JP2819057B2 - Radiation resistant polymer composition - Google Patents
Radiation resistant polymer compositionInfo
- Publication number
- JP2819057B2 JP2819057B2 JP2209534A JP20953490A JP2819057B2 JP 2819057 B2 JP2819057 B2 JP 2819057B2 JP 2209534 A JP2209534 A JP 2209534A JP 20953490 A JP20953490 A JP 20953490A JP 2819057 B2 JP2819057 B2 JP 2819057B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- flexibility
- polymer composition
- radiation resistance
- 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.)
- Expired - Fee Related
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A30/00—Adapting or protecting infrastructure or their operation
- Y02A30/14—Extreme weather resilient electric power supply systems, e.g. strengthening power lines or underground power cables
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Organic Insulating Materials (AREA)
- Insulated Conductors (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、原子力関連施設等において使用されるケー
ブルの被覆材料に適した耐放射線性高分子組成物に関す
る。Description: TECHNICAL FIELD The present invention relates to a radiation-resistant polymer composition suitable for a cable covering material used in nuclear facilities and the like.
原子力発電所の如き原子力関連施設のケーブルの被覆
材料には、従来から、可撓性及び耐放射線性に優れたも
のが求められ、例えばエチレン・プロピレン或いは架橋
ポリエチレンが使用されている。しかしながら、近年の
原子力関連施設における保全作業において、自動化のた
めのロボットの導入が進み、原子力関連施設の心臓部に
向かって屈曲した経路で進入するロボットが出現してい
る。このようなロボット用ケーブルには非常に高い耐放
射線性と充分な可撓性が求められる。Conventionally, materials for covering cables of nuclear power facilities such as nuclear power plants are required to be excellent in flexibility and radiation resistance. For example, ethylene / propylene or cross-linked polyethylene has been used. However, in recent years, robots for automation have been introduced in maintenance work at nuclear facilities, and robots that enter a curved path toward the heart of nuclear facilities have emerged. Such a cable for a robot is required to have extremely high radiation resistance and sufficient flexibility.
高い耐放射線性だけを満足するためなら、ポリエーテ
ルエーテルケトン或いはポリイミド樹脂をブレンドした
りベースレジンにしたものがあるが、これらの硬い樹脂
をケーブルの被覆材料に用いた場合には、加工性が悪
く、得られるケーブルの可撓性に問題があり、ロボット
用ケーブルには不適当である。To satisfy only high radiation resistance, polyetheretherketone or polyimide resin may be blended or used as a base resin.However, when these hard resins are used for the covering material of the cable, the workability is poor. Poor, there is a problem with the flexibility of the resulting cable, which is unsuitable for robot cables.
そこで、放射線により比較的早く劣化するとされるポ
リオレフィン系樹脂に耐放射線性にすぐれる老化防止剤
等を配合した組成物とし、耐放射線性及び可撓性を高め
た耐放射線性高分子組成物が提案されている。Therefore, a radiation-resistant polymer composition with improved radiation resistance and flexibility is considered to be a composition obtained by blending a polyolefin resin, which is considered to deteriorate relatively quickly due to radiation, with an antiaging agent having excellent radiation resistance. Proposed.
従来の技術で説明した老化防止剤を配合したポリオレ
フィン系樹脂でも、厳しい使用条件であるロボット用ケ
ーブル等では、耐放射線性及び可撓性が不十分であると
いう問題点を有していた。Even the polyolefin-based resin containing the anti-aging agent described in the prior art has a problem that the radiation resistance and the flexibility are insufficient for a cable for a robot or the like under severe use conditions.
本発明は、従来の技術の有するこのような問題点に鑑
みてなされたものであり、耐放射線性及び可撓性並びに
加工性や電気絶縁性等に優れ、ケーブルの被覆材料等に
適した耐放射線性高分子組成物を提供しようとするもの
である。The present invention has been made in view of such problems of the prior art, and has excellent radiation resistance, flexibility, workability, electrical insulation, and the like, and is suitable for a cable covering material and the like. It is intended to provide a radioactive polymer composition.
上記目的を達成するために、本発明の耐放射線性高分
子組成物は、ポリオレフィン系樹脂100重量部に対し
て、ベンズイミダゾール系老化防止剤１〜30重量部、フ
ェニルエーテル型合成油１〜30重量部、金属酸化物１〜
50重量部を配合してなるものである。In order to achieve the above object, the radiation-resistant polymer composition of the present invention contains 1 to 30 parts by weight of a benzimidazole antioxidant and 1 to 30 parts by weight of a phenyl ether type synthetic oil based on 100 parts by weight of a polyolefin resin. Parts by weight, metal oxide 1
50 parts by weight are blended.
本発明に使用されるポリオレフィン系樹脂としては、
低密度ポリエチレン、エチレン・プロピレンゴム、エチ
レン・プロピレン・ジエン共重合体、エチレン・酢酸ビ
ニル共重合体、エチレン・エチルアクリレート共重合
体、エチレン・酢酸ビニル・グラフト塩化ビニル共重合
体、エチレン・プロピレン・グラフト塩化ビニル共重合
体ブチルゴム、クロロスルホン化ポリエチレンの１種又
は２種以上の混合物が用いられる。As the polyolefin resin used in the present invention,
Low density polyethylene, ethylene / propylene rubber, ethylene / propylene / diene copolymer, ethylene / vinyl acetate copolymer, ethylene / ethyl acrylate copolymer, ethylene / vinyl acetate / graft vinyl chloride copolymer, ethylene / propylene / One or a mixture of two or more of grafted vinyl chloride copolymer butyl rubber and chlorosulfonated polyethylene is used.
次に、本発明に使用されるベンズイミダゾール系老化
防止剤としては、２−メルカプト・ベンズイミダゾー
ル、２−メルカプト・ベンズイミダゾールの亜鉛塩、２
−メルカプトメチル・ベンズイミダゾール、２−メルカ
プトメチル・ベンズイミダゾールの亜鉛塩が用いられ
る。かかる場合の配合量は、１〜30重量部で、好ましい
配合量は、２〜20重量部である。Next, as the benzimidazole anti-aging agent used in the present invention, 2-mercapto-benzimidazole, zinc salt of 2-mercapto-benzimidazole, 2
-Zinc salts of mercaptomethyl benzimidazole and 2-mercaptomethyl benzimidazole are used. In such a case, the compounding amount is 1 to 30 parts by weight, and the preferable compounding amount is 2 to 20 parts by weight.
また、本発明に使用されるフェニルエーテル型合成油
としては、表１に示される構造式を有するペンタフェニ
ルエーテル、テトラフェニルエーテル、モノアルキルテ
トラフェニルエーテル、ジアルキルテトラフェニルエー
テル、アルキルジフェニルエーテルが用いられる。かか
る場合の配合量は、１〜30重量部で、好ましい配合量
は、２〜20重量部である。As the phenyl ether type synthetic oil used in the present invention, pentaphenyl ether, tetraphenyl ether, monoalkyl tetraphenyl ether, dialkyl tetraphenyl ether, and alkyl diphenyl ether having the structural formulas shown in Table 1 are used. In such a case, the compounding amount is 1 to 30 parts by weight, and the preferable compounding amount is 2 to 20 parts by weight.
そして、本発明に使用される金属酸化物としては、亜
鉛華（ZnO）、炭酸亜鉛（ZnCO3）、酸化マグネシウム
（MgO）リサージ（PbO）、鉛丹（Pb3O4）、三酸化アン
チモン（Sb2O3）等が用いられる。かかる場合の配合量
は、１〜50重量部で、好ましい配合量は、５〜30重量部
である。 Examples of the metal oxide used in the present invention include zinc white (ZnO), zinc carbonate (ZnCO 3 ), magnesium oxide (MgO) litharge (PbO), leadtan (Pb 3 O 4 ), and antimony trioxide ( Sb 2 O 3 ) is used. In such a case, the compounding amount is 1 to 50 parts by weight, and the preferable compounding amount is 5 to 30 parts by weight.
なお、本発明の耐放射線性高分子組成物は、ジクミル
パーオキサイド等の有機過酸化物や電子線照射等により
架橋してもよい。また、ベンズイミダゾール系老化防止
剤以外の老化防止剤、例えば2,2,4−トリメチル−1,2−
ジヒドロキノリン重合物等を併用することもできる。さ
らに、以上の成分の他、耐放射線性及び可撓性を低下さ
せない範囲で、水酸化マグネシウム、カーボンブラッ
ク、赤リン等の難燃剤、充填剤を配合することができ
る。The radiation-resistant polymer composition of the present invention may be cross-linked by irradiation with an organic peroxide such as dicumyl peroxide, or by irradiation with an electron beam. Antioxidants other than benzimidazole antioxidants, for example, 2,2,4-trimethyl-1,2-
A dihydroquinoline polymer or the like can be used in combination. Further, in addition to the above components, a flame retardant such as magnesium hydroxide, carbon black, and red phosphorus, and a filler can be blended within a range that does not reduce radiation resistance and flexibility.
本発明の耐放射線性高分子組成物では、ポリオレフィ
ン系樹脂が本来有する可撓性、加工性、絶縁性を生かし
て、ベンズイミダゾール系老化防止剤、フェニルエーテ
ル型合成油、金属酸化物の３種を所定量配合することの
相乗作用により、耐放射線特性を著しく向上しようとす
るものである。In the radiation-resistant polymer composition of the present invention, three types of benzimidazole antioxidants, phenyl ether type synthetic oils, and metal oxides are utilized by taking advantage of the inherent flexibility, processability, and insulation properties of polyolefin resins. Is intended to remarkably improve the radiation resistance by synergistic action of mixing a predetermined amount of
ベンズイミダゾール系老化防止剤の配合量が１重量部
を下回ると、フェニルエーテル型合成油との相乗作用に
よる耐放射線性の向上が認められない。30重量部を上回
る配合量は、耐放射線性の向上には寄与しなくなるばか
りかコストアップとなり好ましくない。If the amount of the benzimidazole antioxidant is less than 1 part by weight, no improvement in radiation resistance due to synergistic action with phenyl ether type synthetic oil is observed. A compounding amount exceeding 30 parts by weight not only does not contribute to the improvement of radiation resistance but also increases the cost, which is not preferable.
フェニルエーテル型合成油の配合量が１重量部を下回
ると、ベンズイミダゾール系老化防止剤との相乗作用に
よる耐放射線性の向上が認められない。30重量部を上回
る配合量は、耐放射線性の向上には寄与しなくなるばか
りか製品表面にブルームすることになるので好ましくな
い。当然経済性の面からも好ましくない。If the amount of the phenyl ether type synthetic oil is less than 1 part by weight, no improvement in radiation resistance due to synergistic action with the benzimidazole-based antioxidant is observed. A compounding amount exceeding 30 parts by weight is not preferred because it not only contributes to improvement of radiation resistance but also causes blooming on the product surface. Of course, it is not preferable from the viewpoint of economy.
金属酸化物の配合量が１重量部を下回ると、ベンズイ
ミダゾール系老化防止剤及びフェニルエーテル型合成油
との相乗作用が期待できない。逆に50重量部を上回る配
合をおこなっても、相乗作用による耐放射線性の向上が
認められないばかりか、加工性や機械特性が低下するこ
とになるので好ましくない。If the amount of the metal oxide is less than 1 part by weight, a synergistic effect with the benzimidazole antioxidant and the phenyl ether type synthetic oil cannot be expected. Conversely, if the amount is more than 50 parts by weight, not only the improvement in radiation resistance due to the synergistic action is not recognized, but also the processability and mechanical properties are undesirably reduced.
以下、具体的な本発明例を比較例と対比しつつ説明す
る。Hereinafter, specific examples of the present invention will be described in comparison with comparative examples.
表２に示す本発明例１〜10及び比較例１〜５の配合に
ついて、ミキシングロールにより混練した後、プレス12
0℃,10分間予備成形し、150kg/cm2下,170℃,15分で架橋
したものを試料に供した。なお、可撓性の評価について
は、各例について電線を試作し、試料に供した。なお、
電線は2mm2（7/0.6）の銅導体上に0.8mm厚で押出し、直
ちに蒸気架橋（200℃×１分）をおこなって得た。After kneading the compositions of Examples 1 to 10 and Comparative Examples 1 to 5 shown in Table 2, using a mixing roll,
Samples were preformed at 0 ° C. for 10 minutes and crosslinked at 150 ° C. for 15 minutes under 150 kg / cm 2 . In addition, about the evaluation of flexibility, the electric wire was trial-produced about each example and used for the sample. In addition,
The wire was extruded on a 2 mm 2 (7 / 0.6) copper conductor with a thickness of 0.8 mm and immediately subjected to steam crosslinking (200 ° C. × 1 minute).
上記した本発明例１〜10及び比較例１〜５の試料に対
して、Co60γ線を8MGy（メガグレイ）まで照射し、引張
強度（kg/mm2）と伸び（％）と可撓性（屈曲回数）を測
定し、照射前（オリジナル）の試料の引張強度、伸び及
び可撓性と比較した。特に、γ線照射前後での伸び及び
可撓性の低下程度で耐放射線性が評価される。引張強度
と伸びの物理的特性はJIS Ｋ 6301に準じて測定し
た。可撓性は、JIS Ｃ 3005 29項に準拠して測定し
た第１図に示す屈曲試験装置を用いた。すなわち、移動
用ケーブルの許容曲げ半径であるケーブル１外径の６倍
の半径Ｒを有するマンドレル２を用い、ケーブル１を
→と曲げることで屈曲回数１回とし、ケーブル表面に
割れが発生するまでの回数を測定した。また、照射前の
試料の難燃性も評価するため、JIS Ｋ 7201の酸素指
数法による酸素指数も併せて測定した。The above-mentioned samples of the present invention examples 1 to 10 and comparative examples 1 to 5 were irradiated with Co 60 γ-ray up to 8 MGy (mega gray) to obtain tensile strength (kg / mm 2 ), elongation (%) and flexibility. (Bending number) was measured and compared with the tensile strength, elongation and flexibility of the sample before irradiation (original). In particular, radiation resistance is evaluated based on the degree of elongation and flexibility reduction before and after γ-ray irradiation. The physical properties of tensile strength and elongation were measured according to JIS K 6301. The flexibility was measured by using a bending test apparatus shown in FIG. 1 measured according to JIS C 3005 29. That is, using a mandrel 2 having a radius R that is six times the outer diameter of the cable 1 that is the allowable bending radius of the moving cable, bending the cable 1 in the direction of → to make one bending, until a crack occurs on the cable surface Was measured. Further, in order to evaluate the flame retardancy of the sample before irradiation, the oxygen index by the oxygen index method of JIS K 7201 was also measured.
表２に示されるように、下限を下回るベンズイミダゾ
ール系老化防止剤を配合したもの（比較例１）、下限を
下回るフェニルエーテル型合成油を配合したもの（比較
例３）、下限を下回る金属酸化物を配合したもの（比較
例５）は、何れも可撓性と耐放射線性が著しく劣ってお
り、実用上支障を生じる程度となっている。上限を上回
るフェニルエーテル型合成油を配合したもの（比較例
４）は、表面へのしみ出し（ブルーム）が発生する。上
限を上回る金属酸化物を配合したもの（比較例２）は、
オリジナルの引張強度が0.7kg/mm2以下となって規格外
となる（JIS Ｃ 3315による）。これらに対し、所定
量を配合した本発明例１〜10は、可撓性や耐放射線性が
オリジナルに比較して相当低下しているものの、実用に
耐える程度の数値を維持しており、可撓性や耐放射線性
に優れる。また、オリジナルの引張強度も規格の0.7kg/
mm2を越えている。なお、本発明例の配合においては、
難燃性も充分確保されている。As shown in Table 2, a compound containing a benzimidazole-based antioxidant lower than the lower limit (Comparative Example 1), a compound containing a phenyl ether type synthetic oil lower than the lower limit (Comparative Example 3), and a metal oxide lower than the lower limit In each of the compositions containing the compound (Comparative Example 5), the flexibility and the radiation resistance were remarkably inferior, so that practical problems were caused. In the case of blending a phenyl ether type synthetic oil exceeding the upper limit (Comparative Example 4), bleeding (bloom) occurs on the surface. Those containing a metal oxide exceeding the upper limit (Comparative Example 2)
The original tensile strength is 0.7 kg / mm 2 or less, which is out of specification (according to JIS C 3315). On the other hand, in Examples 1 to 10 of the present invention in which a predetermined amount was blended, although the flexibility and radiation resistance were considerably reduced as compared with the originals, the values that could withstand practical use were maintained. Excellent flexibility and radiation resistance. The original tensile strength is 0.7kg /
mm 2 is exceeded. In addition, in the formulation of the present invention example,
Flame retardancy is also sufficiently ensured.
〔発明の効果〕 以上の実施例から明らかなように、ポリオレフィン系
樹脂100重量部に対して、ベンズイミダゾ系老化防止剤
１〜30重量部、フェニルエーテル型合成油１〜30重量
部、金属酸化物１〜50重量部を配合してなる耐放射線性
高分子組成物は、耐放射線特性に優れたベンズイミダゾ
ール系老化防止剤、フェニルエーテル型合成油、金属酸
化物の３種を所定量配合することの相乗作用により、耐
放射線特性及び可撓性が著しく向上し、原子力関連施設
等のロボット用ケーブル等の如く厳しい耐放射線特性及
び可撓性が要求されるものに最適である。 [Effects of the Invention] As is clear from the above examples, 1 to 30 parts by weight of a benzimidazo type antioxidant, 1 to 30 parts by weight of a phenyl ether type synthetic oil, 100 parts by weight of a polyolefin resin, metal oxidation The radiation-resistant polymer composition comprising 1 to 50 parts by weight of the product is a benzimidazole antioxidant having excellent radiation resistance, a phenyl ether type synthetic oil, and a predetermined amount of three kinds of metal oxides. Due to the synergistic effect of the above, the radiation resistance and flexibility are remarkably improved, and it is most suitable for those requiring severe radiation resistance and flexibility, such as cables for robots in nuclear facilities.
【図面の簡単な説明】 第１図は可撓性評価のための屈曲試験装置を示す図であ
る。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a view showing a bending test apparatus for evaluating flexibility.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｈ０１Ｂ 7/28 Ｈ０１Ｂ 7/28 Ｂ (56)参考文献 特開 昭63−61038（ＪＰ，Ａ) 特開 昭60−144345（ＪＰ，Ａ) 特開 昭56−116730（ＪＰ，Ａ) 特開 平３−199249（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) C08L 23/00 - 23/36──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification symbol FI H01B7 / 28 H01B7 / 28B (56) References JP-A-63-61038 (JP, A) JP-A-60-144345 ( JP, A) JP-A-56-116730 (JP, A) JP-A-3-199249 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) C08L 23/00-23/36
Claims (1)
て、ベンズイミダゾール系老化防止剤１〜30重量部、フ
ェニルエーテル型合成油１〜30重量部、金属酸化物１〜
50重量部を配合してなることを特徴とする耐放射線性高
分子組成物。1 to 30 parts by weight of a benzimidazole antioxidant, 1 to 30 parts by weight of a phenyl ether type synthetic oil, 1 to 30 parts by weight of a metal oxide to 100 parts by weight of a polyolefin resin.
A radiation-resistant polymer composition comprising 50 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2209534A JP2819057B2 (en) | 1990-08-07 | 1990-08-07 | Radiation resistant polymer composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2209534A JP2819057B2 (en) | 1990-08-07 | 1990-08-07 | Radiation resistant polymer composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0491147A JPH0491147A (en) | 1992-03-24 |
| JP2819057B2 true JP2819057B2 (en) | 1998-10-30 |
Family
ID=16574392
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2209534A Expired - Fee Related JP2819057B2 (en) | 1990-08-07 | 1990-08-07 | Radiation resistant polymer composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2819057B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2893360B2 (en) * | 1991-04-12 | 1999-05-17 | 三菱電線工業株式会社 | Radiation resistant cable |
| JP4985588B2 (en) * | 2008-08-28 | 2012-07-25 | 日立電線株式会社 | Radiation resistant resin composition and radiation resistant cable |
| JP2016050268A (en) * | 2014-09-01 | 2016-04-11 | 早川ゴム株式会社 | Radiation ray resistant polyethylene composition and radiation resistant polymer product |
-
1990
- 1990-08-07 JP JP2209534A patent/JP2819057B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0491147A (en) | 1992-03-24 |
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