JP3758336B2 - Spiral tubular heater - Google Patents
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Description
【０００１】
【発明の属する技術分野】
この発明は、パイプとの密着性が良く、熱効率の良好なヒ−タ−などの用途に好適で、特に半導体製造装置や分析機器などのパイプの保温などの目的に使用できる、絶縁層の間に可とう性の導電性基材、例えばヒ−タ−のような平面状基材を挟んで一体として設けた、内側層となるテ−プ状高分子材料と外側層となる接着剤付きの耐熱性高分子材料との間に可とう性の導電性基材がポリイミド系接着剤によって積層一体化されてなるスパイラル管状ヒ−タ−に関する。
【０００２】
【従来の技術】
従来、液体クロマトグラフ装置あるいは質量分析装置などの分析機器におけるパイプや医療用機器における薬液等の搬送路を構成するパイプへの搬送対象物質の凝固や付着を防止するためにパイプを加熱して保温することが必要であり、また内面に付着した物質を蒸発させて真空度を確保するためにパイプを加熱する場合がある。さらには、水道管の凍結防止のために水道管を保温・加熱する場合がある。
このような場合、従来は、リボンヒ−タ−のような可とう性の面状発熱体を帯状にしてパイプに巻きつけることが一般的に行われている。
【０００３】
【発明が解決しようとする課題】
しかし、上記のパイプの配管系は一般的に装置と装置との間の狭いところに設けられる場合が多く、パイプに面状発熱体を巻きつけて装着することが困難であり、しかも面状発熱体はパイプとの密着性が悪い。このため熱効率が低く、従って温度の制御も正確に行うことができない。
この発明の目的は、被加熱体に装着が容易で密着性が良いヒ−タ−を提供することである。
【０００４】
【課題を解決するための手段】
この発明は、スパイラル状物の内側層を形成するテ−プ状耐熱性高分子材料Ａ、中間層を形成するポリイミド系接着剤層および外側層を形成するテ−プ状耐熱性高分子材料Ｂの構成を有する積層体のいずれかの層に長手方向の両端間に導電性を与える可とう性の導電性基材が一体として設けられている形状保持性のスパイラル管状ヒ−タ−に関する。
【０００５】
【発明の実施の形態】
以下に本発明の好ましい態様を列記する。
１）スパイラル状物の内層側を形成するテ−プ状耐熱性高分子材料Ａおよび外側層を形成するテ−プ状耐熱性高分子材料Ｂがそれぞれ厚み２５−２００μｍである上記のスパイラル管状ヒ−タ−。
２）可とう性の導電性基材がテ−プ状ヒ−タ−のような平面状基材である上記のスパイラル管状ヒ−タ−。
３）テ−プ状耐熱性高分子材料Ａおよびテ−プ状耐熱性高分子材料Ｂがテ−プ状芳香族ポリイミドフィルムである上記のスパイラル管状ヒ−タ−。
４）可とう性の導電性基材が積層体の長手方向と平行に一体として設けられており、この導電性基材は少なくとも１回折り返しされて両端部がスパイラル状物の片方から取り出されている上記のスパイラル管状ヒ−タ−。
【０００６】
以下、この発明について、図面も参考にして、詳しく説明する。
図１は、この発明のスパイラル管状ヒ−タ−の一例をスパイラル芯に平行に切断した一部断面図である。
図２は、この発明のスパイラル管状ヒ−タ−の一例を示す斜視図である。
図３は、この発明のスパイラル管状ヒ−タ−の一例の使用例を示す一部斜視図である。
【０００７】
図１において、形状保持性のスパイラル管状ヒ−タ−１は、スパイラル状物の内側層を形成するテ−プ状耐熱性高分子材料Ａである２、中間層を形成するポリイミド系接着剤層３（内側層に接するポリイミド系接着剤層３ａと外側層に接するポリイミド系接着剤層３ｂとからなる）および外側層を形成するテ−プ状耐熱性高分子材料Ｂである４の構成を有する積層体のいずれかの層、好適にはポリイミド系接着剤層３ａとポリイミド系接着剤層３ｂとの間に長手方向の両端間に導電性を与える可とう性の導電性基材５が一体として設けられている。
【０００８】
図２において、形状保持性のスパイラル管状ヒ−タ−１は、スパイラル状物の内側層を形成するテ−プ状耐熱性高分子材料Ａである２、中間層を形成するポリイミド系接着剤層（図示せず）および外側層を形成するテ−プ状耐熱性高分子材料Ｂである４の構成を有する積層体のいずれかの層に長手方向の両端間に導電性を与え可とう性の導電性基材５が一体として設けられている。
【０００９】
図３において、被加熱体１０を挿入可能なまでに形状保持性のスパイラル管状ヒ−タ−間を押し拡げて被加熱体１０をスパイラル管状ヒ−タ−間に挿入し、次いで、被加熱体１０をその状態に維持したままでスパイラル管状ヒ−タ−１を図の矢印の方向に回転し、この回転につれて被加熱体１０がスパイラル管状ヒ−タ−１内に取り込まれるので、管状ヒ−タ−１の軸方向に回転させるだけで比較的簡単・迅速に被加熱体１０にスパイラル管状ヒ−タ−１を装着することができ、しかも装着した後はスパイラル管状ヒ−タ−１は元の形状に復帰するから、被加熱体１０に均等にかつ整然と装着することができる。従って、例えば被加熱体の両端部が大型の装置等に接続されて自由度がほとんどない場合でも、比較的容易にかつ迅速に被加熱体１０に巻きつけることができる。また、スパイラル管状ヒ−タ−の径を任意に設定できるため、自由度の少ない被加熱体だけでなく自由度の大きい被加熱体であっても、また径の大小にも制限を受けることなく、棒またはパイプ状であれば任意の被加熱体に適用できるのである。
【００１０】
この発明のスパイラル管状ヒ−タ−は、例えば、内側層となるポリイミド系接着剤付きのテ−プ状耐熱性高分子材料Ａを接着剤を外側にして金属製、例えばステンレス等の耐熱性の棒またはパイプなどの長尺の形状付与部材にスパイラル状に巻き付け、その上に、好適にはそのほぼ中央に可とう性の導電性基材、好適には平面状基材を巻き付け、さらにその上に外側層となる接着剤付きのテ−プ状耐熱性高分子材料Ｂをポリイミド系接着剤を内側にしてスパイラル状に重ねて巻き付け、接着剤を硬化して積層一体化（このプロセス中、形状付与部材に巻いた巻き付け物はほどけないように圧力を加えておく）し、形成された積層体を棒またはパイプなどの長尺の形状付与部材から外して、スパイラル状に形状保持した成形品として得ることができる。
この発明のスパイラル管状ヒ−タ−は、常温で、好適には２００℃程度の高温に加熱した環境下においても、また被加熱体に装着した後もほとんどスパイラル物の外径などの形状や均等・整然さに変化がなく形状保持される。
【００１１】
この発明におけるスパイラル状物の内側層を形成するシ−ト状耐熱性高分子材料Ａとしては、ガラス転移温度あるいは融点が１８０℃以上である芳香族ポリイミドあるいは芳香族ポリアミドからなり、好適には厚みが２５−２００μｍ、幅が３−５０ｍｍのテ−プ状フィルムが使用される。特に、５０−３００℃での線膨張係数（ＣＴＥ）が６０×１０-5ｃｍ／ｃｍ／℃（ｐｐｍで表示することもある）以下、その中でも特に３−５０×１０-5ｃｍ／ｃｍ／℃であって、引張弾性率が２００−１４００ｋｇ／ｍｍ2 である芳香族ポリイミドフィルムあるいは芳香族ポリアミドフィルムや、シリコンラバ−のような耐熱性ゴムが好適に使用される。そのなかでも、吸水率が４％以下、特に３％以下である芳香族ポリイミドフィルムが好適に使用される。
【００１２】
前記の芳香族ポリイミドは、例えば３，３’，４，４’−ビフェニルテトラカルボン酸二無水物、ピロメリット酸二無水物、３，３’，４，４’−ベンゾフェノンテトラカルボン酸二無水物などの芳香族テトラカルボン酸二無水物とｐ−フェニレンジアミン、４，４’−ジアミノジフェニルエ−テルなどの芳香族ジアミンとを重合、イミド化して得られる。特に、芳香族ポリイミドとして３，３’，４，４’−ビフェニルテトラカルボン酸二無水物を芳香族テトラカルボン酸成分中１５モル％以上使用して得られるものが耐熱性、低線膨張係数、低吸水率であることから好ましい。
前記の芳香族ポリアミドは、例えば２−クロロテレフタル酸クロリド、２，５−ジクロロテレフタル酸クロリドなどの芳香族酸クロリドと２−クロロ−ｐ−フェリレンジアミン、４，４’−ジアミノジフェニルエ−テルなどの芳香族ジアミンとの反応で得られる。
【００１３】
この発明において中間層を形成するポリイミド系接着剤層は、耐熱性のポリイミド系の熱可塑性接着剤あるいはポリイミド系の熱硬化性接着剤からなり、好適には積層した接着剤層の乾燥状態での厚みが２−１００μｍ、幅が３−５０ｍｍである。
また、この接着剤層は接着剤付きのテ−プ状フィルムとして設けてもよくあるいはテ−プ状フィルムを巻きつけた後、接着剤を塗布あるいは接着剤シ−トを張り合わせて接着剤付きテ−プを設けてもよい。
【００１４】
前記ポリイミド系熱可塑性接着剤としては、ポリイミド、ポリアミドイミド、ポリエ−テルイミド、ポリエステルイミド等のポリマ−鎖中にイミド結合を含有するポリイミド系ポリマ−が挙げられる。
前記ポリイミド系熱硬化性接着剤としては、ポリイミド、ポリアミドイミド、ポリエ−テルイミド、ポリエステルイミド、ポリイミドシロキサン等のポリマ−鎖中にイミド結合を含有するポリマ−と熱硬化樹脂との組み合わせが一般的である。熱硬化性樹脂としては、エポキシ樹脂、フェノ−ル樹脂、アクリレ−ト樹脂等の熱硬化性樹脂、さらにビスマレイミド樹脂のように末端または側鎖に反応性の官能基を有するポリイミドオリゴマ−等が挙げられる。
前記ポリイミド系熱可塑性接着剤および硬化後のポリイミド系熱硬化性接着剤のＴｇが２０−３８０℃であることが好ましく、特に３０−３４０℃であることが好ましい。
【００１５】
前記ポリイミド系熱可塑性接着剤および硬化後のポリイミド系熱硬化性接着剤の引張弾性率（２５℃）が５−４５０ｋｇ／ｍｍ2 であることが好ましい。さらに好ましくは１０−４００ｋｇ／ｍｍ2 である。
前記ポリイミド系熱可塑性接着剤および硬化後のポリイミド系熱硬化性接着剤はポリイミドを５−１００重量部使用することが好ましい。さらに好ましくはポリイミドを１０重量％以上である。
ポリイミド系接着剤がシランカップリング剤またはチタネ−ト系カップリング剤を含んでも良い。シランカップリング剤の混合量は接着剤１００重量部に対して、０．１−６重量部が好適である。さらに好適には、０．３−５重量である。シランカップリング剤の種類としては、アミノシラン、エポキシシラン、チオ−ルシラン等が好適である。
前記のポリイミド系接着剤は、テ−プ状耐熱性樹脂フィルムＡの片面とテ−プ状耐熱性樹脂フィルムＢの片面とのそれぞれに設けることが好ましい。
【００１６】
この発明における外側層を形成する耐熱性樹脂フィルムＢとしては、ガラス転移温度あるいは融点が１８０℃以上である芳香族ポリイミド、芳香族ポリアミド、芳香族ポリエステル、フッ素樹脂または芳香族ポリアミドイミドからなり、好適には厚みが２５−２００μｍ、幅が３−５０ｍｍのシ−ト状フィルムが使用される。特に、５０−２５０℃での線膨張係数（ＣＴＥ）が６０×１０-5ｃｍ／ｃｍ／℃（ｐｐｍで表示することもある）以下、特に３−５０×１０-5ｃｍ／ｃｍ／℃であって、引張弾性率が２００−１４００ｋｇ／ｍｍ2 である芳香族ポリイミドフィルムあるいは芳香族ポリアミドフィルムが好適に使用される。そのなかでも、吸水率が４％以下、特に３％以下である芳香族ポリイミドフィルムが好適に使用される。
【００１７】
この発明における可とう性の導電性基材としては、スパイラル状物の長手方向の両端間に導電性の機能を与える金属箔、金属線、帯状の金属、好適には厚みが５−１００μｍ、幅が０．４−４０ｍｍ程度の銅箔、ニクロム箔などの金属箔が使用される。
この可とう性の導電性基材は１本のみを設けてもよく複数本を平行して設けてもよく、また、前記のポリイミド系接着剤によってテ−プ状耐熱性樹脂フィルムＢのほぼ全面に設けてもよいが、ほぼ中央部に設けることが好ましい。
また、可とう性の導電性基材の表面をあらかじめ塗布法などによって耐熱性樹脂で薄く被覆したものを使用してもよい。
【００１８】
前記の芳香族ポリイミドフィルムは、例えば、次のようにして得られる。
先ず、ピロメリット酸二無水物や３，３’，４，４’−ビフェニルテトラカルボン酸二無水物などの芳香族テトラカルボン酸二無水物と芳香族ジアミンとをＮ，Ｎ−ジメチルアセトアミドやＮ−メチル−２−ピロリドンなどの有機極性溶媒中で重合して、ポリマ−の対数粘度（測定温度：３０℃、濃度：０．５ｇ／１００ｍｌ溶媒、溶媒：Ｎ−メチル−２−ピロリドン）が１−５、ポリマ−濃度が１５−４０重量％程度であるポリアミック酸溶液を得る。
次いで、好適にはこのポリアミック酸１００重量部に対して０．０１−１重量％のリン化合物、例えば（ポリ）リン酸エステルおよび／またはリン酸エステルのアミン塩などの有機系リン化合物あるいは無機リン化合物および、好適にはさらにポリアミック酸１００重量部に対して０．０２−６重量部のコロイダルシリカ、窒化珪素、タルク、酸化チタンなどの無機フィラ−（好適には平均粒径０．００５−５μｍ、特に０．００５−２μｍ）を添加してポリアミック酸溶液組成物を調製する。
このポリアミック酸溶液組成物をそのままあるいは化学イミド化剤を加えて、平滑な表面を有する支持体表面に流延し、乾燥して固化フィルムを形成し、上記固化フィルムを支持体表面から剥離する。
次いで、固化フィルムの片面または両面にアミノシラン系、エポキシシラン系あるいはチタネ−ト系の表面処理剤を含有する表面処理液を塗布した後、さらに乾燥することもできる。
前記のようにして得られた固化フィルムを、必要であれば両方向に延伸した後乾燥フィルムの幅方向の両端縁を把持した状態で、最高加熱温度：３５０〜５００℃の範囲内の温度で加熱して乾燥およびイミド化して芳香族ポリイミドフィルムとして好適に製造することができる。
上記のようにして得られた芳香族ポリイミドフィルムを、好適には低張力下あるいは無張力下に２００〜４００℃程度の温度で加熱して応力緩和処理し、巻き取る。
この芳香族ポリイミドフィルムは、そのままあるいはコロナ放電処理、プラズマ処理、紫外線照射、グロ−放電処理、火炎処理で表面処理を施した後、接着性を改良した芳香族ポリイミドフィルムとして使用することができる。
【００１９】
前記の芳香族ポリアミドフィルムは、例えば以下のようにして製造することができる。芳香族酸クロリドと芳香族ジアミンとを有機極性溶媒中で溶液重合、あるいは水系媒体を使用する界面重合などで合成される。ポリマ−溶液は単量体として酸クロリドとジアミンとを使用すると塩化水素が副生するためこれを中和するために水酸化カルシウムなどの無機の中和剤、またはエチレンオキサイドなどの有機の中和剤を添加する。
また、イソシアネ−トとカルボン酸との反応は非プロトン性有機極性溶媒中、触媒の存在下で行われる。
これらのポリマ−溶液はそのままフィルムを形成する製膜原液にしてもよく、またポリマ−を一度単離してから上記の溶媒に再溶解して製膜原液を調製してもよい。製膜原液には溶解助剤として無機塩例えば塩化カルシウム、塩化マグネシウムなどを添加してもよい。製膜原液中のポリマ−濃度は２−３５重量％が好ましい。
【００２０】
この発明の形状保持性のスパイラル管状ヒ−タ−は、例えば、被加熱体と同一外形状を有する（形状は、断面円形または角形等任意の形状を有してよい。）長尺の形状付与部材、例えば耐熱性の棒またはパイプにスパイラル状に巻いた内側層となるテ−プ状耐熱性高分子材料Ａ、好適にはテ−プ状芳香族ポリイミドフィルムＡとそれと同じ幅か少し幅の狭い外側層となるテ−プ状耐熱性高分子材料Ｂ、好適にはテ−プ状芳香族ポリイミドフィルムＢとその間にポリイミド系接着剤および長手方向の両端間に導電性を与える可とう性の導電性基材、好適にはテ−プ状ヒ−タ−のような平面状導電性基材を配置し、ポリイミド系熱硬化性接着剤の場合には溶媒を乾燥してＢステ−ジの段階で、ポリイミド系熱可塑性接着剤の場合には積層体に圧力を加えてガラス転移温度あるいは融点以上の温度に加熱することによって、フィルムの内側層と外側層とを重ねたまま、ポリイミド系熱硬化性接着剤の場合には硬化温度以上の温度に加熱して、あるいはポリイミド系熱可塑性接着剤の場合には冷却して、ポリイミド系接着剤を硬化して積層一体化させた後、スパイラル状の積層体を長尺の形状付与部材から外して得られる。
【００２１】
上記の方法は、好適には、例えば次のようにして実施できる。先ず、前記の内側層となる耐熱性高分子材料Ａおよび耐熱性高分子材料Ｂの片面にポリイミド系接着剤を塗布し、ポリイミド系接着剤の乾燥厚みが２−１００μｍであるフィルムを得る。このフィルムを３−５０ｍｍにスリットし、ポリイミド系熱硬化性接着剤付きのテ−プ状耐熱性高分子材料を製造する。このテ−プ状耐熱性高分子材料Ａをポリイミド系接着剤面を外側にして直径が５−５０ｍｍの円状の棒またはパイプにスパイラル状に巻きつけ、両端を固定する。次いで、その上に前記のテ−プよりも幅の狭い導電性基材、好適にはテ−プ状ヒ−タ−をスパイラル状に巻きつける。次いで、さらにその上にポリイミド系接着剤同士が重なるように、外側層となるポリイミド系熱硬化性接着剤付きテ−プ状耐熱性高分子材料Ｂを巻き付け、テ−プ状耐熱性高分子材料Ａ／ポリイミド系熱硬化性接着剤／ヒ−タ−／ポリイミド系熱硬化性接着剤／テ−プ状耐熱性高分子材料Ｂの構成にして、周囲をポリエチレンテレフタレ−トやポリイミドなどの熱収縮性の繊維や組紐で加圧・固定して、１５０−４００℃の範囲内の温度に加熱してポリイミド系接着剤を硬化して積層一体化し、冷却した後、形成された積層体を棒またはパイプから外し、スパイラル管状ヒ−タ−を得ることができる。
【００２２】
この発明のスパイラル管状ヒ−タ−はそのままで被加熱体に適用してもよく、あるいは適当な長さに切断して使用してもよく（この場合、端子を別途設けて使用する）、さらに最外層に保温の目的で耐熱性発砲シ−ト、耐熱性多孔シ−トで覆って使用してもよい。
また、形状が複雑な被加熱体の場合には、スパイラル管状ヒ−タ−と平面状ヒ−タ−とを組み合わせて使用して被加熱体を覆ってもよい。
【００２３】
【実施例】
以下にこの発明の実施例を示す。
以下の記載において、部は重量部を、％は重量％を意味する。
以下の各例において、ポリイミドフィルム等の物性測定は以下の方法によって行った。
吸水率：ＡＳＴＭ Ｄ５７０−６３に従って測定（２３℃×２４時間）
引張弾性率：ＡＳＴＭ Ｄ８８２−６４Ｔに従って測定（ＭＤ）
線膨張係数（５０−２５０℃または５０−３００℃）：３００℃で３０分加熱して応力緩和したサンプルをＴＭＡ装置（引張りモ−ド：２ｇ荷重、試料長さ１０ｍｍ、２０℃／分）で測定
【００２４】
参考例１
内容積１００リットルの重合槽に、Ｎ，Ｎ−ジメチルアセトアミド５４．６ｋｇを加え、次いで、３，３’，４，４’−ビフェニルテトラカルボン酸二無水物８．８２６ｋｇとパラフェニレンジアミン３．２４３ｋｇとを加え、３０℃で１０時間重合反応させてポリマ−の対数粘度（測定温度：３０℃、濃度：０．５ｇ／１００ミリリットル溶媒、溶媒：Ｎ，Ｎ−ジメチルアセトアミド）が１．６０、ポリマ−濃度が１８重量％であるポリアミック酸（イミド化率：５％以下）溶液を得た。
このポリアミック酸溶液に、ポリアミック酸１００重量部に対して０．１重量部の割合でモノステアリルリン酸エステルトリエタノ−ルアミン塩および０．５重量部の割合（固形分基準）で平均粒子０．０８μｍのコロイダルシリカを添加して均一に混合してポリアミック酸溶液組成物を得た。
このポリアミック酸溶液組成物の回転粘度は３０００ポイズであった。このポリアミック酸溶液組成物をＴダイ金型のスリットから連続的に、キャスティング・乾燥炉の平滑な支持体に押出して前記溶液の薄膜を形成し、１３０℃で１０分間乾燥し、支持体から剥がし、幅方向を把持した状態でキュア炉内でキュア−（２００℃から４５０℃、約２０分間）して、厚み７５μｍの芳香族ポリイミドフィルムを得た。このフィルムは、弾性率が７５０ｋｇ／ｍｍ2 、線膨張係数（５０−３００℃）が１６ｐｐｍ、吸水率が１．５％であった。
【００２５】
参考例２
パラフェニレンジアミンの代わりに、４，４’−ジアミノジフェニルエ−テル６．００７ｋｇにし、Ｎ，Ｎ−ジメチルアセトアミド６７．６ｋｇにした他は、参考例１と同様にして厚み７５μｍの芳香族ポリイミドフィルムを得た。
このフィルムは、弾性率が３７０ｋｇ／ｍｍ2 、線膨張係数（５０℃から２５０℃）が４０ｐｐｍ、吸水率が２．５％であった。
【００２６】
参考例３
容量２リットルのガラス製のセパラブルフラスコに、Ｎ−メチル−２−ピロリドン（ＮＭＰ）１０００ｇを入れ、その溶液中に、２，３，３’，４’−ビフェニルテトラカルボン酸二無水物（ａ−ＢＰＤＡ）７３．５６ｇ（２５０ミリモル）と、ジアミノポリシロキサン（ＤＡＰＳ）（東レ・ダウコ−ニング・シリコ−ン株式会社、ＢＹ１６−８５３Ｕ）８８ｇ（１００ミリモル）と、２，２−ビス〔４−（４−アミノフェノキシ）フェニル〕プロパン（ＢＡＰＰ）６１．５８ｇ（１５０ミリモル）とを加え、６０℃で２時間窒素雰囲気下で攪拌する。その後さらに温度を２００℃に昇温させ水を除去させながら３時間重合反応を行った。最後に、その反応液を１０リットル水中に添加して、ホモミキサ−を使用して、３０分間で析出させポリマ−を濾過させ、ポリマ−粉末を単離した。このポリマ−粉末について５リットルの２−プロパノ−ル中でホモミキサ−を使用して８０℃で１時間洗浄を２回行い、１２０℃で５時間熱風乾燥後、１２０℃で２４時間真空乾燥してポリイミドシロキサン粉末２１０ｇを得た。このポリイミドシロキサンは、対数粘度（３０℃）が０．３２であり、イミド化率が実質的に１００％であった。
このポリイミドシロキサン粉末のＴＨＦ溶液からフィルムを作製した。このフィルムの引張弾性率は５７ｋｇ／ｍｍ2 、Ｔｇが１９０℃であった。
【００２７】
参考例４
ａ−ＢＰＤＡを４５０ミリモル、ＤＡＰＳを１００ミリモル、ＢＡＰＰを３５０ミリモルにそれぞれ変えた他は参考例３と同様にしてポリイミドシロキサン粉末を得た。
このポリイミドシロキサン粉末のＴＨＦ溶液からフィルムを作製した。このフィルムの引張弾性率は１１５ｋｇ／ｍｍ2 、Ｔｇが２３５℃であった。
【００２８】
参考例５
容量３００ミリリットルのガラス製のセパラブルフラスコに、Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）１７５．７６ｇを入れ、その溶液中に、２，３，３’，４’−ビフェニルテトラカルボン酸二無水物（ａ−ＢＰＤＡ）１４．７１ｇ（０．０５モル）と、１，３−ビス（４−アミノフェノキシ）ベンゼン（ＴＰＥ−Ｒ）２９．２３ｇ（０．１モル）とを加え、５０℃で１時間窒素雰囲気下で攪拌して、アミック酸オリゴマ−を生成させ、次いで、その反応液を約１６５℃に昇温し、その温度で３時間攪拌して、末端にアミノ基を有するイミドオリゴマ−を生成させた。
その反応液を５０℃まで冷却した後、無水マレイン酸１１．７７ｇ（０．１２モル）およびキシレン３５ｇを添加し、その反応液を１６０℃に昇温し、キシレンを発生する水と共に除去しながら４時間攪拌して、末端に不飽和基を有するイミドオリゴマ−を生成し、最後に、その反応液を室温（約２０℃）に冷却した後水中に投じて粉末状のイミドオリゴマ−を析出させ、その析出したイミドオリゴマ−粉末を濾別した後、２５℃のメタノ−ルで２回洗浄し、減圧状態で乾燥して末端変性イミドオリゴマ−を製造した。
この末端変性イミドオリゴマ−は、イミド化率が９５％以上であり、その対数粘度が０．０４であった。
【００２９】
一方、容量３００ミリリットルのガラス製のフラスコに、Ｎ−メチル−２−ピロリドン３００ｇ、２，３，３’，４’−ビフェニルテトラカルボン酸二無水物（ａ−ＢＰＤＡ）２９．４２ｇ（０．１モル）と、２，２−ビス〔４−（４−アミノフェノキシ）フェニル〕プロパン（ＢＡＰＰ）４１．０７ｇ（０．１モル）とを加え、５０℃で１時間窒素雰囲気下で攪拌して、ポリアミック酸を生成させ、その反応液を約１９０℃に昇温し、その温度で５時間攪拌して芳香族ポリイミドを生成させた。
その反応液を室温（約２０℃）で繊維状に押出して、室温以下の水中に投じる湿式紡糸法により繊維を形成し、その繊維を２５℃のメタノ−ルで２回洗浄した後、減圧下に乾燥して芳香族ポリイミド製繊維（径：２００μｍ）を製造した。
この芳香族ポリイミド繊維のポリイミドは、イミド化率が９５％以上、対数粘度が０．４１であった。
このようにして得たイミドオリゴマ−５０ｇ、芳香族ポリイミド製繊維５０ｇおよび１，４−ジオキサン４００ｇを１リットルのガラス容器に仕込み、室温（約２５℃）で約２時間攪拌して均一な接着剤溶液である、熱硬化性樹脂溶液を調製した。
この溶液組成物は室温に１週間放置しても均一な溶液の状態を保持していた。
前記の溶液組成物をガラス板上に流延して薄膜を形成した後、９０℃で３０分間および１４０℃で３０分間加熱・乾燥し、ガラス板から引き剥がして、熱硬化性を有する厚さ２０μｍのフィルム状接着剤であるドライフィルムを製造した。
このフィルムは、引張弾性率が２００ｋｇ／ｍｍ2 であり、Ｔｇが２６０℃であった。
【００３０】
実施例１
参考例１で製造した７５μｍの芳香族ポリイミドフィルムにポリイミドシロキサン系の熱硬化性接着剤〔参考例３で得られたポリイミドシロキサン８５部、エポキシ樹脂（油化シェル社製、エピコ−ト８２８）１０部、ＢＴレジン（三菱ガス化学社製、ＢＴ２１７０）５部〕のテトラヒドロフラン溶液（固形分濃度：２５％）を乾燥後の厚みが３０μｍになるように塗布し、１００℃で乾燥して接着剤付きポリイミドフィルムを得た。このフィルムを１０ｍｍ幅および９．８ｍｍ幅にスリットして２種類の接着剤付きテ−プを作製した。１０ｍｍ幅のテ−プを接着剤層を外側にして外径１０ｍｍのステンレスの丸棒にスパイラル状に巻き付けた後、両端を固定し、その中央にニクロム製の幅２ｍｍ、厚み４０μｍ、電気抵抗値１４．７Ω／ｍのテ−プを巻き付けた後、両端を固定し、さらにその上に、９ｍｍ幅の接着剤付きテ−プを、接着剤層を内側にしてスパイラル状に巻き付け、両端を固定した。
さらにその上にテトロン製（中外製紐社製、ＴＣＴ−０２５４５）熱収縮テ−プ（組紐、巾４ｍｍ）をスパイラル状に巻き付け、オ−ブン中で１００℃で１時間、２００℃で１時間加熱後、テトロン熱収縮テ−プを外した後、２５０℃で１時間加熱して硬化させた後、放冷して積層体であるスパイラル状物をステンレスの丸棒から外し、長さ１００ｃｍのスパイラル管状ヒ−タ−を得た。
また、このスパイラル管状ヒ−タ−で径１０ｍｍのステンレスパイプを巻いて両端に５０Ｖの電圧を加えた。パイプの温度は１５０℃で、均一にその温度に維持されていた。
【００３１】
実施例２
参考例１で製造した芳香族ポリイミドフィルムに代えて参考例２で製造した７５μｍの芳香族ポリイミドフィルムを使用し、接着剤としてポリイミドシロキサン系の熱硬化性接着剤〔参考例４で得られたポリイミドシロキサン８５部、エポキシ樹脂（油化シェル社製、エピコ−ト８２８）１０部、ＢＴレジン（三菱ガス化学社製、ＢＴ２１７０）５部、シランカップリング剤（東レ・ダウコ−ニング・シリコ−ン社製、ＳＨ６０４０）１部〕を使用した他は実施例１と同様にして長さ１００ｃｍのスパイラル管状ヒ−タ−を得た。
また、このスパイラル管状ヒ−タ−で径１０ｍｍのステンレスパイプを巻いて両端に５０Ｖの電圧を加えた。パイプの温度は１５３℃で、均一にその温度に維持されていた。
【００３２】
実施例３
参考例２で製造した７５μｍの芳香族ポリイミドフィルムに参考例５で得られた接着剤溶液〔イミドオリゴマ−５部、芳香族ポリイミド製繊維５部、１，４−ジオキサン４０部）を乾燥後の厚みが２５μｍになるように塗布し、１５０℃で乾燥して接着剤付きポリイミドフィルムを得た。このフィルムを１０ｍｍ幅および９．８ｍｍ幅にスリットして２種類の接着剤付きテ−プを作製した。１０ｍｍ幅のテ−プを接着剤層を外側にして外径１０ｍｍのステンレスの丸棒にスパイラル状に巻き付けた後、両端を固定し、その中央にニクロム製の幅２ｍｍ、厚み４０μｍ、電気抵抗値１４．７Ω／ｍのテ−プを巻き付けた後、両端を固定し、さらにその上に、９．８ｍｍ幅の接着剤付きテ−プを、接着剤層を内側にしてスパイラル状に巻き付け、両端を固定した。
さらにその上にポリイミド繊維の組紐（レンチング社製のポリイミド繊維Ｐ８４を使用、幅４ｍｍ）をスパイラル状に巻き付け、オ−ブン中で１００℃で１時間、２００℃で１時間、３００℃で１時間加熱後、組紐を外し、さらに３４０℃で１時間加熱して硬化させた後、放冷して積層体であるスパイラル状物をステンレスの丸棒から外し、長さ１００ｃｍのスパイラル管状ヒ−タ−を得た。
また、このスパイラル管状ヒ−タ−で径１０ｍｍのステンレスパイプを巻いて両端に５０Ｖの電圧を加えた。パイプの温度は１５０℃で、均一にその温度に維持されていた。
【００３３】
【発明の効果】
この発明は以上説明したように構成されているので、以下に記載のような効果を奏する。
この発明のスパイラル管状ヒ−タ−は形状保持性を有し、パイプとの密着性が良く、熱効率が良好である。
さらに、ポリイミド系接着剤を使用しているので、耐熱性が高く、電気絶縁性にも優れたスパイラル管状ヒ−タ−である。
また、被加熱体に容易にしかも均等に整然と装着することができる。
【図面の簡単な説明】
【図１】図１は、この発明のスパイラル管状ヒ−タ−の一例をスパイラル芯に平行に切断した一部断面図である。
【図２】図２は、この発明のスパイラル管状ヒ−タ−の一例を示す斜視図である。
【図３】図３は、この発明のスパイラル管状ヒ−タ−の一例の使用例を示す一部斜視図である。
１ スパイラル管状ヒ−タ−
２ 内側層を形成するテ−プ状耐熱性高分子材料Ａ
３ 中間層を形成するポリイミド系接着剤層
３ａ 内側層に接するポリイミド系接着剤層
３ｂ 外側層に接するポリイミド系接着剤層
４ 外側層を形成するテ−プ状耐熱性高分子材料Ｂ
５ 導電性を付与する可とう性の導電性基材
１０ 被加熱体[0001]
BACKGROUND OF THE INVENTION
This invention is suitable for applications such as a heater having good adhesion to a pipe and good thermal efficiency, and is particularly suitable for the purpose of heat insulation of pipes of semiconductor manufacturing equipment and analytical instruments. A flexible conductive base material, for example, a tape-like polymer material as an inner layer and an adhesive as an outer layer provided integrally with a flat base material such as a heater. The present invention relates to a spiral tubular heater in which a flexible conductive base material is laminated and integrated with a heat-resistant polymer material by a polyimide adhesive.
[0002]
[Prior art]
Conventionally, in order to prevent solidification and adhesion of a substance to be transported to a pipe constituting a pipe for an analytical instrument such as a liquid chromatograph apparatus or a mass spectrometer or a chemical solution transport path for a medical instrument, the pipe is heated and kept warm. In some cases, the pipe is heated in order to evaporate the substance adhering to the inner surface and secure a degree of vacuum. Furthermore, the water pipe may be kept warm and heated to prevent the water pipe from freezing.
In such a case, conventionally, a flexible sheet heating element such as a ribbon heater is generally formed in a belt shape and wound around a pipe.
[0003]
[Problems to be solved by the invention]
However, the piping system of the above pipe is generally provided in a narrow space between devices, and it is difficult to wrap a pipe with a sheet heating element, and the sheet heating The body has poor adhesion to the pipe. For this reason, the thermal efficiency is low, and therefore the temperature cannot be accurately controlled.
An object of the present invention is to provide a heater that is easy to attach to an object to be heated and has good adhesion.
[0004]
[Means for Solving the Problems]
The present invention includes a tape-like heat-resistant polymer material A that forms an inner layer of a spiral material, a polyimide-based adhesive layer that forms an intermediate layer, and a tape-like heat-resistant polymer material B that forms an outer layer. The present invention relates to a shape-retaining spiral tubular heater in which a flexible conductive base material that imparts conductivity between both ends in the longitudinal direction is integrally provided on any layer of a laminate having the structure described above.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
Preferred embodiments of the present invention are listed below.
1) The above-described spiral tubular heat resistant polymer material A that forms the inner layer side of the spiral-shaped material and the tape-shaped heat resistant polymer material B that forms the outer layer each have a thickness of 25 to 200 μm. -Ta-.
2) The spiral tubular heater as described above, wherein the flexible conductive substrate is a planar substrate such as a tape heater.
3) The spiral tubular heater as described above, wherein the tape-shaped heat-resistant polymer material A and the tape-shaped heat-resistant polymer material B are tape-shaped aromatic polyimide films.
4) A flexible conductive substrate is integrally provided in parallel with the longitudinal direction of the laminate, and the conductive substrate is folded at least once and both ends are taken out from one of the spiral objects. The above spiral tubular heater.
[0006]
Hereinafter, the present invention will be described in detail with reference to the drawings.
FIG. 1 is a partial sectional view of an example of a spiral tubular heater according to the present invention cut in parallel to a spiral core.
FIG. 2 is a perspective view showing an example of a spiral tubular heater of the present invention.
FIG. 3 is a partial perspective view showing an example of use of an example of the spiral tubular heater of the present invention.
[0007]
In FIG. 1, a shape-retaining spiral tubular heater-1 is a tape-like heat-resistant polymer material A that forms an inner layer of a spiral object, and a polyimide-based adhesive layer that forms an intermediate layer. 3 (consisting of a polyimide-based adhesive layer 3a in contact with the inner layer and a polyimide-based adhesive layer 3b in contact with the outer layer) and a tape-like heat-resistant polymer material B forming the outer layer 4 A flexible conductive base material 5 that imparts conductivity between both ends in the longitudinal direction is integrally formed between any layer of the laminate, preferably between the polyimide-based adhesive layer 3a and the polyimide-based adhesive layer 3b. Is provided.
[0008]
In FIG. 2, a shape-retaining spiral tubular heater-1 is a tape-like heat-resistant polymer material A that forms an inner layer of a spiral object, and a polyimide-based adhesive layer that forms an intermediate layer. (Not shown) and a flexible material which imparts conductivity between both ends in the longitudinal direction to any layer of the laminate having a structure of 4 which is a tape-like heat-resistant polymer material B forming the outer layer. The conductive substrate 5 is provided integrally.
[0009]
In FIG. 3, the heated object 10 is inserted between the spiral tubular heaters by expanding the space between the shape-retaining spiral tubular heaters until the heated object 10 can be inserted, and then the heated object. The spiral tubular heater-1 is rotated in the direction of the arrow in the figure while maintaining 10 in that state, and the object to be heated 10 is taken into the spiral tubular heater-1 with this rotation. The spiral tubular heater-1 can be attached to the object to be heated 10 relatively easily and quickly simply by rotating it in the axial direction of the heater-1, and after the attachment, the spiral tubular heater-1 is Since it returns to the shape, it can be mounted evenly and orderly on the body 10 to be heated. Therefore, for example, even when both ends of the heated object are connected to a large apparatus or the like and there is almost no degree of freedom, the object can be wound around the heated object 10 relatively easily and quickly. In addition, since the diameter of the spiral tubular heater can be set arbitrarily, not only the object to be heated with a small degree of freedom but also the object to be heated with a large degree of freedom is not limited by the size of the diameter. As long as it is in the shape of a rod or pipe, it can be applied to any object to be heated.
[0010]
The spiral tubular heater of the present invention is made of, for example, a tape-like heat-resistant polymer material A with a polyimide-based adhesive serving as an inner layer made of metal, for example, heat-resistant such as stainless steel. A long shape-imparting member such as a rod or pipe is wound in a spiral shape, and a flexible conductive substrate, preferably a planar substrate, is wound around the center of the long shape-imparting member. Tape-like heat-resistant polymer material B with adhesive, which will be the outer layer, is spirally stacked with the polyimide-based adhesive on the inside, and the adhesive is cured and laminated and integrated (in this process, shape Apply pressure so as not to unwind the wound material wrapped around the imparting member), and remove the formed laminate from the long shape imparting member such as a rod or pipe, as a molded product holding the shape in a spiral shape To get Kill.
The spiral tubular heater of the present invention is almost uniform in shape, such as the outer diameter of the spiral object, even in an environment heated to a normal temperature, preferably about 200 ° C.・ There is no change in order and the shape is maintained.
[0011]
The sheet-like heat-resistant polymer material A forming the inner layer of the spiral material in the present invention is made of an aromatic polyimide or an aromatic polyamide having a glass transition temperature or a melting point of 180 ° C. or more, and preferably has a thickness. Is a tape-like film having a width of 25 to 200 μm and a width of 3 to 50 mm. In particular, the coefficient of linear expansion (CTE) at 50-300 ° C. is 60 × 10 -Five cm / cm / ° C. (may be expressed in ppm) or less, especially 3-50 × 10 -Five cm / cm / ° C. and tensile modulus of 200-1400 kg / mm 2 An aromatic polyimide film, an aromatic polyamide film, or a heat resistant rubber such as silicon rubber is preferably used. Among them, an aromatic polyimide film having a water absorption rate of 4% or less, particularly 3% or less is preferably used.
[0012]
Examples of the aromatic polyimide include 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, and 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride. It is obtained by polymerizing and imidizing an aromatic tetracarboxylic dianhydride such as p-phenylenediamine and 4,4′-diaminodiphenyl ether. In particular, what is obtained by using 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride as an aromatic polyimide in an amount of 15 mol% or more in the aromatic tetracarboxylic acid component is heat resistance, low linear expansion coefficient, It is preferable because of its low water absorption.
Examples of the aromatic polyamide include aromatic acid chlorides such as 2-chloroterephthalic acid chloride and 2,5-dichloroterephthalic acid chloride, 2-chloro-p-ferylenediamine, and 4,4′-diaminodiphenyl ether. Obtained by reaction with an aromatic diamine.
[0013]
In this invention, the polyimide-based adhesive layer forming the intermediate layer is composed of a heat-resistant polyimide-based thermoplastic adhesive or a polyimide-based thermosetting adhesive, and preferably in a dry state of the laminated adhesive layers. The thickness is 2-100 μm and the width is 3-50 mm.
The adhesive layer may be provided as a tape-like film with an adhesive, or after the tape-like film is wound, the adhesive is applied or the adhesive sheet is laminated and the adhesive-attached tape is attached. -You may provide a loop.
[0014]
Examples of the polyimide thermoplastic adhesive include polyimide polymers containing an imide bond in a polymer chain such as polyimide, polyamideimide, polyetherimide, and polyesterimide.
As the polyimide-based thermosetting adhesive, a combination of a polymer containing an imide bond in a polymer chain such as polyimide, polyamideimide, polyetherimide, polyesterimide, polyimidesiloxane, and thermosetting resin is generally used. is there. Examples of the thermosetting resin include thermosetting resins such as epoxy resins, phenol resins and acrylate resins, and polyimide oligomers having a reactive functional group at the terminal or side chain such as bismaleimide resins. Can be mentioned.
It is preferable that Tg of the said polyimide-type thermoplastic adhesive and the polyimide-type thermosetting adhesive after hardening is 20-380 degreeC, and it is especially preferable that it is 30-340 degreeC.
[0015]
The tensile modulus (25 ° C.) of the polyimide-based thermoplastic adhesive and the cured polyimide-based thermosetting adhesive is 5-450 kg / mm. 2 It is preferable that More preferably, 10-400 kg / mm 2 It is.
The polyimide-based thermoplastic adhesive and the cured polyimide-based thermosetting adhesive preferably use 5 to 100 parts by weight of polyimide. More preferably, the polyimide is 10% by weight or more.
The polyimide adhesive may contain a silane coupling agent or a titanate coupling agent. The mixing amount of the silane coupling agent is preferably 0.1-6 parts by weight with respect to 100 parts by weight of the adhesive. More preferably, it is 0.3-5 weight. As the type of silane coupling agent, aminosilane, epoxysilane, thiolsilane and the like are suitable.
The polyimide adhesive is preferably provided on one side of the tape-like heat resistant resin film A and one side of the tape-like heat resistant resin film B.
[0016]
The heat-resistant resin film B forming the outer layer in the present invention is preferably composed of an aromatic polyimide, aromatic polyamide, aromatic polyester, fluororesin or aromatic polyamideimide having a glass transition temperature or melting point of 180 ° C. or higher. A sheet-like film having a thickness of 25 to 200 μm and a width of 3 to 50 mm is used. In particular, the coefficient of linear expansion (CTE) at 50-250 ° C. is 60 × 10 -Five cm / cm / ° C. (may be expressed in ppm) or less, especially 3-50 × 10 -Five cm / cm / ° C. and tensile modulus of 200-1400 kg / mm 2 An aromatic polyimide film or an aromatic polyamide film is preferably used. Among them, an aromatic polyimide film having a water absorption rate of 4% or less, particularly 3% or less is preferably used.
[0017]
As a flexible conductive base material in the present invention, a metal foil, a metal wire, a strip-like metal which imparts a conductive function between both ends in the longitudinal direction of a spiral object, preferably a thickness of 5 to 100 μm, a width A metal foil such as a copper foil or nichrome foil having a thickness of about 0.4 to 40 mm is used.
This flexible conductive substrate may be provided alone or in parallel, and the tape-like heat-resistant resin film B is almost entirely covered with the polyimide adhesive. However, it is preferable to be provided almost at the center.
In addition, a flexible conductive substrate whose surface is previously thinly coated with a heat resistant resin by a coating method or the like may be used.
[0018]
The aromatic polyimide film is obtained as follows, for example.
First, an aromatic tetracarboxylic dianhydride such as pyromellitic dianhydride or 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and an aromatic diamine are mixed with N, N-dimethylacetamide or N -Polymerized in an organic polar solvent such as methyl-2-pyrrolidone, and the logarithmic viscosity of the polymer (measurement temperature: 30 ° C., concentration: 0.5 g / 100 ml solvent, solvent: N-methyl-2-pyrrolidone) is 1 -5. A polyamic acid solution having a polymer concentration of about 15-40% by weight is obtained.
Then, 0.01 to 1% by weight of a phosphorus compound, preferably an organic phosphorus compound such as (poly) phosphate ester and / or an amine salt of phosphate ester, or inorganic phosphorus with respect to 100 parts by weight of this polyamic acid. Compound, and preferably 0.02-6 parts by weight of colloidal silica, silicon nitride, talc, titanium oxide and other inorganic fillers (preferably having an average particle size of 0.005-5 μm with respect to 100 parts by weight of polyamic acid In particular, 0.005-2 μm) is added to prepare a polyamic acid solution composition.
This polyamic acid solution composition is cast as it is or added with a chemical imidizing agent, and cast onto a support surface having a smooth surface, dried to form a solidified film, and the solidified film is peeled off from the surface of the support.
Next, after applying a surface treatment liquid containing an aminosilane-based, epoxysilane-based or titanate-based surface treatment agent to one or both sides of the solidified film, it can be further dried.
If necessary, the solidified film obtained as described above is stretched in both directions and then heated at a temperature within the range of 350 to 500 ° C. while holding both edges in the width direction of the dried film. Then, it can be suitably produced as an aromatic polyimide film by drying and imidization.
The aromatic polyimide film obtained as described above is preferably heated at a temperature of about 200 to 400 ° C. under low tension or no tension, and is subjected to stress relaxation treatment and wound.
This aromatic polyimide film can be used as an aromatic polyimide film with improved adhesiveness, as it is or after being subjected to surface treatment by corona discharge treatment, plasma treatment, ultraviolet irradiation, glow discharge treatment or flame treatment.
[0019]
The aromatic polyamide film can be manufactured, for example, as follows. An aromatic acid chloride and an aromatic diamine are synthesized by solution polymerization in an organic polar solvent or by interfacial polymerization using an aqueous medium. Polymer solutions use acid chloride and diamine as monomers, and hydrogen chloride is by-produced. In order to neutralize this, inorganic neutralizers such as calcium hydroxide, or organic neutralization such as ethylene oxide Add agent.
The reaction between isocyanate and carboxylic acid is carried out in an aprotic organic polar solvent in the presence of a catalyst.
These polymer solutions may be used as a film-forming stock solution for forming a film as it is, or the polymer may be isolated once and then redissolved in the above solvent to prepare a film-forming stock solution. An inorganic salt such as calcium chloride or magnesium chloride may be added as a dissolution aid to the film-forming stock solution. The polymer concentration in the stock solution is preferably 2 to 35% by weight.
[0020]
The shape-retaining spiral tubular heater of the present invention has, for example, the same outer shape as that of the object to be heated (the shape may have an arbitrary shape such as a circular cross section or a square shape). Tape-like heat-resistant polymeric material A, preferably tape-like aromatic polyimide film A, which is an inner layer wound in a spiral shape on a member, for example, a heat-resistant rod or pipe, and the tape-like aromatic polyimide film A and the same width or a little width Tape-like heat-resistant polymer material B to be a narrow outer layer, preferably a tape-like aromatic polyimide film B, and a polyimide-based adhesive therebetween, and a flexible material that provides conductivity between both ends in the longitudinal direction. A conductive base material, preferably a planar conductive base material such as a tape heater, is disposed. In the case of a polyimide thermosetting adhesive, the solvent is dried and the B stage In the stage, in the case of polyimide-based thermoplastic adhesive, pressure on the laminate In addition, by heating to a temperature above the glass transition temperature or melting point, with the inner layer and outer layer of the film being stacked, in the case of a polyimide thermosetting adhesive, it is heated to a temperature above the curing temperature, Or in the case of a polyimide-type thermoplastic adhesive, it cools, and after hardening a polyimide-type adhesive and carrying out lamination | stacking integration, it removes a spiral-shaped laminated body from a elongate shape provision member, and is obtained.
[0021]
The above method can be preferably carried out, for example, as follows. First, a polyimide-based adhesive is applied to one side of the heat-resistant polymer material A and the heat-resistant polymer material B to be the inner layer, and a film having a dry thickness of 2-100 μm of the polyimide-based adhesive is obtained. This film is slit to 3-50 mm to produce a tape-like heat-resistant polymer material with a polyimide thermosetting adhesive. The tape-like heat-resistant polymer material A is spirally wound around a circular rod or pipe having a diameter of 5 to 50 mm with the polyimide adhesive surface facing outward, and both ends are fixed. Next, a conductive substrate having a width smaller than that of the tape, preferably a tape-like heater, is wound on the tape. Next, a tape-shaped heat-resistant polymer material B with a polyimide-based thermosetting adhesive that becomes an outer layer is wound around the tape so that the polyimide-based adhesives overlap each other. A / polyimide-based thermosetting adhesive / heater / polyimide-based thermosetting adhesive / tape-like heat-resistant polymer material B, and heat around polyethylene terephthalate, polyimide, etc. Pressurize and fix with shrinkable fibers and braids, heat to a temperature in the range of 150-400 ° C, cure and integrate the polyimide adhesive, cool, then stick the formed laminate Alternatively, it can be removed from the pipe to obtain a spiral tubular heater.
[0022]
The spiral tubular heater of the present invention may be applied to a heated object as it is, or may be used after being cut to an appropriate length (in this case, a terminal is provided separately). The outermost layer may be covered with a heat-resistant foaming sheet or a heat-resistant porous sheet for the purpose of keeping heat.
Further, in the case of a heated object having a complicated shape, the heated object may be covered using a combination of a spiral tubular heater and a planar heater.
[0023]
【Example】
Examples of the present invention will be described below.
In the following description, “part” means “part by weight” and “%” means “% by weight”.
In each of the following examples, the physical properties of the polyimide film and the like were measured by the following method.
Water absorption: measured according to ASTM D570-63 (23 ° C. × 24 hours)
Tensile modulus: measured according to ASTM D882-64T (MD)
Linear expansion coefficient (50-250 ° C. or 50-300 ° C.): A sample subjected to stress relaxation by heating at 300 ° C. for 30 minutes with a TMA apparatus (tensile mode: 2 g load, sample length 10 mm, 20 ° C./min) Measurement
[0024]
Reference example 1
To a polymerization tank having an internal volume of 100 liters, 54.6 kg of N, N-dimethylacetamide was added, and then 8.826 kg of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 3.243 kg of paraphenylenediamine. And a polymerization reaction at 30 ° C. for 10 hours to obtain a polymer having a logarithmic viscosity (measurement temperature: 30 ° C., concentration: 0.5 g / 100 ml solvent, solvent: N, N-dimethylacetamide) of 1.60, polymer -A polyamic acid (imidation rate: 5% or less) solution having a concentration of 18% by weight was obtained.
In this polyamic acid solution, 0.1% by weight of monostearyl phosphate ester triethanolamine salt and 0.5 parts by weight (based on solid content) of 0.1% by weight of the polyamic acid and 0.1% by weight of the average particles. 08 μm colloidal silica was added and mixed uniformly to obtain a polyamic acid solution composition.
The rotational viscosity of this polyamic acid solution composition was 3000 poise. This polyamic acid solution composition is continuously extruded from the slit of the T-die mold onto a smooth support of a casting / drying furnace to form a thin film of the solution, dried at 130 ° C. for 10 minutes, and peeled off from the support Then, curing was performed in a curing furnace with the width direction held (from 200 ° C. to 450 ° C. for about 20 minutes) to obtain an aromatic polyimide film having a thickness of 75 μm. This film has an elastic modulus of 750 kg / mm. 2 The linear expansion coefficient (50-300 ° C.) was 16 ppm, and the water absorption was 1.5%.
[0025]
Reference example 2
An aromatic polyimide film having a thickness of 75 μm as in Reference Example 1 except that 4,4′-diaminodiphenyl ether is 6.007 kg and N, N-dimethylacetamide is 67.6 kg instead of paraphenylenediamine. Got.
This film has an elastic modulus of 370 kg / mm. 2 The linear expansion coefficient (50 ° C. to 250 ° C.) was 40 ppm, and the water absorption was 2.5%.
[0026]
Reference example 3
In a separable flask made of glass having a volume of 2 liters, 1000 g of N-methyl-2-pyrrolidone (NMP) was put, and 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride (a -BPDA), 73.56 g (250 mmol), diaminopolysiloxane (DAPS) (Toray Dow Corning Silicon Co., BY16-853U), 88 g (100 mmol), 2,2-bis [4- Add 61.58 g (150 mmol) of (4-aminophenoxy) phenyl] propane (BAPP) and stir at 60 ° C. for 2 hours under nitrogen atmosphere. Thereafter, the temperature was further raised to 200 ° C., and the polymerization reaction was carried out for 3 hours while removing water. Finally, the reaction solution was added to 10 liters of water, and using a homomixer, the polymer was precipitated by precipitation for 30 minutes and the polymer powder was isolated. This polymer powder was washed twice at 80 ° C. for 1 hour using a homomixer in 5 liters of 2-propanol, dried with hot air at 120 ° C. for 5 hours, and then vacuum dried at 120 ° C. for 24 hours. 210 g of polyimide siloxane powder was obtained. This polyimidesiloxane had a logarithmic viscosity (30 ° C.) of 0.32 and an imidization rate of substantially 100%.
A film was prepared from a THF solution of this polyimidesiloxane powder. This film has a tensile modulus of 57 kg / mm. 2 , Tg was 190 ° C.
[0027]
Reference example 4
A polyimidesiloxane powder was obtained in the same manner as in Reference Example 3 except that a-BPDA was changed to 450 mmol, DAPS was changed to 100 mmol, and BAPP was changed to 350 mmol.
A film was prepared from a THF solution of this polyimidesiloxane powder. This film has a tensile modulus of 115 kg / mm. 2 , Tg was 235 ° C.
[0028]
Reference Example 5
175.76 g of N, N-dimethylacetamide (DMAc) was placed in a separable flask made of glass having a volume of 300 ml, and 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride ( a-BPDA) 14.71 g (0.05 mol) and 1,3-bis (4-aminophenoxy) benzene (TPE-R) 29.23 g (0.1 mol) were added, and the mixture was stirred at 50 ° C. for 1 hour. The mixture is stirred under a nitrogen atmosphere to form an amic acid oligomer, and then the reaction solution is heated to about 165 ° C. and stirred at that temperature for 3 hours to form an imide oligomer having an amino group at the terminal. It was.
After cooling the reaction solution to 50 ° C., 11.77 g (0.12 mol) of maleic anhydride and 35 g of xylene are added, and the reaction solution is heated to 160 ° C. while removing xylene together with water that generates xylene. The mixture is stirred for 4 hours to produce an imide oligomer having an unsaturated group at the end. Finally, the reaction solution is cooled to room temperature (about 20 ° C.) and then poured into water to precipitate a powdered imide oligomer. The precipitated imide oligomer powder was separated by filtration, washed twice with methanol at 25 ° C., and dried under reduced pressure to produce a terminal-modified imide oligomer.
This terminal-modified imide oligomer had an imidation ratio of 95% or more and a logarithmic viscosity of 0.04.
[0029]
On the other hand, in a glass flask having a volume of 300 ml, N-methyl-2-
The reaction solution is extruded into a fiber at room temperature (about 20 ° C.) to form a fiber by a wet spinning method in which the fiber is poured into water at room temperature or lower. The fiber is washed twice with methanol at 25 ° C. To produce an aromatic polyimide fiber (diameter: 200 μm).
The polyimide of this aromatic polyimide fiber had an imidization ratio of 95% or more and a logarithmic viscosity of 0.41.
50 g of the imide oligomer thus obtained, 50 g of aromatic polyimide fiber and 400 g of 1,4-dioxane were charged into a 1 liter glass container and stirred at room temperature (about 25 ° C.) for about 2 hours to obtain a uniform adhesive solution. A thermosetting resin solution was prepared.
This solution composition maintained a uniform solution state even when left at room temperature for 1 week.
After the above solution composition is cast on a glass plate to form a thin film, it is heated and dried at 90 ° C. for 30 minutes and 140 ° C. for 30 minutes, peeled off from the glass plate, and has a thermosetting thickness. A dry film which is a 20 μm film adhesive was produced.
This film has a tensile modulus of 200 kg / mm. 2 And Tg was 260 ° C.
[0030]
Example 1
A polyimidesiloxane thermosetting adhesive [85 parts of polyimidesiloxane obtained in Reference Example 3; epoxy resin (Epicoat 828, Epicoat 828)] 10 on the 75 μm aromatic polyimide film produced in Reference Example 1 Part, BT resin (Mitsubishi Gas Chemical Co., Ltd., BT2170) 5 parts tetrahydrofuran solution (solid content concentration: 25%) was applied so that the thickness after drying was 30 μm, dried at 100 ° C. with adhesive A polyimide film was obtained. This film was slit to 10 mm width and 9.8 mm width to prepare two types of tapes with adhesive. A tape with a width of 10 mm was wound around a stainless steel round bar with an outer diameter of 10 mm with the adhesive layer on the outside, and then fixed at both ends. Nichrome width 2 mm, thickness 40 μm, electrical resistance at the center After winding a tape of 14.7 Ω / m, both ends are fixed, and then a tape with an adhesive of 9 mm width is wound on it in a spiral shape with the adhesive layer inside, and both ends are fixed. did.
Further, a Tetoron (made by Chugai String Corp., TCT-02545) heat-shrink tape (braid,
Further, a stainless pipe having a diameter of 10 mm was wound with this spiral tubular heater, and a voltage of 50 V was applied to both ends. The temperature of the pipe was 150 ° C., and the temperature was uniformly maintained.
[0031]
Example 2
Instead of the aromatic polyimide film produced in Reference Example 1, the 75 μm aromatic polyimide film produced in Reference Example 2 was used, and a polyimidesiloxane thermosetting adhesive [the polyimide obtained in Reference Example 4 was used as the adhesive. 85 parts of siloxane, 10 parts of epoxy resin (manufactured by Yuka Shell, Epicoat 828), 5 parts of BT resin (BT2170, manufactured by Mitsubishi Gas Chemical Company), silane coupling agent (Toray Dow Corning Silicone Co., Ltd.) A spiral tubular heater having a length of 100 cm was obtained in the same manner as in Example 1 except that 1 part of SH6040) was used.
Further, a stainless pipe having a diameter of 10 mm was wound with this spiral tubular heater, and a voltage of 50 V was applied to both ends. The temperature of the pipe was 153 ° C., and the temperature was uniformly maintained.
[0032]
Example 3
Thickness after drying the adhesive solution (5 parts of imide oligomer, 5 parts of aromatic polyimide fiber, 40 parts of 1,4-dioxane) obtained in Reference Example 5 on the 75 μm aromatic polyimide film produced in Reference Example 2 Was applied to a thickness of 25 μm and dried at 150 ° C. to obtain a polyimide film with an adhesive. This film was slit to 10 mm width and 9.8 mm width to prepare two types of tapes with adhesive. A tape with a width of 10 mm was wound around a stainless steel round bar with an outer diameter of 10 mm with the adhesive layer on the outside, and then fixed at both ends. Nichrome width 2 mm, thickness 40 μm, electrical resistance at the center After winding a tape of 14.7 Ω / m, both ends are fixed, and further, a tape with adhesive having a width of 9.8 mm is wound on it in a spiral shape with the adhesive layer inside. Fixed.
Furthermore, a braid of polyimide fibers (using polyimide fiber P84 made by Lenzing Co.,
Further, a stainless pipe having a diameter of 10 mm was wound with this spiral tubular heater, and a voltage of 50 V was applied to both ends. The temperature of the pipe was 150 ° C., and the temperature was uniformly maintained.
[0033]
【The invention's effect】
Since the present invention is configured as described above, the following effects can be obtained.
The spiral tubular heater of the present invention has shape retention, good adhesion to the pipe, and good thermal efficiency.
Furthermore, since a polyimide-based adhesive is used, the spiral tubular heater has high heat resistance and excellent electrical insulation.
Further, it can be easily and evenly mounted on the object to be heated.
[Brief description of the drawings]
FIG. 1 is a partial cross-sectional view of an example of a spiral tubular heater of the present invention cut in parallel to a spiral core.
FIG. 2 is a perspective view showing an example of a spiral tubular heater of the present invention.
FIG. 3 is a partial perspective view showing an example of use of an example of a spiral tubular heater of the present invention.
1 Spiral tubular heater
2 Tape-shaped heat-resistant polymer material A forming the inner layer
3 Polyimide adhesive layer that forms the intermediate layer
3a Polyimide adhesive layer in contact with inner layer
3b Polyimide adhesive layer in contact with outer layer
4 Tape-shaped heat-resistant polymer material B forming the outer layer
5 Flexible conductive base material that imparts electrical conductivity
10 Object to be heated
Claims (6)
前記可とう性の導電性基材が平面状基材であり、前記可とう性の導電性基材が積層体の長手方向と平行に一体として設けられており、さらに、この導電性基材が少なくとも１回折り返しされて両端部がスパイラル状物の片方から取り出されていることを特徴とする形状保持性のスパイラル管状ヒ−タ−。The tape-like heat-resistant polymer material A for forming the inner layer of the spiral material, the polyimide adhesive layer for forming the intermediate layer, and the tape-like heat-resistant polymer material B for forming the outer layer are included. In a shape-retaining spiral tubular heater in which a flexible conductive base material that imparts conductivity between both ends in the longitudinal direction is integrally provided on any layer of the laminate,
The flexible conductive substrate is a planar substrate, the flexible conductive substrate is integrally provided in parallel to the longitudinal direction of the laminate, and the conductive substrate is A shape-retaining spiral tubular heater, wherein both ends are taken out from at least one of the spiral-shaped objects after being folded at least once.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30076097A JP3758336B2 (en) | 1997-10-31 | 1997-10-31 | Spiral tubular heater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30076097A JP3758336B2 (en) | 1997-10-31 | 1997-10-31 | Spiral tubular heater |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11135236A JPH11135236A (en) | 1999-05-21 |
| JP3758336B2 true JP3758336B2 (en) | 2006-03-22 |
Family
ID=17888776
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30076097A Expired - Fee Related JP3758336B2 (en) | 1997-10-31 | 1997-10-31 | Spiral tubular heater |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3758336B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6348696B2 (en) | 2013-09-30 | 2018-06-27 | ニチアス株式会社 | Tape heater |
| DE102020208760A1 (en) * | 2020-07-14 | 2022-01-20 | Siemens Aktiengesellschaft | Insulation system made of solid insulation material and impregnating resin |
-
1997
- 1997-10-31 JP JP30076097A patent/JP3758336B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11135236A (en) | 1999-05-21 |
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