JPS63286457A - Fluororesin composition for crosslinking with radiation - Google Patents
Fluororesin composition for crosslinking with radiationInfo
- Publication number
- JPS63286457A JPS63286457A JP12154387A JP12154387A JPS63286457A JP S63286457 A JPS63286457 A JP S63286457A JP 12154387 A JP12154387 A JP 12154387A JP 12154387 A JP12154387 A JP 12154387A JP S63286457 A JPS63286457 A JP S63286457A
- Authority
- JP
- Japan
- Prior art keywords
- crosslinking
- weight
- parts
- ethylene
- titanium oxide
- 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
- 238000004132 cross linking Methods 0.000 title claims abstract description 21
- 239000000203 mixture Substances 0.000 title claims abstract description 7
- 230000005855 radiation Effects 0.000 title claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920001577 copolymer Polymers 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 8
- 239000011882 ultra-fine particle Substances 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract 1
- 238000001125 extrusion Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 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
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- 229920001780 ECTFE Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229920006172 Tetrafluoroethylene propylene Polymers 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 229910003440 dysprosium oxide Inorganic materials 0.000 description 1
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(iii) oxide Chemical compound O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- -1 ethylene-chlorotrifluoroethylene Chemical group 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 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
- 239000000155 melt Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229920000131 polyvinylidene Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910001954 samarium oxide Inorganic materials 0.000 description 1
- 229940075630 samarium oxide Drugs 0.000 description 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HEKQWIORQJRILW-UHFFFAOYSA-N tetrakis(prop-2-enyl) benzene-1,2,4,5-tetracarboxylate Chemical compound C=CCOC(=O)C1=CC(C(=O)OCC=C)=C(C(=O)OCC=C)C=C1C(=O)OCC=C HEKQWIORQJRILW-UHFFFAOYSA-N 0.000 description 1
- GRPURDFRFHUDSP-UHFFFAOYSA-N tris(prop-2-enyl) benzene-1,2,4-tricarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C(C(=O)OCC=C)=C1 GRPURDFRFHUDSP-UHFFFAOYSA-N 0.000 description 1
- VOSUIKFOFHZNED-UHFFFAOYSA-N tris(prop-2-enyl) benzene-1,3,5-tricarboxylate Chemical compound C=CCOC(=O)C1=CC(C(=O)OCC=C)=CC(C(=O)OCC=C)=C1 VOSUIKFOFHZNED-UHFFFAOYSA-N 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。゛
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。[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. 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助剤を添加して
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 aid 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、単に架橋助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、架橋助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。[Problems to be Solved by the Invention] However, if the crosslinking promoter is simply added and extruded, the crosslinking promoter will decompose and locally aggregate due to extrusion at high temperatures, causing the crosslinking promoter and the fluororesin to separate. This causes a reaction, which results in a rough appearance of the molded product, making it difficult to obtain a good product.
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
を得ることができる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 aims to provide a fluororesin composition for crosslinking by radiation irradiation, which can provide molded products having excellent mechanical properties at high temperatures and a good appearance. It is something.
［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１００重量部に対し、平均粒径が０．２
μｍ以下の超微粒子酸化チタンを０．０５〜１０重量部
および架橋助剤を０．５重量部以上含有することを特徴
とするものである。[Means for Solving the Problems] The fluororesin composition of the present invention has an average particle size of 0.2 parts by weight based on 100 parts by weight of the ethylene-fluoroolefin copolymer.
It is characterized in that it contains 0.05 to 10 parts by weight of ultrafine titanium oxide particles of µm or less and 0.5 parts by weight or more of a crosslinking aid.
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.
酸化チタンは、エチレン−フルオロオレフィン共重合体
と架橋助剤との押出成形時における化学反応を抑制する
働きがある。酸化チタンは、平均粒径が０．２μｍ以下
の超微粒子状のものを使用する必要があり、これ以上の
ものでは化学反応を抑制する作用が十分でなく、外観を
改善することができない。添加量は、エチレン−フルオ
ロオレフィン共重合体１００重量部に対し、０．０５〜
１０重量部の範囲とする必要があり、０．０５重量部未
満では上記の化学反応を抑制する効果が不十分であり、
１０重量部を越えると酸化チタン自身の凝集により粒を
生じ易（なる。Titanium oxide has the function of suppressing the chemical reaction between the ethylene-fluoroolefin copolymer and the crosslinking aid during extrusion molding. It is necessary to use titanium oxide in the form of ultrafine particles with an average particle size of 0.2 μm or less; if the titanium oxide is larger than this, the effect of suppressing chemical reactions is insufficient and the appearance cannot be improved. The amount added is 0.05 to 100 parts by weight of the ethylene-fluoroolefin copolymer.
It is necessary to set the amount in the range of 10 parts by weight, and if it is less than 0.05 parts by weight, the effect of suppressing the above chemical reaction is insufficient,
If it exceeds 10 parts by weight, the titanium oxide itself tends to aggregate and form particles.
架橋助剤としては、アリル型化合物が特に好ましく、ト
リアリルシアヌレート、トリアリルイソシアヌレート、
トリアリルトリメリテート、トリアリルトリメゼート、
テトラアリルピロメリテート等があげられる。架橋助剤
の添加量は、エチレン−フルオロオレフィン共重合体１
００重量部に対し０．５重量部以上とする必要があり、
これ未満では高温での機械的強度を向上する効果が不十
分である。上限は特に規定しないが、２０重量部程度で
架橋助剤の添加による効果が飽和する。As the crosslinking aid, allyl type compounds are particularly preferred, including triallyl cyanurate, triallyl isocyanurate,
triallyl trimellitate, triallyl trimesate,
Examples include tetraallyl pyromellitate. The amount of crosslinking aid added is 1 ethylene-fluoroolefin copolymer.
It is necessary to make it 0.5 parts by weight or more per 00 parts by weight,
If it is less than this, the effect of improving mechanical strength at high temperatures is insufficient. Although the upper limit is not particularly defined, the effect of adding the crosslinking aid is saturated at about 20 parts by weight.
上記成分以外に必要に応じて他の金属酸化物（酸化ネオ
ジウム、酸化ビスマス、酸化サマリウム、酸化ジスプロ
シウム等）、無機充填剤、着色剤、酸化防止剤、滑剤等
を配合してもよく、また、テトラフルオロエチレン−プ
ロピレン系共重合体やポリぶつ化ビニリデン等の他のふ
っ素糸樹脂を配合してもよい。In addition to the above components, other metal oxides (neodymium oxide, bismuth oxide, samarium oxide, dysprosium oxide, etc.), inorganic fillers, colorants, antioxidants, lubricants, etc. may be added as necessary. Other fluorine thread resins such as tetrafluoroethylene-propylene copolymer and polyvinylidene buttride may also be blended.
［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１の温度２６０℃、バレル帯域２の温度２７０
℃、バレル帯域３の温度３００℃、クロスヘッド部温度
３２０℃、ダイ部温度３２０℃、スクリュウ回転数１５
ｒｐｍに設定した押出機（４０ｍｍ、Ｌ／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、続いて比較例３を除いて１０
Ｍｒａｄの電子線を照射して架橋絶縁電線を製造した。[Embodiments of the Invention] The 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 300℃, crosshead temperature 320℃, die temperature 320℃, screw rotation speed 15
The sample was introduced into an extruder (40 mm, L/D = 20, compression ratio = 3) set at rpm, and extrusion coated on the circumference of a conductor with an outer diameter of 0.8 mm to a thickness of 0.2 mm, followed by Comparative Example 3. 10 except
A crosslinked insulated wire was manufactured by irradiating with Mrad's electron beam.
各側の絶縁電線の押出外観、加熱変形率について評価し
た結果を第１表の下欄に示す。なお、押出外観は絶縁電
線の長さ１ｍ当りの粒の個数を目視により数えた結果で
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 evaluating the extrusion appearance and heat deformation rate of the insulated wire on each side are shown in the lower column of Table 1. The extruded appearance is the result of visually counting the number of grains per 1 meter length of the insulated wire, and the heat deformation rate is 300 in accordance with JISC3005.
This is the result of measurement at ℃ under a load of 300g.
本発明の範囲にある実施例１〜４ではいずれも優れた押
出外観および加熱変形率である。比較例１は超微粒子酸
化チタンの添加量が本発明の規定値に満たない場合、比
較例２は平均粒径が本発明の規定値以上の酸化チタンを
使用した場合であり、粒が発生して外観が悪くなってい
る。比較例３は架橋しない場合であり、３００℃で溶融
してしまう。Examples 1 to 4 within the scope of the present invention all have excellent extrusion appearance and thermal deformation rate. Comparative Example 1 is a case where the amount of ultrafine titanium oxide added is less than the specified value of the present invention, and Comparative Example 2 is a case where titanium oxide whose average particle size is equal to or larger than the specified value of the present invention is used, and particles are not generated. It looks bad. Comparative Example 3 is a case without crosslinking, and it melts at 300°C.
［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.
Claims (1)
量部に対し平均粒径が０．２μｍ以下の超微粒子酸化チ
タンを０．０５〜１０重量部および架橋助剤を０．５重
量部以上含有す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) Contain 0.05 to 10 parts by weight of ultrafine titanium oxide with an average particle size of 0.2 μm or less and 0.5 parts by weight or more of a crosslinking aid per 100 parts by weight of the ethylene-fluoroolefin copolymer. A fluororesin composition for crosslinking by radiation irradiation, characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12154387A JPS63286457A (en) | 1987-05-19 | 1987-05-19 | Fluororesin composition for crosslinking with radiation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12154387A JPS63286457A (en) | 1987-05-19 | 1987-05-19 | Fluororesin composition for crosslinking with radiation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63286457A true JPS63286457A (en) | 1988-11-24 |
Family
ID=14813849
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12154387A Pending JPS63286457A (en) | 1987-05-19 | 1987-05-19 | Fluororesin composition for crosslinking with radiation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63286457A (en) |
-
1987
- 1987-05-19 JP JP12154387A patent/JPS63286457A/en active Pending
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