JP3903547B2

JP3903547B2 - Oriented fluororesin molded body and method for producing the same

Info

Publication number: JP3903547B2
Application number: JP27709197A
Authority: JP
Inventors: 康彰山本; 広男草野; 秀樹柳生
Original assignee: Hitachi Cable Ltd
Current assignee: Hitachi Cable Ltd
Priority date: 1997-10-09
Filing date: 1997-10-09
Publication date: 2007-04-11
Anticipated expiration: 2017-10-09
Also published as: JPH11116707A

Description

【０００１】
【発明の属する技術分野】
本発明は、耐磨耗性、耐クリープ性、寸法安定性等に優れた配向ふっ素樹脂成形体及びその製造方法に関するものである。
【０００２】
【従来の技術】
ふっ素樹脂は、低摩擦性、耐熱性、電気特性、耐薬品性及びクリーン性（非汚染性）に優れており、産業用、民生用の各種用途に広く利用されている。しかし、ふっ素樹脂は摺動環境下や高温での圧縮環境下で、摩耗やクリープ変形が大きく、使用できないケースがある。このため、ふっ素樹脂に充填剤を加えることにより摩耗やクリープ変形を改善する対策がとられてきている。
【０００３】
【発明が解決しようとする課題】
しかし、充填剤を加える方法では、充填剤がふっ素樹脂固有の優れた性質を低下させるため、その利用範囲が制限されることが多く、必ずしも満足の行くものではなかった。
【０００４】
従って、本発明の目的は、優れた耐磨耗性、耐クリープ性、寸法安定性を有し、しかも、ふっ素樹脂本来の良好な特性を備えた配向ふっ素樹脂成形体及びその製造方法を提供することにある。
【０００５】
【課題を解決するための手段】
本発明は上記の目的を達成するため、ふっ素樹脂に酸素濃度１０ ^−３ mol ／ｇ以下の不活性ガス雰囲気下で、且つその融点以上に加熱すると共に張力をかけた状態で電離性放射線を照射線量１ｋＧｙ〜１０ＭＧｙの範囲で照射した、結晶化熱量４０Ｊ／ｇ以下、融点３２５℃以下である改質ふっ素樹脂からなり、広角Ｘ線回折（ＷＡＸＤ）による二次配向係数が０．０１〜１であることを特徴とする配向ふっ素樹脂成形体を提供するものである。
【０００６】
【発明の実施の形態】
本発明に使用されるふっ素樹脂としては、テトラフルオロエチレン系重合体（以下ＰＴＦＥという）、テトラフルオロエチレン−パーフルオロ（アルキルビニルエーテル）系共重合体（以下ＰＦＡという）、あるいはテトラフルオロエチレン−ヘキサフルオロプロピレン系共重合体（以下ＦＥＰという）等が挙げられる。
【０００７】
上記ＰＴＦＥの中には、パーフルオロ（アルキルビニルエーテル）、ヘキサフルオロプロピレン、（パーフルオロアルキル）エチレン、あるいはクロロトリフルオロエチレン等の共重合性モノマーに基づく重合単位を１モル％以下含有するものも含まれる。また、上記共重合体形式のふっ素樹脂の場合、その分子構造の中に少量の第３成分を含むことは有り得る。
【０００８】
本発明において、ふっ素樹脂成形体の広角Ｘ線回折（ＷＡＸＤ）による二次配向係数が０．０１〜１と規定しているが、二次の配向係数が０．０１未満では配向が不十分で、電離性放射線照射時に成形体に著しい変形が生じ、寸法安定性が損なわれる。この配向係数を実現するためには、成形体に張力をかけた状態で電離性放射線を照射することが必要である。
【０００９】
本発明において、改質ふっ素樹脂の結晶化熱量が４０Ｊ／ｇ以下、融点が３２５℃以下と規定しているが、結晶化熱量及び融点が上記値を越えると、耐磨耗性や耐クリープ性が著しく低下するためである。なお、ふっ素樹脂がＰＦＡのときは、結晶化熱量が２６Ｊ／ｇ以下、融点が３０５℃以下とすることが好ましく、ＦＥＰのときは結晶化熱量が９Ｊ／ｇ以下、融点が２７５℃以下とすることが好ましい。
【００１０】
本発明において、熱特性の評価には示差走査熱量計（ＤＳＣ）を用い、５０〜３６０℃の間で１０℃／min の昇・降温スピードにより昇温、降温を２サイクル繰り返し、２回目の昇温時のＤＳＣ曲線の吸熱ピーク温度を融点とし、２回目の降温時の発熱ピークとベースラインに囲まれたピーク面積からＪＩＳＫ７１２２に準じ、結晶化熱量を求める。
【００１１】
本発明の配向ふっ素樹脂成形体は、ふっ素樹脂に酸素濃度１０^-3mol ／ｇ以下の不活性ガス雰囲気下で、且つ融点以上に加熱すると共に張力をかけた状態で電離性放射線を照射線量１ｋＧｙ〜１０ＭＧｙの範囲で照射することにより製造することができる。
【００１２】
電離性放射線の照射は、酸素濃度１０^-3mol ／ｇ以下の不活性ガス雰囲気下で行い、また、その照射線量は１ＫＧｙ〜１０ＭＧｙの範囲内が望ましい。本発明においては、電離性放射線としては、γ線、電子線、Ｘ線、中性子線、あるいは高エネルギーイオン等が使用される。
【００１３】
また、電離性放射線の照射を行うに際しては、ふっ素樹脂をその結晶融点以上に加熱しておく必要がある。例えばふっ素樹脂としてＰＴＦＥを使用する場合には、この材料の結晶融点である３２７℃よりも高い温度にふっ素樹脂を加熱した状態で電離性放射線を照射する必要があり、また、ＰＦＡやＦＥＰを使用する場合には、前者が３１０℃、後者が２７５℃に特定される融点よりも高い温度に加熱して照射する。ふっ素樹脂をその融点以上に加熱することは、ふっ素樹脂を構成する主鎖の分子運動を活発化させることになり、その結果、分子間の架橋反応を効率良く促進させることが可能となる。但し、過度の加熱は、逆に分子主鎖の切断と分解を招くようになるので、このような解重合現象の発生を抑制する意味合いから、加熱温度はふっ素樹脂の融点よりも１０〜３０℃高い範囲内に抑えるべきである。
【００１４】
本発明による配向ふっ素樹脂成形体の用途としては、摺動部品、半導体関連製造部品、酸化性の強い薬品を入れる容器等、幅広い用途が期待できる。
【００１５】
【実施例】
〔実施例１〜３〕
ＰＴＦＥ粉体（商品名：Ｇ−１６３、旭硝子社製）を３６０℃、圧力５０ＭＰａで１時間圧縮成形し、縦５０mm、横５０mm、厚さ１mmのシートを得た。このシートに対し、酸素濃度１０^-5mol ／ｇ、窒素雰囲気下、３４０℃の加熱温度のもと、試料の縦方向の両側に幅１０mm当たり１０ｇの張力をかけた状態で電子線（加速電圧２ＭｅＶ）を照射線量５０ｋＧｙ（実施例１）、１００ＫＧｙ（実施例２）、１５０ＫＧｙ（実施例３）照射し、供試試料とした。
【００１６】
〔実施例４〕
ＰＦＡ（商品名：Ｐ−６３Ｐ、旭硝子社製）を、東洋精機製小型押出機ラボプラストミルを用い、３６０℃の設定温度でもって幅３０mm、厚さ１mmのＴダイを使用して帯状シートを押出し、これを縦５０mm、横３０mm、厚さ１mmに裁断して試料シートとした。このシートに対し、酸素濃度１０^-5mol ／ｇ、窒素雰囲気下、３２０℃の加熱温度のもと、試料の縦方向の両側に幅１０mm当たり１０ｇの張力をかけた状態で電子線（加速電圧２ＭｅＶ）を照射線量５０ｋＧｙ照射し、これを供試試料とした。
【００１７】
〔実施例５〕
ＦＥＰ（商品名：Ｎ−２０、ダイキン工業製）を、東洋精機製小型押出機ラボプラストミルを用い、３４０℃の設定温度でもって幅３０mm、厚さ１mmのＴダイを使用して帯状シートを押出し、これを縦５０mm、横３０mm、厚さ１mmに裁断して試料シートとした。このシートに対し、酸素濃度１０^-5mol ／ｇ、窒素雰囲気下、２７５℃の加熱温度のもと、試料の縦方向の両側に幅１０mm当たり１０ｇの張力をかけた状態で電子線（加速電圧２ＭｅＶ）を照射線量４０ｋＧｙ照射し、これを供試試料とした。
【００１８】
〔比較例１〕
ＰＴＦＥ粉体（商品名：Ｇ−１６３、旭硝子社製）を３６０℃、圧力５０ＭＰａで１時間圧縮成形し、縦５０mm、横５０mm、厚さ１mmのシートを得、これを供試試料とした。
【００１９】
〔比較例２〕
ＰＴＦＥ粉体（商品名：Ｇ−１６３、旭硝子社製）を３６０℃、圧力５０ＭＰａで１時間圧縮成形し、縦５０mm、横５０mm、厚さ１mmのシートを得た。このシートに対し、酸素濃度１０^-2mol ／ｇ、窒素雰囲気下、３４０℃の加熱温度のもと、試料の縦方向の両側に幅１０mm当たり１０ｇの張力をかけた状態で電子線（加速電圧２ＭｅＶ）を照射線量１００ｋＧｙ照射し、これを供試試料とした。
【００２０】
〔比較例３〕
ＰＴＦＥ粉体（商品名：Ｇ−１６３、旭硝子社製）を３６０℃、圧力５０ＭＰａで１時間圧縮成形し、縦５０mm、横５０mm、厚さ１mmのシートを得た。このシートに対し、酸素濃度１０^-5mol ／ｇ、窒素雰囲気下、３８０℃の加熱温度のもとで電子線（加速電圧２ＭｅＶ）を照射線量１００ｋＧｙ照射し、供試試料とした。なお、照射時は無張力とした。
【００２１】
実施例及び比較例の各試料の特性評価を表１に示した。なお、測定は各試料３点とし、これらの算術平均値を示した。
【００２２】
（１）熱特性
パーキンエルマー社製ＤＳＣ（ＤＳＣ７）を用い、試料約１０mgを改質ふっ素樹脂からサンプリングし、前述した方法に準じ測定した。
【００２３】
（２）二次の配向係数
ＷＡＸＤにより結晶ｃ軸と遠心方向の角度Θを測定し、これから二次の配向係数ｆを求めた。
【００２４】
ｆ＝（３ｃｏｓ２Θ−１）／２
（３）比摩耗量
試験にはスラスト摩耗試験装置を使用し、ＪＩＳＫ７２１８に準じ、ＳＵＳ３０４製の円筒リング（外径２５．６mm，内径２０．６mm）に試験片（外径２５．６mm，内径２０．６mm，厚さ１mm）を貼り合せ、相手材にはＳＵＳ３０４板（縦３０mm，横３０mm，厚さ５mm）を用い、圧力０．２５ＭＰａ、速度０．５ｍ／sec の条件で行った。
【００２５】
２４時間後重量減少を測定し、比摩耗量Ｖ_SAは下記の式から求めた。
【００２６】
Ｖ_SA＝Ｖ／（Ｐ・Ｌ）
Ｖ：摩耗量、Ｐ：試験荷重、Ｌ：平均滑り距離
（４）圧縮クリープ性
基本的にはＡＳＴＭＤ６２１−６４に準拠して行い、縦，横１０mm，厚さ１mmの試料を５枚重ね、２００℃の空気中雰囲気に２時間置き予熱した。その後、７ＭＰａの荷重を２４時間かけ、その後荷重を取り去り、更に２４時間放置後、試料の厚さを測定し次式から圧縮クリープ（ΔＬ）を求めた。
【００２７】
ΔＬ＝（Ｌ−Ｌｔ）×１００／Ｌ
Ｌ：試験前の室温での試料厚さ（mm）
Ｌｔ：試験終了後、室温で２４時間放置後の試料厚さ（mm）
（５）寸法安定性
図１（ａ）に示すように照射前の試料シート１の縦方向の長さをｌ₀とし、図１（ｂ）に示すように照射後の試料シート１の縦方向の長さをｌとしたとき、寸法安定性ａ＝ｌ／ｌ₀を求めた。
【００２８】
【表１】

【００２９】
【発明の効果】
以上説明してきた本発明によれば、実施例と比較例との対比からも明らかなように、優れた耐磨耗性、耐クリープ性、寸法安定性を有する成形体を実現することが可能となり、ふっ素樹脂の応用範囲を広げる上で大きく貢献するものである。
【図面の簡単な説明】
【図１】寸法安定性の測定方法の説明図であり、（ａ）は照射前のシートを、（ｂ）は照射後のシートをそれぞれ表している。
【符号の説明】
１シート[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an oriented fluororesin molded article having excellent wear resistance, creep resistance, dimensional stability, and the like, and a method for producing the same.
[0002]
[Prior art]
Fluorine resins are excellent in low friction, heat resistance, electrical properties, chemical resistance and cleanliness (non-contaminating), and are widely used in various industrial and consumer applications. However, there are cases where fluororesins cannot be used due to large wear and creep deformation under sliding environments and compression environments at high temperatures. For this reason, measures have been taken to improve wear and creep deformation by adding a filler to the fluororesin.
[0003]
[Problems to be solved by the invention]
However, the method of adding a filler is not always satisfactory because the filler reduces the excellent properties inherent in the fluororesin, so that the range of use is often limited.
[0004]
Accordingly, an object of the present invention is to provide an oriented fluororesin molded product having excellent wear resistance, creep resistance, and dimensional stability, and having good characteristics inherent in the fluororesin, and a method for producing the same. There is.
[0005]
[Means for Solving the Problems]
In order to achieve the above-mentioned object, the present invention irradiates a fluororesin with ionizing radiation in an inert gas atmosphere having an oxygen concentration of 10 ⁻³ mol / g or less, heated above its melting point and under tension. It is composed of a modified fluororesin having a heat of crystallization of 40 J / g or less and a melting point of 325 ° C. or less irradiated in a dose range of 1 kGy to 10 MGy, and has a secondary orientation coefficient of 0.01 to 1 by wide angle X-ray diffraction (WAXD). The present invention provides an oriented fluororesin molded product characterized by being.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
Examples of the fluororesin used in the present invention include a tetrafluoroethylene polymer (hereinafter referred to as PTFE), a tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer (hereinafter referred to as PFA), or tetrafluoroethylene-hexafluoro. Examples thereof include propylene-based copolymers (hereinafter referred to as FEP).
[0007]
The PTFE includes those containing 1 mol% or less of a polymer unit based on a copolymerizable monomer such as perfluoro (alkyl vinyl ether), hexafluoropropylene, (perfluoroalkyl) ethylene, or chlorotrifluoroethylene. It is. In the case of the copolymer type fluororesin, a small amount of the third component may be included in the molecular structure.
[0008]
In the present invention, the secondary orientation coefficient by the wide-angle X-ray diffraction (WAXD) of the fluororesin molding is defined as 0.01 to 1, but the orientation is insufficient if the secondary orientation coefficient is less than 0.01. When the ionizing radiation is irradiated, the molded body is significantly deformed and the dimensional stability is impaired. In order to realize this orientation coefficient, it is necessary to irradiate ionizing radiation in a state where tension is applied to the molded body.
[0009]
In the present invention, the heat of crystallization of the modified fluororesin is specified to be 40 J / g or less and the melting point is 325 ° C. or less. However, if the heat of crystallization and the melting point exceed the above values, wear resistance and creep resistance are specified. This is because remarkably decreases. When the fluororesin is PFA, the crystallization heat amount is preferably 26 J / g or less and the melting point is preferably 305 ° C. or less, and when FEP is used, the crystallization heat amount is 9 J / g or less and the melting point is 275 ° C. or less. It is preferable.
[0010]
In the present invention, a differential scanning calorimeter (DSC) is used for the evaluation of thermal characteristics, and the temperature is raised and lowered at a rate of 10 ° C./min between 50 and 360 ° C. for 2 cycles. The endothermic peak temperature of the DSC curve at the time of warming is taken as the melting point, and the heat of crystallization is determined from the exothermic peak at the second temperature drop and the peak area surrounded by the base line according to JIS K7122.
[0011]
The oriented fluororesin molded article of the present invention is irradiated with ionizing radiation at a dose of 1 kGy in a fluorine resin heated in an inert gas atmosphere having an oxygen concentration of 10 ⁻³ mol / g or less, heated to a melting point or higher and tensioned. It can manufacture by irradiating in the range of -10MGy.
[0012]
Irradiation with ionizing radiation is performed in an inert gas atmosphere having an oxygen concentration of 10 ⁻³ mol / g or less, and the irradiation dose is preferably in the range of 1 KGy to 10 MGy. In the present invention, γ-rays, electron beams, X-rays, neutron beams, or high-energy ions are used as ionizing radiation.
[0013]
Further, when performing irradiation with ionizing radiation, it is necessary to heat the fluororesin to the crystal melting point or higher. For example, when PTFE is used as the fluororesin, it is necessary to irradiate the ionizing radiation while the fluororesin is heated to a temperature higher than 327 ° C., which is the crystalline melting point of this material, and PFA or FEP is used. In this case, irradiation is performed by heating to a temperature higher than the melting point specified by 310 ° C. for the former and 275 ° C. for the latter. Heating the fluororesin beyond its melting point activates the molecular motion of the main chain constituting the fluororesin, and as a result, the cross-linking reaction between molecules can be efficiently promoted. However, excessive heating, on the other hand, leads to cleavage and decomposition of the molecular main chain, so that the heating temperature is 10-30 ° C. higher than the melting point of the fluororesin from the viewpoint of suppressing the occurrence of such depolymerization phenomenon. It should be kept within a high range.
[0014]
As the use of the oriented fluororesin molding according to the present invention, a wide range of uses such as a sliding part, a semiconductor-related manufacturing part, and a container containing a highly oxidative chemical can be expected.
[0015]
【Example】
[Examples 1-3]
PTFE powder (trade name: G-163, manufactured by Asahi Glass Co., Ltd.) was compression molded at 360 ° C. and a pressure of 50 MPa for 1 hour to obtain a sheet having a length of 50 mm, a width of 50 mm, and a thickness of 1 mm. An electron beam (acceleration voltage) was applied to the sheet under a tension of 10 g per 10 mm width on both sides in the longitudinal direction of the sample under an oxygen concentration of 10 ⁻⁵ mol / g under a nitrogen atmosphere at a heating temperature of 340 ° C. 2 MeV) was irradiated at irradiation doses of 50 kGy (Example 1), 100 KGy (Example 2), and 150 KGy (Example 3) to obtain test samples.
[0016]
Example 4
Using PFA (trade name: P-63P, manufactured by Asahi Glass Co., Ltd.) using a T-die having a width of 30 mm and a thickness of 1 mm at a set temperature of 360 ° C. using a small extruder Labo plast mill manufactured by Toyo Seiki. The sample was extruded and cut into a length of 50 mm, a width of 30 mm, and a thickness of 1 mm to obtain a sample sheet. An electron beam (acceleration voltage) was applied to this sheet under a tension of 10 g per 10 mm width on both sides in the longitudinal direction of the sample under an oxygen concentration of 10 ⁻⁵ mol / g and a heating temperature of 320 ° C. in a nitrogen atmosphere. 2 MeV) was irradiated at an irradiation dose of 50 kGy, and this was used as a test sample.
[0017]
Example 5
Using FEP (trade name: N-20, manufactured by Daikin Industries), using a T-die having a width of 30 mm and a thickness of 1 mm at a set temperature of 340 ° C. using a small extruder Laboplast mill manufactured by Toyo Seiki The sample was extruded and cut into a length of 50 mm, a width of 30 mm, and a thickness of 1 mm to obtain a sample sheet. An electron beam (acceleration voltage) was applied to this sheet under a tension of 10 g per 10 mm width on both sides in the longitudinal direction of the sample under an oxygen concentration of 10 ⁻⁵ mol / g under a nitrogen atmosphere at a heating temperature of 275 ° C. 2 MeV) was irradiated at an irradiation dose of 40 kGy, and this was used as a test sample.
[0018]
[Comparative Example 1]
PTFE powder (trade name: G-163, manufactured by Asahi Glass Co., Ltd.) was compression molded at 360 ° C. and a pressure of 50 MPa for 1 hour to obtain a sheet having a length of 50 mm, a width of 50 mm, and a thickness of 1 mm, which was used as a test sample.
[0019]
[Comparative Example 2]
PTFE powder (trade name: G-163, manufactured by Asahi Glass Co., Ltd.) was compression molded at 360 ° C. and a pressure of 50 MPa for 1 hour to obtain a sheet having a length of 50 mm, a width of 50 mm, and a thickness of 1 mm. An electron beam (acceleration voltage) was applied to the sheet in a state where a tension of 10 g per 10 mm width was applied to both sides in the longitudinal direction of the sample under an oxygen concentration of 10 ⁻² mol / g under a nitrogen atmosphere at a heating temperature of 340 ° C. 2 MeV) was irradiated at a dose of 100 kGy, and this was used as a test sample.
[0020]
[Comparative Example 3]
PTFE powder (trade name: G-163, manufactured by Asahi Glass Co., Ltd.) was compression molded at 360 ° C. and a pressure of 50 MPa for 1 hour to obtain a sheet having a length of 50 mm, a width of 50 mm, and a thickness of 1 mm. This sheet was irradiated with an electron beam (acceleration voltage: 2 MeV) at an oxygen concentration of 10 ⁻⁵ mol / g and a heating temperature of 380 ° C. in a nitrogen atmosphere to obtain a test sample. Note that no tension was applied during irradiation.
[0021]
Table 1 shows the characteristic evaluation of each sample of the examples and comparative examples. In addition, each measurement measured 3 points | pieces and showed these arithmetic mean values.
[0022]
(1) Thermal characteristics Using DSC (DSC7) manufactured by Perkin Elmer, about 10 mg of a sample was sampled from the modified fluororesin and measured according to the method described above.
[0023]
(2) An angle Θ in the centrifugal direction with the crystal c axis was measured by a secondary orientation coefficient WAXD, and a secondary orientation coefficient f was determined therefrom.
[0024]
f = (3 cos 2Θ−1) / 2
(3) Thrust wear test equipment was used for the specific wear test, and in accordance with JIS K7218, a test piece (outer diameter 25.6 mm, inner diameter) was formed on a SUS304 cylindrical ring (outer diameter 25.6 mm, inner diameter 20.6 mm). 20.6 mm, thickness 1 mm) were bonded together, and a SUS304 plate (length 30 mm, width 30 mm, thickness 5 mm) was used as the mating material, under the conditions of pressure 0.25 MPa and speed 0.5 m / sec.
[0025]
After 24 hours, the weight loss was measured, and the specific wear amount V _SA was determined from the following equation.
[0026]
V _SA = V / (P · L)
V: Abrasion amount, P: Test load, L: Average slip distance (4) Compression creep property Basically, the test is performed in accordance with ASTM D621-64, and five samples of 10 mm in length, 10 mm in width and 1 mm in thickness are stacked. Preheating was performed in an air atmosphere at 2 ° C. for 2 hours. Thereafter, a load of 7 MPa was applied for 24 hours, the load was then removed, and the sample was further allowed to stand for 24 hours, and then the thickness of the sample was measured to obtain a compression creep (ΔL) from the following formula.
[0027]
ΔL = (L−Lt) × 100 / L
L: Sample thickness at room temperature before test (mm)
Lt: Sample thickness after standing for 24 hours at room temperature after completion of the test (mm)
(5) the dimensional stability Figure 1 the longitudinal length of the sample sheet 1 prior to irradiation, as shown in (a) and l _0, the longitudinal direction of the sample sheet 1 after the irradiation, as shown in FIG. 1 (b) Dimensional stability a = 1 / l ₀ was determined, where l is the length.
[0028]
[Table 1]

[0029]
【The invention's effect】
According to the present invention described above, it becomes possible to realize a molded article having excellent wear resistance, creep resistance, and dimensional stability, as is apparent from the comparison between Examples and Comparative Examples. This greatly contributes to expanding the application range of fluororesin.
[Brief description of the drawings]
1A and 1B are explanatory diagrams of a method for measuring dimensional stability, in which FIG. 1A shows a sheet before irradiation, and FIG. 1B shows a sheet after irradiation.
[Explanation of symbols]
1 sheet

Claims

A crystal in which a fluororesin is irradiated with ionizing radiation in an irradiation dose range of 1 kGy to 10 MGy in an inert gas atmosphere with an oxygen concentration of 10 ⁻³ mol / g or less and heated to a temperature equal to or higher than its melting point and under tension. An oriented fluororesin molded article comprising a modified fluororesin having a heat of conversion of 40 J / g or less and a melting point of 325 ° C. or less, and having a secondary orientation coefficient of 0.01 to 1 by wide angle X-ray diffraction (WAXD) .

The oriented fluororesin molded product according to claim 1, wherein the modified fluororesin comprises a tetrafluoroethylene-based polymer.

The oriented fluororesin molded body according to claim 1, wherein the modified fluororesin has a crystallization heat amount of 26 J / g or less and a melting point of 305 ° C or less.

4. The oriented fluororesin molded body according to claim 3, wherein the modified fluororesin comprises a tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer.

The oriented fluororesin molded product according to claim 1, wherein the modified fluororesin has a crystallization heat of 9 J / g or less and a melting point of 275 ° C or less.

6. The oriented fluororesin molded product according to claim 5, wherein the modified fluororesin comprises a tetrafluoroethylene-hexafluoropropylene copolymer.