【０００１】[0001]
【発明の属する技術分野】本発明は、電子複写機やプリ
ンタなどの熱定着部での使用に適したフッ素樹脂被覆複
合ポリイミドフィルムに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluororesin-coated composite polyimide film suitable for use in a heat fixing section of an electronic copying machine or a printer.
【０００２】[0002]
【従来の技術】従来より、電子写真方式による普通紙複
写機、いわゆる電子複写機としては、光により電荷を発
生する感光体を利用して静電潜像を形成し、その静電潜
像に着色荷電粉体であるトナーを付着させて現像すなわ
ち可視像化し、これを熱により記録紙上に定着させる方
式のものが知られている。定着にあたっては、内部にヒ
ータを備えた熱定着ローラを用いる方式が一般的であ
る。これは、熱定着ローラに圧接して加圧ローラを設
け、この２つのローラ間に、トナー像が形成された記録
紙を順次送りこむことによってトナーの加熱溶融を行
い、トナー像を記録紙上に定着させるという方法であ
る。2. Description of the Related Art Conventionally, a plain paper copying machine of the electrophotographic system, that is, a so-called electronic copying machine, forms an electrostatic latent image by using a photosensitive member that generates electric charges by light, and forms the electrostatic latent image on the electrostatic latent image. There is known a system in which a toner, which is a colored charged powder, is adhered to develop, that is, a visible image, and the image is fixed on recording paper by heat. For fixing, a system using a heat fixing roller having a heater therein is generally used. In this method, a pressure roller is provided in pressure contact with a heat fixing roller, and a recording paper on which a toner image is formed is sequentially fed between the two rollers to heat and melt the toner, thereby fixing the toner image on the recording paper. It is a method to make it.
【０００３】ところで、近年の複写機のめざましい普及
に伴い、機器の簡易化・小型化、そして高速化・省エネ
ルギー化への要求がさらに高まっている。これらの要求
に応えるべく、熱定着ローラを使用しない熱定着方式が
開発されている。この種の方式の一つに、熱定着ローラ
の代わりに、ポリイミドあるいはポリイミド系樹脂フィ
ルムからなるシームレス管状物、すなわちポリイミドチ
ューブを使用するようにした、フィルム定着方式とよば
れるものがある。[0003] With the remarkable spread of copying machines in recent years, demands for simplification and downsizing of devices, as well as speeding up and energy saving are increasing. In order to meet these demands, a heat fixing method without using a heat fixing roller has been developed. As one of such systems, there is a so-called film fixing system in which a seamless tubular member made of polyimide or a polyimide resin film, that is, a polyimide tube is used instead of the heat fixing roller.
【０００４】この方式による定着装置は、薄膜ポリイミ
ドフィルムからなるチューブの内側にヒータと駆動ロー
ルとを備え、ヒータに圧接した部分の外側に加圧ロール
を備えた構造を有しており、さらにポリイミドチューブ
の内側には、フィルムのエンドレス走行を安定させるた
めのテンションローラや、ヒータのホルダーなどが必要
に応じて設けられる。定着にあたっては、トナー像を形
成した記録紙をポリイミドチューブと加圧ロールとの間
に供給しつつ、ポリイミドチューブ内側のヒータからの
加熱により、順次トナー像を定着させる機構となってい
る。A fixing device according to this method has a structure in which a heater and a driving roll are provided inside a tube made of a thin film polyimide film, and a pressure roll is provided outside a portion pressed against the heater. A tension roller for stabilizing the endless running of the film, a heater holder, and the like are provided as needed inside the tube. In fixing, the recording paper on which the toner image is formed is supplied between the polyimide tube and the pressure roll, and the toner image is sequentially fixed by heating from the heater inside the polyimide tube.
【０００５】この熱定着フィルムを用いた定着装置は、
薄いポリイミドフィルムの内側に設置されたヒータが、
外表面上を通過する記録紙上のトナーを加熱し溶融させ
ることによって熱定着を行なうため、熱定着ローラのよ
うに予め定着ローラを予備加熱する時間を必要とせず、
電源スイッチを入れるとすぐに熱定着を開始できる、い
わゆるクィックスタートが可能であり、連続通紙の場合
でも温度低下が小さく高速化も可能という特長を有して
いる。また、可能熱容量の大きいローラを加熱する必要
がないことから、ヒータの電気容量も小さくて済み消費
電力も少ないという省エネルギー効果もある。A fixing device using the heat fixing film is as follows.
The heater installed inside the thin polyimide film,
Since the heat fixing is performed by heating and melting the toner on the recording paper passing on the outer surface, there is no need for the time for pre-heating the fixing roller in advance like the heat fixing roller,
The so-called quick start, in which thermal fixing can be started as soon as the power switch is turned on, is possible. Even when continuous paper is passed, the temperature drop is small and the speed can be increased. Further, since there is no need to heat a roller having a large possible heat capacity, there is also an energy saving effect that the electric capacity of the heater is small and the power consumption is small.
【０００６】熱定着フィルムとしての使用に適して厚み
の一様なポリイミドシームレスチューブを得る代表的な
方法として、たとえば特開平３−１８０３０９号公報や
特開平３−２６１５１８号公報に開示されているよう
に、芯体となる金型の外面にポリアミド酸溶液のような
ポリイミド前駆体溶液を均一な厚さで付着させ、加熱に
より乾燥およびイミド化した後、チューブ状物を芯体か
ら分離するという方法などが、知られている。A typical method for obtaining a polyimide seamless tube having a uniform thickness suitable for use as a heat fixing film is disclosed in, for example, JP-A-3-180309 and JP-A-3-261518. A method in which a polyimide precursor solution such as a polyamic acid solution is adhered to the outer surface of a mold serving as a core in a uniform thickness, dried and imidized by heating, and then the tubular material is separated from the core. Etc. are known.
【０００７】熱定着フィルムとして使用されるポリイミ
ドチューブは、その表面を、トナーとの離型性にすぐれ
たフッ素樹脂により被覆したものが一般的である。通
常、このようなフッ素樹脂被覆ポリイミドチューブの場
合、要求される熱伝導性や機械的強度を満たすため、ポ
リイミド層の厚さは３０〜１００μｍ程度、フッ素樹脂
層の厚さは５〜３０μｍ程度とされている。A polyimide tube used as a heat-fixing film is generally coated on its surface with a fluororesin having excellent releasability from toner. Usually, in the case of such a fluororesin-coated polyimide tube, in order to satisfy the required thermal conductivity and mechanical strength, the thickness of the polyimide layer is about 30 to 100 μm, and the thickness of the fluororesin layer is about 5 to 30 μm. Have been.
【０００８】このようなポリイミド層の表面にフッ素樹
脂を被覆したポリイミド複合フィルムの製造方法とし
て、たとえば基層となるポリイミド層の表面に、直接フ
ッ素樹脂ディスパージョンを塗装するようにした方法な
どがあげられる。しかしながら、このような方法により
得られる複合フィルムにおいては、基層とフッ素樹脂層
との層間の接着強度が不足し、定着フィルムとしての使
用中両層に剥離を生じて画像品質の低下を招くことがあ
った。そこで、両層間の接着強度を高めるために、さら
に様々な提案が成されている。たとえば、形成したポリ
イミド層表面にプライマを塗布した後フッ素樹脂ディス
パージョンを塗布して焼付けるようにした方法、あるい
はポリイミド層の表面をたとえば特開平６−３１４７３
号公報に開示されているエキシマレーザ光の照射などに
よりエッチングし、粗面化されたポリイミド層の表面に
フッ素樹脂ディスパージョンを塗布して焼付けるように
した方法、さらには特開平６−８３５０号公報に開示さ
れているように、ポリイミド層とフッ素樹脂層との間に
接着性の中間層を設けるようにした方法などが知られて
いる。As a method for producing a polyimide composite film in which the surface of a polyimide layer is coated with a fluororesin, for example, a method in which a fluororesin dispersion is directly applied to the surface of a polyimide layer serving as a base layer can be cited. . However, in the composite film obtained by such a method, the adhesive strength between the base layer and the fluororesin layer is insufficient, and the two layers may be peeled off during use as a fixing film, resulting in deterioration of image quality. there were. Therefore, various proposals have been made to increase the adhesive strength between the two layers. For example, a method in which a primer is applied to the surface of the formed polyimide layer, and then a fluororesin dispersion is applied and baked, or the surface of the polyimide layer is coated, for example, as disclosed in Japanese Patent Laid-Open No. 6-31473.
Japanese Patent Application Laid-Open No. 6-8350 discloses a method in which the surface of a roughened polyimide layer is coated with a fluororesin dispersion and baked by etching by excimer laser light irradiation or the like disclosed in As disclosed in the gazette, there is known a method in which an adhesive intermediate layer is provided between a polyimide layer and a fluororesin layer.
【０００９】[0009]
【発明が解決しようとする課題】しかしながら、このよ
うな製造方法によって得られる複合ポリイミドフィルム
においても、層間の接着強度の向上は未だ十分なものと
はいえず、接着強度にもバラツキが生じ易かった。しか
も、定着フィルムとしての使用環境は２００℃もあるた
め、そのような高温で長時間使用されることによる接着
強度の低下、すなわち接着耐久性の低下を防ぐことは、
さらに困難であった。また、複数の層を重ね合わせる製
造方法であれば膜厚のバラツキも生じ易く、さらには基
層となるポリイミド樹脂の成膜工程と、プライマ塗装や
エッチングなどの表面処理工程と、さらにフッ素樹脂の
成膜工程など、工程数が多くなって生産性が劣るように
なるばかりでなく、工程数が増えるにしたがって、その
間に取扱い上の不手際からゴミや異物の付着、あるいは
キズ、ピンホールやシワの発生など、外観上あるいは強
度上の欠陥を生じる危険性が増していた。したがって、
得られる製品の品質も安定せず低下しがちであった。However, even in the composite polyimide film obtained by such a production method, the improvement in the adhesive strength between the layers has not been sufficient yet, and the adhesive strength is likely to vary. . Moreover, since the use environment as a fixing film is as high as 200 ° C., it is possible to prevent a decrease in adhesive strength due to long-time use at such a high temperature, that is, to prevent a decrease in adhesive durability.
It was even more difficult. In addition, a manufacturing method in which a plurality of layers are overlapped tends to cause variations in film thickness. Further, a film forming step of a polyimide resin serving as a base layer, a surface treatment step such as primer coating or etching, and a fluorine resin forming step are further performed. Not only does the productivity increase due to the number of processes such as membrane processes, but also as the number of processes increases, dust or foreign matter adheres, or scratches, pinholes or wrinkles occur during handling during the process. For example, there is an increased risk of causing defects in appearance or strength. Therefore,
The quality of the resulting product was also unstable and tended to decrease.
【００１０】本発明は、このような従来の事情に対処し
て成されたものであり、複雑な工程を必要とせず、外観
的にも強度的にも良好でとくに層間の接着強度がすぐれ
た高品質の複合フィルムを安定して製造し得る方法を提
供することを、その目的としている。The present invention has been made in view of such conventional circumstances, does not require a complicated process, is good in appearance and strength, and has particularly excellent adhesion strength between layers. It is an object of the present invention to provide a method capable of stably producing a high-quality composite film.
【００１１】[0011]
【課題を解決するための手段】本発明の複合フィルムの
製造方法は、フッ素樹脂表層とポリイミド樹脂基層とか
ら成る複合フィルムの製造方法において、芯体の表面に
ポリイミド前駆体溶液を付着させて付着物中間体とした
のち、前記付着物中間体から溶剤を除去しポリイミド前
駆体を主体として成る層を形成し、次いでこのポリイミ
ド前駆体を主体として成る層の表面にフッ素樹脂含有液
を塗装して塗装物中間体とし、しかるのちこの塗装物中
間体に熱処理を施して、ポリイミド前駆体のイミド転化
とフッ素樹脂の焼成とを同時に行って、フッ素樹脂表層
とポリイミド樹脂基層とを形成するようにしたことを特
徴としている。According to the present invention, there is provided a method for producing a composite film comprising a fluororesin surface layer and a polyimide resin base layer, wherein a polyimide precursor solution is attached to the surface of a core. After the kimono intermediate, the solvent is removed from the attached intermediate to form a layer mainly composed of the polyimide precursor, and then the surface of the layer mainly composed of the polyimide precursor is coated with a fluororesin-containing liquid. As a painted intermediate, and then heat-treated this painted intermediate, the imide conversion of the polyimide precursor and the firing of the fluororesin were simultaneously performed to form a fluororesin surface layer and a polyimide resin base layer. It is characterized by:
【００１２】本発明においてポリイミド樹脂原料として
使用可能なポリイミド前駆体の種類にはとくに制限はな
いが、たとえば芳香族ジアミンと芳香族テトラカルボン
酸とを反応させて得られるものなどがあげられ、芳香族
ジアミンとしては、たとえば３，３´−ジメトキシ−
４，４´−ジアミノジフェニルエーテルや３，３´−ジ
アミノフェニルエーテルなど、芳香族テトラカルボン酸
としては、たとえば３，３´，４，４´−ビフェニルテ
トラカルボン酸二無水物やピロメリット酸二無水物など
があげられる。これらの芳香族ジアミンと芳香族テトラ
カルボン酸との反応は、たとえばジメチルアセトアミ
ド、ジメチルホルムアミド、Ｎ−メチル−２−ピロリド
ンなどの有機極性溶剤中で容易に行われる。The type of the polyimide precursor that can be used as a raw material for the polyimide resin in the present invention is not particularly limited, and examples thereof include those obtained by reacting an aromatic diamine with an aromatic tetracarboxylic acid. As the aromatic diamine, for example, 3,3′-dimethoxy-
Examples of aromatic tetracarboxylic acids such as 4,4'-diaminodiphenyl ether and 3,3'-diaminophenyl ether include 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and pyromellitic dianhydride. Things. The reaction between the aromatic diamine and the aromatic tetracarboxylic acid is easily carried out in an organic polar solvent such as dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone and the like.
【００１３】このような反応により形成される重合体、
いわゆるポリアミド酸を、本発明においてはポリイミド
前駆体と称しており、ポリイミド前駆体溶液とは溶剤中
にポリアミド酸が溶解してワニス状となっているものを
表わしている。ポリイミド前駆体溶液は、芯体へ均一な
厚さで付着し易い粘度となるように、その濃度を調節し
て使用される。下記の化１は、代表的な全芳香族ポリイ
ミド前駆体（ポリアミド酸）の一般式を示している。な
お、ＡｒおよびＡｒ´は芳香環を表す。A polymer formed by such a reaction,
In the present invention, a so-called polyamic acid is referred to as a polyimide precursor, and the polyimide precursor solution is a solution in which a polyamic acid is dissolved in a solvent to form a varnish. The concentration of the polyimide precursor solution is adjusted so as to have a viscosity that allows the polyimide precursor solution to easily adhere to the core with a uniform thickness. Formula 1 below shows the general formula of a typical wholly aromatic polyimide precursor (polyamic acid). Note that Ar and Ar ′ represent an aromatic ring.
【００１４】[0014]
【化１】また、ポリイミド前駆体を主体として成る層とは、ポリ
イミド前駆体溶液が芯体に付着してなる付着物中間体か
ら溶剤の大部分が蒸発により除去されて、ポリイミド前
駆体が芯体表面に層状に残留したものを表している。こ
のポリイミド前駆体を主体として成る層においては、必
ずしも溶剤が完全に除去されている必要はなく、ある程
度は残留していてもかまわない。Embedded image In addition, the layer mainly composed of the polyimide precursor means that the polyimide precursor solution adheres to the core, most of the solvent is removed by evaporation from the attached intermediate, and the polyimide precursor is layered on the surface of the core. Represents what remained. In the layer mainly composed of the polyimide precursor, the solvent does not necessarily have to be completely removed, but may remain to some extent.
【００１５】なお、イミド転化とは、ポリイミド前駆体
が加熱により脱水閉環してポリイミド樹脂となる縮合反
応のことを示しており、本発明においてポリイミド樹脂
基層とは、イミド転化により形成されるポリイミド樹脂
を主体としてなる層を意味している。イミド転化は常温
付近ではほとんど進行せず、通常ポリイミドのガラス転
位温度付近にまで段階的に加熱されることにより完結す
るとされる。The term "imide conversion" means a condensation reaction in which a polyimide precursor is dehydrated and ring-closed by heating to form a polyimide resin. In the present invention, the polyimide resin base layer is defined as a polyimide resin formed by the imide conversion. Means a layer mainly composed of It is said that the imide conversion hardly proceeds at around normal temperature, and is usually completed by heating stepwise to around the glass transition temperature of polyimide.
【００１６】本発明において、金属製やセラミックス製
などの耐熱性の材料からなりたとえば円筒形などの形状
の芯体の外面に、ポリイミド前駆体溶液を均一な厚さで
付着させるにあたってどのような方法を用いてもよい
が、たとえば浸漬や塗布などの一般的な塗装方法により
芯体の外周上部に所定量付着させた後、その長手方向を
鉛直に保持した金属芯体の外側に、所定のクリアランス
を有する『通しダイス』状の外金型を嵌め、その自重に
よって外金型を降下させる、いわゆるダイスコート法な
どはとくに好適である。In the present invention, what method is used to adhere the polyimide precursor solution to a uniform thickness on the outer surface of a core made of a heat-resistant material such as metal or ceramics, for example, cylindrical. However, after a predetermined amount is attached to the upper part of the outer periphery of the core body by a general coating method such as dipping or coating, a predetermined clearance is applied to the outside of the metal core body whose longitudinal direction is held vertically. A so-called die coating method or the like, in which a “through die” -shaped outer die having the following characteristics is fitted and the outer die is lowered by its own weight, is particularly suitable.
【００１７】本発明において、上記したように芯体の外
面にポリイミド前駆体溶液を均一な厚さで付着させて付
着物中間体としたのち、付着物中間体から溶剤を除去す
るにあたり、２５℃以上１２０℃以下の温度で加熱する
ことが好ましい。より好ましくは３０℃以上５０℃以下
の温度での加熱である。２５℃以上１２０℃以下の温度
で加熱することにより、イミド転化をほとんど起こさな
いでポリイミド前駆体溶液から溶剤を効率よく除去する
ことができる。このような温度範囲で３０分〜２４時間
程度加熱することが望ましい。１２０℃を越える温度で
加熱した場合には、溶剤の蒸発とポリイミド前駆体のイ
ミド転化が同時に進行してしまうことによって、のちに
形成するフッ素樹脂表層との接着強度が低下するように
なるため、好ましくない。また、２５℃より低い温度で
の加熱は、溶剤除去に長時間を要するので、これも好ま
しくない。In the present invention, as described above, the polyimide precursor solution is applied to the outer surface of the core body with a uniform thickness to form an attached matter intermediate, and then the solvent is removed from the attached matter intermediate at 25 ° C. It is preferable to heat at a temperature of at least 120 ° C. More preferably, the heating is performed at a temperature of 30 ° C. or more and 50 ° C. or less. By heating at a temperature of 25 ° C. or more and 120 ° C. or less, the solvent can be efficiently removed from the polyimide precursor solution with almost no imide conversion. It is desirable to heat in such a temperature range for about 30 minutes to 24 hours. When heated at a temperature exceeding 120 ° C., since the evaporation of the solvent and the imide conversion of the polyimide precursor proceed at the same time, the adhesive strength with the fluororesin surface layer to be formed later decreases, Not preferred. Heating at a temperature lower than 25 ° C. is not preferable because it takes a long time to remove the solvent.
【００１８】本発明において表層を構成するフッ素樹脂
材料としては、たとえばポリテトラフルオロエチレン
（ＰＴＦＥ）、テトラフルオロエチレン−パーフルオロ
アルキルビニルエーテル共重合体（ＰＦＡ）、あるいは
テトラフルオロエチレン−ヘキサフルオロプロピレン共
重合体（ＦＥＰ）など、あるいは必要に応じてこれらの
２種以上を混合したものなどが好適である。これらは、
フッ素樹脂ディスパージョンなど、水中に分散させた状
態の含有液とされて使用され、スプレー塗装など公知の
方法によりフッ素樹脂塗装することができる。In the present invention, examples of the fluororesin material constituting the surface layer include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkylvinylether copolymer (PFA), and tetrafluoroethylene-hexafluoropropylene copolymer. Preferred is a combination (FEP) or a mixture of two or more of these as necessary. They are,
It is used as a contained liquid dispersed in water, such as a fluororesin dispersion, and can be coated with a fluororesin by a known method such as spray coating.
【００１９】本発明において、塗装物中間体に施す熱処
理は、ポリイミド樹脂のイミド転化の完結とフッ素樹脂
の焼成が可能な３１０℃以上の温度で行うようにするこ
とがことが好ましい。３１０℃に達するまで段階的ある
いは連続的に温度を上昇させて熱処理を行なうようにす
れば、イミド転化を効率よく進行させることができる。
なお、この熱処理の最終到達温度は３１０℃以上でかつ
３８０℃以下とすることが好ましい。３８０℃を超える
場合には、フッ素樹脂の劣化が進むため好ましくない。
３１０℃より低い場合には、イミド転化が不十分となっ
て得られるフィルムの強度が低下するためやはり好まし
くない。In the present invention, it is preferable that the heat treatment applied to the intermediate of the coating is performed at a temperature of 310 ° C. or more at which the imide conversion of the polyimide resin can be completed and the fluororesin can be fired. If the temperature is increased stepwise or continuously until the temperature reaches 310 ° C. and the heat treatment is performed, the imide conversion can proceed efficiently.
The final temperature of this heat treatment is preferably set to 310 ° C. or higher and 380 ° C. or lower. When the temperature exceeds 380 ° C., deterioration of the fluororesin proceeds, which is not preferable.
If the temperature is lower than 310 ° C., the imide conversion becomes insufficient and the strength of the obtained film is lowered, which is not preferable.
【００２０】本発明において、塗装物中間体に上記の熱
処理を施すことにより、ポリイミド前駆体のイミド転化
とフッ素樹脂の焼成とを同時に行ってフッ素樹脂表層と
ポリイミド樹脂基層とを同時に形成することができる。
そして、形成された複合フィルムを芯体から分離するこ
とによって、画像定着用に適した複合フィルムを製造す
ることができる。In the present invention, by performing the above-described heat treatment on the intermediate product for coating, the imide conversion of the polyimide precursor and the calcination of the fluororesin are simultaneously performed to simultaneously form the fluororesin surface layer and the polyimide resin base layer. it can.
Then, by separating the formed composite film from the core, a composite film suitable for image fixing can be manufactured.
【００２１】本発明によれば、厚さ５〜１００μｍのフ
ッ素樹脂表層と厚さ５０〜２００μｍのポリイミド樹脂
基層から成る総厚さ５５〜３００μｍの複合フィルムを
製造することができる。According to the present invention, a composite film having a total thickness of 55 to 300 μm comprising a fluororesin surface layer having a thickness of 5 to 100 μm and a polyimide resin base layer having a thickness of 50 to 200 μm can be produced.
【００２２】[0022]
【発明の実施の形態】以下、本発明の詳細を実施例にし
たがって説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS The details of the present invention will be described below with reference to embodiments.
【００２３】実施例１ 外径５０ｍｍ、長さ５００ｍｍ、肉厚２．３ｍｍの管状
で表面を硬質ニッケルメッキ処理したアルミニウム製芯
体の表面に、ポリアミド酸（宇部興産社製、商品名Ｕワ
ニスＳ）を溶剤（ジメチルアセトアミド／ナフサ（９／
１）中に溶解させて得た粘度４０ポアズのポリイミド前
駆体溶液を、ダイスコートした。そしてコートされたこ
の芯体を、温度５０±２℃のオーブンに収容し３５分間
加熱して乾燥させ、ポリイミド前駆体を主体として成る
層を形成した。Example 1 Polyamic acid (trade name: U Varnish S, manufactured by Ube Industries, Ltd.) was applied to the surface of a tubular aluminum core having an outer diameter of 50 mm, a length of 500 mm, and a wall thickness of 2.3 mm, the surface of which was subjected to hard nickel plating. ) With a solvent (dimethylacetamide / naphtha (9 /
A polyimide precursor solution having a viscosity of 40 poise obtained by dissolving in 1) was die-coated. The coated core was placed in an oven at a temperature of 50 ± 2 ° C. and heated and dried for 35 minutes to form a layer mainly composed of a polyimide precursor.
【００２４】次いで、このポリイミド前駆体を主体とし
て成る層を形成した芯体を、常温下で１６０ｒｐｍで回
転させながら、その表面に、フッ素樹脂ディスパージョ
ン（旭硝子社製、商品名ＡＤ−６３９）をスプレーを用
いて塗装し、厚さの均一な２層からなる塗装物中間体を
得た。Next, a fluororesin dispersion (made by Asahi Glass Co., Ltd., trade name: AD-639) is applied to the surface of the core having a layer mainly composed of the polyimide precursor formed thereon while rotating at 160 rpm at room temperature. Coating was performed using a spray to obtain a coated intermediate having two layers having a uniform thickness.
【００２５】このようにして得られた塗装物中間体を、
１５０℃から２３０℃に至る連続雰囲気炉（有効炉長５
ｍ）内を約１５分間で通過させ、さらに２５０℃から３
６０℃に至る同様の連続雰囲気炉内を約８分間で通過さ
せて、熱処理を行なった。The thus obtained intermediate product for coating is
Continuous atmosphere furnace from 150 ° C to 230 ° C (effective furnace length 5
m) for about 15 minutes, and further from 250 ° C. to 3
Heat treatment was performed by passing the same through a similar continuous atmosphere furnace up to 60 ° C. in about 8 minutes.
【００２６】そして、このようにして芯体上に焼成成膜
したフッ素樹脂表層とポリイミド樹脂基層とからなる管
状物を、常温までゆっくりと冷却したのち芯体から剥離
させたところ、総膜厚５１μｍ、長さ４７０ｍｍの透明
な管状複合フィルムが得られた。Then, the tubular body composed of the fluororesin surface layer and the polyimide resin base layer formed by firing on the core in this manner was slowly cooled to room temperature and then peeled off from the core. A transparent tubular composite film having a length of 470 mm was obtained.
【００２７】実施例２ 外径１３０ｍｍ、長さ６５０ｍｍ、肉厚２．３ｍｍの管
状で表面を硬質ニッケルメッキ処理したアルミニウム製
芯体の表面に、ポリアミド酸（デュポン社製、商品名パ
イルＭＬ）をダイスコートした。Example 2 A polyamic acid (Pile ML, trade name, manufactured by DuPont) was coated on the surface of an aluminum core having a diameter of 130 mm, a length of 650 mm and a wall thickness of 2.3 mm and having a hard nickel plated surface. Dice coated.
【００２８】そしてコートされたこの芯体を、温度３０
℃から５０℃に至る連続雰囲気炉（有効炉長５ｍ）内を
約３０分間で通過させて乾燥させ、ポリイミド前駆体を
主体として成る層を形成した。Then, the coated core is heated at a temperature of 30.
The resultant was passed through a continuous atmosphere furnace (effective furnace length: 5 m) from 50 ° C. to 50 ° C. for about 30 minutes and dried to form a layer mainly composed of a polyimide precursor.
【００２９】次いで、このポリイミド前駆体を主体とし
て成る層を形成した芯体を、常温下で１６０ｒｐｍで回
転させながら、その表面に、フッ素樹脂（ＰＴＦＥ）デ
ィスパージョン（ダイキン工業社製、商品名Ｄ−１）を
スプレーを用いて塗装し、厚さの均一な２層からなる塗
装物中間体を得た。Next, while rotating the core having a layer mainly composed of the polyimide precursor at 160 rpm at room temperature, a fluororesin (PTFE) dispersion (trade name: D; -1) was applied using a spray to obtain a coated intermediate having two layers having a uniform thickness.
【００３０】そして、このようにして得られた塗装物中
間体を、２１０℃から３８０℃に至る連続雰囲気炉（有
効炉長５ｍ）内を約２５分間で通過させて、熱処理を行
なった。The coated intermediate thus obtained was passed through a continuous atmosphere furnace (effective furnace length of 5 m) from 210 ° C. to 380 ° C. for about 25 minutes to perform a heat treatment.
【００３１】このようにして芯体上に焼成成膜したフッ
素樹脂表層とポリイミド樹脂基層とからなる管状物を、
常温までゆっくりと冷却したのち芯体から剥離させたと
ころ、総膜厚４３μｍ、厚さのバラツキが±２．５％以
下の透明な管状複合フィルムが得られた。The tubular body comprising the fluororesin surface layer and the polyimide resin base layer formed by firing on the core in this manner is
After slowly cooling to room temperature and peeling from the core, a transparent tubular composite film having a total film thickness of 43 μm and a thickness variation of ± 2.5% or less was obtained.
【００３２】実施例３ フッ素樹脂ディスパージョンをＰＴＦＥ（デュポン社
製、商品名８５１−２０４）に変え、連続雰囲気炉の入
口温度を２１０℃、出口温度を４８０℃、通過時間を１
２分間とした他は実施例１と同様にして、透明でピンホ
ールもない管状複合フィルムを得た。Example 3 The fluororesin dispersion was changed to PTFE (trade name: 851-204, manufactured by DuPont), the inlet temperature of the continuous atmosphere furnace was 210 ° C., the outlet temperature was 480 ° C., and the passage time was 1 hour.
A tubular composite film that was transparent and had no pinholes was obtained in the same manner as in Example 1 except that the time was set to 2 minutes.
【００３３】比較例１ 実施例１と同様の芯体を用いて実施例１と同様のポリア
ミド酸（宇部興産社製、商品名ＵワニスＳ）をダイスコ
ートした。そしてコートされたこの芯体を、温度１５０
℃のオーブンに収容し４０分間加熱して乾燥させた。そ
の後３６０℃で４０分間の熱処理を行なったのち、常温
になるまで放置した。そして、２．５規定の水酸化ナト
リウム溶液中に約１５分間浸漬したのち水道水にて十分
に洗浄し水きりを行なった。Comparative Example 1 Using the same core as in Example 1, the same polyamic acid (U Varnish S, manufactured by Ube Industries, Ltd., trade name, U-varnish S) was die-coated. Then, the coated core is heated to a temperature of 150
The resultant was placed in an oven at a temperature of 40 ° C. and dried by heating for 40 minutes. After that, a heat treatment was performed at 360 ° C. for 40 minutes, and then left until the temperature reached room temperature. Then, it was immersed in a 2.5N sodium hydroxide solution for about 15 minutes, washed sufficiently with tap water and drained.
【００３４】このようにして芯体表面に形成されたポリ
イミド樹脂管状体の表面に、実施例２と同様のフッ素樹
脂（ＰＴＦＥ）ディスパージョン（ダイキン工業社製、
商品名Ｄ−１）をスプレーを用いて塗装し、その後３７
０℃で２０分間焼成した。On the surface of the polyimide resin tubular body thus formed on the surface of the core body, a fluororesin (PTFE) dispersion (manufactured by Daikin Industries,
Paint the product name D-1) by spraying, and then 37
Baking at 0 ° C. for 20 minutes.
【００３５】このようにして芯体上に焼成成膜した管状
物を、常温までゆっくりと冷却したのち芯体から剥離さ
せて透明な管状複合フィルムを得た。The tubular material thus formed by firing on the core was slowly cooled to room temperature and then peeled off from the core to obtain a transparent tubular composite film.
【００３６】比較例２ 実施例１と同様の芯体を用いて実施例１と同様のポリア
ミド酸（宇部興産社製、商品名ＵワニスＳ）をダイスコ
ートした。そしてコートされたこの芯体を、温度１５０
℃のオーブンに収容し４０分間加熱して乾燥させた。そ
してその表面に、フッ素樹脂系プライマ（ダイキン工業
社製、商品名Ｅ１１００）をスプレー塗装した後、常温
で約３０分間乾燥させ、さらに１５０℃に加熱乾燥させ
た。Comparative Example 2 Using the same core as in Example 1, the same polyamic acid as that of Example 1 (trade name U Varnish S, manufactured by Ube Industries, Ltd.) was die-coated. Then, the coated core is heated to a temperature of 150
The resultant was placed in an oven at a temperature of 40 ° C. and dried by heating for 40 minutes. The surface was spray-coated with a fluororesin-based primer (trade name: E1100, manufactured by Daikin Industries, Ltd.), dried at room temperature for about 30 minutes, and further dried by heating to 150 ° C.
【００３７】次いで、このプライマ層の上にフッ素樹脂
（ＰＴＦＥ）ディスパージョン（ダイキン工業社製、商
品名Ｄ−１）をスプレー塗装した後、３４０℃で３０分
間焼成した。Next, a fluororesin (PTFE) dispersion (trade name: D-1 manufactured by Daikin Industries, Ltd.) was spray-coated on the primer layer, and baked at 340 ° C. for 30 minutes.
【００３８】このようにして芯体上に焼成成膜した管状
物を、常温までゆっくりと冷却したのち芯体から剥離さ
せて管状複合フィルムを得た。The tubular material thus formed into a film by firing on the core was slowly cooled to room temperature and then peeled off from the core to obtain a tubular composite film.
【００３９】このようにして本発明の実施例の方法によ
って得られた管状複合フィルムと比較例の方法による管
状複合フィルムの各種物性を測定して、本発明の効果を
調べた。その結果を次の表１に示す。なお、表中の実機
回転強度試験とは、製造された複合フィルムを２５０℃
のオーブン中に連続１０００時間放置して劣化させた後
に行なったものである。The effects of the present invention were examined by measuring various physical properties of the tubular composite film obtained by the method of the example of the present invention and the tubular composite film by the method of the comparative example. The results are shown in Table 1 below. In addition, the actual machine rotational strength test in the table means that the produced composite film was heated at 250 ° C.
This was carried out after standing for 1000 hours in an oven to degrade.
【００４０】[0040]
【表１】表１からも明らかなように、本発明の製造方法によれ
ば、膜厚のバラツキが少なく、ピンホール、シワやハジ
キもみられず美麗な外観を有し、引張り強度の大きい複
合フィルムが得られた。しかも、高温での接着耐久性の
低下もみられなかった。[Table 1] As is clear from Table 1, according to the production method of the present invention, a composite film having a small variation in film thickness, a beautiful appearance without pinholes, wrinkles or cissing, and a large tensile strength can be obtained. Was. In addition, no decrease in adhesion durability at high temperatures was observed.
【００４１】[0041]
【発明の効果】以上説明したように、本発明によれば、
複雑な工程を必要とせず、外観的にも強度的にも良好で
とくに層間の接着強度がすぐれた高品質の複合フィルム
を安定して製造し得る方法を提供することが可能であ
る。As described above, according to the present invention,
It is possible to provide a method capable of stably producing a high-quality composite film which does not require a complicated process, has good appearance and strength, and has particularly excellent adhesive strength between layers.
【００４２】[0042]
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｇ０３Ｇ 15/20 １０１ Ｇ０３Ｇ 15/20 １０１ // Ｂ２９Ｋ 27:12 79:00 Ｂ２９Ｌ 9:00 23:00──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl.6 Identification code FI G03G 15/20 101 G03G 15/20 101 // B29K 27:12 79:00 B29L 9:00 23:00
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29508896AJPH10138264A (en) | 1996-11-07 | 1996-11-07 | Manufacture of composite film |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29508896AJPH10138264A (en) | 1996-11-07 | 1996-11-07 | Manufacture of composite film |
| Publication Number | Publication Date |
|---|---|
| JPH10138264Atrue JPH10138264A (en) | 1998-05-26 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29508896AWithdrawnJPH10138264A (en) | 1996-11-07 | 1996-11-07 | Manufacture of composite film |
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| JP (1) | JPH10138264A (en) |
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| US7553540B2 (en) | 2005-12-30 | 2009-06-30 | E. I. Du Pont De Nemours And Company | Fluoropolymer coated films useful for photovoltaic modules |
| US7981478B2 (en) | 2005-12-30 | 2011-07-19 | E. I. Du Pont De Nemours And Company | Fluoropolymer coating compositions containing adhesive polymers and substrate coating process |
| US8012542B2 (en) | 2005-12-30 | 2011-09-06 | E.I. Du Pont De Nemours And Company | Fluoropolymer coating compositions containing adhesive polymers and substrate coating process |
| US8048518B2 (en) | 2005-12-30 | 2011-11-01 | E.I. Du Pont De Nemours And Company | Fluoropolymer coated films useful for photovoltaic modules |
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| US8197933B2 (en) | 2005-12-30 | 2012-06-12 | E.I. Du Pont De Nemours And Company | Fluoropolymer coated films useful for photovoltaic module |
| US8124221B2 (en) | 2006-12-21 | 2012-02-28 | E. I. Du Pont De Nemours And Company | Crosslinkable vinyl fluoride copolymer coated film and process for making same |
| US8025928B2 (en) | 2007-04-23 | 2011-09-27 | E. I. Du Pont De Nemours And Company | Process for forming fluoropolymer coated film |
| US8168297B2 (en) | 2007-04-23 | 2012-05-01 | E. I. Du Pont De Nemours And Company | Fluoropolymer coated film, process for forming the same, and fluoropolymer liquid composition |
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| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination | Free format text:JAPANESE INTERMEDIATE CODE: A300 Effective date:20040203 |