JPH0824010B2 - Fluorine-containing elastomer-coated insulated wire with improved cut-through resistance - Google Patents
Fluorine-containing elastomer-coated insulated wire with improved cut-through resistanceInfo
- Publication number
- JPH0824010B2 JPH0824010B2 JP62149777A JP14977787A JPH0824010B2 JP H0824010 B2 JPH0824010 B2 JP H0824010B2 JP 62149777 A JP62149777 A JP 62149777A JP 14977787 A JP14977787 A JP 14977787A JP H0824010 B2 JPH0824010 B2 JP H0824010B2
- Authority
- JP
- Japan
- Prior art keywords
- tetrafluoroethylene
- weight
- resistance
- fluorine
- copolymer
- 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
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims description 8
- 229920001971 elastomer Polymers 0.000 title claims description 8
- 239000000806 elastomer Substances 0.000 title claims description 8
- 229910052731 fluorine Inorganic materials 0.000 title claims description 8
- 239000011737 fluorine Substances 0.000 title claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 19
- 229920006172 Tetrafluoroethylene propylene Polymers 0.000 claims description 16
- 238000004132 cross linking Methods 0.000 claims description 16
- 239000011247 coating layer Substances 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 239000011256 inorganic filler Substances 0.000 claims description 7
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 230000005865 ionizing radiation Effects 0.000 claims description 6
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 3
- 239000000378 calcium silicate Substances 0.000 claims description 3
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 4
- 229920001780 ECTFE Polymers 0.000 description 3
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- -1 ethylene-chlorotrifluoroethylene Chemical group 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- HUWSZNZAROKDRZ-RRLWZMAJSA-N (3r,4r)-3-azaniumyl-5-[[(2s,3r)-1-[(2s)-2,3-dicarboxypyrrolidin-1-yl]-3-methyl-1-oxopentan-2-yl]amino]-5-oxo-4-sulfanylpentane-1-sulfonate Chemical compound OS(=O)(=O)CC[C@@H](N)[C@@H](S)C(=O)N[C@@H]([C@H](C)CC)C(=O)N1CCC(C(O)=O)[C@H]1C(O)=O HUWSZNZAROKDRZ-RRLWZMAJSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- 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
- DNJRKFKAFWSXSE-UHFFFAOYSA-N 1-chloro-2-ethenoxyethane Chemical compound ClCCOC=C DNJRKFKAFWSXSE-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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000003381 stabilizer Substances 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
Landscapes
- Organic Insulating Materials (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、優れた機械的強度および押出外観を有し、
しかもカットスルー抵抗が改良された被覆層からなる含
ふっ素エラストマ被覆絶縁電線に関するものである。DETAILED DESCRIPTION OF THE INVENTION INDUSTRIAL FIELD OF APPLICATION The present invention has excellent mechanical strength and extrusion appearance,
Moreover, the present invention relates to a fluorine-containing elastomer-coated insulated wire having a coating layer with improved cut-through resistance.
［従来の技術］ テトラフルオロエチレン−プロピレン系共重合体は、
耐熱性、耐油性、耐薬品性に優れている上に、電気絶縁
性および可撓性に優れており、電気絶縁被覆への適用が
大きく期待される材料である。[Prior art] A tetrafluoroethylene-propylene-based copolymer is
It has excellent heat resistance, oil resistance, and chemical resistance, as well as excellent electric insulation and flexibility, and is a material that is expected to be applied to an electric insulation coating.
この共重合体の架橋は、通常化学架橋剤を添加し、所
定形状に成形後加熱雰囲気下に保持することにより行わ
れているが、架橋時間が比較的長くなることから製造能
率の点で問題がある。Crosslinking of this copolymer is usually carried out by adding a chemical crosslinking agent and holding it in a heating atmosphere after molding into a predetermined shape, but since the crosslinking time becomes relatively long, there is a problem in terms of production efficiency. There is.
このため、電子線等の電離性放射線を照射することに
より架橋することが検討されている。Therefore, cross-linking by irradiation with ionizing radiation such as an electron beam has been studied.
しかし、電離性放射線の照射によって得られる架橋成
形体は、引張り強度などの機械的特性が十分でないとい
う問題がある。However, the crosslinked molded article obtained by irradiation with ionizing radiation has a problem that mechanical properties such as tensile strength are not sufficient.
テトラフルオロエチレン−プロピレン系共重合体に、
エチレン−テトラフルオロエチレン共重合体（ETFE）や
エチレン−クロロトリフルオロエチレン共重合体（ECTF
E）をブレンドすることにより、低温特性を改良するこ
とが提案されている（特公昭56−34018号公報）。Tetrafluoroethylene-propylene-based copolymer,
Ethylene-tetrafluoroethylene copolymer (ETFE) and ethylene-chlorotrifluoroethylene copolymer (ECTF)
It has been proposed to improve low temperature properties by blending E) (Japanese Patent Publication No. 56-34018).
しかしながら、テトラフルオロエチレン−プロピレン
系共重合体とETFEあるいはECTFEのブレンドからなる成
形体を電離性放射線の照射により架橋する際、架橋効率
の向上のため架橋助剤を添加することになるが、ETFEや
ECTFEの融点は250〜260℃と高温であるため押出成形温
度も高温となり、押出機中で架橋助剤が分解してポリマ
成分と反応し、押出外観が悪く、機械的特性も不十分で
あるという問題点が指摘されるに至った。However, when a molded article made of a blend of tetrafluoroethylene-propylene copolymer and ETFE or ECTFE is crosslinked by irradiation with ionizing radiation, a crosslinking aid is added to improve the crosslinking efficiency. Or
Since the melting point of ECTFE is as high as 250 to 260 ° C, the extrusion molding temperature also becomes high, and the crosslinking aid decomposes in the extruder and reacts with the polymer component, resulting in poor extrusion appearance and insufficient mechanical properties. The problem was pointed out.
［発明が解決しようとする問題点］ このため、テトラフルオロエチレン−プロピレン系共
重合体にエチレン−テトラフルオロエチレン−フルオロ
オレフィン共重合体をブレンドし、これを絶縁電線の被
覆に適用したところ、押出外観および機械的強度（引張
特性）の向上をはかることができたものの、カットスル
ー抵抗が不十分であることが新たに指摘されるに至っ
た。[Problems to be Solved by the Invention] Therefore, when a tetrafluoroethylene-propylene-based copolymer was blended with an ethylene-tetrafluoroethylene-fluoroolefin copolymer, and this was applied to the coating of the insulated wire, it was extruded. Although the appearance and mechanical strength (tensile properties) could be improved, it was newly pointed out that the cut-through resistance was insufficient.
本発明は、優れた機械的強度および押出外観を有し、
しかもカットスルー抵抗が改良された被覆層からなる含
ふっ素エラストマ被覆絶縁電線の提供を目的とするもの
である。The present invention has excellent mechanical strength and extrusion appearance,
Moreover, it is an object of the present invention to provide a fluorine-containing elastomer-coated insulated wire comprising a coating layer having improved cut-through resistance.
［問題点を解決するための手段］ 本発明の含ふっ素エラストマ被覆絶縁電線は、テトラ
フルオロエチレン−プロピレン系共重合体90〜20重量％
と融点が180℃〜200℃の範囲にあるエチレン−テトラフ
ルオロエチレン−フルオロオレフィン共重合体10〜80重
量％とを含有する樹脂成分100重量部に対して無水けい
酸、炭酸カルシウムおよびけい酸カルシウムから選ばれ
た少なくとも１種の無機充填剤を40〜100重量部および
架橋助剤を0.5重量部以上配合してなる組成物の被覆層
を電離性放射線の照射により架橋してなることを特徴と
するものである。[Means for Solving Problems] The fluorine-containing elastomer-coated insulated electric wire of the present invention has a tetrafluoroethylene-propylene-based copolymer content of 90 to 20% by weight.
And silicic acid anhydride, calcium carbonate and calcium silicate with respect to 100 parts by weight of a resin component containing 10 to 80% by weight of ethylene-tetrafluoroethylene-fluoroolefin copolymer having a melting point in the range of 180 to 200 ° C. Characterized in that a coating layer of a composition comprising 40 to 100 parts by weight of at least one inorganic filler selected from the above and 0.5 parts by weight or more of a crosslinking aid is crosslinked by irradiation with ionizing radiation. To do.
本発明において、テトラフルオロエチレン−プロピレ
ン系共重合体としては、主成分のテトラフルオロエチレ
ンとプロピレンに加えて、これらと共重合可能な成分、
例えば、エチレン、イソブチレン、アクリル酸およびそ
のアルキルエステル、メタクリル酸およびそのアルキル
エステル、ふっ化ビニル、ふっ化ビニリデン、ヘキサフ
ルオロプロペン、クロロエチルビニルエーテル、クロロ
トリフルオロエチレン、パーフルオロアルキルビニルエ
ーテル等を適宜含有せしめたものでもよい。In the present invention, as the tetrafluoroethylene-propylene-based copolymer, in addition to the main components tetrafluoroethylene and propylene, a component copolymerizable with these,
For example, ethylene, isobutylene, acrylic acid and its alkyl ester, methacrylic acid and its alkyl ester, vinyl fluoride, vinylidene fluoride, hexafluoropropene, chloroethyl vinyl ether, chlorotrifluoroethylene, perfluoroalkyl vinyl ether, etc. It may be a thing.
テトラフルオロエチレン−プロピレン共重合体は耐熱
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95〜30/5〜70の範囲から選定するの
が望ましく、特に好ましくは、90〜45/10〜55である。
また、適宜加えられる主成分以外の成分の含有量として
は50モル％以下、特に30モル％以下の範囲から選定する
ことが好ましい。It is desirable that the tetrafluoroethylene-propylene copolymer is selected from the range of the tetrafluoroethylene / propylene content molar ratio of 95 to 30/5 to 70 in terms of heat resistance and moldability, and particularly preferably 90 to 45 / 10-55.
In addition, the content of components other than the main component that is appropriately added is preferably selected from the range of 50 mol% or less, particularly 30 mol% or less.
テトラフルオロエチレン−プロピレン系共重合体の数
平均分子量は２万〜20万とすることが押出性および機械
的強度の点から好ましく、数平均分子量が大き過ぎると
成形体にクラックが発生しやすくなり、一方小さ過ぎる
と機械的強度が不十分となりやすい。この場合の分子量
の調整は、単量体濃度、重合開始剤濃度、単量体対重合
開始剤量比、重合温度、連鎖移動剤使用等の共重合反応
条件の操作により直接生成重合体の分子量を調整する方
法、あるいは共重合反応時には高分子量共重合体を生成
し、これを酸素存在下に加熱処理するなどして低分子量
化する方法により行うことができる。The number average molecular weight of the tetrafluoroethylene-propylene copolymer is preferably 20,000 to 200,000 from the viewpoint of extrudability and mechanical strength. If the number average molecular weight is too large, cracks are likely to occur in the molded product. On the other hand, if it is too small, the mechanical strength tends to be insufficient. In this case, the molecular weight can be adjusted by operating the monomer concentration, the polymerization initiator concentration, the ratio of the monomer to the polymerization initiator, the polymerization temperature, the copolymerization reaction conditions such as the use of a chain transfer agent, and the like. Or a method of lowering the molecular weight by producing a high molecular weight copolymer during the copolymerization reaction and subjecting this to heat treatment in the presence of oxygen.
本発明において、融点が180℃〜200℃の範囲にあるエ
チレン−テトラフルオロエチレン−フルオロオレフィン
共重合体の代表的なものとしては、エチレン−テトラフ
ルオロエチレン−クロロトリフルオロエチレン共重合体
をあげることができる。また、エチレン／テトラフルオ
ロエチレン／フルオロオレフィンの含有モル比が10〜40
/90〜60/0.1〜20の範囲から選定することが好ましい。In the present invention, a typical ethylene-tetrafluoroethylene-fluoroolefin copolymer having a melting point in the range of 180 ° C to 200 ° C is an ethylene-tetrafluoroethylene-chlorotrifluoroethylene copolymer. You can Also, the content molar ratio of ethylene / tetrafluoroethylene / fluoroolefin is 10-40.
It is preferable to select from the range of / 90 to 60 / 0.1 to 20.
テトラフルオロエチレン−プロピレン系共重合体とエ
チレン−テトラフルオロエチレン−フルオロオレフィン
共重合体の含有重量比は、得られる被覆層の機械的強度
および可撓性を考慮すると、90〜20/10〜80の範囲から
選定するのが好ましく、エチレン−テトラフルオロエチ
レン−フルオロオレフィン共重合体の含有量が少な過ぎ
ると機械的強度の改善効果がなく、多過ぎるとテトラフ
ルオロエチレン−プロピレン共重合体の本来の特徴であ
る可撓性が損なわれる傾向にある。The content weight ratio of the tetrafluoroethylene-propylene copolymer and the ethylene-tetrafluoroethylene-fluoroolefin copolymer is 90 to 20/10 to 80 in consideration of the mechanical strength and flexibility of the obtained coating layer. It is preferable to select from the range of, the effect of improving the mechanical strength is not too small the content of ethylene-tetrafluoroethylene-fluoroolefin copolymer, the original content of the tetrafluoroethylene-propylene copolymer is too large. The characteristic flexibility tends to be impaired.
テトラフルオロエチレン−プロピレン系共重合体とエ
チレン−テトラフルオロエチレン−フルオロオレフィン
共重合体との溶融ブレンドは、前者に後者の粉末をその
融点以下、例えば、50〜150℃の温度でロールやバンバ
リミキサで混練し、次いで融点以上の温度で成形しても
よいし、予め、後者の融点以上の温度でロール、バンバ
リミキサ、押出機等を用いて混練してもよい。A melt blend of a tetrafluoroethylene-propylene-based copolymer and an ethylene-tetrafluoroethylene-fluoroolefin copolymer is the former powder of the latter below its melting point, for example, in a roll or Banbury mixer at a temperature of 50 to 150 ° C. It may be kneaded and then molded at a temperature equal to or higher than the melting point, or may be previously kneaded at a temperature equal to or higher than the melting point by using a roll, a Banbury mixer, an extruder or the like.
本発明においては、被覆層のカットスルー抵抗を改良
するため、無水けい酸、炭酸カルシウム、けい酸カルシ
ウムから選ばれる特定無機充填剤を樹脂成分100重量部
に対して40〜100重量部配合する必要がある。かかる特
定無機充填剤の配合量が40重量部未満ではカットスルー
抵抗の向上効果が小さく、100重量部を越えると引張特
性の低下が大きくなる。In the present invention, in order to improve the cut-through resistance of the coating layer, it is necessary to compound 40 to 100 parts by weight of a specific inorganic filler selected from silicic acid anhydride, calcium carbonate and calcium silicate to 100 parts by weight of the resin component. There is. If the compounding amount of the specific inorganic filler is less than 40 parts by weight, the effect of improving the cut-through resistance is small, and if it exceeds 100 parts by weight, the tensile properties are largely deteriorated.
本発明においては、架橋反応性を高めるために架橋助
剤を添加しており、架橋助剤としては、トリアリルイソ
シアヌレート、トリアリルシアヌレート、トリアリルト
リメリテート、テトラアリルピロメリテートなどのアリ
ル型化合物が特に好ましい。架橋助剤の添加量は、樹脂
成分100重量部に対して0.5重量部以上、好ましくは0.5
〜10重量部である。0.5重量部未満では十分な機械的強
度を得ることが困難であり、10重量部で架橋助剤添加量
の効果は飽和する。In the present invention, a crosslinking aid is added to enhance the crosslinking reactivity, and as the crosslinking aid, triallyl isocyanurate, triallyl cyanurate, triallyl trimellitate, tetraallyl pyromellitate, and the like. Allyl type compounds are particularly preferred. The addition amount of the crosslinking aid is 0.5 parts by weight or more based on 100 parts by weight of the resin component, preferably 0.5 part by weight.
~ 10 parts by weight. If it is less than 0.5 part by weight, it is difficult to obtain sufficient mechanical strength, and if it is 10 parts by weight, the effect of the amount of the crosslinking aid added is saturated.
上記成分以外に、安定材、顔料、酸化防止剤、可塑
材、滑剤等の添加剤を種々配合可能である。In addition to the above components, various additives such as stabilizers, pigments, antioxidants, plasticizers and lubricants can be added.
［発明の実施例］ 第１表および第２表の各例に示す成分をニーダを用い
て溶融混練する。このコンパウンドを40mm押出機（L/D
＝22）を用い、外径1.6mmの導体（錫メッキ銅集合撚
線）に厚さ1.0mmで押出被覆し、その後5Mradの電子線を
照射して架橋した。[Examples of the Invention] The components shown in each of Tables 1 and 2 are melt-kneaded using a kneader. This compound is a 40 mm extruder (L / D
= 22), a conductor having an outer diameter of 1.6 mm (tin-plated copper aggregate stranded wire) was extrusion-coated to a thickness of 1.0 mm, and then irradiated with an electron beam of 5 Mrad to crosslink.
なお、押出機の設定温度は次の通りである。実施例１
〜４および比較例３（ダイス:230℃、ヘッド:230℃、シ
リンダー1:180℃、シリンダー2:230℃）。比較例１、２
（ダイス:260℃、ヘッド:260℃、シリンダー1:230℃、
シリンダー2:260℃）。The set temperature of the extruder is as follows. Example 1
4 and Comparative Example 3 (die: 230 ° C., head: 230 ° C., cylinder 1: 180 ° C., cylinder 2: 230 ° C.). Comparative Examples 1 and 2
(Dice: 260 ℃, Head: 260 ℃, Cylinder 1: 230 ℃,
Cylinder 2: 260 ℃).
上記のようにして製造した各例の絶縁電線について押
出外観、引張特性およびカットスルー抵抗について評価
した結果を第１表および第２表の下欄に示した。The results of evaluating the extruded appearance, tensile properties and cut-through resistance of the insulated electric wires of the respective examples produced as described above are shown in the lower columns of Tables 1 and 2.
なお、カットスルー抵抗は、90゜エッジの上に電線を
おき、電線に350gの荷重をかけて200℃で５分間予熱
し、エッジと導体が導通するまでの時間が10分以上であ
れば合格、10分以内であれば不合格とした。The cut-through resistance is acceptable if the wire is placed on the 90 ° edge, a load of 350 g is applied to the wire, and the wire is preheated at 200 ° C for 5 minutes, and if the time between the edge and the conductor is 10 minutes or more. If it was within 10 minutes, it was rejected.
樹脂成分としてテトラフルオロエチレン−プロピレン
共重合体とエチレン−テトラフルオロエチレン−フルオ
ロオレフィン共重合体のブレンドを使用し、これに特定
の無機充填剤を添加した実施例１〜４ではいずれも優れ
た押出外観、引張特性、カットスルー抵抗を示してい
る。 In Examples 1 to 4 in which a blend of a tetrafluoroethylene-propylene copolymer and an ethylene-tetrafluoroethylene-fluoroolefin copolymer was used as a resin component and a specific inorganic filler was added, excellent extrusion was achieved. Shows appearance, tensile properties, and cut-through resistance.
これに対し、樹脂成分としてテトラフルオロエチレン
−プロピレン共重合体とETFEのブレンドを使用した比較
例１、２では、発泡により押出外観が悪く、引張特性お
よびカットスルー抵抗の測定は不可であった。これは、
押出温度が高いため架橋助剤が分解して発泡ガスを発生
することに起因するものと思われる。また、特定無機充
填剤を使用しない比較例３ではカットスルー抵抗が不合
格である。On the other hand, in Comparative Examples 1 and 2 in which the blend of tetrafluoroethylene-propylene copolymer and ETFE was used as the resin component, the extrusion appearance was poor due to foaming, and the tensile properties and cut-through resistance could not be measured. this is,
It is considered that this is because the crosslinking temperature is high and the crosslinking aid decomposes to generate a foaming gas. Moreover, in Comparative Example 3 in which the specific inorganic filler is not used, the cut-through resistance is unacceptable.
［発明の効果］ 以上説明してきた通り、本発明は、テトラフルオロエ
チレン−プロピレン系共重合体と融点が180℃〜200℃の
範囲にあるエチレン−テトラフルオロエチレン−フルオ
ロオレフィン共重合体とからなる樹脂成分に特定無機充
填剤および架橋助剤を配合した組成物からなる被覆層を
電離性放射線の照射により架橋したものであり、優れた
機械的特性および押出外観を有し、しかもカットスルー
抵抗が改良された被覆層からなる含ふっ素エラストマ被
覆絶縁電線を実現できるようになる。[Effects of the Invention] As described above, the present invention comprises a tetrafluoroethylene-propylene copolymer and an ethylene-tetrafluoroethylene-fluoroolefin copolymer having a melting point in the range of 180 ° C to 200 ° C. A coating layer formed of a composition in which a specific inorganic filler and a cross-linking auxiliary agent are mixed with a resin component is cross-linked by irradiation with ionizing radiation, which has excellent mechanical properties and extrusion appearance, and further has a cut-through resistance. It becomes possible to realize a fluorine-containing elastomer-coated insulated wire comprising an improved coating layer.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 柳生 秀樹 茨城県日立市日高町５丁目１番１号 日立 電線株式会社電線研究所内 (56)参考文献 特開 昭58−4206（ＪＰ，Ａ) 特開 昭59−221903（ＪＰ，Ａ) 特公 昭48−25415（ＪＰ，Ｂ１) 特公 昭56−34018（ＪＰ，Ｂ２) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Hideki Yagyu, 5-1-1 Hidaka-cho, Hitachi, Ibaraki, Hitachi Cable, Ltd. (56) Reference JP-A-58-4206 (JP, A) JP-A-59-221903 (JP, A) JP-B 48-25415 (JP, B1) JP-B 56-34018 (JP, B2)
Claims (3)
重合体90〜20重量％と融点が180℃〜200℃の範囲にある
エチレン−テトラフルオロエチレン−フルオロオレフィ
ン共重合体10〜80重量％とを含有する脂肪成分100重量
部に対して無水けい酸、炭酸カルシウムおよびけい酸カ
ルシウムから選ばれた少なくとも１種の無機充填剤を40
〜100重量部および架橋助剤を0.5重量部以上配合してな
る組成物の被覆層を有し、該被覆層は電離性放射線の照
射により架橋されていることを特徴とするカットスルー
抵抗が改良された含ふっ素エラストマ被覆絶縁電線。1. Containing 90 to 20% by weight of a tetrafluoroethylene-propylene copolymer and 10 to 80% by weight of an ethylene-tetrafluoroethylene-fluoroolefin copolymer having a melting point in the range of 180 to 200 ° C. 40 parts by weight of at least one inorganic filler selected from silicic acid anhydride, calcium carbonate and calcium silicate per 100 parts by weight of fat component
To 100 parts by weight and 0.5 parts by weight or more of a crosslinking aid are included in the coating layer, and the coating layer is crosslinked by irradiation with ionizing radiation to improve cut-through resistance. Fluorine-containing elastomer insulated insulated wire.
重合体におけるテトラフルオロエチレン／プロピレンの
含有モル比が95〜30/5〜70である特許請求の範囲第１項
記載のカットスルー抵抗が改良された含ふっ素エラスト
マ被覆絶縁電線。2. The cut-through resistance according to claim 1, wherein the tetrafluoroethylene-propylene copolymer has a tetrafluoroethylene / propylene content molar ratio of 95 to 30/5 to 70. Fluorine-containing elastomer coated insulated wire.
オロオレフィン共重合体におけるエチレン／テトラフル
オロエチレン／フルオロオレフィンの含有モル比が10〜
40/90〜60/0.1〜20である特許請求の範囲第１項記載の
カットスルー抵抗が改良された含ふっ素エラストマ被覆
絶縁電線。3. The ethylene / tetrafluoroethylene / fluoroolefin content molar ratio in the ethylene-tetrafluoroethylene-fluoroolefin copolymer is from 10 to 10.
A fluorine-containing elastomer-coated insulated electric wire having an improved cut-through resistance according to claim 1, which is 40/90 to 60 / 0.1 to 20.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62149777A JPH0824010B2 (en) | 1987-06-16 | 1987-06-16 | Fluorine-containing elastomer-coated insulated wire with improved cut-through resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62149777A JPH0824010B2 (en) | 1987-06-16 | 1987-06-16 | Fluorine-containing elastomer-coated insulated wire with improved cut-through resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63313411A JPS63313411A (en) | 1988-12-21 |
| JPH0824010B2 true JPH0824010B2 (en) | 1996-03-06 |
Family
ID=15482496
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62149777A Expired - Lifetime JPH0824010B2 (en) | 1987-06-16 | 1987-06-16 | Fluorine-containing elastomer-coated insulated wire with improved cut-through resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0824010B2 (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5634018A (en) * | 1979-08-27 | 1981-04-06 | Tokuyama Soda Co Ltd | Preventing method for corrosion of inside wall of funnel |
-
1987
- 1987-06-16 JP JP62149777A patent/JPH0824010B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63313411A (en) | 1988-12-21 |
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