JPS63284249A - Radiation-crosslinkable fluorocarbon resin composition - Google Patents
Radiation-crosslinkable fluorocarbon resin compositionInfo
- Publication number
- JPS63284249A JPS63284249A JP11926087A JP11926087A JPS63284249A JP S63284249 A JPS63284249 A JP S63284249A JP 11926087 A JP11926087 A JP 11926087A JP 11926087 A JP11926087 A JP 11926087A JP S63284249 A JPS63284249 A JP S63284249A
- Authority
- JP
- Japan
- Prior art keywords
- ethylene
- copolymer
- crosslinking
- tetrafluoroethylene
- fluorine
- 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.)
- Pending
Links
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 title 1
- 239000011342 resin composition Substances 0.000 title 1
- 238000004132 cross linking Methods 0.000 claims abstract description 25
- 229920001577 copolymer Polymers 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 229920001971 elastomer Polymers 0.000 claims abstract description 11
- 239000000806 elastomer Substances 0.000 claims abstract description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 9
- 239000011737 fluorine Substances 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- 230000005855 radiation Effects 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 238000001125 extrusion Methods 0.000 abstract description 12
- 238000000465 moulding Methods 0.000 abstract description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 abstract description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract 3
- 239000005977 Ethylene Substances 0.000 abstract 3
- 229920006172 Tetrafluoroethylene propylene Polymers 0.000 description 3
- -1 ethylene-chlorotrifluoroethylene Chemical group 0.000 description 3
- 239000004020 conductor Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 229920001780 ECTFE Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- ZSTLPJLUQNQBDQ-UHFFFAOYSA-N azanylidyne(dihydroxy)-$l^{5}-phosphane Chemical compound OP(O)#N ZSTLPJLUQNQBDQ-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、高温における機械的強度に優れたふっ素樹脂
成形体を得るための放射線照射架橋用ふっ素樹脂組成物
に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a fluororesin composition for crosslinking by radiation irradiation to obtain a fluororesin molded article having excellent mechanical strength at high temperatures.
［従来の技術］
エチレン−フルオロオレフィン共重合体は、ふっ素樹脂
の中でも特に機械的性質や加工性に優れ、また、電気的
特性、耐薬品性および耐熱性にも優れており、バランス
のとれた材料であり、電線被覆材料をはじめフィルムや
チューブに成形して各種分野に使用されている。[Prior art] Ethylene-fluoroolefin copolymers have particularly excellent mechanical properties and processability among fluororesins, as well as excellent electrical properties, chemical resistance, and heat resistance. It is used in various fields as a material for covering electric wires, as well as in the form of films and tubes.
しかし、融点を越えるような高温雰囲気下においた場合
、外力により容易に変形してしまい、高温での使用には
限界があった。However, when placed in a high-temperature atmosphere that exceeds the melting point, it easily deforms due to external force, and there is a limit to its use at high temperatures.
これを改善するため、電子線等の放射線を照射して架橋
することが知られているが、放射線の照射により架橋と
崩壊が同時に進行し、十分な架橋効率を達成できない。In order to improve this, it is known to perform crosslinking by irradiating with radiation such as an electron beam, but crosslinking and collapse proceed simultaneously due to radiation irradiation, making it impossible to achieve sufficient crosslinking efficiency.
このため、アリル型化合物のような架橋促進剤を添加し
て架橋効率を上げることが検討されている。For this reason, it is being considered to increase the crosslinking efficiency by adding a crosslinking promoter such as an allyl type compound.
［発明が解決しようとする問題点］
しかしながら、単に架橋促進剤を添加して押出成形する
と、高温での押出のため架橋促進剤の分解および局所的
な凝集等によりミ架橋促進剤とふっ素樹脂とが反応を起
こし、成形品の外観が荒れ、良好な製品を得られないと
ういう問題がある。また、エチレン−フルオロオレフィ
ン共重合体の成形温度がかなり高いため、従来の架橋促
進剤では押出成形時に揮散が生じ、環境衛生上好ましく
ないという問題がある。[Problems to be Solved by the Invention] However, if a crosslinking accelerator is simply added and extruded, the crosslinking accelerator and fluororesin will be separated due to decomposition and local aggregation due to extrusion at high temperatures. This causes a reaction, which results in a rough appearance of the molded product, making it difficult to obtain a good product. Further, since the molding temperature of the ethylene-fluoroolefin copolymer is quite high, conventional crosslinking accelerators cause volatilization during extrusion molding, which is unfavorable from an environmental hygiene standpoint.
本発明は、上記に基づいてなされたものであり、高温で
の機械的特性に優れ、しかも良好な外観を有する成形品
を得ることができ、さらに押出成形時に架橋促進剤の揮
散がない放射線照射架橋用ふっ素樹脂組成物の提供を目
的とするものである。The present invention has been made based on the above, and it is possible to obtain a molded product that has excellent mechanical properties at high temperatures and a good appearance, and furthermore, it is possible to obtain a molded product that has excellent mechanical properties at high temperatures and has a good appearance.In addition, it is possible to obtain a molded product that has no volatilization of the crosslinking accelerator during extrusion molding and is irradiated with radiation. The object of the present invention is to provide a fluororesin composition for crosslinking.
［問題点を解決するための手段］
本発明のふっ素樹脂組成物は、エチレン−フルオロオレ
フィン共重合体あるいはエチレン−フルオロオレフィン
共重合体と含ふっ素エラストマとの混合物に、架橋促進
剤として次の一般式で表わされる化合物を添加してなる
ことを特徴とするものである。[Means for Solving the Problems] The fluororesin composition of the present invention includes the following general crosslinking accelerator added to an ethylene-fluoroolefin copolymer or a mixture of an ethylene-fluoroolefin copolymer and a fluorine-containing elastomer. It is characterized by adding a compound represented by the formula.
本発明において、エチレン−フルオロオレフィン共重合
体としては、エチレン−テトラフルオロエチレン共重合
体やエチレン−クロロトリフルオロエチレン共重合体と
いったものがあげられ、単独あるいは２種混合して使用
可能である。In the present invention, examples of the ethylene-fluoroolefin copolymer include ethylene-tetrafluoroethylene copolymer and ethylene-chlorotrifluoroethylene copolymer, which can be used alone or in combination.
本発明においては、上記エチレン−フルオロオレフィン
共重合体と含ふっ素エラストマとの混合物を使用するこ
とも可能である。含ふっ素エラストマとしては特に限定
することなく、テトラフルオロエチレン−プロピレン系
共重合体、ふり化ビニリデン−へキサフルオロプロペン
系共重合体、ふり化ビニリデン−クロロトリフルオロエ
チレン系共重合体、ぶつ化ビニリデン−ペンタフルオロ
プロペン系共重合体、ポリフルオロアルキン基含有アク
リレート系エラストマ、ポリフルオロアルキン基含有ポ
リシロキサン系エラストマ、テトラフルオロエチレン−
ぶつ化ビニリデン−プロピレン系共重合体、テトラフル
オロエチレン−エチレン−イソブチレン系共重合体、エ
チレン−ヘキサフルオロプロペン系共重合体、テトラフ
ルオロエチレン−ブテン−１系共重合体、テトラフルオ
ロエチレン−エチルビニルエーテル系共重合体、含ふっ
素フォスフオニトリル系エラストマ、テトラフルオロエ
チレン−フルオロビニルエーテル系共重合体等があげら
れる。In the present invention, it is also possible to use a mixture of the above ethylene-fluoroolefin copolymer and a fluorine-containing elastomer. Examples of the fluorine-containing elastomer include, but are not limited to, tetrafluoroethylene-propylene copolymers, vinylidene fluoride-hexafluoropropene copolymers, vinylidene fluoride-chlorotrifluoroethylene copolymers, and vinylidene fluoride-chlorotrifluoroethylene copolymers. -Pentafluoropropene copolymer, polyfluoroalkyne group-containing acrylate elastomer, polyfluoroalkyne group-containing polysiloxane elastomer, tetrafluoroethylene-
Vinylidene butylene-propylene copolymer, tetrafluoroethylene-ethylene-isobutylene copolymer, ethylene-hexafluoropropene copolymer, tetrafluoroethylene-butene-1 copolymer, tetrafluoroethylene-ethyl vinyl ether Examples include copolymers, fluorine-containing phosphonitrile elastomers, and tetrafluoroethylene-fluorovinyl ether copolymers.
この中でもテトラフルオロエチレン−プロピレン系共重
合体が特に好適であり、耐熱性、成形性等の面からテト
ラフルオロエチレン／プロピレンの含有モル比が９５１
５〜３０／７０、特に、９０／１０〜４５１５５の範囲
から選定することが好ましい。Among these, tetrafluoroethylene-propylene copolymers are particularly suitable, with a molar ratio of tetrafluoroethylene/propylene of 951 in terms of heat resistance, moldability, etc.
It is preferable to select from the range of 5 to 30/70, particularly 90/10 to 45155.
エチレン−フルオロオレフィン共重合体と含ふっ素エラ
ストマとの配合割合は、エチレン−フルオロオレフィン
共重合体／含ふっ素エラストマの重量比で８０〜２０７
２０〜８０の範囲から選定することが好ましい。The blending ratio of the ethylene-fluoroolefin copolymer and the fluorine-containing elastomer is 80 to 207 in weight ratio of ethylene-fluoroolefin copolymer/fluorine-containing elastomer.
It is preferable to select from the range of 20 to 80.
本発明における架橋促進剤の添加量は、樹脂成分１００
重世部に対して１〜２０重量部が好ましく、１重量部未
満では架橋が不十分であり、２０重量部で架橋促進剤添
加の効果は飽和する。The amount of crosslinking accelerator added in the present invention is 100% of the resin component.
The amount of the crosslinking accelerator is preferably 1 to 20 parts by weight based on the weight of the part, and if it is less than 1 part by weight, crosslinking will be insufficient, and if it is 20 parts by weight, the effect of adding the crosslinking accelerator will be saturated.
上記成分以外に必要に応じて安定剤、無機充填剤（カー
ボンブラック、けい酸系充填剤等）、着色剤、酸化防止
剤、滑剤等を配合してもよい。In addition to the above components, stabilizers, inorganic fillers (carbon black, silicic acid fillers, etc.), colorants, antioxidants, lubricants, etc. may be added as necessary.
［発明の実施例］
第１表の各側に示す各種成分を均一に混練し、これをバ
レル帯域ｌの温度２６０℃、バレル帯域２の温度２７０
℃、バレル帯域３の温度２８０℃、クロスヘッド部温度
３２０℃、グイ部温度３２０℃、スクリュウ回転数１５
ｒｐｍに設定した押出機（４０ｍｍＳＬ／Ｄ＝２０、圧
縮比＝３）に導入し、外径０．８ｍｍの導体周上に厚さ
０．２ｍｍに押出被覆し、続いて１０Ｍｒａｄの電子線
を照射して架橋絶縁電線を製造した。[Embodiments of the Invention] Various components shown on each side of Table 1 are uniformly kneaded, and the mixture is heated at a temperature of 260°C in barrel zone 1 and a temperature of 270°C in barrel zone 2.
℃, Barrel zone 3 temperature 280℃, Cross head temperature 320℃, Gui portion temperature 320℃, Screw rotation speed 15
The conductor was introduced into an extruder set at rpm (40 mm SL/D = 20, compression ratio = 3), extrusion coated to a thickness of 0.2 mm on a conductor having an outer diameter of 0.8 mm, and then irradiated with an electron beam of 10 Mrad. A crosslinked insulated wire was produced.
各側の架橋絶縁電線の押出外観、加熱変形率および架橋
促進剤の揮散について評価した結果を第１表の下欄に示
す。なお、押出後の外観は目視により観察した結果であ
り、加熱変形率はＪＩＳＣ３００５に準拠して３００℃
で３００ｇの荷重をかけて測定した結果である。The results of evaluation of the extruded appearance, thermal deformation rate, and volatilization of the crosslinking accelerator of the crosslinked insulated wire on each side are shown in the lower column of Table 1. The appearance after extrusion is the result of visual observation, and the heat deformation rate is 300°C in accordance with JISC3005.
This is the result of measurement with a load of 300g applied.
＊ｌ アフロンＣ０ＰＣ８８Ａ （旭硝子■製品）＊２
ハーラー３００（アライドケミカル社製品）＊３ ア
フラス１５０Ｅ （旭硝子■製品）＊４
＊５ アエロジルＲ９７２（日本アエロジ／１４１製品
）本発明の範囲にある実施例１〜４ではいずれも押出外
観および加熱変形率において良好であり、架橋促進剤の
揮散も殆ど認められなかった。比較例１．２は架橋促進
剤としてトリアリルイソシアヌレートを使用したもので
あり、押出外観および加熱変形率の双方において劣り、
しかも架橋促進剤の揮散が激しかった。*l Aflon C0PC88A (Asahi Glass ■ product) *2
Hurler 300 (product of Allied Chemical Co., Ltd.) *3 Aflas 150E (product of Asahi Glass) *4 *5 Aerosil R972 (product of Nippon Aerogi/141) In Examples 1 to 4 within the scope of the present invention, the extrusion appearance and heat deformation rate Good results were obtained, and volatilization of the crosslinking accelerator was hardly observed. Comparative Example 1.2 uses triallyl isocyanurate as a crosslinking accelerator, and is inferior in both extrusion appearance and heat deformation rate.
Moreover, volatilization of the crosslinking accelerator was severe.
［発明の効果］
以上説明してきた通り、本発明によれば、押出外観が良
好で、高温での機械的特性に優れた架橋成形品を得るこ
とができ、しかも押出成形時の架橋促進剤の揮散を抑止
できるようになる。[Effects of the Invention] As explained above, according to the present invention, it is possible to obtain a crosslinked molded product with a good extrusion appearance and excellent mechanical properties at high temperatures, and moreover, it is possible to obtain a crosslinked molded product that has a good extrusion appearance and excellent mechanical properties at high temperatures, and moreover, it is possible to obtain a crosslinked molded product that has a good extrusion appearance and excellent mechanical properties at high temperatures. Volatilization can be suppressed.
Claims (1)
エチレン−フルオロオレフィン共重合体と含ふっ素エラ
ストマとの混合物に架橋促進剤として一般式、 ▲数式、化学式、表等があります▼ ［Ｘ：▲数式、化学式、表等があります▼ Ｒ：アルキル基（ＣＨ＿３、Ｃ＿２Ｈ＿５、Ｃ＿３Ｈ＿
７、Ｃ＿４Ｈ＿９など） ｌ、ｍ、ｎ：整数］ で表わされる化合物を添加してなることを特徴とする放
射線照射架橋用ふっ素樹脂組成物。(1) There are general formulas, ▲mathematical formulas, chemical formulas, tables, etc. as crosslinking accelerators for ethylene-fluoroolefin copolymers or mixtures of ethylene-fluoroolefin copolymers and fluorine-containing elastomers▼ [X: ▲mathematical formulas, chemical formulas, etc. , tables, etc. ▼ R: Alkyl group (CH_3, C_2H_5, C_3H_
7, C_4H_9, etc.) l, m, n: integer] A fluororesin composition for crosslinking by radiation irradiation, characterized by adding a compound represented by the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11926087A JPS63284249A (en) | 1987-05-15 | 1987-05-15 | Radiation-crosslinkable fluorocarbon resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11926087A JPS63284249A (en) | 1987-05-15 | 1987-05-15 | Radiation-crosslinkable fluorocarbon resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63284249A true JPS63284249A (en) | 1988-11-21 |
Family
ID=14756930
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11926087A Pending JPS63284249A (en) | 1987-05-15 | 1987-05-15 | Radiation-crosslinkable fluorocarbon resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63284249A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5925379A (en) * | 1982-07-30 | 1984-02-09 | Nippon Kasei Kk | Xylene derivative, its preparation and cured article consisting of xylene derivative as main agent |
| JPS6281440A (en) * | 1985-10-07 | 1987-04-14 | Hitachi Cable Ltd | Radiation-crosslinkable fluororesin composition |
-
1987
- 1987-05-15 JP JP11926087A patent/JPS63284249A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5925379A (en) * | 1982-07-30 | 1984-02-09 | Nippon Kasei Kk | Xylene derivative, its preparation and cured article consisting of xylene derivative as main agent |
| JPS6281440A (en) * | 1985-10-07 | 1987-04-14 | Hitachi Cable Ltd | Radiation-crosslinkable fluororesin composition |
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