JP2537620B2 - Heat-aging resin composition - Google Patents
Heat-aging resin compositionInfo
- Publication number
- JP2537620B2 JP2537620B2 JP62099496A JP9949687A JP2537620B2 JP 2537620 B2 JP2537620 B2 JP 2537620B2 JP 62099496 A JP62099496 A JP 62099496A JP 9949687 A JP9949687 A JP 9949687A JP 2537620 B2 JP2537620 B2 JP 2537620B2
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- heat
- weight
- ethylene
- heat aging
- 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 - Lifetime
Links
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は耐熱老化性に優れた樹脂組成物に関し、更に
詳しくは各種電線、ケーブルの被覆材をはじめ、各種成
形品製造用組成物として使用される樹脂組成物に関す
る。DETAILED DESCRIPTION OF THE INVENTION [Industrial field of use] The present invention relates to a resin composition having excellent heat aging resistance, and more specifically, it is used as a composition for producing various molded articles including coating materials for various electric wires and cables. The present invention relates to a resin composition.
［従来の技術］ 電子機器用、車両用、船舶用あるいはその他の電線や
ケーブルをはじめ各種成形品に使用される樹脂組成物と
しては、過酷な条件下に於いて使用される関係上各種特
性が要求されるが、そのうちの一つの特性として耐熱老
化性がある。[Prior Art] As a resin composition used for various molded products such as electric devices, vehicles, ships, and other electric wires and cables, various characteristics are involved because they are used under severe conditions. Although required, one of the properties is heat aging resistance.
一方これ等樹脂組成物の主成分たる樹脂として最近エ
チレンとハロゲン置換エチレン就中フッ素置換エチレン
との共重合体が耐熱老化性に優れているという理由で注
目を集める様になって来た。この共重合体を使用した組
成物に於いても更に優れた耐熱老化性が要求され、最近
に至り金属酸化物や架橋助剤を配合したこの種組成物も
開発されている。On the other hand, as a resin which is a main component of these resin compositions, a copolymer of ethylene and halogen-substituted ethylene, especially fluorine-substituted ethylene, has recently been attracting attention because of its excellent heat aging resistance. Further excellent heat aging resistance is required even in a composition using this copolymer, and a composition of this kind containing a metal oxide or a crosslinking aid has been recently developed.
しかしながら最近の技術の急速な進歩に伴い、これに
使用される樹脂組成物についても益々過酷な特性が要求
されるようになり、耐熱老化性についても更に優れたも
のが強く要望されるようになって来た。However, with the rapid progress of recent technology, resin compositions used therein are required to have increasingly severe properties, and more excellent heat aging resistance is also strongly demanded. I came.
［発明が解決しようとする問題点］ 本発明が解決しようとする問題点は、従来の上記要望
に応え得る樹脂組成物を開発することであり、更に詳し
くは従来のこの種エチレン−ハロゲン置換エチレン共重
合体を主成分とする樹脂組成物に比し、更に一段と優れ
た耐熱老化性を有する樹脂組成物を開発することであ
る。[Problems to be Solved by the Invention] A problem to be solved by the present invention is to develop a resin composition which can meet the above-mentioned conventional demands, and more specifically, a conventional ethylene-halogen-substituted ethylene of this kind. It is an object of the present invention to develop a resin composition having further excellent heat aging resistance as compared with a resin composition containing a copolymer as a main component.
［問題点を解決するための手段］ この問題点は、エチレン−テトラフルオロエチレン共
重合体にSb2O3、ZrO並びにZnSの少なくとも１種とヒン
ダードフェノール系酸化防止剤を含有せしめることによ
って解決される。[Means for Solving Problems] This problem is solved by incorporating at least one of Sb 2 O 3 , ZrO and ZnS and a hindered phenolic antioxidant into an ethylene-tetrafluoroethylene copolymer. To be done.
即ち本発明は、エチレン−テトラフルオロエチレン共
重合体、Sb2O3、ZrO並びにZnSの少なくとも１種及びヒ
ンダードフェノール系酸化防止剤を含有して成る耐熱老
化性樹脂組成物に係るものである。That is, the present invention relates to a heat-aging resin composition containing an ethylene-tetrafluoroethylene copolymer, at least one of Sb 2 O 3 , ZrO and ZnS and a hindered phenolic antioxidant. .
［発明の構成並びに作用］ 本発明の組成物は基本的にはエチレン−テトラフルオ
ロエチレン共重合体（以下ETFEという）と、Sb2O3、ZrO
及びZnSの少なくとも１種、ヒンダードフェノール系酸
化防止剤必要に応じ更に架橋助剤とを含有した組成物で
ある。[Structure and Action of Invention] The composition of the present invention is basically composed of an ethylene-tetrafluoroethylene copolymer (hereinafter referred to as ETFE), Sb 2 O 3 , and ZrO.
And a composition containing at least one of ZnS and a hindered phenolic antioxidant, if necessary, and a crosslinking aid.
ETFEにSb2O3、ZrO、ZnSという特定の化合物の少なく
とも１種を含有せしめると、優れた耐熱老化性が発現す
る。When ETFE contains at least one of the specific compounds Sb 2 O 3 , ZrO, and ZnS, excellent heat aging resistance is exhibited.
そして上記基本組成成分に更にヒンダードフェノール
系酸化防止剤を含有せしめることにより、基本組成物の
耐熱老化性を更に一段と向上せしめることが出来る。加
えて架橋助剤を更に併用することにより、耐熱老化性が
最も優れたものとなる。Further, by adding a hindered phenolic antioxidant to the above basic composition component, the heat aging resistance of the basic composition can be further improved. In addition, by additionally using a crosslinking aid, the heat aging resistance becomes the best.
本発明で使用するETFEとしては、通常エチレン30〜70
重量％、テトラフルオロエチレン70〜30重量％程度であ
る。特にエチレン50重量％前後、テトラフルオロエチレ
ン50重量％前後である。The ETFE used in the present invention is usually ethylene 30-70.
% By weight, and tetrafluoroethylene 70 to 30% by weight. Particularly, it is around 50% by weight of ethylene and around 50% by weight of tetrafluoroethylene.
本発明に於いてはSb2O3、ZrO及びZnSの少なくとも１
種が使用される。In the present invention, at least one of Sb 2 O 3 , ZrO and ZnS is used.
Seeds are used.
本発明に於いて使用するヒンダードフェノール系酸化
防止剤としては、たとえばポリブチレーテッドビスフェ
ノールＡ、2,6−ジ−ｔ−ブチル−ｐ−クレゾール、2,5
−ジ−ｔ−アミルハイドロキシン、2,5−ジ−ｔ−ブチ
ルハイドロキノン、2,2−メチレン−ビス−（６−ｔ−
ブチル−４−メチル−フェノール）、2,6−ビス（２′
−ハイドロキシン−３′−ｔ−ブチル−５′−メチル−
ベンジル）−４−メチル−フェノール、2,2−メチレン
−ビス（４−メチル−６−ｔ−ブチル−フェノール）、
4,4′−メチレン−ビス（2,6−ジ−ｔ−ブチル−フェノ
ール）、1,3,5−トリ−メチル−2,4,6−トリス（3,5−
ジ−ｔ−ブチル−４−ハイドロキシ−ベンジル）ベンゼ
ン、テトラキス［メチレン−３−（3,5−ジ−ｔ−ブチ
ル−４−ハイドロキシ−フェニル）プロピオネート］メ
タン、ｎ−オクタデシル−３−（４′−ハイドロキシ−
３′５′−ジ−ｔ−ブチルフェノール）プロピオネー
ト、2,5−ジ−ｔ−ブチルハイドロキノン、2,2′−メチ
レン−ビス（４−メチル−６−ｔ−ブチル−フェノー
ル）、4,4′ブチリデン−ビス（３−メチル−６−ｔ−
ブチル−フェノール）、1,1,3−トリス（２−メチル−
４−ハイドロキシ−５−ｔ−ブチル−フェニル）ブタン
等を挙げることが出来る。Examples of the hindered phenol-based antioxidant used in the present invention include polybutylated bisphenol A, 2,6-di-t-butyl-p-cresol, and 2,5.
-Di-t-amylhydroxine, 2,5-di-t-butylhydroquinone, 2,2-methylene-bis- (6-t-
Butyl-4-methyl-phenol), 2,6-bis (2 '
-Hydoxine-3'-t-butyl-5'-methyl-
Benzyl) -4-methyl-phenol, 2,2-methylene-bis (4-methyl-6-t-butyl-phenol),
4,4'-methylene-bis (2,6-di-t-butyl-phenol), 1,3,5-tri-methyl-2,4,6-tris (3,5-
Di-t-butyl-4-hydroxy-benzyl) benzene, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxy-phenyl) propionate] methane, n-octadecyl-3- (4 ' -Hydroxy-
3'5'-di-t-butylphenol) propionate, 2,5-di-t-butylhydroquinone, 2,2'-methylene-bis (4-methyl-6-t-butyl-phenol), 4,4 ' Butylidene-bis (3-methyl-6-t-
Butyl-phenol), 1,1,3-tris (2-methyl-
4-hydroxy-5-t-butyl-phenyl) butane and the like can be mentioned.
これ等のうち特に好ましいのはテトラキス［メチレン
−３−（3,5−ジ−ｔ−ブチル−４−ハイドロキシ−フ
ェニル）プロピオネート］メタンである。Particularly preferred among these is tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxy-phenyl) propionate] methane.
本発明に於いて必要に応じ使用される架橋助剤として
は、脂肪族や芳香族の多官能性化合物類、脂肪族多官能
性環状化合物類、含窒素多官能性環状化合物類、含金属
多官能性化合物類、就中含窒素多官能性環状化合物類、
特にトリアリルイソシアヌレート（TAIC）、トリメタア
リルイソシアヌレート（TMAIC）、トリアリルシアヌレ
ート（TAC）、トリアクロイルヘキサヒドロ−1,3,5−ト
リアジン（TAF）等である。Examples of the crosslinking aid used in the present invention include aliphatic or aromatic polyfunctional compounds, aliphatic polyfunctional cyclic compounds, nitrogen-containing polyfunctional cyclic compounds, and metal-containing polyfunctional compounds. Functional compounds, especially nitrogen-containing polyfunctional cyclic compounds,
In particular, triallyl isocyanurate (TAIC), trimetaallyl isocyanurate (TMAIC), triallyl cyanurate (TAC), triacroylhexahydro-1,3,5-triazine (TAF) and the like.
本発明の組成物の配合割合は、ETFE100重量部に対
し、Sb2O3、ZrO、及びZnSの少なくとも１種が0.5〜10重
量部、好ましくは１〜５重量部、架橋助剤が０〜20重量
部、好ましくは５〜12重量部、ヒンダードフェノール系
酸化防止剤が１〜15重量部程度である。The blending ratio of the composition of the present invention is such that at least one of Sb 2 O 3 , ZrO and ZnS is 0.5 to 10 parts by weight, preferably 1 to 5 parts by weight, and the crosslinking aid is 0 to 100 parts by weight of ETFE. 20 parts by weight, preferably 5 to 12 parts by weight, and the hindered phenol antioxidant is about 1 to 15 parts by weight.
本発明の組成物には更に必要に応じ各種のその他の添
加剤が配合されても良い。この際のその他の添加剤とし
てはたとえばカップリング剤、加工助剤、各種顔料、難
燃剤等を例示出来る。The composition of the present invention may further contain various other additives as necessary. Other additives at this time include, for example, a coupling agent, a processing aid, various pigments, and a flame retardant.
本発明の組成物は、たとえば銅導体上に被覆形成され
た後、あるいは適宜な成形品に成形後通常の方法により
照射架橋することが出来る。この際の照射架橋手段は従
来公知の手段がいずれも採用される。The composition of the present invention can be irradiated and crosslinked by a usual method after being coated on a copper conductor or formed into an appropriate molded product, for example. In this case, any conventionally known means can be employed as the irradiation crosslinking means.
［実施例］ 以下に実施例並びに比較例を挙げて本発明の特徴とす
る所を詳述する。EXAMPLES Hereinafter, features of the present invention will be described in detail with reference to Examples and Comparative Examples.
実施例１ 第１表に示す所定の各成分を所定量配合し、これを２
軸混練押出機で押出し、次いで0.5mm厚のシートを300℃
でプレス成形してシートの両面夫々に電子線量7.5Mrad
で照射架橋して架橋成形体を得た。Example 1 A predetermined amount of each predetermined component shown in Table 1 was blended, and this was added to 2
Extruded with a shaft kneading extruder, then 0.5mm thick sheet at 300 ℃
Electron dose 7.5 Mrad on both sides of the sheet by press molding with
Then, the mixture was irradiated and crosslinked to obtain a crosslinked molded body.
この成形体について耐熱老化性を測定した。この結果
を第２表に示す。The heat aging resistance of this molded article was measured. The results are shown in Table 2.
比較例１〜４ 第１表に示す各成分を所定量配合し、その他は実施例
１と同様に処理して架橋成形体を得た。 Comparative Examples 1 to 4 Each component shown in Table 1 was mixed in a predetermined amount, and the others were treated in the same manner as in Example 1 to obtain a crosslinked molded article.
この成形体について耐熱老化性を測定した。この結果
を第２表に示す。The heat aging resistance of this molded article was measured. The results are shown in Table 2.
但し耐熱老化性は次の方法で測定した。 However, the heat aging resistance was measured by the following method.
耐熱老化性 300℃のギアーオーブン中に曝露して引張伸びが50％
以下に低下する時間を求めた。10時間以上を合格とす
る。50% tensile elongation when exposed to 300 ° C gear oven
The time to decrease below was determined. Pass 10 hours or more.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 (Ｃ０８Ｋ 13/02 (Ｃ０８Ｋ 13/02 3:30 3:30 5:13） 5:13） (56)参考文献 特開 昭49−107350（ＪＰ，Ａ) 特開 昭60−260635（ＪＰ，Ａ) 特開 昭62−15212（ＪＰ，Ａ) 特開 昭62−15250（ＪＰ，Ａ) 特開 昭63−159456（ＪＰ，Ａ) 特公 昭48−38216（ＪＰ，Ｂ１)─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Office reference number FI technical display location (C08K 13/02 (C08K 13/02 3:30 3:30 5:13) 5:13) ( 56) Reference JP 49-107350 (JP, A) JP 60-260635 (JP, A) JP 62-15212 (JP, A) JP 62-15250 (JP, A) JP Sho 63-159456 (JP, A) Japanese Patent Sho 48-38216 (JP, B1)
Claims (3)
体、Sb2O3,ZrO並びにZnSの少なくとも１種、及びヒンダ
ードフェノール系酸化防止剤を含有して成る耐熱老化性
樹脂組成物。1. A heat-aging resin composition containing an ethylene-tetrafluoroethylene copolymer, at least one of Sb 2 O 3 , ZrO and ZnS, and a hindered phenolic antioxidant.
範囲第１項に記載の耐熱老化性樹脂組成物。2. The heat aging resistant resin composition according to claim 1, further comprising a crosslinking aid.
チレン−テトラフルオロエチレン共重合体100重量部に
対し0.5〜10重量部である特許請求の範囲第１項に記載
の耐熱老化性樹脂組成物。3. Heat aging according to claim 1, wherein at least one of Sb 2 O 3 , ZrO and ZnS is 0.5 to 10 parts by weight with respect to 100 parts by weight of the ethylene-tetrafluoroethylene copolymer. Resin composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62099496A JP2537620B2 (en) | 1987-04-22 | 1987-04-22 | Heat-aging resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62099496A JP2537620B2 (en) | 1987-04-22 | 1987-04-22 | Heat-aging resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63265943A JPS63265943A (en) | 1988-11-02 |
| JP2537620B2 true JP2537620B2 (en) | 1996-09-25 |
Family
ID=14248902
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62099496A Expired - Lifetime JP2537620B2 (en) | 1987-04-22 | 1987-04-22 | Heat-aging resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2537620B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0332932A3 (en) * | 1988-03-07 | 1990-09-26 | AUSIMONT U.S.A. Inc. | Modified fluoropolymers for low flame/low smoke plenum cables |
| IL97956A0 (en) * | 1990-05-10 | 1992-06-21 | Raychem Corp | Stabilizing ethylene-tetrafluoroethylene copolymers |
| US9728298B2 (en) | 2015-06-26 | 2017-08-08 | Daikin America, Inc. | Radiation crosslinked fluoropolymer compositions containing low level of extractable fluorides |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5237967B2 (en) * | 1971-09-17 | 1977-09-26 | ||
| US3947525A (en) * | 1973-01-30 | 1976-03-30 | Allied Chemical Corporation | Melt-processable, radiation cross-linkable E-CTFE copolymer compositions |
| JPS60260635A (en) * | 1984-06-06 | 1985-12-23 | Hitachi Cable Ltd | Radiation-crosslinkable fluororesin composition |
| JPS6215250A (en) * | 1985-07-12 | 1987-01-23 | Hitachi Cable Ltd | Fluororesin composition crosslinkable by irradiation |
| DE3677076D1 (en) * | 1985-07-12 | 1991-02-28 | Du Pont | FLUORELASTOMERS. |
-
1987
- 1987-04-22 JP JP62099496A patent/JP2537620B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63265943A (en) | 1988-11-02 |
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