JPS62230810A - Electron radiation crosslinked polyethylene composition - Google Patents
Electron radiation crosslinked polyethylene compositionInfo
- Publication number
- JPS62230810A JPS62230810A JP7492186A JP7492186A JPS62230810A JP S62230810 A JPS62230810 A JP S62230810A JP 7492186 A JP7492186 A JP 7492186A JP 7492186 A JP7492186 A JP 7492186A JP S62230810 A JPS62230810 A JP S62230810A
- Authority
- JP
- Japan
- Prior art keywords
- parts
- weight
- resistance
- crosslinking
- heat
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 13
- 229920003020 cross-linked polyethylene Polymers 0.000 title 1
- 239000004703 cross-linked polyethylene Substances 0.000 title 1
- 230000005855 radiation Effects 0.000 title 1
- 229920001179 medium density polyethylene Polymers 0.000 claims abstract description 12
- 239000004701 medium-density polyethylene Substances 0.000 claims abstract description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 9
- CJKWEXMFQPNNTL-UHFFFAOYSA-N bis(prop-2-enyl) 1,2,3,4,7,7-hexachlorobicyclo[2.2.1]hept-2-ene-5,6-dicarboxylate Chemical compound C=CCOC(=O)C1C(C(=O)OCC=C)C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl CJKWEXMFQPNNTL-UHFFFAOYSA-N 0.000 claims abstract description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011701 zinc Substances 0.000 claims abstract description 7
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910000464 lead oxide Inorganic materials 0.000 claims abstract description 6
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical compound NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 claims abstract description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims abstract description 5
- 150000003751 zinc Chemical class 0.000 claims abstract description 5
- JFGVTUJBHHZRAB-UHFFFAOYSA-N 2,6-Di-tert-butyl-1,4-benzenediol Chemical compound CC(C)(C)C1=CC(O)=CC(C(C)(C)C)=C1O JFGVTUJBHHZRAB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000010894 electron beam technology Methods 0.000 claims description 15
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims description 6
- XGIDEUICZZXBFQ-UHFFFAOYSA-N 1h-benzimidazol-2-ylmethanethiol Chemical compound C1=CC=C2NC(CS)=NC2=C1 XGIDEUICZZXBFQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004719 irradiation crosslinked polyethylene Substances 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 abstract description 26
- 230000000694 effects Effects 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 9
- 239000003963 antioxidant agent Substances 0.000 abstract 2
- UDQCDDZBBZNIFA-UHFFFAOYSA-N 4-methyl-1,3-dihydrobenzimidazole-2-thione Chemical compound CC1=CC=CC2=C1NC(=S)N2 UDQCDDZBBZNIFA-UHFFFAOYSA-N 0.000 abstract 1
- 230000003679 aging effect Effects 0.000 abstract 1
- 230000003078 antioxidant effect Effects 0.000 abstract 1
- 230000032683 aging Effects 0.000 description 21
- -1 Polyethylene Polymers 0.000 description 17
- 239000004698 Polyethylene Substances 0.000 description 17
- 229920000573 polyethylene Polymers 0.000 description 17
- 239000003112 inhibitor Substances 0.000 description 6
- 230000001737 promoting effect Effects 0.000 description 6
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000003712 anti-aging effect Effects 0.000 description 4
- 230000000740 bleeding effect Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 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 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- QEZIKGQWAWNWIR-UHFFFAOYSA-N antimony(3+) antimony(5+) oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[Sb+3].[Sb+5] QEZIKGQWAWNWIR-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- UGQQAJOWXNCOPY-UHFFFAOYSA-N dechlorane plus Chemical compound C12CCC3C(C4(Cl)Cl)(Cl)C(Cl)=C(Cl)C4(Cl)C3CCC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl UGQQAJOWXNCOPY-UHFFFAOYSA-N 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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、難燃性、耐熱変形性、耐熱老化性および耐カ
ツトスルー性にすぐれた機器内配線用絶縁電線に使用す
る電子線照射架橋ポリエチレン組成物に関する。Detailed Description of the Invention (Industrial Field of Application) The present invention relates to electron beam irradiation cross-linked polyethylene used for insulated wires for wiring inside equipment, which has excellent flame retardancy, heat deformation resistance, heat aging resistance, and cut-through resistance. Regarding the composition.
（従来技術）
ポリエチレンは、電気的特性、機械的特性、耐油性、耐
水性、耐候性などにすぐれているために、電気絶縁材、
電線被覆材として広く使用されているが、反面、可燃性
であり、軟化温度が低いことから使用用途に適合するよ
うに、難燃性、耐熱変形性、耐熱老化性、耐カントスル
ー性などの特性を備えたポリエチレン組成物が種々公表
されている。例えば、１２０℃以上の高温で連続使用さ
れる分野では、熱的雰囲気による加熱変形の影響を防止
するために、ポリエチレン中に架橋剤を添加して架橋す
る手段が一般に行われている。例えばポリエチレンの絶
縁被覆が厚い電線では、蒸気架橋、又は乾式架橋方法に
よって行われ、絶縁被覆が薄い機器内配線用の絹物絶縁
電線では、電子線照射架橋方法がとられている。特にｎ
、器内配線用絹物絶縁電線は、機器内の熱的雰囲気で使
用される場合が多いので、難燃性、耐熱変形性、耐熱老
化性などが要求され、更にエッヂ亀裂に強い耐カットス
ルー性を具備したものが要求される場合がある。(Prior art) Polyethylene has excellent electrical properties, mechanical properties, oil resistance, water resistance, weather resistance, etc., so it is used as an electrical insulating material.
It is widely used as a wire coating material, but on the other hand, it is flammable and has a low softening temperature. Various polyethylene compositions with specific properties have been published. For example, in fields where polyethylene is continuously used at high temperatures of 120° C. or higher, it is common practice to add a crosslinking agent to polyethylene for crosslinking in order to prevent the effects of thermal deformation caused by a thermal atmosphere. For example, electric wires with thick polyethylene insulation coatings are crosslinked by steam crosslinking or dry crosslinking methods, and silk insulated electric wires with thin insulation coatings for internal wiring in equipment are crosslinked by electron beam irradiation. Especially n
Silk insulated wires for internal wiring are often used in a thermal atmosphere inside equipment, so they are required to have flame retardancy, heat deformation resistance, heat aging resistance, etc., and cut-through resistance that is resistant to edge cracks. There are cases where something with gender is required.
しかし、架橋によって単に耐熱変形性を向上させても、
ポリエチレン自体の熱的酸化に対する抵抗性を改質しな
いかぎり、到底高温での連続使用には耐えることができ
ず、且つポリエチレンに老化防止剤を入れても加熱によ
って飛散し、その効果が期待できない問題がある。However, even if the heat deformation resistance is simply improved by crosslinking,
Unless polyethylene itself is modified in its resistance to thermal oxidation, it will not be able to withstand continuous use at high temperatures, and even if anti-aging agents are added to polyethylene, they will scatter when heated, making it unlikely to be effective. There is.
一方、ポリエチレンの素材についてみれば、高密度ポリ
エチレン（ρ＝０．９４２以上）では、耐熱変形性や耐
カツトスルー性を具備させることができるが、押出成形
性、架橋性がわるい。On the other hand, regarding polyethylene materials, high-density polyethylene (ρ=0.942 or more) can provide heat deformation resistance and cut-through resistance, but has poor extrusion moldability and crosslinkability.
架橋性がわるいのは、高密度ポリエチレンは分子中に結
晶質を有するためで、架橋に際し電子線照射量が多くな
って、生産コストが高く経済的に不利となる。そのため
、低密度ポリエチレン（ρ＝０．９１０〜０．９３０未
満）が多く使用されてきたが、架橋によって材質を改質
しても耐熱変形性を期待する程に向上できず、耐カツト
スルー性に欠ける問題がある。耐カツトスルー性を要求
されない場合は、低密度ポリエチレンを素材とし、架橋
促進剤と熱老化防止剤とを配して電子線照射架橋によっ
て細物絶縁電線を製造していた。The reason why high-density polyethylene has poor crosslinking properties is that it has crystalline substances in its molecules, and the amount of electron beam irradiation increases during crosslinking, resulting in high production costs and an economic disadvantage. Therefore, low-density polyethylene (ρ = less than 0.910 to 0.930) has been widely used, but even if the material is modified by crosslinking, the heat deformation resistance cannot be improved to the extent expected, and the cut-through resistance has deteriorated. There is a problem that is missing. When cut-through resistance is not required, thin insulated wires are manufactured by using low-density polyethylene as a material, disposing crosslinking accelerators and heat aging inhibitors, and crosslinking with electron beam irradiation.
前記配合に使用する架橋促進剤には、例えば、トリメチ
ロールプロパントリメタクリレート（以下、ＴＭＰＴと
略称する）が、又、熱老化防止剤には、４．４゛−チオ
・ビス（６−ｔ−ブチル−ｍ−クレゾール）（以下、フ
ェノール系老化防止剤と略称する）が使用されていた。The crosslinking accelerator used in the formulation includes, for example, trimethylolpropane trimethacrylate (hereinafter abbreviated as TMPT), and the heat aging inhibitor includes 4.4'-thio bis(6-t- Butyl-m-cresol) (hereinafter abbreviated as phenolic anti-aging agent) was used.
前記の架橋促進剤と熱老化防止剤とをポリエチレンに対
して併用すると、（１）ＴＭＰＴの架橋促進効果があま
り期待できないこと、（２）フェノール系老化防止剤が
ＴＭＰＴの架橋促進効果をより低下させること、（３）
ＴＭＰＴはポリエチレンとの親和性がわるく、ブリード
現象を生じやすいなどの問題があることを把握している
。When the above-mentioned crosslinking accelerator and heat anti-aging agent are used together for polyethylene, (1) the effect of promoting cross-linking of TMPT cannot be expected much, and (2) the phenolic anti-aging agent further reduces the effect of promoting cross-linking of TMPT. (3)
It is understood that TMPT has problems such as poor affinity with polyethylene and a tendency to cause a bleed phenomenon.
（発明が解決しようとする問題点）
本発明の目的は、上記の技術的課題を解決し、押出成形
性が良好であって電子線照射量を低減し、且つ耐熱変形
性、耐熱老化性および耐カツトスルー性にすぐれた機器
内配線用細物絶縁電線に使用する電子線照射架橋ポリエ
チレン組成物を提供することにある。(Problems to be Solved by the Invention) The purpose of the present invention is to solve the above technical problems, to have good extrusion moldability, to reduce the amount of electron beam irradiation, and to have good heat deformation resistance, heat aging resistance, and An object of the present invention is to provide an electron beam irradiation crosslinked polyethylene composition for use in thin insulated wires for internal wiring, which has excellent cut-through resistance.
（問題点を解決するための手段）
本発明者らは、上記の問題を解決するために鋭意検討を
行なった結果、中密度ポリエチレンに、架橋促進剤のジ
アリルクロレンデートと、熱老化防止剤として２−メル
カプトベンゾイミダゾール又は２−メルカプトメチルベ
ンゾイミダゾール若しくはそれらの亜鉛塩とＮ、Ｎ’−
ジー〔ジエチル−ビス−３（３，５−ジ−ｔ−ブチル−
４−ヒドロキシフェノール）プロピオネート〕オキサミ
ドおよび亜鉛又は鉛の酸化物の三種類成分を特定量配合
することによって、耐熱変形性、耐熱老化性および耐カ
ツトスルー性を有することを見出して本発明を完成させ
たものである。(Means for Solving the Problems) As a result of intensive studies to solve the above problems, the present inventors have found that medium density polyethylene contains diallyl chlorendate, a crosslinking accelerator, and a heat aging inhibitor. as 2-mercaptobenzimidazole or 2-mercaptomethylbenzimidazole or a zinc salt thereof and N,N'-
Di[diethyl-bis-3(3,5-di-t-butyl-
The present invention was completed by discovering that 4-hydroxyphenol) propionate has heat deformation resistance, heat aging resistance, and cut-through resistance by blending specific amounts of three types of components: oxamide and zinc or lead oxide. It is something.
すなわち、本発明の構成は、
中密度ポリエチレン１００ｆｆ１１部に対して、（１）
ジアリルクロレンデート０．５〜５．０重量部（２）２
−メルカプトベンゾイ
ミダゾール又は２−メル
カプトメチルベンゾイミ
ダゾール若しくはそれら
の亜鉛塩 １〜２０重量部（３） Ｎ、
Ｎ″−ジー〔ジエチル−ビス−３（３，５−ジーｔ−ブ
チ
ル−４−ヒドロキシフェノ
ール）プロピオネート〕オ
キサミド ０．２〜５．５重量部（４）亜
鉛又は鉛の酸化物 １．５〜１０重量部とを配合し
て成ることを特徴とするものである。That is, the structure of the present invention is as follows: (1) for 11 parts of medium density polyethylene 100ff
Diallylchlorendate 0.5-5.0 parts by weight (2) 2
- Mercaptobenzimidazole or 2-mercaptomethylbenzimidazole or zinc salt thereof 1 to 20 parts by weight (3) N,
N″-di[diethyl-bis-3(3,5-di-t-butyl-4-hydroxyphenol)propionate]oxamide 0.2 to 5.5 parts by weight (4) Zinc or lead oxide 1.5 to 10 parts by weight.
ここに、本発明で使用する中密度ポリエチレンとは、比
重が０．９３０〜０．９４２未満の範囲である。Here, the medium density polyethylene used in the present invention has a specific gravity in the range of 0.930 to less than 0.942.
本発明で使用するジアリルクロレンデートとは、電子線
照射時にポリエチレンのポリマー鎖からの脱水素反応を
促進し、架橋反応を促す作用を有するもので、次の化学
構造式で表される。The diallyl chlorendate used in the present invention has the effect of promoting dehydrogenation reaction from the polymer chain of polyethylene upon electron beam irradiation and promoting crosslinking reaction, and is represented by the following chemical structural formula.
なお、ｎ＝１〜４程度のものが使用されるが、好ましく
は１または２のものである。ジアリルクロレンデートは
液体で、ポリエチレンには極めて親和性があってよく分
散する。その配合量は中密度ポリエチレン１００重量部
に対して０．５〜５．０重量部の範囲であり、好ましく
は、０．５〜３重量部である。その配合量が０．５重量
部未満では、架橋促進効果が認められず、逆に５重量部
を超えるときは、架橋促進効果が飽和に達し、ブリード
現象が生じて外観を著しく阻害するので好ましくない。Note that n=1 to about 4 is used, preferably 1 or 2. Diallylchlorendate is a liquid and has an excellent affinity for polyethylene and is well dispersed. The blending amount is in the range of 0.5 to 5.0 parts by weight, preferably 0.5 to 3 parts by weight, based on 100 parts by weight of medium density polyethylene. If the amount is less than 0.5 parts by weight, no crosslinking promoting effect will be observed, and if it exceeds 5 parts by weight, the crosslinking promoting effect will reach saturation and a bleeding phenomenon will occur, which will significantly impair the appearance. do not have.
本発明で使用する２−メルカプトベンゾイミダゾール（
Ａ）又は２−メルカプトメチルベンゾイミダゾール（Ｂ
）若しくはそれらの亜鉛塩とは、電子線照射時に空気中
の酸素によるポリエチレンの酸化劣化を防止し、架橋反
応を阻害することもなく、ブリード現象も生じない。し
かも耐熱老化性には極めて顕著な効果を示し、粉体であ
るがポリエチレンとは親和性があってよ（分散するもの
で、次の化学構造式で表わされる。2-Mercaptobenzimidazole used in the present invention (
A) or 2-mercaptomethylbenzimidazole (B
) or their zinc salts prevent oxidative deterioration of polyethylene due to oxygen in the air during electron beam irradiation, do not inhibit crosslinking reactions, and do not cause any bleeding phenomenon. Moreover, it has a very remarkable effect on heat aging resistance, and although it is a powder, it has an affinity for polyethylene (it is dispersed and is represented by the following chemical structural formula).
（八）：２−メルカプトベンツ
（Ｂ）：２−メルカプトメチルベンゾイミダゾールその
配合量は、中密度ポリエチレン１００重量部に対して１
〜２０重量部の範囲であり、好ましくは３〜１０重量部
ある。その配合量が１重量部未満では、耐熱老化性が期
待できない。逆に、２０重量部を超えるときは、増量効
果がなく、機械的特性が著しく低下するので好ましくな
い。(8): 2-mercaptobenz (B): 2-mercaptomethylbenzimidazole The blending amount is 1 part by weight per 100 parts by weight of medium density polyethylene.
-20 parts by weight, preferably 3-10 parts by weight. If the amount is less than 1 part by weight, heat aging resistance cannot be expected. On the other hand, when it exceeds 20 parts by weight, there is no effect of increasing the amount and the mechanical properties are significantly deteriorated, which is not preferable.
本発明に使用するＮ．Ｎ’−ジー〔ジエチル−ビス−３
（３．５−ジ−ｔ−ブチル−４−ヒドロキシフェノー
ル）プロピオネート〕オキサミド（以下、ナラガードＸ
Ｌ−１ （米国二二ロイヤル社の商標名）と略称する
）は、次の化学構造式で表わされる。N. used in the present invention. N'-G[diethyl-bis-3
(3.5-di-t-butyl-4-hydroxyphenol)propionate] oxamide (hereinafter referred to as Naragard
L-1 (trade name of 22 Royal Company, USA)) is represented by the following chemical structural formula.
その配合量は、中密度ポリエチレン１００重量部に対し
て、０．２〜５．５重量部の範囲であり、好ましくは０
．２５〜３重量部である。その配合量が０、２重量部未
満では、耐熱老化性が期待できない。The blending amount is in the range of 0.2 to 5.5 parts by weight, preferably 0.2 to 5.5 parts by weight, based on 100 parts by weight of medium density polyethylene.
．． It is 25 to 3 parts by weight. If the amount is less than 0.2 parts by weight, no heat aging resistance can be expected.
逆に、５．５重量部を超えるときは、耐熱老化性が飽和
に達するので経済的にも好ましくなく、ブリード現象が
生じて外観を著しく損ねることになる。On the other hand, if it exceeds 5.5 parts by weight, the heat aging resistance will reach saturation, which is economically undesirable, and a bleed phenomenon will occur, significantly impairing the appearance.
本発明で使用する酸化亜鉛又は酸化鉛とは、通常の製法
で製造されたものであればよく、粒度、形状の如何に関
係しない。The zinc oxide or lead oxide used in the present invention may be one produced by a normal manufacturing method, and is not concerned with particle size or shape.
その配合量は、中密度ポリエチレン１００重里部に対し
て１．５〜１０重量部の範囲であり、好ましくは３〜７
重量部である。その配合量が１、５＼重量部未満では、
耐熱老化性が滅失するので好ましくない。The blending amount is in the range of 1.5 to 10 parts by weight, preferably 3 to 7 parts by weight, per 100 parts by weight of medium density polyethylene.
Parts by weight. If the amount is less than 1.5 parts by weight,
This is not preferred because heat aging resistance is lost.
逆に、１０重量部を超えるときは、増量効果がなく、機
械的特性が著しく低下するので好ましくない。On the other hand, when it exceeds 10 parts by weight, there is no effect of increasing the amount and the mechanical properties are significantly deteriorated, which is not preferable.
本発明に使用する熱老化防止剤、すなわち、２−メルカ
プトベンゾイミダゾールおよびそのＳＭ ６体若しくは
それらの亜鉛４、ナラガードＸＬ−１、および亜鉛又は
鉛の酸化物の３成分を前記特定の割合で配合したことを
特徴とする特ので、これらの組合せにおいて顕著な相剰
効果が発揮されて、高温での耐熱老化性にすぐれた電子
線照射架橋ポリエチレン組成物が得られるのであって、
各成分単独では耐熱老化性を示すものではない。The heat aging inhibitor used in the present invention, that is, 2-mercaptobenzimidazole and 6 SMs thereof, or their three components, zinc 4, Naragard XL-1, and zinc or lead oxide, is blended in the above-mentioned specific ratio. As a special feature, a remarkable additive effect is exhibited in the combination of these, and an electron beam irradiation crosslinked polyethylene composition having excellent heat aging resistance at high temperatures can be obtained.
Each component alone does not exhibit heat aging resistance.
本発明に係るポリエチレン組成物には、難燃性を具備さ
せるために、塩素系難燃剤および二酸化アンチモンが配
合されるが、適宜、滑剤などを配合してもよい。The polyethylene composition according to the present invention contains a chlorine flame retardant and antimony dioxide in order to have flame retardancy, but may also contain a lubricant and the like as appropriate.
（実施例）
以下、実施例および比較例にもとづいて本発明を更に詳
細に説明するが、本発明はかかる実施例にのみ限定され
るものでない。(Examples) Hereinafter, the present invention will be explained in more detail based on Examples and Comparative Examples, but the present invention is not limited only to these Examples.
中密度ポリエチレン（ネオゼックス２０１５Ｍ、三井石
油化学社製＞１００重量部に対して、塩素系難燃剤（デ
クロランプラス２５、フッカ−ケミカル社製）５０重量
部、二酸化アンチモン２０重量部およびステアリン酸カ
ルシウム１．５重量部を添加したものをベースに、第１
表および第２表に示す割合（重量部）で架橋促進剤、熱
老化防止剤を配合し、直径１５０ｍｍのミキシングロー
ルを用いて１５０〜１８０℃の温度範囲で均一に２０〜
３０分間混練りした後、ゲージ圧１５０ ｋｇ／ｃｍ”
、１８０℃ｘｌＯ分間の加熱条件でプレス成形し、厚さ
０．５ｍｍの絶縁シートを作製した後、加速電圧７５０
ＫｅＶ、４４ｍＡの条件で、該絶縁シートに対して大気
中で電子線照射を行ない架橋した。このとき電子線照射
量はいずれも２０ Ｍｒａｄとした。かくして得（注）
カットスルー性の試験とは、架橋絶縁シート片（０、５
ｍｍ厚×１５１巾Ｘ３０ｍｍ長）を直径５＋＋ｍφの金
属マンドレル上にのせ、該絶縁シート上に９０°の角度
をもつ逆刃をあてて、３５０ｇの荷重をかけて１２０℃
×１０分間の加熱雰囲気中に放置し、前記金属マンドレ
ルと逆刃との間に直流
２５Ｖの電圧を印加して短絡電流の有無を調べる。判定
基準は、Ｏ印を良好、×印を不良として評価した。Medium-density polyethylene (Neozex 2015M, manufactured by Mitsui Petrochemical Co., Ltd. >100 parts by weight, 50 parts by weight of a chlorine flame retardant (Dechlorane Plus 25, manufactured by Hooker Chemical Company), 20 parts by weight of antimony dioxide, and 1.0 parts by weight of calcium stearate. Based on the one to which 5 parts by weight was added, the first
A crosslinking accelerator and a heat aging inhibitor are blended in the proportions (parts by weight) shown in Tables 1 and 2, and the mixture is uniformly distributed at a temperature of 150 to 180°C using a mixing roll with a diameter of 150 mm.
After kneading for 30 minutes, the gauge pressure was 150 kg/cm.
, after press molding under heating conditions of 180°C x lO minutes to produce an insulating sheet with a thickness of 0.5 mm, an accelerating voltage of 750
The insulating sheet was cross-linked by irradiating it with an electron beam in the atmosphere at KeV and 44 mA. At this time, the electron beam irradiation amount was 20 Mrad in both cases. Thus obtained (note)
The cut-through property test refers to cross-linked insulating sheet pieces (0, 5
mm thickness x 151 width x 30 mm length) was placed on a metal mandrel with a diameter of 5++ mφ, a reverse blade with a 90° angle was placed on the insulating sheet, and a load of 350 g was applied to the insulating sheet at 120°C.
The sample was left in a heated atmosphere for 10 minutes, and a voltage of 25 V DC was applied between the metal mandrel and the reverse blade to check for short-circuit current. As for the evaluation criteria, an O mark was evaluated as good, and a cross mark was evaluated as poor.
電子線照射後の架橋絶縁シートが１２０°Ｃ以上の温度
での連続使用に保障できるか否かを判断するために、Ｕ
Ｌ規格の１２５℃定格評価法に準じて１５８℃の温度で
熱老化試験機中に、該架橋絶縁シートを７日間保持して
熱老化後の引張強さと伸びを測定し、熱老化試験前の値
に対す残率（％）で求め、前者での残率が７０％以上、
後者での残率が６５％以上をそれぞれ良好なものと判定
し、ブリード現象の有無などをしらべた結果を第１表お
よび第２表の下段に併記した。U
The crosslinked insulating sheet was held in a heat aging tester at a temperature of 158°C for 7 days in accordance with the 125°C rating evaluation method of the L standard, and the tensile strength and elongation after heat aging were measured. Calculated by the remaining rate (%) against the value, and the remaining rate in the former is 70% or more,
A residual ratio of 65% or more in the latter case was judged to be good, and the results of examining the presence or absence of a bleeding phenomenon are also listed in the lower rows of Tables 1 and 2.
ここに、耐カツトスルー性の良好なものは、架橋度が大
きく、又、加熱変形性が小さい関係にあることを意味す
る。Here, a material with good cut-through resistance means a high degree of crosslinking and a low heat deformability.
結果かられかるように、実施例１〜１０は、ＵＬ規格の
１２５℃定格評価法において良好な値を示している。As can be seen from the results, Examples 1 to 10 showed good values in the 125° C. rating evaluation method of the UL standard.
しかし、比較例４．８．１０．は、電子線照射後の架橋
絶縁シートの引張強さが１ｋｆ！／ｍｍ”未満であって
好ましくない。However, Comparative Example 4.8.10. The tensile strength of the crosslinked insulating sheet after electron beam irradiation is 1kf! /mm", which is not preferable.
比較例２．６．１１．１２、は耐カツトスルー性がわる
く、好ましくない。Comparative Examples 2.6.11.12 have poor cut-through resistance and are not preferred.
比較例３．５．７．９．１０．１１．
１３は、１５８℃×７日の熱老化試験後の伸びの残率（
％）の値が低く、好ましくない。比較例１．６は、ポリ
エチレン組成物上にブリード現象を生じ、外観を著しく
損ねるので好ましくない。Comparative example 3.5.7.9.10.11. 13 is the residual elongation rate after the heat aging test at 158°C x 7 days (
%) is low, which is not desirable. Comparative Example 1.6 is not preferred because it causes a bleeding phenomenon on the polyethylene composition and significantly impairs the appearance.
（発明の効果）
以上述べたように、本発明は中密度ポリエチレンに、架
橋促進剤のジアリルクロレンデートと、熱老化防止剤と
して２−メルカプトベンゾイミダゾール又は２−メルカ
プトメチルベンゾイミダゾール若しくはそれらの亜鉛塩
とナラガードＸＬ−１および酸化亜鉛などの三種類成分
を特定量配合することにより、すぐれた耐熱変形性と耐
熱老化性および耐カツトスルー性を有するポリエチレン
組成物が得られ、且つ架橋に際し、経済的な電子線照射
量で架橋することができるのでモータ機器などの又、機
器内配線用の絶縁電線を安価に供給し得る利点がある。(Effects of the Invention) As described above, the present invention provides medium density polyethylene with diallyl chlorendate as a crosslinking accelerator and 2-mercaptobenzimidazole or 2-mercaptomethylbenzimidazole or zinc thereof as a heat aging inhibitor. By blending specific amounts of salt, three types of components such as Naragard XL-1 and zinc oxide, a polyethylene composition with excellent heat deformation resistance, heat aging resistance, and cut-through resistance can be obtained, and it is economical during crosslinking. Since crosslinking can be performed with a moderate amount of electron beam irradiation, there is an advantage that insulated wires for motor equipment and internal wiring of equipment can be supplied at low cost.
Claims (1)
ロレンデート０．５〜５重量部、２−メルカプトベンゾ
イミダゾール又は２−メルカプトメチルベンゾイミダゾ
ール若しくはこれらの亜鉛塩１〜２０重量部、Ｎ，Ｎ′
−ジ−〔ジエチル−ビス−３（３，５−ジ−ｔ−ブチル
−４−ヒドロキシフェノール）プロピオネート〕オキサ
ミド０．２〜５．５重量部、亜鉛又は鉛の酸化物１．５
〜１０重量部を配合して成ることを特徴とする電子線照
射架橋ポリエチレン組成物。[Scope of Claims] 0.5 to 5 parts by weight of diallyl chlorendate, 1 to 20 parts by weight of 2-mercaptobenzimidazole or 2-mercaptomethylbenzimidazole, or a zinc salt thereof, based on 100 parts by weight of medium density polyethylene. , N, N'
-di-[diethyl-bis-3(3,5-di-t-butyl-4-hydroxyphenol)propionate]oxamide 0.2 to 5.5 parts by weight, zinc or lead oxide 1.5 parts
An electron beam irradiation crosslinked polyethylene composition, characterized in that it contains 10 parts by weight of electron beam irradiation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7492186A JPS62230810A (en) | 1986-03-31 | 1986-03-31 | Electron radiation crosslinked polyethylene composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7492186A JPS62230810A (en) | 1986-03-31 | 1986-03-31 | Electron radiation crosslinked polyethylene composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62230810A true JPS62230810A (en) | 1987-10-09 |
| JPH0451566B2 JPH0451566B2 (en) | 1992-08-19 |
Family
ID=13561323
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7492186A Granted JPS62230810A (en) | 1986-03-31 | 1986-03-31 | Electron radiation crosslinked polyethylene composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62230810A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR970021237A (en) * | 1995-10-09 | 1997-05-28 | 황선두 | Flame retardant polyolefin resin composition for wire coating |
-
1986
- 1986-03-31 JP JP7492186A patent/JPS62230810A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR970021237A (en) * | 1995-10-09 | 1997-05-28 | 황선두 | Flame retardant polyolefin resin composition for wire coating |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0451566B2 (en) | 1992-08-19 |
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