JP3662269B2 - Thermoplastic polyimide-based tubular film and method for producing the same - Google Patents
Thermoplastic polyimide-based tubular film and method for producing the same Download PDFInfo
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Description
【０００１】
【産業上の利用分野】
本発明は熱可塑性ポリイミド系チューブ状フィルム及びその製造方法に関する。
【０００２】
【従来の技術】
ポリイミド系樹脂は熱硬化性樹脂、非熱可塑性イミド系樹脂、及び熱可塑性イミド系樹脂に分類され、これらポリイミド系樹脂から成るフィルムは耐熱性フィルムとして各種の用途に使用されている。これらのうち、熱硬化性及び非熱可塑性イミド型樹脂は一般に不溶不融であることが多く、ポリイミドの形では加工できず、また熱可塑性ポリイミド系樹脂においてもその溶融粘度が高いため、製膜する際は主としてポリイミドの前駆体であるポリアミド酸の状態で加工していた。すなわち、ポリイミドの前駆体であるポリアミド酸の溶液から流延（キャスト）法により薄膜を作り、その後、乾燥・閉環させてフィルムを製膜するのが一般的であった。そして、ポリイミド系樹脂から成るチューブ状フィルムは、上記得られたフィルムを円筒状に曲げて端部を重ね合わせ、その端部を接着剤を介して接着したり、あるいは熱可塑性イミド系樹脂の場合は端部を加熱溶融させて接着して製造していた。
【０００３】
【発明が解決しようとする課題】
しかし、流延法により製膜されたポリイミド系フィルムはその製造プロセスの制約上、高価格であり、したがって得られたチューブ状フィルムも高価格であった。しかも、得られたチューブ状フィルムには接合部が残るだけでなく、接着不良の場合や接着剤に劣化が生じた場合等には、接合部で剥がれてしまうという問題があった。特に、接着剤を用いる場合には、チューブ状フィルムの耐熱性等の諸特性は接着剤の特性によって制限され、ポリイミド系樹脂の特性を充分に発揮できないという問題があった。
【０００４】
そこで、本発明者らは上記実情に鑑み、鋭意研究の結果、プラスチックとして熱可塑性ポリイミド系樹脂、特に溶融粘度の低い熱可塑性ポリイミド系樹脂を使用することにより、上記課題が解決されることを見いだし、本発明を完成させたものである。
【０００５】
【課題を解決するための手段】
本発明に係る熱可塑性ポリイミド系チューブ状フィルムの要旨とするところは、熱可塑性ポリイミド系樹脂を主成分とし、溶融押出法によりチューブ状に製膜されてなることにある。
【０００６】
かかる本発明の熱可塑性ポリイミド系チューブ状フィルムにおいて、特に熱可塑性ポリイミド系樹脂として、一般式（１）化５
【化５】
【０００７】
また、かかる熱可塑性ポリイミド系チューブ状フィルムにおいて、前記一般式（１）中のAr1 が化６
【化６】
【０００８】
また、かかる熱可塑性ポリイミド系チューブ状フィルムにおいて、前記一般式（１）中のAr2 が化７
【化７】
【０００９】
また、かかる熱可塑性ポリイミド系チューブ状フィルムにおいて、前記一般式（１）中のAr3 が化８
【化８】
【００１０】
次に、本発明に係る熱可塑性ポリイミド系チューブ状フィルムの製造方法の要旨とするところは、熱可塑性ポリイミド系樹脂の粉粒体を充分に乾燥させた後、溶融押出機に充填し、溶融押出法によりチューブ状に製膜することにある。
【００１１】
【作用】
本発明に係る熱可塑性ポリイミド系チューブ状フィルムは、熱可塑性ポリイミド系樹脂を主成分とし、特に前記一般式（１）で表される熱可塑性ポリイミド系樹脂を主成分とする樹脂を、溶融押出法によりチューブ状に押し出して製膜されたものである。したがって、得られたチューブ状フィルムには接合部はなく、素材である熱可塑性ポリイミド系樹脂の特性を充分に発揮し得るチューブ状フィルムを得ることができる。また、特に前記一般式（１）で表される熱可塑性ポリイミド系樹脂は溶融粘度が低いため、溶融押出法により容易に製膜することができるので、安価で寸法精度・膜厚精度に優れた熱可塑性ポリイミド系チューブ状フィルムを得ることができる。
【００１２】
また、本発明に係る熱可塑性ポリイミド系チューブ状フィルムの製造方法において、熱可塑性ポリイミド系樹脂を充分に乾燥させて用いることにより、樹脂の分解や熱可塑流動性が悪化してフィルムに気泡等が発生する現象を防ぎ、寸法精度・膜厚精度に優れた熱可塑性ポリイミド系チューブ状フィルムを得ることができる。
【００１３】
【実施例】
次に、本発明に係る熱可塑性ポリイミド系チューブ状フィルムとその製造方法の実施例を詳しく説明する。
【００１４】
本発明の熱可塑性ポリイミド系チューブ状フィルムは、一般式（１）化９
【化９】
【００１５】
ここで、前記一般式（１）中のAr1 を具体的に例示すると、化１０
【化１０】
【化１１】
【００１６】
また、前記一般式（１）中のAr2 としては、化１２、化１３
【化１２】
【化１４】
【００１７】
また、前記一般式（１）中のAr3 としては、化１５、化１６
【化１５】
【化１７】
【００１８】
上記一般式（１）で表される熱可塑性ポリイミド系樹脂は、耐熱性、耐放射線性、低吸水率等の優れた特性を備えており、特に従来の熱硬化性、又は非熱可塑性イミド系樹脂のいずれとも異なる点として溶融粘度が低いことを特徴とする。例えば、高化式フローテスター（ダイ１０mm×０．１mm）を用いて融点付近の２００〜３５０℃で測定した溶融粘度は、１０００〜４０００ポイズと実測されている。溶融粘度が上記範囲以外の熱可塑性ポリイミド系樹脂を用いてもよいが、寸法精度・膜厚精度に優れた熱可塑性ポリイミド系チューブ状フィルムを得るためには上記範囲内の溶融粘度を有する樹脂を用いるのが好ましい。なお、溶融粘度が上記範囲以外の樹脂を用いると寸法精度・膜厚精度が低下する傾向になり、また、製膜も困難である場合が多いが、このような樹脂も用途によっては使用可能である。
【００１９】
本発明に用いる熱可塑性ポリイミド系樹脂の製造方法の１例を示すと、公知の方法によりポリアミド酸溶液を得た後、化学量論以上の脱水剤と触媒量の第３級アミンを加えて攪拌することによりポリイミドのスラリーが得られる。得られたスラリーを減圧下に収集した後、乾燥させるとポリイミドの粉体（粒径；５〜２０μｍ）が得られるので、これを粒径４０〜６０μｍまで増粒し、更に熱風等により充分に乾燥させて、本発明に用いる熱可塑性ポリイミド系樹脂を得る。この際、充分に乾燥させることが望ましく、例えば約２５０℃の熱風循環式乾燥オーブン中で２４時間熱処理を行うことにより、乾燥させるのが好ましい。これは、樹脂に対する含有水分量が大きいと、ポリイミド系樹脂の分解や熱可塑流動性が悪化してフィルムに気泡等が発生する現象が生じ、寸法精度・膜厚精度が優れた熱可塑性ポリイミド系チューブ状フィルムを製膜できないからである。また、粒径４０〜６０μｍまで増粒するのは、粒径を揃えて粉粒体を充分に乾燥させるためであり、また溶融させる際にも均一に加熱できるようにするためである。
【００２０】
このようにして得られた熱可塑性ポリイミド系樹脂は単独で用いても良いが、熱伝導性を向上させるために無機系充填材を混合してもなんら差し支えない。この際、いわゆる無機系充填材としては、導電性カーボン、タルク、チタン酸ウイスカー、窒化ボロン等を例示できるが、これらのみに制限されない。また、熱可塑性ポリイミド系樹脂の性能を著しく低下させないならば、安定剤、滑剤、界面活性剤、顔料、ポリイミド系樹脂以外の樹脂等を添加しても良く、このことは特に制限されない。
【００２１】
本発明の熱可塑性ポリイミド系チューブ状フィルムは、溶融押出法によりチューブ状に製膜して製造されるが、この溶融押出法はフィルム、シート、パイプなどのようなエンドレスの長尺物を連続成形する方法で、成形能率がきわめて高く非常に経済性のある成形法である。より具体的には、熱可塑性ポリイミド系樹脂の粉粒体を加熱シリンダ（バレル）内で溶融させて、スクリュで先端のダイ（金型）で形を与えつつ押出し、これを水又は空気で冷却固化させることによって成形するのである。なお、ダイの形状によりさまざまな断面形状の成形品を作ることができる。
【００２２】
本発明の熱可塑性ポリイミド系チューブ状フィルムの製造方法を具体的に例示すると、押出機の先に環状のダイを取付けた溶融押出機を用いて容易に得ることができる。すなわち、上記の充分に乾燥させた熱可塑性ポリイミド系樹脂の粉粒体を該溶融押出機に充填し、樹脂の融点以上の温度に加熱して溶融させ、ダイから薄いフィルムをチューブ状に押出すとともに冷却して本発明の熱可塑性ポリイミド系チューブ状フィルムを得ることができる。なお、必要に応じて上記熱可塑性ポリイミド系樹脂の粉粒体に無機充填材、安定剤等を混合して用いてもよい。ここで用いられる溶融押出機としては、同業者であれば容易に類推できる一般的な溶融押出機を使用することが可能である。このようにして耐熱性、耐放射線性、低吸水率等の特性に優れ、特に、寸法精度・膜厚精度に優れた熱可塑性ポリイミド系チューブ状フィルムを製造することができるのである。
【００２３】
以上、本発明に係る熱可塑性ポリイミド系チューブ状フィルム及びその製造方法の実施例を説明したが、本発明はこれらの実施例のみに限定されるものではなく、本発明はその趣旨を逸脱しない範囲内で当業者の知識に基づき、種々なる改良、変更、修正を加えた態様で実施しうるものである。
【００２４】
以下に実施例により本発明をより具体的に説明するが、本発明はこれら実施例によって限定されるものではない。
【００２５】
実施例 １
５０ミリリットルメスフラスコにエチレングリコールビストリメリット酸二無水物（以下、ＴＭＥＧという。）１．０ｇ及びジメチルホルムアミド（以下、ＤＭＦという。）１０．０ｇを採り、スターラーを用いて攪拌し充分溶かした。他方、攪拌機を備えた５００ミリリットル三口フラスコに２，２−ビス〔４−（４−アミノフェノキシ）フェニル〕プロパン（以下、ＢＡＰＰという。）２０．０ｇ及びＤＭＦ６８．１ｇを入れ、その三口フラスコ中の雰囲気を窒素で置換しながら攪拌し、充分溶かした。次に、１００ミリリットルのナスフラスコにＴＭＥＧ１５．０ｇ、及び３，３’，４，４’−ベンゾフェノンテトラカルボン酸二無水物（以下、ＢＴＤＡという。）３．１ｇを採取し、よく混合した後、ＢＡＰＰ溶液中に固体状で添加した。さらに、この１００ミリリットルのナスフラスコ中の壁面に残存付着するＴＭＥＧ及びＢＴＤＡの混合物を２１．５ｇのＤＭＦにより三口フラスコ中へ流し入れた。約１時間攪拌した後、５０ミリリットルのメスフラスコ中のＴＭＥＧ溶液を三口フラスコ中の溶液の粘度に注目しながら三口フラスコ中に徐々に投入した。最大粘度に達した後、ＴＭＥＧ溶液の投入を終了し、１時間攪拌しながら放置し、ポリアミド酸溶液を得た。
【００２６】
イミド化は、次のようにして行った。まず、１００ミリリットルのメスフラスコにイソキノリン２．０ｇと無水酢酸２０．０ｇを採り、反応器へ導入後、攪拌を継続しているとポリイミドのスラリーが析出した。アスピレーターで減圧下にスラリーを収集した後、減圧下に乾燥して、２８．５ｇのポリイミドの粉体（粒径；５〜２０μｍ）を得た。更に、粒径５０μｍまで増粒し、２５０℃の熱風循環式乾燥オーブン中で２４時間熱処理を行い、充分に乾燥させた。
【００２７】
次に、この熱処理を施したポリイミド粉体を環状ダイス、真空水槽式のサイジングスリーブを取り付けた溶融押出機のホッパーから投入して、厚み５０μｍ、長さ２０cmの熱可塑性ポリイミド系チューブ状フィルムを製膜した。このフィルムに２ＭｅＶの電子線を５ＭＧｙ照射して耐放射線性テストを行ったところ、フィルムに変色は生じなかった。
【００２８】
実施例 ２
５０ミリリットルのメスフラスコに２，２−ビス（４−ヒドロキシフェニル）プロパンジベンゾエート−２，２’，３，３’−テトラカルボン酸二無水物（以下、ＥＳＤＡという。）１．０ｇ及びＤＭＦ１０．０ｇを採り、スターラーを用いて攪拌し充分溶かした。他方、攪拌機を備えた５００ミリリットル三口フラスコにＢＡＰＰ２０．０ｇ及びＤＭＦ６８．１ｇを入れ、その三口フラスコ中の雰囲気を窒素で置換しながら攪拌し、充分溶かした。次に、１００ミリリットルのナスフラスコにＥＳＤＡ２７．１ｇを採取し、ＢＡＰＰ溶液中に固体状で添加した。さらに、この１００ミリリットルのナスフラスコ中の壁面に残存付着するＥＳＤＡを２１．５ｇのＤＭＦにより三口フラスコ中へ流し入れた。約１時間攪拌した後、５０ミリリットルのメスフラスコ中のＥＳＤＡ溶液を三口フラスコ中の溶液の粘度に注目しながら三口フラスコ中に徐々に投入した。最大粘度に達した後、ＥＳＤＡ溶液の投入を終了し、１時間攪拌しながら放置し、ポリアミド酸溶液を得た。
【００２９】
実施例１と同様にして、イミド化を行い粒径５０μｍのポリイミド粉体を得た後、熱処理を行いポリイミド粉体を充分に乾燥させた。更に、実施例１と同様にして製膜を行い、厚み５０μｍ、長さ２０cmの熱可塑性ポリイミド系チューブ状フィルムを得た。このフィルムに２ＭｅＶの電子線を５ＭＧｙ照射して耐放射線性テストを行ったところ、フィルムに変色は生じなかった。
【００３０】
【発明の効果】
本発明の熱可塑性ポリイミド系チューブ状フィルムは、熱可塑性ポリイミド系樹脂を主成分とする樹脂を溶融押出法によりチューブ状にフィルムを押し出して製膜されているため、接合部のないチューブ状フィルムが得られ、その熱可塑性ポリイミド系樹脂の特性を充分に発揮し得るチューブ状フィルムが得られる。特に、熱可塑性ポリイミド系樹脂として前記一般式（１）で表される熱可塑性ポリイミド系樹脂を主成分とする樹脂を用いることにより、樹脂の溶融粘度が低く、溶融押出法により容易に製膜することができる。そのため、流延法により前駆体（ポリアミド酸）の薄膜を作り、その後、乾燥・イミド化させて製膜し、更にチューブ状に接合していた従来の方法に比べ、熱可塑性ポリイミド系チューブ状フィルムを非常に安価に製造することができる。また、このような溶融粘度の低い熱可塑性ポリイミド系樹脂の粉粒体を充分に乾燥させて用いることにより、寸法精度、膜厚精度に優れた熱可塑性ポリイミド系チューブ状フィルムを得ることができる。
【００３１】
また、本発明の熱可塑性ポリイミド系チューブ状フィルムは、特にかかる一般式（１）で表される熱可塑性ポリイミド系樹脂が優れた特性を有するため、耐熱性、耐放射線性、機械的特性、寸法安定性、製膜精度、難燃性、耐摩耗性、耐摩擦性、電気特性等に優れ、特に、吸水率が低く、溶融押出法により製膜すると更に寸法精度、膜厚精度に優れたフィルムとなる。そのため、かかる熱可塑性ポリイミド系チューブ状フィルムは、例えば、ＦＰＣ（フレキシブルプリント基板）、電線の絶縁用フィルム、シートベルト、食品用トレー、医療用部品、光学部品機材、さらに、耐熱性を利用した精密電気電子部材、例えば、複写機、プリンターの各種ベルト、例えば、定着ベルト等に好適である。又、寸法精度が良好なので精密機材等の駆動用ベルトに利用可能である。更に、その他あらゆる分野で各種の用途が期待できるものである。[0001]
[Industrial application fields]
The present invention relates to a thermoplastic polyimide tubular film and a method for producing the same.
[0002]
[Prior art]
Polyimide resins are classified into thermosetting resins, non-thermoplastic imide resins, and thermoplastic imide resins, and films made of these polyimide resins are used for various applications as heat resistant films. Of these, thermosetting and non-thermoplastic imide resins are generally insoluble and infusible, and cannot be processed in the form of polyimide, and thermoplastic polyimide resins also have high melt viscosity, so film formation In doing so, it was processed mainly in the state of polyamic acid which is a precursor of polyimide. That is, it is common to form a thin film from a solution of polyamic acid, which is a precursor of polyimide, by casting (casting) method, and then dry and ring-close it to form a film. And the tube-like film made of polyimide resin is bent in the shape of a cylinder and the ends are overlapped, and the ends are bonded with an adhesive, or a thermoplastic imide resin. Was manufactured by heat melting and bonding the ends.
[0003]
[Problems to be solved by the invention]
However, the polyimide-based film formed by the casting method is expensive due to restrictions on the manufacturing process, and thus the obtained tubular film is also expensive. In addition, there is a problem that not only the joint portion remains in the obtained tubular film, but also peels off at the joint portion in the case of poor adhesion or when the adhesive is deteriorated. In particular, when an adhesive is used, various properties such as heat resistance of the tubular film are limited by the properties of the adhesive, and there is a problem that the properties of the polyimide resin cannot be fully exhibited.
[0004]
In view of the above circumstances, the present inventors have intensively researched and found that the above problems can be solved by using a thermoplastic polyimide resin as a plastic, particularly a thermoplastic polyimide resin having a low melt viscosity. The present invention has been completed.
[0005]
[Means for Solving the Problems]
The gist of the thermoplastic polyimide tube-like film according to the present invention is that the thermoplastic polyimide resin is a main component and is formed into a tube by a melt extrusion method.
[0006]
In the thermoplastic polyimide tube-like film of the present invention, the general formula (1)
[Chemical formula 5]
[0007]
Further, in such a thermoplastic polyimide-based tubular film, Ar 1 in the general formula (1) is
[Chemical 6]
[0008]
Moreover, in such a thermoplastic polyimide tube-like film, Ar 2 in the general formula (1) is
[Chemical 7]
[0009]
Further, in such a thermoplastic polyimide tube-like film, Ar 3 in the general formula (1) is
[Chemical 8]
[0010]
Next, the gist of the method for producing the thermoplastic polyimide tube film according to the present invention is that the thermoplastic polyimide resin particles are sufficiently dried and then filled into a melt extruder and melt extruded. It is to be formed into a tube by the method.
[0011]
[Action]
The thermoplastic polyimide tube-like film according to the present invention comprises a thermoplastic polyimide resin as a main component, in particular, a resin having a thermoplastic polyimide resin represented by the general formula (1) as a main component by a melt extrusion method. Is formed into a tube by extrusion. Therefore, the obtained tubular film does not have a joint portion, and a tubular film that can sufficiently exhibit the characteristics of the thermoplastic polyimide resin that is the material can be obtained. In particular, since the thermoplastic polyimide resin represented by the general formula (1) has a low melt viscosity, it can be easily formed by a melt extrusion method, so it is inexpensive and excellent in dimensional accuracy and film thickness accuracy. A thermoplastic polyimide tubular film can be obtained.
[0012]
Further, in the method for producing a thermoplastic polyimide tube-like film according to the present invention, by using the thermoplastic polyimide resin sufficiently dried, the decomposition of the resin or the thermoplastic fluidity deteriorates, and bubbles or the like are formed in the film. The phenomenon which generate | occur | produces can be prevented and the thermoplastic polyimide-type tubular film excellent in the dimensional accuracy and the film thickness accuracy can be obtained.
[0013]
【Example】
Next, examples of the thermoplastic polyimide tubular film according to the present invention and a method for producing the same will be described in detail.
[0014]
The thermoplastic polyimide tube-like film of the present invention has the general formula (1)
[Chemical 9]
[0015]
Here, Ar 1 in the general formula (1) is specifically exemplified as follows:
[Chemical Formula 10]
Embedded image
[0016]
In addition, Ar 2 in the general formula (1) is
Embedded image
Embedded image
[0017]
In addition, Ar 3 in the general formula (1) is represented by chemical formula 15 or chemical formula 16
Embedded image
Embedded image
[0018]
The thermoplastic polyimide resin represented by the general formula (1) has excellent characteristics such as heat resistance, radiation resistance, and low water absorption, and is particularly conventional thermosetting or non-thermoplastic imide type. The difference from any of the resins is that the melt viscosity is low. For example, the melt viscosity measured at 200 to 350 ° C. near the melting point using a Koka type flow tester (die 10 mm × 0.1 mm) has been actually measured as 1000 to 4000 poise. A thermoplastic polyimide resin having a melt viscosity other than the above range may be used, but in order to obtain a thermoplastic polyimide tube-like film having excellent dimensional accuracy and film thickness accuracy, a resin having a melt viscosity within the above range is used. It is preferable to use it. If a resin with a melt viscosity outside the above range is used, the dimensional accuracy and film thickness accuracy tend to decrease, and film formation is often difficult, but such resins can also be used depending on the application. is there.
[0019]
An example of a method for producing a thermoplastic polyimide resin used in the present invention is as follows. After a polyamic acid solution is obtained by a known method, a stoichiometric or higher amount of a dehydrating agent and a catalytic amount of a tertiary amine are added and stirred. By doing so, a slurry of polyimide is obtained. The obtained slurry is collected under reduced pressure and then dried to obtain a polyimide powder (particle size: 5 to 20 μm). This is increased to a particle size of 40 to 60 μm, and further sufficiently heated with hot air or the like. It is made to dry and the thermoplastic polyimide resin used for this invention is obtained. At this time, it is desirable to sufficiently dry, for example, it is preferable to dry by performing a heat treatment for 24 hours in a hot-air circulating drying oven at about 250 ° C. This is because when the moisture content in the resin is large, the polyimide resin is decomposed and the thermoplastic fluidity deteriorates, causing bubbles and the like in the film, resulting in a thermoplastic polyimide system with excellent dimensional accuracy and film thickness accuracy. This is because a tubular film cannot be formed. The reason why the particle size is increased to a particle size of 40 to 60 μm is to make the particle size uniform and to sufficiently dry the granular material, and to allow uniform heating even when melting.
[0020]
The thermoplastic polyimide resin thus obtained may be used alone, but an inorganic filler may be mixed in order to improve thermal conductivity. In this case, examples of so-called inorganic fillers include, but are not limited to, conductive carbon, talc, titanate whiskers, boron nitride, and the like. Further, if the performance of the thermoplastic polyimide resin is not significantly lowered, a stabilizer, a lubricant, a surfactant, a pigment, a resin other than the polyimide resin, and the like may be added, and this is not particularly limited.
[0021]
The thermoplastic polyimide tube-like film of the present invention is produced by forming into a tube shape by a melt extrusion method. This melt-extrusion method continuously forms an endless long product such as a film, a sheet, and a pipe. This is a very economical molding method with extremely high molding efficiency. More specifically, thermoplastic polyimide resin powder is melted in a heating cylinder (barrel), extruded with a screw at the tip die (die), and cooled with water or air. It is formed by solidifying. Note that molded products having various cross-sectional shapes can be made depending on the shape of the die.
[0022]
If the manufacturing method of the thermoplastic polyimide-type tubular film of this invention is illustrated concretely, it can obtain easily using the melt extruder which attached the cyclic | annular die | dye to the tip of the extruder. That is, the above-mentioned sufficiently dried thermoplastic polyimide resin particles are filled in the melt extruder, heated to a temperature equal to or higher than the melting point of the resin and melted, and a thin film is extruded from a die into a tube shape. The thermoplastic polyimide tube-shaped film of the present invention can be obtained by cooling together. In addition, you may mix and use an inorganic filler, a stabilizer, etc. for the granular material of the said thermoplastic polyimide-type resin as needed. As the melt extruder used here, it is possible to use a general melt extruder that can be easily analogized by those skilled in the art. Thus, it is possible to produce a thermoplastic polyimide tube-like film having excellent characteristics such as heat resistance, radiation resistance and low water absorption, and particularly excellent in dimensional accuracy and film thickness accuracy.
[0023]
As mentioned above, although the Example of the thermoplastic polyimide-type tubular film concerning the present invention and its manufacturing method was described, the present invention is not limited only to these Examples, and the present invention is the range which does not deviate from the meaning. The present invention can be carried out in various modes with various improvements, changes and modifications based on the knowledge of those skilled in the art.
[0024]
The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to these examples.
[0025]
Example 1
In a 50 ml volumetric flask, 1.0 g of ethylene glycol bistrimellitic dianhydride (hereinafter referred to as TMEG) and 10.0 g of dimethylformamide (hereinafter referred to as DMF) were taken, and stirred to dissolve well. On the other hand, 20.0 g of 2,2-bis [4- (4-aminophenoxy) phenyl] propane (hereinafter referred to as BAPP) and 68.1 g of DMF were placed in a 500 ml three-necked flask equipped with a stirrer. The atmosphere was sufficiently dissolved by stirring while replacing the atmosphere with nitrogen. Next, 15.0 g of TMEG and 3.1 g of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (hereinafter referred to as BTDA) were collected in a 100 ml eggplant flask and mixed well. Added as a solid in the BAPP solution. Further, a mixture of TMEG and BTDA remaining on the wall surface in the 100 ml eggplant flask was poured into the three-necked flask with 21.5 g of DMF. After stirring for about 1 hour, the TMEG solution in a 50 ml volumetric flask was gradually introduced into the three-necked flask while paying attention to the viscosity of the solution in the three-necked flask. After reaching the maximum viscosity, the addition of the TMEG solution was completed, and the mixture was left stirring for 1 hour to obtain a polyamic acid solution.
[0026]
The imidization was performed as follows. First, 2.0 g of isoquinoline and 20.0 g of acetic anhydride were placed in a 100 ml volumetric flask and introduced into the reactor. After stirring, a polyimide slurry was deposited. The slurry was collected under reduced pressure with an aspirator and then dried under reduced pressure to obtain 28.5 g of polyimide powder (particle size: 5 to 20 μm). Furthermore, the particle size was increased to 50 μm, and heat treatment was performed in a hot air circulation drying oven at 250 ° C. for 24 hours to sufficiently dry.
[0027]
Next, this heat-treated polyimide powder is introduced from a hopper of a melt extruder equipped with an annular die and a vacuum water tank type sizing sleeve to produce a thermoplastic polyimide tubular film having a thickness of 50 μm and a length of 20 cm. Filmed. When this film was irradiated with 5 MGy of a 2 MeV electron beam for a radiation resistance test, no discoloration occurred in the film.
[0028]
Example 2
In a 50 ml volumetric flask, 1.0 g of 2,2-bis (4-hydroxyphenyl) propanedibenzoate-2,2 ′, 3,3′-tetracarboxylic dianhydride (hereinafter referred to as ESDA) and DMF10. 0 g was taken and stirred using a stirrer and dissolved sufficiently. On the other hand, 20.0 g of BAPP and 68.1 g of DMF were put into a 500 ml three-necked flask equipped with a stirrer, and the atmosphere in the three-necked flask was stirred while replacing the atmosphere with nitrogen, and dissolved sufficiently. Next, 27.1 g of ESDA was collected in a 100 ml eggplant flask and added in solid form into the BAPP solution. Further, ESDA remaining on the wall surface of the 100 ml eggplant flask was poured into the three-necked flask with 21.5 g of DMF. After stirring for about 1 hour, the ESDA solution in a 50 ml volumetric flask was gradually poured into the three-necked flask while paying attention to the viscosity of the solution in the three-necked flask. After reaching the maximum viscosity, the introduction of the ESDA solution was terminated and left standing for 1 hour with stirring to obtain a polyamic acid solution.
[0029]
In the same manner as in Example 1, imidization was performed to obtain a polyimide powder having a particle size of 50 μm, and then heat treatment was performed to sufficiently dry the polyimide powder. Further, a film was formed in the same manner as in Example 1 to obtain a thermoplastic polyimide tubular film having a thickness of 50 μm and a length of 20 cm. When this film was irradiated with a 2 MeV electron beam at 5 MGy for a radiation resistance test, no discoloration occurred on the film.
[0030]
【The invention's effect】
The thermoplastic polyimide tube-like film of the present invention is formed by extruding a resin having a thermoplastic polyimide resin as a main component into a tube shape by a melt extrusion method. As a result, a tubular film that can sufficiently exhibit the characteristics of the thermoplastic polyimide resin is obtained. In particular, by using a resin mainly composed of the thermoplastic polyimide resin represented by the general formula (1) as the thermoplastic polyimide resin, the resin has a low melt viscosity and can be easily formed by a melt extrusion method. be able to. Therefore, a thermoplastic polyimide-based tubular film compared to the conventional method in which a thin film of a precursor (polyamic acid) is made by a casting method, then dried and imidized to form a film, and further joined into a tube shape Can be manufactured at a very low cost. Moreover, the thermoplastic polyimide-based tubular film having excellent dimensional accuracy and film thickness accuracy can be obtained by sufficiently drying and using such a thermoplastic polyimide-based resin particle having a low melt viscosity.
[0031]
In addition, the thermoplastic polyimide tube-like film of the present invention has excellent properties, especially the thermoplastic polyimide resin represented by the general formula (1), so that it has heat resistance, radiation resistance, mechanical properties, dimensions. Film with excellent stability, film-forming accuracy, flame retardancy, abrasion resistance, friction resistance, electrical properties, etc., especially with low water absorption, and excellent in dimensional accuracy and film thickness accuracy when film is formed by melt extrusion It becomes. Therefore, such thermoplastic polyimide tube-like films are, for example, FPC (flexible printed circuit board), electric wire insulation films, seat belts, food trays, medical parts, optical parts and equipment, and precision using heat resistance. It is suitable for electric and electronic members such as various belts of copying machines and printers such as fixing belts. Further, since the dimensional accuracy is good, it can be used as a driving belt for precision equipment. Furthermore, various uses can be expected in all other fields.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01323294A JP3662269B2 (en) | 1994-01-10 | 1994-01-10 | Thermoplastic polyimide-based tubular film and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01323294A JP3662269B2 (en) | 1994-01-10 | 1994-01-10 | Thermoplastic polyimide-based tubular film and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07205255A JPH07205255A (en) | 1995-08-08 |
| JP3662269B2 true JP3662269B2 (en) | 2005-06-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP01323294A Expired - Fee Related JP3662269B2 (en) | 1994-01-10 | 1994-01-10 | Thermoplastic polyimide-based tubular film and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3662269B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0775716B1 (en) * | 1995-01-11 | 1999-07-28 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Novel heat-fusible copolymer, and powder, film, laminated heat insulator, electronic module, and capacitor produced from said copolymer, and process for producing the same |
| DE60016217T2 (en) * | 1999-04-09 | 2005-04-07 | Kaneka Corp. | POLYIMIDE RESIN COMPOSITION WITH IMPROVED MOISTURE RESISTANCE, GLUE SOLUTION, MULTILAYER ADHESIVE FILM AND METHOD FOR THE PRODUCTION THEREOF |
| JPWO2002102883A1 (en) | 2001-06-18 | 2004-09-30 | 鐘淵化学工業株式会社 | Polyimide film with excellent alkali etching workability and punching workability |
| CN118398286B (en) * | 2024-06-28 | 2024-09-20 | 佳腾电业(赣州)股份有限公司 | Insulated wire and preparation method thereof, coil and electronic/electrical device |
-
1994
- 1994-01-10 JP JP01323294A patent/JP3662269B2/en not_active Expired - Fee Related
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| Publication number | Publication date |
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| JPH07205255A (en) | 1995-08-08 |
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