JPH085997B2 - Resin composition for wire coating - Google Patents
Resin composition for wire coatingInfo
- Publication number
- JPH085997B2 JPH085997B2 JP60067975A JP6797585A JPH085997B2 JP H085997 B2 JPH085997 B2 JP H085997B2 JP 60067975 A JP60067975 A JP 60067975A JP 6797585 A JP6797585 A JP 6797585A JP H085997 B2 JPH085997 B2 JP H085997B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- resin composition
- eea
- eva
- 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
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Organic Insulating Materials (AREA)
Description
【発明の詳細な説明】 〔技術分野〕 本発明は樹脂組成物に関し、更に詳しくはエチレン−
酢酸ビニル共重合体（以下EVAという）並びにエチレン
−エチルアクリレート共重合体（以下EEAという）の少
なくとも１種、及び直鎖状ポリエチレン（以下LPEとい
う）を主成分とする電線被覆用樹脂組成物に関する。TECHNICAL FIELD The present invention relates to a resin composition, and more specifically, ethylene-based resin composition.
TECHNICAL FIELD The present invention relates to a resin composition for wire coating, which contains at least one of a vinyl acetate copolymer (hereinafter referred to as EVA) and an ethylene-ethyl acrylate copolymer (hereinafter referred to as EEA), and a linear polyethylene (hereinafter referred to as LPE) as a main component. .
エチレン系重合体又はエチレン−エチルアクリレート
共重合体（EEA）は優れた電気絶縁性を有し、また放射
線架橋、有機過酸化物架橋、シラン化合物を用いるシラ
ン架橋等各種の架橋手段を適宜に採用して架橋出来、惹
いては各種物性を改善出来る利点があるため、従来から
電気絶縁材料を始め、各種の分野に巾広く使用されて来
た。しかしながら最近各種分野の技術レベルが向上し、
電気機器、車輌、自動車等の各分野に於いて絶縁電線就
中電子ワイヤーといわれる絶縁電線のより高度の特性が
要求されるようになり、耐油性、絶縁電線製造時の加工
性、難燃性、ぜい化特性、高温絶縁強度性（Cut throu
gh property）等がより高度に要求されるようになって
来た。The ethylene polymer or ethylene-ethyl acrylate copolymer (EEA) has excellent electrical insulation properties, and various cross-linking means such as radiation cross-linking, organic peroxide cross-linking, and silane cross-linking using a silane compound are appropriately adopted. Since it has the advantage that it can be cross-linked, and thus can improve various physical properties, it has been widely used in various fields including electric insulating materials. However, the technical level in various fields has recently improved,
Insulated electric wires in various fields such as electric equipment, vehicles, automobiles, etc. are becoming required to have more advanced characteristics of insulated electric wires, which are called electronic wires, and oil resistance, workability at the time of manufacturing insulated electric wires, and flame retardancy. , Embrittlement characteristics, high temperature insulation strength (Cut throu
gh property) etc. have become more highly demanded.
本発明者は従来からEVA又はEEA組成物について研究を
続けて来たが、特に最近の技術レベルの向上に応じた各
種物性の特に優れたEVA又はEEA組成物を開発すべく研究
を続けて来た。そしてこの研究に於いてEVA並びにEEAの
少なくとも１種とLPFとを特定量配合するときは、得ら
れる樹脂組成物はこれ等両者の相乗作用に依ってその耐
油性が特に優れることを見出した。本発明は更にこの組
成物について研究を続けている段階に於いて、この組成
物に更にベンズイミダゾール系老化防止剤（以下B.I.防
止剤という）を特定量配合するときは、上記組成物の優
れた耐油性とぜい化特性を毫も損なうことなく、更に耐
熱老化性が優れることを見出しここに本発明を完成する
に至った。即ち本発明は、酢酸ビニル含量が20重量％以
下のエチレン−酢酸ビニル共重合体並びにエチルアクリ
レート含量が20重量％以下のエチレン−エチルアクリレ
ート共重合体の少なくとも１種100重量部、密度0.91〜
0.93g/cm3の直鎖状低密度ポリエチレン５〜120重量部及
びベンズイミダゾール系老化防止剤0.1〜30重量部を含
有して成る電線被覆用樹脂組成物。に係るものである。The present inventor has been continuing research on EVA or EEA compositions, but has continued research to develop particularly excellent EVA or EEA compositions with various physical properties in response to recent improvements in the technical level. It was In this study, it was found that when at least one kind of EVA and EEA and LPF were blended in a specific amount, the resulting resin composition was particularly excellent in oil resistance due to the synergistic action of both. The present invention is still in the stage of continuing research on this composition, and when a specific amount of a benzimidazole anti-aging agent (hereinafter referred to as BI inhibitor) is added to this composition, the composition is excellent. The inventors have found that the heat aging resistance is further excellent without impairing the oil resistance and the embrittlement property, and have completed the present invention. That is, the present invention relates to an ethylene-vinyl acetate copolymer having a vinyl acetate content of 20% by weight or less and an ethylene-ethyl acrylate copolymer having an ethyl acrylate content of 20% by weight or less at least 100 parts by weight, and a density of 0.91 to.
An electric wire coating resin composition comprising 5-120 parts by weight of 0.93 g / cm 3 linear low-density polyethylene and 0.1-30 parts by weight of a benzimidazole-based antioxidant. It is related to.
本発明に於いてはEVA並びにEEAの少なくとも１種に対
し、特にLPEという特定の重合体を特定量配合すること
により、元来EVAやEEAが具備していた優れた特性を損う
ことなく耐油性がこれ等両者の相乗作用により著しく向
上するという効果がある。In the present invention, by blending at least one of EVA and EEA with a specific amount of a specific polymer called LPE, the oil-proof property is not impaired without impairing the excellent characteristics originally possessed by EVA and EEA. There is an effect that the property is remarkably improved by the synergistic action of these two.
また本発明に於いては、特にB.I.防止剤を配合するこ
とにより、上記の優れた各特性に加えて更に耐熱老化性
が向上するという効果が発揮される。In addition, in the present invention, the effect of further improving the heat aging resistance is exerted in addition to the above-mentioned excellent properties by blending the BI inhibitor in particular.
本発明の組成物は基本的には、EVA並びにEEAの少なく
とも１種100重量部、及びLPE5〜120重量部好ましくは20
〜80重量部を含有して成るものである。The composition of the present invention basically comprises 100 parts by weight of at least one of EVA and EEA, and 5 to 120 parts by weight of LPE, preferably 20 parts by weight.
-80 parts by weight.
本発明に於いて使用されるEVAとしては、その酢酸ビ
ニル含量が20重量％以下好ましくは15重量％以下のもの
であり、そのメルトインデックス（以下M.I.という）と
しても0.2〜５程度のものが好ましい。EEAもエチルアク
リレート含量が20重量％以下、M.I.は0.2〜1.0が好まし
い。これ等EVA及びEEAは夫々単独で使用されても、また
併用されても良く、この併用の際の割合もEVA0〜100重
量％並びにEEA100〜０重量％の広い範囲から適宜に選択
されれば良い。またLPEとしては、密度0.91〜0.93g/cm3
の低密度のものが使用され、特に側鎖の炭素数が４〜８
程度のものが好ましい。その分子量としてもかなり広い
範囲のものが使用出来、通常５万〜50万程度好ましくは
８万〜20万程度のものを使用する。またLPE自体はその
製法には何等限定されず本発明の目的に合致するLPEが
得られるかぎり、各種の製法で製造されたものがいずれ
も使用出来る。The EVA used in the present invention has a vinyl acetate content of 20% by weight or less, preferably 15% by weight or less, and a melt index (hereinafter referred to as MI) of about 0.2 to 5 is preferable. . EEA also has an ethyl acrylate content of 20% by weight or less, and MI is preferably 0.2 to 1.0. These EVA and EEA may be used alone or in combination, and the ratio in this combination may be appropriately selected from a wide range of EVA 0 to 100% by weight and EEA 100 to 0% by weight. . As LPE, the density is 0.91 to 0.93 g / cm 3.
Of low density is used, especially the side chain has 4 to 8 carbon atoms.
Something is preferable. A wide range of molecular weight can be used, and a molecular weight of usually about 50,000 to 500,000, preferably about 80,000 to 200,000 is used. Further, the LPE itself is not limited in its production method, and any one produced by various production methods can be used as long as LPE which meets the object of the present invention can be obtained.
本発明に於いて使用されるベンズイミダゾール系老化
防止剤としてはたとえば２−メルカプトベンズイミダゾ
ール（大内新興（株）のNocrac MB）とその亜鉛塩（No
crac MBZ）、２−メルカプトメチルベンズイミダゾー
ル（Nocrac MMB）とその亜鉛塩（Nocrac MMBZ）を例
示出来、その使用量はEVA並びにEEAの少なくとも１種10
0重量部に対して0.1〜30重量部好ましくは１〜10重量部
である（ただし、上記老化防止剤は他の老化防止剤と併
用しない）。Examples of the benzimidazole anti-aging agent used in the present invention include 2-mercaptobenzimidazole (Noracrac MB of Ouchi Shinko Co., Ltd.) and its zinc salt (No.
crac MBZ), 2-mercaptomethylbenzimidazole (Nocrac MMB) and its zinc salt (Nocrac MMBZ) can be exemplified, and the amount used is at least one of EVA and EEA.
It is 0.1 to 30 parts by weight, preferably 1 to 10 parts by weight, based on 0 parts by weight (however, the above antiaging agent is not used in combination with other antiaging agents).
本発明組成物には更に必要に応じてその他の他の通常
の各種添加剤を添加することが出来る。この際の他の添
加剤としては、たとえば難燃剤、無機充填剤等があり、
また架橋剤、架橋助剤等も使用出来することが出来る。If desired, the composition of the present invention may further contain other usual various additives. Other additives at this time include, for example, flame retardants and inorganic fillers,
Further, a cross-linking agent, a cross-linking aid and the like can also be used.
以下に実施例を示して本発明をより具体的に説明す
る。但し下記例に於いて部とあるは重量部を意味するも
のとする。Hereinafter, the present invention will be described more specifically with reference to examples. However, in the following examples, "parts" means "parts by weight".
実施例１〜７並びに比較例１〜６ 第１表に示す配合割合で各成分を所定量配合充分混練
して組成物となした。この組成物について常法に基づい
て電線（導体が0.813mmφの軟銅単線で、絶縁は0.38mm
厚）を製造し、30Mradの電子線量で照射架橋した。各種
物性を測定した。この結果を第１表に併記する。但し物
性は夫々次の方法により測定した。Examples 1 to 7 and Comparative Examples 1 to 6 Predetermined amounts of the respective components were blended at the blending ratios shown in Table 1 and sufficiently kneaded to obtain compositions. About this composition, the electric wire (conductor is 0.813mmφ annealed copper wire, insulation is 0.38mm)
(Thickness) was produced and irradiation crosslinked with an electron dose of 30 Mrad. Various physical properties were measured. The results are also shown in Table 1. However, the physical properties were measured by the following methods.
＜耐油性＞ 100℃のASTM2号オイルの中に96時間浸漬後室温に放置
し、引張強さの残率が初期の50％以上、伸びの残率が65
％以上の時合格とする。<Oil resistance> Immersion in 100 ° C ASTM2 oil for 96 hours and left at room temperature. The residual tensile strength is 50% or more of the initial value and the residual elongation is 65%.
If it is more than%, it will be passed.
〈耐熱性−１〉 UL Subject758に準じ、158℃で７日、老化し、引張
残率70％以上、伸び残率65％以下且つ、破壊電圧残率50
％以上であれば合格とする。<Heat resistance-1> According to UL Subject 758, aged at 158 ° C for 7 days, tensile residual ratio 70% or more, elongation residual ratio 65% or less, and breakdown voltage residual ratio 50.
If it is at least%, it will be passed.
但し第１表中で重合体として使用した各種重合体は夫
々次のものを示す。However, the various polymers used as polymers in Table 1 are as follows.
LPE−1:密度 0.920 M.I. 1.0 炭素数 ８ LPE−2:密度 0.925 M.I. 4.0 炭素数 ４ EVA−1:酢酸ビニル（以下EVという）含量 15wt％ M.I. 0.5 EVA−2:EV含量 10wt％ M.I. 1.0 EEA−1:エチルアクリレート（EAという）含量 15wt％ M.I. 1.5 EEA−2:EA含量 15wt％ M.T. 0.5 HDPE:高密度オリエチレン（ハイゼックス、三井油化学
社製） 密度 0.954g/cm3 LDPE:低密度ポリエチレン（ZF−30、三菱油化社製） 密度 0.920g/cm3 直鎖状ではない 〈耐熱性−２〉 耐熱性−１の試験に於いて、158℃で７日という条件
を200℃で４日の条件に代え、その他はすべて耐熱性−
１に従った。LPE-1: Density 0.920 MI 1.0 Carbon number 8 LPE-2: Density 0.925 MI 4.0 Carbon number 4 EVA-1: Vinyl acetate (hereinafter EV) content 15wt% MI 0.5 EVA-2: EV content 10wt% MI 1.0 EEA- 1: Ethyl acrylate (referred to as EA) content 15 wt% MI 1.5 EEA-2: EA content 15 wt% MT 0.5 HDPE: High density ORI-ethylene (Hi-Zex, manufactured by Mitsui Oil Chemicals) Density 0.954 g / cm 3 LDPE: Low density polyethylene ( ZF-30, manufactured by Mitsubishi Petrochemical Co., Ltd.) Density 0.920g / cm 3 Not linear <Heat resistance-2> In the heat resistance-1 test, the condition of 7 days at 158 ° C and 4 days at 200 ° C In place of the above conditions, all others are heat resistant-
I followed 1.
〈ぜい化特性〉 TIS.K6760に準じ、カミソリによるノツチ付とし、且
つ、温度を−40℃に代えて行った。<Embrittlement characteristics> In accordance with TIS.K6760, a razor was used for notching, and the temperature was changed to -40 ° C.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭58−19810（ＪＰ，Ａ) 特開 昭58−68804（ＪＰ，Ａ) 特開 昭55−116740（ＪＰ，Ａ) 特開 昭57−51746（ＪＰ，Ａ) 特開 昭55−80449（ＪＰ，Ａ) 特開 昭61−225235（ＪＰ，Ａ) 特公 昭46−37280（ＪＰ，Ｂ１) ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-58-19810 (JP, A) JP-A-58-68804 (JP, A) JP-A-55-116740 (JP, A) JP-A-57- 51746 (JP, A) JP-A-55-80449 (JP, A) JP-A-61-225235 (JP, A) JP-B-46-37280 (JP, B1)
Claims (1)
−酢酸ビニル共重合体並びにエチルアクリレート含量が
20重量％以下のエチレン−エチルアクリレート共重合体
の少なくとも１種100重量部、密度0.91〜0.93g/cm3の直
鎖状低密度ポリエチレン５〜120重量部及びベンズイミ
ダゾール系老化防止剤0.1〜30重量部（ただし、上記老
化防止剤は他の老化防止剤と併用しない）を含有して成
る電線被覆用樹脂組成物。1. An ethylene-vinyl acetate copolymer having a vinyl acetate content of 20% by weight or less and an ethyl acrylate content.
100 parts by weight of at least one ethylene-ethyl acrylate copolymer of 20% by weight or less, 5 to 120 parts by weight of linear low-density polyethylene having a density of 0.91 to 0.93 g / cm 3 , and a benzimidazole-based antioxidant 0.1 to 30 A resin composition for electric wire coating, which comprises parts by weight (however, the above antiaging agent is not used in combination with other antiaging agents).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60067975A JPH085997B2 (en) | 1985-03-30 | 1985-03-30 | Resin composition for wire coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60067975A JPH085997B2 (en) | 1985-03-30 | 1985-03-30 | Resin composition for wire coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61228047A JPS61228047A (en) | 1986-10-11 |
| JPH085997B2 true JPH085997B2 (en) | 1996-01-24 |
Family
ID=13360496
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60067975A Expired - Fee Related JPH085997B2 (en) | 1985-03-30 | 1985-03-30 | Resin composition for wire coating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH085997B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0655866B2 (en) * | 1988-01-12 | 1994-07-27 | タツタ電線株式会社 | Watertight admixture |
| CN114773719A (en) * | 2022-03-28 | 2022-07-22 | 金发科技股份有限公司 | Polyolefin material and preparation method and application thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2442870B1 (en) * | 1978-12-01 | 1986-05-23 | Gen Electric | POLYOLEFINIC COMPOUNDS HAVING IMPROVED THERMAL AGING STABILITY, ELECTRICAL CONDUCTORS ISOLATED USING THE SAME, AND PROCESSES FOR PRODUCING THE SAME |
| JPS55116740A (en) * | 1979-03-05 | 1980-09-08 | Showa Electric Wire & Cable Co Ltd | Heat-resistant flame-retardant crosslinked polyethylene resin composition |
| JPS5751746A (en) * | 1980-09-04 | 1982-03-26 | Lion Corp | Thermoplastic resin composition |
| JPS5819810A (en) * | 1981-07-29 | 1983-02-05 | 日立電線株式会社 | Extrusion crosslinking insulator |
| JPS5868804A (en) * | 1981-10-19 | 1983-04-23 | 日立電線株式会社 | Electric insulator |
| JPS61225235A (en) * | 1985-03-30 | 1986-10-07 | Mitsubishi Cable Ind Ltd | Resin composition |
-
1985
- 1985-03-30 JP JP60067975A patent/JPH085997B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61228047A (en) | 1986-10-11 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |