JPH01225003A - Electric insulation composition and power cable - Google Patents
Electric insulation composition and power cableInfo
- Publication number
- JPH01225003A JPH01225003A JP4762588A JP4762588A JPH01225003A JP H01225003 A JPH01225003 A JP H01225003A JP 4762588 A JP4762588 A JP 4762588A JP 4762588 A JP4762588 A JP 4762588A JP H01225003 A JPH01225003 A JP H01225003A
- Authority
- JP
- Japan
- Prior art keywords
- antioxidant
- polyethylene
- grafting
- parts
- insulation composition
- 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.)
- Granted
Links
- 238000009413 insulation Methods 0.000 title abstract description 6
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 35
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 28
- 239000004698 Polyethylene Substances 0.000 claims abstract description 20
- -1 polyethylene Polymers 0.000 claims abstract description 13
- 229920000573 polyethylene Polymers 0.000 claims abstract description 12
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 6
- 229920003020 cross-linked polyethylene Polymers 0.000 claims description 5
- 239000004703 cross-linked polyethylene Substances 0.000 claims description 5
- 239000004020 conductor Substances 0.000 claims description 4
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical group C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000010292 electrical insulation Methods 0.000 claims 3
- 239000004717 peroxide crosslinked polyethylene Substances 0.000 claims 1
- 230000001133 acceleration Effects 0.000 abstract description 4
- 230000032683 aging Effects 0.000 abstract description 3
- 125000003118 aryl group Chemical group 0.000 abstract description 2
- 230000005764 inhibitory process Effects 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract 1
- 238000002425 crystallisation Methods 0.000 abstract 1
- 230000008025 crystallization Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 230000001066 destructive effect Effects 0.000 description 3
- 238000009658 destructive testing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002530 phenolic antioxidant Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- NOSXUFXBUISMPR-UHFFFAOYSA-N 1-tert-butylperoxyhexane Chemical compound CCCCCCOOC(C)(C)C NOSXUFXBUISMPR-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
- MQWCQFCZUNBTCM-UHFFFAOYSA-N 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylphenyl)sulfanyl-4-methylphenol Chemical compound CC(C)(C)C1=CC(C)=CC(SC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O MQWCQFCZUNBTCM-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Insulating Materials (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は電カケープルに用いられる電気絶縁組成物及び
電カケープルに関するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an electrical insulating composition used for electrical cables and electrical cables.
（従来の技術）（発明が解決すべき課題）近時送電電圧
の高電圧化に伴ない架橋ポリエチレン（ＸＬＰＥ）はそ
の加工方法の改良とも相俟って、現在では２７５ ｋＶ
級ケーブルまで実用化されるに至っている。(Prior Art) (Problem to be Solved by the Invention) With the recent increase in power transmission voltage, cross-linked polyethylene (XLPE) has now reached 275 kV due to improvements in its processing method.
Even grade cables have been put into practical use.
−プルの巻取、運搬、施設の障害となり、絶縁厚の低減
が望まれている。- It is a hindrance to the winding of pulls, transportation, and facilities, and it is desired to reduce the insulation thickness.
換言すればＸＬＰＥの絶縁耐力を向上させることによっ
て絶縁厚をできるだけ薄くすることが要求されている。In other words, it is required to reduce the insulation thickness as much as possible by improving the dielectric strength of XLPE.
（課題を解決するための手段〕
本発明は上記の課題を達成するためになされたものでそ
の概要は以下に示すとおりである。(Means for Solving the Problems) The present invention has been made to achieve the above-mentioned problems, and the outline thereof is as shown below.
ポリエチレンに酸化防止剤をグラフトさせ、これを有機
過酸化物を用いて架橋するようにした組成物であり、こ
れを導体の外部の絶縁層とするときは絶縁耐力の向上が
著るしいことを見出した。This is a composition in which an antioxidant is grafted onto polyethylene and this is crosslinked using an organic peroxide, and when this is used as an external insulating layer of a conductor, the dielectric strength is significantly improved. I found it.
而してここに用いられる酸化防止剤としてはチオビスフ
ェノール系又はビニル基含有フェノール系が好ましく、
又、ポリエチレン１００重量部に対する酸化防止剤の添
加量は０．１〜２．０重量部が好ましい。Therefore, the antioxidant used here is preferably a thiobisphenol type or a vinyl group-containing phenol type.
Further, the amount of antioxidant added to 100 parts by weight of polyethylene is preferably 0.1 to 2.0 parts by weight.
（作用）
ここに酸化防止剤そのものはポリエチレンの熱老化防止
のために、必然的に添加される添加剤であるが、特定の
酸化防止剤の場合、有機過酸化物によるポリエチレン（
ＰＥ ）の架橋の際にＰＥ鎖にグラフト化することが認
められ特に絶縁耐力はグラフト化しない酸化防止剤を添
加するものより効果のあることが認められた。このよう
な酸化防止剤を列挙すれば、チオビスフェノール系のも
の、４．４′−チオビス−（６−第３ブチル−３−メチ
ルフェノール）、４，４′−チオビス−（６−第３ブチ
ル−０−クレゾール）、２．２′−チオビス−（６−第
３ブチル−４メチルフエノール）等があげられる。又、
ビニル基を含有する下記化学式に示すようなフェノール
系酸化防止剤等もグラフトし易い酸化防止剤である。(Function) The antioxidant itself is an additive that is inevitably added to prevent heat aging of polyethylene, but in the case of a specific antioxidant, polyethylene (
During the crosslinking of PE), it was observed that the antioxidant was grafted to the PE chains, and in particular, it was found that the dielectric strength was more effective than the addition of an antioxidant that did not cause grafting. Examples of such antioxidants include thiobisphenols, 4,4'-thiobis-(6-tert-butyl-3-methylphenol), 4,4'-thiobis-(6-tert-butyl -0-cresol), 2,2'-thiobis-(6-tert-butyl-4-methylphenol), and the like. or,
Phenolic antioxidants containing vinyl groups as shown in the chemical formula below are also antioxidants that are easily grafted.
Ｂｕ
これらの酸化防止剤のＰＥ鎖へのグラフトは例えば以下
のように考えられる。Bu Grafting of these antioxidants onto PE chains can be considered, for example, as follows.
（チオビスフェノール系酸化防止剤）
ｔ１
ＰＡＯ−ＣＨ＝ ＣＨ２→ＰＡＯ−ＣＨ−ＣＨ２−シμ
！−闇ＡＯ
（ＰＡＯ：フェノール系酸化防止剤）
ここにグラフト化用の酸化防止剤の添加量はポリエチレ
ン１００重ｉｔ部に対し０．１〜２．０重量部が好まし
く、０．１重量部未満では耐電圧性能が向上せず、しか
も熱老化防止の効果も上らない。又、２．０重量部を越
えた場合は、ポリエチレンの架橋効率を著しく低下させ
る。(Thiobisphenol antioxidant) t1 PAO-CH= CH2→PAO-CH-CH2-μ
! - Dark AO (PAO: Phenolic antioxidant) The amount of the antioxidant for grafting added here is preferably 0.1 to 2.0 parts by weight, and less than 0.1 parts by weight, based on 100 parts by weight of polyethylene. In this case, the withstand voltage performance is not improved, and the effect of preventing heat aging is also not improved. Moreover, when it exceeds 2.0 parts by weight, the crosslinking efficiency of polyethylene is significantly reduced.
酸化防止剤のグラフト化及びＰＥの架橋に使用される有
機過酸化物としては、ジクミルノｅ−オキサイド（ＤＣ
Ｐ ） 、α、α′−ビス（ｔ−ブチルノに一オキシ）
ジインプロピルベンゼン、ｔ−ブチルクミルパーオキサ
イド、２，５ツメチル−２，５・ゾ（ｔ−ブチルパーオ
キシ）ヘキサン−（３）等が掲げられる。Organic peroxides used for grafting antioxidants and crosslinking PE include dicumyl-e-oxide (DC
P), α, α'-bis(t-butylmonooxy)
Examples include diinpropylbenzene, t-butylcumyl peroxide, 2,5-methyl-2,5-zo(t-butylperoxy)hexane (3), and the like.
その添加量は酸化防止剤の種類によっても異なるが、１
．０〜５．０重量部程度であり、１，０重量部未満では
架橋及びグラフト化反応が不十分となり、５．０重量部
を超えるとその特性向上に無関係々使用量となシ、押出
時の早期加硫等の問題を発生し易くなる。而して上記の
ような酸化防止剤のグラフトによる耐電圧特性の向上の
理由については以下のように思われる。The amount added varies depending on the type of antioxidant, but 1
．． The amount is about 0 to 5.0 parts by weight, and if it is less than 1.0 parts by weight, the crosslinking and grafting reactions will be insufficient, and if it exceeds 5.0 parts by weight, the amount used will not be used regardless of the improvement of the properties. Problems such as early vulcanization are likely to occur. The reason for the improvement in voltage resistance characteristics by grafting the antioxidant as described above seems to be as follows.
（１） ＰＥの結晶性が多少阻害されることによる絶
縁破壊時の結晶内走行電子の加速抑制
（２）酸化防止剤に含まれる電子共鳴構造を有する芳香
環による電子加速の抑制
（実施例〕
次に本発明の実施例について述べる。(1) Suppression of acceleration of intracrystalline electrons during dielectric breakdown due to some inhibition of PE crystallinity (2) Suppression of electron acceleration due to aromatic ring with electronic resonance structure contained in antioxidant (Example) Next, examples of the present invention will be described.
実施例１〜実施例３
ＭＩ＝ｌ、Ｑの低密度ＰＫに対して酸化防止剤とじてｔ
Ｂｕ ＣＨ３
置部の範囲で用いかつ架橋剤としてＤＣＰ （１，５〜
４．０重量部）を用いてグラフト化させた。Examples 1 to 3 MI=l, t as an antioxidant for low density PK of Q
DCP (1,5~
4.0 parts by weight) was used for grafting.
比較例１
酸化防止剤を全く添加しない外は実施例１と同一である
。Comparative Example 1 Same as Example 1 except that no antioxidant was added.
比較例２，３
酸化防止剤の使用量を０１重量部未満及び２．０重量部
類とした外は実施例１と同時である。Comparative Examples 2 and 3 Same as Example 1 except that the amount of antioxidant used was less than 0.01 parts by weight and 2.0 parts by weight.
実施例４〜６ 酸化防止剤として −Ｂｕ れぞれ実施例１〜３と同様である。Examples 4-6 As an antioxidant -Bu These are the same as Examples 1 to 3, respectively.
比較例４，５
酸化防止剤の使用量金０．１重量部未満及び２．０重量
部類とした外は実施例４と同様である。Comparative Examples 4 and 5 The same as Example 4 except that the amount of antioxidant used was less than 0.1 parts by weight of gold and 2.0 parts by weight.
これらの実施例及び比較例の特性を見るために、第１図
に示すような破壊試験用リセス状シート試料に１８０℃
×３０分の乗件でプレス架橋した。In order to examine the characteristics of these Examples and Comparative Examples, a recessed sheet sample for destructive testing as shown in Figure 1 was heated at 180°C.
Press crosslinking was carried out in a 30 minute ride.
架橋後の各試料のダル分率は、一部を除きいずれも約８
０壬であった。また溶剤抽出により酸化防止剤の分析を
行なったが、抽出溶剤中には酸化防止剤は検出されず、
従って酸化防止剤はＸＬＰＥにグラフトされていること
が確められた。The dull fraction of each sample after crosslinking was approximately 8 except for some.
It was 0. We also analyzed antioxidants by solvent extraction, but no antioxidants were detected in the extraction solvent.
Therefore, it was confirmed that the antioxidant was grafted onto XLPE.
各試料について第１図の電極構成によシ標準インパルス
（ＩＸ４０μｓ）による破壊試験を行なった結果は表１
の通りであった。Table 1 shows the results of a destructive test using a standard impulse (IX 40μs) using the electrode configuration shown in Figure 1 for each sample.
It was as follows.
図において１は試料、２はその上下面の導電性塗料、３
は絶縁油、４は電極でリセス部厚さ２００〜３００μｍ
、ＩＪセス部有効径１０醇φである。In the figure, 1 is the sample, 2 is the conductive paint on the top and bottom surfaces, and 3 is the sample.
is insulating oil, 4 is electrode, recess thickness is 200 to 300 μm
, the effective diameter of the IJ groove is 10 mm.
なお破壊試験に際しては架橋剤分解残渣の影響を除くた
め、８０℃×１日乾燥後、供試試料とした。In the destructive test, in order to eliminate the influence of crosslinking agent decomposition residue, test samples were prepared after drying at 80° C. for 1 day.
表 １ 注：酸化防止剤■、■はＡｉｌ記の■と■を衣す。Table 1 Note: Antioxidants ■ and ■ correspond to ■ and ■ in Ail.
中はダル分率の向上が認められない。No improvement in dull fraction was observed in the medium.
次に本発明において、上記の表１中実施例２゜５及び比
較例２の各絶縁物を導体の外部の絶縁層（］０）
として用いた電カケープルを作った。Next, in the present invention, electric cables were made using each of the insulators of Example 2.5 and Comparative Example 2 in Table 1 as an insulating layer (]0) outside the conductor.
ケーブル構造は導体断面積２５０朋２、絶縁層厚９１１
１１、内部半導電層および外部半導電層を有する３層構
造である。The cable structure has a conductor cross-sectional area of 250 mm and an insulation layer thickness of 91 mm.
11, a three-layer structure having an inner semiconducting layer and an outer semiconducting layer.
上記各ケーブルの商用周波数（ＡＣ）電圧及び標準イン
Ａ？ルス（Ｉｍｐ）ｉｉｕ圧による破壊試験を行なった
ところ、その結果は表２に示すとおりである。What is the commercial frequency (AC) voltage and standard in A of each cable above? A destructive test using Imp IIU pressure was conducted, and the results are shown in Table 2.
表 ２
（発明の効果）
本発明によれば前記した比較試験からも明らかなとおシ
、単に酸化防止剤を添加したものと異なシポリエチレン
のグラフト化によシ耐電圧性能を著しく向上させること
ができる。Table 2 (Effects of the Invention) According to the present invention, it is clear from the above comparative tests that the withstand voltage performance can be significantly improved by grafting polyethylene, which is different from simply adding an antioxidant. can.
第１図は混和物シートの破壊試験方法を示す概略図であ
る。
代理人 弁理士 竹 内 守FIG. 1 is a schematic diagram showing a method for destructive testing of an admixture sheet. Agent Patent Attorney Mamoru Takeuchi
Claims (4)
ポリエチレンに酸化防止剤がグラフト化されていること
を特徴とする電気絶縁組成物(1) An electrical insulation composition characterized in that an antioxidant is grafted onto polyethylene in crosslinked polyethylene using an organic peroxide.
含有フェノール系である請求項１の電気絶縁組成物(2) The electrical insulation composition according to claim 1, wherein the antioxidant is a thiobisphenol type or a vinyl group-containing phenol type.
加量が０．１〜２．０重量部である請求項１の電気絶縁
組成物(3) The electrical insulation composition according to claim 1, wherein the amount of the antioxidant added is 0.1 to 2.0 parts by weight per 100 parts by weight of polyethylene.
せたポリエチレンの有機過酸化物架橋体を主として形成
されていることを特徴とする電力ケーブル(4) A power cable characterized in that the external insulating layer of the conductor is mainly formed of an organic peroxide crosslinked polyethylene grafted with an antioxidant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63047625A JPH0828136B2 (en) | 1988-03-02 | 1988-03-02 | Electrical insulation composition and power cable |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63047625A JPH0828136B2 (en) | 1988-03-02 | 1988-03-02 | Electrical insulation composition and power cable |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01225003A true JPH01225003A (en) | 1989-09-07 |
| JPH0828136B2 JPH0828136B2 (en) | 1996-03-21 |
Family
ID=12780395
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63047625A Expired - Lifetime JPH0828136B2 (en) | 1988-03-02 | 1988-03-02 | Electrical insulation composition and power cable |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0828136B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107746492A (en) * | 2017-10-20 | 2018-03-02 | 日丰企业（佛山）有限公司 | Antioxidant master batch and its application in PEX pipes are prepared |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59154711A (en) * | 1983-02-23 | 1984-09-03 | 住友電気工業株式会社 | high voltage cable |
-
1988
- 1988-03-02 JP JP63047625A patent/JPH0828136B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59154711A (en) * | 1983-02-23 | 1984-09-03 | 住友電気工業株式会社 | high voltage cable |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107746492A (en) * | 2017-10-20 | 2018-03-02 | 日丰企业（佛山）有限公司 | Antioxidant master batch and its application in PEX pipes are prepared |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0828136B2 (en) | 1996-03-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| FI82320C (en) | Insulation composition for cables | |
| KR100581459B1 (en) | Electrical cables and methods and compositions for making them | |
| JPH01225003A (en) | Electric insulation composition and power cable | |
| JPS64767B2 (en) | ||
| US3163705A (en) | Oil insulated impregnant for high voltage electrical apparatus | |
| JP2681158B2 (en) | Power cable | |
| JPH11224542A (en) | Crosslinked polyethylene insulated power cable | |
| JP2001325834A (en) | Dc power cable | |
| US4780576A (en) | Insulated electrical cable | |
| JPH09231839A (en) | Direct current cable | |
| US3145258A (en) | Treated insulation impregnant for high voltage electrical cable | |
| JPH0562529A (en) | Power cable | |
| JPH0765633A (en) | DC cable | |
| JP2001266650A (en) | Electrical insulating composition and electric cable | |
| JPS5998403A (en) | semiconductive composition | |
| JPS6344247B2 (en) | ||
| JPS63150811A (en) | Power cable | |
| JPH0831241A (en) | Power cable | |
| JP2620960B2 (en) | Polyolefin composition | |
| Hirota et al. | The influence of antioxidants on electrical tree generation in XLPE | |
| JPH0127223Y2 (en) | ||
| JPH0515007B2 (en) | ||
| JPH11224543A (en) | DC power cable | |
| JPS6346929B2 (en) | ||
| Del Mar | Paper for High-Voltage Cables |