JP2002079535A - Cylindrical molding mold, its production method, and method for producing cylindrical film - Google Patents
Cylindrical molding mold, its production method, and method for producing cylindrical filmInfo
- Publication number
- JP2002079535A JP2002079535A JP2000270052A JP2000270052A JP2002079535A JP 2002079535 A JP2002079535 A JP 2002079535A JP 2000270052 A JP2000270052 A JP 2000270052A JP 2000270052 A JP2000270052 A JP 2000270052A JP 2002079535 A JP2002079535 A JP 2002079535A
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- Prior art keywords
- cylindrical
- mold
- cylindrical film
- cylindrical mold
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Electrostatic Charge, Transfer And Separation In Electrography (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
- Moulding By Coating Moulds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、複写機、プリンタ
ー、ファクシミリ等の静電複写装置において中間トナー
担持体として用いられる無端ベルトされる円筒膜を成形
するための円筒成形型及びその製造方法並びに円筒膜の
製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cylindrical mold for forming a cylindrical film to be an endless belt used as an intermediate toner carrier in an electrostatic copying machine such as a copying machine, a printer, a facsimile, etc., and a method of manufacturing the same. The present invention relates to a method for manufacturing a cylindrical film.
【０００２】[0002]
【従来の技術】静電複写装置において中間トナー担持体
として用いられる無端ベルトは、耐熱性、引っ張り強
さ、曲げ強さ、等の性質が要求されるので、耐熱性、引
っ張り強さ、曲げ強さ、等の性質の優れた樹脂で形成さ
れている。このような無端ベルトとされる円筒膜は、遠
心塗布成形法により、樹脂溶液から円筒膜を成形するこ
とによって製造されている。2. Description of the Related Art An endless belt used as an intermediate toner carrier in an electrostatic copying machine is required to have properties such as heat resistance, tensile strength and bending strength. It is formed of a resin having excellent properties such as the above. Such a cylindrical film as an endless belt is manufactured by forming a cylindrical film from a resin solution by a centrifugal coating molding method.
【０００３】図５は、従来の遠心塗布成形法による円筒
膜の製造方法の縦断面説明図であって、（ａ）は、その
剥離層上に円筒膜を形成する状態を示し、そして、
（ｂ）は、円筒膜が剥離した状態を示す。図５に示すよ
うに、遠心塗布成形法は、高速に回転するアルミニウ
ム、真鍮、ステンレス等より構成される円筒成形型１０
１の内面に形成された剥離層１０２上にスプレー塗布等
の手段により樹脂溶液を流し込み、その遠心力で塗布液
を軸方向に拡げて均一な膜厚の円筒膜１０３を成形する
成形法である。このように遠心塗布成形法により成形さ
れた円筒膜１０３は、乾燥固化され、必要に応じて、硬
化された後、円筒成形型から取り出されて、無端ベルト
とされる。FIG. 5 is an explanatory longitudinal sectional view of a conventional method for producing a cylindrical film by centrifugal coating and molding, in which (a) shows a state in which a cylindrical film is formed on the release layer,
(B) shows a state where the cylindrical film has peeled off. As shown in FIG. 5, the centrifugal coating molding method uses a cylindrical mold 10 made of aluminum, brass, stainless steel or the like which rotates at a high speed.
1 is a molding method in which a resin solution is poured onto the release layer 102 formed on the inner surface of the substrate 1 by means of spray coating or the like, and the coating liquid is spread in the axial direction by the centrifugal force to form a cylindrical film 103 having a uniform thickness. . The cylindrical film 103 formed by the centrifugal coating molding method is dried and solidified, and, if necessary, cured, and then removed from the cylindrical mold to form an endless belt.
【０００４】ポリイミド樹脂は、耐熱性、引っ張り強
さ、曲げ強さ、電気絶縁性等の性質において優れた樹脂
であるので、電子写真装置の無端ベルトの材料として好
適に用いられている。しかし、ポリイミド樹脂は、接着
性が良いために接着剤としても使用されるほどの樹脂で
あるので、これを直接遠心塗布成形法により成形してポ
リイミド無端ベルトとすることはできない。そのため
に、従来においては、例えば、ポリイミドの前駆体であ
るポリアミド酸の溶液をステンレス等の円筒成形型に遠
心塗布して円筒膜を成形し、そして、この円筒膜を加熱
して乾燥固化した後、硬化（即ち、イミド化）すること
により、ポリイミド無端ベルトを製造している。ポリア
ミド酸の溶液は、例えば、無水ピロメリット酸及び４，
４´−ジアミノジフェニルエーテルよりなる２種のモノ
マーをジメチルホルムアミドのような極性溶媒中で溶液
重合させることにより得ている。[0004] Polyimide resin is a resin excellent in properties such as heat resistance, tensile strength, bending strength, and electrical insulation, and is therefore suitably used as a material for an endless belt of an electrophotographic apparatus. However, since the polyimide resin is a resin that is used as an adhesive because of its good adhesiveness, it cannot be directly molded into a polyimide endless belt by a centrifugal coating molding method. For that purpose, conventionally, for example, a solution of polyamic acid, which is a precursor of polyimide, is centrifugally applied to a cylindrical mold such as stainless steel to form a cylindrical film, and then the cylindrical film is dried and solidified by heating. The polyimide endless belt is manufactured by curing (i.e., imidizing). The polyamic acid solution is, for example, pyromellitic anhydride and 4,
It is obtained by solution polymerization of two kinds of monomers consisting of 4'-diaminodiphenyl ether in a polar solvent such as dimethylformamide.
【０００５】かかる遠心塗布成型法によれば、 (イ) 円筒膜の膜厚の調整が円筒成形型に塗布する樹脂溶
液量で任意に調整できること、 (ロ) 必要量のみの樹脂溶液を円筒成形型に遠心塗布すれ
ば良いので材料効率がよいこと、 (ハ) 円筒成形型内部は閉空間となっているので、乾燥に
よる溶剤除去の際には、排気経路に溶剤トラップを設け
るだけで、外部に排出する溶剤を効率よく回収すること
ができること、等の利点がある。According to such a centrifugal coating molding method, (a) the thickness of the cylindrical film can be adjusted arbitrarily by the amount of the resin solution applied to the cylindrical mold, and (b) only the required amount of the resin solution is cylindrically formed. (C) Since the inside of the cylindrical mold is a closed space, when removing the solvent by drying, simply install a solvent trap in the exhaust path, and In addition, there is an advantage that the solvent discharged to the tank can be efficiently collected.
【０００６】遠心塗布成型法においては、円筒成形型に
塗布した円筒膜は、その溶剤乾燥、硬化時には、円筒成
形型に貼り付いていることが必要であり、そして、脱型
時には、円筒膜が円筒成形型から容易に剥離できること
が必要であが、このような相矛盾する必要性を同時に満
足する円筒成形型は、未だ得られていない。In the centrifugal coating molding method, the cylindrical film applied to the cylindrical mold needs to be adhered to the cylindrical mold at the time of drying and curing the solvent, and at the time of demolding, the cylindrical film must be adhered. It is necessary to be able to easily peel off from the cylindrical mold, but a cylindrical mold that simultaneously satisfies such contradictory needs has not yet been obtained.
【０００７】[0007]
【発明が解決しようとする課題】従来、円筒成形型を構
成する剥離層として種々の剥離性材質が検討されてきた
が、ガラス、フッ素樹脂等の材料で剥離層を形成した円
筒成形型は、円筒膜を塗布、指触乾燥するまでは、円筒
成形型内壁にへばりついていて問題ないが、剥離層が高
剥離性であるために、円筒膜を加熱して硬化させる段階
で該円筒膜の端部から剥離して浮き始め、甚だしい時
は、円筒膜全体が浮いてしまい、さらには、該円筒膜の
浮いた部分が不均一に収縮して所望の径の円筒膜が得ら
れないという問題があった。Conventionally, various releasable materials have been studied as a release layer constituting a cylindrical mold. However, a cylindrical mold having a release layer formed of a material such as glass or fluororesin has been proposed. Until the cylindrical film is applied and dried to the touch, there is no problem because it sticks to the inner wall of the cylindrical mold, but since the release layer has high releasability, the end of the cylindrical film is heated and cured at the stage where the cylindrical film is cured. In a severe case, the entire cylindrical film floats, and furthermore, the floating portion of the cylindrical film shrinks unevenly and a cylindrical film having a desired diameter cannot be obtained. there were.
【０００８】このような問題の回避策として、円筒膜を
一旦指触乾燥レベルに乾燥した時点で円筒成形型から剥
がし、この円筒膜の内側に円筒形の型を新たに挿入し
て、その状態で円筒膜を加熱硬化させるという方法が採
られてきたが、このような方法は、工程が多くなるとい
う基本的な問題があり、また、円筒成形型と円筒膜との
間に空気が入ると、その空気が抜け出せなくなって、円
筒膜が凸状に変形してしまうという問題があり、さらに
は、円筒成形型と円筒膜との間に空気が入らないように
するためにクリヤランスを大きくすると円筒膜の収縮が
不均一になってシワが発生してしまうという問題があっ
た。As a measure for avoiding such a problem, when the cylindrical film is once dried to the touch dry level, the cylindrical film is peeled off from the cylindrical mold, and a new cylindrical mold is inserted inside the cylindrical film. Although the method of heating and curing the cylindrical film has been adopted, such a method has a basic problem that the number of steps is increased, and when air enters between the cylindrical mold and the cylindrical film. However, there is a problem that the air cannot escape and the cylindrical film is deformed in a convex shape, and furthermore, if the clearance is increased to prevent air from entering between the cylindrical mold and the cylindrical film, the cylindrical film is deformed. There is a problem that the shrinkage of the film becomes uneven and wrinkles are generated.
【０００９】本発明者は、これらの問題を解決するため
には、剥離性材質よりなる円筒成形型の内周面に円筒膜
を形成し、円筒膜をこのままで硬化させればよいのでは
ないかと考えたが、円筒膜の端部に浮きが発生すること
がわかった。そこで、円筒膜の浮きがその端部から発生
することに着目して、円筒膜の乾燥硬化時にその端部を
リング状の枠架で押さえることにより、円筒膜の浮きを
防止することを提案した。この円筒膜の浮きを防止する
技術は、円筒膜の端部をきちんと押さえるだけで、硬化
した円筒膜に浮きを生じさせないので、有用なものであ
ることが判ったが、枠架が所定の位置にきちんとセット
されないとか、或いは、枠架と塗布された円筒膜との間
に隙間が生じたりすると、円筒膜の硬化時に浮きが生じ
るという問題があることもわかった。In order to solve these problems, the present inventor does not have to form a cylindrical film on the inner peripheral surface of a cylindrical mold made of a releasable material and cure the cylindrical film as it is. However, it was found that lifting occurred at the end of the cylindrical film. Therefore, focusing on the fact that floating of the cylindrical film occurs from its end, it was proposed to prevent the floating of the cylindrical film by holding the end with a ring-shaped frame during drying and curing of the cylindrical film. . This technique of preventing the lifting of the cylindrical film has been found to be useful because it only presses the end of the cylindrical film properly and does not cause the floating of the cured cylindrical film. It has also been found that there is a problem that, if the cylindrical film is not set properly, or if there is a gap between the frame and the applied cylindrical film, floating occurs when the cylindrical film is cured.
【００１０】そこで、本発明者は、塗布される円筒膜の
中央部に対応する円筒成形型の内表面を高剥離性の材料
で被覆して高剥離性部とし、そして、塗布される円筒膜
の両端に懸かる部分に対応する円筒成形型の内表面を相
対的に低剥離性の材質で被覆して低剥離性部とした、円
筒成形型を提案した。この円筒成形型によれば、これを
用いて成形した円筒膜を良好に剥離することができ、し
かも、成形した円筒膜に浮きがない、という利点がある
が、円筒成形型の製作過程で「高剥離性部」及び「低剥
離性部」をそれぞれ形成するために複雑な処理を施さな
ければならず、それらのために、製作費用が高くつき、
しかも、かかる処理が化学的処理であるために処理液の
後の始末にも費用がかかるという問題があった。Therefore, the present inventor has proposed that the inner surface of a cylindrical mold corresponding to the central portion of a cylindrical film to be applied is coated with a highly peelable material to form a highly peelable portion. A cylindrical mold was proposed in which the inner surface of the cylindrical mold corresponding to the portions suspended on both ends of the mold was coated with a relatively low-peelable material to form a low-peelable portion. According to this cylindrical mold, there is an advantage that the cylindrical film formed by using the cylindrical mold can be peeled off satisfactorily and there is no floating in the formed cylindrical film. Complicated processing must be performed to form the “high-peelability part” and “low-peelability part”, respectively, and due to them, the production cost is high
In addition, there is a problem that since the treatment is a chemical treatment, it is costly to clean up the treatment liquid.
【００１１】本発明は、かかる問題を解決することを目
的としている。即ち、本発明は、円筒膜を良好に剥離す
ることができると共に、浮き、凸状変形、シワ等のない
均一な円筒膜を得ることができる円筒成形型及びその製
造方法並びに円筒膜の製造方法を低コストで提供するこ
とを目的とする。An object of the present invention is to solve such a problem. That is, the present invention provides a cylindrical mold, a method for manufacturing the same, and a method for manufacturing the cylindrical film, which can satisfactorily peel off the cylindrical film, and can obtain a uniform cylindrical film free of floating, convex deformation, wrinkles, etc. At low cost.
【００１２】[0012]
【課題を解決するための手段】本発明者は、前記従来の
問題点を考察したところ、次の事実がわかった。 (1) 加熱硬化時の円筒膜の浮きはかならず端部から起こ
ること。 (2) 円筒膜の端部の浮き防止には、塗布円筒膜が端部領
域でのみ密着性があればよいこと。 (3) 円筒成形型の中央部分は、画像に影響が無いように
平滑面が望ましく、また、円筒膜と密着性が強いと円筒
膜の剥離脱型時に円筒膜にキンクが生じるので円筒膜と
密着性が小さい方がよいこと、 (4) 円筒成形型と塗布円筒膜との密着性は、円筒成形型
の材質と塗布液との親和性が大きく関係しており、剥離
が容易なためには親和性が小さい方が良いこと。Means for Solving the Problems The present inventor has studied the above conventional problems and found the following facts. (1) The lifting of the cylindrical film during heat curing must always occur from the end. (2) In order to prevent the end of the cylindrical film from floating, it is only necessary that the applied cylindrical film has adhesion only in the end region. (3) The central part of the cylindrical mold is desirably a smooth surface so as not to affect the image.In addition, if the cylindrical film has strong adhesion, a kink occurs in the cylindrical film at the time of peeling off the cylindrical film, so that the cylindrical film is The smaller the adhesion, the better. (4) The adhesion between the cylindrical mold and the coated cylindrical film is largely related to the affinity between the material of the cylindrical mold and the coating liquid, and is easy to peel. Means that the lower the affinity, the better.
【００１３】そこで、本発明者は、かかる事実を踏まえ
て、従来の問題の解決を鋭意探求したところ、アナター
ゼ型酸化チタンは、疎水性であるが、光（紫外線）の照
射で親水性に変化することに鑑み、アナターゼ型酸化チ
タンを含有する剥離層を円筒成形型のない表面に形成
し、その剥離層における、塗布円筒膜との密着性が必要
な部分には、光（紫外線）を照射し、そして、剥離性が
必要な部分には、光（紫外線）を照射しないか又は遮光
すれば、目的とする円筒成形型が得られることを見出し
て本発明を完成するに至った。In view of this fact, the present inventor has diligently sought to solve the conventional problems. As a result, the anatase type titanium oxide is hydrophobic, but changes to hydrophilic upon irradiation with light (ultraviolet light). In view of this, a release layer containing anatase-type titanium oxide is formed on the surface without the cylindrical mold, and light (ultraviolet light) is applied to a portion of the release layer that requires adhesion to the coated cylindrical film. Then, it was found that a desired cylindrical mold could be obtained by not irradiating or shielding light (ultraviolet light) to a portion requiring peelability, and completed the present invention.
【００１４】即ち、請求項１に記載された発明は、上記
目的を達成するために、疎水性のアナターゼ型酸化チタ
ンを含有する剥離層を円筒成形型の内面全域に有する円
筒成形型において、その円筒膜塗布個所となる剥離層の
中央部分に成形型内より光照射をして親水性部としたこ
とを特徴とする円筒成形型である。That is, in order to achieve the above object, the invention described in claim 1 provides a cylindrical mold having a release layer containing hydrophobic anatase-type titanium oxide over the entire inner surface of the cylindrical mold. A cylindrical mold having a hydrophilic portion formed by irradiating light from the inside of the mold to a central portion of a release layer which is a coating portion of a cylindrical film.
【００１５】請求項２に記載された発明は、請求項１に
記載された発明において、円筒成形型がアルミニウム又
はアルミニウム合金よりなり、そして、その内周面が陽
極処理処理されていることを特徴とするものである。According to a second aspect of the present invention, in the first aspect of the invention, the cylindrical mold is made of aluminum or an aluminum alloy, and an inner peripheral surface thereof is anodized. It is assumed that.
【００１６】請求項３に記載された発明は、請求項１に
記載された発明において、円筒成形型が硬質ガラスより
なり、そして、その内周面がエッチングにより微細に粗
されていることを特徴とするものである。According to a third aspect of the present invention, in the first aspect of the invention, the cylindrical mold is made of hard glass, and the inner peripheral surface thereof is finely roughened by etching. It is assumed that.
【００１７】請求項４に記載された発明は、請求項１〜
３のいずれかに記載された発明において、アナターゼ型
酸化チタンがナノ分散性二酸化チタンで構成されている
ことを特徴とするものである。[0017] The invention described in claim 4 is the first invention.
3. The invention according to any one of 3), wherein the anatase-type titanium oxide is composed of nano-dispersible titanium dioxide.
【００１８】請求項５に記載された発明は、請求項１〜
４のいずれかに記載された発明において、剥離層がフッ
素樹脂で構成されていることを特徴とするものである。The invention described in claim 5 is the first invention.
4. In the invention described in any one of 4 above, the release layer is made of a fluorine resin.
【００１９】請求項６に記載された発明は、疎水性のア
ナターゼ型酸化チタンを含有する剥離層を円筒成形型の
内面全域に有する円筒成形型において、円筒膜塗布個所
となる剥離層の中央部分の両端の内側に成形型内より所
定幅に光照射をして親水性部としたことを特徴とする円
筒成形型である。According to a sixth aspect of the present invention, there is provided a cylindrical mold having a release layer containing hydrophobic anatase-type titanium oxide on the entire inner surface of the cylindrical mold, the central portion of the release layer being a coating portion of the cylindrical film. A cylindrical mold having a hydrophilic portion formed by irradiating light to a predetermined width inside the mold from both ends of the mold.
【００２０】請求項７に記載された発明は、請求項６に
記載された発明において、円筒成形型がアルミニウム又
はアルミニウム合金よりなり、そして、その内周面が陽
極処理されていることを特徴とするものである。The invention described in claim 7 is characterized in that, in the invention described in claim 6, the cylindrical mold is made of aluminum or an aluminum alloy, and the inner peripheral surface thereof is anodized. Is what you do.
【００２１】請求項８に記載された発明は、請求項６に
記載された発明において、円筒成形型が硬質ガラスより
なり、そして、その内周面がエッチングにより微細に粗
されていることを特徴とするものである。According to an eighth aspect of the present invention, in the sixth aspect of the invention, the cylindrical mold is made of hard glass, and the inner peripheral surface thereof is finely roughened by etching. It is assumed that.
【００２２】請求項９に記載された発明は、請求項６〜
８のいずれかに記載された発明において、アナターゼ型
酸化チタンがナノ分散性二酸化チタンで構成されている
ことを特徴とするものである。[0022] The invention described in claim 9 is the invention of claims 6 to
8. The invention according to any one of the above items 8, wherein the anatase type titanium oxide is composed of nano-dispersible titanium dioxide.
【００２３】請求項１０に記載された発明は、請求項６
〜９のいずれかに記載された発明において、剥離層をフ
ッ素樹脂で構成したことを特徴とするものである。The invention described in claim 10 is the sixth invention.
In the invention described in any one of the above-described embodiments, the release layer is made of a fluororesin.
【００２４】請求項１１に記載された発明は、透明な成
形型の内面全域に疎水性のアナターゼ型酸化チタンを含
有する剥離層を形成し、そして、透明な円筒成形型の円
筒膜塗布個所となる剥離層の中央部分に成形型外より光
照射をして親水性部とすることを特徴とする円筒成形型
の製造方法である。According to the present invention, a release layer containing hydrophobic anatase-type titanium oxide is formed on the entire inner surface of the transparent mold, and a cylindrical film coating portion of the transparent cylindrical mold is provided. A method for producing a cylindrical mold, comprising irradiating a central portion of a release layer with light from outside the mold to form a hydrophilic portion.
【００２５】請求項１２に記載された発明は、透明な成
形型の内面全域に疎水性のアナターゼ型酸化チタンを含
有する剥離層を形成し、そして、透明な円筒成形型の円
筒膜塗布個所となる剥離層の中央部分の両端の内側に成
形型外より所定幅に光照射をして親水性部とすることを
特徴とする円筒成形型の製造方法である。According to a twelfth aspect of the present invention, a release layer containing hydrophobic anatase-type titanium oxide is formed on the entire inner surface of a transparent mold, and a cylindrical film coating portion of the transparent cylindrical mold is provided. A method for producing a cylindrical mold, comprising irradiating a predetermined width from outside the mold to the inside of both ends of the center portion of the release layer to form a hydrophilic portion.
【００２６】請求項１３に記載された発明は、請求項１
〜５のいずれかに記載の円筒成形型を用いて円筒膜を製
造する方法において、回転する円筒成形型の剥離層の中
央部分にポリアミド酸溶液を塗布する工程、塗布したポ
リアミド酸円筒膜を加熱乾燥する工程、及び、乾燥した
ポリアミド酸円筒膜を加熱硬化させる工程、を順次有す
ることを特徴とする円筒膜の製造方法である。The invention described in claim 13 is the first invention.
5. A method for producing a cylindrical film using the cylindrical mold according to any one of the above-mentioned items, wherein a step of applying a polyamic acid solution to a central portion of a peeling layer of the rotating cylindrical mold, heating the applied polyamide acid cylindrical film. A method of manufacturing a cylindrical film, comprising sequentially a drying step and a step of heating and curing the dried polyamic acid cylindrical film.
【００２７】請求項１４に記載された発明は、請求項６
〜１０のいずれかに記載の円筒成形型を用いて円筒膜を
製造する方法において、回転する円筒成形型の剥離層の
中央部分にポリアミド酸溶液を塗布する工程、塗布した
ポリアミド酸円筒膜を加熱乾燥する工程、及び、乾燥し
たポリアミド酸円筒膜を加熱硬化させる工程、を順次有
することを特徴とする円筒膜の製造方法である。The invention described in claim 14 is the sixth invention.
In the method for producing a cylindrical film using the cylindrical mold according to any one of claims 10 to 10, a step of applying a polyamic acid solution to a central portion of a peeling layer of the rotating cylindrical mold, heating the applied polyamide acid cylindrical film. A method of manufacturing a cylindrical film, comprising sequentially a drying step and a step of heating and curing the dried polyamic acid cylindrical film.
【００２８】[0028]
【発明の実施の形態】本発明の実施の形態を図面に基づ
いて説明する。図１は、本発明の一実施の形態を示す円
筒成形型の縦断面説明図であって、（ａ）は、その剥離
層の中央部に親水性部を形成する状態を示し、そして、
（ｂ）は、その剥離層上に円筒膜を形成する状態を示
す。図２は、本発明の他の一実施の形態を示す円筒成形
型の縦断面説明図であって、（ａ）は、その剥離層の中
央部の両端に親水性部を形成する状態を示し、そして、
（ｂ）は、その剥離層上に円筒膜を形成する状態を示
す。図３は、本発明の他の一実施の形態を示す透明な円
筒成形型の剥離層の中央部に親水性部を形成する状態を
示す縦断面説明図であ。図４は、本発明の一実施の形態
を示す円筒成形型の剥離層上に円筒膜を形成する状態を
示す部分拡大縦断面説明図であって、（ａ）は、円筒膜
を剥離層の親水性部を越えて疎水性部まで塗布した状態
を示し、そして、（ｂ）は、塗布した円筒膜が親水性部
と疎水性部との境界まで縮退した状態を示す。Embodiments of the present invention will be described with reference to the drawings. FIG. 1 is an explanatory longitudinal sectional view of a cylindrical mold showing one embodiment of the present invention, in which (a) shows a state in which a hydrophilic portion is formed at a central portion of the release layer,
(B) shows a state in which a cylindrical film is formed on the release layer. FIG. 2 is an explanatory longitudinal sectional view of a cylindrical mold showing another embodiment of the present invention. FIG. 2 (a) shows a state in which hydrophilic portions are formed at both ends of a central portion of the release layer. And
(B) shows a state in which a cylindrical film is formed on the release layer. FIG. 3 is an explanatory longitudinal sectional view showing a state in which a hydrophilic portion is formed at the center of a release layer of a transparent cylindrical mold according to another embodiment of the present invention. FIG. 4 is a partially enlarged longitudinal sectional view showing a state in which a cylindrical film is formed on a release layer of a cylindrical mold according to an embodiment of the present invention. FIG. (B) shows a state in which the applied cylindrical film has shrunk to the boundary between the hydrophilic part and the hydrophobic part.
【００２９】本発明は、疎水性のアナターゼ型酸化チタ
ンが光（紫外線）照射により親水性に変化することに着
目してなされたものである。即ち、図１に示すように、
本発明の一実施の形態の円筒成形型１は、疎水性のアナ
ターゼ型酸化チタンを含有する剥離層２をその内面全域
に有している。この剥離層２は、例えば、アナターゼ型
酸化チタン（ＴｉＯ2 ）微粉末を分散したフッ素樹脂塗
布液を円筒成形型の内面全域に塗布し、これを乾燥した
後、フッ素樹脂粉末を融着させることにより形成する。
このような円筒成形型１を回転させ、その円筒膜３の塗
布個所となる剥離層２の中央部分に、円筒成形型内１に
挿入した光照射部４より、矢印方向に紫外線（ＵＶ）等
による光照射をすると、その中央部分は、親水性部２ａ
に変化する。そのために、図１に示される本発明の実施
の形態における剥離層２は、前記親水性部２ａ及び光照
射されていない両端部分の疎水性部２ｂ，２ｂから構成
される。The present invention has been made by paying attention to the fact that hydrophobic anatase type titanium oxide changes to hydrophilic by light (ultraviolet) irradiation. That is, as shown in FIG.
The cylindrical mold 1 according to one embodiment of the present invention has a release layer 2 containing hydrophobic anatase-type titanium oxide on the entire inner surface thereof. The release layer 2 is formed, for example, by applying a fluororesin coating liquid in which anatase-type titanium oxide (TiO 2 ) fine powder is dispersed over the entire inner surface of the cylindrical mold, drying this, and then fusing the fluororesin powder. Is formed.
By rotating such a cylindrical mold 1, ultraviolet light (UV) or the like is applied in a direction indicated by an arrow from a light irradiating section 4 inserted into the cylindrical mold 1 to a central portion of the peeling layer 2 where the cylindrical film 3 is applied. Irradiates the hydrophilic portion 2a
Changes to For this purpose, the release layer 2 in the embodiment of the present invention shown in FIG. 1 is composed of the hydrophilic portion 2a and the hydrophobic portions 2b, 2b at both end portions not irradiated with light.
【００３０】本発明において使用される「アナターゼ型
酸化チタン」としては、斯界でよく知られた通常のアナ
ターゼ型の酸化チタンを使用することができるが、粒子
サイズが１〜１０ｎｍであるアナターゼ型のナノ分散性
二酸化チタン（例えば、特開平９−１６５２１８号公報
を参照。）（本明細書においては、かかる粒子サイズの
アナターゼ型二酸化チタンを「ナノ分散性二酸化チタ
ン」という。）をも使用することができる。As the "anatase-type titanium oxide" used in the present invention, ordinary anatase-type titanium oxide well-known in the art can be used, and anatase-type titanium oxide having a particle size of 1 to 10 nm is used. Nanodisperse titanium dioxide (see, for example, JP-A-9-165218) (here, anatase-type titanium dioxide having such a particle size is also referred to as "nanodisperse titanium dioxide"). Can be.
【００３１】このように、円筒膜塗布個所となる「疎水
性のアナターゼ型酸化チタンを含有する剥離層２」の中
央部分に成形型内より光照射をして親水性部２ａとした
ので、円筒膜３を良好に剥離することができると共に、
浮き、凸状変形、シワ等のない均一な円筒膜３を得るこ
とができ、しかも、円筒成形型１を使用した後において
は、放置しておくと、前記親水性部２ａが元の疎水性に
もどるので、この円筒成形型１を再使用することができ
る。さらに、円筒成形型の制作が簡単であり、その製作
コストも低い。As described above, the central portion of the “release layer 2 containing hydrophobic anatase-type titanium oxide”, which is the coating portion of the cylindrical film, is irradiated with light from the inside of the mold to form the hydrophilic portion 2a. The film 3 can be peeled off satisfactorily,
A uniform cylindrical film 3 free from floating, convex deformation, wrinkles, etc. can be obtained. Moreover, after the cylindrical mold 1 has been used, the hydrophilic portion 2a is left in its original hydrophobic state when left unattended. Since the process returns, the cylindrical mold 1 can be reused. Furthermore, the production of the cylindrical mold is simple and the production cost is low.
【００３２】このような円筒成形型１を用いて円筒膜３
を製造する場合には、円筒膜３は、例えば、次の工程を
順次経て製造することができる。即ち、円筒膜３は、回
転する円筒成形型１の剥離層２の中央部分（親水性部２
ａ）にポリアミド酸溶液を塗布する工程、塗布したポリ
アミド酸円筒膜３を加熱乾燥する工程、及び、乾燥した
ポリアミド酸円筒膜３を加熱硬化させる工程、を順次経
て製造することができる。Using such a cylindrical mold 1, a cylindrical film 3 is formed.
Is manufactured, the cylindrical film 3 can be manufactured, for example, through the following steps in order. That is, the cylindrical film 3 is formed at the central portion (the hydrophilic portion 2) of the release layer 2 of the rotating cylindrical mold 1.
The step (a) of applying a polyamic acid solution, the step of heating and drying the applied polyamic acid cylindrical film 3, and the step of heating and curing the dried polyamic acid cylindrical film 3 can be sequentially performed.
【００３３】また、図２に示すように、本発明の他の一
実施の形態の円筒成形型１は、疎水性のアナターゼ型酸
化チタンを含有する剥離層２をその内面全域に有してい
る。この剥離層２は、例えば、アナターゼ型酸化チタン
（ＴｉＯ2 ）微粉末を分散したフッ素樹脂塗布液を円筒
成形型の内面全域に塗布し、これを乾燥した後、フッ素
樹脂粉末を融着させることにより形成する。このような
円筒成形型１を回転させ、その円筒膜３の塗布個所とな
る剥離層２の中央部分の両端の内側に、成形型内の挿入
した光照射部４より、矢印方向に紫外線（ＵＶ）等によ
る光照射を所定幅にすると、その中央部分の両端の内側
は、親水性部２ａ，２ａに変化する。そのために、図２
に示される本発明の他の実施の形態における剥離層２
は、前記親水性部２ａ，２ａ及び光照射されていない両
端部分及び中央部分の疎水性部２ｂ，２ｂ，２ｂから構
成されている。As shown in FIG. 2, a cylindrical mold 1 according to another embodiment of the present invention has a release layer 2 containing hydrophobic anatase-type titanium oxide on the entire inner surface thereof. . The release layer 2 is formed, for example, by applying a fluororesin coating liquid in which anatase-type titanium oxide (TiO 2 ) fine powder is dispersed over the entire inner surface of the cylindrical mold, drying this, and then fusing the fluororesin powder. Is formed. By rotating such a cylindrical mold 1, ultraviolet light (UV) is applied in the direction of the arrow from the light irradiation section 4 inserted into the mold inside both ends of the central portion of the peeling layer 2, which is the application point of the cylindrical film 3. When the light irradiation is performed to a predetermined width, the inside of both ends of the central portion is changed to hydrophilic portions 2a, 2a. Therefore, FIG.
Release layer 2 in another embodiment of the present invention shown in FIG.
Is composed of the hydrophilic portions 2a, 2a and the hydrophobic portions 2b, 2b, 2b at both end portions and the central portion which are not irradiated with light.
【００３４】このように、円筒膜塗布個所となる「疎水
性のアナターゼ型酸化チタンを含有する剥離層２」の中
央部分の両端の内側に成形型内より所定幅に光照射をし
て親水性部２ａ，２ａとしたので、円筒膜３を良好に剥
離することができると共に、浮き、凸状変形、シワ等の
ない均一な円筒膜３を得ることができ、しかも、円筒成
形型１を使用した後においては、放置しておくと、前記
親水性部２ａ，２ａが元の疎水性にもどるので、この円
筒成形型１を再使用することができる。さらに、円筒成
形型１の制作が簡単であり、その製作コストも低い。As described above, the inside of both ends of the central portion of the "release layer 2 containing hydrophobic anatase-type titanium oxide", which is a coating portion of the cylindrical film, is irradiated with light to a predetermined width from the inside of the molding die to thereby obtain hydrophilicity. Since the portions 2a and 2a are used, the cylindrical film 3 can be satisfactorily peeled off, and a uniform cylindrical film 3 free from floating, convex deformation, wrinkles, etc. can be obtained. After this, if left untreated, the hydrophilic portions 2a return to their original hydrophobicity, so that the cylindrical mold 1 can be reused. Furthermore, the production of the cylindrical mold 1 is simple and the production cost is low.
【００３５】このような円筒成形型１を用いて円筒膜３
を製造する場合には、円筒膜３は、例えば、次の工程を
順次経て製造することができる。即ち、円筒膜３は、回
転する円筒成形型１の剥離層２の中央部分（親水性部２
ａ，２ａ及疎水性部２ｂ）にポリアミド酸溶液を塗布す
る工程、塗布したポリアミド酸円筒膜を加熱乾燥する工
程、及び、乾燥したポリアミド酸円筒膜を加熱硬化させ
る工程、を順次経て製造することができる。Using such a cylindrical mold 1, a cylindrical film 3 is formed.
Is manufactured, the cylindrical film 3 can be manufactured, for example, through the following steps in order. That is, the cylindrical film 3 is formed at the central portion (the hydrophilic portion 2) of the release layer 2 of the rotating cylindrical mold 1.
a, 2a and a hydrophobic part 2b), a step of applying a polyamic acid solution, a step of heating and drying the applied polyamic acid cylindrical membrane, and a step of heating and curing the dried polyamic acid cylindrical membrane. Can be.
【００３６】本発明においては、円筒成形型１は、アル
ミニウム又はアルミニウム合金、硬質ガラス、ステンレ
ス合金、真鍮等の金属よりなる。円筒成形型１がアルミ
ニウム又はアルミニウム合金よりなる場合には、円筒成
形型の内周面は、陽極酸化処理されていることが好まし
い。また、円筒成形型１が硬質ガラスよりなる場合に
は、円筒成形型１の内周面は、エッチングにより微細に
粗されていることが好ましい。In the present invention, the cylindrical mold 1 is made of a metal such as aluminum or aluminum alloy, hard glass, stainless alloy, brass or the like. When the cylindrical mold 1 is made of aluminum or an aluminum alloy, it is preferable that the inner peripheral surface of the cylindrical mold is anodized. When the cylindrical mold 1 is made of hard glass, the inner peripheral surface of the cylindrical mold 1 is preferably finely roughened by etching.
【００３７】円筒成形型１の内周面を陽極酸化処理又は
エッチングにより微細に粗すと、直径２５ｎｍ程度の微
少な孔が多数形成される。このような微少な孔が多数形
成された円筒成形型１の内周面にアナターゼ型酸化チタ
ンを含有する樹脂分散体、例えば、フッ素樹脂分散体を
塗布し、焼き付けして剥離層２を形成すると、剥離層２
を構成する樹脂が微少な孔に入り込んでむことにより奏
するアンカー効果により、剥離層２は、円筒成形型１の
内周面に密着して剥がれることはなく、そのために、円
筒成形型の耐久性が向上する。また、このような微少な
孔が多数形成された円筒成形型１の内周面にアナターゼ
型のナノ分散性二酸化チタンの液分散体を塗布すると、
ナノ分散性二酸化チタンが円筒成形型１の内周面の微少
な孔に入り込んで微少な孔を封孔し、剥離層２が形成さ
れることとなる。When the inner peripheral surface of the cylindrical mold 1 is finely roughened by anodic oxidation treatment or etching, many small holes having a diameter of about 25 nm are formed. When a resin dispersion containing anatase-type titanium oxide, for example, a fluororesin dispersion, is applied to the inner peripheral surface of the cylindrical mold 1 in which a large number of such minute holes are formed, and baked to form the release layer 2, , Release layer 2
The peeling layer 2 does not come into close contact with the inner peripheral surface of the cylindrical mold 1 due to the anchor effect exerted by the resin constituting the resin entering the minute holes, and therefore, the durability of the cylindrical mold 1 Is improved. Further, when a liquid dispersion of anatase-type nano-dispersible titanium dioxide is applied to the inner peripheral surface of the cylindrical mold 1 in which many such minute holes are formed,
The nano-dispersible titanium dioxide enters the minute holes on the inner peripheral surface of the cylindrical mold 1 and seals the minute holes, so that the release layer 2 is formed.
【００３８】図３に示されているように、円筒成形型１
にガラスのような透明な材料を用いる場合には、その内
面全域にアナターゼ型酸化チタンを含有する剥離層２を
形成し、そして、回転する透明な円筒成形型１の円筒膜
塗布個所となる剥離層２の中央部分に配置した光照射部
４より、矢印方向に紫外線（ＵＶ）等による光照射をす
ると、その剥離層２の中央部分は、親水性部２ａに変化
する。そのために、図３に示される剥離層２は、前記親
水性部２ａ及び光照射されていない両端部分の疎水性部
２ｂ，２ｂから構成される。As shown in FIG. 3, the cylindrical mold 1
When a transparent material such as glass is used, a peeling layer 2 containing anatase-type titanium oxide is formed on the entire inner surface thereof, and the peeling which becomes a cylindrical film application portion of the rotating transparent cylindrical mold 1 is performed. When light irradiation with ultraviolet light (UV) or the like is performed in the direction of the arrow from the light irradiation unit 4 arranged at the center of the layer 2, the center of the release layer 2 changes to a hydrophilic part 2a. For this purpose, the release layer 2 shown in FIG. 3 is composed of the hydrophilic portion 2a and the hydrophobic portions 2b, 2b at both ends which are not irradiated with light.
【００３９】同様にして、本発明の成形型は、透明な成
形型の内面全域にアナターゼ型酸化チタンを含有する剥
離層を形成し、そして、回転する透明な円筒成形型の円
筒膜塗布個所となる剥離層の中央部分の両端の内側に成
形型外より所定幅に光照射をして親水性部にすることに
よっても製造することができる（図示せず）。Similarly, the mold of the present invention forms a release layer containing anatase-type titanium oxide on the entire inner surface of the transparent mold, and provides a coating portion of the rotating transparent cylindrical mold with the cylindrical film. It can also be manufactured by irradiating light to the inside of both ends of the center portion of the release layer to a predetermined width from outside the mold to make it a hydrophilic portion (not shown).
【００４０】[0040]
【実施例】（実施例１）回転するアルミニウム円筒成形
型の内面全域に光活性な疎水性のアナターゼ型酸化チタ
ン（ＴｉＯ2 ）微粉末を分散したフッ素樹脂塗布液を塗
布した後、加熱してそのフッ素樹脂を融着させて剥離層
を形成し、この剥離層を形成した円筒成形型の内部に紫
外線（ＵＶ光）光源を挿入して、円筒成形型を回転させ
ながら円筒膜塗布個所となる剥離層の中央部分に光照射
をして親水性部を形成した。そして、ポリイミド前駆体
のポリアミド酸溶液（東レ社製、トレニース＃３００
０）に導電性のカーボンブラックを分散し、この分散液
をＮ，Ｎ−ジメチルアセトアミド（ＤＭＡＣ）で３０％
に希釈して塗布液とした。この塗布液を前記円筒成形型
の内側に該円筒成形型を低速に回転させながら塗布して
ポリアミド酸塗布膜を形成し、続いて、成形型を高速に
回転して該塗布膜を均一な厚さの膜とした後、この膜を
８０℃で乾燥させて溶媒を除去してポリアミド酸円筒膜
を形成した。次に、このポリアミド酸円筒膜が形成され
た円筒成形型をその回転を止めて取り出してこれを恒温
槽に移し、そこで、ポリアミド酸円筒膜を１００℃の温
度で加熱して溶剤を完全に除去した後、３００℃の温度
で加熱して完全に硬化させてポリイミド円筒膜を形成し
た。このようにポリイミド円筒膜を形成した円筒成形型
を冷却して取り出したが、ポリイミド円筒膜に浮きはな
く、良質のポリイミド円筒膜が形成されていた。このポ
リイミド円筒膜の両端部縁をナイフエッジで僅かに浮か
し、手で端部より剥離したが、ポリイミド円筒膜の剥離
はスムーズに行うことができ、そのために、ポリイミド
円筒膜に剥離跡が残らなかった。また、得られたポリイ
ミド円筒膜の中央部は、型内面に接する外面も光沢を持
ち、極めて平滑な面を有していた。EXAMPLES (Example 1) after applying the rotating aluminum cylindrical mold photoactive hydrophobic anatase type titanium oxide entire inner surface of the (TiO 2) coated fluororesin prepared by dispersing a fine powder and heated to The release layer is formed by fusing the fluororesin, and an ultraviolet (UV) light source is inserted into the inside of the cylindrical mold on which the release layer is formed. Light irradiation was performed on the central portion of the release layer to form a hydrophilic portion. Then, a polyamic acid solution of a polyimide precursor (Trenice # 300 manufactured by Toray Industries, Inc.)
0) is dispersed with conductive carbon black, and this dispersion is treated with N, N-dimethylacetamide (DMAC) at 30%.
To obtain a coating solution. This coating solution is applied to the inside of the cylindrical mold while rotating the cylindrical mold at a low speed to form a polyamic acid coating film. Subsequently, the mold is rotated at a high speed so that the coating film has a uniform thickness. After forming the film, the film was dried at 80 ° C. to remove the solvent to form a polyamic acid cylindrical film. Next, the rotation of the cylindrical mold on which the polyamic acid cylindrical film was formed was stopped, and the cylindrical mold was taken out and transferred to a thermostat. The polyamic acid cylindrical film was heated at a temperature of 100 ° C. to completely remove the solvent. After that, it was heated at a temperature of 300 ° C. to be completely cured to form a polyimide cylindrical film. The cylindrical mold on which the polyimide cylindrical film was formed was cooled and taken out. However, the polyimide cylindrical film did not float, and a good quality polyimide cylindrical film was formed. Both edges of the polyimide cylindrical film were slightly lifted with a knife edge and peeled off from the ends by hand, but the polyimide cylindrical film can be smoothly peeled off, so that no peeling marks remain on the polyimide cylindrical film. Was. In addition, the central portion of the obtained polyimide cylindrical film had an extremely smooth outer surface in contact with the inner surface of the mold, and had an extremely smooth surface.
【００４１】（実施例２）回転するアルミニウム円筒成
形型の内面全域に光活性な疎水性のアナターゼ型酸化チ
タン（ＴｉＯ2 ）微粉末を分散したフッ素樹脂塗布液を
塗布した後、加熱してそのフッ素樹脂を融着させて剥離
層を形成し、この剥離層を形成した円筒成形型の内部に
紫外線（ＵＶ光）光源を挿入して、円筒成形型を回転さ
せながら円筒膜塗布個所となる剥離層の中央部分の両端
の内側の幅２０ｍｍのみにＵＶ光を照射して親水性部と
した。そして、この円筒成形型に実施例１と同様にして
ポリイミド円筒膜を形成した。このようにポリイミド円
筒膜を形成した円筒成形型を冷却し取り出したが、ポリ
イミド円筒膜に浮きはなく、良質のポリイミド円筒膜が
形成されていた。このポリイミド円筒膜の両端部縁をナ
イフエッジで僅かに浮かし、手で端部より剥離したが、
ポリイミド円筒膜の剥離は親水性部を過ぎるとスムース
に行うことができ、そのために、ポリイミド円筒膜に剥
離跡が残らなかった。また、得られたポリイミド円筒膜
の中央部は、型内面に接する外面も光沢を持ち、極めて
平滑な面を有していた。(Example 2) A fluororesin coating liquid in which a fine powder of photoactive hydrophobic anatase type titanium oxide (TiO 2 ) was applied to the entire inner surface of a rotating aluminum cylindrical mold was heated and heated. A release layer is formed by fusing the fluororesin, and an ultraviolet (UV) light source is inserted into the cylindrical mold having the release layer formed thereon, and the cylindrical mold is rotated while the cylindrical film is being applied. Only the inner width 20 mm at both ends of the central portion of the layer was irradiated with UV light to make a hydrophilic portion. Then, a polyimide cylindrical film was formed on this cylindrical mold in the same manner as in Example 1. The cylindrical mold on which the polyimide cylindrical film was formed was cooled and taken out, but the polyimide cylindrical film did not float, and a good quality polyimide cylindrical film was formed. The edges of both ends of this polyimide cylindrical film were slightly lifted with a knife edge and peeled off from the ends by hand,
Peeling of the polyimide cylindrical film could be performed smoothly after passing through the hydrophilic part, and therefore, no trace of peeling remained on the polyimide cylindrical film. In addition, the central portion of the obtained polyimide cylindrical film had an extremely smooth outer surface in contact with the inner surface of the mold, and had an extremely smooth surface.
【００４２】（実施例３）実施例１と同様にして、回転
するアルミニウム円筒成形型の内面全域に光活性な疎水
性のアナターゼ型酸化チタン（ＴｉＯ2 ）微粉末を分散
したフッ素樹脂塗布液を塗布した後、加熱してそのフッ
素樹脂を融着させて剥離層を形成し、この剥離層を形成
した円筒成形型の内部に紫外線（ＵＶ光）光源を挿入し
て、円筒成形型を回転させながら円筒膜塗布個所となる
剥離層の中央部分に光照射をして親水性部に形成した。
そして、ポリイミド前駆体のポリアミド酸溶液（東レ社
製、トレニース＃３０００）に導電性のカーボンブラッ
クを分散し、この分散液をＮ，Ｎ−ジメチルアセトアミ
ド（ＤＭＡＣ）で３０％に希釈して塗布液とした。この
塗布液を前記円筒成形型の内側に該円筒成形型を低速に
回転させながら親水性部よりわずかにはみ出して塗布し
てポリアミド酸塗布膜を形成した（図４参照）。続い
て、円筒成形型の回転数を減らして、型内面での遠心力
が２Ｇ以下になるような回転数で回転させながら、円筒
膜を８０℃で乾燥させ、指触乾燥した段階で回転を止め
て観察したところ、塗布膜は疎水性部（ＵＶ非照射部
分）から後退して親水性部（ＵＶ照射部分）の端部で丸
くなっていた（図４参照）。次に、このポリアミド酸円
筒膜を実施例１と同様に硬化させてポリイミド円筒膜を
形成した。このようにポリイミド円筒膜を形成した円筒
成形型を冷却して取り出したが、ポリイミド円筒膜に浮
きはなく、良質のポリイミド円筒膜が形成されていた。
このポリイミド円筒膜の両端部縁をナイフエッジで僅か
に浮かし、手で端部より剥離したが、ポリイミド円筒膜
の剥離はスムーズに行うことができ、そのために、ポリ
イミド円筒膜に剥離跡が残らなかった。また、得られた
ポリイミド円筒膜の中央部は、型内面に接する外面も光
沢を持ち、極めて平滑な面を有していた。Example 3 In the same manner as in Example 1, a fluororesin coating liquid in which photoactive hydrophobic fine powder of anatase-type titanium oxide (TiO 2 ) was dispersed over the entire inner surface of a rotating aluminum cylindrical mold was used. After the application, heating is performed to fuse the fluororesin to form a release layer. An ultraviolet (UV) light source is inserted into the cylindrical mold having the release layer formed thereon, and the cylindrical mold is rotated. While irradiating the central portion of the release layer, which is a coating portion of the cylindrical film, with light, a hydrophilic portion was formed.
Then, a conductive carbon black is dispersed in a polyamic acid solution of a polyimide precursor (Trenice # 3000, manufactured by Toray Industries, Inc.), and this dispersion is diluted to 30% with N, N-dimethylacetamide (DMAC) to form a coating solution. And This coating solution was applied to the inside of the cylindrical mold while slightly rotating out of the hydrophilic portion while rotating the cylindrical mold at a low speed to form a polyamic acid coating film (see FIG. 4). Subsequently, the cylindrical film is dried at 80 ° C. while rotating at a rotational speed such that the centrifugal force on the inner surface of the cylindrical mold is reduced to 2 G or less while reducing the rotational speed of the cylindrical mold. When stopped and observed, the coating film receded from the hydrophobic part (UV non-irradiated part) and was rounded at the end of the hydrophilic part (UV irradiated part) (see FIG. 4). Next, this polyamide acid cylindrical film was cured in the same manner as in Example 1 to form a polyimide cylindrical film. The cylindrical mold on which the polyimide cylindrical film was formed was cooled and taken out. However, the polyimide cylindrical film did not float, and a good quality polyimide cylindrical film was formed.
Both edges of the polyimide cylinder film were slightly lifted with a knife edge and peeled off by hand, but the polyimide cylinder film could be peeled off smoothly, so that no trace of peeling remained on the polyimide cylinder film. Was. In addition, the central portion of the obtained polyimide cylindrical film had an extremely smooth outer surface in contact with the inner surface of the mold, and had an extremely smooth surface.
【００４３】（実施例４）回転するアルミニウム円筒成
形型円筒形の内面全域を陽極酸化処理をして多孔質のア
ルマイト表面を形成した。この多孔質のアルマイト表面
をアナターゼ型酸化チタン微粉末を分散したフッ素樹脂
塗布液を塗布した後、加熱してそのフッ素樹脂を融着さ
せて剥離層を形成し、この剥離層を形成した円筒成形型
の内部に紫外線（ＵＶ光）光源を挿入して、円筒成形型
を回転させながら円筒膜塗布個所となる剥離層の中央部
分に光照射をして親水性部を形成した。そして、この円
筒成形型に実施例１と同様にしてポリイミド酸円筒膜を
形成し、次に、実施例１と同様にしてポリイミド酸円筒
膜を形成した。このようにポリイミド円筒膜を形成した
円筒成形型を冷却して取り出したが、ポリイミド円筒膜
に浮きはなく、良質のポリイミド円筒膜が形成されてい
た。このポリイミド円筒膜の両端部縁をナイフエッジで
僅かに浮かし、手で端部より剥離したが、ポリイミド円
筒膜の剥離は親水性部を過ぎるとスムースに行うことが
でき、そのために、ポリイミド円筒膜に剥離跡が残らな
かった。また、得られたポリイミド円筒膜の中央部は、
型内面に接する外面も光沢を持ち、極めて平滑な面を有
していた。(Example 4) A rotating aluminum cylindrical molding die The entire inner surface of a cylindrical shape was anodized to form a porous alumite surface. This porous alumite surface is coated with a fluororesin coating liquid in which anatase-type titanium oxide fine powder is dispersed, and then heated to fuse the fluororesin to form a release layer. An ultraviolet (UV) light source was inserted into the mold, and while rotating the cylindrical mold, light was applied to the central portion of the release layer, which was to be a coating portion of the cylindrical film, to form a hydrophilic portion. Then, a polyimide acid cylindrical film was formed on this cylindrical mold in the same manner as in Example 1, and then a polyimide acid cylindrical film was formed as in Example 1. The cylindrical mold on which the polyimide cylindrical film was formed was cooled and taken out. However, the polyimide cylindrical film did not float, and a good quality polyimide cylindrical film was formed. The edges of both ends of this polyimide cylindrical film were slightly lifted with a knife edge and peeled off by hand, but the polyimide cylindrical film could be peeled off smoothly after passing the hydrophilic part. No traces of peeling were left. In addition, the central portion of the obtained polyimide cylindrical film,
The outer surface in contact with the inner surface of the mold also had a gloss, and had an extremely smooth surface.
【００４４】（実施例５）回転するアルミニウム円筒成
形型円筒形の内面全域を陽極酸化処理をして多孔質のア
ルマイト表面を形成した。この多孔質のアルマイト表面
にアナターゼ型酸化チタン微粉末を分散したフッ素樹脂
塗布液を塗布した後、加熱してそのフッ素樹脂を融着さ
せて剥離層を形成し、この剥離層を形成した円筒成形型
の内部に紫外線（ＵＶ光）光源を挿入して、円筒成形型
を回転させながら円筒膜塗布個所となる剥離層の中央部
分に光照射をして親水性部を形成した。そして、この円
筒成形型に実施例１と同様にしてポリイミド酸円筒膜を
形成し、次に、実施例１と同様にしてポリイミド酸円筒
膜を形成した。このようにポリイミド円筒膜を形成した
円筒成形型を冷却して取り出したが、ポリイミド円筒膜
に浮きはなく、良質のポリイミド円筒膜が形成されてい
た。このポリイミド円筒膜の両端部縁をナイフエッジで
僅かに浮かし、手で端部より剥離したが、ポリイミド円
筒膜の剥離は親水性部を過ぎるとスムースに行うことが
でき、そのために、ポリイミド円筒膜に剥離跡が残らな
かった。また、得られたポリイミド円筒膜の中央部は、
型内面に接する外面も光沢を持ち、極めて平滑な面を有
していた。(Example 5) A rotating aluminum cylindrical molding die The entire inner surface of the cylindrical shape was anodized to form a porous alumite surface. After applying a fluororesin coating liquid in which anatase-type titanium oxide fine powder is dispersed to the surface of the porous alumite, heating is performed to fuse the fluororesin to form a release layer, and a cylindrical molding on which the release layer is formed is formed. An ultraviolet (UV) light source was inserted into the mold, and while rotating the cylindrical mold, light was applied to the central portion of the release layer, which was to be a coating portion of the cylindrical film, to form a hydrophilic portion. Then, a polyimide acid cylindrical film was formed on this cylindrical mold in the same manner as in Example 1, and then a polyimide acid cylindrical film was formed as in Example 1. The cylindrical mold on which the polyimide cylindrical film was formed was cooled and taken out. However, the polyimide cylindrical film did not float, and a good quality polyimide cylindrical film was formed. The edges of both ends of this polyimide cylindrical film were slightly lifted with a knife edge and peeled off by hand, but the polyimide cylindrical film could be peeled off smoothly after passing the hydrophilic part. No traces of peeling were left. In addition, the central portion of the obtained polyimide cylindrical film,
The outer surface in contact with the inner surface of the mold also had a gloss, and had an extremely smooth surface.
【００４５】（実施例６）回転するアルミニウム円筒成
形型円筒形の内面全域を陽極酸化処理をして多孔質のア
ルマイト表面を形成した。この多孔質のアルマイト表面
にアナターゼ型のナノ分散性二酸化チタンの液分散体を
塗布した後、加熱乾燥して、ナノ分散性二酸化チタンで
アルマイト表面の微少な孔を封孔することにより剥離層
を形成した。次に、この剥離層を形成した円筒成形型の
内部に紫外線（ＵＶ光）光源を挿入して、円筒成形型を
回転させながら円筒膜塗布個所となる剥離層の中央部分
に光照射をして親水性部を形成した。そして、この円筒
成形型に実施例１と同様にしてポリイミド酸円筒膜を形
成し、次に、実施例１と同様にしてポリイミド酸円筒膜
を形成した。このようにポリイミド円筒膜を形成した円
筒成形型を冷却して取り出したが、ポリイミド円筒膜に
浮きはなく、良質のポリイミド円筒膜が形成されてい
た。このポリイミド円筒膜の両端部縁をナイフエッジで
僅かに浮かし、手で端部より剥離したが、ポリイミド円
筒膜の剥離は親水性部を過ぎるとスムースに行うことが
でき、そのために、ポリイミド円筒膜に剥離跡が残らな
かった。また、得られたポリイミド円筒膜の中央部は、
型内面に接する外面も光沢を持ち、極めて平滑な面を有
していた。(Example 6) A rotating aluminum cylindrical mold Anodizing treatment was performed on the entire inner surface of the cylindrical shape to form a porous alumite surface. After applying a liquid dispersion of anatase-type nano-dispersible titanium dioxide to the surface of this porous alumite, heating and drying, the nano-dispersible titanium dioxide seals the fine pores on the alumite surface to form a release layer. Formed. Next, an ultraviolet (UV) light source is inserted into the cylindrical mold having the release layer formed thereon, and light is applied to the central portion of the release layer, which is to be a cylindrical film application point, while rotating the cylindrical mold. A hydrophilic portion was formed. Then, a polyimide acid cylindrical film was formed on this cylindrical mold in the same manner as in Example 1, and then a polyimide acid cylindrical film was formed as in Example 1. The cylindrical mold on which the polyimide cylindrical film was formed was cooled and taken out. However, the polyimide cylindrical film did not float, and a good quality polyimide cylindrical film was formed. The edges of both ends of this polyimide cylindrical film were slightly lifted with a knife edge and peeled off by hand, but the polyimide cylindrical film could be peeled off smoothly after passing the hydrophilic part. No traces of peeling were left. In addition, the central portion of the obtained polyimide cylindrical film,
The outer surface in contact with the inner surface of the mold also had a gloss, and had an extremely smooth surface.
【００４６】（実施例７）回転するアルミニウム円筒成
形型円筒形の内面全域を陽極酸化処理をして多孔質のア
ルマイト表面を形成した。この多孔質のアルマイト表面
にアナターゼ型のナノ分散性二酸化チタン重量５０％以
上を分散したフッ素樹脂塗布液を塗布した後、加熱して
そのフッ素樹脂を融着させて剥離層を形成し、この剥離
層を形成した円筒成形型の内部に紫外線（ＵＶ光）光源
を挿入して、円筒成形型を回転させながら円筒膜塗布個
所となる剥離層の中央部分に光照射をして親水性部を形
成した。そして、この円筒成形型に実施例１と同様にし
てポリイミド酸円筒膜を形成し、次に、実施例１と同様
にしてポリイミド酸円筒膜を形成した。このようにポリ
イミド円筒膜を形成した円筒成形型を冷却して取り出し
たが、ポリイミド円筒膜に浮きはなく、良質のポリイミ
ド円筒膜が形成されていた。このポリイミド円筒膜の両
端部縁をナイフエッジで僅かに浮かし、手で端部より剥
離したが、ポリイミド円筒膜の剥離は親水性部を過ぎる
とスムースに行うことができ、そのために、ポリイミド
円筒膜に剥離跡が残らなかった。また、得られたポリイ
ミド円筒膜の中央部は、型内面に接する外面も光沢を持
ち、極めて平滑な面を有していた。(Example 7) Rotating aluminum cylindrical mold The entire inner surface of the cylindrical shape was anodized to form a porous alumite surface. After applying a fluororesin coating liquid in which at least 50% by weight of anatase-type nanodispersible titanium dioxide is dispersed on the surface of the porous alumite, heating is performed to fuse the fluororesin to form a release layer. An ultraviolet (UV) light source is inserted into the cylindrical mold on which the layer is formed, and while rotating the cylindrical mold, light is irradiated to the central part of the release layer, which is the coating position of the cylindrical film, to form a hydrophilic portion. did. Then, a polyimide acid cylindrical film was formed on this cylindrical mold in the same manner as in Example 1, and then a polyimide acid cylindrical film was formed as in Example 1. The cylindrical mold on which the polyimide cylindrical film was formed was cooled and taken out. However, the polyimide cylindrical film did not float, and a good quality polyimide cylindrical film was formed. The edges of both ends of this polyimide cylindrical film were slightly lifted with a knife edge and peeled off by hand, but the polyimide cylindrical film could be peeled off smoothly after passing the hydrophilic part. No traces of peeling were left. In addition, the central portion of the obtained polyimide cylindrical film had an extremely smooth outer surface in contact with the inner surface of the mold, and had an extremely smooth surface.
【００４７】（実施例８）硬質ガラス円筒成形型の内面
全域をエッチング処理して微細に粗した表面を形成し
た。この微細に粗した円筒成形型の表面に回転させなが
らアナターゼ型酸化チタン微粉末を分散したフッ素樹脂
塗布液を塗布した後、そのフッ素樹脂を融着させて剥離
層を形成し、次に、この剥離層を形成した円筒成形型の
内部に紫外線（ＵＶ光）光源を挿入して、円筒型を回転
させながら円筒膜塗布個所となる剥離層の中央部分に光
照射をして親水性部を形成した。そして、ポリイミド前
駆体のポリアミド酸溶液（東レ社製、トレニース＃３０
００）をＮ，Ｎ−ジメチルアセトアミド（ＤＭＡＣ）で
３０％に希釈して塗布液とし、この塗布液を前記円筒成
形型の内側に該円筒成形型を低速に回転させながら塗布
してポリアミド酸塗布膜を形成し、続いて、成形型を高
速に回転して該塗布膜を均一な厚さの膜とした後、この
膜を８０℃で乾燥させ、溶媒を除去して半イミド化した
ポリアミド酸円筒膜を形成した。さらに、ポリイミド前
駆体のポリアミド酸溶液（東レ社製、トレニース＃３０
００）に導電性のカーボンブラックを分散し、この分散
液をＮ，Ｎ−ジメチルアセトアミド（ＤＭＡＣ）で３０
％に希釈して塗布液とし、この塗布液を前記円筒成形型
の内側に該円筒成形型を低速に回転させながら塗布して
ポリアミド酸塗布膜を形成し、続いて、成形型を高速に
回転して該塗布膜を均一な厚さの膜とした後、この膜を
８０℃で乾燥させて溶媒を除去してポリアミド酸円筒膜
を形成した。そして、この円筒成形型に実施例１と同様
にしてポリイミド酸円筒膜を形成し、次に、実施例１と
同様にしてポリイミド酸円筒膜を形成した。このようポ
リイミド円筒膜を形成した円筒成形型を冷却して取り出
したが、ポリイミド円筒膜に浮きはなく、良質のポリイ
ミド円筒膜が形成されていた。このポリイミド円筒膜の
両端部縁をナイフエッジで僅かに浮かし、手で端部より
剥離したが、ポリイミド円筒膜の剥離は親水性部を過ぎ
るとスムースに行うことができ、そのために、ポリイミ
ド円筒膜に剥離跡が残らなかった。また、得られたポリ
イミド円筒膜の中央部は、型内面に接する外面も光沢を
持ち、極めて平滑な面を有していた。Example 8 The entire inner surface of a hard glass cylindrical mold was etched to form a fine and rough surface. After applying a fluororesin coating liquid in which anatase type titanium oxide fine powder is dispersed while rotating on the surface of this finely rough cylindrical mold, a release layer is formed by fusing the fluororesin, and then An ultraviolet (UV) light source is inserted into the cylindrical mold on which the release layer is formed, and while the cylindrical mold is rotated, light is irradiated to the central part of the release layer, which is the coating position of the cylindrical film, to form a hydrophilic portion. did. Then, a polyamic acid solution of a polyimide precursor (Trenice # 30 manufactured by Toray Industries, Inc.)
00) was diluted with N, N-dimethylacetamide (DMAC) to 30% to form a coating solution, and the coating solution was applied to the inside of the cylindrical mold while rotating the cylindrical mold at a low speed to apply polyamic acid. After forming a film, the mold is rotated at a high speed to form the coating film having a uniform thickness, and then the film is dried at 80 ° C., and the solvent is removed to obtain a semi-imidized polyamic acid. A cylindrical film was formed. Further, a polyamic acid solution of a polyimide precursor (Trenice # 30 manufactured by Toray Industries, Inc.)
00), conductive carbon black is dispersed therein, and this dispersion is treated with N, N-dimethylacetamide (DMAC) for 30 minutes.
% To form a coating solution, and applying the coating solution to the inside of the cylindrical mold while rotating the cylindrical mold at a low speed to form a polyamic acid coating film, and then rotating the mold at a high speed. After the coating film was formed into a film having a uniform thickness, the film was dried at 80 ° C. to remove the solvent to form a polyamic acid cylindrical film. Then, a polyimide acid cylindrical film was formed on this cylindrical mold in the same manner as in Example 1, and then a polyimide acid cylindrical film was formed in the same manner as Example 1. The cylindrical mold on which the polyimide cylindrical film was formed was cooled and taken out. However, the polyimide cylindrical film did not float and a good quality polyimide cylindrical film was formed. The edges of both ends of this polyimide cylindrical film were slightly lifted with a knife edge and peeled off by hand, but the polyimide cylindrical film can be peeled off smoothly after passing the hydrophilic part. No traces of peeling were left. In addition, the central portion of the obtained polyimide cylindrical film had an extremely smooth outer surface in contact with the inner surface of the mold, and had an extremely smooth surface.
【００４８】（実施例９）前記実施例１及び実施例５の
円筒成形型を繰り返し使用して、ポリイミド円筒膜を製
造したが、良好なポリイミド円筒膜をが得られることが
わかった。Example 9 A polyimide cylindrical film was produced by repeatedly using the cylindrical molds of Examples 1 and 5, and it was found that a good polyimide cylindrical film could be obtained.
【００４９】（比較例１）実施例１と同様に、アナター
ゼ型酸化チタン微粉末を含有する剥離層を有する円筒成
形型を用いてポリイミド円筒膜を形成する際に、該剥離
層の中央部分（ポリイミド円筒膜形成領域）にＵＶ照射
しない場合は、加熱硬化処理時にポリイミド円筒膜の端
部が浮いてしまい、良好なポリイミド円筒膜を得ること
ができなかった。(Comparative Example 1) As in Example 1, when a polyimide cylindrical film was formed using a cylindrical mold having a release layer containing fine anatase-type titanium oxide powder, the central portion of the release layer ( When UV irradiation was not performed on the polyimide cylindrical film forming region), the end of the polyimide cylindrical film floated during the heat curing treatment, and a good polyimide cylindrical film could not be obtained.
【００５０】（比較例２）実施例５と同様に、アナター
ゼ型酸化チタン微粉末を含有する剥離層を有する硬質ガ
ラス円筒成形型を用いてポリイミド円筒膜を製造する際
に、該剥離層の中央部分（ポリイミド円筒膜形成領域）
にＵＶ照射しない場合は、加熱硬化処理時にポリイミド
円筒膜の端部が浮いてしまい、良好なポリイミド円筒膜
を形成することができなかった。Comparative Example 2 As in Example 5, when a polyimide cylindrical film was produced using a hard glass cylindrical mold having a release layer containing fine anatase-type titanium oxide powder, the center of the release layer was removed. Part (polyimide cylindrical film formation area)
When UV irradiation was not performed, the end of the polyimide cylindrical film floated during the heat curing treatment, and a good polyimide cylindrical film could not be formed.
【００５１】[0051]
【発明の効果】(1) 請求項１に記載された発明によれ
ば、円筒膜塗布個所となる「疎水性のアナターゼ型酸化
チタンを含有する剥離層」の中央部分に成形型内より光
照射をして親水性部としたので、円筒膜を良好に剥離す
ることができると共に、浮き、凸状変形、シワ等のない
均一な円筒膜を得ることができ、しかも、円筒成形型を
使用した後においては、放置しておくと、前記親水性部
が元の疎水性にもどるので、この円筒成形型を再使用す
ることができる。さらに、円筒成形型の制作が簡単であ
り、その制作コストも低い。(1) According to the first aspect of the present invention, light is irradiated from the inside of the mold to the central portion of the "release layer containing hydrophobic anatase-type titanium oxide", which is to be applied to the cylindrical film. As a result, the cylindrical film can be peeled off satisfactorily, and a uniform cylindrical film free of floating, convex deformation, wrinkles, etc. can be obtained. After that, if left as it is, the hydrophilic portion returns to the original hydrophobicity, so that this cylindrical mold can be reused. Further, the production of the cylindrical mold is simple and the production cost is low.
【００５２】(2) 請求項２，７に記載された発明によれ
ば、円筒成形型がアルミニウム又はアルミニウム合金よ
りなり、そして、その内周面が陽極処理されているの
で、例えば、アナターゼ型酸化チタン（ＴｉＯ2 ）微粉
末を分散したフッ素樹脂塗布液を塗布し、フッ素樹脂を
融着させて、密着性のよい剥離層を形成することがで
き、耐久性を向上させることができる。(2) According to the second and seventh aspects of the present invention, the cylindrical mold is made of aluminum or an aluminum alloy, and the inner peripheral surface thereof is anodized. By applying a fluororesin coating liquid in which titanium (TiO 2 ) fine powder is dispersed and fusing the fluororesin, a peeling layer having good adhesion can be formed, and the durability can be improved.
【００５３】(3) 請求項３，８に記載された発明によれ
ば、円筒成形型が硬質ガラスよりなり、そして、その内
周面がエッチングにより微細に粗されているので、例え
ば、アナターゼ型酸化チタン（ＴｉＯ2 ）微粉末を分散
したフッ素樹脂塗布液を塗布し、フッ素樹脂を融着させ
ると、アンカー硬化により密着性のよい剥離層を形成す
ることができ、そのために、耐久性を向上させることが
できる。(3) According to the third and eighth aspects of the present invention, the cylindrical mold is made of hard glass, and the inner peripheral surface thereof is finely roughened by etching. When a fluororesin coating liquid in which titanium oxide (TiO 2 ) fine powder is dispersed is applied and the fluororesin is fused, an exfoliation layer having good adhesion can be formed by anchor curing, thereby improving durability. Can be done.
【００５４】(4) 請求項４，９に記載された発明によれ
ば、アナターゼ型酸化チタンがナノ分散性二酸化チタン
で構成されているので、陽極酸化処理又はエッチングに
より微少な孔が多数形成された円筒成形型の内周面にア
ナターゼ型のナノ分散性二酸化チタンの液分散体を塗布
すると、ナノ分散性二酸化チタンが円筒成形型の内周面
の微少な孔に入り込んで微少な孔を封孔し、剥離層を形
成することができる。(4) According to the fourth and ninth aspects of the present invention, since the anatase type titanium oxide is composed of nano-dispersible titanium dioxide, a large number of fine pores are formed by anodizing treatment or etching. When a liquid dispersion of anatase-type nano-dispersible titanium dioxide is applied to the inner peripheral surface of the cylindrical mold, the nano-dispersible titanium dioxide enters the minute holes in the inner peripheral surface of the cylindrical mold and seals the minute holes. Holes can be formed to form a release layer.
【００５５】(5) 請求項５，１０に記載された発明によ
れば、剥離層をフッ素樹脂で構成したので、剥離層は、
その剥離性が良好であり、しかも、熱、溶剤等による耐
久性が良好である。(5) According to the invention set forth in claims 5 and 10, since the release layer is made of a fluororesin, the release layer is
Its peelability is good, and its durability by heat, solvent and the like is good.
【００５６】(6) 請求項６に記載された発明によれば、
円筒膜塗布個所となる「疎水性のアナターゼ型酸化チタ
ンを含有する剥離層」の中央部分の両端の内側に成形型
内より所定幅に光照射をして親水性部としたので、円筒
膜を良好に剥離することができると共に、浮き、凸状変
形、シワ等のない均一な円筒膜を得ることができ、しか
も、円筒成形型を使用した後においては、放置しておく
と、前記親水性部が元の疎水性にもどるので、この円筒
成形型を再使用することができる。さらに、円筒成形型
の制作が簡単であり、その制作コストも低い。(6) According to the invention described in claim 6,
Since the inside of both ends of the central part of the "release layer containing hydrophobic anatase-type titanium oxide", which is a coating part of the cylindrical film, was irradiated with light to a predetermined width from the inside of the mold to form a hydrophilic part, the cylindrical film was formed. In addition to being able to be peeled off favorably, a uniform cylindrical film free of floating, convex deformation, wrinkles, etc. can be obtained. Since the part returns to its original hydrophobicity, the cylindrical mold can be reused. Further, the production of the cylindrical mold is simple and the production cost is low.
【００５７】(7) 請求項１１に記載された発明によれ
ば、透明な成形型の内面全域に疎水性のアナターゼ型酸
化チタンを含有する剥離層を形成し、そして、円筒成形
型の円筒膜塗布個所となる剥離層の中央部分に成形型外
より光照射をして親水性部とするので、成形型外より照
射することで装置条件が簡素単純になり、しかも、円筒
膜を形成する塗布液がカーボン等の照射光を吸収する材
質を含有するものでは、外部照射しても熱吸収の面で有
利である。(7) According to the eleventh aspect of the present invention, a release layer containing hydrophobic anatase-type titanium oxide is formed on the entire inner surface of the transparent mold, and the cylindrical film of the cylindrical mold is formed. Light is applied from outside the mold to the center of the release layer, which is the application point, to make it a hydrophilic part. Therefore, irradiation from outside the mold simplifies the equipment conditions, and furthermore, coats to form a cylindrical film. If the liquid contains a material that absorbs irradiation light, such as carbon, it is advantageous in terms of heat absorption even when irradiated externally.
【００５８】(8) 請求項１２に記載された発明によれ
ば、透明な成形型の内面全域に疎水性のアナターゼ型酸
化チタンを含有する剥離層を形成し、そして、透明な円
筒成形型の円筒膜塗布個所となる剥離層の中央部分の両
端の内側に成形型外より所定幅に光照射をして親水性部
とするので、成形型外より照射することで装置条件が簡
素単純になり、しかも、円筒膜を形成する塗布液がカー
ボン等の照射光を吸収する材質を含有するものでは、外
部照射しても熱吸収の面で有利である。(8) According to the twelfth aspect of the present invention, a release layer containing hydrophobic anatase-type titanium oxide is formed on the entire inner surface of the transparent mold, and the transparent cylindrical mold is formed. Light is applied to the inside of both ends of the central part of the release layer, which is the coating part of the cylindrical film, from the outside of the mold to a predetermined width from the outside of the mold to make it a hydrophilic part. In addition, when the coating liquid for forming the cylindrical film contains a material such as carbon that absorbs irradiation light, it is advantageous in terms of heat absorption even if it is irradiated externally.
【００５９】(9) 請求項１３，１４に記載された発明に
よれば、回転する円筒成形型の剥離層の中央部分にポリ
アミド酸溶液を塗布する工程、塗布したポリアミド酸円
筒膜を加熱乾燥する工程、及び、乾燥したポリアミド酸
円筒膜を加熱硬化させる工程、を順次有するので、円筒
膜を良好に剥離することができると共に、浮き、凸状変
形、シワ等のない均一な円筒膜を得ることができる。(9) According to the invention as set forth in claims 13 and 14, a step of applying a polyamic acid solution to a central portion of a peeling layer of a rotating cylindrical mold, and heating and drying the applied polyamic acid cylindrical film. Since the step and the step of heating and curing the dried polyamic acid cylindrical film are sequentially provided, the cylindrical film can be peeled off satisfactorily, and a uniform cylindrical film free of floating, convex deformation, wrinkles, etc. can be obtained. Can be.
【図１】本発明の一実施の形態を示す円筒成形型の縦断
面説明図であって、（ａ）は、その剥離層の中央部に親
水性部を形成する状態を示し、そして、（ｂ）は、その
剥離層上に円筒膜を形成する状態を示す。FIG. 1 is an explanatory longitudinal sectional view of a cylindrical mold showing one embodiment of the present invention, in which (a) shows a state in which a hydrophilic portion is formed at a central portion of a release layer, and b) shows a state in which a cylindrical film is formed on the release layer.
【図２】本発明の他の一実施の形態を示す円筒成形型の
縦断面説明図であって、（ａ）は、その剥離層の中央部
の両端に親水性部を形成する状態を示し、そして、
（ｂ）は、その剥離層上に円筒膜を形成する状態を示
す。FIG. 2 is an explanatory longitudinal sectional view of a cylindrical mold according to another embodiment of the present invention, in which (a) shows a state in which hydrophilic portions are formed at both ends of a central portion of the release layer. And
(B) shows a state in which a cylindrical film is formed on the release layer.
【図３】本発明の他の一実施の形態を示す透明な円筒成
形型の剥離層の中央部に親水性部を形成する状態を示す
縦断面説明図である。FIG. 3 is an explanatory longitudinal sectional view showing a state in which a hydrophilic portion is formed in the center of a release layer of a transparent cylindrical mold according to another embodiment of the present invention.
【図４】本発明の一実施の形態を示す円筒成形型の剥離
層上に円筒膜を形成する状態を示す部分拡大縦断面説明
図であって、（ａ）は、円筒膜を剥離層の疎溶剤性層を
越えて親溶剤性層まで塗布した状態を示し、そして、
（ｂ）は、塗布した円筒膜が疎溶剤性層と親溶剤性層と
の境界まで縮退した状態を示す。FIG. 4 is a partially enlarged vertical cross-sectional explanatory view showing a state in which a cylindrical film is formed on a release layer of a cylindrical mold according to an embodiment of the present invention. Shows the state of application to the solvent-philic layer beyond the solvent-phobic layer, and
(B) shows a state in which the applied cylindrical film has shrunk to the boundary between the lyophobic layer and the lyophilic layer.
【図５】従来の遠心塗布成形法による円筒膜の製造方法
の縦断面説明図であって、（ａ）は、その剥離層上に円
筒膜を形成する状態を示し、そして、（ｂ）は、円筒膜
が剥離した状態を示す。FIG. 5 is an explanatory longitudinal sectional view of a conventional method for producing a cylindrical film by a centrifugal coating method, in which (a) shows a state in which a cylindrical film is formed on the release layer, and (b) shows a state in which the cylindrical film is formed. And the state in which the cylindrical film was peeled off.
１ 円筒成形型 ２ 剥離層 ２ａ 親水性部 ２ｂ 疎水性部 ３ 円筒膜 Reference Signs List 1 cylindrical mold 2 release layer 2a hydrophilic portion 2b hydrophobic portion 3 cylindrical film
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｇ０３Ｇ 15/16 Ｇ０３Ｇ 15/16 // Ｂ２９Ｋ 77:00 Ｂ２９Ｋ 77:00 Ｂ２９Ｌ 23:00 Ｂ２９Ｌ 23:00 31:00 31:00 Ｆターム(参考） 2H032 BA08 BA09 BA23 4D075 AC65 BB14Y BB26Z BB46X CA03 CA18 DA15 DA19 DB04 DB06 DB07 DB13 DB14 DC18 DC21 EA07 EB39 EB47 4F202 AA29 AC05 AF14 AG08 AH04 AJ02 AJ03 AJ06 CA07 CB01 CD08 CD22 CD30 CK41 CL04 CN01 4F205 AA29 AC05 AG08 AG16 AH04 AJ02 AJ03 AJ06 GA02 GA05 GA07 GA17 GB01 GC04 GD02 GE03 GE07 GF24 GN01 GN13 GW06 GW15 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) G03G 15/16 G03G 15/16 // B29K 77:00 B29K 77:00 B29L 23:00 B29L 23:00 31 : 00 31:00 F term (reference) 2H032 BA08 BA09 BA23 4D075 AC65 BB14Y BB26Z BB46X CA03 CA18 DA15 DA19 DB04 DB06 DB07 DB13 DB14 DC18 DC21 EA07 EB39 EB47 4F202 AA29 AC05 AF14 AG08 AH04 AJ02 AJ03 CD04 CD04 4F205 AA29 AC05 AG08 AG16 AH04 AJ02 AJ03 AJ06 GA02 GA05 GA07 GA17 GB01 GC04 GD02 GE03 GE07 GF24 GN01 GN13 GW06 GW15
Claims (14)
する剥離層を円筒成形型の内面全域に有する円筒成形型
において、円筒膜塗布個所となる剥離層の中央部分に成
形型内より光照射をして親水性部としたことを特徴とす
る円筒成形型。In a cylindrical mold having a release layer containing hydrophobic anatase-type titanium oxide on the entire inner surface of the cylindrical mold, light is irradiated from the inside of the mold to a central portion of the release layer which is a coating portion of the cylindrical film. A cylindrical mold, characterized in that a hydrophilic portion is formed.
ウム合金よりなり、そして、その内周面が陽極処理処理
されていることを特徴とする請求項１に記載の円筒成形
型。2. The cylindrical mold according to claim 1, wherein the cylindrical mold is made of aluminum or an aluminum alloy, and an inner peripheral surface thereof is anodized.
て、その内周面がエッチングにより微細に粗されている
ことを特徴とする請求項１に記載の円筒成形型。3. The cylindrical mold according to claim 1, wherein the cylindrical mold is made of hard glass, and an inner peripheral surface thereof is finely roughened by etching.
酸化チタンで構成されていることを特徴とする請求項１
〜３のいずれかに記載の円筒成形型。4. The method according to claim 1, wherein the anatase type titanium oxide is composed of nano-dispersible titanium dioxide.
4. The cylindrical mold according to any one of claims 1 to 3.
とを特徴とする請求項１〜４のいずれかに記載の円筒成
形型。5. The cylindrical mold according to claim 1, wherein the release layer is made of a fluororesin.
する剥離層を円筒成形型の内面全域に有する円筒成形型
において、円筒膜塗布個所となる剥離層の中央部分の両
端の内側に成形型内より所定幅に光照射をして親水性部
としたことを特徴とする円筒成形型。6. A cylindrical mold having a release layer containing hydrophobic anatase-type titanium oxide on the entire inner surface of the cylindrical mold, wherein the inside of the mold is provided inside both ends of a central portion of the release layer which is to be coated with the cylindrical film. A cylindrical mold, wherein light is irradiated to a predetermined width to form a hydrophilic portion.
ウム合金よりなり、そして、その内周面が陽極処理処理
されていることを特徴とする請求項６に記載の円筒成形
型。7. The cylindrical mold according to claim 6, wherein the cylindrical mold is made of aluminum or an aluminum alloy, and an inner peripheral surface thereof is anodized.
て、その内周面がエッチングにより微細に粗されている
ことを特徴とする請求項６に記載の円筒成形型。8. The cylindrical mold according to claim 6, wherein the cylindrical mold is made of hard glass, and an inner peripheral surface thereof is finely roughened by etching.
酸化チタンで構成されていることを特徴とする請求項６
〜８のいずれかに記載の円筒成形型。9. The method according to claim 6, wherein the anatase type titanium oxide is composed of nano-dispersible titanium dioxide.
9. The cylindrical mold according to any one of items 1 to 8.
ことを特徴とする請求項６〜９のいずれかに記載の円筒
成形型。10. The cylindrical mold according to claim 6, wherein the release layer is made of a fluororesin.
ナターゼ型酸化チタンを含有する剥離層を形成し、そし
て、透明な円筒成形型の円筒膜塗布個所となる剥離層の
中央部分に成形型外より光照射をして親水性部とするこ
とを特徴とする円筒成形型の製造方法。11. A release layer containing hydrophobic anatase-type titanium oxide is formed on the entire inner surface of the transparent mold, and is formed on the center of the release layer which is to be applied to the cylindrical film of the transparent cylindrical mold. A method for producing a cylindrical mold, comprising irradiating light from outside the mold into a hydrophilic part.
ナターゼ型酸化チタンを含有する剥離層を形成し、そし
て、透明な円筒成形型の円筒膜塗布個所となる剥離層の
中央部分の両端の内側に成形型外より所定幅に光照射を
して親水性部とすることを特徴とする円筒成形型の製造
方法。12. A release layer containing hydrophobic anatase-type titanium oxide is formed on the entire inner surface of the transparent mold, and both ends of a central portion of the release layer which is to be applied to the cylindrical film of the transparent cylindrical mold. Forming a hydrophilic portion by irradiating light to a predetermined width from inside the mold outside the mold.
成形型を用いて円筒膜を製造する方法において、回転す
る円筒成形型の剥離層の中央部分にポリアミド酸溶液を
塗布する工程、塗布したポリアミド酸円筒膜を加熱乾燥
する工程、及び、乾燥したポリアミド酸円筒膜を加熱硬
化させる工程、を順次有することを特徴とする円筒膜の
製造方法。13. A method for producing a cylindrical film using the cylindrical mold according to any one of claims 1 to 5, wherein a polyamic acid solution is applied to a central portion of a release layer of the rotating cylindrical mold. A method for producing a cylindrical film, comprising: a step of heating and drying the applied polyamide acid cylindrical film; and a step of heating and curing the dried polyamic acid cylindrical film.
筒成形型を用いて円筒膜を製造する方法において、回転
する円筒成形型の剥離層の中央部分にポリアミド酸溶液
を塗布する工程、塗布したポリアミド酸円筒膜を加熱乾
燥する工程、及び、乾燥したポリアミド酸円筒膜を加熱
硬化させる工程、を順次有することを特徴とする円筒膜
の製造方法。14. A method for producing a cylindrical film using the cylindrical mold according to any one of claims 6 to 10, wherein a step of applying a polyamic acid solution to a central portion of a release layer of the rotating cylindrical mold. A method for producing a cylindrical film, comprising: a step of heating and drying the applied polyamide acid cylindrical film; and a step of heating and curing the dried polyamic acid cylindrical film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000270052A JP2002079535A (en) | 2000-06-28 | 2000-09-06 | Cylindrical molding mold, its production method, and method for producing cylindrical film |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000-194013 | 2000-06-28 | ||
| JP2000194013 | 2000-06-28 | ||
| JP2000270052A JP2002079535A (en) | 2000-06-28 | 2000-09-06 | Cylindrical molding mold, its production method, and method for producing cylindrical film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002079535A true JP2002079535A (en) | 2002-03-19 |
Family
ID=26594835
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000270052A Withdrawn JP2002079535A (en) | 2000-06-28 | 2000-09-06 | Cylindrical molding mold, its production method, and method for producing cylindrical film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2002079535A (en) |
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|---|---|---|---|---|
| JP2006116821A (en) * | 2004-10-21 | 2006-05-11 | Ricoh Co Ltd | Cylindrical curing mold, method for producing cylindrical cured film using the mold, intermediate transfer unit, and image forming device |
| WO2009107294A1 (en) * | 2008-02-27 | 2009-09-03 | シャープ株式会社 | Roller type nano-imprint device, mold roll for the roller type nano-imprint device, fixed roll for the roller type nano-imprint device, and nano-imprint sheet manufacturing method |
| USRE43694E1 (en) | 2000-04-28 | 2012-10-02 | Sharp Kabushiki Kaisha | Stamping tool, casting mold and methods for structuring a surface of a work piece |
| CN103213252A (en) * | 2013-04-19 | 2013-07-24 | 中山市合曜高分子材料有限公司 | Manufacturing method of rubber roller |
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-
2000
- 2000-09-06 JP JP2000270052A patent/JP2002079535A/en not_active Withdrawn
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USRE43694E1 (en) | 2000-04-28 | 2012-10-02 | Sharp Kabushiki Kaisha | Stamping tool, casting mold and methods for structuring a surface of a work piece |
| USRE44830E1 (en) | 2000-04-28 | 2014-04-08 | Sharp Kabushiki Kaisha | Stamping tool, casting mold and methods for structuring a surface of a work piece |
| USRE46606E1 (en) | 2000-04-28 | 2017-11-14 | Sharp Kabushiki Kaisha | Stamping tool, casting mold and methods for structuring a surface of a work piece |
| JP2006116821A (en) * | 2004-10-21 | 2006-05-11 | Ricoh Co Ltd | Cylindrical curing mold, method for producing cylindrical cured film using the mold, intermediate transfer unit, and image forming device |
| WO2009107294A1 (en) * | 2008-02-27 | 2009-09-03 | シャープ株式会社 | Roller type nano-imprint device, mold roll for the roller type nano-imprint device, fixed roll for the roller type nano-imprint device, and nano-imprint sheet manufacturing method |
| JP4521479B1 (en) * | 2008-02-27 | 2010-08-11 | シャープ株式会社 | Roller type nanoimprinting device |
| JP2010188731A (en) * | 2008-02-27 | 2010-09-02 | Sharp Corp | Roller type nano-imprinting device |
| US7938640B2 (en) | 2008-02-27 | 2011-05-10 | Sharp Kabushiki Kaisha | Roller nanoimprint apparatus, mold roller for use in roller nanoimprint apparatus, fixing roller for use in roller nanoimprint apparatus, and production method of nanoimprint sheet |
| JP4875203B2 (en) * | 2008-02-27 | 2012-02-15 | シャープ株式会社 | Roller type nanoimprint apparatus and method for producing nanoimprint sheet |
| US8673193B2 (en) | 2008-02-27 | 2014-03-18 | Sharp Kabushiki Kaisha | Roller nanoimprint apparatus, mold roller for use in roller nanoimprint apparatus, fixing roller for use in roller nanoimprint apparatus, and production method of nanoimprint sheet |
| JP2014074139A (en) * | 2012-10-05 | 2014-04-24 | Dexerials Corp | Circuit connection material, method of producing the same and method of producing package using the same |
| CN103213252A (en) * | 2013-04-19 | 2013-07-24 | 中山市合曜高分子材料有限公司 | Manufacturing method of rubber roller |
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| Date | Code | Title | Description |
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| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20071106 |