JP4844739B2 - Modified fluororesin composition and molded body - Google Patents
Modified fluororesin composition and molded body Download PDFInfo
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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・配管等の組成物及び成形体に関するものである。 The present invention comprises a composition such as a sliding part, a seal product, a packing, a gasket, a semiconductor manufacturing container, jig, and piping made of a modified fluororesin having excellent wear resistance and creep resistance under a high surface pressure. The present invention relates to a molded body.
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。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く、ふっ素樹脂にガラス繊維やカーボン繊維等の充てん材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。しかしこのような手法を施しても、高面圧下で使用される場合、ふっ素樹脂組成物の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、ふっ素樹脂に種々の充てん材を添加する手法が検討されている。 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. However, wear and creep deformation are large in sliding environments and compression environments at high temperatures, and measures to improve wear and creep deformation have been taken by adding fillers such as glass fiber and carbon fiber to fluororesin. It was. However, even when such a method is applied, the abrasion resistance of the fluororesin composition is not sufficient when used under high surface pressure, and there is a problem in durability. As a countermeasure against this, a technique of adding various fillers to the fluororesin has been studied.
ところが、上述した種々の充てん材を添加したふっ素樹脂組成物であっても、用途によっては耐摩耗性が十分とは言えない状況にある。 However, even in the fluororesin composition to which the various fillers described above are added, the wear resistance is not sufficient depending on the application.
従って本発明の目的は、高面圧下での耐摩耗性に優れ、しかもふっ素樹脂本来の良好な特性を保持しうる改質ふっ素樹脂組成物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 composition and a molded article that are excellent in wear resistance under high surface pressure and that can retain the original good properties of the fluororesin.
上記の目的を達成するために、請求項１の発明は、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重合体から選ばれた少なくとも１種以上である有機ポリマと電離性放射線により改質したふっ素樹脂に、ポリアミドイミド及び有機繊維を混合してなり、上記改質ふっ素樹脂、ポリアミドイミド、及び有機繊維のトータル重量は、全重量の１０重量部〜５０重量部であり、その中で改質ふっ素樹脂は全重量の５重量部〜３０重量部、ポリアミドイミドは全重量の２重量部〜１５重量部、有機繊維は全重量の３重量部〜１０重量部であることを特徴とする改質ふっ素樹脂組成物である。
In order to achieve the above object, the invention of claim 1 is selected from a tetrafluoroethylene polymer, a tetrafluoroethylene-perfluoro (alkyl vinyl ether) polymer, and a tetrafluoroethylene-hexafluoropropylene polymer. and a fluorine resin modified by an organic polymer with ionizing radiation is at least 1 or more, Ri Na were mixed polyamideimide and organic fibers, the modified fluoropolymer, total weight of the polyamide-imide and organic fibers, is 10 to 50 parts by weight of the total weight, of which the modified fluororesin is 5 to 30 parts by weight of the total weight, the polyamideimide is 2 to 15 parts by weight of the total weight, and the organic fibers are all It is a modified fluororesin composition characterized by being 3 to 10 parts by weight .
請求項２の発明は、上記有機繊維がカーボン繊維である請求項１記載の改質ふっ素樹脂組成物である。
The invention of claim 2 is a modified fluoropolymer composition of claim 1 Symbol mounting said organic fiber is a carbon fiber.
請求項３の発明は、上記有機繊維が、長さ１〜３００μｍ、アスペクト比１〜５００である請求項１または２記載の改質ふっ素樹脂組成物である。
The invention according to claim 3 is the modified fluororesin composition according to claim 1 or 2 , wherein the organic fiber has a length of 1 to 300 μm and an aspect ratio of 1 to 500.
請求項４の発明は、上記ポリテトラフルオロエチレン共重合体が、１モル％以内の第２成分もしくは複数の第３成分の異種フルオロモノマを含有する請求項１記載の改質ふっ素樹脂組成物である。
A fourth aspect of the present invention, the polytetrafluoroethylene copolymer, in modified fluoropolymer composition according to claim 1, containing 1 mol% within the second component or a plurality of third component heterologous fluoromonomer is there.
請求項５の発明は、上記改質ふっ素樹脂の結晶化熱量が４０Ｊ／ｇ以下、融点が３２５℃以下である請求項１〜４いずれか記載の改質ふっ素樹脂組成物である。
The invention according to claim 5 is the modified fluororesin composition according to any one of claims 1 to 4 , wherein the heat of crystallization of the modified fluororesin is 40 J / g or less and the melting point is 325 ° C. or less.
請求項６の発明は、上記改質ふっ素樹脂のふっ素樹脂が、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重合体から選ばれた少なくとも１種以上である請求項１〜５いずれか記載の改質ふっ素樹脂組成物である。
In the invention of claim 6, the fluororesin of the modified fluororesin is selected from a tetrafluoroethylene polymer, a tetrafluoroethylene-perfluoro (alkyl vinyl ether) polymer, and a tetrafluoroethylene-hexafluoropropylene polymer. The modified fluororesin composition according to any one of claims 1 to 5, which is at least one selected from the above.
請求項７の発明は、上記改質ふっ素樹脂が、ふっ素樹脂を酸素濃度１０ｔｏｒｒ以下の不活性化ガス雰囲気下で、且つその融点以上に加熱し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請求項１〜６いずれか記載の改質ふっ素樹脂組成物である。
In the invention of claim 7, the modified fluororesin has a dose of 1 kGy to 10 MGy of ionizing radiation in an inert gas atmosphere having an oxygen concentration of 10 torr or less and heated above its melting point. The modified fluororesin composition according to any one of claims 1 to 6, which is irradiated with
請求項８の発明は、請求項１〜７いずれか記載の改質ふっ素樹脂組成物を用いて成形したことを特徴とする成形体である。
The invention according to claim 8 is a molded article formed by using the modified fluororesin composition according to any one of claims 1 to 7 .
本発明によれば、改質ふっ素樹脂組成物に高面圧下で優れた耐摩耗性を付与でき、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 modified fluororesin composition can be provided with excellent wear resistance under high surface pressure, and can greatly contribute to widening the application range of organic polymers.
本実施の形態に係る改質ふっ素樹脂組成物は、有機ポリマと電離性放射線により改質したふっ素樹脂（以下、改質ふっ素樹脂という）に、ポリアミドイミド及び有機繊維を混合してなるものである。 The modified fluororesin composition according to the present embodiment is formed by mixing polyamideimide and organic fibers in an organic polymer and a fluororesin modified with ionizing radiation (hereinafter referred to as a modified fluororesin). .
本実施の形態に係る改質ふっ素樹脂組成物における改質ふっ素樹脂、ポリアミドイミド、及び有機繊維のトータル重量は、改質ふっ素樹脂組成物の全重量の１０重量部〜５０重量部であり、その中で改質ふっ素樹脂は全重量の５重量部〜３０重量部、ポリアミドイミドは全重量の２重量部〜１５重量部、有機繊維は全重量の３重量部〜１０重量部とされる。 The total weight of the modified fluororesin, the polyamideimide, and the organic fiber in the modified fluororesin composition according to the present embodiment is 10 to 50 parts by weight of the total weight of the modified fluororesin composition, Among them, the modified fluororesin is 5 to 30 parts by weight of the total weight, the polyamideimide is 2 to 15 parts by weight of the total weight, and the organic fiber is 3 to 10 parts by weight of the total weight.
改質ふっ素樹脂組成物に用いる有機繊維としては、カーボン繊維が最も好ましく、長さ１〜３００μｍ、アスペクト比１〜５００であることが望ましい。繊維長さが規定値以下では耐摩耗性向上に大きな効果が認められず、規定値を超えると分散性が低下し、耐摩耗性の大幅な向上が損なわれる。アスペクト比（繊維径に対する繊維長さの比）についても規定値以下では耐摩耗性向上に有効な効果が見られず、また規定値を超えると分散性が著しく劣り、結果として耐摩耗性の低下を招く。 The organic fiber used in the modified fluororesin composition is most preferably a carbon fiber, and preferably has a length of 1 to 300 μm and an aspect ratio of 1 to 500. If the fiber length is less than the specified value, no significant effect on improving the wear resistance is observed. If the fiber length exceeds the specified value, the dispersibility is lowered and the significant improvement in wear resistance is impaired. When the aspect ratio (ratio of fiber length to fiber diameter) is less than the specified value, no effective effect for improving the wear resistance is observed, and when the specified value exceeds the specified value, the dispersibility is remarkably inferior, resulting in a decrease in wear resistance. Invite.
改質ふっ素樹脂組成物に用いるポリアミドイミドとしては、分散性を考慮してパウダ状が望ましく、最大粒径で２００μｍ以下が好適である。これを超えると、引張特性、特に伸びの低下が著しくなる。 The polyamideimide used in the modified fluororesin composition is preferably powdery in consideration of dispersibility, and the maximum particle size is preferably 200 μm or less. Beyond this, the tensile properties, particularly the elongation, are significantly reduced.
有機ポリマとしては、ニトリルゴム、ふっ素ゴム等や、エポキシ樹脂、ナイロン、芳香族系ポリマ等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い。ふっ素樹脂として、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）が挙げられる。 Examples of the organic polymer include nitrile rubber, fluorine rubber and the like, and plastics such as epoxy resin, nylon and aromatic polymer, among which fluorine resin is most preferable. Specific examples of the fluororesin include tetrafluoroethylene copolymer (PTFE), tetrafluoroethylene-fluoroalkoxytrifluoroethylene copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), poly A tetrafluoroethylene-perfluorodioxysol copolymer (THF / PDD) is mentioned.
上記ＰＴＦＥの中には、第２成分、例えばパーフルオロ（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、好ましくは０．２モル％以下含有するものも含まれる。また、上記ふっ素樹脂の場合、その分子構造中に少量の第３成分、例えば異種フルオロモノマを含むこともできる。第３成分は、１種類又は２種類以上のいずれであってもよい。 The PTFE contains 1 mol% or less of a polymer component based on a second component, for example, a copolymerizable monomer such as perfluoro (alkyl vinyl ether), hexafluoropropylene, (perfluoroalkyl) ethylene, or chlorotrifluoroethylene. Further, those containing 0.2 mol% or less are also included. Moreover, in the case of the said fluororesin, a small amount of 3rd components, for example, a different fluoromonomer, can also be included in the molecular structure. The third component may be one type or two or more types.
改質ふっ素樹脂は、その融点が３２５℃以下、結晶化熱量が４０Ｊ／ｇ以下であることが望ましく、これらが規定値を超えると、耐摩耗性や耐クリープ性が著しく低下する。改質ふっ素樹脂を構成するふっ素樹脂がＰＦＡのときは、融点を３０５℃以下、結晶化熱量を２６Ｊ／ｇ以下とすることが好ましく、ＦＥＰのときは融点を２７５℃以下、結晶化熱量を１１Ｊ／ｇ以下とすることが好ましい。 The modified fluororesin preferably has a melting point of 325 ° C. or less and a crystallization heat of 40 J / g or less, and when these exceed the specified values, the wear resistance and creep resistance are significantly reduced. When the fluorine resin constituting the modified 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.
これらの融点及び結晶化熱量（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。 A differential scanning calorimeter (DSC) is used for evaluation of these melting points and crystallization calorific values (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 second temperature increase is the melting point, and the crystallization heat quantity is determined from the exothermic peak at the second temperature decrease and the peak area surrounded by the baseline according to JIS K7122.
改質ふっ素樹脂は、ふっ素樹脂を酸素濃度１０ｔｏｒｒ以下の不活性化ガス雰囲気下で、且つその融点以上に加熱した状態において、そのふっ素樹脂に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できる。 The modified fluororesin irradiates the fluororesin with ionizing radiation within a dose range of 1 kGy to 10 MGy in an inert gas atmosphere having an oxygen concentration of 10 torr or less and in a state of being heated above its melting point. Can be manufactured.
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。 As ionizing radiation, γ-rays, electron beams, X-rays, neutron beams, high-energy ions, or the like 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、この融点である３２７℃よりも高い温度に加熱して電離性放射線を照射する必要があり、またＰＦＡ、ＦＥＰを使用する場合には、前者を３１０℃、後者を２７５℃に特定される融点よりも高い温度に加熱して電離性放射線を照射する。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よ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 PTFE is used as the fluororesin, it is necessary to irradiate with ionizing radiation by heating to a temperature higher than the melting point of 327 ° C. When using PFA and FEP, the former is 310 The latter is heated to a temperature higher than the melting point specified at 275 ° C. and irradiated with ionizing radiation. Heating the fluororesin above 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 should be kept within a range of 10 to 30 ° C. higher than the melting point of the fluororesin.
また、本実施の形態に係る改質ふっ素樹脂組成物に、この他に２硫化モリブデン、グラファイト等の固体潤滑剤等を併用して混合し、潤滑性を上げることも可能である。 In addition, the modified fluororesin composition according to the present embodiment can be mixed with a solid lubricant such as molybdenum disulfide and graphite to improve lubricity.
次に、本実施の形態の作用を説明する。 Next, the operation of the present embodiment will be described.
本発明者らが高面圧下での耐摩耗性向上について種々検討した結果、改質ふっ素樹脂、ポリアミドイミド及び有機繊維を併用することにより、耐摩耗性が著しく向上することが分かり、本発明に至った。よって、本実施の形態に係る改質ふっ素樹脂組成物では、有機ポリマ及び改質ふっ素樹脂に、ポリアミドイミド及び有機繊維を添加、混合している。 As a result of various studies on the improvement of wear resistance under high surface pressure by the present inventors, it was found that the wear resistance is remarkably improved by using a modified fluororesin, polyamideimide and organic fiber in combination. It came. Therefore, in the modified fluororesin composition according to the present embodiment, polyamideimide and organic fibers are added to and mixed with the organic polymer and the modified fluororesin.
改質ふっ素樹脂、ポリアミドイミド及び有機繊維を併用することによって耐摩耗性が著しく向上する理由についての詳細は不明であるが、改質ふっ素樹脂とポリアミドイミドと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、及びポリアミドイミドと有機繊維との組み合わせにより、組成全体の弾性率が上がり高面圧での変形が抑制されると共に加重集中点として作用する結果、バルク（改質ふっ素樹脂組成物の成形体）への負荷が低減されることが推定される。これらの相乗的な作用で、大幅な耐摩耗性の向上が発現するものと推察される。 Details on the reason why the wear resistance is remarkably improved by using the modified fluororesin, polyamideimide and organic fiber in combination are unknown, but the combination of the modified fluororesin and polyamideimide makes it possible to As a result of the ease of forming a transition film and the combination of polyamideimide and organic fibers, the modulus of elasticity of the entire composition increases and deformation at high surface pressure is suppressed and it acts as a weighted concentration point. It is estimated that the load on the fluororesin composition molded body) is reduced. These synergistic actions are presumed to cause a significant improvement in wear resistance.
ポリアミドイミドと併用する有機繊維として、カーボン繊維が最も好ましい理由は、ふっ素樹脂にポリアミドイミドを混和した組成物を成形段階において高温で焼成する場合、ポリアミドイミドの一部が熱分解して成形体にボイドが生じやすくなり、結果として機械特性の低下を生じるおそれがあるが、ポリアミドイミドとカーボン繊維を併用することによって、ボイド発生を抑制することが可能となるためである。ボイド発生を抑制することができる理由についての詳細は不明であるが、ポリアミドイミドの熱分解をカーボン繊維が抑制する効果があるためと考えられる。 Carbon fiber is the most preferable organic fiber used in combination with polyamideimide. When a composition in which polyamideimide is mixed with a fluororesin is baked at a high temperature in the molding stage, part of the polyamideimide is thermally decomposed into a molded body. This is because voids are likely to occur, resulting in a decrease in mechanical properties, but it is possible to suppress the generation of voids by using polyamideimide and carbon fibers in combination. Although the details about the reason why the generation of voids can be suppressed are unclear, it is considered that the carbon fibers have an effect of suppressing the thermal decomposition of polyamideimide.
以上より、有機ポリマと改質ふっ素樹脂に、ポリアミドイミド及び有機繊維を混合することで、ふっ素樹脂本来の良好な特性、すなわち低摩擦性、耐熱性、電気特性、耐薬品性やクリーン性（非汚染性）を保持したまま、高面圧下での耐摩耗性に優れた改質ふっ素樹脂組成物を得ることができる。 As described above, by mixing polyamideimide and organic fiber with organic polymer and modified fluororesin, the original good characteristics of fluororesin, that is, low friction, heat resistance, electrical characteristics, chemical resistance and cleanliness (non- A modified fluororesin composition excellent in abrasion resistance under high surface pressure can be obtained while maintaining (contamination).
また、上述した本実施の形態に係る改質ふっ素樹脂組成物を、任意の所定形状を有する金型に充填し、任意の所定圧力で成形することで、改質ふっ素樹脂成形体を得ることができる。この改質ふっ素樹脂成形体の用途としては、しゅう動部品、シール品、パッキン、ガスケット、半導体関連製造部品（容器・治具・配管）等の幅広い用途が期待できる。 Moreover, the modified fluororesin composition according to the present embodiment described above can be filled into a mold having an arbitrary predetermined shape and molded at an arbitrary predetermined pressure to obtain a modified fluororesin molded body. it can. A wide range of uses such as sliding parts, sealing products, packings, gaskets, semiconductor-related manufacturing parts (containers, jigs, and piping) can be expected as uses of the modified fluororesin molding.
実施例及び比較例を基にして、本発明を具体的に説明する。 The present invention will be specifically described based on Examples and Comparative Examples.
ＰＴＦＥ（旭硝子社製、商品名：Ｐ−１９２）に、酸素濃度１ｔｏｒｒ、窒素雰囲気下、３４０℃の温度のもとで電子線（加速電圧２ＭｅＶ）を１００ｋＧｙ照射し、改質を行った。これをジェットミルにより平均粒径２０μｍに微粉砕した。 Modification was performed by irradiating PTFE (manufactured by Asahi Glass Co., Ltd., trade name: P-192) with 100 kGy of an electron beam (acceleration voltage 2 MeV) under an oxygen concentration of 1 torr and a nitrogen atmosphere at a temperature of 340 ° C. This was finely pulverized to a mean particle size of 20 μm by a jet mill.
この改質ＰＴＦＥ（改質ふっ素樹脂）、ＰＴＦＥ（有機ポリマ）、ポリアミドイミド（平均粒径３０μｍ、最大粒径８０μｍ）、及びカーボン繊維（有機繊維）を組み合わせて混合し、各種コンパウンド（実施例１〜４及び比較例１〜３）を製造した。各種コンパウンドの組成を表１に示す。これらの材料の混合は、ミキサを用い、材料温度及び雰囲気温度を共に１５℃として行った。カーボン繊維としては、カーボン繊維Ａ（繊維径５μｍ、繊維長５０μｍ、アスペクト比１０）とカーボン繊維Ｂ（繊維径５μｍ、繊維長１００μｍ、アスペクト比２０）の２種類を用いた。実施例４のコンパウンドは、これらの材料の他に、２重量部の２硫化モリブデン（ダウコーニング社製、商品名：モリコートＺ）を含
む。
This modified PTFE (modified fluororesin), PTFE (organic polymer), polyamideimide (average particle size 30 μm, maximum particle size 80 μm), and carbon fiber (organic fiber) are combined and mixed to produce various compounds (Example 1). -4 and Comparative Examples 1-3) were produced. Table 1 shows the composition of various compounds. These materials were mixed using a mixer and the material temperature and the ambient temperature were both 15 ° C. Two types of carbon fibers, carbon fiber A (fiber diameter 5 μm, fiber length 50 μm, aspect ratio 10) and carbon fiber B (fiber diameter 5 μm, fiber length 100 μm, aspect ratio 20), were used. In addition to these materials, the compound of Example 4 contains 2 parts by weight of molybdenum disulfide (manufactured by Dow Corning, trade name: Moricoat Z).
各種コンパウンドを用いた成形体の作製では、実施例１及び比較例１ではフリーシンタ法を用い、他はホットホーミング法を用いた。圧縮成形にはφ４５×高さ８０ｍｍの金型を使用し、常温で５０ＭＰａの圧力を加え圧縮成形した。続いてフリーシンタ法では大気圧で３６０℃×２時間焼成することによりブロック成形体を作製し、一方、ホットホーミング法では焼成後、常温下に金型ごと取出し、成形圧２０ＭＰａで圧縮成形することによりブロック成形体を作製した。このようにして作製した各ブロック成形体に対して切削によって切り出しを行い、それぞれ試験片を作製した。 In the production of the molded body using various compounds, the free sintering method was used in Example 1 and Comparative Example 1, and the hot homing method was used for the others. For compression molding, a mold having a diameter of 45 mm and a height of 80 mm was used, and compression molding was performed by applying a pressure of 50 MPa at room temperature. Subsequently, in the free sintering method, a block molded body is prepared by firing at 360 ° C. for 2 hours at atmospheric pressure. On the other hand, in the hot homing method, after firing, the whole mold is taken out at room temperature and compression molded at a molding pressure of 20 MPa. Thus, a block molded body was produced. Each block molded body produced in this manner was cut out by cutting to produce a test piece.
得られた試験片の特性（ボイドの有無、しゅう動特性）評価を次に述べる。なお、各特性評価のための測定数は各試験片について３点とし、これらの算術平均を平均値とした。
各試験片の特性を表２に示す。
The characteristics (existence of voids, sliding characteristics) evaluation of the obtained test pieces are described below. The number of measurements for each characteristic evaluation was 3 points for each test piece, and the arithmetic average of these was the average value.
Table 2 shows the characteristics of each test piece.
ボイドの有無は、各ブロック成形体から厚さ１ｍｍのシートをスライスし、各シート表面を倍率２０倍の顕微鏡で観察し、ボイドの有無を調べた。 The presence or absence of voids was obtained by slicing a sheet having a thickness of 1 mm from each block molded body, and observing the surface of each sheet with a microscope with a magnification of 20 times to determine the presence or absence of voids.
しゅう動特性（耐摩耗性）の評価は、リングオンディスク摩耗試験装置を使用し、ＪＩＳ Ｋ７２１８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、表面粗さＲａ０．２μｍ）を用い、圧力４ＭＰａ、速度６０ｍ／ｍｉｎの条件で行った。試験雰囲気は空気中、２０℃とした。試験開始から２４時間後、重量減少を測定し、比摩耗量ＶSAを下記の式から求めると共に、摩擦係数を測定した。 The evaluation of the sliding characteristics (abrasion resistance) is performed using a ring-on-disk wear test device, and in accordance with JIS K7218, a cylindrical ring made of SUS304 (outer diameter 25.6 mm, inner diameter 20.6 mm) with a specimen (outer diameter 25.6 mm, inner diameter 20.6 mm, thickness 1 mm), SUS304 plate (length 30 mm, width 30 mm, thickness 5 mm, surface roughness Ra 0.2 μm) was used as the mating material, pressure 4 MPa, speed 60 m / It carried out on condition of min. The test atmosphere was 20 ° C. in air. After 24 hours from the start of the test, the weight loss was measured, the specific wear amount V SA was determined from the following formula, and the friction coefficient was measured.
ＶSA＝Ｖ／（Ｐ・Ｌ）
Ｖ：摩耗量、Ｐ：試験荷重、Ｌ：平均滑り距離
V SA = V / (P · L)
V: wear amount, P: test load, L: average slip distance
表２に示すように、実施例１〜４の各試験片は、何れもボイドは見られなかった。また、各試験片は、何れも比摩耗量が３５〜９５（×１０-8ｍｍ3／Ｎｍ）と小さいと共に摩擦係数も０．１８前後と低く、耐摩耗性に優れていた。 As shown in Table 2, no void was found in any of the test pieces of Examples 1 to 4. Further, each test piece had a small specific wear amount of 35 to 95 (× 10 −8 mm 3 / Nm) and a low friction coefficient of around 0.18, and was excellent in wear resistance.
これに対し比較例１の試験片では、成形体にボイドが見られ、更には比摩耗量が１５００（×１０-8ｍｍ3／Ｎｍ）と高く、耐摩耗性に劣っていた。 On the other hand, in the test piece of Comparative Example 1, voids were observed in the molded body, and the specific wear amount was as high as 1500 (× 10 −8 mm 3 / Nm), which was inferior in wear resistance.
また、ポリアミドイミドを含まない比較例２、改質ふっ素樹脂を含まない比較例３の各試験片は、何れも比摩耗量が高くなっており、実施例１〜４の各試験片に比べて耐摩耗性が大幅に劣っていた。 In addition, each of the test pieces of Comparative Example 2 that does not contain polyamideimide and Comparative Example 3 that does not contain the modified fluororesin has a high specific wear amount, compared with the test pieces of Examples 1 to 4. The wear resistance was significantly inferior.
Claims (8)
上記改質ふっ素樹脂、ポリアミドイミド、及び有機繊維のトータル重量は、全重量の１０重量部〜５０重量部であり、その中で改質ふっ素樹脂は全重量の５重量部〜３０重量部、ポリアミドイミドは全重量の２重量部〜１５重量部、有機繊維は全重量の３重量部〜１０重量部であることを特徴とする改質ふっ素樹脂組成物。 Modification by at least one organic polymer selected from tetrafluoroethylene polymer, tetrafluoroethylene-perfluoro (alkyl vinyl ether) polymer, tetrafluoroethylene-hexafluoropropylene polymer and ionizing radiation in the fluorine resin, Ri Na were mixed polyamideimide and organic fibers,
The total weight of the modified fluororesin, polyamideimide, and organic fiber is 10 to 50 parts by weight of the total weight. Among them, the modified fluororesin is 5 to 30 parts by weight of the total weight, polyamide. The modified fluororesin composition is characterized in that the imide is 2 to 15 parts by weight of the total weight, and the organic fiber is 3 to 10 parts by weight of the total weight.
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