc. Ethylene / unsaturated carboxylic acid copolymer obtained by copolymerization of carboxylic acid; ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-te Ethylene / α-olefin copolymer obtained by copolymerizing α-olefin such as tradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicocene, 4-methyl-1-pentene; Examples include isoprene copolymers. In addition, an ethylene / α-olefin / non-conjugated polyene copolymer other than the ethylene / α-olefin / non-conjugated polyene copolymer satisfying the above-mentioned requirements (i) to (iii) can also be used. From the viewpoint of adding a large amount of conductive carbon, among them, ethylene / vinyl acetate copolymer (EVA), ethylene / vinyl propionate copolymer, ethylene / ethyl acrylate copolymer (EEA), ethylene / acrylic, etc. An acid methyl copolymer, an ethylene / methyl methacrylate copolymer, and an ethylene / ethyl methacrylate copolymer are preferable, and an ethylene / vinyl acetate copolymer and an ethylene / ethyl acrylate copolymer are particularly preferable.
なお、上述した（ｉ）〜（iii）の要件を満たすエチレン・α−オレフィン・非共役ポリエン共重合体以外のエチレン・α−オレフィン・非共役ポリエン共重合体を使用する場合は、（Ａ）成分中の第３成分として使用することが好ましい。 In the case of using an ethylene / α-olefin / non-conjugated polyene copolymer other than the ethylene / α-olefin / non-conjugated polyene copolymer that satisfies the above-mentioned requirements (i) to (iii), (A) It is preferable to use it as the third component in the components.
（ｉ）〜（iii）の要件を満たすエチレン・α−オレフィン・非共役ポリエン共重合体の（Ａ）成分中の割合は３０〜８０質量％であり、好ましくは３０〜７０質量％であり、より好ましくは４０〜６０質量％である。（Ａ）成分中の割合が３０質量％未満では、体積抵抗率の温度依存性を改善することができない。また、押出加工性も低下する。逆に、８０質量％を超えても、体積抵抗率の温度依存性を改善する効果はさほど変わらず、材料コストが上昇する。 The proportion in the component (A) of the ethylene / α-olefin / non-conjugated polyene copolymer that satisfies the requirements (i) to (iii) is 30 to 80% by mass, preferably 30 to 70% by mass, More preferably, it is 40-60 mass%. When the proportion in the component (A) is less than 30% by mass, the temperature dependency of the volume resistivity cannot be improved. Moreover, extrusion processability also falls. On the contrary, even if it exceeds 80 mass%, the effect of improving the temperature dependency of the volume resistivity does not change so much, and the material cost increases.
本発明の半導電性樹脂組成物において使用される（Ｂ）成分の導電性カーボンブラックとしては、アセチレンブラック、ファーネスブラック、サーマルブラック、ケッチェンブラックなどが挙げられる。これらは１種を単独で使用してもよく、２種以上を組み合わせて使用してもよい。（Ｂ）成分の導電性カーボンブラックとしては、なかでも、アセチレンブラックが好ましい。 Examples of the conductive carbon black as the component (B) used in the semiconductive resin composition of the present invention include acetylene black, furnace black, thermal black, and ketjen black. These may be used individually by 1 type and may be used in combination of 2 or more type. As the conductive carbon black as the component (B), acetylene black is particularly preferable.
この（Ｂ）成分の導電性カーボンブラックの配合量は、（Ａ）成分のオレフィン系ポリマー１００質量部に対して、４０〜９０質量部、好ましくは４５〜８０質量部、より好ましくは５０〜７０質量部である。配合量が４０質量部未満では、体積抵抗率が大きくなり、また、９０質量部を超えると、組成物の粘度が上昇して押出加工が実質的にできなくなる。また、機械的強度、特に伸びが低下する。 The blending amount of the conductive carbon black as the component (B) is 40 to 90 parts by weight, preferably 45 to 80 parts by weight, and more preferably 50 to 70 parts by weight with respect to 100 parts by weight of the olefin polymer of the component (A). Part by mass. When the blending amount is less than 40 parts by mass, the volume resistivity increases. When the blending amount exceeds 90 parts by mass, the viscosity of the composition increases and the extrusion process becomes substantially impossible. Also, the mechanical strength, particularly the elongation, decreases.
本発明の半導電性樹脂組成物は、被覆後もしくは成形後にポリマー成分を架橋させてもよい。架橋させることにより耐熱性を向上させることができる。架橋方法は、予め半導電性樹脂組成物に架橋剤を添加しておき、成形後に架橋させる化学架橋法や、電子線照射による電子線架橋法などを用いることができる。化学架橋法を行う場合に用いる架橋剤としては、ジクミルパーオキサイド、ジ−ｔｅｒｔ−ブチルパーオキサイド、２，５−ジメチルー２，５−ジ−（ｔｅｒｔ−ブチルパーオキシ）ヘキサン、２，５−ジメチルー２，５−ジ−（ｔｅｒｔ−ブチルパーオキシ）ヘキシン−３、ジ−（tｅｒｔ−ブチルパーオキシ）ジイソプロピルベンゼン、１，３−ビス（ｔｅｒｔ−ブチルパーオキシイソプロピル）ベンゼン、１，１−ビス（ｔｅｒｔ−ブチルパーオキシ）−３，３，５−トリメチルシクロヘキサン、ｎ−ブチル−４，４−ビス（ｔｅｒｔ−ブチルパーオキシ）バレレート、ベンゾイルオキサイド、２，４−ジクロロベンゾイルパーオキサイド、ｔｅｒｔ−ブチルパーオキシベンゾエート、ｔｅｒｔ−ブチルパーオキシイソプロピルカーボネート、ジアセチルパーオキサイド、ラウロイルパーオキサイド、ｔｅｒｔ−ブチルクミルパーオキサイドなどが挙げられる。 In the semiconductive resin composition of the present invention, the polymer component may be crosslinked after coating or molding. The heat resistance can be improved by crosslinking. As the crosslinking method, a chemical crosslinking method in which a crosslinking agent is added to the semiconductive resin composition in advance and crosslinked after molding, an electron beam crosslinking method by electron beam irradiation, or the like can be used. Examples of the crosslinking agent used in the chemical crosslinking method include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5- Dimethyl-2,5-di- (tert-butylperoxy) hexyne-3, di- (tert-butylperoxy) diisopropylbenzene, 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (Tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl oxide, 2,4-dichlorobenzoyl peroxide, tert-butyl Peroxybenzoate, tert-butyl peroxyisopropyl carbonate And diacetyl peroxide, lauroyl peroxide, tert-butyl cumyl peroxide and the like.
なお、架橋を行わない場合、エチレン・α−オレフィン・非共役ポリエン共重合体以外のオレフィン系ポリマーとして、融点の高い（例えば、１２０℃以上）ポリエチレンを使用すると、耐熱性を高めることができる。また、架橋を行う場合、エチレン・α−オレフィン・非共役ポリエン共重合体以外のオレフィン系ポリマーとして、エチレン・アクリル酸エチル共重合体の使用が好ましい。 In addition, when not performing bridge | crosslinking, heat resistance can be improved when polyethylene with a high melting | fusing point (for example, 120 degreeC or more) is used as olefin type polymers other than an ethylene-alpha-olefin and nonconjugated polyene copolymer. In addition, when crosslinking is performed, it is preferable to use an ethylene / ethyl acrylate copolymer as the olefin polymer other than the ethylene / α-olefin / non-conjugated polyene copolymer.
本発明の半導電性樹脂組成物には、以上説明した成分の他、さらに、本発明の効果を阻害しない範囲で、必要に応じて、無機充填剤、加工助剤、架橋助剤、難燃剤、酸化防止剤、老化防止剤、紫外線吸収剤、軟化剤、可塑剤、滑剤、その他の添加剤を配合することができる。 In addition to the components described above, the semiconductive resin composition of the present invention may further include an inorganic filler, a processing aid, a crosslinking aid, a flame retardant, as long as the effects of the present invention are not impaired. Antioxidants, antioxidants, UV absorbers, softeners, plasticizers, lubricants, and other additives can be blended.
本発明の半導電性樹脂組成物は、以上の各成分をバンバリーミキサ、タンブラー、加圧ニーダ、混練押出機、ミキシングローラなどの通常の混練機を用いて均一に混合することにより容易に製造することができる。 The semiconductive resin composition of the present invention is easily produced by uniformly mixing the above components using a conventional kneader such as a Banbury mixer, tumbler, pressure kneader, kneading extruder, mixing roller, or the like. be able to.
本発明の半導電性樹脂組成物は、１０５℃における体積抵抗率が、２３℃における体積抵抗率の１０倍以下であることが好ましく、３倍以下であることがより好ましい。 In the semiconductive resin composition of the present invention, the volume resistivity at 105 ° C. is preferably 10 times or less, more preferably 3 times or less of the volume resistivity at 23 ° C.
次に、上記半導電性樹脂組成物を用いた本発明の電力ケーブルについて説明する。
本発明の電線・ケーブルは、前述した方法で調製した組成物を、導体外周に直接もしくは他の被覆を介して押出し被覆するか、あるいはテープ状に成形したものを巻き付けることにより製造される。なお、前述したように、組成物は、被覆後もしくは成形後、架橋することができる。
Next, the power cable of the present invention using the semiconductive resin composition will be described.
The electric wire / cable of the present invention is produced by extruding and coating the composition prepared by the above-described method directly or through another coating on the outer periphery of the conductor, or by winding a tape-shaped one. As described above, the composition can be crosslinked after coating or molding.
図１は、本発明の電線・ケーブルの一実施形態（電力ケーブル）を示す横断面図である。 FIG. 1 is a cross-sectional view showing an embodiment (electric power cable) of an electric wire / cable of the present invention.
図１において、１１は、例えば多数本の銅素線を撚り合わせ円形圧縮加工を施してなる導体を示している。この導体１１上には、内部半導電層１２、架橋ポリエチレンなどからなる絶縁体１３、外部半導電層１４、遮蔽層１５、アルミなどからなる金属シース１６およびポリエチレン樹脂などからなる防食層１７が順に設けられている。そして、このケーブルにおいては、内部半導電層１２および外部半導電層１４が前述した半導電性樹脂組成物の押出被覆により形成されている。
In FIG. 1,
このように構成される電力ケーブルにおいては、内部半導電層１２および外部半導電層１４がいずれも体積抵抗率の温度依存率の小さい半導電性樹脂組成物で形成されているため、高温時でも良好かつ安定したケーブル特性を有している。
In the power cable configured in this way, both the internal
本発明の電線・ケーブルは、半導電層を備えたものであれば、従来知られる各種電線・ケーブルに広く適用可能である。 The electric wire / cable of the present invention can be widely applied to various conventionally known electric wires / cables as long as it has a semiconductive layer.
例えば、図２は、遮蔽層１５上に、防食層を兼ねるポリエチレン樹脂などからなるプラスチックシース１８が設けられている点を除いて、図１に示す電力ケーブルと同様に構成されている。このように構成される電力ケーブルにおいても、内部半導電層１２および外部半導電層１４がいずれも体積抵抗率の温度依存率の小さい半導電性樹脂組成物で形成されているため、高温時でも良好かつ安定したケーブル特性を有している。
For example, FIG. 2 is configured in the same manner as the power cable shown in FIG. 1 except that a
本発明は、以上説明した実施の形態の記載内容に限定されるものではなく、構造や材質、各部材の配置等は、本発明の要旨を逸脱しない範囲で適宜変更可能である。 The present invention is not limited to the description of the embodiment described above, and the structure, material, arrangement of each member, and the like can be appropriately changed without departing from the gist of the present invention.
次に、本発明を実施例によりさらに詳細に説明するが、本発明はこれらの実施例に何ら限定されるものではない。実施例および比較例で用いた成分は以下の通りである。
・高密度ポリエチレン：
日本ポリエチレン（株）製 商品名 ノバテックＨＤ２３０
（密度０．９４６ｇ／ｃｍ３、ＭＦＲ０．９ｇ／１０分）
・エチレン・アクリル酸エチル共重合体：
日本ユニカー（株）製 商品名 ＤＰＤＪ−９１６９
・エチレン・ブテン−１・ジシクロペンタジエン共重合体：
三井化学（株）製 商品名 ＥＰＴ Ｘ−７５
（エチレン：７６質量％ ブテン−１：１９．５質量％
ジシクロペンタジエン：４．５質量％）
・アセチレンブラック：
電気化学工業（株）製 商品名 デンカブラック
・酸化防止剤：
チバジャパン（株）製 商品名 イルガノックス１０３５
・架橋剤：
ジ−（tｅｒｔ−ブチルパーオキシ）ジイソプロピルベンゼン；
日油（株）製 商品名 パーブチルＰ
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples at all. The components used in Examples and Comparative Examples are as follows.
・ High density polyethylene:
Product name Novatec HD230 made by Nippon Polyethylene Co., Ltd.
(Density 0.946g / cm 3 , MFR 0.9g / 10min)
・ Ethylene / ethyl acrylate copolymer:
Product name DPDJ-9169 manufactured by Nippon Unicar Co., Ltd.
-Ethylene / Butene-1 / Dicyclopentadiene copolymer:
Product name EPT X-75 manufactured by Mitsui Chemicals, Inc.
(Ethylene: 76% by mass Butene-1: 19.5% by mass
Dicyclopentadiene: 4.5% by mass)
・ Acetylene black:
Product name Denka Black, antioxidant manufactured by Denki Kagaku Kogyo Co., Ltd .:
Product name manufactured by Ciba Japan Co., Ltd. Irganox 1035
・ Crosslinking agent:
Di- (tert-butylperoxy) diisopropylbenzene;
Product name Perbutyl P manufactured by NOF Corporation
実施例１
エチレン・アクリル酸エチル共重合体７０質量部、エチレン・ブテン−１・ジシクロペンタジエン共重合体３０質量部、アセチレンブラック６０質量部、酸化防止剤０．５質量部、および架橋剤１質量部を加圧ニーダを用いて均一に混練して半導電性樹脂組成物を調製した。
Example 1
70 parts by mass of an ethylene / ethyl acrylate copolymer, 30 parts by mass of an ethylene / butene-1 / dicyclopentadiene copolymer, 60 parts by mass of acetylene black, 0.5 parts by mass of an antioxidant, and 1 part by mass of a crosslinking agent A semiconductive resin composition was prepared by uniformly kneading using a pressure kneader.
実施例２〜６、比較例１、２
配合成分および配合量を表１に示すように変えた以外は、実施例１と同様にして半導電性樹脂組成物を調製した。
Examples 2 to 6, Comparative Examples 1 and 2
A semiconductive resin composition was prepared in the same manner as in Example 1 except that the blending components and blending amounts were changed as shown in Table 1.
上記各実施例および各比較例で得られた導電性樹脂組成物について、下記に示す方法で各種特性を評価した。 About the conductive resin composition obtained by each said Example and each comparative example, various characteristics were evaluated by the method shown below.
［体積抵抗率］
半導電性樹脂組成物を１８０℃で２０分間プレス成形して作成した厚さ約１ｍｍのシートを、φ５０ｍｍの主電極およびφ８０ｍｍの対電極で挟み込み、デジタルマルチメータにて測定した。測定は２３℃、６０℃、９０℃および１０５℃の各温度にて実施した。
[Volume resistivity]
A sheet having a thickness of about 1 mm prepared by press-molding the semiconductive resin composition at 180 ° C. for 20 minutes was sandwiched between a main electrode of φ50 mm and a counter electrode of φ80 mm and measured with a digital multimeter. The measurement was carried out at each temperature of 23 ° C., 60 ° C., 90 ° C. and 105 ° C.
［押出加工性］
ＪＩＳ Ｋ ６３００に準拠して１５０℃におけるムーニースコーチテストを行い、その測定により得たムーニースコーチ時間により評価した。
［ゲル分率］
ＪＩＳ Ｃ ３００５に準拠して測定した。
[Extrudability]
A Mooney scorch test at 150 ° C. was performed in accordance with JIS K 6300, and the Mooney scorch time obtained by the measurement was evaluated.
[Gel fraction]
It measured based on JISC3005.
これらの結果を表１の下欄に示す。 These results are shown in the lower column of Table 1.
表１から明らかなように、実施例に係る半導電性樹脂組成物は、いずれも体積抵抗率の温度依存性が小さく、かつ押出加工性にも優れていた。これに対し、エチレン・ブテン−１・ジシクロペンタジエン共重合体が過少配合された比較例１、２では、体積抵抗率の温度依存性が大きいうえに押出加工性も不良であった。 As is clear from Table 1, each of the semiconductive resin compositions according to the examples had a small temperature dependency of the volume resistivity and was excellent in extrusion processability. On the other hand, in Comparative Examples 1 and 2 in which the ethylene / butene-1 / dicyclopentadiene copolymer was blended in an insufficient amount, the temperature dependency of the volume resistivity was large and the extrusion processability was also poor.
１１…導体、１２…内部半導電層、１３…架橋ポリエチレン絶縁体、１４…外部半導電層、１５…遮蔽層、１６…金属シース、１８…プラスチックシース。
DESCRIPTION OF
Claims (7)
（ｉ）α−オレフィンが、１−ブテンである
（ii）非共役ポリエンが、ジシクロペンタジエン、１，４−ヘキサジエン、エチリデンノルボルネンおよびビニルノルボルネンからなる群より選ばれる少なくとも１種である
（iii）非共役ポリエン含有量が５質量％以下である (A) With respect to 100 parts by mass of an olefin-based polymer containing 30 to 80% by mass of an ethylene / α-olefin / non-conjugated polyene copolymer that satisfies the following requirements (i) to (iii), (B) conductive carbon A semiconductive resin composition comprising 40 to 90 parts by mass of black.
(I) The α-olefin is 1-butene (ii) The non-conjugated polyene is at least one selected from the group consisting of dicyclopentadiene, 1,4-hexadiene, ethylidene norbornene and vinyl norbornene. (Iii) Non-conjugated polyene content is 5% by mass or less
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| JP2015059172A (en) * | 2013-09-18 | 2015-03-30 | 株式会社フジクラ | Semiconductive resin composition and power cable |
| 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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| 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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