JPH07126450A - Non-halogenic flame-retardant insulating composition useful under radiation exposure environment - Google Patents
Non-halogenic flame-retardant insulating composition useful under radiation exposure environmentInfo
- Publication number
- JPH07126450A JPH07126450A JP29593693A JP29593693A JPH07126450A JP H07126450 A JPH07126450 A JP H07126450A JP 29593693 A JP29593693 A JP 29593693A JP 29593693 A JP29593693 A JP 29593693A JP H07126450 A JPH07126450 A JP H07126450A
- Authority
- JP
- Japan
- Prior art keywords
- flame
- weight
- retardant insulating
- radiation exposure
- polyolefin
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、放射線被曝環境下で用
いる非ハロゲン系難燃性絶縁組成物に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a halogen-free flame-retardant insulating composition used in a radiation exposure environment.
【０００２】[0002]
【従来の技術】従来から、原子力発電所を始めとする放
射線被曝環境下で使用される電線・ケーブルの電気絶縁
物は耐放射線性に優れていることが要求されている。ま
た同時に、高い安全性を維持するため、万一の火災時に
も優れた耐延焼性を有することも要求されている。これ
らの要求を満たすため、現用材では、ポリエチレン等の
ポリオレフィンにハロゲン系難燃剤を配合した難燃性絶
縁組成物が使用されている。しかしながら、このような
ハロゲン系難燃剤を配合した難燃性絶縁組成物は、燃焼
時に金属腐食性ガスや多量の煙を発生するなどの問題が
あった。一方、最近、ポリオレフィンに金属水和物を多
量に配合した非ハロゲン系難燃材料の開発・実用化が進
んでいる。このような非ハロゲン系難燃材料は、発煙量
が少なく、金属腐食性のハロゲン系ガスを発生させない
等の利点があるため、高度の安全性を必要とする原子力
利用分野にも、その応用が期待されている。しかしなが
ら、このような非ハロゲン系難燃材料は、大量の放射線
を被曝すると、非常に脆くなり、伸び特性が低下し、実
用性が著しく損なわれる欠点があった。従来の非ハロゲ
ン系難燃材料に見られた大量の放射線被曝時の機械的特
性の低下を改善する一手段として、特開昭６３−２８６
４５０号においては、芳香族系老化防止剤の添加効果に
ついて検討し、特に、ポリ（２，２，４−トリメチル−
１，２−ジヒドロキノリン）を配合した非ハロゲン系難
燃性ポリエチレン組成物が提案されている。2. Description of the Related Art Conventionally, it has been required that electric insulators of electric wires and cables used in a radiation exposure environment such as a nuclear power plant have excellent radiation resistance. At the same time, in order to maintain high safety, it is required to have excellent fire spread resistance even in the event of a fire. In order to meet these requirements, currently used materials use a flame-retardant insulating composition obtained by blending a polyolefin such as polyethylene with a halogen-based flame retardant. However, the flame-retardant insulating composition containing such a halogen-based flame retardant has a problem that it generates a metal corrosive gas or a large amount of smoke during combustion. On the other hand, recently, development and practical use of non-halogen flame-retardant materials in which a large amount of metal hydrate is blended with polyolefin have been advanced. Such non-halogen flame-retardant materials have the advantages that they emit less smoke and do not generate metal-corrosive halogen-based gas, so they are also applicable to the field of nuclear power applications requiring a high degree of safety. Is expected. However, such a non-halogen flame-retardant material has the drawbacks that when exposed to a large amount of radiation, it becomes extremely brittle, its elongation properties deteriorate, and its practicality is significantly impaired. As one means for improving the deterioration of mechanical properties of conventional non-halogen flame-retardant materials when exposed to a large amount of radiation, JP-A-63-286 is known.
In No. 450, the effect of adding an aromatic anti-aging agent was examined, and in particular, poly (2,2,4-trimethyl-
A non-halogen flame-retardant polyethylene composition containing 1,2-dihydroquinoline) has been proposed.
【０００３】[0003]
【発明が解決しようとする課題】本発明者は、従来の耐
放射線性の良好な非ハロゲン系難燃性ポリエチレン組成
物につき、更に、その耐放射線性を向上させるべく研究
を続けた結果、上記非ハロゲン系難燃性ポリエチレン組
成物のベース樹脂である低密度ポリエチレンの一部量
を、ポリオレフィンに不飽和カルボン酸またはその誘導
体を導入した変性ポリオレフィンにて置き換えることに
より、前記組成物の耐放射線性が、更に一段と向上する
ことを見出し、本発明に至ったものである。DISCLOSURE OF INVENTION Problems to be Solved by the Invention The inventors of the present invention continued research on conventional non-halogen flame-retardant polyethylene compositions having good radiation resistance to further improve their radiation resistance. Radiation resistance of the composition by replacing a part of the low-density polyethylene, which is the base resin of the halogen-free flame-retardant polyethylene composition, with a modified polyolefin obtained by introducing an unsaturated carboxylic acid or its derivative into the polyolefin. However, the present invention has been found to be further improved, and the present invention has been achieved.
【０００４】[0004]
【課題を解決するための手段】即ち、本発明の非ハロゲ
ン系難燃性絶縁組成物は、密度が０. ８５〜０. ９１ｇ
／ｃｍ3 の低密度ポリエチレン７０〜９７重量％とポリ
オレフィンに不飽和カルボン酸またはその誘導体を導入
した変性ポリオレフイン３〜３０重量％との混合物を主
体とするベース樹脂１００重量部に対して、水酸化マグ
ネシウム８０〜２００重量部およびポリ（２，２，４−
トリメチル−１，２−ジヒドロキノリン）３〜１０重量
部を配合したことを特徴とするものである。That is, the non-halogen flame retardant insulating composition of the present invention has a density of 0.85 to 0.91 g.
100 to 100 parts by weight of a base resin mainly composed of a mixture of 70 to 97% by weight of low-density polyethylene / cm 3 and 3 to 30% by weight of modified polyolefin in which an unsaturated carboxylic acid or a derivative thereof is introduced into a polyolefin. 80-200 parts by weight of magnesium and poly (2,2,4-
Trimethyl-1,2-dihydroquinoline) 3 to 10 parts by weight are blended.
【０００５】本発明の組成物におけるベース樹脂は、低
密度ポリエチレン７０〜９７重量％とポリオレフィンに
不飽和カルボン酸またはその誘導体を導入した変性ポリ
オレフイン３〜３０重量％との混合物を主体とする。な
お、低密度ポリエチレンとしては、密度が０. ８５〜
０. ９１ｇ／ｃｍ3 の範囲内のものが、得られる組成物
の機械特性が良好であり好ましい。本発明にて用いる変
性ポリオレフィンは、ポリオレフィンに不飽和カルボン
酸またはその誘導体を導入した所謂接着性ポリマーで、
ポリオレフィンを骨格として共重合や高分子化反応によ
り官能基を導入してポリオレフィンに接着性を付与した
ポリマーである。その官能基の導入方法は、例えばエチ
レン−アクリル酸（ＥＡＡ）のようなエチレンと官能基
含有モノマーとを重合する高圧法エチレン共重合により
導入する方法や、ポリオレフィンに不飽和カルボン酸ま
たはその誘導体をグラフト反応等により導入する方法が
一般的である。本発明において、変性ポリオレフィンと
しては、特に、後者のグラフト反応により官能基を導入
した変性ポリオレフィンが効果的であり好ましい。具体
的には、直鎖状低密度ポリエチレン（ＬＬＤＰＥ）やエ
チレン−酢酸ビニル共重合体（ＥＶＡ）等の各種のポリ
オレフィンに対して、０. １〜１０重量％のマレイン酸
等の酸無水物をベンゾイルパーオキサイド、ラウリルパ
ーオキサイド等の有機過酸化物の存在下でグラフトさせ
たものである。The base resin in the composition of the present invention is mainly composed of a mixture of 70 to 97% by weight of low-density polyethylene and 3 to 30% by weight of modified polyolefin obtained by introducing unsaturated carboxylic acid or its derivative into polyolefin. The low density polyethylene has a density of 0.85-
The range of 0.91 g / cm 3 is preferable because the resulting composition has good mechanical properties. The modified polyolefin used in the present invention is a so-called adhesive polymer in which an unsaturated carboxylic acid or a derivative thereof is introduced into polyolefin,
It is a polymer in which a polyolefin has a skeleton and a functional group is introduced by copolymerization or a polymerization reaction to impart adhesiveness to the polyolefin. The method of introducing the functional group is, for example, a method of introducing ethylene such as ethylene-acrylic acid (EAA) by high-pressure ethylene copolymerization in which a functional group-containing monomer is polymerized, or an unsaturated carboxylic acid or its derivative is added to a polyolefin. The method of introducing by a graft reaction or the like is common. In the present invention, as the modified polyolefin, a modified polyolefin having a functional group introduced by the latter graft reaction is particularly effective and preferable. Specifically, 0.1 to 10% by weight of acid anhydride such as maleic acid is added to various polyolefins such as linear low density polyethylene (LLDPE) and ethylene-vinyl acetate copolymer (EVA). It is grafted in the presence of an organic peroxide such as benzoyl peroxide or lauryl peroxide.
【０００６】本発明の組成物において、ベース樹脂の主
体となる樹脂混合物中の変性ポリオレフィンの配合量を
３〜３０重量％とした理由は、変性ポリオレフィンの含
有量が３重量％未満では、得られる組成物の耐放射線性
向上の効果が薄く、また、３０重量％を超えると組成物
全体が硬くなり過ぎ、伸び等の機械的特性が低下するよ
うになるためである。好ましい配合量は、５〜２０重量
％である。また、難燃剤を水酸化マグネシウムに、そし
て、その配合量を、ベース樹脂１００重量部に対して８
０〜２００重量部に限定した理由は、水酸化マグネシウ
ム以外の金属水酸化物では電気特性が著しく低下するた
めである。また、その配合量がベース樹脂１００重量部
に対して８０重量部未満の配合量では、得られる組成物
の難燃性が低く、また、２００重量部を超えて多量に配
合すると、得られる組成物の機械的特性が著しく低下す
るなどの問題が生じるためである。好ましい配合量は、
９０〜１４０重量部である。なお、水酸化マグネシウム
の粒径については、特に限定するものでないが、平均粒
径が０. ８〜５μｍの範囲内のものが好ましい。In the composition of the present invention, the reason why the content of the modified polyolefin in the resin mixture which is the main component of the base resin is 3 to 30% by weight is that the content of the modified polyolefin is less than 3% by weight. This is because the effect of improving the radiation resistance of the composition is small, and when it exceeds 30% by weight, the entire composition becomes too hard and mechanical properties such as elongation deteriorate. A preferred blending amount is 5 to 20% by weight. Further, the flame retardant was magnesium hydroxide, and its blending amount was 8 parts with respect to 100 parts by weight of the base resin.
The reason why the content is limited to 0 to 200 parts by weight is that the electrical properties of metal hydroxides other than magnesium hydroxide are significantly deteriorated. Further, when the amount of the compound is less than 80 parts by weight with respect to 100 parts by weight of the base resin, the flame retardancy of the resulting composition is low, and when the amount is more than 200 parts by weight, the composition obtained is large. This is because there arises a problem that the mechanical properties of the product are significantly reduced. The preferred amount is
90 to 140 parts by weight. The particle size of magnesium hydroxide is not particularly limited, but the average particle size is preferably in the range of 0.8 to 5 μm.
【０００７】ポリ（２，２，４−トリメチル−１，２−
ジヒドロキノリン）は、既に、ゴム薬品の中の老化防止
剤として多量に使用されている化合物であるが、該化合
物が他の芳香族系の老化防止剤に比べて優れた耐放射線
性を付与できることは先の発明にて見出したものであ
る。このポリ（２，２，４−トリメチル−１，２−ジヒ
ドロキノリン）の配合量は、ベース樹脂１００重量部に
対して３重量部未満では、組成物に耐放射線性付与の効
果が見られず、また、１０重量部を超えて多量に配合す
ると得られる組成物の電気特性が低下するため、３〜１
０重量部の範囲内が望ましい。Poly (2,2,4-trimethyl-1,2-
Dihydroquinoline) is a compound that has already been used in large amounts as an anti-aging agent in rubber chemicals, but the compound can impart superior radiation resistance to other aromatic anti-aging agents. Is the one found in the previous invention. If the compounding amount of this poly (2,2,4-trimethyl-1,2-dihydroquinoline) is less than 3 parts by weight with respect to 100 parts by weight of the base resin, the composition is not effective in imparting radiation resistance. In addition, when a large amount of more than 10 parts by weight is blended, the electrical characteristics of the obtained composition are deteriorated, so that it is 3-1.
It is preferably within the range of 0 parts by weight.
【０００８】本発明の組成物には、その難燃性などの他
の特性を改善するために、ベース樹脂として、前記樹脂
混合物に加えてエチレン系共重合体を配合しても良い
が、その場合には、得られる組成物の耐放射線性や電気
特性を低下させないために、酢酸ビニル含有量が２０％
以下のエチレン−酢酸ビニル共重合体、アクリル酸エチ
ル含有量が２０％以下のエチレン−アクリル酸エチル共
重合体などの共重合体をベース樹脂の２０重量％以下の
範囲で配合するのが望ましい。また、本発明の組成物に
は、通常使用される老化防止剤、着色剤、架橋剤、架橋
助剤、加工助剤等を適当量添加しても差し支えない。な
お、前記の低密度ポリエチレン、変性ポリオレフィン、
水酸化マグネシウム、ポリ（２，２，４−トリメチル−
１，２−ジヒドロキノリン）などを、前記の配合割合で
配合した組成物を架橋せしめる手段は、過酸化物による
化学架橋法、電子線による放射線照射架橋法等その手段
は限定されるものでない。The composition of the present invention may contain an ethylene-based copolymer as a base resin in addition to the above resin mixture in order to improve other properties such as flame retardancy. In some cases, the vinyl acetate content is 20% in order to prevent deterioration of the radiation resistance and electrical characteristics of the resulting composition.
The following copolymers such as ethylene-vinyl acetate copolymer and ethylene-ethyl acrylate copolymer having an ethyl acrylate content of 20% or less are preferably blended in the range of 20% by weight or less of the base resin. In addition, the composition of the present invention may be added with an appropriate amount of an antioxidant, a colorant, a cross-linking agent, a cross-linking aid, a processing aid and the like which are usually used. The low-density polyethylene, modified polyolefin,
Magnesium hydroxide, poly (2,2,4-trimethyl-
1,2-dihydroquinoline) and the like are mixed in the above-described mixing ratio, and the means for crosslinking the composition is not limited to such means as a chemical crosslinking method using a peroxide and a radiation irradiation crosslinking method using an electron beam.
【０００９】[0009]
【作用】本発明の組成物は、ポリオレフィンに不飽和カ
ルボン酸またはその誘導体を導入した変性ポリオレフィ
ンの配合により、低密度ポリエチレンと多量に配合した
水酸化マグネシウムとの結合性が高められるので、得ら
れる組成物の機械的特性が向上し、しかも放射線被曝に
よる低密度ポリエチレンと水酸化マグネシウムの界面に
おける劣化が抑制されて耐放射線性が向上する。The composition of the present invention can be obtained because the composition of the modified polyolefin prepared by introducing unsaturated carboxylic acid or its derivative into the polyolefin enhances the binding property between the low density polyethylene and the magnesium hydroxide mixed in a large amount. The mechanical properties of the composition are improved, and further, deterioration at the interface between low density polyethylene and magnesium hydroxide due to radiation exposure is suppressed, and radiation resistance is improved.
【００１０】[0010]
【実施例】以下、本発明の実施例について、比較例を挙
げて説明する。 （実施例１〜５、比較例１〜５）表１に示す各成分をそ
れぞれ混合した組成物をロールにて均一に混練した後、
温度１６０℃で３０分間、プレス成形して試験用シート
をそれぞれ作製した。作製したそれぞれの試験用シート
についてγ線照射前後の引張強度、伸び並びに体積抵抗
率を測定評価した。得られた結果を表２に示した。EXAMPLES Examples of the present invention will be described below with reference to comparative examples. (Examples 1 to 5 and Comparative Examples 1 to 5) After uniformly kneading the composition obtained by mixing the components shown in Table 1 with a roll,
A test sheet was produced by press molding at a temperature of 160 ° C. for 30 minutes. The tensile strength, elongation, and volume resistivity of the produced test sheets before and after γ-ray irradiation were measured and evaluated. The obtained results are shown in Table 2.
【００１１】[0011]
【表１】 [Table 1]
【００１２】[0012]
【表２】 [Table 2]
【００１３】上記表２から明らかなように、ベース樹脂
としてポリオレフィンに不飽和カルボン酸またはその誘
導体を導入した変性ポリオレフィンを所定量配合した本
発明の難燃性絶縁組成物の放射線被曝後の伸び特性は、
変性ポリオレフィンを何ら配合しない比較例１〜２の難
燃性絶縁組成物、変性ポリオレフィンを配合してもポリ
（２，２，４−トリメチル−１，２−ジヒドロキノリ
ン）が配合されていない比較例３の難燃性絶縁組成物、
変性ポリオレフィンの配合量が本発明の規定量より過剰
である比較例４の難燃性絶縁組成物、およびベース樹脂
中の低密度ポリエチレンの密度が本発明にて規定した数
値外のものである比較例５の難燃性絶縁組成物などの値
の約３倍以上の伸び特性を保有しているものであり、本
発明の難燃性絶縁組成物が優れた耐放射線性を具備して
いることが判る。As is clear from Table 2 above, the elongation characteristics after radiation exposure of the flame-retardant insulating composition of the present invention in which a predetermined amount of a modified polyolefin prepared by introducing an unsaturated carboxylic acid or a derivative thereof into a polyolefin as a base resin is blended. Is
The flame-retardant insulating compositions of Comparative Examples 1 and 2 containing no modified polyolefin, and the comparative example containing no modified polyolefin but no poly (2,2,4-trimethyl-1,2-dihydroquinoline). 3 flame-retardant insulating composition,
Comparison of the flame-retardant insulating composition of Comparative Example 4 in which the amount of the modified polyolefin compounded is more than the specified amount of the present invention, and the density of the low-density polyethylene in the base resin is outside the numerical values specified in the present invention. The flame retardant insulating composition according to the present invention has an elongation property of about 3 times or more of the value of the flame retardant insulating composition of Example 5 and the like, and the flame retardant insulating composition of the present invention has excellent radiation resistance. I understand.
【００１４】[0014]
【発明の効果】以上、説明した如く、本発明の非ハロゲ
ン系難燃性絶縁組成物は、多量の放射線を被曝した後に
おいても、高い電気絶縁性および機械的特性を保持して
いるものであり、原子力発電所などの放射線被曝環境下
で使用される電気機器などの難燃性絶縁材料として好適
なものである。As described above, the non-halogen flame-retardant insulating composition of the present invention retains high electrical insulation and mechanical properties even after being exposed to a large amount of radiation. Therefore, it is suitable as a flame-retardant insulating material for electric equipment used in a radiation exposure environment such as a nuclear power plant.
Claims (2)
低密度ポリエチレン７０〜９７重量％とポリオレフィン
に不飽和カルボン酸またはその誘導体を導入した変性ポ
リオレフイン３〜３０重量％との混合物を主体するベー
ス樹脂１００重量部に対して、水酸化マグネシウム８０
〜２００重量部およびポリ（２，２，４−トリメチル−
１，２−ジヒドロキノリン）３〜１０重量部を配合した
ことを特徴とする放射線被曝環境下用非ハロゲン系難燃
性絶縁組成物。1. A mixture of 70 to 97% by weight of low-density polyethylene having a density of 0.85 to 0.91 g / cm 3 and 3 to 30% by weight of a modified polyolefin in which an unsaturated carboxylic acid or a derivative thereof is introduced into a polyolefin. 80 parts magnesium hydroxide based on 100 parts by weight of the base resin
~ 200 parts by weight and poly (2,2,4-trimethyl-
1,2-dihydroquinoline) in an amount of 3 to 10 parts by weight, and a non-halogen flame-retardant insulating composition for a radiation exposure environment.
ィンに不飽和カルボン酸またはその誘導体をグラフト反
応により導入した変性ポリオレフインであることを特徴
とする請求項１記載の放射線被曝環境下用非ハロゲン系
難燃性絶縁組成物。2. The non-halogen flame-retardant material for a radiation exposure environment according to claim 1, wherein the modified polyolefin is a modified polyolefin obtained by introducing an unsaturated carboxylic acid or a derivative thereof into a polyolefin by a graft reaction. Insulation composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29593693A JPH07126450A (en) | 1993-11-02 | 1993-11-02 | Non-halogenic flame-retardant insulating composition useful under radiation exposure environment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29593693A JPH07126450A (en) | 1993-11-02 | 1993-11-02 | Non-halogenic flame-retardant insulating composition useful under radiation exposure environment |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07126450A true JPH07126450A (en) | 1995-05-16 |
Family
ID=17827038
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29593693A Pending JPH07126450A (en) | 1993-11-02 | 1993-11-02 | Non-halogenic flame-retardant insulating composition useful under radiation exposure environment |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07126450A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014101455A (en) * | 2012-11-20 | 2014-06-05 | Hitachi Metals Ltd | Non-halogen resin composition, wire and cable |
| JP2016056295A (en) * | 2014-09-10 | 2016-04-21 | 日本ポリエチレン株式会社 | High radiation resistant flame retardant resin composition and wire and cables using the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6211745A (en) * | 1985-07-10 | 1987-01-20 | Nippon Petrochem Co Ltd | Flame-retardant olefin polymer composition having excellent heat-resistance |
| JPS63286450A (en) * | 1987-05-20 | 1988-11-24 | Agency Of Ind Science & Technol | Non-halogenated flame-retardant composition for electrical insulation with improved radiation resistance |
| JPH02206632A (en) * | 1988-12-21 | 1990-08-16 | Nippon Petrochem Co Ltd | Flame-retardant polyolefin resin composition having improved surface haze properties |
-
1993
- 1993-11-02 JP JP29593693A patent/JPH07126450A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6211745A (en) * | 1985-07-10 | 1987-01-20 | Nippon Petrochem Co Ltd | Flame-retardant olefin polymer composition having excellent heat-resistance |
| JPS63286450A (en) * | 1987-05-20 | 1988-11-24 | Agency Of Ind Science & Technol | Non-halogenated flame-retardant composition for electrical insulation with improved radiation resistance |
| JPH02206632A (en) * | 1988-12-21 | 1990-08-16 | Nippon Petrochem Co Ltd | Flame-retardant polyolefin resin composition having improved surface haze properties |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014101455A (en) * | 2012-11-20 | 2014-06-05 | Hitachi Metals Ltd | Non-halogen resin composition, wire and cable |
| JP2016056295A (en) * | 2014-09-10 | 2016-04-21 | 日本ポリエチレン株式会社 | High radiation resistant flame retardant resin composition and wire and cables using the same |
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