JP3724665B2 - Resin for metal coating, resin-coated metal member and method for producing the member - Google Patents

Description

を満足するポリアリーレンスルフィド樹脂からなることを特徴とする金属被覆用樹脂が提供される。
【０００６】
また、本発明によれば、アルカリ金属硫化物とジハロ芳香族化合物をトリハロ芳香族化合物の存在下に重合して得られる分岐型ポリアリーレンスルフィド樹脂であって、３１０℃、剪断速度２００／秒で測定した溶融粘度η_２００が３００〜２０００Ｐａ・ｓで、該溶融粘度η_２００と３１０℃、剪断速度１２００／秒で測定した溶融粘度η_１２００との比Ｒ（η_２００／η_１２００）が下記の関係式（１）：
【数５】

を満足するポリアリーレンスルフィド樹脂からなる金属被覆用樹脂を金属基材上に被覆してなることを特徴とする樹脂被覆金属部材が提供される。
【０００７】
さらに、本発明によれば、アルカリ金属硫化物とジハロ芳香族化合物をトリハロ芳香族化合物の存在下に重合して得られる分岐型ポリアリーレンスルフィド樹脂であって、３１０℃、剪断速度２００／秒で測定した溶融粘度η _２００ が３００〜２０００Ｐａ・ｓで、該溶融粘度η _２００ と３１０℃、剪断速度１２００／秒で測定した溶融粘度η _１２００ との比Ｒ（η _２００ ／η _１２００ ）が下記の関係式（１）：
【数６】

を満足するポリアリーレンスルフィド樹脂からなる金属被覆用樹脂を、押出機を用いて、該樹脂の（融点＋２０℃）〜３５０℃の範囲の温度で溶融させた後、パリソンを形成させながらダイ外被覆により金属基材上に被覆し、次いで、被覆体を冷却後、熱処理温度２００〜２７０℃及び熱処理時間０．１秒以上１０分間以下の条件で熱処理して、被覆層の樹脂の結晶化度を１５〜３０％の範囲とすることを特徴とする樹脂被覆金属部材の製造方法が提供される。
【０００８】
【発明の実施の形態】
本発明では、次のような特定の選択されたポリアリーレンスルフィドを金属被覆用樹脂として使用する点に特徴を有する。
１．アルカリ金属硫化物とジハロ芳香族化合物をトリハロ芳香族化合物の存在下に重合して得られる分岐型ポリアリーレンスルフィド樹脂であること。
２．３１０℃、剪断速度２００／秒で測定した溶融粘度η_２００が次式（２）の範囲にあること。
【０００９】
【数７】

３．該溶融粘度η_２００と３１０℃、剪断速度１２００／秒で測定した溶融粘度η_１２００との比Ｒ（Ｒ＝η_２００／η_１２００）が関係式（１）を満足すること。
【００１０】
【数８】

【００１１】
本発明者らは、ポリアリーレンスルフィド樹脂を用いて金属基材への連続被覆の検討を鋭意重ねた結果、前記１〜３の要件を満足する選択されたポリアリーレンスルフィド樹脂を使用することにより、安定して溶融被覆加工をすることができ、かつ、機械的物性に優れた被覆物の得られることを見出した。
本発明で使用するポリアリーレンスルフィド樹脂は、アルカリ金属硫化物とジハロ芳香族化合物のみから得られる完全な直鎖型樹脂ではなく、三官能モノマーであるトリハロ芳香族化合物を少量共存させて得られる分岐型樹脂である。このような分岐型とすることにより、前記関係式（１）を満足するポリアリーレンスルフィド樹脂を得ることができ、しかも該樹脂を金属基材に被覆した場合に、優れた加工性と機械的物性を得ることができる。これに対して、低分子量のポリアリーレンスルフィド樹脂を空気の存在下に酸化架橋（キュアリング）して得られる架橋型樹脂は、溶融延伸の際にゲル状物が発生し、加工性が劣悪であることに加えて、被覆層の強度、金属基材への密着性、耐摩耗性、絶縁破壊抵抗性、耐熱性等の点で実用性に乏しい。
【００１２】
本発明で使用するポリアリーレンスルフィド樹脂は、３１０℃、剪断速度２００／秒で測定した溶融粘度η_２００ が３００〜２０００Ｐａ・ｓである。溶融粘度η_２００が３００Ｐａ・ｓ未満であると、ポリアリーレンスルフィド樹脂をダイから押し出した際、溶融状態での弾性が乏しく、延伸することが困難となる。溶融粘度η_２００が２０００Ｐａ・ｓを超えると、ゲル状物の発生が顕著になり、加工性が低下すると共に、被覆層の耐屈曲性や可撓性が低下する。本発明で使用するポリアリーレンスルフィド樹脂は、前記関係式（１）を満足することが必要である。Ｒ（η_２００／η_１２００）が下記式（３）で表される範囲にあると、溶融した樹脂をダイスから押出した場合、溶融状態での弾性が乏しいため、延伸することが困難となる。
【００１３】
【数９】

Ｒが下記式（４）で表される範囲にあると、均一な延伸が困難となり、被覆層に凹凸状の不均一部分が多数発生する。
【００１４】
【数１０】

【００１５】
図１に、ポリアリーレンスルフィド樹脂の溶融粘度η_２００（横軸）とＲ値（縦軸）との関係を示す。本発明で使用するポリアリーレンスルフィド樹脂は、図１のＡＢＣＤの４つの点で囲まれた範囲内で、さらにＥＦＧＨの４つの点で囲まれた範囲内のものである。図１の白四角印は、各実施例と参考例１で得られた樹脂の特性値をプロットしたものであり、黒三角印は、各比較例の樹脂の特性値をプロットしたものである。上記の如き溶融粘度及び溶融特性を持ったポリアリーレンスルフィド樹脂は、アルカリ金属硫化物とジハロ芳香族化合物をトリハロ芳香族化合物の存在下に重合する際に、各モノマーの割合や重合条件を適切なものとすることにより得ることができる。
【００１６】
アルカリ金属硫化物としては、例えば、硫化ナトリウム、硫化カリウム、硫化リチウム、硫化ルビジウム、硫化セシウム、及びこれらの混合物などが挙げられる。また、アルカリ金属硫化物は、常法により反応容器中でｉｎ ｓｉｔｕで生成させてもよい。これらのアルカリ金属硫化物は、水和物、水性混合物、または無水物の形で用いることができる。アルカリ金属硫化物中に微量存在するアルカリ金属重硫化物やアルカリ金属チオ硫酸塩と反応させるために、少量のアルカリ金属水酸化物を添加して、これらの不純物を除去するか、あるいは硫化物へ転化させてもよい。これらの中でも硫化ナトリウムが最も安価であるため、工業的には好ましい。
【００１７】
ジハロ芳香族化合物としては、例えば、ｐ−ジクロロベンゼン、ｍ−ジクロロベンゼン、ｏ−ジクロロベンゼン、ｐ−ジブロモベンゼン等のジハロベンゼン；２，５−ジクロロトルエン、１−メトキシ−２，５−ジクロロベンゼン等の置換ジハロベンゼン；１，４−ジクロロナフタレン等のジハロナフタレン；４，４′−ジクロロビフェニル、３，３′−ジクロロビフェニル等のジハロビフェニル；３，５−ジクロロ安息香酸等のジハロ安息香酸；４，４′−ジクロロベンゾフェノン等のジハロベンゾフェノン；４，４′−ジクロロジフェニルスルホン、３，３′−ジクロロジフェニルスルホン等のジハロジフェニルスルホン；４，４′−ジクロロジフェニルエーテル等のジハロフェニルエーテル；などを挙げることができる。
これらの中でも、経済性や物性等の観点から、ジハロベンゼンが好ましく、ｐ−ジクロロベンゼンなどのｐ−ジハロベンゼンがより好ましい。特に、ジハロ芳香族化合物として、ｐ−ジハロベンゼンを、好ましくは７０重量％以上、より好ましくは８０重量％以上、さらに好ましくは９０重量％以上の割合で含有するものが好ましい。
【００１８】
トリハロ芳香族化合物としては、例えば、１，２，３−トリクロロベンゼン、１，２，３−トリブロモベンゼン、１，２，４−トリクロロベンゼン、１，２，４−トリブロモベンゼン、１，３，５−トリクロロベンゼン、１，３，５−トリブロモベンゼン、１，３−ジクロロ−５−ブロムベンゼン等のトリハロベンゼン；トリハロベンゼンのアルキル置換体；これらの混合物等が挙げられる。これらの中でも、経済性、反応性、物性等の観点から、１，２，４−トリハロベンゼン、１，３，５−トリハロベンゼン、及び１，２，３−トリクロロベンゼンが好ましい。
【００１９】
ポリアリーレンスルフィド樹脂の製造方法としては、水を含有する極性有機溶媒中で、アルカリ金属硫化物とジハロ芳香族化合物とをトリハロ芳香族化合物の存在下に重縮合反応させる方法を採用することができる。水としては、例えば、アルカリ金属硫化物の水和水、添加水、反応水、アルカリ金属硫化物水溶液の水などが挙げられる。有機アミド溶媒としては、例えば、Ｎ−メチルピロリドン、Ｎ−エチルピロリドン、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチルカプロラクタム、ジメチルイミダゾリジノン、テトラメチル尿素、ヘキサメチルホスホン酸アミドなどが挙げられる。これらの中でも、経済性や安定性の観点から、Ｎ−メチル−２−ピロリドン（ＮＭＰ）が特に好ましい。
【００２０】
仕込みジハロ芳香族化合物のモル数ａと仕込みアルカリ金属硫化物のモル数ｂとの比ａ／ｂは、好ましくは１．００〜１．０６の範囲内になるように調製する。トリハロ芳香族化合物は、仕込みアルカリ金属硫化物１モルに対して、好ましくは０．０００５〜０．００７モルの範囲内となるように調整して、重合反応系に添加する。
仕込みアルカリ金属化合物１モルに対して、トリハロ芳香族化合物が０．０００５モル未満では、生成ポリアリーレンスルフィド樹脂の溶融状態における弾性が十分でないため、溶融状態から直接延伸した場合、十分に配向することができない。このため、得られた被覆層の強度が低下する。逆に、トリハロ芳香族化合物が０．００７モル超過では、生成ポリアリーレンスルフィド樹脂の溶融粘度が高くなるため、被覆時に樹脂切れを引き起こし、連続して均一な被覆物を得ることが困難となるため好ましくない。重合反応系へのトリハロ芳香族化合物の添加は、重合の初期であっても後期であってもよいが、初期の場合の方が少量の添加でもより効果的である。
【００２１】
重合方法については、従来公知の方法を採用することができ、特に限定されないが、具体例として、例えば、仕込みアルカリ金属硫化物１モル当たり０．５〜２．４モルの水が存在する状態で、１５０〜２３５℃の温度で反応を行って、ジハロ芳香族化合物の転化率５０〜９８モル％程度まで反応させ、次いで、仕込みアルカリ金属硫化物１モル当たり２．５〜７．０モルの水を反応系内に存在させて、２４５〜２８０℃の温度に昇温して反応を継続する方法を挙げることができる。極性有機溶媒の使用量は、アルカリ金属硫化物１モル当たり、通常、０．２〜２．０ｋｇ、好ましくは０．３〜１．０ｋｇである。
【００２２】
上記ポリアリーレンスルフィド樹脂を用いて連続して金属基材の被覆を行うには、押出機を用いて該樹脂の融点以上、好ましくは（融点＋２０℃）〜３５０℃の範囲の温度で溶融させた後、パリソンを形成させながらダイ外被覆により金属基材上に被覆する。被覆工程中、被覆金属体（即ち、樹脂被覆金属部材）は、ピンチローラによって一定の速度で引き取られ、ダイを通過する時、均一な被覆層が連続して形成される。次いで、被覆金属体は、冷却ゾーンで冷却された後、通常、巻き取り機等によって巻き取られる。
【００２３】
本発明では、被覆層の結晶化度及び機械的物性をコントロールし、所望の被覆金属体を得るために、押出機のダイから溶融樹脂を押し出し、パリソンを形成して金属基材を被覆した後、ピンチローラへ至るまでの間で、必要に応じ加熱ゾーンを設けて被覆金属体を熱処理することができる。被覆金属体の熱処理温度は、通常、１２０〜２９０℃、好ましくは１３０〜２７０℃である。熱処理時間（即ち、加熱ゾーンでの滞在時間）は、生産性、被覆膜厚、引き取り速度、樹脂の結晶化速度及び結晶化温度により変わり、一概には規定できないが、通常０．１秒以上１０分間以下の時間である。
【００２４】
また、本発明では、被覆層の結晶化度及び機械的物性をコントロールし、所望の被覆体を得るために、一旦引き取った被覆金属体を必要に応じ熱処理することができる。この場合、被覆金属体の熱処理温度は、通常、１２０〜２９０℃、好ましくは１３０〜２７０℃の範囲である。熱処理時間は、生産性、膜厚、引き取り速度、樹脂の結晶化速度及び結晶化温度により変わり、一概には規定できないが、通常１秒以上１００時間以下の時間である。１２０℃未満の温度で熱処理を行うと、十分に結晶化することができず、高温での寸法安定性あるいは表面性が損なわれることがあるため好ましくない。２９０℃を越える温度で熱処理を行うと、被覆層の変形により、表面性が損なわれることがある。熱処理時間が１秒未満では、十分に結晶化することができず、高温での寸法安定性あるいは表面性が損なわれることがあり、好ましくない。また、熱処理時間が長過ぎると、被覆層の変形により表面性が損なわれるので、好ましくない。一旦引き取った被覆金属体を熱処理する場合、被覆膜の伸度の面からは、熱処理温度を１９０℃以上とすることが好ましい。特に、好ましくは２００〜２７０℃、より好ましくは２３０〜２６０℃の熱処理温度で、１秒〜１０分間、より好ましくは１〜６０秒程度の熱処理時間の熱処理条件を採用することにより、高い破断伸度を達成することができる。
【００２５】
熱処理による被覆層の樹脂の結晶化度は、通常、３０％以下とすることが好ましい。結晶化度が３０％を越えると、被覆層が脆くなるおそれが生じる。被覆層の樹脂の結晶化度は、１５〜３０％の範囲とすることが好ましい。ただし、被覆層の伸度は、樹脂の結晶化度が同じであっても、熱処理温度が異なれば異なる傾向を示す。熱処理温度が高いほど、樹脂の結晶化度が同じかあるいは高い場合であっても、大きな伸度が得られやすい。一方、比較的低い熱処理温度で、熱処理時間を長くして結晶化度を高めた場合には、伸度が低下する傾向を示す。したがって、前記したとおり、熱処理温度を２００〜２７０℃とし、結晶化度が３０％を越えない熱処理時間で熱処理することが好ましい。
【００２６】
本発明における樹脂、被覆金属体においては、本発明の目的を損なわない範囲において、ポリアリーレンスルフィド樹脂の他に、混合可能な少量の別の成分を含んでいてもよい。他の成分としては、例えば、シリカ、タルク、マイカ、カオリン、炭酸カルシウム、リン酸マグネシウム、ガラス等の、粒状、粉末状あるいは鱗片状の無機充填剤、ガラス繊維、炭素繊維、マイカセラミック繊維等の繊維状の無機充填剤、ポリテトラフルオロエチレン、四フッ化・六フッ化エチレンコポリマー、エチレン・テトラフルオロエチレンコポリマー等のフッ素系樹脂、シリコン系エラストマー、アクリル系エラストマー、オレフィン系エラストマー、ポリアミド系エラストマー、フッ素系エラストマー等の耐衝撃剤、他の熱可塑性樹脂、熱硬化性樹脂、カップリング剤、滑剤、離型剤、安定剤、核剤等が例示される。
【００２７】
本発明のポリアリーレンスルフィド樹脂は、金属基材との密着性に優れているが、例えば、被覆電線などのように、作業上、被覆層が金属基材に対して適度なストリップ性を有することが要求される分野では、少量の離型剤を樹脂中に含有させることができる。離型剤としては、例えば、ペンタエリスリトールトリステアレート、ジアステアリルペンタエリスリトールジホスフェートなどの脂肪酸エステル類を挙げることができる。このような離型剤を配合することにより、金属基材と樹脂被覆層との間の密着性を適度に弱めて、ストリップ性を有する樹脂被覆金属部材を得ることができる。離型剤は、樹脂１００重量部に対して、通常、０．１〜３重量部の割合で使用する。安定剤としては、ポリアリーレンスルフィド樹脂用の公知のものを用いることができるが、樹脂を押出機のダイから安定的に溶融押出して被覆するには、例えば、水酸化バリウムなどが好ましい。安定剤は、樹脂１００重量部に対して、通常、０．１〜３重量部の割合で使用する。
【００２８】
金属基材としては、電線等の金属導体（金属導線）、金属棒、金属管、ワイヤー等の長尺の金属基材が挙げられる。ポリアリーレンスルフィド樹脂被覆層の厚みは、各用途及び所望の物性に応じて適宜定めることができる。
本発明によれば、耐熱性、耐フレオン性、難燃性、耐薬品性、耐放射線性、低温物性、電気絶縁性、機械的物性等に優れたポリアリーレンスルフィド樹脂からなる被覆層が形成された被覆電線などの樹脂被覆金属部材が得られる。その具体例としては、自動車や船舶のコントロールケーブル用索導管やコントロールケーブル用内索、耐熱性コイルやモーターの巻線、自動車ソレノイドリード線、コンプレッサーの耐フレオン電線、変圧器の巻線、原子力発電所用の耐放射線性機器配線、及びケーブル、金属棒、金属管、その他の耐熱配線、シース管、ワイヤー等の被覆金属部材が挙げられる。
【００２９】
【実施例】
以下に実施例、参考例及び比較例を挙げて、本発明についてより具体的に説明する。
【００３０】
［実施例１］
ポリマー合成例（１）
含水硫化ソーダ（純度４６．０６％）３７３ｋｇ、及びＮ−メチルピロリドン（以下、ＮＭＰと略記）８００ｋｇをチタン張り重合缶に仕込み、窒素ガス雰囲気下で徐々に約２００℃まで昇温しながら、５４．４モルの硫化水素と共に、水１４１ｋｇを留出させた。次に、ｐ−ジクロロベンゼン（以下、ｐ−ＤＣＢと略記）３２４．７ｋｇ、１，２，４−トリクロロベンゼン０．７９６ｋｇ、及びＮＭＰ２７４ｋｇの混合溶液を供給して、２２０℃で５時間重合反応を行った。次に、反応系に水９６．６ｋｇを圧入し、２５５℃で５時間重合反応を行った後、２４５℃に降温して５時間重合反応を継続した。重合反応終了後、反応系を冷却し、次いで、反応混合液を目開き１５０μｍ（１００メッシュ）のスクリーンで篩分し、粒状ポリマーを分離した。粒状ポリマーは、メタノール洗と水洗をそれぞれ３回行った後、脱水し、乾燥した。得られたポリマーの３１０℃、剪断速度２００／秒における溶融粘度は、１３１５Ｐａ・ｓで、Ｒ値は、２．６４であった。
【００３１】
金属被覆実験
上記で得られたポリマーを、３０ｍｍφ二軸混練押出機（プラスチック工学研究所製ＢＴ−３０型機）へ供給し、シリンダー温度３００℃〜３３０℃にて混練を行い、ペレット状物を得た。得られたペレット状物を、電線被覆用ダイを備えた二軸押出機（東洋精機製作所製ラボプラストミル）へ供給し、導線を被覆した。導線被覆条件は、シリンダー温度３３５℃、押出量８ｇ／分、引き取り速度１８ｍ／分、延伸倍率９．５、パリソンコーン長さ１５ｍｍ、導線と被覆膜間のエアー抜き減圧−１５ｃｍＨｇであった。導線として、電気用硬銅線０．４ｍｍφ（ＪＩＳ Ｃ３１０１）を用いた。被覆ダイは、マンドレル先端外径１．３ｍｍφで、ダイ内径２．２ｍｍφのものを用いた。
導線被覆中、樹脂切れを生ずることなく、６時間連続して安定的に被覆することができ、外径が０．７ｍｍφで、表面に凹凸のない被覆体が得られた。被覆体を冷却後、加熱ゾーンに導き、２５０℃、滞在時間３秒の条件で熱処理して、被覆樹脂を結晶化させてからロールに巻き取った。このようにして得られた被覆体は、曲げても被覆膜にクラック及び割れが生じなかった。被覆体から導線を抜き取り、被覆膜の引張試験を次の条件で行った。
引張試験
・試験機 ：（株）東洋ボールドウィン社製テンシロン
・試料長 ：１００ｍｍ
・引張速度：１００ｍｍ／分
その結果、被覆膜の引張破断強さは１３６ＭＰａで、破断伸びは１５０％であった。
【００３２】
［実施例２］
実施例１と同じペレット状物及び導線を用い、延伸倍率が５０倍となるように被覆条件を変えて被覆をした。導線被覆条件は、シリンダー温度３４０℃、押出量３４ｇ／分、引き取り速度１００ｍ／分、延伸倍率５０、パリソンコーン長さ４０ｍｍ、導線と被覆膜間のエアー抜き減圧−１５ｃｍＨｇ、被覆ダイのマンドレス先端外径２．８ｍｍφ、ダイ内径４．９ｍｍφであった。
被覆の実験の結果、外径０．７ｍｍφの被覆体が得られ、実施例１と同様の加熱処理を行った。得られた被覆体は、曲げても被覆膜にクラック及び割れが生じなかった。実施例１と同様にして引張試験を行った結果、被覆膜の引張破断強さは１７０ＭＰａで、破断伸びは１３５％であった。
【００３３】
［実施例３］
ポリマー合成例（２）
含水硫化ソーダ（純度４６．２１％）３７０ｋｇ、及びＮＭＰ８００ｋｇをチタン張り重合缶に仕込み、窒素ガス雰囲気下で徐々に約２００℃まで昇温しながら、５３．４モルの硫化水素と共に、水１４０．５ｋｇを留出させた。次に、ｐ−ＤＣＢ３２４ｋｇ、１，２，４−トリクロロベンゼン０．７９０ｋｇ、及びＮＭＰ２７０ｋｇの混合溶液を供給して、２２０℃で５時間重合反応を行った。次に、反応系に水９６．７ｋｇを圧入し、２５５℃で５時間重合反応を行った後、２４５℃に降温して５時間重合反応を継続した。重合反応終了後、反応系を冷却し、次いで、反応混合液を目開き１５０μｍ（１００メッシュ）のスクリーンで篩分して、粒状ポリマーを分離した。粒状ポリマーは、メタノール洗と水洗をそれぞれ３回行った後、脱水し、乾燥した。得られたポリマーの３１０℃、剪断速度２００／秒における溶融粘度は、７４９Ｐａ・ｓで、Ｒ値は、２．４３であった。
【００３４】
金属被覆実験
上記で得られたポリマーを、３０ｍｍφ二軸混練押出機（プラスチック工学研究所製ＢＴ−３０型機）へ供給し、シリンダー温度３００℃〜３２０℃にて混練を行い、ペレット状物を得た。得られたペレット状物を、電線被覆用ダイを備えた二軸押出機（東洋精機製作所製ラボプラストミル）へ供給し、シリンダー温度及び導線と被覆膜間のエアー抜き減圧を除く条件を実施例１と同じにして被覆を行った。シリンダー温度は３２０℃とし、導線と被覆膜間のエアー抜き減圧を−１３ｍｍＨｇとした。
導線被覆中、樹脂切れを生ずることなく、６時間連続して安定的に被覆することができ、外径が０．７ｍｍφで、表面に凹凸のない被覆体が得られた。被覆体を実施例１と同様に熱処理した。得られた被覆体は、曲げても被覆膜にクラック及び割れが生じなかった。実施例１と同様にして引張試験を行った結果、被覆膜の引張破断強さは１２５ＭＰａで、破断伸びは１１０％であった。
【００３５】
［実施例４］
ポリマー合成例（３）
含水硫化ソーダ（純度４６．１０％）３７１ｋｇ、及びＮＭＰ８００ｋｇをチタン張り重合缶に仕込み、窒素ガス雰囲気下で徐々に約２００℃まで昇温しながら、５４．０モルの硫化水素と共に、水１４０．０ｋｇを留出させた。次に、ｐ−ＤＣＢ３２５ｋｇ、１，２，４−トリクロロベンゼン０．８８５ｋｇとＮＭＰ２７０ｋｇとの混合溶液を供給して、２２０℃で５時間重合反応を行った。次いで、水９５．８ｋｇを圧入し、２５５℃で５時間重合反応を行った後、２４５℃に降温して５時間重合反応を継続した。重合反応終了後、反応系を冷却し、次いで、反応混合液を目開き１５０μｍ（１００メッシュ）のスクリーンで篩分し、粒状ポリマーを分離した。粒状ポリマーは、メタノール洗と水洗をそれぞれ３回行った後、脱水し、乾燥した。得られたポリマーの３１０℃、剪断速度２００／秒における溶融粘度は、７２６Ｐａ・ｓで、Ｒ値は、２．７２であった。
【００３６】
金属被覆実験
上記で得られたポリマーを、３０ｍｍφ二軸混練押出機（プラスチック工学研究所製ＢＴ−３０型機）へ供給し、シリンダー温度３００℃〜３２０℃にて混練を行い、ペレット状物を得た。得られたペレット状物を、電線被覆用ダイを備えた二軸押出機（東洋精機製作所製ラボプラストミル）へ供給し、エアー抜き減圧を−１０ｃｍＨｇとしたこと以外は実施例３と同じ被覆条件で導線被覆を行った。
導線被覆中、樹脂切れを生ずることなく、６時間連続して安定的に被覆することができ、外径が０．７ｍｍφで、表面に凹凸のない被覆体が得られた。被覆体を実施例１と同様に熱処理した。得られた被覆体は、曲げても被覆膜にクラック及び割れが生じなかった。実施例１と同様にして引張試験を行った結果、被覆膜の引張破断強さは１１０ＭＰａで、破断伸びは１０５％であった。
【００３７】
［実施例５］
ポリマー合成例（４）
含水硫化ソーダ（純度４６．１０％）３７３ｋｇ、及びＮＭＰ８１０ｋｇをチタン張り重合缶に仕込み、窒素ガス雰囲気下で徐々に約２００℃まで昇温しながら、５３．８モルの硫化水素と共に、水１４０．０ｋｇを留出させた。次に、ｐ−ＤＣＢ３２１．０ｋｇ、１，２，４−トリクロロベンゼン０．７９５ｋｇ、及びＮＭＰ２６６ｋｇの混合溶液を供給して、２２０℃で５時間重合反応を行った。次に、水９５．８ｋｇを圧入し、２５５℃で５時間重合反応を行った後、２４５℃に降温して５時間重合反応を継続した。重合反応終了後、反応系を冷却し、次いで、反応混合液を目開き１５０μｍ（１００メッシュ）のスクリーンで篩分し、粒状ポリマーを分離した。粒状ポリマーは、メタノール洗と水洗をそれぞれ３回行った後、脱水し、乾燥した。得られたポリマーの３１０℃、剪断速度２００／秒における溶融粘度は、１６００Ｐａ・ｓで、Ｒ値は、２．８８であった。
【００３８】
金属被覆実験
上記で得られたポリマーを、３０ｍｍφ二軸混練押出機（プラスチック工学研究所製ＢＴ−３０型機）へ供給し、シリンダー温度３００℃〜３３０℃にて混練を行い、ペレット状物を得た。得られたペレット状物を電線被覆用ダイを備えた二軸押出機（東洋精機製作所製ラボプラストミル）へ供給し、シリンダー温度３４５℃、押出量８ｇ／分、引き取り速度１８ｍ／分、延伸倍率９．５、パリソンコーン長さ２３ｍｍ、導線と被覆膜間のエアー抜き減圧−１５ｃｍＨｇの条件で、導線に被覆した。導線及び被覆ダイは、実施例１と同じものを用いた。
導線被覆中、樹脂切れを生ずることなく、６時間連続して安定的に被覆することができ、外径が０．７ｍｍφで、表面に凹凸のない被覆体が得られた。被覆体を実施例１と同様に熱処理した。得られた被覆体は、曲げても被覆膜にクラック及び割れが生じなかった。実施例１と同様にして引張試験を行った結果、被覆膜の引張破断強さは１４５ＭＰａで、破断伸びは１７０％であった。
【００３９】
［実施例６］
ポリマー合成例（５）
含水硫化ソーダ（純度４６．２１％）３７２ｋｇ、及びＮＭＰ８２０ｋｇをチタン張り重合缶に仕込み、窒素ガス雰囲気下で徐々に約２００℃まで昇温しながら、５３．９モルの硫化水素と共に、水１４０．５ｋｇを留出させた。次に、ｐ−ＤＣＢ３２６ｋｇ、１，２，４−トリクロロベンゼン０．８５６ｋｇ、及びＮＭＰ２５５ｋｇの混合溶液を供給して、２２０℃で５時間重合反応を行った。次に、水９６．２ｋｇを圧入し、２５５℃で５時間重合反応を行った後、２４５℃に降温して５時間重合反応を継続した。重合反応終了後、反応系を冷却し、次いで、反応混合液を目開き１５０μｍ（１００メッシュ）のスクリーンで篩分し、粒状ポリマーを分離した。粒状ポリマーは、メタノール洗と水洗をそれぞれ３回行った後、脱水し、乾燥した。得られたポリマーの３１０℃、剪断速度２００／秒における溶融粘度は、１１００Ｐａ・ｓで、Ｒ値は、２．８５であった。
【００４０】
金属被覆実験
上記で得られたポリマーを、３０ｍｍφ二軸混練押出機（プラスチック工学研究所製ＢＴ−３０型機）へ供給し、シリンダー温度３００℃〜３２０℃にて混練を行い、ペレット状物を得た。
得られたペレット状物を電線被覆用ダイを備えた二軸押出機（東洋精機製作所製ラボプラストミル）へ供給し、シリンダー温度３３０℃、押出量８ｇ／分、引き取り速度１８ｍ／分、延伸倍率９．５、パリソンコーン長さ１５ｍｍ、導線と被覆膜間のエアー抜き減圧−１８ｃｍＨｇの条件で、導線に被覆した。導線及び被覆ダイは、実施例１と同じものを用いた。
導線被覆中、樹脂切れを生ずることなく、６時間連続して安定的に被覆することができ、外径が０．７ｍｍφで、表面に凹凸のない被覆体が得られた。被覆体を実施例１と同様に熱処理した。得られた被覆体は、曲げても被覆膜にクラック及び割れが生じなかった。実施例１と同様にして引張試験を行った結果、被覆膜の引張破断強さは１４０ＭＰａで、破断伸びは１４０％であった。
【００４１】
［実施例７］
実施例６と同じペレット状物を用いて被覆を行った。被覆に際し、シリンダー温度３３０℃、押出量１０ｇ／分、引き取り速度２０ｍ／分、延伸倍率６．６、パリソンコーン長さ１５ｍｍ、導線と被覆膜間のエアー抜き減圧−１５ｃｍＨｇとした。導線及び被覆ダイは実施例１と同じものを用いた。
導線被覆中、樹脂切れを生ずることなく、６時間連続して安定的に被覆することができ、外径が０．８ｍｍφで、表面に凹凸のない被覆体が得られた。被覆体を温度２５０℃、滞在時間５秒で加熱処理を行った。得られた被覆体は、曲げても被覆膜にクラック及び割れが生じなかった。実施例１と同様にして引張試験を行った結果、引張破断強さは１３０ＭＰａで、破断伸びは１４５％であった。
【００４２】
［実施例８］
ポリマー合成例（６）
含水硫化ソーダ（純度４６．４０％）３７０ｋｇ、及びＮＭＰ８１０ｋｇをチタン張り重合缶に仕込み、窒素ガス雰囲気下で徐々に約２００℃まで昇温しながら、５４．０モルの硫化水素と共に、水１４０．０ｋｇを留出させた。次に、ｐ−ＤＣＢ３２０ｋｇ、１，２，４−トリクロロベンゼン０．４６５ｋｇ、及びＮＭＰ２６３ｋｇの混合溶液を供給して、２２０℃で５時間重合反応を行った。次に、水９６．５ｋｇを圧入し、２５５℃で５時間重合反応を行った後、２４５℃に降温して５時間重合反応を継続した。重合反応終了後、反応系を冷却し、次いで、反応混合液を目開き１５０μｍ（１００メッシュ）のスクリーンで篩分し、粒状ポリマーを分離した。粒状ポリマーは、メタノール洗と水洗をそれぞれ３回行った後、脱水し、乾燥した。得られたポリマーの３１０℃、剪断速度２００／秒における溶融粘度は、３４０Ｐａ・ｓで、Ｒ値は、２．１８であった。
【００４３】
金属被覆実験
上記で得られたポリマーを、３０ｍｍφ二軸混練押出機（プラスチック工学研究所製ＢＴ−３０型機）へ供給し、シリンダー温度２９０℃〜３１５℃にて混練を行い、ペレット状物を得た。得られたペレット状物を、電線被覆用ダイを備えた二軸押出機（東洋精機製作所製ラボプラストミル）へ供給し、シリンダー温度３１５℃、押出量８ｇ／分、引き取り速度１８ｍ／分、延伸倍率９．５、パリソンコーン長さ１０ｍｍ、導線と被覆膜間のエアー抜き減圧−１０ｃｍＨｇの条件で、導線に被覆した。導線及び被覆ダイは、実施例１と同じものを用いた。
導線被覆中、樹脂切れを生ずることなく、６時間連続して安定的に被覆することができ、外径が０．７ｍｍφで、表面に凹凸のない被覆体が得られた。被覆体を実施例１と同様に熱処理した。得られた被覆体は、曲げても被覆膜にクラック及び割れが生じなかった。実施例１と同様にして引張試験を行った結果、被覆膜の引張破断強さは１００ＭＰａで、破断伸びは１００％であった。
【００４４】
［参考例１］
ポリマー合成例（７）
含水硫化ソーダ（純度４６．２１％）３７２ｋｇ、及びＮＭＰ８２４ｋｇをチタン張り重合缶に仕込み、窒素ガス雰囲気下で徐々に約２００℃まで昇温しながら、５６．６モルの硫化水素と共に、水１４２．０ｋｇを留出させた。次いで、ｐ−ＤＣＢ３２２．２ｋｇ、１，２，４−トリクロロベンゼン０．７９６ｋｇ、及びＮＭＰ２４９ｋｇの混合溶液を供給して、２２０℃で５時間重合反応を行った。次に、水９６．８ｋｇを圧入して、２５５℃で５時間重合反応を行った後、２４５℃に降温して５時間重合反応を継続した。重合反応終了後、反応系を冷却し、次いで、反応混合液を目開き１５０μｍ（１００メッシュ）のスクリーンで篩分し、粒状ポリマーを分離した。粒状ポリマーは、メタノール洗と水洗をそれぞれ３回行った後、脱水し、乾燥した。得られたポリマーの３１０℃、剪断速度２００／秒における溶融粘度は、２１２５Ｐａ・ｓで、Ｒ値は、２．８０であった。
【００４５】
金属被覆実験
上記で得られたポリマーを、３０ｍｍφ二軸混練押出機（プラスチック工学研究所製ＢＴ−３０型機）へ供給し、シリンダー温度３１０℃〜３５０℃にて混練を行い、ペレット状物を得た。得られたペレット状物を、電線被覆用ダイを備えた二軸押出機（東洋精機製作所製ラボプラストミル）へ供給し、シリンダー温度３５０℃、押出量８ｇ／分、引き取り速度１５ｍ／分、延伸倍率６．６、パリソンコーン長さ１５ｍｍ、導線と被覆膜間のエアー抜き減圧−１５ｃｍＨｇの条件で、導線に被覆した。導線及び被覆ダイは、実施例１と同じものを用いた。
導線被覆中、樹脂切れを生ずることなく、６時間連続して安定的に被覆することができ、外径が０．８ｍｍφで、表面に凹凸のない被覆体が得られた。被覆体を実施例１と同様に熱処理した。得られた被覆体は、曲げても被覆膜にクラック及び割れが生じなかった。実施例１と同様にして引張試験を行った結果、被覆膜の引張破断強さは１２０ＭＰａで、破断伸びは６５％であった。
これらの実施例及び参考例のペレット化条件、電線被覆条件、熱処理条件、及び被覆体の評価結果を表１に一括して示す。
【００４６】
【表１】

【００４７】
［比較例１］
ポリマー合成例（８）
含水硫化ソーダ（純度４６．４０％）３９０ｋｇ、及びＮＭＰ８００ｋｇをチタン張り重合缶に仕込み、窒素ガス雰囲気下で徐々に約２００℃まで昇温しながら、５７．８モルの硫化水素と共に、水１４８．０ｋｇを留出させた。次いで、ｐ−ＤＣＢ３５４．６ｋｇ、１，２，４−トリクロロベンゼン８．２１０ｋｇ、及びＮＭＰ２１８ｋｇの混合溶液を供給して、２２０℃で４時間重合反応を行った。次に、水８５．６ｋｇを圧入し、０．６℃／分の速度で２５５℃まで昇温し、２５５℃で５時間重合反応を行った。重合反応終了後、反応系を冷却し、次いで、反応混合液を目開き１５０μｍ（１００メッシュ）のスクリーンで篩分し、粒状ポリマーを分離した。粒状ポリマーは、アセトン洗３回、水洗４回、０．６％の塩化アンモニウム水溶液洗１回、水洗１回、０．０６％の塩化アンモニウム水溶液洗１回を施し、脱水、乾燥した。得られたポリマーの３１０℃、剪断速度２００／秒における溶融粘度は、３１００Ｐａ・ｓで、Ｒ値は、４．０８であった。
金属被覆実験
上記で得られたポリマーを、３０ｍｍφ二軸混練押出機（プラスチック工学研究所製ＢＴ−３０型機）へ供給し、ペレット化しようとしたが、樹脂が溶融せず、ペレット状物を得ることができなかった。
【００４８】
［比較例２］
ポリマー合成例（９）
含水硫化ソーダ（純度４６．４０％）３９０ｋｇ、及びＮＭＰ８００ｋｇをチタン張り重合缶に仕込み、窒素ガス雰囲気下で徐々に約２００℃まで昇温しながら、５７．２モルの硫化水素と共に、水１４７．０ｋｇを留出させた。次いで、ｐ−ＤＣＢ３３７．５ｋｇとＮＭＰ２１９ｋｇとの混合溶液を供給して、２２０℃で４．５時間重合反応を行った。次に、水８０．８ｋｇを圧入し、２５５℃で２時間重合反応を行った後、２４５℃に降温して１１時間重合反応を継続した。重合反応終了後、反応系を冷却し、次いで、反応混合液を目開き１５０μｍ（１００メッシュ）のスクリーンで篩分し、粒状ポリマーを分離した。粒状ポリマーは、メタノール洗と水洗をそれぞれ３回行った後、脱水し、乾燥した。得られたポリマーの３１０℃、剪断速度２００／秒における溶融粘度は、９１６Ｐａ・ｓで、Ｒ値は、１．９０であった。
【００４９】
金属被覆実験
上記で得られたポリマーを、３０ｍｍφ二軸混練押出機（プラスチック工学研究所製ＢＴ−３０型機）へ供給し、シリンダー温度２９０℃〜３２０℃にて混練を行い、ペレット状物を得た。得られたペレット状物を、電線被覆用ダイを備えた二軸押出機（東洋精機製作所製ラボプラストミル）へ供給し、シリンダー温度３２０℃、押出量８ｇ／分、引き取り速度１８ｍ／分、延伸倍率９．５、パリソンコーン長さ２ｍｍ、導線と被覆膜間のエアー抜き減圧−０．５ｃｍＨｇの条件で、導線に被覆した。導線及び被覆ダイは、実施例１と同じものを用いた。
導線被覆中、１回／３時間の頻度で樹脂切れが起こった。樹脂の弾力性が乏しいため、導線と被覆膜間のエアー抜き減圧が困難であり、パリソンコーン長さを長くすることができなかった。なお、得られた被覆体の外径は０．７ｍｍφで、表面には凹凸がなく平滑であった。得られた被覆体を実施例１と同様の加熱処理を行った後、実施例１と同様にして引張試験を行った結果、引張破断強さは６７ＭＰａで、破断伸びは４％であった。この被覆体は、曲げると被覆膜にクラックが生じた。
【００５０】
［比較例３］
比較例２と同じペレット状物及び導線を用い、延伸倍率を変えて被覆をした。被覆条件は、シリンダー温度３３０℃、押出量１８ｇ／分、引き取り速度５０ｍ／分、延伸倍率５０、パリソンコーン長さ２ｍｍ、導線と被覆膜間のエアー抜き減圧−０．５５ｍＨｇ、被覆ダイのマンドレル先端外径２．８ｍｍφ、ダイのダイ内径４．９ｍｍφとした。導線被覆中、頻繁に樹脂切れが生じ、安定した被覆が困難であった。
【００５１】
［比較例４］
ポリマー合成例（１０）
含水硫化ソーダ（純度４６．２１％）４２０ｋｇ、及びＮＭＰ７２０ｋｇをチタン張り重合缶に仕込み、窒素ガス雰囲気下で徐々に約２００℃まで昇温しながら、６１．８モルの硫化水素と共に、水１６０．０ｋｇを留出させた。次いで、ｐ−ＤＣＢ３６３．６ｋｇとＮＭＰ２５０ｋｇとの混合溶液を供給して、２２０℃で４．５時間重合反応を行った。次に、水５６．５ｋｇを圧入し、２５５℃で５時間重合反応させた。重合反応終了後、反応系を冷却し、次いで、反応混合液を目開き１５０μｍ（１００メッシュ）のスクリーンで篩分し、粒状ポリマーを分離した。粒状ポリマーは、メタノール洗３回、水洗を３回、３％の塩化アンモニウム溶液洗１回、水洗２回を行い、水でリスラリーした後、塩酸を添加しｐＨ約５に調整し、脱水、乾燥した。得られたポリマーの３１０℃、剪断速度２００／秒における溶融粘度は、１９２Ｐａ・ｓで、Ｒ値は、１．３７であった。
【００５２】
金属被覆実験
上記で得られたポリマーを、３０ｍｍφ二軸混練押出機（プラスチック工学研究所製ＢＴ−３０型機）へ供給し、シリンダー温度２９０℃〜３０５℃にて混練を行い、ペレット状物を得た。得られたペレット状物を電線被覆用ダイを備えた二軸押出機（東洋精機製作所製ラボプラストミル）へ供給し、シリンダー温度３１０℃、押出量８ｇ／分、引き取り速度１８ｍ／分、延伸倍率９．５、パリソンコーン長さ２ｍｍ、導線と被覆膜間のエアー抜き減圧−０．４ｃｍＨｇの条件で、導線に被覆した。導線及び被覆ダイは、実施例１と同じものを用いた。
導線被覆中、２回／１時間の頻度で樹脂切れが起こった。樹脂の弾力性が乏しいため、導線と被覆膜間のエアー抜き減圧が困難であり、パリソンコーン長さを長くすることができなかった。得られた被覆体の外径は０．７ｍｍφで、表面には凹凸がなく平滑であった。得られた被覆体を、実施例１と同様の加熱処理を行った後、実施例１と同様にして引張試験を行った結果、引張破断強さは５８ＭＰａで、破断伸びは３％であった。この被覆体は、曲げると被覆膜にクラックが生じた。
【００５３】
［比較例５］
ポリマー合成例（１１）
含水硫化ソーダ（純度４６．４０％）３７２ｋｇ、及びＮＭＰ８０５ｋｇをチタン張り重合缶に仕込み、窒素ガス雰囲気下で徐々に約２００℃まで昇温しながら、５３．９モルの硫化水素と共に、水１４０．３ｋｇを留出させた。次いで、ｐ−ＤＣＢ３３０ｋｇ、１，２，４−トリクロロベンゼン０．９８９ｋｇ、及びＮＭＰ２７４ｋｇの混合溶液を供給して、２２０℃で５時間重合反応を行った。次に、水９７．３ｋｇを圧入し、２５５℃で１時間重合反応を行った後、２４０℃に降温して５時間重合反応を継続した。重合反応終了後、反応系を冷却し、次いで、反応混合液を目開き１５０μｍ（１００メッシュ）のスクリーンで篩分して、粒状ポリマーを分離した。粒状ポリマーは、メタノール洗と水洗をそれぞれ３回行った後、脱水し、乾燥した。得られたポリマーの３１０℃、剪断速度２００／秒における溶融粘度は、６００Ｐａ・ｓで、Ｒ値は、２．９８であった。
【００５４】
金属被覆実験
上記で得られたポリマーを、３０ｍｍφ二軸混練押出機（プラスチック工学研究所製ＢＴ−３０型機）へ供給し、シリンダー温度２９０℃〜３１０℃にて混練を行い、ペレット状物を得た。得られたペレット状物を、電線被覆用ダイを備えた二軸押出機（東洋精機製作所製ラボプラストミル）へ供給し、シリンダー温度３１５℃、押出量８ｇ／分、引き取り速度１８ｍ／分、延伸倍率９．５、パリソンコーン長さ５ｍｍ、導線と被覆膜間のエアー抜き減圧−０．５ｃｍＨｇの条件で、導線に被覆した。導線及び被覆ダイは、実施例１と同じものを用いた。
樹脂の延伸性が乏しく、導線被覆中、４回／１時間の頻度で樹脂切れが起こり連続して安定に被覆することが困難であった。得られた被覆体の外径は０．７ｍｍφで、表面には凹凸がなく平滑であった。得られた被覆体を実施例１と同様の加熱処理を行った後、実施例１と同様にして引張試験を行った結果、引張破断強さは５２Ｍｐａで、破断伸びは３％であった。この被覆体は、曲げると被覆膜にクラックが生じた。
これらの比較例のペレット化条件、電線被覆条件、熱処理条件、及び被覆体の評価結果を表２に一括して示す。
【００５５】
【表２】

【００５６】
［実施例１０］
実施例１のポリマー合成例（１）と同様にして、ポリマーを合成し、次いで、該ポリマーを用いて、実施例１と同様にして金属被覆実験を行い、被覆体（樹脂被覆導線）を得た。得られた被覆体を加熱ゾーンに導き、表３の各実験番号に示す熱処理温度と熱処理時間（滞留時間）の条件で熱処理して、被覆樹脂を結晶化させてからロールに巻き取った。実施例１と同様にして引張試験を行った。また、下記の方法により、被覆樹脂の結晶化度を測定した。結果を表３に示す。
結晶化度の測定法
密度勾配管法により被覆樹脂の密度を測定し、結晶密度１．４３ｇ／ｃｍ^３及び非晶密度１．３１９５ｇ／ｃｍ^３を基準にして、体積分率により、測定密度から結晶化度を算出した。
【００５７】
【表３】

表３の結果は、熱処理温度が異なれば、結晶化度がほぼ同じでも、破断伸度が異なることを示している。また、実験番号１、１１〜１４などに見られるように、熱処理温度が高いほど、高い破断伸度が得られやすい。
【００５８】
［実施例１１］
実施例１のポリマー合成例（１）と同様にして、ポリマーを合成し、次いで、該ポリマー１００重量部とペンタエリスリトールトリステアレート（日本油脂社製、ユニスターＨ４７６）１重量部をタンブラーミキサーで３分間混合して、樹脂組成物を得た。前記ポリマーに代えて、該樹脂組成物を用いたこと以外は、実施例１と同様にして金属被覆実験を行い、被覆体（樹脂被覆導線）を得た。得られた被覆体を冷却後、加熱ゾーンに導き、実施例１と同じ条件で熱処理して、被覆樹脂を結晶化させてからロールに巻き取った。実施例１と同様にして引張試験を行った結果、引張破断強度は１３４ＭＰａで、破断伸度は１８０％であった。この被覆体は、ストリップ性が良好であった。
【００５９】
［実施例１２］
実施例１のポリマー合成例（１）と同様にして、ポリマーを合成し、次いで、該ポリマー１００重量部と水酸化バリウム０．５重量部をタンブラーミキサーで３分間混合して、樹脂組成物を得た。前記ポリマーに代えて、該樹脂組成物を用いたこと以外は、実施例１と同様にして金属被覆実験を行い、被覆体（樹脂被覆導線）を得た。得られた被覆体を冷却後、加熱ゾーンに導き、実施例１と同じ条件で熱処理して、被覆樹脂を結晶化させてからロールに巻き取った。実施例１と同様にして引張試験を行った結果、引張破断強度は１２５ＭＰａで、破断伸度は１２０％であった。金属被覆実験では、１０時間連続して安定的に被覆することができた。
【００６０】
［実施例１３］
実施例１のポリマー合成例（１）と同様にして、ポリマーを合成し、次いで、該ポリマー１００重量部と水酸化バリウム０．５重量部とジステアリルペンタエリスリトールジホスフェート（Ｓｐｅｃｉａｌｌｙ Ｃｈｅｍｉｃａｌｓ社製）０．５重量部をタンブラーミキサーで３分間混合して、樹脂組成物を得た。前記ポリマーに代えて、該樹脂組成物を用いたこと以外は、実施例１と同様にして金属被覆実験を行い、被覆体（樹脂被覆導線）を得た。得られた被覆体を冷却後、加熱ゾーンに導き、実施例１と同じ条件で熱処理して、被覆樹脂を結晶化させてからロールに巻き取った。実施例１と同様にして引張試験を行った結果、引張破断強度は１２３ＭＰａで、破断伸度は１００％であった。金属被覆実験では、１０時間連続して安定的に被覆することができた。また、この被覆体は、ストリップ性が良好であった。
【００６１】
【発明の効果】
本発明によれば、金属基材上に被覆を行った場合に樹脂切れを起こすことなく安定して連続的に被覆することができ、被覆後に熱処理をした場合に、被覆層の樹脂割れを生じることがない金属被覆用ポリアリーレンスルフィド樹脂が提供される。また、本発明によれば、耐熱性、耐フレオン性、難燃性、耐薬品性、耐放射線性、低温物性、電気絶縁性、機械的物性等に優れた樹脂被覆層を有する樹脂被覆金属部材とその製造方法が提供される。
本発明は、自動車や船舶のコントロールケーブル用索導管やコントロールケーブル用内索、耐熱性コイルやモーター等の巻き線、自動車ソレノイドリード線、コンプレッサー等の耐フレオン電線、変圧器の巻線、原子力発電所用の耐放射線性機器配線及びケーブル、金属棒、金属管、その他の耐熱電線、シース管、ワイヤー等々の被覆に適用することができる。
【図面の簡単な説明】
【図１】 図１は、ポリアリーレンスルフィド樹脂の溶融粘度η_２００とＲ値との関係を示すグラフである。ＥＦＧＨの枠内が、本発明で使用する金属被覆用ポリアリーレンスルフィド樹脂の範囲である。[0001]
BACKGROUND OF THE INVENTION
  The present invention relates to a resin for metal coatingAndResin coated metal partsAnd method for producing the resin-coated metal memberMore specifically, a resin for metal coating comprising a polyarylene sulfide resin excellent in heat resistance, freon resistance, flame retardancy, chemical resistance, radiation resistance, low temperature properties, electrical insulation properties, mechanical properties, etc.,Resin-coated metal member coated with the resin, And method for manufacturing the memberAbout.
  The resin for metal coating and the resin-coated metal member of the present invention are a cable conduit for a control cable for automobiles and ships, an inner cable for a control cable, a winding of a heat resistant coil and a motor, a motor solenoid lead wire, a freon resistant such as a compressor. Used in a wide range of fields such as electric wires, transformer windings, radiation resistant equipment wiring for nuclear power plants, and cables, metal bars, metal tubes, other heat resistant wires, sheath tubes, wires.
[0002]
[Prior art]
  Polyarylene sulfide resins (PAS resins) represented by polyphenylene sulfide resins (PPS resins) are used in a wide range of fields as engineering plastics with excellent heat resistance, chemical resistance, flame retardancy, electrical insulation, etc. . Taking advantage of such excellent properties, polyarylene sulfide resin is expected to be used as a coating resin for electric wires, metal bars, and the like, and specific proposals have been made.
  For example, JP-A-60-185306 discloses melt extrusion at 310 ° C. from a nozzle having a pore diameter of 0.5 mm at a melt viscosity of 300 to 100,000 poise measured at 310 ° C. and a shear rate of 200 / sec. There has been proposed a method for producing an enameled wire-type covered electric wire by melt-extruding a polyphenylene sulfide resin having a primary draw ratio of 10 or more when spinning into a metal conductor. Japanese Patent Application Laid-Open No. 62-143307 proposes an insulated wire formed by extruding a polyphenylene sulfide resin composition having a melt index of 0.5 to 100 g / 10 min onto a conductor.
[0003]
  However, when polyarylene sulfide resin is melt-extruded onto a metal substrate such as a metal wire and a coating layer is continuously formed, the stretchability of the resin is poor. It was difficult to get things. Further, when the polyarylene sulfide resin-coated metal member is coated and then exposed to a high temperature to crystallize the resin, there is a problem that the coating layer breaks.
  Generally, when a resin is continuously coated on a metal substrate by a melt extrusion method, the resin is stretched in a molten state. At this time, it is necessary that a uniform coating layer is stably obtained without causing the resin to run out. Furthermore, it is necessary that the coating layer does not crack even if heat treatment is performed after coating. However, at present, no polyarylene sulfide resin for metal coating having physical properties suitable for applications such as coated electric wires has been found.
[0004]
[Problems to be solved by the invention]
  The object of the present invention is to provide a continuous coating stably without causing resin breakage when continuous coating is carried out on a metal substrate by a melt extrusion method. An object of the present invention is to provide a polyarylene sulfide resin for metal coating that does not cause cracking.
  Another object of the present invention is to form a polyarylene sulfide resin coating layer excellent in heat resistance, freon resistance, flame resistance, chemical resistance, radiation resistance, low temperature properties, electrical insulation properties, mechanical properties, etc. Resin-coated metal memberAnd its manufacturing methodIs to provide.
  As a result of diligent research to overcome the problems of the prior art, the present inventors have found that branched polyarylene sulfides obtained by polymerizing alkali metal sulfides and dihaloaromatic compounds in the presence of trihaloaromatic compounds. When using a selected resin that has a specific melt viscosity range and melting characteristics, it is excellent in processing without causing resin breakage even when stretched during melt coating on a metal substrate. It has been found that the coating layer does not crack when it is crystallized by heat treatment after coating.
  The coated metal member such as a coated electric wire coated with such a selected polyarylene sulfide resin has a coating layer with heat resistance, flame resistance, chemical resistance, freon resistance, radiation resistance, electrical insulation, low temperature In addition to exhibiting excellent properties inherent in polyarylene sulfide resins such as properties, they are excellent in mechanical properties such as flex resistance, tensile strength, tensile elongation, and flexibility.
  The present invention has been completed based on these findings.
[0005]
[Means for Solving the Problems]
  According to the present invention, a branched polyarylene sulfide resin obtained by polymerizing an alkali metal sulfide and a dihaloaromatic compound in the presence of a trihaloaromatic compound, measured at 310 ° C. and a shear rate of 200 / sec. Melt viscosity η₂₀₀But300-2000Pa · s, the melt viscosity η₂₀₀And melt viscosity η measured at 310 ° C. and a shear rate of 1200 / sec.₁₂₀₀Ratio R (η₂₀₀/ Η₁₂₀₀) Is the following relational expression (1):
[Expression 4]

TheProvided is a metal coating resin characterized by comprising a satisfactory polyarylene sulfide resin.The
[0006]
  According to the present invention, there is also provided a branched polyarylene sulfide resin obtained by polymerizing an alkali metal sulfide and a dihaloaromatic compound in the presence of a trihaloaromatic compound, which is 310 ° C. at a shear rate of 200 / sec. Measured melt viscosity η₂₀₀But300-2000Pa · s, the melt viscosity η₂₀₀And melt viscosity η measured at 310 ° C. and a shear rate of 1200 / sec.₁₂₀₀Ratio R (η₂₀₀/ Η₁₂₀₀) Is the following relational expression (1):
[Equation 5]

There is provided a resin-coated metal member obtained by coating a metal substrate with a metal coating resin comprising a polyarylene sulfide resin satisfying the above.
[0007]
  Furthermore, according to the present invention, there is provided a branched polyarylene sulfide resin obtained by polymerizing an alkali metal sulfide and a dihaloaromatic compound in the presence of a trihaloaromatic compound, which is obtained at 310 ° C. and a shear rate of 200 / sec. Measured melt viscosity η ₂₀₀ Is 300 to 2000 Pa · s, the melt viscosity η ₂₀₀ And melt viscosity η measured at 310 ° C. and a shear rate of 1200 / sec. ₁₂₀₀ Ratio R (η ₂₀₀ / Η ₁₂₀₀ ) Is the following relational expression (1):
[Formula 6]

A metal coating resin comprising a polyarylene sulfide resin satisfying the above conditions is melted at a temperature in the range of (melting point + 20 ° C.) to 350 ° C. using an extruder, and then coated with a die outside while forming a parison. Then, after cooling the coated body, the coated body is cooled and then heat treated under the conditions of a heat treatment temperature of 200 to 270 ° C. and a heat treatment time of 0.1 seconds to 10 minutes to increase the crystallinity of the resin of the coating layer. There is provided a method for producing a resin-coated metal member characterized by being in the range of 15 to 30%.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
  The present invention is characterized in that the following specific selected polyarylene sulfide is used as the metal coating resin.
  1. A branched polyarylene sulfide resin obtained by polymerizing an alkali metal sulfide and a dihaloaromatic compound in the presence of a trihaloaromatic compound.
  2. Melt viscosity η measured at 310 ° C. and shear rate 200 / sec₂₀₀Is within the range of the following formula (2).
[0009]
[Expression 7]

  3. The melt viscosity η₂₀₀And melt viscosity η measured at 310 ° C. and a shear rate of 1200 / sec.₁₂₀₀And the ratio R (R = η₂₀₀/ Η₁₂₀₀) Satisfies the relational expression (1).
[0010]
[Equation 8]

[0011]
  As a result of earnestly studying continuous coating on a metal substrate using a polyarylene sulfide resin, the present inventors have used the selected polyarylene sulfide resin that satisfies the above requirements 1 to 3, It has been found that a coating that can be stably melt-coated and has excellent mechanical properties can be obtained.
  The polyarylene sulfide resin used in the present invention is not a complete linear resin obtained only from an alkali metal sulfide and a dihaloaromatic compound, but a branch obtained by coexisting a small amount of a trihaloaromatic compound that is a trifunctional monomer. Mold resin. By adopting such a branched type, a polyarylene sulfide resin satisfying the relational expression (1) can be obtained, and when the resin is coated on a metal substrate, excellent workability and mechanical properties are obtained. Can be obtained. On the other hand, the crosslinkable resin obtained by oxidative crosslinking (curing) of polyarylene sulfide resin having a low molecular weight in the presence of air generates a gel-like substance during melt stretching and has poor processability. In addition, the practicality is poor in terms of the strength of the coating layer, adhesion to the metal substrate, wear resistance, dielectric breakdown resistance, heat resistance, and the like.
[0012]
  The polyarylene sulfide resin used in the present invention has a melt viscosity η measured at 310 ° C. and a shear rate of 200 / sec.₂₀₀ 3It is 00 to 2000 Pa · s. Melt viscosity η₂₀₀But300When it is less than Pa · s, when the polyarylene sulfide resin is extruded from the die, the elasticity in the molten state is poor and it becomes difficult to stretch. Melt viscosity η₂₀₀But2000When it exceeds Pa · s, the generation of gel-like substances becomes remarkable, the workability is lowered, and the bending resistance and flexibility of the coating layer are lowered. The polyarylene sulfide resin used in the present invention needs to satisfy the relational expression (1). R (η₂₀₀/ Η₁₂₀₀) Is in the range represented by the following formula (3), when the molten resin is extruded from a die, it is difficult to stretch because the elasticity in the molten state is poor.
[0013]
[Equation 9]

  When R is in the range represented by the following formula (4), uniform stretching becomes difficult, and a lot of uneven uneven portions are generated in the coating layer.
[0014]
[Expression 10]

[0015]
  FIG. 1 shows the melt viscosity η of polyarylene sulfide resin.₂₀₀The relationship between (horizontal axis) and R value (vertical axis) is shown. The polyarylene sulfide resin used in the present invention is within the range surrounded by four points of ABCD in FIG.And within the range surrounded by four points of EFGHbelongs to. The white square marks in FIG.And Reference Example 1The characteristic values of the resin obtained in (1) are plotted, and the black triangle marks plot the characteristic values of the resins of the comparative examples. The polyarylene sulfide resin having the above-described melt viscosity and melt characteristics can be obtained by appropriately controlling the ratio of each monomer and polymerization conditions when polymerizing an alkali metal sulfide and a dihaloaromatic compound in the presence of a trihaloaromatic compound. Can be obtained.
[0016]
  Examples of the alkali metal sulfide include sodium sulfide, potassium sulfide, lithium sulfide, rubidium sulfide, cesium sulfide, and a mixture thereof. Moreover, you may produce | generate an alkali metal sulfide in situ in reaction container by a conventional method. These alkali metal sulfides can be used in the form of hydrates, aqueous mixtures or anhydrides. Add a small amount of alkali metal hydroxide to react with alkali metal bisulfide or alkali metal thiosulfate present in trace amounts in the alkali metal sulfide to remove these impurities, or to the sulfide It may be converted. Among these, sodium sulfide is industrially preferable because it is the cheapest.
[0017]
  Examples of dihaloaromatic compounds include dihalobenzenes such as p-dichlorobenzene, m-dichlorobenzene, o-dichlorobenzene, and p-dibromobenzene; 2,5-dichlorotoluene, 1-methoxy-2,5-dichlorobenzene, and the like Dihalobenzenes such as 1,4-dichloronaphthalene; dihalobiphenyls such as 4,4′-dichlorobiphenyl and 3,3′-dichlorobiphenyl; dihalobenzoic acids such as 3,5-dichlorobenzoic acid; Dihalobenzophenones such as 4,4'-dichlorobenzophenone; dihalodiphenyl sulfones such as 4,4'-dichlorodiphenylsulfone and 3,3'-dichlorodiphenylsulfone; dihalophenyl ethers such as 4,4'-dichlorodiphenyl ether And the like.
  Among these, from the viewpoints of economy and physical properties, dihalobenzene is preferable, and p-dihalobenzene such as p-dichlorobenzene is more preferable. In particular, the dihaloaromatic compound preferably contains p-dihalobenzene in a proportion of preferably 70% by weight or more, more preferably 80% by weight or more, and still more preferably 90% by weight or more.
[0018]
  Examples of the trihalo aromatic compound include 1,2,3-trichlorobenzene, 1,2,3-tribromobenzene, 1,2,4-trichlorobenzene, 1,2,4-tribromobenzene, 1,3. , 5-trichlorobenzene, 1,3,5-tribromobenzene, trihalobenzene such as 1,3-dichloro-5-bromobenzene; alkyl substituent of trihalobenzene; a mixture thereof. Among these, 1,2,4-trihalobenzene, 1,3,5-trihalobenzene, and 1,2,3-trichlorobenzene are preferable from the viewpoints of economy, reactivity, physical properties, and the like.
[0019]
  As a method for producing the polyarylene sulfide resin, a method in which an alkali metal sulfide and a dihaloaromatic compound are subjected to a polycondensation reaction in the presence of a trihaloaromatic compound in a polar organic solvent containing water can be employed. . Examples of water include hydration water of alkali metal sulfide, added water, reaction water, water of alkali metal sulfide aqueous solution, and the like. Examples of the organic amide solvent include N-methylpyrrolidone, N-ethylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylcaprolactam, dimethylimidazolidinone, tetramethylurea, hexamethylphosphonic acid amide. Etc. Among these, N-methyl-2-pyrrolidone (NMP) is particularly preferable from the viewpoints of economy and stability.
[0020]
  The ratio a / b between the number of moles of charged dihaloaromatic compound a and the number of moles of charged alkali metal sulfide b is:GoodPreferably, it prepares so that it may become in the range of 1.00-1.06. The trihaloaromatic compound is used for 1 mole of the alkali metal sulfide charged.GoodPreferably, it adjusts so that it may become in the range of 0.0005-0.007 mol, and adds to a polymerization reaction system.
  Trihaloaromatic compound is added to 1 mol of charged alkali metal compound.0.0005If it is less than the mole, the resulting polyarylene sulfide resin is not sufficiently elastic in the molten state, and therefore, when it is stretched directly from the molten state, it cannot be sufficiently oriented. For this reason, the intensity | strength of the obtained coating layer falls. Conversely, trihaloaromatic compounds0.007If the molar excess is exceeded, the melt viscosity of the resulting polyarylene sulfide resin will be high, and this will lead to a loss of resin during coating, making it difficult to obtain a uniform coating continuously. The addition of the trihaloaromatic compound to the polymerization reaction system may be early or late in the polymerization, but the initial case is more effective with a small amount.
[0021]
  The polymerization method may be a conventionally known method, and is not particularly limited. As a specific example, for example, in a state where 0.5 to 2.4 mol of water per 1 mol of charged alkali metal sulfide exists. The reaction is carried out at a temperature of 150 to 235 ° C. until the conversion of the dihaloaromatic compound is about 50 to 98 mol%, and then 2.5 to 7.0 mol of water per mol of the charged alkali metal sulfide. Can be present in the reaction system, and the reaction can be continued by raising the temperature to 245 to 280 ° C. The amount of the polar organic solvent used is usually 0.2 to 2.0 kg, preferably 0.3 to 1.0 kg per mole of alkali metal sulfide.
[0022]
  In order to continuously coat the metal substrate using the polyarylene sulfide resin, it was melted at a temperature equal to or higher than the melting point of the resin, preferably (melting point + 20 ° C.) to 350 ° C., using an extruder. Then, it coat | covers on a metal base material by die | dye coating | covering, forming a parison. During the coating process, the coated metal body (that is, the resin-coated metal member) is taken up at a constant speed by a pinch roller, and a uniform coating layer is continuously formed as it passes through the die. Next, after the coated metal body is cooled in the cooling zone, it is usually wound up by a winder or the like.
[0023]
  In the present invention, after controlling the crystallinity and mechanical properties of the coating layer and obtaining a desired coated metal body, after extruding the molten resin from the die of the extruder, forming a parison, and coating the metal substrate In the period up to the pinch roller, if necessary, a heating zone can be provided to heat-treat the coated metal body. The heat treatment temperature of the coated metal body is usually 120 to 290 ° C, preferably 130 to 270 ° C. The heat treatment time (that is, the residence time in the heating zone) varies depending on productivity, coating film thickness, take-off speed, resin crystallization speed and crystallization temperature, and cannot generally be specified, but usually 0.1 seconds or longer The time is 10 minutes or less.
[0024]
  Moreover, in this invention, in order to control the crystallinity degree and mechanical physical property of a coating layer, and to obtain a desired coating body, the coated metal body once taken can be heat-processed as needed. In this case, the heat treatment temperature of the coated metal body is usually in the range of 120 to 290 ° C, preferably 130 to 270 ° C. The heat treatment time varies depending on productivity, film thickness, take-off speed, resin crystallization speed and crystallization temperature, and cannot be generally specified, but is usually 1 second to 100 hours. When heat treatment is performed at a temperature of less than 120 ° C., it is not preferable because crystallization cannot be sufficiently performed and dimensional stability or surface properties at high temperatures may be impaired. When heat treatment is performed at a temperature exceeding 290 ° C., surface properties may be impaired due to deformation of the coating layer. If the heat treatment time is less than 1 second, it cannot be sufficiently crystallized, and the dimensional stability or surface property at high temperature may be impaired, which is not preferable. Further, if the heat treatment time is too long, the surface property is impaired by deformation of the coating layer, which is not preferable. When the coated metal body once taken is heat-treated, the heat treatment temperature is preferably set to 190 ° C. or higher from the viewpoint of the elongation of the coating film. In particular, by adopting heat treatment conditions of a heat treatment time of preferably 200 to 270 ° C., more preferably 230 to 260 ° C. for 1 second to 10 minutes, more preferably about 1 to 60 seconds, Degree can be achieved.
[0025]
  In general, the crystallinity of the resin of the coating layer by heat treatment is preferably 30% or less. If the crystallinity exceeds 30%, the coating layer may become brittle. The crystallinity of the resin of the coating layer is preferably in the range of 15 to 30%. However, even if the degree of crystallinity of the resin is the same, the elongation of the coating layer tends to be different if the heat treatment temperature is different. The higher the heat treatment temperature, the easier it is to obtain a high degree of elongation even when the crystallinity of the resin is the same or higher. On the other hand, when the crystallinity is increased by increasing the heat treatment time at a relatively low heat treatment temperature, the elongation tends to decrease. Therefore, as described above, it is preferable to perform the heat treatment at a heat treatment temperature of 200 to 270 ° C. and a heat treatment time in which the crystallinity does not exceed 30%.
[0026]
  The resin and the coated metal body in the present invention may contain a small amount of other components that can be mixed in addition to the polyarylene sulfide resin as long as the object of the present invention is not impaired. Other components include, for example, silica, talc, mica, kaolin, calcium carbonate, magnesium phosphate, glass, etc., granular, powdery or scale-like inorganic fillers, glass fiber, carbon fiber, mica ceramic fiber, etc. Fibrous inorganic fillers, polytetrafluoroethylene, tetrafluoride / hexafluoroethylene copolymers, fluorine resins such as ethylene / tetrafluoroethylene copolymers, silicone elastomers, acrylic elastomers, olefin elastomers, polyamide elastomers, Examples include impact resistance agents such as fluorine-based elastomers, other thermoplastic resins, thermosetting resins, coupling agents, lubricants, mold release agents, stabilizers, and nucleating agents.
[0027]
  The polyarylene sulfide resin of the present invention is excellent in adhesion to a metal substrate. For example, the coated layer has an appropriate strip property with respect to the metal substrate, such as a covered electric wire. In a field that requires a small amount, a small amount of a release agent can be contained in the resin. Examples of the releasing agent include fatty acid esters such as pentaerythritol tristearate and distearyl pentaerythritol diphosphate. By blending such a release agent, the adhesiveness between the metal substrate and the resin coating layer is moderately weakened, and a resin-coated metal member having stripping properties can be obtained. The release agent is usually used at a ratio of 0.1 to 3 parts by weight with respect to 100 parts by weight of the resin. As the stabilizer, known ones for polyarylene sulfide resins can be used, but for example, barium hydroxide is preferable in order to stably melt and extrude the resin from a die of an extruder. The stabilizer is usually used at a ratio of 0.1 to 3 parts by weight with respect to 100 parts by weight of the resin.
[0028]
  Examples of the metal substrate include long metal substrates such as metal conductors (metal conductors) such as electric wires, metal rods, metal tubes, and wires. The thickness of the polyarylene sulfide resin coating layer can be appropriately determined according to each application and desired physical properties.
  According to the present invention, a coating layer made of a polyarylene sulfide resin excellent in heat resistance, freon resistance, flame resistance, chemical resistance, radiation resistance, low temperature properties, electrical insulation properties, mechanical properties, etc. is formed. A resin-coated metal member such as a coated electric wire is obtained. Specific examples include control cable ropes and control cable inner cables for automobiles and ships, heat-resistant coils and motor windings, automobile solenoid leads, compressor freon-resistant wires, transformer windings, and nuclear power generation. Examples of the radiation-resistant equipment wiring for use, and coated metal members such as cables, metal rods, metal tubes, other heat-resistant wires, sheath tubes, and wires.
[0029]
【Example】
  Examples belowReference exampleThe present invention will be described more specifically with reference to comparative examples.
[0030]
[Example 1]
Polymer synthesis example (1)
  373 kg of hydrous sodium sulfide (purity 46.06%) and 800 kg of N-methylpyrrolidone (hereinafter abbreviated as NMP) were charged into a titanium-clad polymerization can and gradually heated to about 200 ° C. in a nitrogen gas atmosphere. 141 kg of water was distilled with 4 mol of hydrogen sulfide. Next, a mixed solution of 324.7 kg of p-dichlorobenzene (hereinafter abbreviated as p-DCB), 0.796 kg of 1,2,4-trichlorobenzene and 274 kg of NMP was supplied, and the polymerization reaction was performed at 220 ° C. for 5 hours. went. Next, 96.6 kg of water was injected into the reaction system, a polymerization reaction was performed at 255 ° C. for 5 hours, and then the temperature was lowered to 245 ° C. and the polymerization reaction was continued for 5 hours. After completion of the polymerization reaction, the reaction system was cooled, and then the reaction mixture was sieved with a screen having an opening of 150 μm (100 mesh) to separate the granular polymer. The granular polymer was dehydrated and dried after washing with methanol and washing with water three times. The obtained polymer had a melt viscosity of 1315 Pa · s at 310 ° C. and a shear rate of 200 / sec, and an R value of 2.64.
[0031]
Metal coating experiment
  The polymer obtained above was supplied to a 30 mmφ twin-screw kneading extruder (BT-30 machine manufactured by Plastics Engineering Laboratory) and kneaded at a cylinder temperature of 300 ° C. to 330 ° C. to obtain a pellet. The obtained pellet-like material was supplied to a twin-screw extruder (laboroplast mill manufactured by Toyo Seiki Seisakusho Co., Ltd.) equipped with a wire coating die, and the conductive wire was coated. The conducting wire coating conditions were a cylinder temperature of 335 ° C., an extrusion rate of 8 g / min, a take-up speed of 18 m / min, a draw ratio of 9.5, a parison cone length of 15 mm, and an air venting reduced pressure of 15 cmHg between the conducting wire and the coating film. As the conducting wire, an electric hard copper wire 0.4 mmφ (JIS C3101) was used. A coating die having a mandrel tip outer diameter of 1.3 mmφ and a die inner diameter of 2.2 mmφ was used.
  During the coating of the lead wire, it was possible to stably coat continuously for 6 hours without causing the resin to run out, and a coated body having an outer diameter of 0.7 mmφ and having no irregularities on the surface was obtained. After cooling the coated body, it was led to a heating zone and heat-treated under the conditions of 250 ° C. and a residence time of 3 seconds to crystallize the coated resin and wound up on a roll. The coated body thus obtained did not crack or crack in the coating film even when bent. A conducting wire was extracted from the covering, and a tensile test of the covering film was performed under the following conditions.
Tensile test
・ Testing machine: Tensilon manufactured by Toyo Baldwin Co., Ltd.
・ Sample length: 100 mm
・ Tensile speed: 100 mm / min
  As a result, the tensile breaking strength of the coating film was 136 MPa, and the breaking elongation was 150%.
[0032]
[Example 2]
  Using the same pellets and conducting wire as in Example 1, the coating conditions were changed so that the draw ratio was 50 times. Conductor coating conditions are: cylinder temperature 340 ° C., extrusion rate 34 g / min, take-off speed 100 m / min, draw ratio 50, parison cone length 40 mm, air venting reduced pressure between conductor and coating film −15 cmHg, coated die mandrel The tip outer diameter was 2.8 mmφ and the die inner diameter was 4.9 mmφ.
  As a result of the coating experiment, a coated body having an outer diameter of 0.7 mmφ was obtained, and the same heat treatment as in Example 1 was performed. Even if the obtained covering was bent, cracks and cracks did not occur in the covering film. As a result of conducting a tensile test in the same manner as in Example 1, the tensile breaking strength of the coating film was 170 MPa and the breaking elongation was 135%.
[0033]
[Example 3]
Polymer synthesis example (2)
  370 kg of hydrous sodium sulfide (purity: 46.21%) and 800 kg of NMP were charged into a titanium-clad polymerization can and gradually heated to about 200 ° C. in a nitrogen gas atmosphere, together with 53.4 mol of hydrogen sulfide and 140. 5 kg was distilled off. Next, a mixed solution of 324 kg of p-DCB, 0.790 kg of 1,2,4-trichlorobenzene and 270 kg of NMP was supplied, and a polymerization reaction was performed at 220 ° C. for 5 hours. Next, 96.7 kg of water was injected into the reaction system, a polymerization reaction was carried out at 255 ° C. for 5 hours, and then the temperature was lowered to 245 ° C. and the polymerization reaction was continued for 5 hours. After completion of the polymerization reaction, the reaction system was cooled, and then the reaction mixture was sieved with a screen having an opening of 150 μm (100 mesh) to separate the granular polymer. The granular polymer was dehydrated and dried after washing with methanol and washing with water three times. The melt viscosity of the obtained polymer at 310 ° C. and a shear rate of 200 / sec was 749 Pa · s, and the R value was 2.43.
[0034]
Metal coating experiment
  The polymer obtained above was supplied to a 30 mmφ biaxial kneader-extruder (BT-30 machine manufactured by Plastics Engineering Laboratory) and kneaded at a cylinder temperature of 300 ° C. to 320 ° C. to obtain a pellet. Supply the obtained pellets to a twin-screw extruder equipped with a wire coating die (laboro plast mill, manufactured by Toyo Seiki Seisakusho) under conditions other than the cylinder temperature and the air pressure reduction between the conductor and the coating film. Coating was carried out in the same manner as in Example 1. The cylinder temperature was 320 ° C., and the decompression pressure between the conductor and the coating film was −13 mmHg.
  During the coating of the lead wire, it was possible to stably coat continuously for 6 hours without causing the resin to run out, and a coated body having an outer diameter of 0.7 mmφ and having no irregularities on the surface was obtained. The coated body was heat-treated as in Example 1. Even if the obtained covering was bent, cracks and cracks did not occur in the covering film. As a result of conducting a tensile test in the same manner as in Example 1, the tensile breaking strength of the coating film was 125 MPa, and the breaking elongation was 110%.
[0035]
[Example 4]
Polymer synthesis example (3)
  371 kg of hydrous sodium sulfide (purity: 46.10%) and 800 kg of NMP were charged into a titanium-clad polymerization can and gradually heated to about 200 ° C. in a nitrogen gas atmosphere. 0 kg was distilled off. Next, a mixed solution of 325 kg of p-DCB, 0.885 kg of 1,2,4-trichlorobenzene and 270 kg of NMP was supplied, and a polymerization reaction was performed at 220 ° C. for 5 hours. Next, 95.8 kg of water was injected and the polymerization reaction was carried out at 255 ° C. for 5 hours, and then the temperature was lowered to 245 ° C. and the polymerization reaction was continued for 5 hours. After completion of the polymerization reaction, the reaction system was cooled, and then the reaction mixture was sieved with a screen having an opening of 150 μm (100 mesh) to separate the granular polymer. The granular polymer was dehydrated and dried after washing with methanol and washing with water three times. The obtained polymer had a melt viscosity of 726 Pa · s at 310 ° C. and a shear rate of 200 / sec, and an R value of 2.72.
[0036]
Metal coating experiment
  The polymer obtained above was supplied to a 30 mmφ biaxial kneader-extruder (BT-30 machine manufactured by Plastics Engineering Laboratory) and kneaded at a cylinder temperature of 300 ° C. to 320 ° C. to obtain a pellet. The obtained pellet-like material was supplied to a twin-screw extruder (Laboplast Mill manufactured by Toyo Seiki Seisakusho Co., Ltd.) equipped with a wire coating die, and the same coating conditions as in Example 3 except that the air vent pressure was reduced to -10 cmHg. Conductive wire coating was performed.
  During the coating of the lead wire, it was possible to stably coat continuously for 6 hours without causing the resin to run out, and a coated body having an outer diameter of 0.7 mmφ and having no irregularities on the surface was obtained. The coated body was heat-treated as in Example 1. Even if the obtained covering was bent, cracks and cracks did not occur in the covering film. As a result of conducting a tensile test in the same manner as in Example 1, the tensile breaking strength of the coating film was 110 MPa, and the breaking elongation was 105%.
[0037]
[Example 5]
Polymer synthesis example (4)
  373 kg of hydrous sodium sulfide (purity 46.10%) and 810 kg of NMP were charged into a titanium-clad polymerization can and gradually heated to about 200 ° C. in a nitrogen gas atmosphere, together with 53.8 mol of hydrogen sulfide and water 140. 0 kg was distilled off. Next, a mixed solution of 321.0 kg of p-DCB, 0.795 kg of 1,2,4-trichlorobenzene and 266 kg of NMP was supplied, and a polymerization reaction was performed at 220 ° C. for 5 hours. Next, 95.8 kg of water was injected and the polymerization reaction was carried out at 255 ° C. for 5 hours, and then the temperature was lowered to 245 ° C. and the polymerization reaction was continued for 5 hours. After completion of the polymerization reaction, the reaction system was cooled, and then the reaction mixture was sieved with a screen having an opening of 150 μm (100 mesh) to separate the granular polymer. The granular polymer was dehydrated and dried after washing with methanol and washing with water three times. The melt viscosity of the obtained polymer at 310 ° C. and a shear rate of 200 / sec was 1600 Pa · s, and the R value was 2.88.
[0038]
Metal coating experiment
  The polymer obtained above was supplied to a 30 mmφ twin-screw kneading extruder (BT-30 machine manufactured by Plastics Engineering Laboratory) and kneaded at a cylinder temperature of 300 ° C. to 330 ° C. to obtain a pellet. The obtained pellets were supplied to a twin-screw extruder equipped with a wire coating die (Laboplast Mill manufactured by Toyo Seiki Seisakusho), cylinder temperature 345 ° C., extrusion rate 8 g / min, take-up speed 18 m / min, draw ratio The conductor wire was coated under the conditions of 9.5, parison cone length of 23 mm, and air-bleeding reduced pressure between the conductor wire and the coating film—15 cmHg. The same conductors and coating dies as in Example 1 were used.
  During the coating of the lead wire, it was possible to stably coat continuously for 6 hours without causing the resin to run out, and a coated body having an outer diameter of 0.7 mmφ and having no irregularities on the surface was obtained. The coated body was heat-treated as in Example 1. Even if the obtained covering was bent, cracks and cracks did not occur in the covering film. As a result of conducting a tensile test in the same manner as in Example 1, the tensile breaking strength of the coating film was 145 MPa and the breaking elongation was 170%.
[0039]
[Example 6]
Polymer synthesis example (5)
  372 kg of hydrous sodium sulfide (purity: 46.21%) and 820 kg of NMP were charged into a titanium-clad polymerization can and gradually heated to about 200 ° C. in a nitrogen gas atmosphere, together with 53.9 mol of hydrogen sulfide and 140. 5 kg was distilled off. Next, a mixed solution of 326 kg of p-DCB, 0.856 kg of 1,2,4-trichlorobenzene and 255 kg of NMP was supplied, and a polymerization reaction was performed at 220 ° C. for 5 hours. Next, 96.2 kg of water was injected and the polymerization reaction was performed at 255 ° C. for 5 hours, and then the temperature was lowered to 245 ° C. and the polymerization reaction was continued for 5 hours. After completion of the polymerization reaction, the reaction system was cooled, and then the reaction mixture was sieved with a screen having an opening of 150 μm (100 mesh) to separate the granular polymer. The granular polymer was dehydrated and dried after washing with methanol and washing with water three times. The melt viscosity of the obtained polymer at 310 ° C. and a shear rate of 200 / sec was 1100 Pa · s, and the R value was 2.85.
[0040]
Metal coating experiment
  The polymer obtained above was supplied to a 30 mmφ biaxial kneader-extruder (BT-30 machine manufactured by Plastics Engineering Laboratory) and kneaded at a cylinder temperature of 300 ° C. to 320 ° C. to obtain a pellet.
  The obtained pellet-like material is supplied to a twin screw extruder (laboroplast mill manufactured by Toyo Seiki Seisakusho) equipped with a wire coating die, cylinder temperature 330 ° C., extrusion rate 8 g / min, take-up speed 18 m / min, draw ratio The conductor wire was coated under the conditions of 9.5, parison cone length of 15 mm, and air-bleeding reduced pressure between the conductor wire and the coating film—18 cmHg. The same conductors and coating dies as in Example 1 were used.
  During the coating of the lead wire, it was possible to stably coat continuously for 6 hours without causing the resin to run out, and a coated body having an outer diameter of 0.7 mmφ and having no irregularities on the surface was obtained. The coated body was heat-treated as in Example 1. Even if the obtained covering was bent, cracks and cracks did not occur in the covering film. As a result of conducting a tensile test in the same manner as in Example 1, the tensile breaking strength of the coating film was 140 MPa, and the breaking elongation was 140%.
[0041]
[Example 7]
  The same pellets as in Example 6 were used for coating. In coating, the cylinder temperature was 330 ° C., the extrusion rate was 10 g / min, the take-up speed was 20 m / min, the draw ratio was 6.6, the parison cone length was 15 mm, and the air venting pressure between the conductor and the coating film was reduced to −15 cmHg. The same conductor and covering die as in Example 1 were used.
  In the conductor coating, a coating that could be stably coated continuously for 6 hours without causing resin breakage, had an outer diameter of 0.8 mmφ, and had no irregularities on the surface was obtained. The coated body was heat-treated at a temperature of 250 ° C. and a residence time of 5 seconds. Even if the obtained covering was bent, cracks and cracks did not occur in the covering film. As a result of conducting a tensile test in the same manner as in Example 1, the tensile strength at break was 130 MPa and the elongation at break was 145%.
[0042]
[Example 8]
Polymer synthesis example (6)
  370 kg of hydrous sodium sulfide (purity 46.40%) and 810 kg of NMP were charged into a titanium-clad polymerization can and gradually heated to about 200 ° C. in a nitrogen gas atmosphere, together with 54.0 mol of hydrogen sulfide and 140. 0 kg was distilled off. Next, a mixed solution of 320 kg of p-DCB, 0.465 kg of 1,2,4-trichlorobenzene and 263 kg of NMP was supplied, and a polymerization reaction was performed at 220 ° C. for 5 hours. Next, 96.5 kg of water was injected and the polymerization reaction was carried out at 255 ° C. for 5 hours, and then the temperature was lowered to 245 ° C. and the polymerization reaction was continued for 5 hours. After completion of the polymerization reaction, the reaction system was cooled, and then the reaction mixture was sieved with a screen having an opening of 150 μm (100 mesh) to separate the granular polymer. The granular polymer was dehydrated and dried after washing with methanol and washing with water three times. The melt viscosity of the obtained polymer at 310 ° C. and a shear rate of 200 / sec was 340 Pa · s, and the R value was 2.18.
[0043]
Metal coating experiment
  The polymer obtained above was supplied to a 30 mmφ biaxial kneader-extruder (BT-30 machine manufactured by Plastics Engineering Laboratory) and kneaded at a cylinder temperature of 290 ° C. to 315 ° C. to obtain pellets. The obtained pellet-like material is supplied to a twin-screw extruder (laboroplast mill manufactured by Toyo Seiki Seisakusho Co., Ltd.) equipped with a wire coating die, and the cylinder temperature is 315 ° C., the extrusion rate is 8 g / min, the take-up speed is 18 m / min, and the stretching is performed. The conductor wire was coated under the conditions of a magnification of 9.5, a parison cone length of 10 mm, and a reduced pressure of -10 cmHg between the conductor wire and the coating film. The same conductors and coating dies as in Example 1 were used.
  During the coating of the lead wire, it was possible to stably coat continuously for 6 hours without causing the resin to run out, and a coated body having an outer diameter of 0.7 mmφ and having no irregularities on the surface was obtained. The coated body was heat-treated as in Example 1. Even if the obtained covering was bent, cracks and cracks did not occur in the covering film. As a result of conducting a tensile test in the same manner as in Example 1, the tensile breaking strength of the coating film was 100 MPa, and the breaking elongation was 100%.
[0044]
[Reference example 1]
Polymer synthesis example (7)
  372 kg of hydrous sodium sulfide (purity: 46.21%) and 824 kg of NMP were charged into a titanium-clad polymerization can and gradually heated to about 200 ° C. in a nitrogen gas atmosphere, together with 56.6 mol of hydrogen sulfide and water 142. 0 kg was distilled off. Next, a mixed solution of 322.2 kg of p-DCB, 0.796 kg of 1,2,4-trichlorobenzene and 249 kg of NMP was supplied, and a polymerization reaction was performed at 220 ° C. for 5 hours. Next, 96.8 kg of water was injected and the polymerization reaction was carried out at 255 ° C. for 5 hours, and then the temperature was lowered to 245 ° C. and the polymerization reaction was continued for 5 hours. After completion of the polymerization reaction, the reaction system was cooled, and then the reaction mixture was sieved with a screen having an opening of 150 μm (100 mesh) to separate the granular polymer. The granular polymer was dehydrated and dried after washing with methanol and washing with water three times. The melt viscosity of the obtained polymer at 310 ° C. and a shear rate of 200 / sec was 2125 Pa · s, and the R value was 2.80.
[0045]
Metal coating experiment
  The polymer obtained above was supplied to a 30 mmφ twin-screw kneading extruder (BT-30 machine manufactured by Plastics Engineering Laboratory) and kneaded at a cylinder temperature of 310 ° C. to 350 ° C. to obtain pellets. The obtained pellet-like material is supplied to a twin-screw extruder (laboroplast mill manufactured by Toyo Seiki Seisakusho Co., Ltd.) equipped with a wire coating die. The conductor was coated under the conditions of a magnification of 6.6, a parison cone length of 15 mm, and a reduced pressure of air between the conductor and the coating film—15 cmHg. The same conductors and coating dies as in Example 1 were used.
  In the conductor coating, a coating that could be stably coated continuously for 6 hours without causing resin breakage, had an outer diameter of 0.8 mmφ, and had no irregularities on the surface was obtained. The coated body was heat-treated as in Example 1. Even if the obtained covering was bent, cracks and cracks did not occur in the covering film. As a result of conducting a tensile test in the same manner as in Example 1, the tensile breaking strength of the coating film was 120 MPa, and the elongation at break was 65%.
  These examplesAnd reference examplesTable 1 collectively shows the pelletizing conditions, the wire coating conditions, the heat treatment conditions, and the evaluation results of the coated bodies.
[0046]
[Table 1]

[0047]
[Comparative Example 1]
Polymer synthesis example (8)
  390 kg of hydrous sodium sulfide (purity 46.40%) and 800 kg of NMP were charged into a titanium-clad polymerization can and gradually heated to about 200 ° C. in a nitrogen gas atmosphere, together with 57.8 mol of hydrogen sulfide and water 148. 0 kg was distilled off. Next, a mixed solution of 354.6 kg of p-DCB, 8.210 kg of 1,2,4-trichlorobenzene and 218 kg of NMP was supplied, and a polymerization reaction was performed at 220 ° C. for 4 hours. Next, 85.6 kg of water was injected, the temperature was raised to 255 ° C. at a rate of 0.6 ° C./min, and a polymerization reaction was performed at 255 ° C. for 5 hours. After completion of the polymerization reaction, the reaction system was cooled, and then the reaction mixture was sieved with a screen having an opening of 150 μm (100 mesh) to separate the granular polymer. The granular polymer was dehydrated and dried by washing with acetone three times, washing with water four times, washing with 0.6% ammonium chloride aqueous solution once, washing with water once, and washing with 0.06% ammonium chloride aqueous solution once. The melt viscosity of the obtained polymer at 310 ° C. and a shear rate of 200 / sec was 3100 Pa · s, and the R value was 4.08.
Metal coating experiment
  The polymer obtained above was supplied to a 30 mmφ twin-screw kneading extruder (BT-30 machine manufactured by Plastics Engineering Laboratory) and attempted to be pelletized, but the resin did not melt and a pellet-like product could be obtained. could not.
[0048]
[Comparative Example 2]
Polymer synthesis example (9)
  390 kg of hydrous sodium sulfide (purity 46.40%) and 800 kg of NMP were charged into a titanium-clad polymerization can and gradually heated to about 200 ° C. in a nitrogen gas atmosphere, together with 57.2 mol of hydrogen sulfide and 147. 0 kg was distilled off. Subsequently, a mixed solution of 337.5 kg of p-DCB and 219 kg of NMP was supplied, and a polymerization reaction was performed at 220 ° C. for 4.5 hours. Next, 80.8 kg of water was injected and the polymerization reaction was carried out at 255 ° C. for 2 hours, and then the temperature was lowered to 245 ° C. and the polymerization reaction was continued for 11 hours. After completion of the polymerization reaction, the reaction system was cooled, and then the reaction mixture was sieved with a screen having an opening of 150 μm (100 mesh) to separate the granular polymer. The granular polymer was dehydrated and dried after washing with methanol and washing with water three times. The obtained polymer had a melt viscosity of 916 Pa · s at 310 ° C. and a shear rate of 200 / sec, and an R value of 1.90.
[0049]
Metal coating experiment
  The polymer obtained above was supplied to a 30 mmφ twin-screw kneading extruder (BT-30 machine manufactured by Plastics Engineering Laboratory) and kneaded at a cylinder temperature of 290 ° C. to 320 ° C. to obtain pellets. The obtained pellet-like material is supplied to a twin-screw extruder (laboroplast mill manufactured by Toyo Seiki Seisakusho Co., Ltd.) equipped with a wire coating die, and the cylinder temperature is 320 ° C., the extrusion amount is 8 g / min, the take-up speed is 18 m / min. The conducting wire was coated under the conditions of a magnification of 9.5, a parison cone length of 2 mm, and a reduced pressure of air between the conducting wire and the coating film-0.5 cmHg. The same conductors and coating dies as in Example 1 were used.
  During the conductor coating, the resin runs out once every 3 hours. Since the resiliency of the resin is poor, it is difficult to reduce the pressure between the conductor and the coating film, and the length of the parison cone cannot be increased. In addition, the outer diameter of the obtained covering was 0.7 mmφ, and the surface was smooth without any unevenness. The obtained coated body was subjected to the same heat treatment as in Example 1 and then subjected to a tensile test in the same manner as in Example 1. As a result, the tensile strength at break was 67 MPa and the elongation at break was 4%. When this coating was bent, cracks occurred in the coating film.
[0050]
[Comparative Example 3]
  Using the same pellets and conductive wire as in Comparative Example 2, coating was performed while changing the draw ratio. Coating conditions are: cylinder temperature 330 ° C., extrusion rate 18 g / min, take-off speed 50 m / min, draw ratio 50, parison cone length 2 mm, air venting reduced pressure between conductor and coating film -0.55 mHg, coating die mandrel The outer diameter of the tip was 2.8 mmφ and the die inner diameter of the die was 4.9 mmφ. During the coating of the lead wire, the resin was frequently cut and stable coating was difficult.
[0051]
[Comparative Example 4]
Polymer synthesis example (10)
  420 kg of hydrous sodium sulfide (purity 46.21%) and 720 kg of NMP were charged into a titanium-clad polymerization can and gradually heated to about 200 ° C. in a nitrogen gas atmosphere, together with 61.8 mol of hydrogen sulfide and 160. 0 kg was distilled off. Subsequently, a mixed solution of 363.6 kg of p-DCB and 250 kg of NMP was supplied, and a polymerization reaction was performed at 220 ° C. for 4.5 hours. Next, 56.5 kg of water was injected and polymerized at 255 ° C. for 5 hours. After completion of the polymerization reaction, the reaction system was cooled, and then the reaction mixture was sieved with a screen having an opening of 150 μm (100 mesh) to separate the granular polymer. The granular polymer is washed three times with methanol, three times with water, once with 3% ammonium chloride solution and twice with water, reslurried with water, adjusted to pH about 5 by adding hydrochloric acid, dehydrated and dried. did. The obtained polymer had a melt viscosity of 192 Pa · s at 310 ° C. and a shear rate of 200 / sec, and an R value of 1.37.
[0052]
Metal coating experiment
  The polymer obtained above was supplied to a 30 mmφ twin-screw kneading extruder (BT-30 machine manufactured by Plastics Engineering Laboratory) and kneaded at a cylinder temperature of 290 ° C. to 305 ° C. to obtain a pellet. The obtained pellets were supplied to a twin-screw extruder equipped with a wire coating die (laboroplast mill manufactured by Toyo Seiki Seisakusho), cylinder temperature 310 ° C., extrusion rate 8 g / min, take-up speed 18 m / min, draw ratio The conductor wire was coated under the conditions of 9.5, parison cone length of 2 mm, and reduced pressure of air between the conductor wire and the coating film-0.4 cmHg. The same conductors and coating dies as in Example 1 were used.
  During the conductor coating, the resin runs out at a frequency of 2 times / hour. Since the resiliency of the resin is poor, it is difficult to reduce the pressure between the conductor and the coating film, and the length of the parison cone cannot be increased. The outer diameter of the obtained covering was 0.7 mmφ, and the surface was smooth with no irregularities. The obtained coated body was subjected to the same heat treatment as in Example 1, and then subjected to a tensile test in the same manner as in Example 1. As a result, the tensile strength at break was 58 MPa and the elongation at break was 3%. . When this coating was bent, cracks occurred in the coating film.
[0053]
[Comparative Example 5]
Polymer synthesis example (11)
  372 kg of hydrous sodium sulfide (purity 46.40%) and 805 kg of NMP were charged into a titanium-clad polymerization can and gradually heated to about 200 ° C. in a nitrogen gas atmosphere, together with 53.9 mol of hydrogen sulfide and water 140. 3 kg was distilled off. Next, a mixed solution of 330 kg of p-DCB, 0.989 kg of 1,2,4-trichlorobenzene and 274 kg of NMP was supplied, and a polymerization reaction was performed at 220 ° C. for 5 hours. Next, 97.3 kg of water was injected and the polymerization reaction was carried out at 255 ° C. for 1 hour, and then the temperature was lowered to 240 ° C. and the polymerization reaction was continued for 5 hours. After completion of the polymerization reaction, the reaction system was cooled, and then the reaction mixture was sieved with a screen having an opening of 150 μm (100 mesh) to separate the granular polymer. The granular polymer was dehydrated and dried after washing with methanol and washing with water three times. The melt viscosity of the obtained polymer at 310 ° C. and a shear rate of 200 / sec was 600 Pa · s, and the R value was 2.98.
[0054]
Metal coating experiment
  The polymer obtained above was supplied to a 30 mmφ twin-screw kneading extruder (BT-30 machine manufactured by Plastics Engineering Laboratory) and kneaded at a cylinder temperature of 290 ° C. to 310 ° C. to obtain a pellet. The obtained pellet-like material is supplied to a twin-screw extruder (laboroplast mill manufactured by Toyo Seiki Seisakusho Co., Ltd.) equipped with a wire coating die, and the cylinder temperature is 315 ° C., the extrusion rate is 8 g / min, the take-up speed is 18 m / min, and the stretching is performed. The conducting wire was coated under the conditions of a magnification of 9.5, a parison cone length of 5 mm, and a reduced pressure of air between the conducting wire and the coating film-0.5 cmHg. The same conductors and coating dies as in Example 1 were used.
  The stretchability of the resin was poor, and during the conductor coating, the resin was cut out at a frequency of 4 times / 1 hour, and it was difficult to continuously and stably coat the resin. The outer diameter of the obtained covering was 0.7 mmφ, and the surface was smooth with no irregularities. The obtained coated body was subjected to the same heat treatment as in Example 1 and then subjected to a tensile test in the same manner as in Example 1. As a result, the tensile strength at break was 52 MPa and the elongation at break was 3%. When this coating was bent, cracks occurred in the coating film.
  Table 2 collectively shows the pelletizing conditions, the electric wire covering conditions, the heat treatment conditions, and the evaluation results of the coverings of these comparative examples.
[0055]
[Table 2]

[0056]
[Example 10]
  A polymer was synthesized in the same manner as in the polymer synthesis example (1) of Example 1, and then a metal coating experiment was conducted using the polymer in the same manner as in Example 1 to obtain a coated body (resin-coated conductor). It was. The obtained coated body was introduced into a heating zone and heat treated under the conditions of heat treatment temperature and heat treatment time (residence time) shown in each experiment number in Table 3 to crystallize the coating resin, and then wound up on a roll. A tensile test was conducted in the same manner as in Example 1. Further, the crystallinity of the coating resin was measured by the following method. The results are shown in Table 3.
Method for measuring crystallinity
  The density of the coating resin is measured by the density gradient tube method, and the crystal density is 1.43 g / cm.³And amorphous density 1.3195 g / cm³Based on the above, the crystallinity was calculated from the measured density by the volume fraction.
[0057]
[Table 3]

  The results in Table 3 indicate that the break elongation differs when the heat treatment temperature is different, even though the crystallinity is almost the same. Moreover, as can be seen from Experiment Nos. 11, 11 to 14, etc., the higher the heat treatment temperature, the higher the elongation at break.
[0058]
[Example 11]
  A polymer was synthesized in the same manner as in the polymer synthesis example (1) of Example 1, and then 100 parts by weight of the polymer and 1 part by weight of pentaerythritol tristearate (manufactured by NOF Corporation, Unistar H476) were mixed with a tumbler mixer. The resin composition was obtained by mixing for minutes. A metal coating experiment was performed in the same manner as in Example 1 except that the resin composition was used in place of the polymer to obtain a coated body (resin-coated conductor). The obtained coated body was cooled, guided to the heating zone, and heat-treated under the same conditions as in Example 1 to crystallize the coating resin, and then wound on a roll. As a result of conducting a tensile test in the same manner as in Example 1, the tensile breaking strength was 134 MPa and the breaking elongation was 180%. This covering had good stripping properties.
[0059]
[Example 12]
  In the same manner as in the polymer synthesis example (1) of Example 1, a polymer was synthesized, and then 100 parts by weight of the polymer and 0.5 parts by weight of barium hydroxide were mixed with a tumbler mixer for 3 minutes to obtain a resin composition. Obtained. A metal coating experiment was performed in the same manner as in Example 1 except that the resin composition was used in place of the polymer to obtain a coated body (resin-coated conductor). The obtained coated body was cooled, guided to the heating zone, and heat-treated under the same conditions as in Example 1 to crystallize the coating resin, and then wound on a roll. As a result of conducting a tensile test in the same manner as in Example 1, the tensile breaking strength was 125 MPa and the breaking elongation was 120%. In the metal coating experiment, it was possible to coat stably for 10 hours continuously.
[0060]
[Example 13]
  A polymer was synthesized in the same manner as in the polymer synthesis example (1) of Example 1, and then 100 parts by weight of the polymer, 0.5 parts by weight of barium hydroxide and distearyl pentaerythritol diphosphate (manufactured by Specially Chemicals) 0 .5 parts by weight were mixed with a tumbler mixer for 3 minutes to obtain a resin composition. A metal coating experiment was conducted in the same manner as in Example 1 except that the resin composition was used in place of the polymer to obtain a coated body (resin-coated conductor). The obtained coated body was cooled, guided to the heating zone, and heat-treated under the same conditions as in Example 1 to crystallize the coating resin, and then wound on a roll. As a result of conducting a tensile test in the same manner as in Example 1, the tensile breaking strength was 123 MPa and the breaking elongation was 100%. In the metal coating experiment, it was possible to coat stably for 10 hours continuously. Further, this covering had good stripping properties.
[0061]
【The invention's effect】
  According to the present invention, when coating is performed on a metal substrate, it can be stably and continuously coated without causing the resin to run out, and when the heat treatment is performed after coating, resin cracking of the coating layer occurs. A polyarylene sulfide resin for metal coating is provided. Further, according to the present invention, the resin-coated metal member having a resin coating layer excellent in heat resistance, freon resistance, flame resistance, chemical resistance, radiation resistance, low-temperature physical properties, electrical insulation properties, mechanical physical properties, etc.And its manufacturing methodIs provided.
  The present invention relates to a control cable rope for a motor vehicle or a ship, a control cable inner cable, a winding for a heat-resistant coil or a motor, an automobile solenoid lead wire, a freon-resistant wire such as a compressor, a winding for a transformer, nuclear power generation It can be applied to coatings for required radiation resistant equipment wiring and cables, metal rods, metal tubes, other heat-resistant electric wires, sheath tubes, wires, and the like.
[Brief description of the drawings]
FIG. 1 shows the melt viscosity η of polyarylene sulfide resin.₂₀₀It is a graph which shows the relationship between R value.EFGHThe inside of the frame is the range of the polyarylene sulfide resin for metal coating used in the present invention.

Claims (3)

A branched polyarylene sulfide resin obtained by polymerizing an alkali metal sulfide and a dihalo-aromatic compound in the presence of a trihalo aromatic compounds, 310 ° C., a melt viscosity eta ₂₀₀ as measured at a shear rate of 200 / sec 300 in to 2000 Pa · s, and the melt viscosity eta ₂₀₀ 310 ° C., the ratio R (eta ₂₀₀ / eta ₁₂₀₀₎ is the following relationship between melt viscosity eta ₁₂₀₀ as measured at a shear rate of 1200 / sec (1):

Metallizing tree characterized by comprising the polyarylene sulfide resin satisfying the fat. A branched polyarylene sulfide resin obtained by polymerizing an alkali metal sulfide and a dihalo-aromatic compound in the presence of a trihalo aromatic compounds, 310 ° C., a melt viscosity eta ₂₀₀ as measured at a shear rate of 200 / sec 300 in to 2000 Pa · s, and the melt viscosity eta ₂₀₀ 310 ° C., the ratio R (eta ₂₀₀ / eta ₁₂₀₀₎ is the following relationship between melt viscosity eta ₁₂₀₀ as measured at a shear rate of 1200 / sec (1):

Resin-coated metal member to the metal-coated resin comprising a satisfactory polyarylene sulfide resin, characterized in that formed by coating on a metal substrate a. A branched polyarylene sulfide resin obtained by polymerizing an alkali metal sulfide and a dihaloaromatic compound in the presence of a trihaloaromatic compound, which has a melt viscosity η measured at 310 ° C. and a shear rate of 200 / sec. ₂₀₀ Is 300 to 2000 Pa · s, the melt viscosity η ₂₀₀ And melt viscosity η measured at 310 ° C. and a shear rate of 1200 / sec. ₁₂₀₀ Ratio R (η ₂₀₀ / Η ₁₂₀₀ ) Is the following relational expression (1):

A metal coating resin comprising a polyarylene sulfide resin satisfying the above conditions is melted at a temperature in the range of (melting point + 20 ° C.) to 350 ° C. of the resin using an extruder, and then coated with a die outside while forming a parison. Then, after cooling the coated body, heat treatment is performed under the conditions of a heat treatment temperature of 200 to 270 ° C. and a heat treatment time of 0.1 seconds to 10 minutes, and the resin crystallinity of the coating layer is increased. A method for producing a resin-coated metal member, wherein the content is in the range of 15 to 30%.

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