JP2017222073A - Silicone oil penetration film and manufacturing method therefor - Google Patents
Silicone oil penetration film and manufacturing method therefor Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 230000035515 penetration Effects 0.000 title abstract 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 171
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 171
- 239000013078 crystal Substances 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000001125 extrusion Methods 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000005096 rolling process Methods 0.000 claims abstract description 3
- 238000009998 heat setting Methods 0.000 claims description 38
- -1 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000011148 porous material Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 38
- 230000000052 comparative effect Effects 0.000 description 36
- 238000002844 melting Methods 0.000 description 18
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- 238000010438 heat treatment Methods 0.000 description 14
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- 229920001296 polysiloxane Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000992 sputter etching Methods 0.000 description 2
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
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- 238000000605 extraction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
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- 239000011490 mineral wool Substances 0.000 description 1
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- URXNVXOMQQCBHS-UHFFFAOYSA-N naphthalene;sodium Chemical compound [Na].C1=CC=CC2=CC=CC=C21 URXNVXOMQQCBHS-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
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- 239000000047 product Substances 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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Landscapes
- Fixing For Electrophotography (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
Description
本発明は、シリコーンオイル透過フィルムとその製法に関し、特に電子複写機やレーザープリンターに内蔵される電子写真装置におけるトナー像を定着させるための電子写真定着器具に使用されるシリコーンオイル塗布部材に適したシリコーンオイル透過フィルムとその製法に関する。 The present invention relates to a silicone oil permeable film and a method for producing the same, and is particularly suitable for a silicone oil coating member used in an electrophotographic fixing device for fixing a toner image in an electrophotographic apparatus incorporated in an electrophotographic copying machine or a laser printer. The present invention relates to a silicone oil permeable film and its manufacturing method.
複写機やプリンター等の電子写真装置において、その定着器具におけるオフセット現象を防止するために、トナー像転写後の紙等の記録媒体に定着させる定着器具における加熱ローラや加圧ローラに、シリコーンオイル等の離型性オイルを塗布することが一般的である。 In an electrophotographic apparatus such as a copying machine or a printer, in order to prevent an offset phenomenon in the fixing device, silicone oil or the like is used for a heating roller or a pressure roller in a fixing device fixed on a recording medium such as paper after toner image transfer. It is common to apply a releasable oil.
そして、電子写真定着器具用オイル塗布部材として、ポリテトラフルオロエチレン（以下、単に「ＰＴＦＥ」という。）が有する耐熱性、耐油性及びトナー付着防止等の利点から、下記特許文献１及び２に示されるようにＰＴＦＥからなる透過フィルムが使用されている。 Patent Documents 1 and 2 below show the heat resistance, oil resistance, toner adhesion prevention, and the like of polytetrafluoroethylene (hereinafter simply referred to as “PTFE”) as an oil application member for an electrophotographic fixing device. Thus, a transparent film made of PTFE is used.
下記特許文献１には、多孔質ＰＴＦＥの表面層を有するオイル塗布ロールの欠点であるオイル塗布量のムラ及び使用中にトナーによる目詰まりを起こしてオイル塗布量が減少する問題を解消し、更に画像汚れを防ぐ性能も改良された電子写真定着用オイル塗布ロールが示されている。 Patent Document 1 listed below solves the problem of oil application amount unevenness, which is a defect of an oil application roll having a porous PTFE surface layer, and a problem that the oil application amount decreases due to clogging with toner during use. An electrophotographic fixing oil coating roll with improved performance to prevent image smearing is shown.
当該電子写真定着用オイル塗布ロールは、ロール基体上にオイル保持体を設けると共に、その表層に多孔質ＰＴＦＥ層を設けてなるオイル塗布ロールであって、該多孔質ＰＴＦＥ層は、最大孔径（コールターポロメータ（コールターエレクトレット社製）で測定）が０．１μｍ以下であり、空気の透過速度（ガーレー数）（Ｂ型ガーレー式デンソメータ（テスター産業社製）で測定）が５００秒／１００ｃｃ〜６０００秒／１００ｃｃの範囲内にあり、表面粗さ（表面粗さ形状測定器サーフコム４７０Ａ（東京精密社製）で測定）がＲａ０．５μｍ以下であり、厚さ（スクリューマイクロメータで測定）が０．０５ｍｍ以上のものである。 The electrophotographic fixing oil application roll is an oil application roll in which an oil holding body is provided on a roll base and a porous PTFE layer is provided on the surface layer. The porous PTFE layer has a maximum pore diameter (Coulter). Porometer (measured with Coulter Electret) is 0.1 μm or less, and air transmission rate (Gurley number) (measured with B-type Gurley Densometer (Tester Sangyo Co., Ltd.)) is 500 seconds / 100 cc to 6000 seconds. / 100cc, surface roughness (measured with a surface roughness profile measuring device Surfcom 470A (manufactured by Tokyo Seimitsu Co., Ltd.)) is Ra 0.5 μm or less, and thickness (measured with a screw micrometer) is 0.05 mm. That's all.
上記電子写真定着用オイル塗布ロールの製造方法としては、ロール基体上にオイル保持体を設けたのち、３０％以上の加熱収縮性を有する多孔質ＰＴＦＥからなる筒状フィルム、すなわち下記特許文献３に記載の、テトラフルオロエチレン（以下、単に「ＴＦＥ」という。）重合体粉末のペースト押出成形後、焼成されたＴＦＥ重合体管を、該ＴＦＥ重合体の溶融開始温度以下の温度に加熱しつつ、管内に圧力を作用させて管の径方向又は管の径方向と管の長手方向に膨張させた後、加圧した状態で冷却して製造される、熱収縮性を有し、孔径が非常に細かい多孔質ＴＦＥ重合体管（未焼結のＴＦＥ重合体管の場合は、膨張工程において亀裂が生じる。ＴＦＥ重合体とは、変性ＰＴＦＥを意味する。）、を装着したロール体を形成し、次いで該ロール体を加熱して該筒状フィルムを該ロール基体端部まで被覆するように密着させることにより製造され、前記多孔質ＰＴＦＥフィルムとして最大孔径（コールターポロメータ（コールターエレクトレット社製）で測定）が０．１μｍ以下であり、空孔率（比重測定により次式により算出。空孔率＝（ｄ１ −ｄ２ ）／ｄ１×１００（ｄ１：膨張前樹脂管の比重、ｄ２：膨張後樹脂管の比重））が２５〜５０％であり、空気の透過速度（Ｂ型ガーレー式デンソメータ（テスター産業社製）で測定）が５００／１００ｃｃ〜４０００秒／１００ｃｃであって、かつ表面粗さ（表面粗さ形状測定器サーフコム４７０Ａ（東京精密社製）で測定）がＲａ０．５μｍ以下である電子写真定着用オイル塗布ロールを作製することが示されている。 As a method for producing the electrophotographic fixing oil coating roll, a cylindrical film made of porous PTFE having a heat shrinkage of 30% or more after providing an oil holder on a roll base, that is, in Patent Document 3 below, After the paste extrusion molding of the tetrafluoroethylene (hereinafter simply referred to as “TFE”) polymer powder described above, the calcined TFE polymer tube is heated to a temperature below the melting start temperature of the TFE polymer, Manufactured by applying pressure in the tube to expand in the radial direction of the tube or in the radial direction of the tube and the longitudinal direction of the tube, and then cooled in a pressurized state. Forming a roll body equipped with a fine porous TFE polymer tube (in the case of an unsintered TFE polymer tube, cracking occurs in the expansion process. TFE polymer means modified PTFE), Then It is manufactured by heating the roll body and bringing the cylindrical film into close contact with the end of the roll substrate, and has a maximum pore size (measured by Coulter Porometer (manufactured by Coulter Electret)) as the porous PTFE film. 0.1 μm or less, porosity (calculated by the following equation based on specific gravity measurement. Porosity = (d1−d2) / d1 × 100 (d1: specific gravity of resin tube before expansion, d2: specific gravity of resin tube after expansion) )) Is 25 to 50%, the air permeation rate (measured with a B-type Gurley densometer (manufactured by Tester Sangyo)) is 500/100 cc to 4000 sec / 100 cc, and the surface roughness (surface roughness) It is shown that an oil application roll for electrophotographic fixing whose shape measuring device Surfcom 470A (manufactured by Tokyo Seimitsu Co., Ltd.) is Ra 0.5 μm or less is prepared.
下記特許文献２には、オイル塗布部材の外部からの紙粉やトナーかす等の汚染物の付着を抑制させ、またはオイル塗布量の調節が容易であるオイル塗布部材が示されている。 Patent Document 2 below discloses an oil application member that suppresses adhesion of contaminants such as paper dust and toner residue from the outside of the oil application member, or easily adjusts the oil application amount.
当該オイル塗布部材は、オイルゲル化剤を用いてシリコーンオイルをゲル化させたオイル固形化物の表面の一部又は全表面に形成された、厚さ３μｍ〜１ｍｍ、孔径０．０５μｍ〜１５μｍ、空孔率２０％〜９８％の多孔質ＰＴＦＥフィルムの一部をオイル塗布面としたもの、又は多孔質ＰＴＦＥフィルムの多孔空間内にゲル化したシリコーンオイルが充填された構造のものである。 The oil application member has a thickness of 3 μm to 1 mm, a hole diameter of 0.05 μm to 15 μm, a hole formed on a part or all of the surface of an oil solidified product obtained by gelling silicone oil using an oil gelling agent A part of the porous PTFE film having a rate of 20% to 98% is used as an oil-coated surface, or a structure in which gelled silicone oil is filled in the porous space of the porous PTFE film.
また、下記特許文献４及び５は、ＰＰＣ複写機におけるトナー像定着装置において、離型液等を適切に塗布操作することができる塗布機構や塗布部体に関するものであって、当該文献には、ＰＴＦＥ多孔質フィルムを使用することが記載されている。 Patent Documents 4 and 5 listed below relate to a coating mechanism and a coating unit that can appropriately apply a release liquid in a toner image fixing device in a PPC copying machine. The use of a PTFE porous film is described.
上記特許文献１に記載の電子写真定着用オイル塗布ロールにおける筒状フィルムは、熱収縮性であるため、定着時における定着ロールの熱により電子写真定着用オイル塗布ロールが加熱されて収縮するので、この収縮により筒状フィルムの内部を構成するオイル保持体には熱により変形する不織布やフェルト等が使用できず、オイル含有性能が低いロックウール紙や人工皮革材を使用せざるを得ず、材料が制限されるので、性能を十分に発揮し得るオイル塗布ロールを作製できない問題がある。 Since the cylindrical film in the electrophotographic fixing oil application roll described in Patent Document 1 is heat-shrinkable, the electrophotographic fixing oil application roll is heated and contracted by the heat of the fixing roll during fixing. Non-woven fabric, felt, etc. that are deformed by heat cannot be used for the oil holder that constitutes the inside of the cylindrical film due to this shrinkage, and it is necessary to use rock wool paper or artificial leather material with low oil-containing performance, Therefore, there is a problem that it is impossible to produce an oil coating roll that can sufficiently exhibit performance.
上記特許文献２に記載のオイル塗布部材は、オイル塗布面にゲル化したシリコーンオイルが露出するので、紙粉やトナーかす等の汚染物の付着を完全になくすことができない欠点がある。 The oil application member described in Patent Document 2 has a drawback that it cannot completely eliminate the adhesion of contaminants such as paper dust and toner residue because the gelled silicone oil is exposed on the oil application surface.
上記特許文献４及び５に記載のオイル塗布機構又はオイル塗布部体は、これらに使用されるＰＴＦＥはいずれも未焼成又は焼成されたものであり、半焼成のＰＴＦＥ多孔質フィルムを使用することについては開示も示唆もされていない。 Regarding the oil application mechanism or the oil application part described in Patent Documents 4 and 5, the PTFE used in these is either unfired or fired, and a semi-fired PTFE porous film is used. Is not disclosed or suggested.
また、ペースト押出により得られた未焼成のＰＴＦＥフィルムを延伸して多孔質フィルムを製造する方法として、結晶化度９５％以上のＰＴＦＥファインパウダーをその融点より低い温度でペースト押出し、押出助剤の抽出および乾燥などを行った後、ＰＴＦＥの結晶融点より低い温度で延伸を行って多孔質フィルムを得る方法がある（特公昭４８−４４６６４号公報および特公昭５１−１８９９１号公報参照）。しかし、この方法では、結晶化度が少なくとも９５％のＰＴＦＥファインパウダーを用いなければならず、延伸多孔質ＰＴＦＥフィルムをＰＴＦＥの融点以上に加熱して熱固定セットする工程が必要であり、得られる多孔質ＰＴＦＥフィルムの表面は粘着性があり、汚れやすい欠点がある。また、ＰＴＦＥ焼成フィルムを３２７℃より高い温度で加熱し、次いできわめてゆるやかに冷却して結晶化を高めた後、延伸する方法がある（特公昭５３−４２７９４号公報参照）。しかし、この方法では、ＰＴＦＥ焼成フィルムは一軸延伸しかできず、延伸倍率も４倍までと低く、また工程が長く、少なくとも２回の加熱工程を含むからエネルギーの消費が大きい欠点がある。さらに、ＰＴＦＥ未焼成フィルムを３２７℃より低くない温度で焼成し、ＰＴＦＥ焼成フィルムをペースト押出成形における押出方向（カレンダ方向）と直交する方向へ延伸する方法がある（特開昭５５−５５３７８号公報参照）（以下、本明細書においては、ペースト押出成形により押し出されたフィルムの押出方向（カレンダ方向）を単に「長尺方向」といい、ペースト押出成形により押し出されたフィルムの押出方向（カレンダ方向）と直交する幅方向を単に「幅方向」という。）。しかし、この方法では、ＰＴＦＥ焼成フィルムは２５０℃以下の温度において幅方向へ延伸倍率４．２以下でしか延伸できない欠点がある。 Further, as a method for producing a porous film by stretching an unfired PTFE film obtained by paste extrusion, PTFE fine powder having a crystallinity of 95% or more is paste extruded at a temperature lower than its melting point, There is a method in which a porous film is obtained by performing extraction and drying and then stretching at a temperature lower than the crystalline melting point of PTFE (see Japanese Patent Publication Nos. 48-44664 and 51-18991). However, in this method, PTFE fine powder having a crystallinity of at least 95% must be used, and a process of heating and setting the stretched porous PTFE film above the melting point of PTFE is necessary and obtained. The surface of the porous PTFE film is sticky and has a drawback of being easily soiled. Also, there is a method in which a PTFE fired film is heated at a temperature higher than 327 ° C., then cooled very slowly to enhance crystallization, and then stretched (see Japanese Examined Patent Publication No. 53-42794). However, in this method, the PTFE fired film can only be uniaxially stretched, the stretch ratio is as low as 4 times, the process is long, and at least two heating steps are involved, so that there is a disadvantage that energy consumption is large. Furthermore, there is a method in which an unsintered PTFE film is fired at a temperature not lower than 327 ° C., and the PTFE fired film is stretched in a direction orthogonal to the extrusion direction (calendar direction) in paste extrusion molding (Japanese Patent Laid-Open No. 55-55378). (Hereinafter, in this specification, the extrusion direction (calendar direction) of the film extruded by paste extrusion molding is simply referred to as “long direction”, and the extrusion direction of the film extruded by paste extrusion molding (calendar direction). The width direction orthogonal to) is simply referred to as “width direction”.) However, this method has a drawback that the PTFE fired film can be stretched only in the width direction at a stretch ratio of 4.2 or less at a temperature of 250 ° C. or less.
さらに、ＰＴＦＥ半焼性フィルムについては、その結晶転化率が低くなればなるほど、幅方向の引っ張り強度が低く、このＰＴＦＥ半焼性フィルムを幅方向に延伸すると不均一になることが知られている。また、結晶転化率が高くなればなるほどＰＴＦＥ半焼性フィルムを幅方向に延伸すると破断することが知られている（特公平３−５３１０３）。 Furthermore, it is known that the PTFE semi-firing film has a lower tensile strength in the width direction as the crystal conversion rate becomes lower, and becomes non-uniform when the PTFE semi-firing film is stretched in the width direction. Further, it is known that the higher the crystal conversion ratio, the more the PTFE semi-fireable film is broken when it is stretched in the width direction (Japanese Patent Publication No. 3-53103).
本発明者は、鋭意研究した結果、均一に延伸でき、孔径が非常に小さく、種々のシリコーンオイルに汎用でき、熱による収縮作用がなく、オイル含油部材との接着等による一体化が可能なシリコーンオイル透過フィルムを開発した。 As a result of diligent research, the present inventor has found that a silicone that can be uniformly stretched, has a very small pore diameter, can be widely used for various silicone oils, has no shrinking action due to heat, and can be integrated by adhesion to an oil-containing member. An oil permeable film was developed.
本発明の請求項１に係るシリコーンオイル透過フィルムの製法は、ＰＴＦＥファインパウダーを主とする原料からペースト押出成形及び圧延加工によりＰＴＦＥ未焼成フィルムを作製し、前記ＰＴＦＥ未焼成フィルムから結晶転化率が５０％〜８０％のＰＴＦＥ半焼成フィルムを作製し、前記ＰＴＦＥ半焼成フィルムを、所定の延伸処理温度で前記ペースト押出成形における幅方向のみに３倍以上１０倍以下に延伸してＰＴＦＥ半焼成延伸フィルムを作製し、当該ＰＴＦＥ半焼成延伸フィルムを２５０℃〜３２０℃の熱固定処理温度で熱固定して製造することを特徴とする。 The method for producing a silicone oil permeable film according to claim 1 of the present invention is to produce a PTFE green film from a raw material mainly made of PTFE fine powder by paste extrusion molding and rolling, and the crystal conversion rate from the PTFE green film is A PTFE semi-fired film of 50% to 80% is produced, and the PTFE semi-fired film is stretched 3 times to 10 times only in the width direction in the paste extrusion molding at a predetermined stretching temperature to be PTFE semi-fired stretched A film is produced, and the PTFE semi-baked stretched film is manufactured by heat setting at a heat setting temperature of 250 ° C. to 320 ° C.
上記の製法により得られたシリコーンオイル透過フィルムは、ガーレメーターでの空気の透過速度が５００秒／１００ｃｃ〜３０００秒／１００ｃｃであり、本発明が求める好適な特性を有するシリコーン透過フィルムが得られる。 The silicone oil permeable film obtained by the above production method has a permeation speed of air in a galemeter of 500 seconds / 100 cc to 3000 seconds / 100 cc, and a silicone permeable film having suitable characteristics required by the present invention can be obtained.
結晶転化率が５０％未満のＰＴＦＥ半焼性フィルムは、幅方向の引っ張り強度が低くなる傾向があり、かつ、幅方向への延伸において確実な均一さが期待できなくなる。結晶転化率が８０％を越えるＰＴＦＥ半焼性フィルムは、幅方向への延伸において破断する可能性が高くなる。そのため、本発明におけるＰＴＦＥ半焼性フィルムは、幅方向へ確実にかつ均一に延伸ができるように、その結晶転化率を５０％〜８０％に限定した。 A PTFE semi-fireable film having a crystal conversion rate of less than 50% tends to have a low tensile strength in the width direction, and reliable uniformity cannot be expected in stretching in the width direction. A PTFE semi-sinterable film having a crystal conversion rate exceeding 80% has a high possibility of breaking in stretching in the width direction. Therefore, the crystal conversion rate of the PTFE semi-fireable film in the present invention is limited to 50% to 80% so that the film can be reliably and uniformly stretched in the width direction.
ＰＴＦＥ半焼成フィルムを延伸する際の延伸処理温度は２５℃〜３００℃が好適である。 The stretching temperature for stretching the PTFE semi-baked film is preferably 25 ° C to 300 ° C.
なお、ＰＴＦＥ半焼成フィルムを長尺方向に延伸すると、得られたシリコーンオイル透過フィルムは、本発明が求める、ガーレメーターでの空気の透過速度の下限値５００秒／１００ｃｃ未満となるため、適切ではない。 When the PTFE semi-baked film is stretched in the longitudinal direction, the obtained silicone oil permeable film is less than 500 seconds / 100 cc of the lower limit of the air permeation rate in the galemeter required by the present invention. Absent.
ＰＴＦＥ半焼成フィルムを幅方向に３倍未満の倍率で延伸した場合には、得られたシリコーンオイル透過フィルムは、本発明が求める、ガーレメーターでの空気の透過速度の上限値３０００秒／１００ｃｃを超えるため、適切でない。 When the PTFE semi-baked film is stretched in the width direction at a magnification of less than 3 times, the obtained silicone oil permeable film has an upper limit value of 3000 seconds / 100 cc of the air permeation speed required by the present invention. Because it exceeds, it is not appropriate.
ＰＴＦＥ半焼成フィルムを幅方向に１０倍を超える倍率で延伸した場合には、得られたシリコーンオイル透過フィルムは、本発明が求める、ガーレメーターでの空気の透過速度の下限値５００秒／１００ｃｃ未満となるため、適切ではない。 When a PTFE semi-fired film is stretched in the width direction at a magnification exceeding 10 times, the obtained silicone oil permeable film is less than the lower limit value of 500 seconds / 100 cc of the air permeation rate required by the present invention. Therefore, it is not appropriate.
熱固定処理温度が２５０℃未満又は３２０℃を超える場合は、得られたシリコーンオイル透過フィルムは、本発明が求める、ガーレメーターでの空気の透過速度の下限値５００秒／１００ｃｃ未満となるため、適切ではない。 When the heat setting treatment temperature is less than 250 ° C. or more than 320 ° C., the obtained silicone oil permeable film has a lower limit value of less than 500 seconds / 100 cc of the air permeation rate in the galemeter required by the present invention. Not appropriate.
本発明の請求項２に係るシリコーンオイル透過フィルムの製法は、請求項１又は２の構成に加え、延伸前のＰＴＦＥ半焼成フィルムにおいて、その片面のみを脱フッ素処理することを特徴とする。 In addition to the structure of Claim 1 or 2, the manufacturing method of the silicone oil permeable film which concerns on Claim 2 of this invention is characterized by defluorinating only the single side | surface in the PTFE semi-baked film before extending | stretching.
ＰＴＦＥは非接着性に優れた特性を有するが、接着加工を行うにはその特性がマイナス要素であり、これを解消するために、ＰＴＦＥに接着性を持たせる脱フッ素処理を行う。脱フッ素処理には、金属ナトリウム−ナフタレン錯体溶液（テトラエッチ（登録商標）（株式会社潤工社製））による処理やスパッターエッチングによる処理が例示される。また、熱固定処理後においてはコロナ放電照射による表面改質処理を行うことにより接着性を向上させることもできる。 PTFE has excellent non-adhesive properties, but the properties are a negative factor for performing the bonding process, and in order to eliminate this, a defluorination treatment for imparting adhesive properties to PTFE is performed. Examples of the defluorination treatment include a treatment with a metal sodium-naphthalene complex solution (Tetraetch (registered trademark) (manufactured by Junko Co., Ltd.)) and a treatment by sputter etching. In addition, after the heat setting treatment, adhesion can be improved by performing a surface modification treatment by corona discharge irradiation.
本発明の請求項３に係るシリコーンオイル透過フィルムは、結晶転化率が５０％〜８０％のＰＴＦＥ半焼成フィルムからなり、ガーレメーターでの空気の透過速度が５００秒／１００ｃｃ〜３０００秒／１００ｃｃであり、厚みが２５μｍ〜３００μｍであることを特徴とする。 The silicone oil permeable film according to claim 3 of the present invention is made of a PTFE semi-baked film having a crystal conversion rate of 50% to 80%, and an air permeation speed in a galemeter is 500 seconds / 100 cc to 3000 seconds / 100 cc. And having a thickness of 25 μm to 300 μm.
ガーレメーターでの空気の透過速度が５００秒／１００ｃｃ〜３０００秒／１００ｃｃであると種々のシリコーンオイルに対応できて汎用性がある。厚みが２５μｍ未満であると強度不足となり、厚みが３００μｍを越えると厚くなりすぎてフィット性に欠ける。 When the air permeation speed in the galemeter is 500 seconds / 100 cc to 3000 seconds / 100 cc, it can be used for various silicone oils and is versatile. When the thickness is less than 25 μm, the strength is insufficient, and when the thickness exceeds 300 μm, the thickness becomes too thick and lacks fit.
本発明に係るシリコーンオイル透過フィルムの製法によれば、確実に均一な延伸が可能であり、ガーレメーターでの空気の透過速度が５００秒／１００ｃｃ〜３０００秒／１００ｃｃであって種々のシリコーンオイルに汎用可能であり、定着器において発生する熱による収縮作用がなく、オイル塗布部材に対するフィット性があり、オイル含油部材との接着等による一体化が可能なシリコーンオイル透過フィルムを提供することができる。 According to the method for producing a silicone oil permeable film according to the present invention, uniform stretching is possible, and the air permeation speed in a gallometer is 500 seconds / 100 cc to 3000 seconds / 100 cc. It is possible to provide a silicone oil permeable film that can be used in general, has no shrinkage effect due to heat generated in the fixing device, has a fitting property to an oil application member, and can be integrated by adhesion with an oil-containing member.
本発明におけるシリコーンオイル透過フィルムは、ＰＴＦＥ未焼成フィルムをＰＴＦＥ焼成フィルムの融点以上の温度で加熱することにより製造され、示差走査熱量計による結晶融解曲線上で３４５±５℃の温度に吸熱ピークを持ち、ＰＴＦＥ未焼成フィルム、ＰＴＦＥ半焼成フィルムおよびＰＴＦＥ焼成フィルムの融解熱量により定義される下記の結晶転化率の中で、結晶転化率が５０％〜８０％であるＰＴＦＥ半焼成フィルムを使用する。 The silicone oil permeable film in the present invention is produced by heating an unsintered PTFE film at a temperature equal to or higher than the melting point of the PTFE fired film, and has an endothermic peak at a temperature of 345 ± 5 ° C. on a crystal melting curve by a differential scanning calorimeter. Among the following crystal conversion ratios defined by the heat of fusion of the PTFE green film, PTFE semi-baked film and PTFE fired film, a PTFE semi-baked film having a crystal conversion ratio of 50% to 80% is used.
なお、本発明において、未焼成、半焼成および焼成の状態とはそれぞれつぎの状態をいう。未焼成状態とは、吸熱カーブにおいて最大ピークが焼成前と同じ位置にあってかつ結晶転化率が２０％未満の状態であり、半焼成状態とは、吸熱カーブにおいて最大ピークが焼成前と同じ位置にあってかつ結晶転化率が２０％以上で９０％未満の状態であり、焼成状態とは、吸熱カーブにおいて最大ピークが焼成前から低温側にシフトしかつ結晶転化率が９０％以上の状態である。 In the present invention, the unfired, semi-fired and fired states refer to the following states. The unfired state is a state where the maximum peak in the endothermic curve is at the same position as before firing and the crystal conversion is less than 20%, and the semi-fired state is the position where the maximum peak in the endothermic curve is the same as before firing. And the crystal conversion rate is 20% or more and less than 90%, and the fired state is a state in which the maximum peak in the endothermic curve is shifted to the low temperature side from before firing and the crystal conversion rate is 90% or more. is there.
ここで「ＰＴＦＥ」とは、ＴＦＥのホモポリマーだけでなく、ＴＦＥと２重量％を越えない共重合可能な他のモノマーとの共重合体をも包含する。 Here, “PTFE” includes not only a homopolymer of TFE but also a copolymer of TFE and another copolymerizable monomer not exceeding 2 wt%.
［ＰＴＦＥ半焼成フィルムの製法］
本発明のＰＴＦＥ半焼成フィルムは、ペースト押出または圧縮成形により得られるＰＴＦＥ未焼成フィルムを、ＰＴＦＥ焼成フィルムの融点以上、好ましくはＰＴＦＥ焼成フィルムの融点とＰＴＦＥ未焼成フィルムの融点との間の温度において、加熱することにより製造できる。具体的には、ＰＴＦＥ未焼成フィルムを焼成炉又はソルトバス中で適当な温度に十分な時間加熱した後、炉又はバスから取り出し、冷却してＰＴＦＥ半焼成フィルムを得る。また、本発明の半焼成フィルムは、ＰＴＦＥ未焼成フィルムを、ＰＴＦＥ未焼成フィルムの融点より高い温度において非常に短時間、たとえば、３６０℃で２０秒以下加熱することによっても製造できる。しかし、ＰＴＦＥ未焼成フィルムをＰＴＦＥ焼成フィルムの融点より低い温度でいくら長く加熱してもＰＴＦＥ半焼成フィルムは得られない。
[Production method of PTFE semi-baked film]
The PTFE semi-baked film of the present invention is a PTFE green film obtained by paste extrusion or compression molding at a temperature equal to or higher than the melting point of the PTFE fired film, preferably between the melting point of the PTFE fired film and the melting point of the PTFE green film. It can be manufactured by heating. Specifically, the PTFE green film is heated to an appropriate temperature for a sufficient time in a baking furnace or a salt bath, and then taken out from the furnace or bath and cooled to obtain a PTFE semi-baked film. The semi-fired film of the present invention can also be produced by heating a PTFE green film at a temperature higher than the melting point of the PTFE green film for a very short time, for example, at 360 ° C. for 20 seconds or less. However, no matter how long the PTFE unfired film is heated at a temperature lower than the melting point of the PTFE fired film, a PTFE semi-fired film cannot be obtained.
本発明のＰＴＦＥ半焼成フィルムの結晶転化率は、次の様にして決定される。 The crystal conversion rate of the PTFE semi-baked film of the present invention is determined as follows.
ＰＴＦＥ未焼成フィルムから１０．０±０．１ｍｇ秤量して切取って試料とし、当該試料を用いて、示差走査熱量計（Ｐｅｒｋｉｎ−Ｅｌｍｅｒ社製ＤＳＣ−２型）により、試料を１６０℃／分の加熱速度で室温から２７７℃に加熱し、次いで１０℃／分の加熱速度で２７７℃から３６０℃まで加熱して、結晶融解曲線を記録する。この工程において現われる吸熱カーブのピークの位置をＰＴＦＥ未焼成フィルムの融点と定義する。 10.0 ± 0.1 mg is weighed out from the PTFE unfired film and cut into a sample. Using the sample, the sample is measured at 160 ° C./min by a differential scanning calorimeter (DSC-2 manufactured by Perkin-Elmer). Heat from room temperature to 277 ° C. at a heating rate of 10 ° C./min, then heat from 277 ° C. to 360 ° C. at a heating rate of 10 ° C./min and record the crystal melting curve. The position of the endothermic curve peak appearing in this step is defined as the melting point of the PTFE green film.
前記のように試料を３６０℃まで加熱した直後に、８０℃／分の冷却速度で２７７℃に冷却し、当該試料を再び１０℃／分の加熱速度で３６０℃に加熱して、結晶融解曲線を記録する。この工程において現われる吸熱カーブのピークの位置をＰＴＦＥ焼成フィルムの融点と定義する。 Immediately after heating the sample to 360 ° C. as described above, the sample was cooled to 277 ° C. at a cooling rate of 80 ° C./min, and the sample was again heated to 360 ° C. at a heating rate of 10 ° C./min. Record. The position of the endothermic curve peak appearing in this step is defined as the melting point of the PTFE fired film.
次にＰＴＦＥ半焼成フィルムから１０．０±０．１ｍｇ秤量して切取って試料とし、当該試料を用いて、前記示差走査熱量計により、試料を１６０℃／分の加熱速度で室温から２７７℃に加熱し、次いで１０℃／分の加熱速度で２７７℃から３６０℃まで加熱して、結晶融解曲線を記録する。この工程において現われる吸熱カーブのピークの位置をＰＴＦＥ半焼成フィルムの融点と定義する。 Next, 10.0 ± 0.1 mg was weighed and cut from the PTFE semi-baked film to prepare a sample, and the sample was used from the room temperature to 277 ° C. at a heating rate of 160 ° C./min using the differential scanning calorimeter. And then from 277 ° C. to 360 ° C. at a heating rate of 10 ° C./min and record the crystal melting curve. The position of the endothermic curve peak appearing in this step is defined as the melting point of the PTFE semi-baked film.
ＰＴＦＥ未焼成フィルムの融解熱ΔＨ１は、その吸熱カーブとベースラインとの間の面積Ｓ１に比例し、ＰＴＦＥ焼成フィルムの融解熱ΔＨ２は、その吸熱カーブとベースラインとの間の面積Ｓ２に比例し、ＰＴＦＥ半焼製フィルムの融解熱ΔＨ３は、その吸熱カーブとベースラインとの間の面積Ｓ３に比例する。ベースラインは、示差走査熱量計の結晶融解曲線上の３０７℃の点から吸熱カーブの右端の基部に接するように引いた直線である。 The heat of fusion ΔH1 of the PTFE unfired film is proportional to the area S1 between the endothermic curve and the baseline, and the heat of fusion ΔH2 of the PTFE fired film is proportional to the area S2 between the endothermic curve and the baseline. The heat of fusion ΔH3 of the PTFE semi-baked film is proportional to the area S3 between the endothermic curve and the baseline. The base line is a straight line drawn from the point of 307 ° C. on the crystal melting curve of the differential scanning calorimeter so as to be in contact with the base at the right end of the endothermic curve.
そこで、結晶転化率は次の式によって計算される。
結晶転化率（％）＝（Ｓ１−Ｓ３）／（Ｓ１−Ｓ２）×１００
＝（ΔＨ１−ΔＨ３）／（ΔＨ１−ΔＨ２）×１００
本発明のＰＴＦＥ半焼成フィルムは、結晶転化率が５０％〜８０％のものを使用する。
Therefore, the crystal conversion rate is calculated by the following formula.
Crystal conversion rate (%) = (S1-S3) / (S1-S2) × 100
= (ΔH1-ΔH3) / (ΔH1-ΔH2) × 100
The PTFE semi-baked film of the present invention has a crystal conversion rate of 50% to 80%.
［ＰＴＦＥ半焼成体の延伸］
本発明のＰＴＦＥ半焼成フィルムの表面は延伸前は無孔であるが、延伸すると多孔性になる。本発明のＰＴＦＥ半焼成延伸フィルムは、ＰＴＦＥ半焼成フィルムを所定の延伸処理温度で幅方向のみに３倍以上１０倍以下に延伸したものである。一般に、延伸倍率は、用途によって変るが通常約１０倍まである。ＰＴＦＥ半焼成フィルムの延伸において、寸法的な変化は、ＰＴＦＥ未焼成フィルムの変化よりも大きい。例えば、２５μより薄いフィルムを製造する場合、未焼成フィルムを延伸する場合には大きな寸法変化が生じないので、非常に薄いＰＴＦＥ未焼成フィルムを延伸する必要がある。しかも、カレンダ成形された非常に薄いＰＴＦＥ未焼成フィルムはわかめ状になり、粒子の配向は均一ではないので、フィルムの強度も不均一になる。従って、薄い多孔質ＰＴＦＥフィルムを工業的に製造することは非常に困難である。また市販されている多孔質ＰＴＦＥフィルムは５０μより大きい厚さを有している。これに対し、ＰＴＦＥ半焼成フィルムから得られる多孔質ＰＴＦＥフィルムは、厚い多孔質ＰＴＦＥフィルムだけでなく、薄い多孔質ＰＴＦＥフィルムも容易に製造でき、カレンダ方向に対し垂直および平行な方向にすぐれた強度を有しており、単層フィルムとして用いることができる。
[Stretching of PTFE semi-fired body]
The surface of the PTFE semi-fired film of the present invention is non-porous before stretching, but becomes porous when stretched. The PTFE semi-fired stretched film of the present invention is obtained by stretching a PTFE semi-fired film at a predetermined stretching temperature only in the width direction by 3 to 10 times. In general, the draw ratio varies depending on the application but is usually up to about 10 times. In the stretching of the PTFE semi-fired film, the dimensional change is larger than that of the PTFE green film. For example, in the case of producing a film thinner than 25 μm, when a non-fired film is stretched, a large dimensional change does not occur. Therefore, it is necessary to stretch a very thin PTFE green film. Moreover, the calendered very thin PTFE unfired film has a wrinkle shape, and the orientation of the particles is not uniform, so that the strength of the film is not uniform. Therefore, it is very difficult to industrially manufacture a thin porous PTFE film. A commercially available porous PTFE film has a thickness of more than 50 μm. In contrast, a porous PTFE film obtained from a PTFE semi-fired film can easily produce not only a thick porous PTFE film but also a thin porous PTFE film, and has excellent strength in a direction perpendicular to and parallel to the calendar direction. It can be used as a single layer film.
本発明のＰＴＦＥ延伸半焼成フィルムは、所定の延伸処理温度、例えば２５℃〜３００℃、で幅方向のみに３倍以上１０倍以下に延伸して作製する。 The PTFE stretched and semi-baked film of the present invention is produced by stretching 3 times or more and 10 times or less only in the width direction at a predetermined stretching temperature, for example, 25 ° C to 300 ° C.
［ＰＴＦＥ延伸半焼成フィルムの熱固定］
本発明のシリコーンオイル透過フィルムは、ＰＴＦＥ延伸半焼成フィルムをＰＴＦＥの結晶転移が発生する温度（通常、３２６℃付近）以下の熱固定処理温度、好ましくは電子写真装置における定着器具付近での温度が２００℃を越える場合があることを考慮して２５０℃〜３２０℃で熱固定処理して作製する。
[Thermal fixation of PTFE stretched and semi-baked film]
The silicone oil permeable film of the present invention has a heat setting treatment temperature of the PTFE stretched and semi-baked film below the temperature at which PTFE crystal transition occurs (usually around 326 ° C.), preferably the temperature near the fixing device in the electrophotographic apparatus. Considering that it may exceed 200 ° C., it is prepared by heat setting at 250 ° C. to 320 ° C.
［ＰＴＦＥ半焼成フィルムの接着性向上］
本発明のＰＴＦＥ半焼成フィルムの表面における接着性を改良するため、例えば、ナトリウムの液体アンモニウム溶液またはナトリウムとナフタレン錯化合物の環状エーテル溶液により表面を処理するか、またはスパッターエッチングにより処理することによりエッチングしてもよい。また、熱固定処理後にコロナ放電により接着性を向上させる方法がある。
[Adhesion improvement of PTFE semi-baked film]
In order to improve the adhesion on the surface of the PTFE semi-baked film of the present invention, for example, the surface is treated with a liquid ammonium solution of sodium or a cyclic ether solution of sodium and naphthalene complex compound, or etched by sputter etching. May be. There is also a method for improving the adhesion by corona discharge after the heat setting treatment.
ＰＴＦＥファインパウダー（ダイキン工業製Ｆ１０４）で作製されたＰＴＦＥ圧延フィルム（幅２００ｍｍ、厚み１００μｍ）を３４０℃のソルトバス中で３０秒間の加熱処理を行い結晶転化率６０％のＰＴＦＥ半焼成フィルムを作製した。 A PTFE rolled film (width 200 mm, thickness 100 μm) made of PTFE fine powder (Daikin Industries F104) is heat-treated in a salt bath at 340 ° C. for 30 seconds to produce a PTFE semi-baked film having a crystal conversion rate of 60%. did.
このＰＴＦＥ半焼成フィルムを用いて下記実施例１〜６、比較例１〜１０に示す延伸と熱固定処理とを行って多孔質ＰＴＦＥ半焼成延伸フィルムを作製した。この多孔質ＰＴＦＥ半焼成延伸フィルムについて、１００ｃｃの空気の通過速度を測定し、空孔率を算出し、厚みを測定し及び加熱収縮率を算出した。 Using this PTFE semi-baked film, the stretching and heat setting treatment shown in Examples 1 to 6 and Comparative Examples 1 to 10 below were performed to prepare a porous PTFE semi-baked stretched film. With respect to this porous PTFE semi-fired stretched film, the passage speed of 100 cc of air was measured, the porosity was calculated, the thickness was measured, and the heat shrinkage rate was calculated.
１００ｃｃの空気の通過速度は、Ｂ型ガーレー式デンソメータ（テスター産業株式会社製）で測定した。空孔率は、多孔質ＰＴＦＥ半焼成延伸フィルムを５ｃｍ角に裁断し、その重量を天秤で測定し、体積を計算して比重を割り出し、ＰＴＦＥの比重２．２ｇ／ｃｃを１として算出した。厚みは、シックネスゲージ（ＴＥＣＬＯＣＫ（登録商標）ＳＭ−１１２（株式会社テクロック製））で測定した。熱収縮率は、２５０℃で１０分間加熱したときの面積を測定し、面積減少率を算出した。 The passage speed of 100 cc of air was measured with a B-type Gurley type densometer (manufactured by Tester Sangyo Co., Ltd.). The porosity was calculated by cutting a porous PTFE semi-fired stretched film into 5 cm square, measuring the weight with a balance, calculating the volume and calculating the specific gravity, and taking PTFE specific gravity of 2.2 g / cc as 1. The thickness was measured with a thickness gauge (TECLOCK (registered trademark) SM-112 (manufactured by Teclock Co., Ltd.)). For the heat shrinkage, the area when heated at 250 ° C. for 10 minutes was measured, and the area reduction rate was calculated.
実施例により作製したＰＴＦＥ半焼成フィルムを、長尺方向には延伸せず、幅方向に４倍延伸し、熱固定処理温度３２０℃で１０分間の熱固定を行った結果、空気の透過速度１１００秒／１００ｃｃ、空孔率４０％、厚み８５μｍ、熱収縮率０％の多孔質ＰＴＦＥ半焼成延伸フィルムが得られた。 The PTFE semi-fired film produced according to the example was stretched 4 times in the width direction without stretching in the longitudinal direction, and subjected to heat setting at a heat setting temperature of 320 ° C. for 10 minutes. A porous PTFE semi-fired stretched film having a second / 100 cc, a porosity of 40%, a thickness of 85 μm, and a heat shrinkage rate of 0% was obtained.
実施例により作製したＰＴＦＥ半焼成フィルムを、長尺方向には延伸せず、幅方向に５倍延伸し、熱固定処理温度３２０℃で１０分間の熱固定を行った結果、空気の透過速度７００秒／１００ｃｃ、空孔率４８％、厚み８０μｍ、熱収縮率０％の多孔質ＰＴＦＥ半焼成延伸フィルムが得られた。 The PTFE semi-fired film produced according to the example was stretched 5 times in the width direction without stretching in the longitudinal direction, and subjected to heat setting at a heat setting temperature of 320 ° C. for 10 minutes. A porous PTFE semi-fired stretched film having a second / 100 cc, a porosity of 48%, a thickness of 80 μm, and a heat shrinkage rate of 0% was obtained.
実施例により作製したＰＴＦＥ半焼成フィルムを、長尺方向には延伸せず、幅方向に３倍延伸し、熱固定処理温度３２０℃で１０分間の熱固定を行った結果、空気の透過速度２２００秒／１００ｃｃ、空孔率３０％、厚み９０μｍ、熱収縮率０％の多孔質ＰＴＦＥ半焼成延伸フィルムが得られた。 The PTFE semi-fired film produced according to the example was stretched 3 times in the width direction without stretching in the longitudinal direction, and subjected to heat setting at a heat setting treatment temperature of 320 ° C. for 10 minutes. A porous PTFE semi-fired stretched film having a second / 100 cc, a porosity of 30%, a thickness of 90 μm, and a heat shrinkage rate of 0% was obtained.
実施例により作製したＰＴＦＥ半焼成フィルムを、長尺方向には延伸せず、幅方向に１０倍延伸し、熱固定処理温度３２０℃で１０分間の熱固定を行った結果、空気の透過速度５００秒／１００ｃｃ、空孔率５５％、厚み７０μｍ、熱収縮率０％の多孔質ＰＴＦＥ半焼成延伸フィルムが得られた。 The PTFE semi-fired film produced according to the example was stretched 10 times in the width direction without being stretched in the longitudinal direction, and was subjected to heat setting at a heat setting temperature of 320 ° C. for 10 minutes. A porous PTFE semi-fired stretched film having a second / 100 cc, a porosity of 55%, a thickness of 70 μm, and a heat shrinkage rate of 0% was obtained.
実施例により作製したＰＴＦＥ半焼成フィルムを、長尺方向には延伸せず、幅方向に４倍延伸し、熱固定処理温度２８０℃で１０分間の熱固定を行った結果、空気の透過速度１３００秒／１００ｃｃ、空孔率４０％、厚み８５μｍ、熱収縮率０％の多孔質ＰＴＦＥ半焼成延伸フィルムが得られた。 The PTFE semi-fired film produced according to the example was stretched 4 times in the width direction without stretching in the longitudinal direction, and subjected to heat setting at a heat setting temperature of 280 ° C. for 10 minutes. A porous PTFE semi-fired stretched film having a second / 100 cc, a porosity of 40%, a thickness of 85 μm, and a heat shrinkage rate of 0% was obtained.
実施例により作製したＰＴＦＥ半焼成フィルムを、長尺方向には延伸せず、幅方向に４倍延伸し、熱固定処理温度２５０℃で１０分間の熱固定を行った結果、空気の透過速度５００秒／１００ｃｃ、空孔率３８％、厚み８５μｍ、熱収縮率０％の多孔質ＰＴＦＥ半焼成延伸フィルムが得られた。 The PTFE semi-fired film produced according to the example was stretched 4 times in the width direction without being stretched in the longitudinal direction, and was subjected to heat setting at a heat setting temperature of 250 ° C. for 10 minutes. A porous PTFE semi-fired stretched film having a second / 100 cc, a porosity of 38%, a thickness of 85 μm, and a heat shrinkage rate of 0% was obtained.
［比較例１］
実施例により作製したＰＴＦＥ半焼成フィルムを、長尺方向には延伸せず、幅方向に２倍延伸し、熱固定処理温度３２０℃で１０分間の熱固定を行った結果、空気の透過速度７５００秒／１００ｃｃ、空孔率２５％、厚み９５μｍ、熱収縮率０％の多孔質ＰＴＦＥ半焼成延伸フィルムが得られた。
[Comparative Example 1]
The PTFE semi-fired film produced according to the example was stretched twice in the width direction without being stretched in the longitudinal direction, and subjected to heat setting at a heat setting treatment temperature of 320 ° C. for 10 minutes. A porous PTFE semi-fired stretched film having a second / 100 cc, a porosity of 25%, a thickness of 95 μm, and a heat shrinkage rate of 0% was obtained.
［比較例２］
実施例により作製したＰＴＦＥ半焼成フィルムを、長尺方向には延伸せず、幅方向に１１倍延伸し、熱固定処理温度３２０℃で１０分間の熱固定を行った結果、空気の透過速度２００秒／１００ｃｃ、空孔率５７％、厚み７０μｍ、熱収縮率０％の多孔質ＰＴＦＥ半焼成延伸フィルムが得られた。
[Comparative Example 2]
The PTFE semi-fired film produced according to the example was stretched 11 times in the width direction without being stretched in the longitudinal direction, and was subjected to heat setting at a heat setting temperature of 320 ° C. for 10 minutes. A porous PTFE semi-fired stretched film having a second / 100 cc, a porosity of 57%, a thickness of 70 μm, and a heat shrinkage rate of 0% was obtained.
［比較例３］
実施例により作製したＰＴＦＥ半焼成フィルムを、長尺方向に４倍延伸し、幅方向には延伸せず、熱固定処理温度３２０℃で１０分間の熱固定を行った結果、空気の透過速度５０秒／１００ｃｃ、空孔率４５％、厚み８０μｍ、熱収縮率０％の多孔質ＰＴＦＥ半焼成延伸フィルムが得られた。
[Comparative Example 3]
The PTFE semi-fired film produced according to the example was stretched 4 times in the longitudinal direction, not stretched in the width direction, and heat-fixed for 10 minutes at a heat-fixing treatment temperature of 320 ° C. As a result, an air transmission rate of 50 A porous PTFE semi-fired stretched film having a second / 100 cc, a porosity of 45%, a thickness of 80 μm, and a heat shrinkage rate of 0% was obtained.
［比較例４］
実施例により作製したＰＴＦＥ半焼成フィルムを、長尺方向には延伸せず、幅方向に４倍延伸し、熱固定処理温度２００℃で１０分間の熱固定を行った結果、空気の透過速度３５０秒／１００ｃｃ、空孔率３８％、厚み８５μｍ、熱収縮率１０％の多孔質ＰＴＦＥ半焼成延伸フィルムが得られた。
[Comparative Example 4]
The PTFE semi-fired film produced according to the example was stretched 4 times in the width direction without being stretched in the longitudinal direction, and was subjected to heat setting at a heat setting treatment temperature of 200 ° C. for 10 minutes. A porous PTFE semi-fired stretched film having a second / 100 cc, a porosity of 38%, a thickness of 85 μm, and a heat shrinkage of 10% was obtained.
［比較例５］
実施例により作製したＰＴＦＥ半焼成フィルムを、長尺方向には延伸せず、幅方向に４倍延伸し、熱固定処理温度２４０℃で１０分間の熱固定を行った結果、空気の透過速度３００秒／１００ｃｃ、空孔率３８％、厚み８５μｍ、熱収縮率１％の多孔質ＰＴＦＥ半焼成延伸フィルムが得られた。
[Comparative Example 5]
The PTFE semi-fired film produced according to the example was stretched 4 times in the width direction without being stretched in the longitudinal direction, and was subjected to heat setting at a heat setting temperature of 240 ° C. for 10 minutes. A porous PTFE semi-fired stretched film having a second / 100 cc, a porosity of 38%, a thickness of 85 μm, and a heat shrinkage rate of 1% was obtained.
［比較例６］
実施例により作製したＰＴＦＥ半焼成フィルムを、長尺方向には延伸せず、幅方向に４倍延伸し、熱固定処理温度３３０℃で１０分間の熱固定を行った結果、空気の透過速度１００秒／１００ｃｃ、空孔率３８％、厚み８５μｍ、熱収縮率０％の多孔質ＰＴＦＥ半焼成延伸フィルムが得られた。
[Comparative Example 6]
The PTFE semi-fired film produced according to the example was stretched 4 times in the width direction without being stretched in the longitudinal direction, and subjected to heat setting at a heat setting treatment temperature of 330 ° C. for 10 minutes. A porous PTFE semi-fired stretched film having a second / 100 cc, a porosity of 38%, a thickness of 85 μm, and a heat shrinkage rate of 0% was obtained.
［比較例７］
実施例により作製したＰＴＦＥ半焼成フィルムを、長尺方向には延伸せず、幅方向に４倍延伸し、熱固定処理温度３６０℃で１０分間の熱固定を行った結果、空気の透過速度２５秒／１００ｃｃ、空孔率４２％、厚み８５μｍ、熱収縮率０％の多孔質ＰＴＦＥ半焼成延伸フィルムが得られた。
[Comparative Example 7]
The PTFE semi-fired film produced according to the example was stretched 4 times in the width direction without being stretched in the longitudinal direction, and was subjected to heat setting at a heat setting temperature of 360 ° C. for 10 minutes. A porous PTFE semi-fired stretched film having a second / 100 cc, a porosity of 42%, a thickness of 85 μm, and a heat shrinkage rate of 0% was obtained.
［比較例８］
実施例により作製したＰＴＦＥ半焼成フィルムを、長尺方向に２倍延伸し、幅方向に４倍延伸し、熱固定処理温度３６０℃で１０分間の熱固定を行った結果、空気の透過速度１７秒／１００ｃｃ、空孔率６４％、厚み７０μｍ、熱収縮率０％の多孔質ＰＴＦＥ半焼成延伸フィルムが得られた。
[Comparative Example 8]
The PTFE semi-fired film produced according to the example was stretched twice in the longitudinal direction, stretched 4 times in the width direction, and heat-fixed for 10 minutes at a heat-fixing treatment temperature of 360 ° C. As a result, an air transmission rate of 17 A porous PTFE semi-fired stretched film having a second / 100 cc, a porosity of 64%, a thickness of 70 μm, and a heat shrinkage rate of 0% was obtained.
［比較例９］
実施例により作製したＰＴＦＥ半焼成フィルムを、長尺方向に６倍延伸し、幅方向に５倍延伸し、熱固定処理温度３６０℃で１０分間の熱固定を行った結果、空気の透過速度１４秒／１００ｃｃ、空孔率７５％、厚み４０μｍ、熱収縮率０％の多孔質ＰＴＦＥ半焼成延伸フィルムが得られた。
[Comparative Example 9]
The PTFE semi-fired film produced according to the example was stretched 6 times in the longitudinal direction, stretched 5 times in the width direction, and heat fixed for 10 minutes at a heat setting treatment temperature of 360 ° C. As a result, an air permeation rate of 14 A porous PTFE semi-fired stretched film having a second / 100 cc, a porosity of 75%, a thickness of 40 μm, and a heat shrinkage rate of 0% was obtained.
［比較例１０］
実施例により作製したＰＴＦＥ半焼成フィルムを、長尺方向に６倍延伸し、幅方向には延伸せず、熱固定処理温度３２０℃で１０分間の熱固定を行った結果、空気の透過速度２０秒／１００ｃｃ、空孔率８０％、厚み７０μｍ、熱収縮率０％の多孔質ＰＴＦＥ半焼成延伸フィルムが得られた。
[Comparative Example 10]
The PTFE semi-fired film produced according to the example was stretched 6 times in the longitudinal direction, not stretched in the width direction, and heat-fixed for 10 minutes at a heat-fixing treatment temperature of 320 ° C. As a result, an air transmission rate of 20 A porous PTFE semi-fired stretched film having a second / 100 cc, a porosity of 80%, a thickness of 70 μm, and a heat shrinkage of 0% was obtained.
上記、実施例１〜６、比較例１〜１０の物性の比較を下記表１に表す。
上記の結果、実施例に記載の結晶転化率５０％〜８０％の範囲に入る結晶転化率６０％のＰＴＦＥ半焼成フィルムを、実施例１〜４のように、幅方向のみに３倍以上１０倍以下の範囲に入る４倍（実施例１）、５倍（実施例２）、３倍（実施例３）及び１０倍（実施例４）に延伸し、２５０℃〜３２０℃（ＰＴＦＥの融点３２７℃の直下）の範囲に入る３２０℃で熱固定処理を行った場合には、所期の目的である空気の透過速度５００秒／１００ｃｃ〜３０００秒／１００ｃｃの範囲に入る１１００秒／１００ｃｃ（実施例１）、７００秒／１００ｃｃ（実施例２）、２２００秒／１００ｃｃ（実施例３）及び５００秒／１００ｃｃ（実施例４）の多孔質ＰＴＦＥ半焼成延伸フィルムが得られた。 As a result, a PTFE semi-baked film having a crystal conversion rate of 60%, which falls within the range of 50% to 80% described in the examples, is 3 times or more in the width direction only as in Examples 1-4. Stretched 4 times (Example 1), 5 times (Example 2), 3 times (Example 3) and 10 times (Example 4), which falls within the range of less than 250 times, 250 ° C to 320 ° C (melting point of PTFE) When the heat fixation treatment is performed at 320 ° C., which falls within the range of 327 ° C. (directly below 327 ° C.), the intended air permeation speed of 500 seconds / 100 cc to 3000 seconds / 100 cc falls within the range of 1100 seconds / 100 cc ( Porous PTFE semi-fired stretched films of Example 1), 700 seconds / 100 cc (Example 2), 2200 seconds / 100 cc (Example 3) and 500 seconds / 100 cc (Example 4) were obtained.
また、比較例１〜３のように、ＰＴＦＥ半焼成フィルムを幅方向のみに２倍（比較例１）、幅方向のみに１１倍（比較例２）及び長尺方向のみに４倍（比較例３）に延伸した場合には、２５０℃〜３２０℃の範囲に入る３２０℃で熱固定処理を行っても、得られた多孔質ＰＴＦＥ半焼成延伸フィルムの空気の透過速度は７５００秒／１００ｃｃ（比較例１）、２００秒／１００ｃｃ（比較例２）及び５０秒／１００ｃｃ（比較例３）であり、目的とする空気の透過速度５００秒／１００ｃｃ〜３０００秒／１００ｃｃの範囲には入らなかった。この原因は幅方向のみに３倍〜１０倍延伸しなかったことによる。 Further, as in Comparative Examples 1 to 3, the PTFE semi-baked film was doubled only in the width direction (Comparative Example 1), 11 times in the width direction only (Comparative Example 2), and 4 times in the long direction only (Comparative Example) When stretched in 3), the air permeation rate of the obtained porous PTFE semi-fired stretched film is 7500 seconds / 100 cc (even if heat setting is performed at 320 ° C. which falls within the range of 250 ° C. to 320 ° C. Comparative Example 1), 200 seconds / 100 cc (Comparative Example 2), and 50 seconds / 100 cc (Comparative Example 3), which did not fall within the target air permeation speed of 500 seconds / 100 cc to 3000 seconds / 100 cc. . This is because the film was not stretched 3 to 10 times only in the width direction.
実施例５及び実施例６のように、ＰＴＦＥ半焼成フィルムを幅方向のみに３倍以上１０倍以下の範囲に入る４倍に延伸し、２５０℃〜３２０℃の範囲に入る２８０℃（実施例５）及び２５０℃（実施例６）の温度で熱固定処理した場合には、目的とする空気の透過速度５００秒／１００ｃｃ〜３０００秒／１００ｃｃの範囲に入る１３００秒／１００ｃｃ（実施例５）及び５００秒／１００ｃｃ（実施例６）の多孔質ＰＴＦＥ半焼成延伸フィルムが得られた。 As in Example 5 and Example 6, the PTFE semi-baked film was stretched 4 times in the range of 3 to 10 times only in the width direction, and 280 ° C. in the range of 250 ° C. to 320 ° C. (Examples) 5) and 1300 seconds / 100 cc that falls within the range of the air permeation speed of 500 seconds / 100 cc to 3000 seconds / 100 cc when heat-fixed at a temperature of 250 ° C. (Example 6) (Example 5) And a porous PTFE semi-fired stretched film of 500 seconds / 100 cc (Example 6) was obtained.
一方、比較例４〜７のように、幅方向のみに３倍以上１０倍以下の範囲に入る４倍に延伸しても、２００℃（比較例４）、２４０℃（比較例５）、３３０℃（比較例６）及び３６０℃（比較例７）の温度で熱固定処理した場合には、空気の透過速度は３５０秒／１００ｃｃ（比較例４）、３００秒／１００ｃｃ（比較例５）、１００秒／１００ｃｃ（比較例６）及び２５秒／１００ｃｃ（比較例７）であり、目的とする空気の透過速度５００秒／１００ｃｃ〜３０００秒／１００ｃｃの範囲には入らなかった。この原因は熱固定処理温度が２５０℃〜３２０℃の範囲でないことによる。 On the other hand, as in Comparative Examples 4 to 7, 200 ° C. (Comparative Example 4), 240 ° C. (Comparative Example 5), 330 even when stretched 4 times in the range of 3 to 10 times only in the width direction. When heat-set at a temperature of ℃ (Comparative Example 6) and 360 ℃ (Comparative Example 7), the air permeation rate is 350 seconds / 100 cc (Comparative Example 4), 300 seconds / 100 cc (Comparative Example 5), They were 100 seconds / 100 cc (Comparative Example 6) and 25 seconds / 100 cc (Comparative Example 7), and did not fall within the target air transmission speed range of 500 seconds / 100 cc to 3000 seconds / 100 cc. This is because the heat setting temperature is not in the range of 250 ° C to 320 ° C.
また、比較例８〜１０のように、長尺方向に２倍、幅方向に４倍延伸して３６０℃の温度で熱固定処理した場合（比較例８）、長尺方向に６倍、幅方向に５倍延伸して３６０℃の温度で熱固定処理した場合（比較例９）及び長尺方向にのみ６倍延伸し、幅方向には延伸せず、３２０℃の温度で熱固定処理した場合（比較例１０）は、それぞれの空気透過速度１７秒／１００ｃｃ（比較例８）、１４秒／１００ｃｃ（比較例９）及び２０秒／１００ｃｃ（比較例１０）であり、目的とする空気の透過速度５００秒／１００ｃｃ〜３０００秒／１００ｃｃ（比較例１０）の範囲には入らなかった。この原因は長尺方向に延伸したことによる。 Further, as in Comparative Examples 8 to 10, when stretched twice in the longitudinal direction and 4 times in the width direction and heat-set at a temperature of 360 ° C. (Comparative Example 8), 6 times in the longitudinal direction and the width When the film was stretched 5 times in the direction and heat-set at a temperature of 360 ° C. (Comparative Example 9), it was stretched 6 times only in the longitudinal direction and not stretched in the width direction, and was heat-set at a temperature of 320 ° C. The cases (Comparative Example 10) are the air permeation speeds of 17 seconds / 100 cc (Comparative Example 8), 14 seconds / 100 cc (Comparative Example 9) and 20 seconds / 100 cc (Comparative Example 10), respectively. The transmission speed was not within the range of 500 seconds / 100 cc to 3000 seconds / 100 cc (Comparative Example 10). This is due to stretching in the longitudinal direction.
以上のことから、ＰＴＦＥ半焼性フィルムを長尺方向に延伸した場合は、幅方向に延伸するか否かに関係なく、空気の透過速度の数値が大幅に下がって空気が透過しやすい状態となり、その結果、電子写真定着器具用オイル塗布部材としてシリコーンオイルの塗布量が多すぎる結果となる。 From the above, when the PTFE semi-fired film is stretched in the longitudinal direction, regardless of whether or not it is stretched in the width direction, the numerical value of the air permeation rate is greatly reduced, and the air easily passes through. As a result, the application amount of silicone oil is too large as an oil application member for an electrophotographic fixing device.
また、ＰＴＦＥ半焼性フィルムを幅方向のみに延伸する場合において、３倍未満の場合は、空気の透過速度の数値が上がって空気が透過しにくい状態となり、その結果、電子写真定着器具用オイル塗布部材としてシリコーンオイルの塗布量が少なすぎる結果となる。 In addition, when the PTFE semi-fireable film is stretched only in the width direction, if it is less than 3 times, the numerical value of the air permeation speed is increased and the air is hardly transmitted. As a result, the oil application for the electrophotographic fixing device is performed. As a result, the amount of silicone oil applied as a member is too small.
さらに、ＰＴＦＥ半焼性フィルムを幅方向のみに延伸する場合において、１０倍を越える場合は、空気の透過速度の数値が下がって空気が透過しやすい状態となり、その結果、電子写真定着器具用オイル塗布部材としてシリコーンオイルの塗布量が多すぎる結果となる。 Further, when the PTFE semi-fireable film is stretched only in the width direction, if it exceeds 10 times, the numerical value of the air permeation rate is lowered, and the air is likely to permeate. As a result, oil application for an electrophotographic fixing device is performed. As a result, the amount of silicone oil applied as a member is too large.
さらにまた、熱固定処理温度が２５０℃未満の場合には、空気の透過速度の数値が下がって空気が透過しやすい状態となり、電子写真定着器具用オイル塗布部材としてシリコーンオイルの塗布量が多すぎる結果となる。また、定着器具において発生する２５０℃程度の加熱によりＰＴＦＥ半焼性延伸フィルムは熱収縮する結果となる。 Furthermore, when the heat setting treatment temperature is less than 250 ° C., the numerical value of the air permeation rate is lowered and air is likely to permeate, and the amount of silicone oil applied as an oil application member for an electrophotographic fixing device is too large. Result. Further, the PTFE semi-fired stretched film is thermally contracted by heating at about 250 ° C. generated in the fixing device.
また、熱固定処理温度が３２０℃を超える場合には、空気の透過速度の数値が下がって空気が透過しやすい状態となり、その結果、電子写真定着器具用オイル塗布部材としてシリコーンオイルの塗布量が多すぎる結果となる。 In addition, when the heat setting treatment temperature exceeds 320 ° C., the numerical value of the air permeation rate decreases, and the air easily penetrates. As a result, the amount of silicone oil applied as an oil application member for an electrophotographic fixing device is reduced. Too many results.
前記の実施例で作製されたＰＴＦＥ半焼成フィルムにおいて、その片面に金属ナトリウムを分散したフッ素樹脂表面処理剤テトラエッチ（登録商標）（株式会社潤工社製）を塗布して脱フッ素処理をした。その後に、実施例１の要領で多孔質ＰＴＦＥ半焼成延伸フィルムを作製した。当該多孔質ＰＴＦＥ半焼成延伸フィルムの物性は実施例１と変わらなかった。 In the PTFE semi-baked film produced in the above-described example, a fluorine resin surface treatment agent Tetraetch (registered trademark) (manufactured by Junko Co., Ltd.) in which metallic sodium was dispersed was applied to one side of the PTFE semi-fired film for defluorination. Thereafter, a porous PTFE semi-fired stretched film was produced in the same manner as in Example 1. The physical properties of the porous PTFE semi-fired stretched film were not different from those in Example 1.
そして、脱フッ素した多孔質ＰＴＦＥ半焼成延伸フィルムの面にシリコン接着剤を介してアラミド不織布を容易にラミネートすることができた。 And the aramid nonwoven fabric was able to be easily laminated on the surface of the defluorinated porous PTFE semi-fired stretched film via a silicon adhesive.
このようして多孔質ＰＴＦＥ半焼成延伸フィルムをシリコーンオイル透過フィルムとする離型層とし、アラミド不織布層をシリコーンオイル含油層としたブレード、すなわち電子写真装置用定着器具のローラにシリコーンオイルを塗布するブレードを完成することができた。 In this way, the silicone oil is applied to the blade, ie, the roller of the fixing device for an electrophotographic apparatus, in which the porous PTFE semi-fired stretched film is a release layer using a silicone oil permeable film and the aramid nonwoven fabric layer is a silicone oil-containing layer. The blade was completed.
以上、本発明の実施形態を説明したが、この実施形態は、例として提示したものであり、発明の範囲を限定することは意図していない。この実施形態は、その他の様々な形態で実施されることが可能であり、発明の要旨を逸脱しない範囲で、種々の省略、置き換え、変更を行うことができる。この実施形態やその変形は、発明の範囲や要旨に含まれると同様に、特許請求の範囲に記載された発明とその均等の範囲に含まれるものである。 As mentioned above, although embodiment of this invention was described, this embodiment is shown as an example and is not intending limiting the range of invention. This embodiment can be implemented in various other forms, and various omissions, replacements, and changes can be made without departing from the spirit of the invention. This embodiment and its modifications are included in the scope of the present invention and the gist thereof, and are also included in the invention described in the claims and the equivalent scope thereof.
Claims (3)
前記ポリテトラフルオロエチレン未焼成フィルムから結晶転化率が５０％〜８０％のポリテトラフルオロエチレン半焼成フィルムを作製し、
前記ポリテトラフルオロエチレン半焼成フィルムを、所定の延伸処理温度で前記ペースト押出成形における押出方向と直交する幅方向のみに３倍以上１０倍以下に延伸してポリテトラフルオロエチレン半焼成延伸フィルムを作製し、
当該ポリテトラフルオロエチレン半焼成延伸フィルムを２５０℃〜３２０℃の熱固定処理温度で熱固定して製造する
ことを特徴とするシリコーンオイル透過フィルムの製法。 A polytetrafluoroethylene unfired film is produced by paste extrusion and rolling from a raw material mainly composed of polytetrafluoroethylene fine powder,
A polytetrafluoroethylene semi-baked film having a crystal conversion rate of 50% to 80% is produced from the polytetrafluoroethylene unfired film,
The polytetrafluoroethylene semi-baked stretched film is stretched 3 times to 10 times only in the width direction perpendicular to the extrusion direction in the paste extrusion molding at a predetermined stretching temperature to produce a polytetrafluoroethylene semi-fired stretched film. And
A method for producing a silicone oil permeable film, wherein the polytetrafluoroethylene semi-fired stretched film is heat-set at a heat setting temperature of 250 ° C to 320 ° C.
ことを特徴とする請求項１又は２に記載のシリコーンオイル透過フィルムの製法。 3. The method for producing a silicone oil permeable film according to claim 1, wherein only one surface of the polytetrafluoroethylene semi-baked film before stretching is defluorinated.
ガーレメーターでの空気の透過速度が５００秒／１００ｃｃ〜３０００秒／１００ｃｃであり、
厚みが２５μｍ〜３００μｍである
ことを特徴とするシリコーンオイル透過フィルム。 It consists of a polytetrafluoroethylene semi-baked film having a crystal conversion rate of 50% to 80%,
The air permeation speed in the galemeter is 500 seconds / 100 cc to 3000 seconds / 100 cc,
A silicone oil permeable film having a thickness of 25 μm to 300 μm.
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