JP4868272B2 - Heat resistant wire - Google Patents
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- JP4868272B2 JP4868272B2 JP2004250025A JP2004250025A JP4868272B2 JP 4868272 B2 JP4868272 B2 JP 4868272B2 JP 2004250025 A JP2004250025 A JP 2004250025A JP 2004250025 A JP2004250025 A JP 2004250025A JP 4868272 B2 JP4868272 B2 JP 4868272B2
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Description
本発明は、耐熱電線に関する。 The present invention relates to a heat resistant electric wire.
フッ素樹脂は、耐熱性、電気絶縁性、耐ストレスクラック性に優れることから、耐熱電線の被覆材料として使用される。特に、高い信頼性が要求される、航空機、半導体、自動車、ＯＡ機器やＩＴ機器の配線用の電線として使用されている。 Fluororesin is excellent in heat resistance, electrical insulation, and stress crack resistance, and is therefore used as a coating material for heat resistant wires. In particular, they are used as wires for wiring of aircraft, semiconductors, automobiles, office automation equipment, and IT equipment that require high reliability.
現在、エチレン／テトラフルオロエチレン共重合体（以下、ＥＴＦＥともいう。）で導体を被覆後、架橋させた電線が航空機用の耐熱電線として使用されている（例えば、非特許文献１を参照。）。しかし、航空機の安全性をさらに向上するためにＥＴＦＥよりも耐熱性に優れる被覆材料が求められ、その候補材料として、テトラフルオロエチレン（以下、ＴＦＥという。）に基づく繰り返し単位（Ａ）及びペルフルオロ（プロピルビニルエーテル）（以下、ＰＰＶＥという。）に基づく繰り返し単位（Ｂ）からなり、（Ａ）／（Ｂ）のモル比が９９／１〜９８／２であるＴＦＥ／ＰＰＶＥ共重合体（従来のＰＦＡ）がある。しかし、従来のＰＦＡは、ＥＴＦＥに比較して、耐熱温度が高いものの、カットスルー抵抗性が充分でなかった。本発明者らは、カットスルー抵抗性を向上するため、ＰＦＡに絶縁性の充填材を含有させて、被覆材料の硬度を高くする方法を試みたが、この方法では、カットスルー抵抗性は向上するが耐ストレスクラック性が低下することがわかった。 At present, an electric wire that has been coated with a conductor with an ethylene / tetrafluoroethylene copolymer (hereinafter also referred to as ETFE) and then cross-linked is used as a heat-resistant electric wire for aircraft (for example, see Non-Patent Document 1). . However, in order to further improve the safety of aircraft, a coating material that is superior in heat resistance to ETFE is required. As candidate materials, a repeating unit (A) based on tetrafluoroethylene (hereinafter referred to as TFE) and perfluoro ( TFE / PPVE copolymer (conventional PFA) comprising a repeating unit (B) based on (propyl vinyl ether) (hereinafter referred to as PPVE) and having a molar ratio (A) / (B) of 99/1 to 98/2 ) However, although the conventional PFA has a higher heat resistance temperature than ETFE, the cut-through resistance is not sufficient. In order to improve the cut-through resistance, the present inventors tried to increase the hardness of the coating material by adding an insulating filler to PFA, but this method improved the cut-through resistance. However, it was found that the stress crack resistance was lowered.
本発明の目的は、耐熱性及び耐ストレスクラック性に優れ、カットスルー抵抗性に優れ、信頼性に優れる耐熱電線を提供することである。 An object of the present invention is to provide a heat-resistant electric wire having excellent heat resistance and stress crack resistance, excellent cut-through resistance, and excellent reliability.
本発明は、ＴＦＥに基づく繰り返し単位（Ａ）、ＰＰＶＥに基づく繰り返し単位（Ｂ）を含有し、（Ａ）／（Ｂ）のモル比が９７．５／２．５〜８５／１５であり、３８０℃における容量流速が０．１〜２０ｍｍ３／秒であり、かつＭＩＴ折り曲げ寿命が３００万回以上である含フッ素共重合体と絶縁性の充填剤とを含有する被覆材料で導体を被覆してなる耐熱電線を提供する。 The present invention contains a repeating unit (A) based on TFE, a repeating unit (B) based on PPVE, and the molar ratio of (A) / (B) is 97.5 / 2.5 to 85/15, The conductor is coated with a coating material containing a fluorine-containing copolymer and an insulating filler having a capacity flow rate at 380 ° C. of 0.1 to 20 mm 3 / sec and an MIT bending life of 3 million times or more. A heat-resistant electric wire is provided.
本発明の耐熱電線は、耐熱性に優れ、耐ストレスクラック性に優れ、カットスルー抵抗性に優れ、信頼性に優れる。 The heat-resistant electric wire of the present invention is excellent in heat resistance, excellent in stress crack resistance, excellent in cut-through resistance, and excellent in reliability.
本発明における含フッ素共重合体は、ＴＦＥに基づく繰り返し単位（Ａ）、ＰＰＶＥに基づく繰り返し単位（Ｂ）を含有し、（Ａ）／（Ｂ）のモル比が９７．５／２．５〜８５／１５である。繰り返し単位（Ｂ）が、この範囲より少ないと、含フッ素共重合体は耐ストレスクラック性が充分でなく、多いと耐熱性が充分でない。（Ａ）／（Ｂ）は、好ましくは９７／３〜９０／１０であり、さらに好ましくは９６／４〜９２／８である。 The fluorine-containing copolymer in the present invention contains a repeating unit (A) based on TFE and a repeating unit (B) based on PPVE, and the molar ratio of (A) / (B) is 97.5 / 2.5 to 85/15. When the repeating unit (B) is less than this range, the fluorine-containing copolymer does not have sufficient stress crack resistance, and when it is large, the heat resistance is not sufficient. (A) / (B) is preferably 97/3 to 90/10, more preferably 96/4 to 92/8.
含フッ素共重合体において、前記繰り返し単位（Ａ）及び繰り返し単位（Ｂ）に加えて、さらに、ＴＦＥと共重合可能な、その他のモノマーに基づく繰り返し単位（Ｃ）を含有することも好ましい。その他のモノマーの具体例としては、エチレン等の炭化水素系オレフィン、フッ化ビニル、フッ化ビニリデン、トリフルオロエチレン、ＣＨ２＝ＣＸ（ＣＦ２）ｎＹ（ここで、Ｘ及びＹは、それぞれ独立に水素又はフッ素原子、ｎは２〜８の整数である。）等の不飽和基に水素原子を有するフルオロオレフィン、ヘキサフルオロプロピレン（以下、ＨＦＰという。）、クロロトリフルオロエチレン（以下、ＣＴＦＥという。）等の不飽和基に水素原子を有しないフルオロオレフィン（ただし、ＴＦＥを除く。）、ペルフルオロ（メチルビニルエーテル）、ペルフルオロ（エチルビニルエーテル）、ペルフルオロ（ブチルビニルエーテル）等のペルフルオロ（アルキルビニルエーテル）（以下、ＰＡＶＥという。）（ただし、ＰＰＶＥを除く。）、酢酸ビニル等のビニルエステル、アルキルビニルエーテル、グリシジルビニルエーテル、ヒドロキシブチルビニルエーテル、メチルビニロキシブチルカーボネート等のビニルエーテル等が挙げられる。 In addition to the repeating unit (A) and the repeating unit (B), the fluorine-containing copolymer preferably further contains a repeating unit (C) based on another monomer that can be copolymerized with TFE. Specific examples of other monomers include hydrocarbon olefins such as ethylene, vinyl fluoride, vinylidene fluoride, trifluoroethylene, CH 2 ═CX (CF 2 ) n Y (where X and Y are independent of each other). Or a hydrogen atom or a fluorine atom, n is an integer of 2 to 8.) A fluoroolefin having a hydrogen atom in an unsaturated group such as hexafluoropropylene (hereinafter referred to as HFP), chlorotrifluoroethylene (hereinafter referred to as CTFE). ) Fluoroolefins that do not have hydrogen atoms in unsaturated groups (excluding TFE), perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (butyl vinyl ether), etc. , PAVE.) (However, excluding PPVE .), Vinyl esters such as vinyl acetate, alkyl vinyl ether, glycidyl vinyl ether, hydroxybutyl vinyl ether, and vinyl ether such as methyl vinyloxy butyl carbonate.
その他のモノマーとしては、ＨＦＰ、ＣＴＦＥ、ＰＡＶＥ（ただし、ＰＰＶＥを除く。）からなる群から選ばれる１種以上が好ましい。その他のモノマーに基づく繰り返し単位（Ｃ）を含有すると含フッ素共重合体は、耐熱性及び耐薬品性に優れる。繰り返し単位（Ｃ）の含有量は、（Ｃ）／（（Ａ）＋（Ｂ）＋（Ｃ））がモル比で０．１／１００〜１０／１００が好ましく、０．２／１００〜８／１００がより好ましい。
含フッ素共重合体としては、繰り返し単位（Ａ）及び繰り返し単位（Ｂ）のみからなる含フッ素共重合体が好ましい。
The other monomer is preferably at least one selected from the group consisting of HFP, CTFE, and PAVE (excluding PPVE). When the repeating unit (C) based on other monomers is contained, the fluorine-containing copolymer is excellent in heat resistance and chemical resistance. The content of the repeating unit (C) is preferably (C) / ((A) + (B) + (C)) in a molar ratio of 0.1 / 100 to 10/100, preferably 0.2 / 100 to 8 / 100 is more preferable.
As the fluorine-containing copolymer, a fluorine-containing copolymer consisting only of the repeating unit (A) and the repeating unit (B) is preferable.
本発明のおける含フッ素共重合体の３８０℃における容量流速は０．１〜２０ｍｍ３／秒である。容量流速は分子量の目安であり、容量流速が小さいと分子量が高く、大きいと分子量が低いことを示す。容量流速がこの範囲よりも小さいと溶融成形性が低く、この範囲よりも大きいと耐熱電線の耐ストレスクラック性が充分でない。好ましくは０．５〜１５ｍｍ３／秒、より好ましくは１〜１０ｍｍ３／秒である。 The volume flow rate at 380 ° C. of the fluorinated copolymer in the present invention is 0.1 to 20 mm 3 / sec. The volume flow rate is a measure of the molecular weight, and when the volume flow rate is small, the molecular weight is high and when large, the molecular weight is low. When the capacity flow rate is smaller than this range, the melt moldability is low, and when it is larger than this range, the stress crack resistance of the heat-resistant electric wire is not sufficient. Preferably 0.5 to 15 mm 3 / sec, more preferably from 1 to 10 mm 3 / sec.
本発明における含フッ素共重合体のＭＩＴ折り曲げ寿命は３００万回以上である。ここで、ＭＩＴ折り曲げ寿命とは、ＡＳＴＭ Ｄ２１７６に準じて実施される折り曲げ試験において、試料が破断するまでの折り曲げ回数である。この値が大きいほど、耐ストレスクラック性に優れることを示す。ＭＩＴ折り曲げ寿命が、これより短いと、耐熱電線の耐ストレスクラック性が低い。好ましくは４００万回以上、より好ましくは５００万回以上である。 The MIT bending life of the fluorinated copolymer in the present invention is 3 million times or more. Here, the MIT bending life is the number of bendings until the sample breaks in a bending test performed in accordance with ASTM D2176. It shows that it is excellent in stress crack resistance, so that this value is large. When the MIT bending life is shorter than this, the stress crack resistance of the heat-resistant electric wire is low. Preferably it is 4 million times or more, more preferably 5 million times or more.
本発明における含フッ素共重合体の製造方法は、特に制限はなく、一般に用いられているラジカル重合開始剤を用いる重合方法が用いられる。重合方法としては、塊状重合、フッ化炭化水素、塩化炭化水素、フッ化塩化炭化水素、含フッ素アルキルエーテル、アルコール、炭化水素等の有機溶媒を使用する溶液重合、水性媒体及び必要に応じて適当な有機溶剤を使用する懸濁重合、水性媒体及び乳化剤を使用する乳化重合等が挙げられる。特に、懸濁重合が好ましい。また、懸濁重合で用いる有機溶媒としては、フッ化炭化水素、フッ化塩化炭化水素及び含フッ素アルキルエーテルからなる群から選ばれる１種以上が好ましい。 There is no restriction | limiting in particular in the manufacturing method of the fluorine-containing copolymer in this invention, The polymerization method using the radical polymerization initiator generally used is used. Polymerization methods include bulk polymerization, solution polymerization using organic solvents such as fluorinated hydrocarbons, chlorinated hydrocarbons, fluorinated chlorinated hydrocarbons, fluorinated alkyl ethers, alcohols and hydrocarbons, aqueous media, and as appropriate. And suspension polymerization using an organic solvent, and emulsion polymerization using an aqueous medium and an emulsifier. In particular, suspension polymerization is preferable. Further, the organic solvent used in the suspension polymerization is preferably one or more selected from the group consisting of fluorinated hydrocarbons, fluorinated chlorohydrocarbons, and fluorinated alkyl ethers.
ラジカル重合開始剤としては、半減期が１０時間である温度が０〜１００℃である開始剤が好ましく、２０〜９０℃である開始剤がより好ましい。具体例としては、アゾビスイソブチロニトリル等のアゾ化合物、ジイソプロピルパーオキシジカーボネート等のパーオキシジカーボネート、ｔｅｒｔ−ブチルパーオキシピバレート、ｔｅｒｔ−ブチルパーオキシイソブチレート、ｔｅｒｔ−ブチルパーオキシアセテート等のパーオキシエステル、イソブチリルパーオキシド、オクタノイルパーオキシド、ベンゾイルパーオキシド、ラウロイルパーオキシド等の非フッ素系ジアシルパーオキシド、（Ｚ（ＣＦ２）ｐＣＯＯ）２（ここで、Ｚは水素原子、フッ素原子又は塩素原子であり、ｐは１〜１０の整数である。）等の含フッ素ジアシルパーオキシド、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム等の無機過酸化物等が挙げられる。 As the radical polymerization initiator, an initiator having a half-life of 10 hours and a temperature of 0 to 100 ° C. is preferable, and an initiator having a temperature of 20 to 90 ° C. is more preferable. Specific examples include azo compounds such as azobisisobutyronitrile, peroxydicarbonates such as diisopropyl peroxydicarbonate, tert-butyl peroxypivalate, tert-butyl peroxyisobutyrate, and tert-butyl peroxy. Peroxyesters such as acetate, non-fluorinated diacyl peroxides such as isobutyryl peroxide, octanoyl peroxide, benzoyl peroxide, lauroyl peroxide, (Z (CF 2 ) p COO) 2 (where Z is hydrogen Fluorine-containing diacyl peroxide such as an atom, fluorine atom or chlorine atom, and p is an integer of 1 to 10, and inorganic peroxides such as potassium persulfate, sodium persulfate and ammonium persulfate.
重合条件としては、重合温度は０〜１００℃が好ましく、２０〜９０℃がより好ましい。重合圧力は０．１〜１０ＭＰａが好ましく、０．５〜３ＭＰａがより好ましい。重合時間は１〜３０時間が好ましい。
本発明において、含フッ素共重合体の容量流速を制御するために、連鎖移動剤を使用することも好ましい。連鎖移動剤としては、メタノール、エタノール等のアルコール、１，３−ジクロロ−１，１，２，２，３−ペンタフルオロプロパン、１，１−ジクロロ−１−フルオロエタン等のクロロフルオロハイドロカーボン、ペンタン、ヘキサン、シクロヘキサン等のハイドロカーボン等が挙げられる。
As polymerization conditions, the polymerization temperature is preferably 0 to 100 ° C, more preferably 20 to 90 ° C. The polymerization pressure is preferably from 0.1 to 10 MPa, more preferably from 0.5 to 3 MPa. The polymerization time is preferably 1 to 30 hours.
In the present invention, it is also preferable to use a chain transfer agent in order to control the volume flow rate of the fluorine-containing copolymer. Chain transfer agents include alcohols such as methanol and ethanol, chlorofluorohydrocarbons such as 1,3-dichloro-1,1,2,2,3-pentafluoropropane, 1,1-dichloro-1-fluoroethane, Examples thereof include hydrocarbons such as pentane, hexane, and cyclohexane.
本発明における被覆材料は、含フッ素共重合体と絶縁性の充填材とを含有する。絶縁性の充填剤としては、マイカ、シリカ、タルク、アルミナ、カオリン、硫酸カルシウム、炭酸カルシウム、酸化チタン、酸化亜鉛などの無機充填剤、ガラス繊維、チタン酸カリウムやホウ酸アルミニウムなどのウィスカ、ポリイミド繊維等の有機充填剤が挙げられる。絶縁性の充填材としては、マイカ、シリカ、タルク、アルミナ、カオリン、硫酸カルシウム、炭酸カルシウム、酸化チタン及び酸化亜鉛からなる群から選ばれる１種以上が好ましい。
絶縁性の充填剤の含有量として前記含フッ素共重合体と絶縁性の充填剤との質量比が９９．９／０．１〜１０／９０が好ましく、さらに好ましくは９９／１〜３０／７０であり、最も好ましくは９０／１０〜４０／６０である。
The coating material in the present invention contains a fluorine-containing copolymer and an insulating filler. Insulating fillers include inorganic fillers such as mica, silica, talc, alumina, kaolin, calcium sulfate, calcium carbonate, titanium oxide and zinc oxide, glass fibers, whiskers such as potassium titanate and aluminum borate, polyimide Examples include organic fillers such as fibers. The insulating filler is preferably at least one selected from the group consisting of mica, silica, talc, alumina, kaolin, calcium sulfate, calcium carbonate, titanium oxide and zinc oxide.
The content ratio of the insulating filler is preferably 99.9 / 0.1 to 10/90, more preferably 99/1 to 30/70, as the mass ratio of the fluorine-containing copolymer to the insulating filler. And most preferably 90/10 to 40/60.
本発明における被覆材料は、含フッ素共重合体と絶縁性の充填材とを押出混錬機で混錬して製造することが好ましい。混錬方法としては、含フッ素共重合体と絶縁性の充填材とをタンブラやＶミキサ、ヘンシェルミキサなどで予備混合した上で同方向又は異方向の２軸押出混錬機に供給するか、又は予備混合しないで、含フッ素共重合体及び絶縁性の充填剤を投入した複数のホッパーから同方向又は異方向の２軸押出混錬機に供給することにより、溶融混練してペレット化する方法が好ましい。２軸押出混錬機の混錬用スクリューとしては、ニーディング機能付きのスクリューが好ましい。また、混練温度としては、含フッ素共重合体の融点以上、分解温度以下が好ましい。具体的には３００℃〜４００℃が好ましい。 The coating material in the present invention is preferably produced by kneading a fluorine-containing copolymer and an insulating filler with an extrusion kneader. As a kneading method, a fluorine-containing copolymer and an insulating filler are premixed with a tumbler, a V mixer, a Henschel mixer or the like and then supplied to a twin-screw extrusion kneader in the same direction or different directions, Alternatively, a method of melt-kneading and pelletizing by supplying from a plurality of hoppers charged with a fluorine-containing copolymer and an insulating filler to a biaxial extrusion kneader in the same direction or different direction without premixing Is preferred. As the kneading screw of the twin-screw extrusion kneader, a screw with a kneading function is preferable. The kneading temperature is preferably not less than the melting point of the fluorinated copolymer and not more than the decomposition temperature. Specifically, 300 to 400 ° C is preferable.
本発明の耐熱電線の製造方法としては、公知の技術を使用することができる。押出し機を用いて溶融させた被覆材料で導体を被覆する方法、テープ状に加工した被覆材料を導体に巻きつける方法、被覆材料の粉末を流動させた槽に導体を浸漬させた後、導体に付着した粉末を加熱溶融して被覆層を形成する方法等が挙げられる。特に、押出し機を用いて溶融させた被覆材料で導体を被覆する方法が好ましい。 A well-known technique can be used as a manufacturing method of the heat-resistant electric wire of the present invention. A method of coating a conductor with a melted coating material using an extruder, a method of winding a tape-shaped coating material around a conductor, a dipping conductor in a bath in which a powder of the coating material is flowed, and Examples thereof include a method of forming a coating layer by heating and melting the attached powder. In particular, a method of coating a conductor with a coating material melted using an extruder is preferable.
押出し機としては、単軸又は２軸押出し機が好ましく、押出し条件としては、シリンダー温度が２５０〜３８０℃、クロスヘッド温度が３００〜４００℃、ダイ温度が３２０〜４２０℃であることが好ましい。 As an extruder, a single screw or a twin screw extruder is preferable. As extrusion conditions, a cylinder temperature is 250 to 380 ° C, a crosshead temperature is 300 to 400 ° C, and a die temperature is preferably 320 to 420 ° C.
本発明の耐熱電線の芯線として用いられる導体としては、特に限定されず、銅、銅合金、アルミニウム及びアルミニウム合金、スズメッキ、銀メッキ、ニッケルメッキ等の各種メッキ線、より線、超電導体、半導体素子リード用メッキ線等が挙げられる。また、導体の径及び被覆材料の被覆厚さは、適宜選定できる。その他に、束ねた複数の耐熱電線の外周を本発明における被覆材料で被覆することも好ましい。 The conductor used as the core wire of the heat-resistant electric wire of the present invention is not particularly limited, and various plated wires such as copper, copper alloy, aluminum and aluminum alloy, tin plating, silver plating, nickel plating, stranded wire, superconductor, and semiconductor element. Examples include lead plating wires. The diameter of the conductor and the coating thickness of the coating material can be selected as appropriate. In addition, it is also preferable to coat the outer periphery of the bundled heat-resistant electric wires with the coating material in the present invention.
以下、実施例及び比較例を挙げて本発明を詳細に説明するが、本発明はこれらに限定されない。なお、含フッ素共重合体の組成、容量流速、ＭＩＴ折り曲げ寿命は、以下に記載の方法で測定した。 EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited to these. The composition, the capacity flow rate, and the MIT bending life of the fluorinated copolymer were measured by the methods described below.
［ＴＦＥ共重合体の組成］旭硝子研究報告１９９０、４０（１）、７５の記載に準じて、熱溶融状態で含フッ素共重合体の１９Ｆ−ＮＭＲ測定する方法によって求めた。 [Composition of TFE copolymer] According to the description of Asahi Glass Research Report 1990, 40 (1), 75, it was determined by a method of 19 F-NMR measurement of the fluorinated copolymer in a hot melt state.
［容量流速］フローテスター（島津製作所社製）を用いて３８０℃、７ｋｇの荷重下に、直径２．１ｍｍ、長さ８ｍｍのオリフィス中に含フッ素共重合体を押出したときの含フッ素共重合体の流量（ｍｍ３／秒）を容量流速とした。 [Capacity flow rate] Fluorine-containing copolymer when a fluorine-containing copolymer is extruded into an orifice having a diameter of 2.1 mm and a length of 8 mm under a load of 380 ° C. and 7 kg using a flow tester (manufactured by Shimadzu Corporation) The combined flow rate (mm 3 / sec) was taken as the volume flow rate.
［ＭＩＴ折り曲げ寿命］含フッ素共重合体を３４０℃で圧縮成形して得た厚さ０．２２０〜０．２３６μｍのフィルムを幅１２．５ｍｍの短冊状に打ち抜いて測定試料を得た。ＡＳＴＭ Ｄ２１７６に準じて、荷重１．２５ｋｇ、折り曲げ角度±１３５度、室温で折り曲げ試験機ＭＩＴ−Ｄ（東洋精機製作社製）を用いて測定試料の折り曲げ試験を行った。破断するまでの折り曲げ回数をＭＩＴ折り曲げ寿命とした。 [MIT Bending Life] A measurement sample was obtained by punching a film having a thickness of 0.220 to 0.236 μm obtained by compression molding of a fluorine-containing copolymer at 340 ° C. into a strip shape having a width of 12.5 mm. In accordance with ASTM D2176, a bending test of the measurement sample was performed using a bending tester MIT-D (manufactured by Toyo Seiki Seisakusho) at a load of 1.25 kg, a bending angle of ± 135 degrees, and room temperature. The number of folds until rupture was defined as the MIT fold life.
［耐ストレスクラック性試験］耐熱電線を自己径に巻きつけ、２５０℃のオーブン中に２週間保持した後の耐熱電線の被覆材料にクラックの有無を目視で観察した。クラックが生じないものを、耐ストレスクラック性が良好と評価した。 [Stress crack resistance test] A heat-resistant electric wire was wound around its own diameter, and the coating material of the heat-resistant electric wire after being held in an oven at 250 ° C for 2 weeks was visually observed for cracks. Those having no cracks were evaluated as having good stress crack resistance.
［カットスルー抵抗性試験］芯線の径が０．２６ｍｍ、被覆厚さが０．１５ｍｍ、仕上がり径が０．５６ｍｍの被覆電線を軟鋼製角柱のエッジの上に乗せ、温度１５０℃で荷重２ｋｇを加え１時間以上絶縁性を保持していた場合にカットスルー抵抗性が良好と評価した。 [Cut-through resistance test] A covered electric wire having a core wire diameter of 0.26 mm, a coating thickness of 0.15 mm, and a finished diameter of 0.56 mm was placed on the edge of a mild steel prism, and a load of 2 kg was applied at a temperature of 150 ° C. In addition, when the insulating property was maintained for 1 hour or more, the cut-through resistance was evaluated as good.
［実施例１］
内容積４００Ｌの撹拌機付き重合槽内を真空に脱気し、水の２０４Ｌ、メタノールの１．８２Ｌ、ＣＦＨＣｌＣＦ２ＣＦ２Ｃｌ（以下、ＡＫ２２５ｃｂという。）の４１．７Ｌ、ＰＰＶＥの３３．９Ｌを仕込み、重合槽内を５０℃に昇温後、ＴＦＥを１．２１ＭＰａ／Ｇまで導入した。重合開始剤としてジ（ペルフルオロブチリル）ペルオキシドの０．１２質量％２２５ｃｂ溶液を仕込み重合反応を開始した。重合の進行に伴い圧力が低下するので、ＴＦＥを追加添加して圧力を一定に保った。重合中、開始剤溶液を連続的に合計２．５Ｌ仕込み、ＴＦＥの追加添加量が３８ｋｇになったところで重合槽内の温度を２５℃まで冷却し、未反応ＴＦＥをパージした。重合時間は、７時間であった。得られた重合溶液を静置し、水と含フッ素共重合体のスラリーとに分離し、該スラリ−を１５０℃にて８時間乾燥することにより、４６．４ｋｇの含フッ素共重合体１が得られた。含フッ素共重合体１の組成は、ＴＦＥに基づく繰り返し単位／ＰＰＶＥに基づく繰り返し単位のモル比が９３．７／６．３であり、容量流速は１．２３ｍｍ３／秒であった。ＭＩＴ折り曲げ寿命は１２００万回であった。
[Example 1]
The inside of the polymerization tank equipped with a stirrer with an internal volume of 400 L was evacuated to vacuum, and 204 L of water, 1.82 L of methanol, 41.7 L of CFHClCF 2 CF 2 Cl (hereinafter referred to as AK225cb), and 33.9 L of PPVE were added. After charging and raising the temperature in the polymerization tank to 50 ° C., TFE was introduced to 1.21 MPa / G. A 0.12% by mass 225 cb solution of di (perfluorobutyryl) peroxide was charged as a polymerization initiator to initiate the polymerization reaction. Since the pressure decreased as the polymerization progressed, additional TFE was added to keep the pressure constant. During the polymerization, a total of 2.5 L of the initiator solution was continuously charged. When the additional amount of TFE reached 38 kg, the temperature in the polymerization tank was cooled to 25 ° C., and unreacted TFE was purged. The polymerization time was 7 hours. The obtained polymerization solution was allowed to stand, separated into water and a fluorinated copolymer slurry, and the slurry was dried at 150 ° C. for 8 hours, whereby 46.4 kg of the fluorinated copolymer 1 was obtained. Obtained. In the composition of the fluorinated copolymer 1, the molar ratio of the repeating unit based on TFE / the repeating unit based on PPVE was 93.7 / 6.3, and the volume flow rate was 1.23 mm 3 / sec. The MIT bending life was 12 million times.
２カ所のニーディング部を有するスクリューがセットされた同方向２軸押出混練機の第１フィーダのホッパに炭酸カルシウム（日東粉化工業社製ＮＳ２００）を、第２フィーダのホッパに含フッ素共重合体１を炭酸カルシウム／含フッ素共重合体１の質量比が１／１となるように投入し、シリンダ温度３８０℃、スクリュー回転数１００ｒｐｍの条件下に、ベント部から真空ポンプで吸引しながら炭酸カルシウムと含フッ素共重合体１とを混練し、吐出されたストランドを徐冷し、ペレタイザで３ｍｍ長さに切断してペレット１を作成した。 Calcium carbonate (NS200 manufactured by Nitto Flour Chemical Co., Ltd.) is used as the hopper of the first feeder of the same-direction twin-screw extrusion kneader in which screws having two kneading parts are set, and fluorine-containing co-polymer is used as the hopper of the second feeder. The coalescence 1 was charged so that the mass ratio of calcium carbonate / fluorinated copolymer 1 was 1/1, and carbonation was performed while sucking with a vacuum pump from the vent section under the conditions of a cylinder temperature of 380 ° C. and a screw rotation speed of 100 rpm. Calcium and the fluorinated copolymer 1 were kneaded, the discharged strand was gradually cooled, and cut into a 3 mm length with a pelletizer to prepare a pellet 1.
得られたペレット１を用いて電線を成形した。押出し機は短軸、スクリュー径４０ｍｍ、スクリュータイプはメタリング、スクリューＬ／Ｄは２５、スクリュー圧縮比は２．６：１とした。ダイは内径４．３ｍｍ、ニップル外径２．０ｍｍ、ランド長２０ｍｍであった。成形条件としては、シリンダーＣ１温度３２０℃、Ｃ２温度３５０℃、Ｃ３温度３８０℃、クロスヘッド温度３９０℃、ダイ温度４００℃、引落とし比５９、引取速度１００ｍ／分を採用した。導体としては、スズメッキ銅線を用いた。得られた耐熱電線１は、芯線の径が０．２６ｍｍ、被覆厚さが０．１５ｍｍ、仕上がり径が０．５６ｍｍであった。得られた耐熱電線１の被覆材料の耐ストレスクラック性は良好であった。カットスルー抵抗性は良好であった。 An electric wire was formed using the obtained pellet 1. The extruder was a short shaft, the screw diameter was 40 mm, the screw type was metalling, the screw L / D was 25, and the screw compression ratio was 2.6: 1. The die had an inner diameter of 4.3 mm, a nipple outer diameter of 2.0 mm, and a land length of 20 mm. As the molding conditions, a cylinder C1 temperature of 320 ° C., a C2 temperature of 350 ° C., a C3 temperature of 380 ° C., a crosshead temperature of 390 ° C., a die temperature of 400 ° C., a draw ratio of 59, and a take-up speed of 100 m / min were employed. A tin-plated copper wire was used as the conductor. The obtained heat-resistant electric wire 1 had a core wire diameter of 0.26 mm, a coating thickness of 0.15 mm, and a finished diameter of 0.56 mm. The stress crack resistance of the coating material of the obtained heat-resistant electric wire 1 was good. Cut-through resistance was good.
［実施例２］
初期に、水の２０４Ｌ、メタノールの２．９６Ｌ、２２５ｃｂの５４．３Ｌ、ＰＰＶＥの２１．３Ｌを仕込み、実施例１と同様にして含フッ素共重合体２を製造した。重合開始剤溶液は合計１．４Ｌ仕込み、ＴＦＥの追加添加量が４３ｋｇであった。重合時間は７時間であった。含フッ素共重合体２の４７．３ｋｇを得た。含フッ素共重合体２の組成はＴＦＥに基づく繰り返し単位／ＰＰＶＥに基づく繰り返し単位のモル比は９５．５／４．５であり、容量流速は１．１０ｍｍ3／秒であった。ＭＩＴ折り曲げ寿命は７５０万回であった。上記のようにして得られた含フッ素共重合体２を用いて実施例１と同様に耐熱電線２を製造した。耐熱電線２の被覆材料の耐ストレスクラック性は良好であった。カットスルー抵抗性は良好であった。
[Example 2]
Initially, 204 L of water, 2.96 L of methanol, 54.3 L of 225 cb, and 21.3 L of PPVE were charged, and a fluorinated copolymer 2 was produced in the same manner as in Example 1. A total of 1.4 L of the polymerization initiator solution was charged, and the additional amount of TFE added was 43 kg. The polymerization time was 7 hours. 47.3 kg of fluorinated copolymer 2 was obtained. As for the composition of the fluorinated copolymer 2, the molar ratio of the repeating unit based on TFE / the repeating unit based on PPVE was 95.5 / 4.5, and the capacity flow rate was 1.10 mm 3 / sec. The MIT bending life was 7.5 million times. A heat-resistant electric wire 2 was produced in the same manner as in Example 1 using the fluorine-containing copolymer 2 obtained as described above. The stress crack resistance of the coating material of the heat resistant electric wire 2 was good. Cut-through resistance was good.
［比較例］
組成がＴＦＥに基づく繰り返し単位／ＰＰＶＥに基づく繰り返し単位のモル比が９８．７／１．３であり、容量流速が１．８ｍｍ３／秒であるＴＦＥ／ＰＰＶＥ共重合体（従来のＰＦＡ、旭硝子社製）のＭＩＴ折り曲げ寿命は６０万回であった。該ＰＦＡを用いて、実施例１と同様に耐熱電線３を製造した。耐熱電線３の耐ストレスクラック性試験を実施した。耐熱電線３の被覆材料には無数の微細クラックが生じ、耐ストレスクラック性が不良であった。カットスルー抵抗性は良好であった。
[Comparative example]
TFE / PPVE copolymer (conventional PFA, Asahi Glass Co., Ltd.) having a molar ratio of repeating unit based on TFE / repeating unit based on PPVE of 98.7 / 1.3 and a capacity flow rate of 1.8 mm 3 / sec. MIT bending life was 600,000 times. A heat-resistant electric wire 3 was produced in the same manner as in Example 1 using the PFA. A stress crack resistance test of the heat resistant electric wire 3 was performed. Innumerable fine cracks occurred in the coating material of the heat-resistant electric wire 3, and the stress crack resistance was poor. Cut-through resistance was good.
本発明の耐熱電線は、航空機、半導体、自動車、ＯＡ機器、ＩＴ機器等の耐熱性、信頼性が要求される電線用途に用いられる。
The heat-resistant electric wire of the present invention is used for electric wire applications that require heat resistance and reliability, such as aircraft, semiconductors, automobiles, OA equipment, and IT equipment.
Claims (3)
前記被覆材料における含フッ素共重合体と絶縁性の充填剤との質量比が９９／１〜３０／７０であり、
前記被覆材料中の充填剤が、マイカ、シリカ、タルク、アルミナ、カオリン、硫酸カルシウム、炭酸カルシウム、酸化チタン及び酸化亜鉛からなる群から選ばれる１種以上であり、
当該被覆材料で被覆された耐熱電線は、（i）芯線の径が０．２６ｍｍ、被覆厚さが０．１５ｍｍ、仕上がり径が０．５６ｍｍの耐熱電線を自己径に巻き付け２５０℃で２週間保持した後で当該耐熱電線の被覆材料にクラックが生じない耐ストレスクラッキング性を有し、かつ、（ii）芯線の径が０．２６ｍｍ、被覆厚さが０．１５ｍｍ、仕上がり径が０．５６ｍｍの耐熱電線を導体である軟鋼製角柱のエッジの上に乗せ、１５０℃で荷重２kgを印加した場合、１時間以上、導体である軟鋼製角柱のエッジが、当該被覆を貫通して芯線と通電することのない絶縁性を保持しているカットスルー抵抗性を有していることを特徴とする耐熱電線。 It contains a repeating unit (A) based on tetrafluoroethylene and a repeating unit (B) based on perfluoro (propyl vinyl ether), and the molar ratio (A) / (B) is 97.5 / 2.5 to 90/10 Yes, the conductor is coated with a coating material containing a fluorine-containing copolymer and an insulating filler having a capacity flow rate at 380 ° C. of 0.1 to 20 mm 3 / sec and an MIT bending life of 3 million times or more. A heat-resistant electric wire formed by coating,
The mass ratio of the fluorine-containing copolymer and the insulating filler in the coating material is 99/1 to 30/70,
The filler in the coating material is at least one selected from the group consisting of mica, silica, talc, alumina, kaolin, calcium sulfate, calcium carbonate, titanium oxide and zinc oxide,
The heat-resistant electric wire coated with the coating material is (i) a heat-resistant electric wire having a core wire diameter of 0.26 mm, a coating thickness of 0.15 mm, and a finished diameter of 0.56 mm is wound around its own diameter and held at 250 ° C. for 2 weeks. has a stress cracking resistance that no crack occurs in the coating material of the heat wire after, and the diameter of (ii) core is 0.26 mm, the coating thickness is 0.15 mm, the finished diameter of 0.56mm When a heat-resistant electric wire is placed on the edge of a mild steel prism that is a conductor and a load of 2 kg is applied at 150 ° C., the edge of the mild steel prism that is a conductor passes through the sheath and energizes the core wire for 1 hour or longer. heat wires, characterized in that it has a no insulation cut-through resistance that holds the thing.
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