JPS6157857B2 - - Google Patents
Info
- Publication number
- JPS6157857B2 JPS6157857B2 JP54047063A JP4706379A JPS6157857B2 JP S6157857 B2 JPS6157857 B2 JP S6157857B2 JP 54047063 A JP54047063 A JP 54047063A JP 4706379 A JP4706379 A JP 4706379A JP S6157857 B2 JPS6157857 B2 JP S6157857B2
- Authority
- JP
- Japan
- Prior art keywords
- flame
- polyethylene
- density
- phr
- retardant
- 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
Links
- 239000003063 flame retardant Substances 0.000 claims description 13
- 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 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 229920003020 cross-linked polyethylene Polymers 0.000 claims description 5
- 239000004703 cross-linked polyethylene Substances 0.000 claims description 5
- 229920001903 high density polyethylene Polymers 0.000 claims description 5
- 239000004700 high-density polyethylene Substances 0.000 claims description 5
- 229920001179 medium density polyethylene Polymers 0.000 claims description 5
- 239000004701 medium-density polyethylene Substances 0.000 claims description 5
- -1 polyethylene Polymers 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 6
- 230000032683 aging Effects 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 4
- 229920005601 base polymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000000654 additive Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- 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
- 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
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Organic Insulating Materials (AREA)
- Insulated Conductors (AREA)
Description
本発明は、特に耐熱老化特性に優れ、ケーブル
絶縁体材料として有用な耐熱性難燃ポリエチレン
組成物に関する。
従来から耐熱性の要求される電線、ケーブルの
絶縁層には、架橋ポリエチレンが使用されてお
り、また、更に、難燃性を必要とする場合には、
ベースポリエチレン中に難燃剤を配合することも
すでに行われているところである。
しかるに、かかる従来の耐熱性難燃架橋ポリエ
チレン組成物では、耐カツトスルー性および耐熱
老化特性が不充分であるという欠点があつた。
耐カツトスルー性を向上させるには、高密度あ
るいは中密度のポリエチレンを使用することが考
えられるが、一般にこれらのポリエチレンは加工
性に乏しく、添加剤の混入が困難であるという欠
点がある。
更に、従来ポリエチレン用に使用されている酸
化防止剤は、耐熱特性がさほど良好ではなく、多
量に添加するとブルームするという欠点があり、
更に、架橋効率を低下させたり汚染性を有すると
いう難点もあつた。
本発明は、かかる従来の欠点を解消すべくなさ
れたもので、(イ)高密度又は中密度のポリエチレン
70〜90%、(ロ)エチレン・酢酸ビニル共重合体30〜
10%から成るベースポリマーに、3〜7PHRのビ
ス〔2−メチル−4−{3−n−アルキル(C12又
はC14)チオプロピオニルオキシ}−5−t−ブチ
ルフエニル〕スルフイド〔次の式
で表わされる〕
と有効量の難燃剤とを配合して成る耐熱性難燃架
橋ポリエチレン組成物を提供しようとするもので
ある。
本発明において、エチレン・酢酸ビニル共重合
体を使用するのは、高密度あるいは中密度ポリエ
チレンの加工性を補ない、添加剤の相溶性を向上
させるためであつて、その配合量が10%未満で
は、効果が不充分であり、逆に30%を越えると、
高密度あるいは中密度のポリエチレンによる耐カ
ツトスルー性を減殺するに至る。
本発明に使用する前記のビス〔2−メチル−4
−{3−n−アルキル(C12又はC14)チオプロピオ
ニルオキシ}−5−t−ブチルフエニル〕スルフ
イドは、アデカアーガス社より、Mark AO−23
という商品名で市販されている。この化合物は、
ベースポリマーに対して3〜8PHR、好ましくは
4〜7PHRの範囲で配合される。3PHR未満であ
ると耐熱老化特性向上の効果が小さく、逆に
8PHRを越えても効果はそれ以上向上せず、かえ
つてブレームする傾向が見られるので、いずれも
好ましくない。
また、本発明に使用する難燃剤としては、ハロ
ゲン系有機難燃剤、金属酸化物系難燃剤のいずれ
も使用が可能である。これらの難燃剤は、15〜
35PHRの範囲でベースポリマーへ配合される。
更に、本発明において、架橋を化学架橋により
行なう場合には、ジクミルパーオキサイド、2・
5−ジメチル−2・5−ジ(t−ブチルパーオキ
シ)ヘキシン−3のような有機過酸化物を0.5〜
5PHRの範囲で配合する必要があり、また架橋を
電子線照射架橋により行なう場合には、トリメチ
ロールプロパントリメタクリレート(TMPT)
の如き多管能性モノマーを、1〜5PHR配合する
ことが望ましい。
なお、必要に応じて、ステアリン酸、ステアリ
ン酸誘導体あるいは低分子量のポリエチレンのよ
うな加工助剤を0.2〜1PHR配合することもでき
る。
以上の配合組成から成る本発明の組成物は、耐
熱老化特性に極めて優れており、CSA規格Type
CL1502 Coil−Lead Wire(150℃グレード難燃
架橋ポリエチレン)の158℃×60日、伸び残率65
%以上を充分満足する特性を有しており、電線、
ケーブルの絶縁被覆をはじめ、難燃性および耐熱
性を要求される広汎な用途に適用することが可能
である。
次に実施例について記載する。
実施例
The present invention relates to a heat-resistant, flame-retardant polyethylene composition that has particularly excellent heat aging resistance and is useful as a cable insulator material. Cross-linked polyethylene has traditionally been used in the insulation layers of electric wires and cables that require heat resistance, and when flame retardancy is required,
Combining flame retardants into base polyethylene has already been carried out. However, such conventional heat-resistant flame-retardant crosslinked polyethylene compositions have the drawback of insufficient cut-through resistance and heat aging resistance. In order to improve the cut-through resistance, it is possible to use high-density or medium-density polyethylene, but these polyethylenes generally have the disadvantage that they have poor processability and are difficult to incorporate additives into. Furthermore, the antioxidants conventionally used for polyethylene do not have very good heat resistance properties, and have the disadvantage of blooming when added in large amounts.
Furthermore, there were also drawbacks such as reduced crosslinking efficiency and staining properties. The present invention has been made to solve these conventional drawbacks, and includes (a) high-density or medium-density polyethylene
70~90%, (b) Ethylene/vinyl acetate copolymer 30~
10% of the base polymer with 3 to 7 PHR of bis[2-methyl-4-{3-n-alkyl ( C12 or C14 ) thiopropionyloxy}-5-t-butylphenyl] sulfide [formula It is an object of the present invention to provide a heat-resistant, flame-retardant crosslinked polyethylene composition, which contains a flame retardant and an effective amount of a flame retardant. In the present invention, the ethylene/vinyl acetate copolymer is used to supplement the processability of high-density or medium-density polyethylene and to improve the compatibility of additives, and the amount thereof is less than 10%. Then, the effect is insufficient, and on the other hand, if it exceeds 30%,
This reduces the cut-through resistance provided by high-density or medium-density polyethylene. The above-mentioned bis[2-methyl-4
-{3-n-alkyl (C 12 or C 14 ) thiopropionyloxy}-5-t-butylphenyl] sulfide is available from Adeka Argus, Mark AO-23.
It is marketed under the product name. This compound is
It is blended in an amount of 3 to 8 PHR, preferably 4 to 7 PHR, based on the base polymer. If it is less than 3PHR, the effect of improving heat aging resistance will be small;
Even if it exceeds 8 PHR, the effect does not improve any further, and there is a tendency to cause damage, so neither is preferable. Further, as the flame retardant used in the present invention, both halogen-based organic flame retardants and metal oxide-based flame retardants can be used. These flame retardants range from 15 to
It is blended into the base polymer in a range of 35PHR. Furthermore, in the present invention, when crosslinking is carried out by chemical crosslinking, dicumyl peroxide, 2.
Organic peroxides such as 5-dimethyl-2,5-di(t-butylperoxy)hexyne-3 are added to
Trimethylolpropane trimethacrylate (TMPT) must be blended within the range of 5PHR, and when crosslinking is performed by electron beam irradiation crosslinking.
It is desirable to blend 1 to 5 PHR of a multifunctional monomer such as the following. Note that, if necessary, a processing aid such as stearic acid, a stearic acid derivative, or low molecular weight polyethylene may be blended in an amount of 0.2 to 1 PHR. The composition of the present invention, which has the above-mentioned composition, has extremely excellent heat aging resistance, and has a CSA standard Type
CL1502 Coil-Lead Wire (150℃ grade flame-retardant cross-linked polyethylene) at 158℃ x 60 days, elongation retention rate 65
% or more, and has characteristics that fully satisfy the
It can be applied to a wide range of applications that require flame retardancy and heat resistance, including insulation coatings for cables. Next, examples will be described. Example
【表】
上表の配合の組成物により試料シートを作成
し、この試料シートについて158℃ギヤーオープ
ン中での熱老化特性を測定した。測定結果は、図
示の通り優れた耐熱老化特性を有することを示し
ている。なお比較例として示したものは、マーク
AO−23にかえて従来ポリエチレンについて汎用
されている酸化防止剤(アンテージクリスタル)
を使用した以外は実施例と同一の配合から成る試
料であつて本発明との比較のために掲げたもので
ある。[Table] A sample sheet was prepared using the composition shown in the above table, and the heat aging characteristics of this sample sheet at 158°C in gear open were measured. As shown in the figure, the measurement results show that the material has excellent heat aging resistance. In addition, the items shown as comparative examples are marked
Antioxidant (Antage Crystal) that is commonly used for polyethylene instead of AO-23
This sample has the same formulation as in the example except that .
図面は、本発明の組成物の耐熱老化特性を示す
グラフである。
The drawing is a graph showing the heat aging properties of the composition of the present invention.
Claims (1)
%、(ロ)エチレン・酢酸ビニル共重合体30〜10%か
ら成るベースポリマーへ、3〜7PHRのビス〔2
−メチル−4−{3−n−アルキル(C12又は
C14)チオプロピオニルオキシ}−5−t−ブチル
フエニル〕スルフイドと有効量の難燃剤とを配合
して成ることを特徴とする耐熱性難燃架橋ポリエ
チレン組成物。[Claims] 1. (a) High-density or medium-density polyethylene 70 to 90
%, (b) 3 to 7 PHR of bis [2
-Methyl-4-{3-n-alkyl ( C12 or
A heat-resistant flame-retardant crosslinked polyethylene composition comprising C14 ) thiopropionyloxy}-5-t-butylphenyl sulfide and an effective amount of a flame retardant.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4706379A JPS55139443A (en) | 1979-04-17 | 1979-04-17 | Heat-resisting, flame-retardant crosslinked polyethylene composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4706379A JPS55139443A (en) | 1979-04-17 | 1979-04-17 | Heat-resisting, flame-retardant crosslinked polyethylene composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS55139443A JPS55139443A (en) | 1980-10-31 |
JPS6157857B2 true JPS6157857B2 (en) | 1986-12-09 |
Family
ID=12764689
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP4706379A Granted JPS55139443A (en) | 1979-04-17 | 1979-04-17 | Heat-resisting, flame-retardant crosslinked polyethylene composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS55139443A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0439031B2 (en) * | 1987-01-19 | 1992-06-26 |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5787447A (en) * | 1980-11-20 | 1982-05-31 | Nippon Synthetic Chem Ind Co Ltd:The | Resin composition |
GB2185262B (en) * | 1985-02-09 | 1989-04-05 | Dainichi Nippon Cables Ltd | Polyolefin compositions |
KR100625804B1 (en) | 2004-05-18 | 2006-09-20 | 엘에스전선 주식회사 | Insulation material for high voltage instrumental wire and cable using thereof |
JP2013194214A (en) * | 2012-03-22 | 2013-09-30 | Sumitomo Electric Ind Ltd | Non-halogen flame-retardant resin composition, and wire and cable produced by using the same |
-
1979
- 1979-04-17 JP JP4706379A patent/JPS55139443A/en active Granted
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0439031B2 (en) * | 1987-01-19 | 1992-06-26 |
Also Published As
Publication number | Publication date |
---|---|
JPS55139443A (en) | 1980-10-31 |
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