JP2010037382A - Modified fluororesin composition and modified fluororesin molded product - Google Patents
Modified fluororesin composition and modified fluororesin molded product Download PDFInfo
- Publication number
- JP2010037382A JP2010037382A JP2008199544A JP2008199544A JP2010037382A JP 2010037382 A JP2010037382 A JP 2010037382A JP 2008199544 A JP2008199544 A JP 2008199544A JP 2008199544 A JP2008199544 A JP 2008199544A JP 2010037382 A JP2010037382 A JP 2010037382A
- Authority
- JP
- Japan
- Prior art keywords
- modified
- modified fluororesin
- weight
- aromatic polyamide
- fluororesin
- 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.)
- Granted
Links
Abstract
Description
本発明は、改質ふっ素樹脂からなる高面圧下での耐摩耗性、耐クリープ性に優れたしゅう動部品、シール品、パッキン、ガスケット、半導体製造用容器・治具（ジグ）・配管などに用いられる改質ふっ素樹脂組成物及び改質ふっ素樹脂成形体に関する。 The present invention is applied to sliding parts, seal products, packings, gaskets, semiconductor manufacturing containers, jigs (jigs), pipes, etc., which are made of a modified fluororesin and have excellent wear resistance and creep resistance under high surface pressure. The present invention relates to a modified fluororesin composition and a modified fluororesin molded body to be used.
ゴムやプラスチックの有機ポリマが広範囲の用途に使用されており、中でもふっ素樹脂は低摩擦性、耐熱性、電気特性、耐薬品性やクリーン性（非汚染性）に優れ、産業、民生用の各種用途に広く利用されている。 Rubber and plastic organic polymers are used in a wide range of applications. Among them, fluororesins are excellent in low friction, heat resistance, electrical properties, chemical resistance and cleanliness (non-contamination). Widely used in applications.
しかし、しゅう動環境下や高温での圧縮環境下では摩耗やクリープ変形が大きいため、ふっ素樹脂にガラス繊維やカーボン繊維などの充てん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た。 However, since wear and creep deformation are large in sliding environments and compression environments at high temperatures, measures to improve wear and creep deformation can be taken by adding a filler such as glass fiber or carbon fiber to the fluororesin. I came.
なお、この出願の発明に関連する先行技術文献情報としては、次のものがある。 The prior art document information related to the invention of this application includes the following.
しかしながら、このような手法でも高面圧下で使用される場合、耐摩耗性が十分ではなく耐久性に問題があった。この対策として特許文献１〜４に開示されているような手法が検討されているが、用途によっては、従来よりも面圧の高いしゅう動環境下（例えば、４ＭＰａよりも大きい面圧が印加されるようなしゅう動環境下）で使用される場合がある。このため、従来の改質ふっ素樹脂組成物、或いはこれを用いて成形したふっ素樹脂成形体が有する耐摩耗性では十分とは言えない状況にある。 However, even when such a method is used under high surface pressure, the wear resistance is not sufficient and there is a problem in durability. As measures against this, methods such as those disclosed in Patent Documents 1 to 4 have been studied. However, depending on the application, a sliding environment having a higher surface pressure than conventional ones (for example, a surface pressure greater than 4 MPa is applied). In such a sliding environment). For this reason, it exists in the situation where it cannot be said that the abrasion resistance which the conventional modified fluororesin composition or the fluororesin molded object shape | molded using this has has enough.
そこで、本発明の目的は、高面圧下での耐摩耗性を向上させ、従来よりも高面圧のしゅう動環境下でも使用することができる改質ふっ素樹脂組成物及び改質ふっ素樹脂成形体を提供することにある。 Accordingly, an object of the present invention is to improve the abrasion resistance under high surface pressure and to use a modified fluororesin composition and a modified fluororesin molded product that can be used in a sliding environment with a higher surface pressure than before. Is to provide.
前記目的を達成するために創案された本発明は、有機ポリマと、未改質のふっ素樹脂に電離性放射線を照射して改質させた改質ふっ素樹脂と、芳香族ポリアミドと、カーボンブラックとを少なくとも混合してなる改質ふっ素樹脂組成物である。 Invented to achieve the above object, the present invention provides an organic polymer, a modified fluorine resin obtained by modifying an unmodified fluorine resin by irradiating with ionizing radiation, an aromatic polyamide, and carbon black. Is a modified fluororesin composition obtained by mixing at least.
前記芳香族ポリアミドが繊維状芳香族ポリアミドであるとよい。 The aromatic polyamide is preferably a fibrous aromatic polyamide.
前記カーボンブラックは、一次粒子の平均粒径が５０ｎｍ以下であるとよい。 The carbon black may have an average primary particle size of 50 nm or less.
前記カーボンブラックは、一次粒子の結晶子の大きさが５ｎｍ以下、前記結晶子の厚さが０．５ｎｍ以下であるとよい。 The carbon black may have a primary particle crystallite size of 5 nm or less and a crystallite thickness of 0.5 nm or less.
前記改質ふっ素樹脂、前記芳香族ポリアミド、前記カーボンブラックの総重量が全重量に対し１０〜５０重量部であり、かつ前記改質ふっ素樹脂の重量が全重量に対し５〜３０重量部であり、前記芳香族ポリアミドの重量が全重量に対し２〜１５重量部であり、前記カーボンブラックの重量が全重量に対し１〜１０重量部であるとよい。 The total weight of the modified fluororesin, the aromatic polyamide, and the carbon black is 10 to 50 parts by weight with respect to the total weight, and the weight of the modified fluororesin is 5 to 30 parts by weight with respect to the total weight. The weight of the aromatic polyamide is 2 to 15 parts by weight with respect to the total weight, and the weight of the carbon black is preferably 1 to 10 parts by weight with respect to the total weight.
また本発明は、前記改質ふっ素樹脂組成物を用いて成形された改質ふっ素樹脂成形体である。 The present invention also provides a modified fluororesin molded body molded using the modified fluororesin composition.
本発明によれば、高面圧下での耐摩耗性を向上させ、従来よりも高面圧のしゅう動環境下でも使用することができるため、有機ポリマの応用範囲を広げる上で大きく貢献することができる。 According to the present invention, the wear resistance under high surface pressure is improved, and it can be used in a sliding environment with higher surface pressure than before, so that it greatly contributes to expanding the application range of organic polymers. Can do.
以下、本発明の好適な実施形態を説明する。 Hereinafter, preferred embodiments of the present invention will be described.
本発明者らは、改質ふっ素樹脂組成物の高面圧下での耐摩耗性向上について種々検討した結果、有機ポリマ、改質ふっ素樹脂に加え、さらに芳香族ポリアミドおよびカーボンブラックを添加することにより、改質ふっ素樹脂組成物の耐摩耗性が著しく向上することがわかり、本発明を完成するに至った。 As a result of various studies on the improvement of the wear resistance of the modified fluororesin composition under high surface pressure, the present inventors have found that by adding an aromatic polyamide and carbon black in addition to the organic polymer and the modified fluororesin. Thus, it was found that the wear resistance of the modified fluororesin composition was remarkably improved, and the present invention was completed.
本実施の形態に係る改質ふっ素樹脂組成物は、少なくとも有機ポリマと、未改質のふっ素樹脂に電離性放射線を照射して改質させた改質ふっ素樹脂と、芳香族ポリアミドと、カーボンブラックとを混合してなる。 The modified fluororesin composition according to the present embodiment includes at least an organic polymer, a modified fluororesin modified by irradiating an unmodified fluororesin with ionizing radiation, an aromatic polyamide, and carbon black And mixed.
（有機ポリマ）
有機ポリマとしては、ニトリルゴムやふっ素ゴム、あるいはエポキシ樹脂、ナイロン、芳香族系ポリマなどのプラスチックが挙げられるが、中でもふっ素樹脂が最も好ましく、具体的には、テトラフルオロエチレン共重合体（ＰＴＦＥ）、テトラフルオロエチレン−フルオロアルコキシトリフルオロエチレン共重合体（ＰＦＡ）、テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体（ＦＥＰ）、ポリテトラフルオロエチレン−パーフルオロジオキシソール共重合体（ＴＨＦ／ＰＤＤ）から選ばれた１種以上の未改質のふっ素樹脂が挙げられる。
(Organic polymer)
Examples of the organic polymer include nitrile rubber, fluorine rubber, and plastics such as epoxy resin, nylon, and aromatic polymer, among which fluorine resin is most preferable, and specifically, tetrafluoroethylene copolymer (PTFE). , Tetrafluoroethylene-fluoroalkoxytrifluoroethylene copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), polytetrafluoroethylene-perfluorodioxysol copolymer (THF / PDD) One or more selected unmodified fluorine resins may be mentioned.
前記ＰＴＦＥの中には、第２成分となる異種フルオロモノマとして、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などの共重合性モノマーが重合単位で１モル％以下、好ましくは０．２モル％以下含有するものも含まれる。また、前記ふっ素樹脂の場合、その分子構造中に少量の第３成分となる異種フルオロモノマを含むこともできる。 In the PTFE, a copolymerizable monomer such as perfluoro (alkyl vinyl ether), hexafluoropropylene, (perfluoroalkyl) ethylene, or chlorotrifluoroethylene is used as a polymer unit as a heterogeneous fluoromonomer as a second component. Those containing not more than mol%, preferably not more than 0.2 mol% are also included. In the case of the fluororesin, a small amount of a different fluoromonomer serving as a third component can be included in the molecular structure.
また、改質ふっ素樹脂に用いる未改質のふっ素樹脂としては、前述した未改質のふっ素樹脂を用いるのが好ましい。 Further, as the unmodified fluorine resin used for the modified fluorine resin, it is preferable to use the above-mentioned unmodified fluorine resin.
（改質ふっ素樹脂）
本発明において改質ふっ素樹脂は、融点が３２５℃以下、結晶化熱量が４０Ｊ／ｇ以下であることが望ましく、これらが限定値を超えると耐摩耗性や対クリープ性が著しく低下する。なお、ふっ素樹脂がＰＦＡのときは融点が３０５℃以下、結晶化熱量が２６Ｊ／ｇ以下とすることが好ましく、ＦＥＰのときは融点が２７５℃以下、結晶化熱量が１１Ｊ／ｇ以下とすることが好ましい。
(Modified fluorine resin)
In the present invention, the modified fluororesin preferably has a melting point of 325 ° C. or less and a crystallization heat of 40 J / g or less, and if these exceed the limit values, the wear resistance and creep resistance are remarkably lowered. When the fluororesin is PFA, the melting point is preferably 305 ° C. or less and the crystallization heat amount is preferably 26 J / g or less, and when FEP is used, the melting point is 275 ° C. or less and the crystallization heat amount is 11 J / g or less. Is preferred.
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, a differential scanning calorimeter (DSC) is used for evaluation of thermal characteristics, and the temperature is raised and lowered at a rate of 10 ° C./min. The endothermic peak temperature of the DSC curve at the time is taken as the melting point, and the amount of crystallization heat is determined from the exothermic peak at the second temperature drop and the peak area surrounded by the baseline according to JIS K7122.
改質ふっ素樹脂は、未改質のふっ素樹脂を酸素分圧約１３３３Ｐａ（１０ｔｏｒｒ）以下の不活性化ガス雰囲気下で、かつ未改質のふっ素樹脂の融点以上に加熱した状態において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のがよい。 The modified fluororesin is irradiated with ionizing radiation in an inert gas atmosphere having an oxygen partial pressure of about 1333 Pa (10 torr) or less and heated to the melting point of the unmodified fluororesin or higher. It is good to manufacture by irradiating in a dose range of 1 kGy to 10 MGy.
電離性放射線としては、ガンマ線、電子線、Ｘ線、中性子線あるいは高エネルギーイオンなどを使用する。 As ionizing radiation, gamma rays, electron beams, X-rays, neutron rays or high energy ions are used.
電離性放射線の照射を行う際は、ふっ素樹脂をその結晶融点以上に加熱しておく。例えばふっ素樹脂としてＰＴＦＥを使用する場合には、この融点である３２７℃よりも高い温度で照射し、またＰＦＡ、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性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。ただ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、加熱温度はふっ素樹脂の融点よりも１０〜３０℃高い温度範囲内に抑えるのが好ましい。 When irradiating with ionizing radiation, the fluororesin is heated above its crystalline melting point. For example, when PTFE is used as the fluororesin, irradiation is performed at a temperature higher than the melting point of 327 ° C., and when PFA or FEP is used, the former is specified as 310 ° C. and the latter is specified as 275 ° C. Irradiate by heating to a temperature higher than the melting point. Heating the fluororesin beyond its melting point activates the molecular motion of the main chain constituting the fluororesin, and as a result, the intermolecular cross-linking reaction can be efficiently promoted. However, excessive heating leads to the cleavage and decomposition of the molecular main chain, so the heating temperature is preferably kept within a temperature range 10 to 30 ° C. higher than the melting point of the fluororesin.
（芳香族ポリアミド及びカーボンブラック）
本発明で用いる芳香族ポリアミドは、耐熱性および補強性から繊維状芳香族ポリアミドが望ましい。ここで繊維状芳香族ポリアミドとは、芳香族ポリアミドの繊維径に対し繊維長さが１０倍以上のものである。繊維長さが１０倍以上であれば、改質ふっ素樹脂組成物の耐摩耗性向上への著しい効果が得られる。
(Aromatic polyamide and carbon black)
The aromatic polyamide used in the present invention is preferably a fibrous aromatic polyamide in view of heat resistance and reinforcement. Here, the fibrous aromatic polyamide has a fiber length of 10 times or more with respect to the fiber diameter of the aromatic polyamide. When the fiber length is 10 times or more, a remarkable effect for improving the abrasion resistance of the modified fluororesin composition can be obtained.
本発明で用いるカーボンブラックとしては、一次粒子の平均粒径が５０ｎｍ以下であることが望ましい。ここで平均粒径とは、電子顕微鏡により測定した一次粒子の粒径の粒度分布から算術平均にて算出して得られる平均値である。また、一次粒子の結晶子の大きさが５ｎｍ以下、かつ結晶子の厚さが０．５ｎｍ以下であることが好ましい。これらの範囲内であれば、改質ふっ素樹脂組成物の特に耐摩耗性向上への大幅な効果が得られる。ここで結晶子とは、単位結晶とみなせる最大の集まりのことをいう。また、結晶子の大きさ、結晶子の厚さは、例えば、Ｘ線回折によって求めることができる。 The carbon black used in the present invention desirably has an average primary particle size of 50 nm or less. Here, the average particle diameter is an average value obtained by arithmetic mean calculation from the particle size distribution of the primary particle diameter measured by an electron microscope. Moreover, it is preferable that the primary particle has a crystallite size of 5 nm or less and a crystallite thickness of 0.5 nm or less. If it is in these ranges, the significant effect for the abrasion resistance improvement of the modified fluororesin composition can be obtained. Here, the crystallite means the largest group that can be regarded as a unit crystal. Further, the size of the crystallite and the thickness of the crystallite can be obtained by, for example, X-ray diffraction.
改質ふっ素樹脂、芳香族ポリアミド、カーボンブラックの総重量は、有機ポリマ、改質ふっ素樹脂、芳香族ポリアミド、カーボンブラックを含む混合物の全重量に対し１０〜５０重量部であり、その中で前記改質ふっ素樹脂の重量が前記混合物の全重量に対し５〜３０重量部、望ましくは１５〜３０重量部、前記芳香族ポリアミドの重量が前記混合物の全重量に対し２〜１５重量部、より望ましくは５〜１０重量部、前記カーボンブラックの重量が前記混合物の全重量に対し１〜１０重量部、より望ましくは１〜５重量部の範囲となるように、それぞれ混合させることが望ましい。これらの範囲を下回る場合、改質ふっ素樹脂組成物の耐摩耗性向上への効果が小さく、またこれらの範囲を超えた場合には、改質ふっ素樹脂組成物の引張特性、曲げ強度などの機械的特性や加工性などの低下を招く。 The total weight of the modified fluororesin, aromatic polyamide, and carbon black is 10 to 50 parts by weight with respect to the total weight of the mixture containing the organic polymer, modified fluororesin, aromatic polyamide, and carbon black. The weight of the modified fluororesin is 5 to 30 parts by weight, preferably 15 to 30 parts by weight with respect to the total weight of the mixture, and the weight of the aromatic polyamide is more preferably 2 to 15 parts by weight with respect to the total weight of the mixture. Is preferably mixed so that the weight of the carbon black is 1 to 10 parts by weight, more preferably 1 to 5 parts by weight with respect to the total weight of the mixture. Below these ranges, the effect of improving the abrasion resistance of the modified fluororesin composition is small, and when exceeding these ranges, the mechanical properties such as tensile properties and bending strength of the modified fluororesin composition are low. Cause deterioration of mechanical properties and workability.
また、本実施の形態に係る改質ふっ素樹脂組成物には、前記構成に加え、さらに固体潤滑剤が含まれていてもよく、潤滑性をさらに上げることも可能である。固体潤滑剤としては、グラファイトと２硫化モリブデンから選ばれた１種以上のものを用いる。 Further, the modified fluororesin composition according to the present embodiment may further contain a solid lubricant in addition to the above-described configuration, and the lubricity can be further improved. As the solid lubricant, one or more selected from graphite and molybdenum disulfide are used.
以上の構成である改質ふっ素樹脂組成物を焼成、圧縮成形するなどして、本実施の形態に係る改質ふっ素樹脂成形体が得られる。 The modified fluororesin composition according to the present embodiment is obtained by firing and compression molding the modified fluororesin composition having the above configuration.
本実施の形態の作用を説明する。 The operation of the present embodiment will be described.
本実施の形態に係る改質ふっ素樹脂組成物は、有機ポリマと、未改質のふっ素樹脂に電離性放射線を照射することにより改質した改質ふっ素樹脂と、芳香族ポリアミドと、カーボンブラックとを混合してなる。 The modified fluororesin composition according to the present embodiment includes an organic polymer, a modified fluororesin modified by irradiating an unmodified fluororesin with ionizing radiation, an aromatic polyamide, and carbon black. Mixed.
このため、改質ふっ素樹脂組成物及びこれを用いて成形された改質ふっ素樹脂成形体の耐摩耗性が著しく向上する。この理由について詳細は不明であるが、改質ふっ素樹脂と芳香族ポリアミドの組み合わせにより、しゅう動面相手材に転移膜を形成しやすくなること、および芳香族ポリアミドとカーボンブラックとの組み合わせにより、組成全体の弾性率が上がり、高温下や高面圧下での変形が抑制されること、さらには加重集中点として作用する結果、バルクへの負荷が軽減されるためと推定する。これらの相乗的な作用で、改質ふっ素樹脂組成物及び改質ふっ素樹脂成形体の大幅な耐摩耗性の向上が発現するものと推定している。 For this reason, the abrasion resistance of the modified fluororesin composition and the modified fluororesin molded body molded using the same is significantly improved. Although the details of this reason are unknown, the combination of the modified fluororesin and the aromatic polyamide makes it easier to form a transition film on the sliding surface mating material, and the combination of the aromatic polyamide and carbon black It is estimated that the overall elastic modulus is increased, the deformation under high temperature and high surface pressure is suppressed, and further, the load on the bulk is reduced as a result of acting as a weighted concentration point. These synergistic effects are presumed to significantly improve the wear resistance of the modified fluororesin composition and the modified fluororesin molded article.
したがって、本実施形態に係る改質ふっ素樹脂組成物及び改質ふっ素樹脂成形体は、高温下や高面圧下での耐摩耗性を向上させ、従来よりも高面圧のしゅう動環境下でも使用することができるため、耐摩耗性に優れ、クリープ変形が小さく、しかもふっ素樹脂本来の良好な特性を保持しうる。これにより、本発明は有機ポリマの応用範囲を広げる上で大きく貢献するものである。 Therefore, the modified fluororesin composition and the modified fluororesin molded body according to the present embodiment have improved wear resistance at high temperatures and high surface pressures, and are used even in a sliding environment with higher surface pressure than before. Therefore, the wear resistance is excellent, the creep deformation is small, and the original good characteristics of the fluororesin can be maintained. Thus, the present invention greatly contributes to expanding the application range of organic polymers.
本実施の形態に係る改質ふっ素樹脂成形体の用途としては、しゅう動部品、半導体関連製造部品などがあり、幅広い用途が期待できる。 Applications of the modified fluororesin molding according to the present embodiment include sliding parts and semiconductor-related manufacturing parts, and a wide range of uses can be expected.
有機ポリマとしてはＰＴＦＥ（旭硝子社の商品名Ｐ−６３Ｐ）を使用した。また、このＰＴＦＥを用い、酸素分圧約１３３３Ｐａ（１０ｔｏｒｒ）、窒素（１０１３２５Ｐａ（７６０ｔｏｒｒ））雰囲気下、３４０℃の温度のもとで電子線（加速電圧１．５ＭｅＶ）を１２０ｋＧｙ照射し、改質を行って改質ふっ素樹脂を作製した。その後、増幸産業（株）のスーパーマスコライダーＭＫＺＡ１０−１５Ｊにより平均粒径２０μｍ、最大粒径９０μｍに微粉砕し、粉末状の改質ふっ素樹脂とした。この粉末状の改質ふっ素樹脂を窒素雰囲気の下、３２５℃で１．５時間熱処理を行い、さらにホソカワミクロン（株）のコントラプレックス２５０ＣＷを用いて解砕し、熱処理した粉末状の改質ふっ素樹脂を作製した。この熱処理した粉末状の改質ふっ素樹脂の融点は、パーキンエルマー社製の示差走査熱量計Pyris１ ＴＧＡによる窒素中、昇温速度１０℃／分での測定により、３１８℃であった。降温速度１０℃／分での測定では２７０〜３１０℃の結晶化曲線の面積から、熱処理した粉末状の改質ふっ素樹脂の結晶化熱量は３３．５Ｊ／ｇであった。 PTFE (trade name P-63P, Asahi Glass Co., Ltd.) was used as the organic polymer. Further, this PTFE was used to irradiate an electron beam (acceleration voltage of 1.5 MeV) at 120 kGy under an oxygen partial pressure of about 1333 Pa (10 torr) and nitrogen (101325 Pa (760 torr)) at a temperature of 340 ° C. A modified fluororesin was produced. Thereafter, it was finely pulverized to an average particle size of 20 μm and a maximum particle size of 90 μm by Supermass Collider MKZA10-15J from Masuyuki Sangyo Co., Ltd. to obtain a powdery modified fluororesin. This powdery modified fluororesin was heat-treated at 325 ° C. for 1.5 hours in a nitrogen atmosphere, and further pulverized using Hosokawa Micron's Contraplex 250CW, and the heat-treated powdered modified fluororesin Was made. The melting point of the heat-treated powdery modified fluororesin was 318 ° C. as measured by a differential scanning calorimeter Pyris1 TGA manufactured by PerkinElmer in nitrogen at a heating rate of 10 ° C./min. In the measurement at a temperature lowering rate of 10 ° C./min, from the area of the crystallization curve of 270 to 310 ° C., the crystallization heat amount of the heat-treated powdered modified fluororesin was 33.5 J / g.
この熱処理した粉末状の改質ふっ素樹脂を用い、表１に示す組成に基づき配合し、実施例１〜６、比較例１〜４の各試料を作製し、これらの特性評価を行った。材料の混合にはヘンシェルミキサを用い、１０℃の雰囲気下で３分間行った。このコンパウンドをホットホーミングにより成形した。粉体をφ４５、高さ８０ｍｍの金型に充填し、３６０℃で２時間加熱後、常温に冷却して金型ごと取り出す。その直後に圧力５０ＭＰａで圧縮成形し、ビットを作製した。これを厚さ１ｍｍおよび２ｍｍに切削し、評価用シートを得た。厚さ１ｍｍの評価用シートは引張試験用、厚さ２ｍｍの評価用シートはしゅう動特性評価用とした。なお、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。 Using this heat-treated powdery modified fluororesin, it was blended based on the composition shown in Table 1, and samples of Examples 1 to 6 and Comparative Examples 1 to 4 were prepared, and their characteristics were evaluated. The materials were mixed using a Henschel mixer for 3 minutes in an atmosphere of 10 ° C. This compound was molded by hot homing. The powder is filled in a mold having a diameter of 45 mm and a height of 80 mm, heated at 360 ° C. for 2 hours, cooled to room temperature, and taken out together with the mold. Immediately after that, compression molding was performed at a pressure of 50 MPa to produce a bit. This was cut into a thickness of 1 mm and 2 mm to obtain an evaluation sheet. The evaluation sheet having a thickness of 1 mm was used for a tensile test, and the evaluation sheet having a thickness of 2 mm was used for evaluation of sliding characteristics. The number of measurements was 3 points for each sample, and the arithmetic average of these was the average value.
（１）しゅう動特性
試験にはスラスト摩耗試験装置を使用し、ＪＩＳ ７２１８に準じ、表面粗さＲａ０．２μｍに加工したＳＵＳ３０４製の円筒リング（外径２５．６ｍｍ、内径２０．６ｍｍ）に対し試験片（外径２５．６ｍｍ、内径２０．６ｍｍ、厚さ２ｍｍ）を接触させ、試験を行った。この試験はオイル雰囲気中で行い、オイルには圧縮機用で使用される日立スクリュー圧縮機用オイル（New Screw オイル2000）を用いた。しゅう動特性評価は圧力５ＭＰａ、速度１ｍ／ｓｅｃ、温度２４℃の条件で行った。２４時間後の重量減少を測定し、比摩耗量（×１０-8ｍｍ3／Ｎｍ）を算出すると共に、定常状態のトルク曲線から摩擦係数を求めた。
(1) Sliding property test A thrust wear tester was used for the test. For a cylindrical ring made of SUS304 (outer diameter 25.6 mm, inner diameter 20.6 mm) processed to surface roughness Ra 0.2 μm according to JIS 7218. A test piece (outer diameter 25.6 mm, inner diameter 20.6 mm, thickness 2 mm) was brought into contact and tested. This test was performed in an oil atmosphere, and the oil for Hitachi screw compressor (New Screw oil 2000) used for the compressor was used as the oil. The sliding characteristics were evaluated under conditions of a pressure of 5 MPa, a speed of 1 m / sec, and a temperature of 24 ° C. The weight loss after 24 hours was measured, the specific wear amount (× 10 −8 mm 3 / Nm) was calculated, and the friction coefficient was determined from the steady state torque curve.
（２）引張試験
前記摩耗試験片と同様の厚さ１ｍｍシートを用い、これを２３℃に１昼夜放置後、ＪＩＳ Ｋ７１１３に準拠し、引張速度２００ｍｍ／分の条件で引張試験を行った。使用したダンベルは２（１／２）号形である。
(2) Tensile test A 1 mm thick sheet similar to the above-mentioned abrasion test piece was used, and this was left to stand at 23 ° C for one day and night, and then a tensile test was performed in accordance with JIS K7113 under a tensile speed of 200 mm / min. The dumbbell used is a 2 (1/2) type.
実施例１〜６、比較例１〜４の各試験片について、しゅう動特性を示す比摩耗量と摩擦係数の測定結果と、引張特性を示す引張強さと伸びの測定結果とを、表１に示す。 Table 1 shows the measurement results of the specific wear amount and the friction coefficient indicating the sliding characteristics, and the tensile strength and elongation measurement results indicating the tensile characteristics for each of the test pieces of Examples 1 to 6 and Comparative Examples 1 to 4. Show.
表１に示すように、実施例１〜６は、ＰＴＦＥ、改質ＰＴＦＥ、芳香族ポリアミド、カーボンブラックを含む組成からなるので、いずれも比摩耗量が小さく耐摩耗性に優れ、かつ摩擦係数も低いレベルを保持している。さらに引張強さおよび伸びも高い値を示している。 As shown in Table 1, Examples 1 to 6 are composed of a composition containing PTFE, modified PTFE, aromatic polyamide, and carbon black. Holding a low level. Furthermore, the tensile strength and elongation are also high.
これに対し、芳香族ポリアミドおよびカーボンブラックを併用していない比較例１は、比摩耗量が大きく耐摩耗性に劣る。また、カーボンブラックを併用していない比較例２、芳香族ポリアミドを併用していない比較例３、改質ＰＴＦＥを混和していない比較例４は、いずれも比摩耗量が大きく、比較例１と同様、耐摩耗性に劣る。 On the other hand, the comparative example 1 which does not use aromatic polyamide and carbon black together has a large specific wear amount and is inferior in wear resistance. Further, Comparative Example 2 in which carbon black is not used in combination, Comparative Example 3 in which aromatic polyamide is not used in combination, and Comparative Example 4 in which no modified PTFE is mixed are large in specific wear amount. Similarly, it is inferior in abrasion resistance.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008199544A JP4956505B2 (en) | 2008-08-01 | 2008-08-01 | MODIFIED FLUORINE RESIN COMPOSITION AND MODIFIED FLUORINE RESIN MOLDED BODY |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008199544A JP4956505B2 (en) | 2008-08-01 | 2008-08-01 | MODIFIED FLUORINE RESIN COMPOSITION AND MODIFIED FLUORINE RESIN MOLDED BODY |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2010037382A true JP2010037382A (en) | 2010-02-18 |
| JP4956505B2 JP4956505B2 (en) | 2012-06-20 |
Family
ID=42010267
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2008199544A Active JP4956505B2 (en) | 2008-08-01 | 2008-08-01 | MODIFIED FLUORINE RESIN COMPOSITION AND MODIFIED FLUORINE RESIN MOLDED BODY |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4956505B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020007442A (en) * | 2018-07-06 | 2020-01-16 | 日立金属株式会社 | Process for producing fluororesin powder |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05112723A (en) * | 1991-10-22 | 1993-05-07 | Sutaaraito Kogyo Kk | Conductive composition for sliding member |
| JP2000169738A (en) * | 1998-09-29 | 2000-06-20 | Oiles Ind Co Ltd | Resin composition for sliding member and plain bearing |
| JP2000290409A (en) * | 1999-04-08 | 2000-10-17 | Hitachi Cable Ltd | Modified fluoreresin, modified fluororesin composition and molded product of modified fluoreoresin |
| JP2004331814A (en) * | 2003-05-07 | 2004-11-25 | Hitachi Cable Ltd | Modified fluororesin composition and modified fluororesin molded product |
-
2008
- 2008-08-01 JP JP2008199544A patent/JP4956505B2/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05112723A (en) * | 1991-10-22 | 1993-05-07 | Sutaaraito Kogyo Kk | Conductive composition for sliding member |
| JP2000169738A (en) * | 1998-09-29 | 2000-06-20 | Oiles Ind Co Ltd | Resin composition for sliding member and plain bearing |
| JP2000290409A (en) * | 1999-04-08 | 2000-10-17 | Hitachi Cable Ltd | Modified fluoreresin, modified fluororesin composition and molded product of modified fluoreoresin |
| JP2004331814A (en) * | 2003-05-07 | 2004-11-25 | Hitachi Cable Ltd | Modified fluororesin composition and modified fluororesin molded product |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020007442A (en) * | 2018-07-06 | 2020-01-16 | 日立金属株式会社 | Process for producing fluororesin powder |
| JP7159653B2 (en) | 2018-07-06 | 2022-10-25 | 日立金属株式会社 | Method for producing fluororesin powder |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4956505B2 (en) | 2012-06-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3566805B2 (en) | Sliding member | |
| JP5472689B2 (en) | Modified fluororesin composition and molded body | |
| US6465575B1 (en) | Product having reduced friction and improved abrasion resistance | |
| JP4844739B2 (en) | Modified fluororesin composition and molded body | |
| JP2004210839A (en) | Fluororesin composition | |
| JP3948313B2 (en) | Sliding member | |
| JP2004331814A (en) | Modified fluororesin composition and modified fluororesin molded product | |
| JP2021105179A (en) | Uncrosslinked rubber composition, rubber product produced using the same, and method for producing the same | |
| JP6645606B2 (en) | Resin composition | |
| JP4956505B2 (en) | MODIFIED FLUORINE RESIN COMPOSITION AND MODIFIED FLUORINE RESIN MOLDED BODY | |
| JP3672428B2 (en) | Modified fluoroplastic molding | |
| JP5193083B2 (en) | Engineering plastic composition and molded article thereof | |
| JP4044725B2 (en) | Method for producing modified engineering plastics | |
| JP4645453B2 (en) | Modified fluororesin composition and molded article comprising the same | |
| JP4973021B2 (en) | Modified fluororesin composition and molded body | |
| JP3672429B2 (en) | Modified fluororesin powder | |
| JP2009013402A (en) | Modified fluoropolymer composition and modified fluoropolymer molding | |
| US6989415B1 (en) | Modified fluoroplastic composition and modified fluoroplastic molded article | |
| JP2003026883A (en) | Abrasion-resistant fluororesin composition and member for sliding | |
| JP2010037357A (en) | Modified fluororesin composition and modified fluororesin molded product | |
| JP3624730B2 (en) | Modified fluororesin | |
| JP3903547B2 (en) | Oriented fluororesin molded body and method for producing the same | |
| JP4978081B2 (en) | Modified fluororesin composition and molded body using the same | |
| JP2001082611A (en) | Valve seat or packing | |
| JP2001240682A (en) | Method for producing modified fluororesin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20100917 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20111226 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120110 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120127 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20120306 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20120316 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4956505 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150323 Year of fee payment: 3 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313115 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |