JPH11116623A - Modified fluororesin and molded form - Google Patents
Modified fluororesin and molded formInfo
- Publication number
- JPH11116623A JPH11116623A JP27709297A JP27709297A JPH11116623A JP H11116623 A JPH11116623 A JP H11116623A JP 27709297 A JP27709297 A JP 27709297A JP 27709297 A JP27709297 A JP 27709297A JP H11116623 A JPH11116623 A JP H11116623A
- Authority
- JP
- Japan
- Prior art keywords
- fluororesin
- melting point
- modified fluororesin
- less
- crystallization
- 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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- Treatments Of Macromolecular Shaped Articles (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、表面平滑性に優れ
た改質ふっ素樹脂及びこの改質ふっ素樹脂からなる成形
体に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a modified fluororesin having excellent surface smoothness and a molded article made of the modified fluororesin.
【０００２】[0002]
【従来の技術】半導体製造装置関連の容器や配管等に
は、耐熱性、耐薬品性やクリーン性（非汚染性）等の点
から、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）系共重合体を始めとする各種ふっ素
樹脂が使用されている。2. Description of the Related Art Tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymers are used in containers and pipes for semiconductor manufacturing equipment in view of heat resistance, chemical resistance and cleanliness (non-staining). And various fluororesins are used.
【０００３】[0003]
【発明が解決しようとする課題】しかし、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）
系共重合体に代表されるふっ素樹脂成形体は、成形体表
面の平滑性が劣るため、表面に汚染性物質が付着しやす
く、しかも洗浄除去も難しく、半導体製造における品質
管理上の問題となっている。ふっ素樹脂の表面平滑性が
劣る理由は、結晶性であるふっ素樹脂が結晶化時に大き
な球晶を形成し、球晶境界面で溝を形成するためと考え
られている。このため、球晶密度、大きさを抑制する試
みが種々検討されており、例えば、結晶核剤を添加する
ことが提案されているが、耐薬品性の低下や溶出等の問
題を生じることが指摘されている。However, tetrafluoroethylene-perfluoro (alkyl vinyl ether)
Fluororesin molded products represented by copolymers have poor smoothness on the surface of the molded products, so that contaminants can easily adhere to the surface and are difficult to remove by washing, which poses a quality control problem in semiconductor manufacturing. ing. It is considered that the reason why the surface smoothness of the fluororesin is inferior is that the crystalline fluororesin forms large spherulites during crystallization and forms grooves at the spherulite interface. For this reason, various attempts have been made to reduce the spherulite density and size, for example, it has been proposed to add a crystal nucleating agent, but this may cause problems such as a decrease in chemical resistance and elution. It is pointed out.
【０００４】従って、本発明の目的は、成形体表面の平
滑性を向上させることができる改質ふっ素樹脂及び成形
体を提供することにある。Accordingly, an object of the present invention is to provide a modified fluororesin and a molded article which can improve the smoothness of the surface of the molded article.
【０００５】[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、結晶化熱量２６Ｊ／ｇ以下、融点３０５℃
以下、平均球晶径１５μｍ以下であることを特徴とする
改質ふっ素樹脂及びこの改質ふっ素樹脂からなる成形体
を提供するものである。SUMMARY OF THE INVENTION In order to achieve the above object, the present invention provides a crystallization heat of 26 J / g or less and a melting point of 305 ° C.
Hereinafter, the present invention provides a modified fluororesin characterized by having an average spherulite diameter of 15 μm or less, and a molded article made of the modified fluororesin.
【０００６】[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−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）
や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）といった熱溶融成形性
ふっ素樹脂が挙げられる。DETAILED DESCRIPTION OF THE INVENTION The fluororesin used in the present invention is a tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer (hereinafter referred to as PFA).
And a hot-melt-moldable fluororesin such as tetrafluoroethylene-hexafluoropropylene-based copolymer (hereinafter referred to as FEP).
【０００７】本発明においては、改質ふっ素樹脂の結晶
化熱量が２６Ｊ／ｇ以下、融点が３０５℃以下、平均球
晶径が１５μｍ以下と規定しているが、結晶化熱量、融
点及び平均球晶径が上記値を越えると、成形体表面の平
滑性が著しく損なわれる。なお、ふっ素樹脂がＰＦＡ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。In the present invention, the modified fluororesin is specified to have a heat of crystallization of 26 J / g or less, a melting point of 305 ° C. or less, and an average spherulite diameter of 15 μm or less. If the crystal diameter exceeds the above-mentioned value, the smoothness of the surface of the molded article is significantly impaired. When the fluororesin is PFA, the heat of crystallization is preferably 9 J / g or less, and the melting point is preferably 275 ° C. or less.
【０００８】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ＪＩＳ Ｋ７１２２
に準じ、結晶化熱量を求める。In the present invention, thermal characteristics are evaluated using a differential scanning calorimeter (DSC) at a temperature of 50 to 360 ° C.
The temperature was increased and decreased at a rate of ° C / min by repeating two cycles of heating and cooling, and the endothermic peak temperature of the DSC curve at the time of the second heating was used as the melting point, and the exothermic peak at the time of the second cooling was surrounded by the baseline. JIS K7122 from peak area
Determine the heat of crystallization according to
【０００９】平均球晶径の測定には、成形体から切り出
した薄片を３３０℃、１０分加熱後、室温に戻し再結晶
化させたものを試料として用いる。その後、直交偏光子
を使用し、偏光顕微鏡観察により倍率４００倍で平均結
晶径を求める。For the measurement of the average spherulite diameter, a slice cut out from a molded article is heated at 330 ° C. for 10 minutes, returned to room temperature and recrystallized, and used as a sample. Thereafter, the average crystal diameter is determined at 400 times magnification by observation with a polarizing microscope using an orthogonal polarizer.
【００１０】本発明の改質ふっ素樹脂は、ふっ素樹脂を
酸素濃度１０-3mol ／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され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。本発明の改質ふっ素樹脂成形
体は、ふっ素樹脂粉体に電離性放射線を照射した後加圧
成形等により成形体としてもよく、又、ふっ素樹脂を溶
融成形したシート、ブロック又はその他の形状のふっ素
樹脂成形体に電離性放射線を照射してもよい。更には、
ふっ素樹脂を溶融成形した成形体に電離性放射線を照射
後粉砕してなる粉体を、加圧成形成形等により成形体と
してもよい。[0010] The modified fluororesin of the present invention is obtained by subjecting the fluororesin to an inert gas atmosphere having an oxygen concentration of 10 -3 mol / g or less.
In addition, it can be manufactured by irradiating with ionizing radiation in an irradiation dose range of 1 kGy to 10 MGy in a state of being heated to the melting point or more. The modified fluororesin molded article of the present invention may be formed into a molded article by pressure molding or the like after irradiating the fluororesin powder with ionizing radiation, or a sheet, block or other shape obtained by melt-molding the fluororesin. The fluororesin molding may be irradiated with ionizing radiation. Furthermore,
A powder obtained by irradiating ionizing radiation to a molded body obtained by melt-molding a fluororesin and then pulverizing the powder may be formed into a molded body by pressure molding or the like.
【００１１】ふっ素樹脂を改質するときの電離性放射線
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〜１０Ｍ
Ｇｙ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。Irradiation with ionizing radiation when modifying the fluororesin is performed in an inert gas atmosphere having an oxygen concentration of 10 −3 mol / g or less, and the irradiation dose is 1 KGy to 10 M
It is desirable to be within the range of Gy. In the present invention, γ-rays, electron beams, X-rays, neutron rays, high-energy ions, or the like are used as ionizing radiation.
【００１２】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ＰＦＡを使用する場合
には、この材料の融点である３１０℃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、ＦＥＰを使用する場合には、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。When irradiating with ionizing radiation, it is necessary to heat the fluororesin above its crystalline melting point. For example, when using PFA as a fluororesin, it is necessary to irradiate ionizing radiation while heating the fluororesin to a temperature higher than the melting point of this material, 310 ° C., and when using FEP, Is 275 ° C
Irradiation by heating to a temperature higher than the melting point specified in (1).
Heating the fluororesin above its melting point activates the molecular motion of the main chain constituting the fluororesin, and as a result, it is possible to efficiently promote a cross-linking reaction between molecules. However, excessive heating, on the contrary, causes the breaking and decomposition of the main chain of the molecule, so from the viewpoint of suppressing the occurrence of such a depolymerization phenomenon, the heating temperature is 10 to 30 ° C. lower than the melting point of the fluororesin. Should be kept within a high range.
【００１３】改質ふっ素樹脂粉体を加圧成形する場合、
単一の又は２種以上の改質ふっ素樹脂粉体で成形しても
よく、又、これら改質ふっ素樹脂粉体と未改質ふっ素樹
脂を混合したものを成形してもよい。When the modified fluororesin powder is subjected to pressure molding,
A single or two or more kinds of modified fluororesin powders may be molded, or a mixture of these modified fluororesin powders and unmodified fluororesin may be molded.
【００１４】未改質の高分子材料材料としては、テトラ
フルオロエチレン系重合体、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、
テトラフルオロエチレン−ヘキサフルオロプロピレン系
共重合体等をあげることができる。Unmodified polymer materials include tetrafluoroethylene polymers and tetrafluoroethylene-
Perfluoro (alkyl vinyl ether) copolymer,
Examples include tetrafluoroethylene-hexafluoropropylene-based copolymers.
【００１５】[0015]
〔実施例１〜４〕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１０mm、厚さ２mmの
Ｔダイを使用して帯状シートを作製した。このシートに
対し、酸素濃度１０-5mol ／ｇ、窒素雰囲気下、３２０
℃の加熱温度のもとで電子線（加速電圧２ＭｅＶ）を照
射線量１０ｋＧｙ（実施例１）、５０ＫＧｙ（実施例
２）、１００ＫＧｙ（実施例３）、１５０ｋＧｙ（実施
例４）照射し、供試試料とした。[Examples 1 to 4] PFA (trade name: P-63P, manufactured by Asahi Glass Co., Ltd.) was manufactured using a small extruder Labo Plast Mill manufactured by Toyo Seiki Co., Ltd. at a set temperature of 360 ° C. and a T-die having a width of 10 mm and a thickness of 2 mm. Was used to produce a belt-like sheet. With respect to this sheet, an oxygen concentration of 10 −5 mol / g,
An electron beam (acceleration voltage: 2 MeV) was irradiated at a heating temperature of 10 ° C. at an irradiation dose of 10 kGy (Example 1), 50 KGy (Example 2), 100 KGy (Example 3), and 150 kGy (Example 4). A sample was used.
【００１６】〔実施例５〕ＰＦＡ（商品名：Ｐ−６３
Ｐ、旭硝子社製）の約３mm角ペレットに酸素濃度１０-5
mol ／ｇ、窒素雰囲気下、３２０℃の加熱温度のもとで
電子線（加速電圧２ＭｅＶ）を照射線量３０ｋＧｙ照射
し、その後摩砕式により平均粒径約５０μｍまで微粉砕
して改質ＰＦＡを得た。この改質ＰＦＡを３０重量部と
未改質ＰＦＡを７０重量部ブレンドし、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１０mm、厚さ２mmのＴダイを使用して帯状シー
トを作製し、これを供試試料とした。[Example 5] PFA (trade name: P-63)
P, manufactured by Asahi Glass Co., Ltd.) with an oxygen concentration of 10 -5
mol / g, under nitrogen atmosphere, at a heating temperature of 320 ° C., an electron beam (acceleration voltage: 2 MeV) is irradiated with an irradiation dose of 30 kGy, and then finely pulverized by a grinding method to an average particle size of about 50 μm to obtain the modified PFA. Obtained. 30 parts by weight of this modified PFA and 70 parts by weight of unmodified PFA are blended, and a T-die having a width of 10 mm and a thickness of 2 mm is used at a set temperature of 360 ° C. using a small extruder Labo Plastmill manufactured by Toyo Seiki. Thus, a belt-shaped sheet was prepared, and this was used as a test sample.
【００１７】〔実施例６〕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１０mm、
厚さ２mmのＴダイを使用して帯状シートを作製した。こ
のシートに対し、酸素濃度１０-5mol ／ｇ、窒素雰囲気
下、２７５℃の加熱温度のもとで電子線（加速電圧２Ｍ
ｅＶ）を照射線量１００ｋＧｙ照射し、供試試料とし
た。[Embodiment 6] FEP (trade name: N-20,
Daikin Industries Co., Ltd.), using a small extruder Labo Plastmill manufactured by Toyo Seiki Co., Ltd.
A belt-shaped sheet was prepared using a T-die having a thickness of 2 mm. An electron beam (acceleration voltage 2M) was applied to this sheet under a heating temperature of 275 ° C under an oxygen concentration of 10 -5 mol / g and a nitrogen atmosphere.
eV) was irradiated at an irradiation dose of 100 kGy to obtain a test sample.
【００１８】〔比較例１〕実施例１〜４と同様にして作
製したＰＦＡ帯状シートに対し、酸素濃度１０-5mol ／
ｇ、窒素雰囲気下、２９０℃（ＰＦＡの融点以下）の加
熱温度のもとで電子線（加速電圧２ＭｅＶ）を照射線量
１０ｋＧｙ（照射し、供試試料とした。Comparative Example 1 An oxygen concentration of 10 −5 mol / cm 2 was applied to a PFA strip sheet produced in the same manner as in Examples 1 to 4.
g, an electron beam (acceleration voltage of 2 MeV) was applied at a heating temperature of 290 ° C. (lower than the melting point of PFA) in a nitrogen atmosphere at an irradiation dose of 10 kGy (a test sample).
【００１９】〔比較例２〕ＰＦＡ（商品名：Ｐ−６３
Ｐ、旭硝子社製）の約３mm角ペレットに酸素濃度１０-5
mol ／ｇ、窒素雰囲気下、３００℃（ＰＦＡの融点以
下）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、その後摩砕式により平均
粒径約５０μｍまで微粉砕して改質ＰＦＡを得た。この
改質ＰＦＡを５０重量部と未改質ＰＦＡを５０重量部ブ
レンドし、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１０mm、厚さ２mmの
Ｔダイを使用して帯状シートを作製し、これを供試試料
とした。Comparative Example 2 PFA (trade name: P-63)
P, manufactured by Asahi Glass Co., Ltd.) with an oxygen concentration of 10 -5
In a nitrogen atmosphere, an electron beam (acceleration voltage: 2 MeV) is irradiated with an irradiation dose of 100 kGy in a nitrogen atmosphere at a heating temperature of 300 ° C. (lower than the melting point of PFA), and then finely ground to an average particle size of about 50 μm by a grinding method. Thus, a modified PFA was obtained. 50 parts by weight of this modified PFA and 50 parts by weight of unmodified PFA are blended, and a T-die having a width of 10 mm and a thickness of 2 mm is used at a set temperature of 360 ° C. using a small extruder Labo Plastmill manufactured by Toyo Seiki. Thus, a belt-shaped sheet was prepared, and this was used as a test sample.
【００２０】〔比較例３〕実施例１〜４と同様にして作
製したＰＦＡ帯状シートを供試試料とした（照射な
し）。Comparative Example 3 A PFA strip sheet produced in the same manner as in Examples 1 to 4 was used as a test sample (no irradiation).
【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。Table 1 shows the characteristic evaluation of each sample of the examples and comparative examples.
【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。測定数は各試料３点とし、これ
らの算術平均を平均値とした。(1) Thermal Characteristics Using a DSC (DSC7) manufactured by PerkinElmer, about 10 mg of a sample was sampled from a modified fluororesin and measured according to the method described above. The number of measurements was three for each sample, and the arithmetic average of these was taken as the average value.
【００２３】（２）平均球晶径 押出し物を径方向に厚さ約５０μｍに切り出し、メトラ
ーＦＰ８２ＨＴ型ホットステージに取り付けた。その後
３３０℃まで２０℃／min の速度で昇温し、１０分保持
した後、室温まで２０℃／min で降温して再結晶化させ
た。直交偏光子を使用し、偏光顕微鏡により４００倍で
平均球晶径を調べた。観測される１００個の直径を測定
し、その算術平均を平均球晶径とした。(2) Average Spherulite Diameter The extrudate was cut out to a thickness of about 50 μm in the radial direction, and attached to a METTLER FP82HT hot stage. Thereafter, the temperature was raised to 330 ° C. at a rate of 20 ° C./min, maintained for 10 minutes, and then lowered to room temperature at a rate of 20 ° C./min for recrystallization. Using a crossed polarizer, the average spherulite diameter was examined at 400 times with a polarizing microscope. 100 diameters observed were measured, and the arithmetic average thereof was defined as an average spherulite diameter.
【００２４】（３）表面荒さ 押出し物表面の荒さを触針式荒さ計で測定し、ＪＩＳ
Ｂ０６０１により算術平均荒さを求めた。(3) Surface roughness The roughness of the surface of the extruded material was measured with a stylus-type roughness meter and measured according to JIS.
The arithmetic average roughness was determined by B0601.
【００２５】（４）曲げ強さ ＪＩＳ Ｋ７１７１に準じ、試験片形状：長さ８０mm，
幅１０mm，厚さ２mm、半径５mmの圧子を用い、試験速度
２mm／min ，たわみ量が２０mmになるまで曲げを加え
た。各試料３点行い、曲げにより３点ともクラック及び
破断の見られないものを合格、１点でもクラックあるい
は破断が観測された場合を不合格とした。(4) Bending strength According to JIS K7171, test piece shape: length 80 mm,
Using an indenter having a width of 10 mm, a thickness of 2 mm and a radius of 5 mm, bending was performed until the test speed became 2 mm / min and the amount of deflection became 20 mm. Each sample was subjected to three points, and a sample in which no cracks or breaks were observed at all three points due to bending was accepted, and a sample in which cracks or breaks were observed even at one point was rejected.
【００２６】[0026]
【表１】 [Table 1]
【００２７】[0027]
【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、ふっ素樹脂
成形体表面の平滑性を改良でき、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。According to the present invention described above, the surface smoothness of the fluororesin molded body can be improved and the application range of the fluororesin can be expanded, as is clear from the comparison between the examples and the comparative examples. It will contribute greatly.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０８Ｊ 7/00 ３０５ Ｃ０８Ｊ 7/00 ３０５ ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code FI C08J 7/00 305 C08J 7/00 305
Claims (10)
以下、平均球晶径１５μｍ以下であることを特徴とする
改質ふっ素樹脂。1. Heat of crystallization: 26 J / g or less, melting point: 305 ° C.
Hereinafter, a modified fluororesin having an average spherulite diameter of 15 μm or less.
（アルキルビニルエーテル）系共重合体からなる請求項
１記載の改質ふっ素樹脂。2. The modified fluororesin according to claim 1, comprising a tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer.
下、平均球晶径１５μである請求項１記載の改質ふっ素
樹脂。3. The modified fluororesin according to claim 1, which has a heat of crystallization of 9 J / g or less, a melting point of 275 ° C. or less, and an average spherulite diameter of 15 μm.
プロピレン系共重合体からなる請求項３記載の改質ふっ
素樹脂。4. The modified fluororesin according to claim 3, comprising a tetrafluoroethylene-hexafluoropropylene-based copolymer.
mol ／ｇ以下の不活性ガス雰囲気下で、且つその融点以
上に加熱された状態で電離性放射線を照射線量１ｋＧｙ
〜１０ＭＧｙの範囲で照射したものであるである請求項
１記載の改質ふっ素樹脂。5. An oxygen concentration of 10 -3 in a hot-melt moldable fluororesin.
In an inert gas atmosphere of not more than mol / g and heated to a temperature higher than its melting point, ionizing radiation is applied at a dose of 1 kGy.
The modified fluororesin according to claim 1, which has been irradiated in the range of 10 to 10 MGy.
以下、平均球晶径１５μｍ以下である改質ふっ素樹脂か
らなることを特徴とする成形体。6. A heat of crystallization of 26 J / g or less, and a melting point of 305 ° C.
Hereinafter, a molded article comprising a modified fluororesin having an average spherulite diameter of 15 μm or less.
チレン−パーフルオロ（アルキルビニルエーテル）系共
重合体からなる請求項５記載の成形体。7. The molded article according to claim 5, wherein said modified fluororesin comprises a tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer.
ｇ以下、融点２７５℃、平均球晶１５μｍ以下である請
求項５記載の成形体。8. The modified fluororesin has a heat of crystallization of 9 J /
The molded product according to claim 5, which has a melting point of 275 ° C or less and an average spherulite of 15 µm or less.
チレン−ヘキサフルオロプロピレン系共重合体からなる
請求項７記載の成形体。9. The molded article according to claim 7, wherein said modified fluororesin comprises a tetrafluoroethylene-hexafluoropropylene-based copolymer.
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、且つその融点以上に加熱された状態で電離性
放射線を照射線量１ｋＧｙ〜１０ＭＧｙの範囲で照射し
たものであるである請求項６記載の成形体。10. The modified fluororesin is exposed to ionizing radiation while being heated to a temperature higher than its melting point in an inert gas atmosphere having an oxygen concentration of 10 −3 mol / g or less. The molded article according to claim 6, which is irradiated at an irradiation dose of 1 kGy to 10 MGy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27709297A JPH11116623A (en) | 1997-10-09 | 1997-10-09 | Modified fluororesin and molded form |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27709297A JPH11116623A (en) | 1997-10-09 | 1997-10-09 | Modified fluororesin and molded form |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11116623A true JPH11116623A (en) | 1999-04-27 |
Family
ID=17578671
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27709297A Pending JPH11116623A (en) | 1997-10-09 | 1997-10-09 | Modified fluororesin and molded form |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11116623A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001070854A1 (en) * | 2000-03-24 | 2001-09-27 | Daikin Industries, Ltd. | Seal ring |
| JP2002265629A (en) * | 2001-03-14 | 2002-09-18 | Hitachi Cable Ltd | Method for modified fluororesin production |
| JP2007137982A (en) * | 2005-11-17 | 2007-06-07 | Japan Atomic Energy Agency | Radiation-crosslinkable fluorine-containing copolymer |
| JP2017014468A (en) * | 2015-07-06 | 2017-01-19 | 住友電工ファインポリマー株式会社 | Fluororesin film and method for producing fluororesin film |
| JP2017066239A (en) * | 2015-09-29 | 2017-04-06 | 住友電気工業株式会社 | Molded body and manufacturing method therefor |
| WO2019087939A1 (en) * | 2017-10-31 | 2019-05-09 | Ａｇｃ株式会社 | Molded article, metal-coated layered product, printed wiring board, and methods for producing these |
| WO2021006258A1 (en) * | 2019-07-10 | 2021-01-14 | Ａｇｃ株式会社 | Long film, method for producing long film, method for producing long multilayer body, and long multilayer body |
-
1997
- 1997-10-09 JP JP27709297A patent/JPH11116623A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001070854A1 (en) * | 2000-03-24 | 2001-09-27 | Daikin Industries, Ltd. | Seal ring |
| US6930142B2 (en) | 2000-03-24 | 2005-08-16 | Daikin Industries, Ltd. | Seal ring |
| JP2002265629A (en) * | 2001-03-14 | 2002-09-18 | Hitachi Cable Ltd | Method for modified fluororesin production |
| JP2007137982A (en) * | 2005-11-17 | 2007-06-07 | Japan Atomic Energy Agency | Radiation-crosslinkable fluorine-containing copolymer |
| JP2017014468A (en) * | 2015-07-06 | 2017-01-19 | 住友電工ファインポリマー株式会社 | Fluororesin film and method for producing fluororesin film |
| JP2017066239A (en) * | 2015-09-29 | 2017-04-06 | 住友電気工業株式会社 | Molded body and manufacturing method therefor |
| WO2019087939A1 (en) * | 2017-10-31 | 2019-05-09 | Ａｇｃ株式会社 | Molded article, metal-coated layered product, printed wiring board, and methods for producing these |
| JPWO2019087939A1 (en) * | 2017-10-31 | 2020-12-17 | Ａｇｃ株式会社 | Molded bodies, metal-clad laminates, printed wiring boards and their manufacturing methods |
| WO2021006258A1 (en) * | 2019-07-10 | 2021-01-14 | Ａｇｃ株式会社 | Long film, method for producing long film, method for producing long multilayer body, and long multilayer body |
| CN114026158A (en) * | 2019-07-10 | 2022-02-08 | Ａｇｃ株式会社 | Long film, method for producing long laminate, and long laminate |
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