JP2002309004A - Modified fluororesin - Google Patents
Modified fluororesinInfo
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- JP2002309004A JP2002309004A JP2001113578A JP2001113578A JP2002309004A JP 2002309004 A JP2002309004 A JP 2002309004A JP 2001113578 A JP2001113578 A JP 2001113578A JP 2001113578 A JP2001113578 A JP 2001113578A JP 2002309004 A JP2002309004 A JP 2002309004A
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- Prior art keywords
- fluororesin
- ionizing radiation
- modified
- melting point
- raw material
- Prior art date
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は改質ふっ素樹脂に関
するものである。更に詳述すれば本発明は摺動環境下に
おいても優れた耐摩耗性及び耐クリープ変形防止性を発
揮できる改質ふっ素樹脂に関するものである。[0001] The present invention relates to a modified fluororesin. More specifically, the present invention relates to a modified fluororesin capable of exhibiting excellent wear resistance and creep deformation resistance even in a sliding environment.
【０００２】[0002]
【従来の技術】ふっ素樹脂は優れた耐熱性、電気的特
性、低摩擦性、耐薬品性、非汚染性（クリーン性）等を
有しており、これらの特長を生かして産業分野、民生分
野の多方面に広く利用されている。しかし、ふっ素樹脂
は摺動環境下において摩耗劣化及びクリープ変形が大き
いという難点があった。2. Description of the Related Art Fluororesins have excellent heat resistance, electrical properties, low friction, chemical resistance, non-staining properties (cleanliness), and the like. Is widely used in many fields. However, the fluororesin has a drawback in that abrasion deterioration and creep deformation are large in a sliding environment.
【０００３】このような訳でふっ素樹脂の摺動環境下に
おける摩耗劣化及びクリープ変形を改善する試みが為さ
れてきた。[0003] For this reason, attempts have been made to improve wear deterioration and creep deformation of a fluororesin in a sliding environment.
【０００４】従来のふっ素樹脂の摺動環境下における摩
耗劣化及びクリープ変形を最小限にする改質方法は、ふ
っ素樹脂の中へ充填剤を加える方法である。A conventional modification method for minimizing wear deterioration and creep deformation in a sliding environment of a fluororesin is a method of adding a filler to the fluororesin.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら従来のふ
っ素樹脂の中へ充填剤を加える方法では、ふっ素樹脂が
有する優れた耐薬品性、非汚染性（クリーン性）を損な
うという難点があった。However, the conventional method of adding a filler to a fluororesin has a disadvantage in that the excellent chemical resistance and non-staining property (cleanness) of the fluororesin are impaired.
【０００６】本発明はかかる点に立って為されたもので
あって、その目的とするところは前記した従来技術の欠
点を解消し、ふっ素樹脂が有する耐薬品性、非汚染性
（クリーン性）を何等損なうことなく、摺動環境下にお
いて優れた耐摩耗性及び耐クリープ変形防止性を発揮で
きる改質ふっ素樹脂を提供することにある。The present invention has been made in view of such a point, and an object of the present invention is to solve the above-mentioned disadvantages of the prior art, and to provide the chemical resistance and non-staining (cleanness) of fluororesin. An object of the present invention is to provide a modified fluororesin capable of exhibiting excellent abrasion resistance and creep deformation resistance under a sliding environment without impairing the above.
【０００７】[0007]
【課題を解決するための手段】本発明の要旨とするとこ
ろは、原材料ふっ素樹脂をその融点以上の温度下で、且
つ酸素濃度１００torr以下の雰囲気中において電離放射
線を照射することにより電離放射線架橋物とされてお
り、且つ該電離放射線架橋物は微粉砕処理によりアスペ
クト比が２以上の微粉砕粒子にされたものであることを
特徴とする改質ふっ素樹脂にある。SUMMARY OF THE INVENTION The gist of the present invention is to provide a cross-linked ionizing radiation product by irradiating a raw material fluororesin with an ionizing radiation at a temperature not lower than its melting point and in an atmosphere having an oxygen concentration of not more than 100 torr. And the ionized radiation cross-linked product is a modified fluororesin characterized by being finely pulverized particles having an aspect ratio of 2 or more by a finely pulverizing treatment.
【０００８】[0008]
【発明の実施の形態】次に、本発明の改質ふっ素樹脂の
実施の形態について説明する。Next, an embodiment of the modified fluororesin of the present invention will be described.
【０００９】本発明において原材料ふっ素樹脂としては
工業的に生産されているふっ素樹脂ならよく、例えばテ
トラフルオロエチレン樹脂（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）共重合樹脂（以下、ＰＦＡという）、テト
ラフルオロエチレン−ヘキサフルオロプロピレン（以
下、ＦＥＰという）等がある。In the present invention, the raw material fluororesin may be any industrially produced fluororesin, for example, tetrafluoroethylene resin (hereinafter referred to as PTFE),
There are tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer resin (hereinafter, referred to as PFA) and tetrafluoroethylene-hexafluoropropylene (hereinafter, referred to as FEP).
【００１０】ここにおいて、ＰＴＦＥ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、クロロトリフ
ルオロエチレン等の共重合モノマーに基づく重合単位が
１モル％以下含有するものも含まれる。Here, PTFE includes those containing 1 mol% or less of polymerized units based on copolymerized monomers such as perfluoro (alkyl vinyl ether), hexafluoropropylene, (perfluoroalkyl) ethylene, and chlorotrifluoroethylene. It is.
【００１１】また、ＰＦＡ、ＦＥＰには、他の第３モノ
マー成分を共重合して得られるものも含まれる。[0011] PFA and FEP also include those obtained by copolymerizing other third monomer components.
【００１２】本発明において改質ふっ素樹脂はアスペク
ト比が２以上のものと限定したが、これはアスペクト比
が２以下のものでは配向効果が不十分であり、その結果
改質ふっ素樹脂の成形体の成形安定性や寸法安定性が悪
化するからである。In the present invention, the modified fluororesin is limited to those having an aspect ratio of 2 or more. If the aspect ratio is 2 or less, the orientation effect is insufficient. This is because the molding stability and the dimensional stability of the rubber composition deteriorate.
【００１３】このアスペクト比が２以下の改質ふっ素樹
脂を得るには、照射架橋したふっ素樹脂を湿式ジェット
ミルと乾式ジェットミルとを適宜組み合わせて微粉砕す
ることにより得られる。The modified fluororesin having an aspect ratio of 2 or less can be obtained by pulverizing the irradiated and crosslinked fluororesin by appropriately combining a wet jet mill and a dry jet mill.
【００１４】本発明において改質ふっ素樹脂はその結晶
化熱量を４０Ｊ／ｇ以下で、且つ融点を３２５℃以下と
限定したのは、結晶化熱量が４０Ｊ／ｇ以上で、且つ融
点が３２５℃以上の改質ふっ素樹脂では摺動環境下にお
ける耐摩耗性及び耐クリープ変形防止性の顕著なる改善
効果が得られないためである。In the present invention, the modified fluororesin is limited to have a heat of crystallization of 40 J / g or less and a melting point of 325 ° C. or less because it has a heat of crystallization of 40 J / g or more and a melting point of 325 ° C. or more. This is because the remarkable improvement effect of wear resistance and anti-creep deformation resistance in a sliding environment cannot be obtained with the modified fluororesin.
【００１５】なお、ふっ素樹脂がＰＦＡのときには結晶
化熱量が２６Ｊ／ｇ以下で、且つ融点が３０５℃以下で
あることが好ましい。また、ふっ素樹脂がＦＥＰのとき
には結晶化熱量が９Ｊ／ｇ以下で、且つ融点が２７５℃
以下であることが好ましい。 （１）示差走査熱量計による熱特性値の測定 本発明においてふっ素樹脂の下記の熱特性値は示差走査
熱量計（ＤＳＣ）を用いて測定した。When the fluororesin is PFA, the heat of crystallization is preferably 26 J / g or less and the melting point is preferably 305 ° C. or less. When the fluororesin is FEP, the heat of crystallization is 9 J / g or less and the melting point is 275 ° C.
The following is preferred. (1) Measurement of Thermal Characteristics Using Differential Scanning Calorimeter In the present invention, the following thermal characteristics of the fluororesin were measured using a differential scanning calorimeter (DSC).
【００１６】ａ．昇温・降温スピード 示差走査熱量計の５０〜３６０℃の温度範囲の昇温・降
温スピードは１０℃／minで行い、これら昇温・降温を
２サイクル繰り返した。A. Temperature rise / fall speed The temperature rise / fall speed of the differential scanning calorimeter in the temperature range of 50 to 360 ° C. was set at 10 ° C./min, and the temperature rise / fall was repeated two cycles.
【００１７】ｂ．融点 融点は２サイクル目の昇温時のＤＳＣ曲線の吸熱ピーク
を融点とした。B. Melting point The melting point was defined as the endothermic peak of the DSC curve at the time of temperature rise in the second cycle.
【００１８】ｃ．結晶化熱量 結晶化熱量は、まず２サイクル目の降温時のＤＳＣ曲線
の発熱ピークとベースラインに囲まれたピーク面積を求
め、次にＪＩＳ Ｋ７１２２に準じて結晶化熱量を求め
た。 （２）電離性放射線の照射 本発明において電離性放射線の種類としてはγ線、電子
線、Ｘ線、中性子線、高エネルギーイオン線等がある。
この電離性放射線の照射量は１ｋＧｙ〜１０ＭＧｙの範
囲が望ましい。C. Heat of crystallization The heat of crystallization was obtained by first determining the exothermic peak of the DSC curve and the peak area surrounded by the baseline at the time of the temperature decrease in the second cycle, and then calculating the heat of crystallization according to JIS K7122. (2) Irradiation with ionizing radiation In the present invention, types of ionizing radiation include γ-ray, electron beam, X-ray, neutron beam, high energy ion beam and the like.
The dose of this ionizing radiation is preferably in the range of 1 kGy to 10 MGy.
【００１９】また、電離性放射線の照射雰囲気は酸素濃
度が１００ｔｏｒｒ以下の不活性ガス雰囲気下が望まし
い。The ionizing radiation irradiation atmosphere is desirably in an inert gas atmosphere having an oxygen concentration of 100 torr or less.
【００２０】なお、原材料ふっ素樹脂へ電離性放射線を
照射するときには、その原材料ふっ素樹脂をその融点以
上に加熱しておくことが効果的である。これは原材料ふ
っ素樹脂を加熱するとにより分子主鎖の運動を活発化さ
せ、それにより分子間の架橋反応を効率的に行わせるた
めである。従ってＰＴＦＥへ電離性放射線を照射すると
きには、ＰＴＦＥの融点３２７℃より高い温度に加熱し
た状態で行う。また、ＰＦＡへ電離性放射線を照射する
ときには、ＰＦＡの融点３１５℃より高い温度に加熱し
た状態で行う。そしてまた、ＦＥＰへ電離性放射線を照
射するときには、ＦＥＰの融点２７５℃より高い温度に
加熱した状態で行う。When the raw material fluororesin is irradiated with ionizing radiation, it is effective to heat the raw material fluororesin above its melting point. This is because heating the raw material fluororesin activates the movement of the molecular main chain, thereby efficiently performing a cross-linking reaction between molecules. Therefore, when irradiating the PTFE with ionizing radiation, the PTFE is heated to a temperature higher than the melting point of 327 ° C. Further, when the PFA is irradiated with ionizing radiation, the irradiation is performed in a state where the PFA is heated to a temperature higher than the melting point of 315 ° C. When irradiating the FEP with ionizing radiation, the FEP is heated to a temperature higher than the melting point of 275 ° C. of the FEP.
【００２１】しかし、過度の加熱は原材料ふっ素樹脂の
分子主鎖の切断と分解とを招くことになるので、望まし
い加熱温度はふっ素樹脂の融点より１０〜３０℃高い温
度範囲である。However, since excessive heating causes the breaking and decomposition of the molecular main chain of the raw material fluororesin, a desirable heating temperature is a temperature range higher by 10 to 30 ° C. than the melting point of the fluororesin.
【００２２】本発明において改質ふっ素樹脂の用途とし
ては摺動部品、半導体関連部品、酸化性薬品用容器等が
ある。In the present invention, applications of the modified fluororesin include sliding parts, semiconductor-related parts, containers for oxidizing chemicals, and the like.
【００２３】[0023]
【実施例】次に、本発明の改質ふっ素樹脂の実施例を従
来の比較例の改質ふっ素樹脂と共に説明する。 （比較例１）原材料ふっ素樹脂として融点が３２７℃の
ＰＴＦＥを用い、このＰＴＦＥの１００重量部に充填剤
として酸化チタンを２５重量部配合して成る比較例１の
改質ふっ素樹脂を得た。 （比較例２）原材料ふっ素樹脂として融点が３２７℃の
ＰＴＦＥを用い、このＰＴＦＥを酸素濃度が１００ｔｏ
ｒｒ以下の不活性ガス雰囲気下で８０℃に加熱し、それ
から電子線を１００ｋＧｙ照射することにより照射ＰＴ
ＦＥを得た。Next, examples of the modified fluororesin of the present invention will be described together with a modified fluororesin of a conventional comparative example. (Comparative Example 1) A modified fluororesin of Comparative Example 1 was prepared by using PTFE having a melting point of 327 ° C as a raw material fluororesin and blending 25 parts by weight of titanium oxide as a filler with 100 parts by weight of this PTFE. (Comparative Example 2) PTFE having a melting point of 327 ° C was used as a raw material fluororesin, and this PTFE was used at an oxygen concentration of 100 ton.
heated to 80 ° C. in an inert gas atmosphere of rr or less, and then irradiated with 100 kGy of an electron beam.
FE was obtained.
【００２４】次に、ここで得られた照射ＰＴＦＥを湿式
ジェットミルによる粉砕処理と乾式ジェットミルによる
粉砕処理とを組み合わせてアスペクト比が１．２の比較
例２の改質ふっ素樹脂を得た。Next, the modified PTFE of Comparative Example 2 having an aspect ratio of 1.2 was obtained by combining the obtained irradiated PTFE with a wet jet mill and a dry jet mill.
【００２５】図２はかくして得られた比較例２の改質ふ
っ素樹脂の粉砕粒子のアスペクト比モデルを示した斜視
説明図である。FIG. 2 is an explanatory perspective view showing an aspect ratio model of the pulverized particles of the modified fluororesin of Comparative Example 2 thus obtained.
【００２６】図２においてａはアスペクト比、Ｈは高
さ、Ｄ0は外径である。In FIG. 2, a is the aspect ratio, H is the height, and D 0 is the outer diameter.
【００２７】ａ＝Ｈ／Ｄ0 即ち、比較例２の改質ふっ素樹脂の粉砕粒子は、高さＨ
に対して外径Ｄ0が大きい粒子、つまり偏平な粒子であ
る。 （比較例３）原材料ふっ素樹脂として融点が３２７℃の
ＰＴＦＥを用い、このＰＴＦＥを酸素濃度が１００ｔｏ
ｒｒ以下の不活性ガス雰囲気下で３８０℃に加熱し、そ
から電子線を１００ｋＧｙ照射することにより比較例３
の改質ふっ素樹脂を得た。 （実施例１）原材料ふっ素樹脂として融点が３２７℃の
ＰＴＦＥを用い、このＰＴＦＥを酸素濃度が１００ｔｏ
ｒｒ以下の不活性ガス雰囲気下で３３７℃に加熱し、そ
れから電子線を１００ｋＧｙ照射することにより照射Ｐ
ＴＦＥを得た。A = H / D 0 That is, the pulverized particles of the modified fluororesin of Comparative Example 2 have a height H
Are particles having a larger outer diameter D 0 , that is, flat particles. (Comparative Example 3) PTFE having a melting point of 327 ° C. was used as a raw material fluororesin, and this PTFE was used at an oxygen concentration of 100 ton.
Comparative Example 3 was heated to 380 ° C. in an inert gas atmosphere of rr or less and then irradiated with 100 kGy of an electron beam.
A modified fluororesin was obtained. (Example 1) PTFE having a melting point of 327 ° C was used as a raw material fluororesin, and this PTFE was treated with an oxygen concentration of 100 ton.
heating to 337 ° C. in an inert gas atmosphere of rr or less, and then irradiating with an electron beam at 100 kGy to irradiate P
TFE was obtained.
【００２８】次に、ここで得られた照射ＰＴＦＥを湿式
ジェットミルによる粉砕処理と乾式ジェットミルによる
粉砕処理とを組み合わせてアスペクト比が２．５の実施
例１の改質ふっ素樹脂を得た。Next, the modified PTFE of Example 1 having an aspect ratio of 2.5 was obtained by combining the pulverization treatment of the irradiated PTFE obtained here with a wet jet mill and a pulverization treatment with a dry jet mill.
【００２９】図１はかくして得られた実施例１の改質ふ
っ素樹脂の粉砕粒子のアスペクト比モデルを示した斜視
説明図である。FIG. 1 is an explanatory perspective view showing an aspect ratio model of the pulverized particles of the modified fluororesin of Example 1 thus obtained.
【００３０】図１においてａはアスペクト比、Ｈは高
さ、Ｄ1は実施例１の改質ふっ素樹脂の粉砕粒子の外径
である。In FIG. 1, a is the aspect ratio, H is the height, and D 1 is the outer diameter of the pulverized particles of the modified fluororesin of Example 1.
【００３１】ａ＝Ｈ／Ｄ1 即ち、実施例１の改質ふっ素樹脂の粉砕粒子は、高さＨ
に対して外径Ｄ1が小さい粒子、つまり背高ノッポ粒子
である。 （実施例２）原材料ふっ素樹脂として融点が３１５℃の
ＰＦＡを用い、このＰＦＡを酸素濃度が１００ｔｏｒｒ
以下の不活性ガス雰囲気下で３２５℃に加熱し、それか
ら電子線を７０ｋＧｙ照射することにより照射ＰＦＡを
得た。A = H / D 1 That is, the pulverized particles of the modified fluororesin of Example 1 have a height H
Particles having a smaller outer diameter D 1 , that is, tall noppo particles. Example 2 PFA having a melting point of 315 ° C. was used as a raw material fluororesin, and the PFA was used at an oxygen concentration of 100 torr.
The mixture was heated to 325 ° C. in an inert gas atmosphere described below, and then irradiated with an electron beam at 70 kGy to obtain irradiated PFA.
【００３２】次に、ここで得られた照射ＰＦＡを湿式ジ
ェットミルによる粉砕処理と乾式ジェットミルによる粉
砕処理とを組み合わせてアスペクト比が２．８の実施例
２の改質ふっ素樹脂を得た。 （実施例３）原材料ふっ素樹脂として融点が２７５℃の
ＦＥＰを用い、このＦＥＰを酸素濃度が１００ｔｏｒｒ
以下の不活性ガス雰囲気下で２８５℃に加熱し、それか
ら電子線を１００ｋＧｙ照射することにより照射ＦＥＰ
を得た。Then, the modified PFA of Example 2 having an aspect ratio of 2.8 was obtained by combining the obtained irradiated PFA with a wet jet mill and a dry jet mill. Example 3 FEP having a melting point of 275 ° C. was used as a raw material fluororesin, and this FEP was used at an oxygen concentration of 100 torr.
Heating to 285 ° C. under the following inert gas atmosphere, and then irradiating 100 kGy of an electron beam to irradiate FEP
I got
【００３３】次に、ここで得られた照射ＦＥＰを湿式ジ
ェットミルによる粉砕処理と乾式ジェットミルによる粉
砕処理とを組み合わせてアスペクト比が３．１の実施例
３の改質ふっ素樹脂を得た。 （試験方法） ａ．摺動環境下における非汚染性試験 まず、実施例若しくは比較例の改質ふっ素樹脂を改質ふ
っ素樹脂製摺動部品に成形加工した。Next, the irradiated FEP obtained here was subjected to a combination of pulverization by a wet jet mill and pulverization by a dry jet mill to obtain a modified fluororesin of Example 3 having an aspect ratio of 3.1. (Test method) a. Non-Staining Property Test in Sliding Environment First, the modified fluororesin of the example or the comparative example was molded into a sliding part made of modified fluororesin.
【００３４】次に、その得られた改質ふっ素樹脂製摺動
部品を潤滑油を補給できるモデル摺動試験装置に装着し
た。Next, the obtained sliding parts made of modified fluororesin were mounted on a model sliding test apparatus capable of supplying lubricating oil.
【００３５】次に、その摺動試験装置を１００時間運転
した。Next, the sliding test apparatus was operated for 100 hours.
【００３６】次に、その１００時間運転した摺動試験装
置より改質ふっ素樹脂製摺動部品を取り出し、油汚れの
程度を調べた。Next, the sliding parts made of the modified fluororesin were taken out from the sliding test apparatus operated for 100 hours, and the degree of oil contamination was examined.
【００３７】結果は油汚れのないものを○、油汚れのあ
るものを×で示した。The results are shown by ○ for those without oil stains and × for those with oil stains.
【００３８】ｂ．摺動環境下における耐摩耗性 上と同様に、実施例若しくは比較例の改質ふっ素樹脂を
改質ふっ素樹脂製摺動部品に成形加工した。B. Abrasion Resistance in Sliding Environment Similarly to the above, the modified fluororesin of the example or the comparative example was molded into a modified fluororesin sliding part.
【００３９】次に、その得られた改質ふっ素樹脂製摺動
部品を潤滑油を補給できるモデル摺動試験装置に装着し
た。Next, the obtained sliding parts made of modified fluororesin were mounted on a model sliding test apparatus capable of supplying lubricating oil.
【００４０】次に、その摺動試験装置を１００時間運転
した。Next, the sliding test apparatus was operated for 100 hours.
【００４１】次に、その１００時間運転した摺動試験装
置より改質ふっ素樹脂製摺動部品を取り出し、摩耗の程
度を調べた。Next, the sliding parts made of the modified fluororesin were taken out from the sliding test apparatus operated for 100 hours, and the degree of wear was examined.
【００４２】結果は摩耗が殆どみられないものを○、摩
耗損傷が酷いものを×で示した。The results are indicated by を when hardly any abrasion is observed, and by X when severely damaged by abrasion.
【００４３】ｃ．摺動環境下における耐クリープ変形防
止性 上と同様に、実施例若しくは比較例の改質ふっ素樹脂を
改質ふっ素樹脂製摺動部品に成形加工した。C. Resistance to Creep Deformation Under Sliding Environment In the same manner as above, the modified fluororesin of the example or the comparative example was molded into a sliding part made of modified fluororesin.
【００４４】次に、その得られた改質ふっ素樹脂製摺動
部品を潤滑油を補給できるモデル摺動試験装置に装着し
た。Next, the obtained sliding parts made of modified fluororesin were mounted on a model sliding test apparatus capable of supplying lubricating oil.
【００４５】次に、その摺動試験装置を１００時間運転
した。Next, the sliding test apparatus was operated for 100 hours.
【００４６】次に、その１００時間運転した摺動試験装
置より改質ふっ素樹脂製摺動部品を取り出し、クリープ
変形量の程度を調べた。Next, the sliding parts made of the modified fluororesin were taken out from the sliding test apparatus operated for 100 hours, and the degree of creep deformation was examined.
【００４７】結果はクリープ変形量が殆どみられないも
のを○、クリープ変形量がが酷いものを×で示した。 （試験結果）表１はこれらの試験結果を示したものであ
る。The results are indicated by を when the amount of creep deformation is scarcely observed and by X when the amount of creep deformation is severe. (Test results) Table 1 shows the results of these tests.
【００４８】[0048]
【表１】 [Table 1]
【００４９】表１から分かるようにＰＴＦＥに充填剤と
して酸化チタンを配合して成る比較例１の改質ふっ素樹
脂のものは非汚染性が劣る。As can be seen from Table 1, the modified fluororesin of Comparative Example 1 comprising PTFE mixed with titanium oxide as a filler is inferior in non-staining properties.
【００５０】また、原材料ふっ素樹脂として融点が３２
７℃のＰＴＦＥを用い、その融点より遥かに低い温度の
８０℃の加熱下で電子線を照射して成り、且つアスペク
ト比が１．２の比較例２の改質ふっ素樹脂のものは架橋
反応が小さく、その結果耐摩耗性及び耐クリープ変形防
止性が共に悪い。The raw material fluororesin has a melting point of 32.
The modified fluororesin of Comparative Example 2, which is made by irradiating an electron beam using PTFE at 7 ° C. under heating at 80 ° C. which is much lower than its melting point, and having an aspect ratio of 1.2, has a crosslinking reaction. Therefore, both abrasion resistance and creep deformation resistance are poor.
【００５１】また、原材料ふっ素樹脂として融点が３２
７℃のＰＴＦＥを用い、その融点より遥かに高い温度の
３８０℃の加熱下で電子線を照射して成る比較例３の改
質ふっ素樹脂のものは、架橋反応より分解反応が多く起
こり、その結果耐摩耗性及び耐クリープ変形防止性が著
しく悪い。The raw material fluororesin has a melting point of 32.
The modified fluororesin of Comparative Example 3, which is obtained by irradiating an electron beam under heating at 380 ° C., which is a temperature much higher than its melting point, using PTFE at 7 ° C., causes more decomposition reaction than crosslinking reaction. As a result, wear resistance and creep deformation resistance are extremely poor.
【００５２】これらに対して本発明の実施例１〜３の改
質ふっ素樹脂は非汚染性、耐摩耗性、耐クリープ変形防
止性がいずれも優れている。On the other hand, the modified fluororesins of Examples 1 to 3 of the present invention are all excellent in non-staining, abrasion resistance and creep deformation resistance.
【００５３】[0053]
【発明の効果】本発明の改質ふっ素樹脂は摺動環境下に
おいて優れた非汚染性、耐摩耗性、耐クリープ変形防止
性を発揮できるものであり、工業上有用である。The modified fluororesin of the present invention can exhibit excellent non-staining, abrasion resistance and creep deformation resistance in a sliding environment and is industrially useful.
【図１】本発明の実施例１の改質ふっ素樹脂の粉砕粒子
のアスペクト比モデルを示した斜視説明図である。FIG. 1 is a perspective explanatory view showing an aspect ratio model of pulverized particles of a modified fluororesin of Example 1 of the present invention.
【図２】比較例２の改質ふっ素樹脂の粉砕粒子のアスペ
クト比モデルを示した斜視説明図である。FIG. 2 is a perspective explanatory view showing an aspect ratio model of pulverized particles of a modified fluororesin of Comparative Example 2.
ａ アスペクト比 Ｈ 高さ Ｄ1 実施例１の改質ふっ素樹脂の粉砕粒子の外径 Ｄ0 比較例２の改質ふっ素樹脂の粉砕粒子の外径a Aspect ratio H Height D 1 Outer diameter of pulverized particles of modified fluororesin of Example 1 D 0 Outer diameter of pulverized particles of modified fluororesin of Comparative Example 2
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4F070 AA23 AA24 AA25 AB23 DA42 DB08 DC07 GA04 GB02 GB03 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F070 AA23 AA24 AA25 AB23 DA42 DB08 DC07 GA04 GB02 GB03
Claims (3)
で、且つ酸素濃度１００torr以下の雰囲気中において電
離放射線を照射することにより電離放射線架橋物とされ
ており、且つ該電離放射線架橋物は微粉砕処理によりア
スペクト比が２以上の微粉砕粒子にされたものであるこ
とを特徴とする改質ふっ素樹脂。An ionizing radiation cross-linked product is obtained by irradiating a raw material fluororesin at a temperature not lower than its melting point and in an atmosphere having an oxygen concentration of 100 torr or less, and the ionizing radiation cross-linked product is fine. A modified fluororesin characterized by being pulverized into particles having an aspect ratio of 2 or more by a pulverizing treatment.
レン樹脂、テトラフルオロエチレン〜パーフルオロ（ア
ルキルビニルエーテル）共重合樹脂、テトラフルオロエ
チレン〜ヘキサフルオロプロピレンの中から選ばれた１
種、又はこれらの中から選ばれた１種に異種フルオロモ
ノマが１モル％以下含有したものであることを特徴とす
る請求項１記載の改質ふっ素樹脂。2. The raw material fluororesin is selected from tetrafluoroethylene resins, tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer resins, and tetrafluoroethylene-hexafluoropropylene.
2. The modified fluororesin according to claim 1, wherein the species or one selected from the foregoing contains 1 mol% or less of a different fluoromonomer.
で、且つ酸素濃度１００torr以下の雰囲気中において電
離放射線を照射することにより電離放射線架橋物とされ
ており、且つ該電離放射線架橋物は微粉砕処理によりア
スペクト比が２以上の微粉砕粒子にされ、しかも該微粉
砕粒子物は結晶化熱量が４０Ｊ／ｇ以下で、且つ融点が
３２５℃以下のものであることを特徴とする改質ふっ素
樹脂。3. A crosslinked product of ionizing radiation is obtained by irradiating a raw material fluorocarbon resin with ionizing radiation at a temperature equal to or higher than its melting point and in an atmosphere having an oxygen concentration of 100 torr or less. Modified fluorine characterized in that the pulverized particles are formed into finely pulverized particles having an aspect ratio of 2 or more by pulverization, and the finely pulverized particles have a heat of crystallization of 40 J / g or less and a melting point of 325 ° C. or less. resin.
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| Publication Number | Publication Date |
|---|---|
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| JP3726697B2 JP3726697B2 (en) | 2005-12-14 |
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