JP3193694B2 - Manufacturing method for tubular objects - Google Patents

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、ポリイミド、ポリ
アミドイミド、芳香族ポリエステル、ポリエーテルスル
ホン、ポリエステルイミド、熱硬化性ブタジエン、ポリ
ベンゾイミダゾール、ビスマレイミドトリアジン樹脂等
の耐熱性樹脂及び前駆体溶液よりなる管状物の製造方法
に関する。The present invention relates to a heat-resistant resin such as polyimide, polyamideimide, aromatic polyester, polyether sulfone, polyesterimide, thermosetting butadiene, polybenzimidazole, bismaleimide triazine resin and a precursor solution. The present invention relates to a method for producing a tubular article.

【０００２】[0002]

【従来の技術】上記の耐熱樹脂は、その優れた物理特性
及び化学特性により多くの形状に成型され使用されてい
る。特に、進歩目覚ましい航空宇宙産業、電子機器等最
先端をゆく技術分野においては、その優れた耐熱性、機
械的強度、寸法安定性、化学安定性により多くの分野に
適用されるようになって来た。2. Description of the Related Art The above-mentioned heat-resistant resins are molded into many shapes and used due to their excellent physical and chemical properties. In particular, in the most advanced technological fields such as the aerospace industry and electronic equipment, which are making remarkable progress, their excellent heat resistance, mechanical strength, dimensional stability, and chemical stability have come to be applied to many fields. Was.

【０００３】しかし、その反面、イミド化、硬化反応さ
せるためには、長時閥の高熱処理等が必要で、簡単な熱
処理によリ溶融硬化しないため、一般のプラスチック材
料のような成型加工が難しい等、その樹脂の特性を充分
に生かした加工をすることが難しい。即ち、成型技術を
確立する事は非常に困難であるのが現状である。However, on the other hand, a high heat treatment or the like for a long time is required for imidization and curing reaction, and a simple heat treatment does not cause re-melting and hardening. It is difficult, for example, to perform processing that makes full use of the characteristics of the resin. That is, at present, it is very difficult to establish a molding technique.

【０００４】従来より、薄膜シームレス管状物として
は、プラスチック高分子材料のチューブ、ゴムチューブ
等多くのものが開発され、用途も非常に多様である。[0004] Conventionally, many thin-film seamless tubular articles have been developed, such as plastic polymer material tubes and rubber tubes, and their uses are very diverse.

【０００５】しかし、それらのチューブすなわち、管状
物を製造する方法としては、押出成型法（インジェクシ
ョン法）、押出ブロー成型（インフレーション法）等が
主体であり、薄膜特に数μｍ〜数１０μｍの均一な膜厚
のシームレス管状物の製造は非常に困難である。それで
も、最近は何とか膜厚の薄い管状物を製造するため、押
出インフレーションを行い膜厚を薄くした後、さらに、
長手方向に延伸をかけたり、加圧ロールの間を通過させ
薄くしたリする方法も試みられているが、偏肉や部分的
膜厚の違いが生じ、均一な薄膜管状物を得る事は不可能
であった。又、ポリイミド樹脂を用いて管状物を製造す
る方法としては、例えば、四フッ化エチレンー六フッ化
プロピレン共重合体フィルム表面をコロナ放電処理後、
ポリイミドフィルムを熱ラミネートし、その２層構造体
のテープを一定のラップ幅を設けて芯金に巻き付け、そ
のラップ部を四フッ化エチレン−六フッ化プロピレン共
重合体によリ加熱溶着し、芯金を抜き取って管状物とす
る方法等がある。However, as a method for producing these tubes, that is, tubular articles, extrusion molding (injection), extrusion blow molding (inflation) and the like are mainly used, and thin films, particularly several μm to several tens μm, are uniformly formed. It is very difficult to produce a seamless tubular article having a film thickness. Still, recently, in order to somehow produce a thin tubular material, after extruding inflation to reduce the film thickness,
Methods of stretching in the longitudinal direction or passing between pressure rolls to reduce the thickness have been attempted, but uneven thickness and partial thickness differences occur, and it is not possible to obtain a uniform thin film tubular article. It was possible. In addition, as a method for producing a tubular material using a polyimide resin, for example, after corona discharge treatment of the tetrafluoroethylene-hexafluoropropylene copolymer film surface,
The polyimide film is heat-laminated, the tape of the two-layer structure is wound around a core bar with a fixed wrap width, and the wrap portion is heat-welded with an ethylene tetrafluoride-propylene hexafluoride copolymer, There is a method of extracting a core metal and forming a tubular object.

【０００６】しかしながら、これら方法で製造された管
状物は、四フッ化エチレン−六フッ化プロピレン共重合
体の耐熱性を越える温度領域では使用不可能であり、ポ
リイミドの持つ優れた耐熱性が生かし切れないばかりで
なく、更に、構造上螺旋状のラップ部分が残り、管状物
の厚みも均一なものが得られにくい。However, the tubular articles produced by these methods cannot be used in a temperature range exceeding the heat resistance of ethylene tetrafluoride-propylene hexafluoride copolymer, and take advantage of the excellent heat resistance of polyimide. Not only is it not cut, but also a helical wrap remains on the structure, and it is difficult to obtain a tubular article having a uniform thickness.

【０００７】又、一様の厚みのポリイミド管状物を得る
ための方法の一例が、特開平１−１５６０１７号公報
（国際特許分類 Ｂ２９Ｃ ４１／１２）に開示されて
いる。この方法は、内面が平滑なガラス管やステンレス
管等の成形管の内面に、ポリイミド前駆体液を流し込ん
だ後、この成形管を垂直に保持して、この内面に弾丸状
体などの走行体を自重により落下させて、一定の厚みに
形成する。そして、加熱によリ乾燥及びイミド化し管状
物として、成形管から抜き出すものである。An example of a method for obtaining a polyimide tube having a uniform thickness is disclosed in Japanese Patent Application Laid-Open No. 1-156017 (International Patent Classification B29C 41/12). In this method, after pouring a polyimide precursor liquid into the inner surface of a molded tube such as a glass tube or a stainless steel tube having a smooth inner surface, the molded tube is held vertically, and a running body such as a bullet-shaped body is placed on the inner surface. It is dropped by its own weight to form a certain thickness. Then, it is dried and imidized by heating, and is withdrawn from the molded tube as a tubular material.

【０００８】しかし、この方法では、ポリイミド前駆体
液の粘度が高い場合、下方に行くほどポリイミド前駆体
液がたまり、弾丸状の走行体の落下速度にバラツキが発
生し、膜厚が不均一になったり、管状物の外径に制限が
出来、小径のものは製造出来ないという問題がある。
又、この方法は、実験的生産は出来ても量産性にはとぼ
しく、しかも、後工程の、乾燥、硬化、焼成等の処理も
難しい。However, in this method, when the viscosity of the polyimide precursor liquid is high, the polyimide precursor liquid accumulates downward, causing a variation in the falling speed of the bullet-shaped traveling body, resulting in an uneven film thickness. In addition, there is a problem that the outer diameter of the tubular article can be limited, and a small one cannot be manufactured.
In addition, this method is inferior in mass productivity even though it can be produced experimentally, and it is also difficult to carry out subsequent processes such as drying, curing, and firing.

【０００９】さらには、薄膜平状フィルムを製作する方
法、いわゆるキャスティング方法を利用し、膜厚の薄い
ものが得られないかとの検討がなされてきた。キャステ
イング方法としては、形成しようとする被膜材料及びそ
の被膜材料の前駆体材料を液体化しておき、その中へ芯
体をどぶ付けし、引き上げるデッピング方法や、芯体の
表面に被膜材料前駆体の液状物又は粉体等を吹き付ける
方法等にて塗布する方法等多くの方法が考えられ検討さ
れているが、いずれも被膜材料の前駆体材料の液体化物
質の粘度に限界があり、粘度が高くなると芯体にあらゆ
る方法を講じて塗布しても、膜厚を薄くしかも均一にす
ることは不可能であった。勿論このようにして、芯体に
塗布された被膜を、乾燥、硬化、反応をさせた後、芯体
より被膜を引き抜く等して分離しても、均一な管状物は
得られない。さらに粘度の高い被膜材料を均一に塗布す
るには、芯体に被膜材料を塗布しておき、芯体といくら
かの間隔をもったダイス状外型を作成して、それを通過
させ、膜厚を均一にする方法が考えられる。しかし、均
一な薄膜を芯体外側に形成するという事は、芯体と外型
ダイスとの平行度をとる事が非常に重要となるが、その
平行度をとる事は難しい。少し長尺の管状物になると、
芯体と外型ダイスとの平行度、偏心度を形成しようとす
る管状物の厚みの±１０％以内さらには、±５％以下に
おさえてコントロールする事は不可能であった。もし、
このような耐熱材料を用いたシームレス管状物の製作が
可能になると、高性能精密機械用搬送ベルト、複写機、
レーザープリンター等の画像処理フイルム等、精密機器
の機能性材料等に使用することができる。さらに、この
ような用途に利用される場合、シームレス管状物の内外
層の表面状態、すなわち外層表面は出来る限り平滑で、
内層表面は随意に表面状態を変える事が要求される。Further, it has been studied whether a thin film can be obtained by utilizing a method of producing a thin film, that is, a so-called casting method. As a casting method, a coating material to be formed and a precursor material of the coating material are liquefied, and a core is dipped into the liquid and then pulled up, or a coating material precursor is applied to the surface of the core. Many methods such as a method of spraying a liquid material or a powder or the like have been considered and examined, but all have a limit on the viscosity of the liquefied substance of the precursor material of the coating material, and the viscosity is high. In other words, it was impossible to make the film thickness thin and uniform even if it was applied to the core by any method. Of course, even if the coating applied to the core is dried, cured, and reacted in this way, the coating is pulled out from the core and separated to obtain a uniform tubular product. In order to apply a more viscous coating material evenly, apply the coating material to the core, create a die-shaped outer mold with some space from the core, pass it through, Can be considered. However, in order to form a uniform thin film on the outside of the core, it is very important to take parallelism between the core and the outer die, but it is difficult to take the parallelism. When it becomes a slightly long tube,
It was impossible to control the thickness of the tubular object to be formed within ± 10%, or even ± 5% or less, of the thickness of the tubular object for forming the degree of parallelism and eccentricity between the core and the outer die. if,
When it becomes possible to manufacture seamless tubular articles using such heat-resistant materials, conveyor belts for high-performance precision machines, copiers,
It can be used for functional materials of precision equipment such as image processing films such as laser printers. Further, when used in such applications, the surface state of the inner and outer layers of the seamless tubular article, that is, the outer layer surface is as smooth as possible,
The surface of the inner layer is required to change the surface condition at will.

【００１０】[0010]

【発明が解決しようとする課題】前述したように、ポリ
イミド、ポリアミドイミド、芳香族ポリエステル、ポリ
エーテルスルホン、ポリエステルイミド、ポリベンゾイ
ミダソール、熱硬化性ブタジエン、ビスマレイミドトリ
アジン樹脂のように耐熱温度が高くしかも熱硬化型又は
熱可塑性樹脂でも非常に溶点の高い樹脂は薄膜シームレ
ス状管状物を均一に製作する事は非常に困難である。As described above, as described above, polyimides, polyamide imides, aromatic polyesters, polyether sulfones, polyester imides, polybenzimidazoles, thermosetting butadiene, and bismaleimide triazine resins have heat resistant temperatures. It is very difficult to uniformly produce a thin-film seamless tubular article using a resin having a high melting point and a very high melting point even with a thermosetting or thermoplastic resin.

【００１１】このような耐熱樹脂は、熱で溶融させ溶融
状態で変型したり薄膜成型したりする事が困難なため、
これらの耐熱樹脂の前駆体である芳香族テトラカルボン
酸無水物の反応によって作られる中間体（ポリアミック
酸）や、ピロメリット酸無水物と芳香族ジアミンとから
なる中間体、ポリエステルイミド中間体、ポリエーテル
スルホン中間体、芳香族ジアミン酸エステル樹脂中間
体、ビスマレイミドトリアジン樹脂中間体、ポリベンゾ
−イミダゾール中間体、熱硬化性ブタジエン中間体等、
乾燥、硬化、反応を行う前の中間体、前駆体を溶媒等を
用いてゲル状、ワニス状にした物を用いて成型する方法
が考えらる。Since it is difficult for such a heat-resistant resin to be melted by heat and deformed in a molten state or formed into a thin film,
Intermediates (polyamic acids) produced by the reaction of aromatic tetracarboxylic anhydrides that are precursors of these heat-resistant resins, intermediates composed of pyromellitic anhydride and aromatic diamines, polyesterimide intermediates, Ether sulfone intermediate, aromatic diamine ester resin intermediate, bismaleimide triazine resin intermediate, polybenzo-imidazole intermediate, thermosetting butadiene intermediate, etc.
A method is considered in which an intermediate or precursor before drying, curing, or reaction is formed into a gel or varnish using a solvent or the like.

【００１２】しかし、これらのゲル状、ワニス状の中間
体は、一般的には高粘度を示し、接着剤的な状態を保つ
事から、非常に成型加工がしにくく、しかも、均一な薄
膜にする事は不可能とされていた。However, these gel-like and varnish-like intermediates generally show high viscosity and maintain a state like an adhesive, so that they are extremely difficult to mold and process, and furthermore, a uniform thin film is formed. It was impossible to do so.

【００１３】本発明は、これらの難問を完全に解決し、
しかも非常に合理的に量産性にも対応出来る技術を提供
することを目的とするものである。The present invention completely solves these difficulties,
Moreover, it is an object of the present invention to provide a technology that can reasonably cope with mass production.

【００１４】さらに、本発明は、均一な膜厚、周長、周
長差を示し、しかも、３〜３００μｍの極薄いシームレ
ス状の管状物を得、管状物の外面が空気層に接した自然
表面状態を示し、内面は人工表面、すなわち、芯体面表
面状態を示す管状物の製作を目的とする。Further, the present invention provides an extremely thin seamless tubular article having a uniform thickness, a circumferential length, and a circumferential length difference of 3 to 300 μm, and the outer surface of the tubular article is in contact with an air layer. The purpose is to produce a tubular article that shows the surface condition and the inner surface is an artificial surface, that is, the surface condition of the core body surface.

【００１５】[0015]

【課題を解決するための手段】本発明者等は、芯体の表
面に高精度で被膜を形成する方法として、種々の検討を
行った結果、あらかじめ芯体の表面に、管状成形物の前
駆体液を最終被膜形成厚みよりも厚く付着させた後、外
型又は芯体の両方もしくは少なくとも一方を拘束させる
ことなく、その管状成型物前駆体液の反発力を用いて、
外型を芯体の外側を通過させ、芯体の外面に所定の膜厚
の被膜を形成した後、管状成型物前駆体液を乾燥、硬
化、抽出、焼成等の手段を用いて、少なくとも管状物と
して強度を保持出来る状態まで管状物被膜材料を芯体に
保持した後、芯体より管状物を分離して、３μ〜３００
μｍの範囲の厚みの薄膜で、しかも、均一な厚み精度を
もち、さらに外面が空気層に接した表面状態をもち、内
面が芯体面に接した表面状態をもった管状物を得る事を
見出した。Means for Solving the Problems The present inventors have conducted various studies as a method of forming a coating on the surface of a core with high precision. As a result, the precursor of a tubular molded product was previously formed on the surface of the core. After attaching the bodily fluid thicker than the final film formation thickness, without restraining both or at least one of the outer mold and the core, using the repulsive force of the tubular molded product precursor liquid,
After passing the outer mold outside the core to form a coating of a predetermined thickness on the outer surface of the core, the tubular molded product precursor liquid is dried, cured, extracted, and baked by means of at least a tubular material. After holding the tubular material coating material on the core until the strength can be maintained, the tubular material is separated from the core and 3 μm to 300 μm.
A thin film with a thickness in the range of μm, uniform thickness accuracy, and a tubular object whose outer surface is in contact with the air layer and whose inner surface is in contact with the core surface has been found. Was.

【００１６】即ち、芯体に管状成型物前駆体液を均一に
塗布する方法として、まず芯体を管状成型物前駆体液に
どぶ付けして引き上げるか、あるいは前駆体液をハケ塗
り、フロー塗布等の一般的な塗布方法を用いて、芯体と
用意された外型ダイスとの間隔よりも厚く塗布した後、
外型ダイスを、外型ダイスあるいは芯体の両方、もしく
は片方を拘束させない、すなわち、芯体に外型ダイスを
通し外型ダイスの自重により落下させるかあるいは外型
ダイス固定又は融通性のある状態で外型ダイスを固定し
て、芯体を自由に動く状態で（糸のようなもので芯体を
つる等）引上げる事により、芯体と外型ダイスとの間隔
を自動調整させる事により、均一に、管状成型物前駆体
液被膜を成型させた。さらに、その管状成型物前駆体液
被膜膜厚を均一に（長手方向前後は多少の膜厚バラツキ
はある）させるためには、その芯体引上げ速度又は外型
ダイス降下速度は、管状成型物前駆体液の粘度に大きく
関係し、膜成型速度を２ｍｍ／ｓｅｃ〜２１０ｍｍ／ｓ
ｅｃにする事が最適である事を見出した。すなわち、最
適条件としては、芯体の外側を外型ダイスとして自然落
下によリ通過させる事で、その自然落下速度が管状成型
物前駆体液の粘度と外型ダイスの重量バランスにより２
ｍｍ／ｓｅｃ〜２１０ｍｍ／ｓｅｃになるよう調整する
事が最適であることを見出した。That is, as a method of uniformly applying the tubular molded product precursor solution to the core, first, the core material is dipped in the tubular molded product precursor solution and pulled up, or the precursor solution is brush-coated, flow-coated, or the like. After applying thicker than the gap between the core and the prepared outer die using a typical coating method,
The outer die, the outer die and / or the core are not restrained, that is, the outer die is passed through the core and dropped by the weight of the outer die, or the outer die is fixed or flexible. By fixing the outer die and pulling it up with the core moving freely (such as hanging the core with a thread), the distance between the core and the outer die is automatically adjusted. Then, a tubular molded product precursor liquid coating was uniformly formed. Further, in order to make the film thickness of the tubular molded product precursor liquid uniform (there is some variation in thickness before and after the longitudinal direction), the core pulling speed or the outer die lowering speed is determined by adjusting the tubular molded product precursor liquid. Is greatly related to the viscosity of the film, and the film forming speed is 2 mm / sec to 210 mm / s.
ec was found to be optimal. That is, the optimal condition is that the outside of the core body is allowed to pass through the outer die as an outer die by natural fall, and the natural fall speed depends on the viscosity of the tubular molded product precursor liquid and the weight balance of the outer die.
It has been found that it is optimal to adjust the distance between mm / sec and 210 mm / sec.

【００１７】[0017]

【作用】上述したように、芯体に均一に管状物成型物前
駆体液を塗布した後、この管状成型物前駆体液を加熱、
自然乾燥、加熱硬化、溶媒抽出法等を用いて、少なくと
も、管状物としての強度を保持できる状態まで芯体に保
持した後、芯体より管状物を分離することにより、膜
厚、周長、周長差が均一な、極薄膜管状物を得る事が出
来た。As described above, after uniformly applying the tubular molded product precursor liquid to the core, the tubular molded product precursor liquid is heated,
Using natural drying, heat curing, solvent extraction, etc., at least, after holding the core to a state that can maintain the strength as a tubular body, by separating the tubular body from the core, film thickness, perimeter, An ultra-thin tubular article with a uniform circumferential difference was obtained.

【００１８】本発明の方法は、極薄膜、すなわち、３μ
〜５００μｍの厚みの管状物得る事に適している事、管
状成型物前駆体液粘度が５０〜１００００ポイズ位の高
粘度液を用いた成型に適している事等が判った。又、こ
のようにして得た管状物において、途中の工程で管状物
の表面を他の材料にて処理する、いわゆる複合化を行う
方法も本発明に含まれる。[0018] The method of the present invention is applied to an extremely thin film, ie, 3 μm.
It has been found that it is suitable for obtaining a tubular article having a thickness of about 500 μm, and is suitable for molding using a high-viscosity liquid having a viscosity of a tubular molded article precursor liquid of about 50 to 10,000 poise. The present invention also includes a method of so-called compounding, in which the surface of the tubular article thus obtained is treated with another material in an intermediate step.

【００１９】[0019]

【発明の実施の形態】以下、この本発明の実施の形態に
つき説明する。Embodiments of the present invention will be described below.

【００２０】ポリイミド、ポリアミドイミド、芳香族ポ
リエステル、ポリエーテルスルホン、ポリエステルイミ
ド、ポリベンゾイミダゾール、熱硬化性ブタジエン、ビ
スマレイミドトリアジン樹脂のように耐熱温度が高くし
かも熱硬化型又は熱可塑性樹脂でも非常に溶点の高い樹
脂は薄膜シームレス状管状物を均一に製作する事は非常
に困難である。このような耐熱樹脂は、熱で溶融させ溶
融状態で変型したり薄膜成型したりする事が困難なた
め、この発明では、これらの耐熱樹脂の前駆体である芳
香族テトラカルボン酸無水物の反応によって作られる中
間体（ポリアミド酸）や、ピロメリット酸無水物と芳香
族ジアミンとからなる中間体、ポリエステルイミド中間
体、ポリエーテルスルホン中間体、芳香族ジアミン酸エ
ステル樹脂中間体、ビスマレイミドトリアジン樹脂中間
体、ポリベンゾ−イミダゾール中間体、熱硬化性ブタジ
エン中間体等、乾燥、硬化、反応を行う前の中間体、前
駆体を溶媒等を用いてゲル状、ワニス状にした物を用い
て成型する。The heat resistance is high, such as polyimide, polyamide imide, aromatic polyester, polyether sulfone, polyester imide, polybenzimidazole, thermosetting butadiene and bismaleimide triazine resin, and even thermosetting or thermoplastic resin is very high. It is very difficult to uniformly produce a thin-film seamless tubular material with a resin having a high melting point. Since such heat-resistant resins are difficult to be melted by heat and deformed or formed into a thin film in a molten state, in the present invention, the reaction of the aromatic tetracarboxylic anhydride which is a precursor of these heat-resistant resins is performed. (Polyamic acid), intermediate composed of pyromellitic anhydride and aromatic diamine, polyesterimide intermediate, polyether sulfone intermediate, aromatic diamine ester resin intermediate, bismaleimide triazine resin Intermediates, polybenzo-imidazole intermediates, thermosetting butadiene intermediates, and other intermediates and precursors before drying, curing, and reaction are molded into a gel or varnish using a solvent or the like. .

【００２１】まず、金属材料、例えば、ステンレス、ア
ルミニウム、鉄に表面メッキ処理を行ったものや、ガラ
スパイプ、ロッド等の芯体材科を用意し、次にその表面
を被膜管状物の内面に必要な形状に切削、成型等の手段
を用いて仕上げる。First, a metal material, for example, stainless steel, aluminum, or iron, which has been subjected to surface plating, or a core material such as a glass pipe or a rod, is prepared, and then the surface is coated on the inner surface of the coated tubular article. Finish to the required shape using means such as cutting and molding.

【００２２】次に、芯材とした材料の表面に必要に応じ
て、離型材となる材料を塗布する。例えば、もし、離型
材料塗布が必要な場合、シリコン処理、フッソ樹脂処理
等、管状物を芯体より分離する時点で必要とする温度に
たえる材料を塗布することが望ましい。Next, a material to be a release material is applied to the surface of the material as the core material, if necessary. For example, if it is necessary to apply a release material, it is desirable to apply a material that reaches the required temperature when the tubular material is separated from the core, such as silicon treatment or fluoro resin treatment.

【００２３】この様にして準備した芯体を、管状物被膜
材料、例えば、ポリイミド（以下、管状物被膜体材料は
ポリイミドを例にあげ説明する。）前駆体液の中に浸漬
し、引上げ、芯体の周辺にポリイミド前駆体溶液を付着
させる。勿論この場合、ポリイミド前駆体は芯体に不規
則に付着した状態である。ポリイミド前駆体を芯体に付
着させる方法としては、前駆体液を垂れ流す方法、刷毛
塗布等、種々の方法を用いる事が可能である。The core thus prepared is immersed in a precursor solution for a tubular material coating material, for example, a polyimide (hereinafter, the tubular material coating material is exemplified by polyimide) precursor solution, pulled up, and pulled up. A polyimide precursor solution is deposited around the body. Of course, in this case, the polyimide precursor is in a state of irregularly adhering to the core. As a method of attaching the polyimide precursor to the core body, various methods such as a method of pouring the precursor solution, a brush application, and the like can be used.

【００２４】次に、芯体上部より、事前に管状物被膜厚
みに必要な間隔をもたせて準備された外型リングを挿入
し、自重で落下させる。外型は芯体にそって降下する。
その際、外型は、ポリイミド前駆体液の粘度と外型の自
重により降下速度が決定される。Next, from the upper part of the core, an outer ring prepared in advance with a necessary interval for the thickness of the tubular material coating is inserted and dropped by its own weight. The outer mold descends along the core.
At that time, the lowering speed of the outer mold is determined by the viscosity of the polyimide precursor liquid and the weight of the outer mold.

【００２５】外型が降下する速度が、均一な管状物被膜
を成型する上には重要な要素となる。即ち、例えば、被
膜材料の粘度が高く、外型のリングと芯体との間隔が少
なく、しかも、外型リングの自重が軽い場合は、外型リ
ングが芯体外側を降下する速度が極端に遅くなるため、
外型リングが波うって降下する形となり、管状物被膜の
厚みにムラが生じる。又、逆に被膜材料の粘度が低い
か、あるいは、管状物に必要な外型リングと芯体との間
隔が極端に広い場合、外型リングはほとんど抵抗もなく
落下するため、管状物の膜厚に偏肉をきたし、均一な厚
みの管状物被膜は得られない。The speed at which the outer mold descends is an important factor in forming a uniform tubular coating. That is, for example, if the viscosity of the coating material is high, the distance between the outer ring and the core is small, and the weight of the outer ring is light, the speed at which the outer ring descends outside the core is extremely high. To be late,
The outer ring is wavy and descends, causing unevenness in the thickness of the tubular film. Conversely, if the viscosity of the coating material is low, or if the distance between the outer ring and the core required for the tubular object is extremely wide, the outer ring falls with almost no resistance. Thickness is uneven, and a tubular coating having a uniform thickness cannot be obtained.

【００２６】すなわち、本発明は、均一な管状物被膜を
得るためには、被膜材料の粘度、外型と芯体との間隔、
すなわち、管状物の被膜厚み、外型芯体の径、外型の自
重、外型の形状と多くの要素によるが、外型が、芯体を
通過する速度が、２ｍｍ／ｓｅｃ〜２１０ｍｍ／ｓｅｃ
の間に入っておれば、均一な管状物被膜を得る事が出来
る事を見いだした。換言すると、外型が芯体を通過する
速度が２ｍｍ／ｓｅｃ〜２１０ｍｍ／ｓｅｃになるよう
外型を固定、もしくは、融通性のある固定とし、芯体を
自由度のある状態で引上げる。例えば、芯体をヒモ、糸
等でつり上げるか、又は芯体が非常に細く多少変型する
ような状態（例えばワイヤ等）である場合にも、本発明
は適用出来る。勿論、外型を固定もしくは融通性のある
固定とし、芯体を落下させ、外型の内側を芯体が通過す
る方法をとる事も可能である。That is, according to the present invention, in order to obtain a uniform tubular material coating, the viscosity of the coating material, the distance between the outer mold and the core,
That is, depending on the thickness of the coating of the tubular material, the diameter of the outer core, the weight of the outer die, the shape of the outer die, and many factors, the speed at which the outer die passes through the core is 2 mm / sec to 210 mm / sec.
It was found that a uniform tubular coating could be obtained if it was in between. In other words, the outer die is fixed or has a flexible fixing so that the speed at which the outer die passes through the core is 2 mm / sec to 210 mm / sec, and the core is pulled up with a degree of freedom. For example, the present invention can be applied to a case where the core is hung with a string, a thread, or the like, or when the core is very thin and slightly deformed (for example, a wire). Of course, it is also possible to adopt a method in which the outer mold is fixed or flexible, the core body is dropped, and the core body passes inside the outer mold.

【００２７】又、当然の事ながら、管状物被膜材料に使
用する耐熱性樹脂前駆体の粘度にも制限があり、その粘
度が５０〜１００００ポイズのような高粘度液にする事
が望ましい。換言すると、５０ポイズ以下の粘度液に対
しては、外型リングを芯体の外側で通過速度を２ｍｍ／
ｓｅｃ以上に保つ事が非常に難しく、１００００ポイズ
以上となると、本発明の適用は困難となる。Naturally, the viscosity of the heat-resistant resin precursor used for the tubular material coating material is also limited, and it is desirable to use a high-viscosity liquid having a viscosity of 50 to 10,000 poise. In other words, for a viscosity liquid of 50 poise or less, the passing speed of the outer ring outside the core body is 2 mm /
It is very difficult to maintain the temperature for more than sec, and if it is 10,000 poise or more, it becomes difficult to apply the present invention.

【００２８】本発明にもとづく実験の結果よリ得た管状
物の最終製品膜厚と、外型ダイス及び芯体との通過速度
との関係、管状物被膜成型前駆体液粘度との関係、芯体
径と外型ダイス及び芯体の通過速度との関係等につき夫
々測定した結果の一例を表１、表２、表３に示す。As a result of the experiment based on the present invention, the relationship between the final product film thickness of the tubular article obtained and the speed of passage through the outer die and the core, the relationship between the viscosity of the tubular article coating precursor liquid, and the core Tables 1, 2, and 3 show examples of the results of measurements of the relationship between the diameter, the outer die, and the passing speed of the core, respectively.

【００２９】[0029]

【表１】 [Table 1]

【００３０】[0030]

【表２】 [Table 2]

【００３１】[0031]

【表３】 [Table 3]

【００３２】次に、このようにして、芯体の表面に管状
被膜材料前駆体を形成した後、乾燥（自然乾燥、加熱乾
燥等）、硬化、反応、抽出等の工程を経て、少なくとも
管状物としての強度を保持できる状態まで管状物被膜材
料を芯体に保持しておく。例えば、被膜材料がポリイミ
ドの場合は、１２０℃〜２００℃での加熱乾燥を行い、
ポリイミド前駆体液中に含まれている溶媒を除去する事
により、管状物としての強度が保持できる状態となる。
その状態、もしくは、さらに加熱等の方法によリイミド
化反応を進行させたり、完全にイミド化反応をさせた
後、芯体より強制的に分離して薄膜管状物が得られる。
勿論、このようにして得た薄膜管状物は、外面が空気層
に接した表面状態となっており、管状物の内面は芯体の
外形状そのままの形状を示す。従って、芯体に特殊な表
面状態をもたせておく事により、そのまま管状物内面型
状を形成する事が可能である。Next, after the tubular coating material precursor is formed on the surface of the core body in this manner, it is subjected to drying (natural drying, heat drying, etc.), curing, reaction, extraction, etc. The tubular material coating material is held on the core until the strength can be maintained. For example, when the coating material is polyimide, heat drying at 120 ° C to 200 ° C is performed,
By removing the solvent contained in the polyimide precursor liquid, a state in which the strength as a tubular object can be maintained.
In this state, or after the imidization reaction is advanced by a method such as heating or the like, or completely imidization reaction is performed, the thin film tubular article is forcibly separated from the core body.
Of course, the thin-film tubular article thus obtained has a surface state in which the outer surface is in contact with the air layer, and the inner face of the tubular article shows the same shape as the outer shape of the core. Therefore, by giving the core body a special surface condition, it is possible to form the inner shape of the tubular object as it is.

【００３３】ポリイミドを主に説明を行って来たが、ポ
リベンゾイミダゾールの前駆体等についても検討を行っ
た結果、同様に均一な管状物を得る事も出来た。Although polyimide has been mainly described, a study on a precursor of polybenzimidazole and the like also revealed that a uniform tubular product could be similarly obtained.

【００３４】[0034]

【実施例】次に、具体的な実施例及び比較例を示すが、
本実施例は本発明の内容を制限するものではない。EXAMPLES Next, specific examples and comparative examples will be described.
The present embodiment does not limit the contents of the present invention.

【００３５】参考実施例１ 外型φ４０ｍｍ、長さ１０００ｍｍのステンレス棒の表
面状態をなし地状に処理した芯体の表面に、離型剤とし
てシリコン液を希釈し、うすく塗布した後、乾燥させて
芯体とした。REFERENCE EXAMPLE 1 The surface of a stainless steel rod having an outer mold diameter of 40 mm and a length of 1000 mm was made into a surface, and a silicon solution was diluted as a mold release agent on the surface of the core body which had been processed into a ground shape. Core.

【００３６】次に、粘度１０００ポイズに調整された
３、３’、４、４’−ビフェニルテトラカルボン酸２無
水物と芳香族ジアミンをＮ−メチル−２−ピロリドン中
で反応させて得られたポリイミド前駆体溶液の中に、８
００ｍｍまで浸漬した。次に、内径４０．５ｍｍ、重さ
６６５ｇ、接液部角度４５゜、ランド長さ３ｍｍのアル
ミニウム製リング状外型を用意し、垂直にたてた芯体の
上部よリ自然落下させた。外型は、ポリイミド前駆体が
塗布されている部分を通過する際、初期はかなり早い速
度で落下したが、すぐに、ポリイミド前駆体の粘度抵抗
によリー定化され、かなりゆっくりした速度で降下し
た。その外型の降下する速度を測定した所、７．２ｍｍ
／ｓｅｃの速度で降下している事が判った。外型リング
が降下し、芯体の最下点に達した所で、芯体よリ外型リ
ングを除去した後、芯体を１２０℃の乾燥炉中に３０分
放置した後、２００℃に乾燥温度を上げ更に２０分放置
した。続いて、乾燥炉温度を３００℃にし、６０分放
置、３５０℃にし、６０分放置し、イミド化反応させ、
乾燥炉よリ取リ出す。この後空冷して芯体及び芯体に形
成されている管状物被膜を冷却した。その後、管状物被
膜が流れ落ちない又手でふれてもべたつかない事を確認
した後、丁寧に芯体よリ管状物を除去分離した。このよ
うにして得た管状物は、上下端３ｃｍを除いて全く均一
な厚み及び周長を有する管状物を得た。この管状物をさ
らに詳しく測定した所、膜厚は、２２μｍ±１μｍ、周
長４０ｍｍφ±２％、周長差上、中、下と測定して１％
以内に入る完壁な均一薄膜管状物となっていた。Next, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride adjusted to a viscosity of 1000 poise was reacted with an aromatic diamine in N-methyl-2-pyrrolidone. 8 in the polyimide precursor solution
It was immersed to 00 mm. Next, an aluminum ring-shaped outer die having an inner diameter of 40.5 mm, a weight of 665 g, a liquid contacting part angle of 45 °, and a land length of 3 mm was prepared, and was naturally dropped from the upper portion of the vertically placed core body. The outer die dropped at a very high speed at the beginning when passing through the area where the polyimide precursor was applied, but immediately fell due to the viscosity resistance of the polyimide precursor and dropped at a much slower speed. did. When the descending speed of the outer mold was measured, it was 7.2 mm.
It was found that the vehicle was descending at a speed of / sec. When the outer ring is lowered and reaches the lowest point of the core, the outer ring is removed from the core, and the core is left in a drying oven at 120 ° C. for 30 minutes. The drying temperature was increased and the mixture was left for another 20 minutes. Subsequently, the temperature of the drying furnace was set to 300 ° C., left for 60 minutes, then set to 350 ° C., left for 60 minutes, and subjected to an imidization reaction.
Remove it from the drying oven. Thereafter, the core body and the tubular film formed on the core body were cooled by air cooling. Thereafter, after confirming that the tubular material coating did not flow down or was not sticky even when touched by hand, the tubular material was carefully removed from the core and separated. The thus obtained tubular article had a completely uniform thickness and a circumferential length except for the upper and lower ends of 3 cm. When this tubular material was measured in more detail, the film thickness was 22 μm ± 1 μm, the perimeter was 40 mmφ ± 2%, and the perimeter difference was 1% when measured as upper, middle, and lower.
It was a complete thin-walled tubular article that entered within.

【００３７】さらに、この管状物の内面を見るため切り
開き、内面型状を表面粗度計にてチャートを描かせた
所、最初に目的としたなし地状形状、すなわち、芯体の
表面状態と全く同等で、しかも、外表面はＲｚ１μｍ以
下の自然空気と接触した状態の形状をなしていた。Further, the tubular material was cut open to view the inner surface, and the inner surface shape was charted by a surface roughness meter. It was completely equivalent, and the outer surface had a shape in contact with natural air having an Rz of 1 μm or less.

【００３８】参考比較例１ 参考実施例１の条件において、あらかじめ、芯体の上部
で芯体外径とリング状外型の内径との間隙を出来る限り
正確に位置合せを行い固定した後、ポリイミド前駆体溶
液タンクに芯体を所定位置まで浸漬し、芯体表面にポリ
イミド前駆体溶液を付着された後、芯体とポリイミド前
駆体溶液面が離れると同時にリング状外型との間隙を精
密に保持したまま２０ｍｍ／ｓｅｃの速度で機械的に走
行させ芯体表面に５００μｍの厚みでポリイミド前駆体
溶液被膜を成型させた後、リング状外型を芯体より抜き
取った。REFERENCE COMPARATIVE EXAMPLE 1 Under the conditions of Reference Example 1, the gap between the outer diameter of the core and the inner diameter of the ring-shaped outer die was positioned and fixed as accurately as possible at the top of the core, and then the polyimide precursor was fixed. After the core is immersed in the body solution tank to a predetermined position and the polyimide precursor solution is attached to the surface of the core, the core and the polyimide precursor solution are separated and the gap between the ring-shaped outer mold is held precisely. The polyimide precursor solution coating was formed with a thickness of 500 μm on the surface of the core body by mechanically traveling at a speed of 20 mm / sec while the ring-shaped outer die was removed from the core body.

【００３９】然る後、参考実施例１と同じ条件で加熱反
応させ完全にイミド化したポリイミド管状物を得た。Thereafter, a heat-reaction was conducted under the same conditions as in Reference Example 1 to obtain a completely imidized polyimide tube.

【００４０】この管状物のフィルム厚みの平均値は４２
μｍであり、最大及び最小厚みの差は１６μｍであっ
た。又、この方法で数回繰リ返して、管状物を製造した
結果でも、毎回データーのバラツキがあり、再現性が得
られなかった。又、管状物のフィルムで厚みの薄い部分
には不自然な凹凸が発生し、管状物としての特性を満た
すことが不可能であった。The average value of the film thickness of this tubular article was 42
μm, and the difference between the maximum and minimum thickness was 16 μm. In addition, even in the result of producing a tubular article by repeating the method several times by this method, there were variations in data every time, and reproducibility was not obtained. In addition, unnatural irregularities are generated in a thin portion of the tubular film, and it is impossible to satisfy the characteristics as a tubular material.

【００４１】参考比較例２ アルミニウム製リング状外型の重さを２０２５ｇとする
以外は、すべて参考実施例１と同様にして芯体外面にポ
リイミド前駆体溶液を付着させた。その後、内径４０．
５ｍｍ、重さ２０２５ｇ、接液部角度４５゜外型を芯体
上部のポリイミド前駆体溶液上に載置すると、ポリイミ
ド前駆体溶液の反発カによる外型の釣り合いが得られ
ず、外型内径と、芯体外径との間隙のバランスが採れな
いまま、急速度で落下してしまい、厚み精度の高い管状
物を得ることが不可能であった。REFERENCE COMPARATIVE EXAMPLE 2 A polyimide precursor solution was adhered to the outer surface of the core body in the same manner as in Reference Example 1 except that the weight of the aluminum ring-shaped outer mold was changed to 2025 g. After that, the inner diameter 40.
When the outer mold is placed on the polyimide precursor solution at the upper part of the core, the outer mold cannot be balanced by the repulsion of the polyimide precursor solution, and the outer mold inner diameter and However, it fell at a rapid speed without keeping the gap with the outer diameter of the core body, and it was impossible to obtain a tubular article with high thickness accuracy.

【００４２】参考比較例３ 外径４０ｍｍ、内径２０ｍｍのシリンダ状のステンレス
ミガキパイプ１ｍとφ１９．５ｍｍで、長さ３ｃｍの円
筒状ステンレス棒を用意し、その片方の先端を４５゜の
角度の円錐状に切削した。シリンダーの内側に、参考実
施例１で使用したシリコン希釈液をシリンダーないに塗
布した後、参考実施例１で使用したポリイミド前駆体を
パイプ内に吹き付け、円錐状ロッドを入れ自然落下させ
た所、ロッドは、パイプ下まで達せずつまってしまっ
た。ロッドの重量を測定した所、約７５ｇであった事か
ら軽すぎると判断、次に、ロッドの長さを２４ｃｍ、約
６００ｇとし、パイプ内を通して見たが、やはり、パイ
プの下まで達せずパイプ内面への被膜成型は出来なかっ
た。Reference Comparative Example 3 A cylindrical stainless steel rod 1 m in diameter and 19.5 mm in diameter and 3 cm in length was prepared with a cylindrical stainless steel pipe of 40 mm in outer diameter and 20 mm in inner diameter. Shape. After the silicone diluent used in Reference Example 1 was applied to the inside of the cylinder without the cylinder, the polyimide precursor used in Reference Example 1 was sprayed into a pipe, a conical rod was put therein, and allowed to fall naturally. The rod reached the bottom of the pipe. When the weight of the rod was measured, it was determined to be too light because it was about 75 g. Then, the length of the rod was set to 24 cm and about 600 g, and it was seen through the inside of the pipe. The coating on the inner surface could not be formed.

【００４３】参考実施例２ 参考実施例１と全く同じ外型、芯材を用い同じ前駆体液
を用いて、今度は、芯体上端中心部にヒモをつけ、外型
ダイスを固定させ、下方より、前駆体液の付着された芯
材の上部を通し後、芯材に取り付けたヒモを一定の速度
で引き上げることによリ外型内面を芯体が通過するよう
にした。勿論、芯体は自由度があり、その平行度は前駆
体液によりコントロールされる形となった。芯体の引上
げ速度を、参考実施例１の７．２ｍｍ／ｓｅｃに合わせ
た後、参考実施例１と同じ後処理を行ったところ、全く
参考実施例１と同等の均一な管状物を得る事が出来た。REFERENCE EXAMPLE 2 Using exactly the same outer mold and core material as in Reference Example 1 and using the same precursor solution, a string is formed at the center of the upper end of the core body, and the outer die is fixed. After passing through the upper part of the core material to which the precursor liquid was attached, the string attached to the core material was pulled up at a constant speed so that the core body passed through the inner surface of the outer mold. Of course, the core had a degree of freedom, and the parallelism was controlled by the precursor liquid. After adjusting the pulling speed of the core to 7.2 mm / sec of Reference Example 1, the same post-treatment as in Reference Example 1 was performed. Was completed.

【００４４】参考比較例４ 参考実施例１と同様の方法で、ポリイミド前駆体の粘度
を２００００ポイズに上げた所、外型リングは全く降下
せず管状物は得られなかった。REFERENCE COMPARATIVE EXAMPLE 4 In the same manner as in Reference Example 1, when the viscosity of the polyimide precursor was raised to 20,000 poise, the outer ring did not drop at all and no tubular product was obtained.

【００４５】参考比較例５ 参考比較例２と同方法で、外型リングの重量のみを５０
００ｇにして降下させてみた。外型リングは、降下速度
は２１７ｍｍ／ｓｅｃであったが、外型リングの降下状
態が不安定できれいな状態の被膜は出来なかった。Reference Comparative Example 5 In the same manner as Reference Comparative Example 2, only the weight of the outer ring was reduced to 50
I tried it down to 00g. The descent speed of the outer ring was 217 mm / sec, but the descent state of the outer ring was unstable, and a clean film could not be formed.

【００４６】参考実施例３ 外型１０ｍｍ長さ２ｍのガラスロッド、及び、内径１
０．８ｍｍで重量５００ｇの外型リングを用意した。さ
らに、管状被膜材料として、ビスマレイミドトリアジン
樹脂前駆体であるビスマレイシドとシアン酸エステル
液、粘度５００ポイズの液をガラスロッドに塗布した。
その後、外型リングを通し自然落下させた所、外型リン
グのガラスロッド通過速度は１９８ｍｍ／ｓｅｃであっ
た。この後、３００℃で３時間熱硬化させ、ガラスロッ
ド上に管状物被膜体を得た。Reference Example 3 Outer die 10 mm, glass rod 2 m long, and inner diameter 1
An outer ring of 0.8 mm and weighing 500 g was prepared. Further, a bismaleimide triazine resin precursor, bismaleide, a cyanate ester liquid, and a liquid having a viscosity of 500 poise were applied to a glass rod as a tubular coating material.
After that, the glass was naturally dropped through the outer ring, and the glass rod passing speed of the outer ring was 198 mm / sec. Thereafter, heat curing was performed at 300 ° C. for 3 hours to obtain a tubular material coated body on a glass rod.

【００４７】さらに、ガラスロッドと管状被膜体を分離
し、上下端５０ｍｍを除去して、約１．８ｍのビスマレ
イミドトリアジン樹脂管状物を得た。その寸法を測定し
た所、内径φ１０ｍｍ、膜厚５３μｍ±２％内の非常に
均一なシームレス管状物であった。さらに、外表面、内
表面の表面状態を測定した所、芯体にガラスロッドを使
用したため、非常に平滑にはなっていたが、外面はＲｚ
１μｍ以下、内面は１．５μｍ以下という状態であっ
た。Further, the glass rod and the tubular coating were separated, and the upper and lower ends of 50 mm were removed to obtain a bismaleimide triazine resin tubular article of about 1.8 m. When its dimensions were measured, it was a very uniform seamless tubular article with an inner diameter of 10 mm and a film thickness of 53 μm ± 2%. Furthermore, when the surface conditions of the outer surface and the inner surface were measured, the glass rod was used for the core body, so that the outer surface was very smooth.
1 μm or less, and the inner surface was 1.5 μm or less.

【００４８】実施例１ 外径１８０ｍｍ、長さ５００ｍｍのアルミニウム製芯体
の表面にサンドブラスト処理を行い、その後、ポリテト
ラフロロエチレン樹脂を被覆し、これを芯体とした。こ
の芯体表面粗度は、Ｒｚ３．０μｍである。次に、この
芯体の上部３ケ所にワイヤーを取付け宙吊りが出来るよ
うにした。Example 1 A surface of an aluminum core having an outer diameter of 180 mm and a length of 500 mm was subjected to sandblasting, and then coated with a polytetrafluoroethylene resin to obtain a core. The surface roughness of the core body is Rz 3.0 μm. Next, wires were attached to the upper three places of this core so that it could be suspended in the air.

【００４９】粘度１００ポイズの３．３’、４．４’−
ビフェニルテトラカルボン酸２無水物と芳香族ジアミン
をＮ−メチル−２−ビロリドン中で反応させて得られポ
リイミド前駆体溶液を用意し、このポリイミド前駆体溶
液を芯体の長さ４３０ｍｍまで、厚み約１ｍｍ以上にな
るようにはけ塗りした。その後、内径１８１ｍｍ、重さ
１０５０ｇ、接液部角度３０゜のアルミニウム製リング
状外型を芯体上部より通し、ポリイミド前駆体溶液上に
載置すると同時に、芯体を３本のワイヤーでつり上げた
この外型は、ポリイミド前駆体溶液の反発力により、外
型が一旦釣り合った後、その自重のみで芯体の外側を通
過した。この場合、芯体、外型とも全く固定される所が
なく、自由に調整されながら製膜化され、芯体の表面に
０．５ｍｍの厚みでポリイミド前駆体溶液を被膜形成し
た。3.3 ', 4.4'- having a viscosity of 100 poise
A polyimide precursor solution is prepared by reacting biphenyltetracarboxylic dianhydride and an aromatic diamine in N-methyl-2-virolidone, and the polyimide precursor solution is coated with a core having a thickness of about 430 mm and a thickness of about 430 mm. Brush painting was performed so as to be 1 mm or more. Thereafter, an aluminum ring-shaped outer die having an inner diameter of 181 mm, a weight of 1050 g, and a liquid contact part angle of 30 ° was passed through the upper part of the core body, and was placed on the polyimide precursor solution. At the same time, the core body was lifted with three wires. This outer mold once passed the outside of the core by its own weight only after the outer mold was once balanced by the repulsive force of the polyimide precursor solution. In this case, there was no place where the core and the outer mold were fixed at all, and the film was formed while being adjusted freely, and a 0.5 mm-thick polyimide precursor solution was formed on the surface of the core.

【００５０】なお、芯体表面を通過するリング状外型の
平均落下速度は１０．０ｍｍ／ｓｅｃであった。The average falling speed of the ring-shaped outer die passing through the surface of the core was 10.0 mm / sec.

【００５１】その後、このポリイミド前駆体溶液を被覆
した芯体を、１５０℃の温度で８０分、及び、２３０℃
の温度で３０分間夫々加熱し、イミド化反応させ冷却し
た後、芯体とポリイミド管状物を分離し、内径１８０ｍ
ｍ，長さ３００ｍｍの管状物を得ることができた。Thereafter, the core coated with the polyimide precursor solution was heated at 150 ° C. for 80 minutes and at 230 ° C.
After heating at a temperature of 30 minutes respectively, and performing an imidization reaction and cooling, the core and the polyimide tubular material were separated, and the inner diameter was 180 m.
m, a tubular article having a length of 300 mm was obtained.

【００５２】然る後、この管状物を、再び外径１８０ｍ
ｍのステンレス製芯体に挿入し、さらに、管状物の表面
に、四フッ化エチレン、及び、その共重合金混合液を塗
布し乾燥した。後、３００℃の温度で４０分及び４００
℃の温度で５０分夫々加熱し、その後、常温まで冷却
し、芯体から管状物を取外し、完全にイミド化したポリ
イミドの表面にフッソ樹脂が塗布された管状物を得た。
この管状物の厚みは４５μｍであり、その厚みのバラツ
キ±２．３μｍであった。After that, this tubular object was again re-formed with an outer diameter of 180 m.
m of stainless steel core, and further, ethylene tetrafluoride and a mixed solution of gold copolymer were coated on the surface of the tubular material and dried. After that, at a temperature of 300 ° C. for 40 minutes and 400
Each of them was heated at a temperature of 50 ° C. for 50 minutes, then cooled to room temperature, and the tube was removed from the core to obtain a tube obtained by applying a fluoro resin to the surface of completely imidized polyimide.
The thickness of this tubular article was 45 μm, and the thickness variation was ± 2.3 μm.

【００５３】このバラツキの厚みの範囲内に入る管状物
長さは、３８０ｍｍであった。The length of the tubular object falling within the range of the thickness of the variation was 380 mm.

【００５４】又、この管状物の外表面粗度、Ｒｚ０．２
μｍであり内表面粗度はＲｚ２．８〜３．０μｍであっ
た。The outer surface roughness of this tubular article, Rz 0.2
μm, and the inner surface roughness was Rz 2.8 to 3.0 μm.

【００５５】このようにして得た管状物を、複写機画像
処理用フィルムに使用した所、非常に高性能を示した。When the thus obtained tubular article was used as a film for image processing in a copying machine, it showed very high performance.

【００５６】[0056]

【発明の効果】以上説明したように、この発明は、芯体
に均一に管状物成型物前駆体液を塗布した後、この管状
成型物前駆体液を加熱、自然乾燥、加熱硬化、溶媒抽出
法等を用いて、少なくとも、管状物としての強度を保持
できる状態まで芯体に保持した後、芯体よリ管状物を分
離することにより、膜厚、周長、周長差が均一な、極薄
膜管状物を得る事が出来る。As described above, according to the present invention, a tubular molded product precursor solution is uniformly applied to a core body, and then the tubular molded product precursor solution is heated, naturally dried, heat-cured, and a solvent extraction method. At least, by holding the core to a state where the strength as a tubular object can be maintained, by separating the tubular material from the core, the film thickness, perimeter, difference in perimeter uniform, ultra-thin film A tubular object can be obtained.

───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平３−130149（ＪＰ，Ａ) 特開 平２−43046（ＪＰ，Ａ) 特公 昭60−38982（ＪＰ，Ｂ２) (58)調査した分野(Int.Cl.⁷，ＤＢ名) B29C 41/00 - 41/52 B05D 1/00 - 7/26 B05C 9/00 - 21/00 ──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-3-130149 (JP, A) JP-A-2-43046 (JP, A) JP-B-60-38982 (JP, B2) (58) Survey Field (Int.Cl. ⁷ , DB name) B29C 41/00-41/52 B05D 1/00-7/26 B05C 9/00-21/00

Claims (6)

(57)【特許請求の範囲】(57) [Claims] 【請求項１】 ポリイミドからなる内層とフッ素樹脂か
らなる外層とを有する管状物の製造方法であって、 芯体の外面にポリイミドの前駆体液からなる被膜を所定
の膜厚で形成し、少なくとも管状物としての強度を保持
できる状態まで前記前駆体液を熱処理して内層を形成す
る工程と、前記内層の外側にフッ素樹脂を塗布し熱処理
してフッ素樹脂よりなる外層を形成する工程とを有する
管状物の製造方法。1. A method for producing a tubular article having an inner layer made of polyimide and an outer layer made of a fluororesin, comprising: forming a film made of a polyimide precursor solution on an outer surface of a core to a predetermined thickness; A tubular article having a step of heat-treating the precursor liquid to a state where the strength of the article can be maintained, and a step of applying a fluororesin to the outside of the inner layer and heat-treating to form an outer layer made of the fluororesin. Manufacturing method. 【請求項２】 芯体と前記芯体の外径に対して所定の間
隙の内径を有する外型とを用意し、予め芯体の表面にポ
リイミドの前駆体液を最終被膜形成厚みよりも厚く付着
させた後、外型又は芯体の少なくとも一方を拘束させる
ことなく外型を芯体の外側を通過させることにより、芯
体の外面にポリイミドの前駆体液からなる被膜を所定の
膜厚で形成する請求項１に記載の管状物の製造方法。2. A core body and an outer mold having an inner diameter of a predetermined gap with respect to the outer diameter of the core body are prepared, and a polyimide precursor solution is previously adhered to the surface of the core body so as to be thicker than a final coating film forming thickness. After that, by passing the outer die outside the core without restraining at least one of the outer die or the core, a coating made of a polyimide precursor liquid is formed on the outer surface of the core with a predetermined thickness. A method for producing a tubular article according to claim 1. 【請求項３】 前記外型が前記芯体の外側を通過する速
度を２ｍｍ／ｓｅｃ以上２１０ｍｍ／ｓｅｃ以下とする
請求項２に記載の管状物の製造方法。3. The method for producing a tubular article according to claim 2, wherein a speed at which the outer mold passes outside the core body is 2 mm / sec or more and 210 mm / sec or less. 【請求項４】 前記ポリイミドの前駆体液の粘度が５０
〜１００００ポイズである請求項１に記載の管状物の製
造方法。4. The polyimide precursor liquid has a viscosity of 50%.
The method for producing a tubular article according to claim 1, wherein the pressure is from 1 to 10,000 poise. 【請求項５】 最終的に得られる管状物の厚みが３〜３
００μｍである請求項１に記載の管状物の製造方法。5. The finally obtained tubular article has a thickness of 3 to 3
The method for producing a tubular article according to claim 1, wherein the thickness is 00 µm. 【請求項６】 管状物が複写機画処理用フィルムである
請求項１〜５のいずれかに記載の管状物の製造方法。6. The method for producing a tubular article according to claim 1, wherein the tubular article is a film for copier image processing.