JPH04258640A - Fluororesin composition - Google Patents
Fluororesin compositionInfo
- Publication number
- JPH04258640A JPH04258640A JP3946491A JP3946491A JPH04258640A JP H04258640 A JPH04258640 A JP H04258640A JP 3946491 A JP3946491 A JP 3946491A JP 3946491 A JP3946491 A JP 3946491A JP H04258640 A JPH04258640 A JP H04258640A
- Authority
- JP
- Japan
- Prior art keywords
- fluororesin
- carbon fiber
- carbon fibers
- fluorine
- fluororesin composition
- 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.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 21
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 26
- 239000004917 carbon fiber Substances 0.000 claims abstract description 26
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011737 fluorine Substances 0.000 claims abstract description 17
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 17
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 16
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 abstract description 10
- 239000011261 inert gas Substances 0.000 abstract description 3
- 238000000465 moulding Methods 0.000 abstract 1
- 238000003682 fluorination reaction Methods 0.000 description 13
- 239000000835 fiber Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- -1 Polytetrafluoroethylene Polymers 0.000 description 7
- 239000000945 filler Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 230000003014 reinforcing effect Effects 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 239000011357 graphitized carbon fiber Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920001780 ECTFE Polymers 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 239000011300 coal pitch Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000009840 oxygen flask method Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、炭素繊維強化フッ素樹
脂組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to carbon fiber reinforced fluororesin compositions.
【０００２】0002
【従来の技術】ポリテトラフルオロエチレン（以下、Ｐ
ＴＦＥと略称する）は耐熱性、耐薬品性に優れているだ
けでなく、特に摩擦係数が小さく摺動特性にも優れてい
るので、軸受け、歯車、パッキン、ピストンリングなど
のエンジニアリングプラスチック材料として広く利用さ
れている。しかしながら、耐摩耗性は必ずしも十分では
なく、また荷重による変形（クリープ）、特に高温荷重
下での変形が大きく、使用に際して大きな制約を受ける
。[Prior art] Polytetrafluoroethylene (hereinafter referred to as P
TFE (abbreviated as TFE) not only has excellent heat resistance and chemical resistance, but also has a particularly low coefficient of friction and excellent sliding properties, so it is widely used as an engineering plastic material for bearings, gears, packing, piston rings, etc. It's being used. However, wear resistance is not necessarily sufficient, and deformation (creep) under load, especially deformation under high-temperature loads, is large, and there are significant restrictions on use.
【０００３】このため、ＰＴＦＥに、ガラス繊維、ガラ
ス粉末又はビーズ、炭素繊維、グラファイト、二硫化モ
リブデンなどの充填剤を添加することが検討されている
。これらの充填剤を添加した樹脂組成物は、マトリック
ス樹脂単体と比較して摩擦係数が低下し、摩耗量も低減
する。しかしながら、これらの充填剤を添加すると、機
械的強度が大幅に低下する。特に、炭素繊維を添加した
フッ素樹脂組成物からなる成型品を、高温高負荷の条件
下で使用する場合には、炭素繊維による補強効果が少な
い。さらにクリープ特性も向上しない。また、炭素繊維
がマトリックスから脱落し易く、クラックなどが生じ易
い。このことは、マトリックスであるＰＴＦＥと炭素繊
維との濡れ性が悪いことに起因すると推測される。一方
、前記炭素繊維以外の充填剤を添加する場合には、前記
ＰＴＦＥに対する濡れ性が炭素繊維よりもさらに劣るた
め、高い補強性を付与することが困難であり、成型品の
機械的強度の低下が著しい。[0003] For this reason, it is being considered to add fillers such as glass fiber, glass powder or beads, carbon fiber, graphite, molybdenum disulfide, etc. to PTFE. A resin composition to which these fillers are added has a lower coefficient of friction and a lower amount of wear than the matrix resin alone. However, the addition of these fillers significantly reduces mechanical strength. In particular, when a molded product made of a fluororesin composition containing carbon fibers is used under high temperature and high load conditions, the reinforcing effect of the carbon fibers is small. Furthermore, the creep properties are not improved either. Furthermore, the carbon fibers tend to fall off from the matrix, and cracks are likely to occur. This is presumed to be due to poor wettability between the PTFE matrix and the carbon fibers. On the other hand, when adding fillers other than the carbon fibers, the wettability of the PTFE is even worse than that of carbon fibers, so it is difficult to impart high reinforcing properties, and the mechanical strength of the molded product decreases. is remarkable.
【０００４】特公昭５２−２２７７１号公報には、ポリ
フェニレンサルファイドで表面処理した充填剤をフッ素
樹脂に添加したフッ素樹脂製品が開示されている。しか
しながら、フッ素樹脂と充填剤との濡れ性が未だ十分で
ないためか、機械的強度、特に高温高荷重下での強度や
クリープ特性の低下が未だ大きい。Japanese Patent Publication No. 52-22771 discloses a fluororesin product in which a filler surface-treated with polyphenylene sulfide is added to a fluororesin. However, probably because the wettability between the fluororesin and the filler is still insufficient, the mechanical strength, especially the strength under high temperature and high load, and creep properties are still significantly reduced.
【０００５】[0005]
【発明が解決しようとする課題】従って、本発明の目的
は、機械的強度が大きく、一体性及びクリープ特性に優
れた成型品を得ることができるフッ素樹脂組成物を提供
することにある。SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a fluororesin composition from which a molded article having high mechanical strength and excellent integrity and creep properties can be obtained.
【０００６】[0006]
【発明の構成】上記の目的を達成するため、本発明者ら
は、フッ素樹脂組成物からなる成型品の機械的強度を向
上させるべく鋭意検討した結果、フッ素化処理した炭素
繊維を用いる場合には、フッ素樹脂との濡れ性、フッ素
樹脂に対する補強性が大幅に改善され、成型品の機械的
強度が著しく大きくなることを見いだし、本発明を完成
した。すなわち、本発明は、フッ素樹脂と、フッ素化処
理された炭素繊維とを含むフッ素樹脂組成物を提供する
。[Structure of the Invention] In order to achieve the above object, the present inventors conducted intensive studies to improve the mechanical strength of molded products made of fluororesin compositions, and found that when using fluorinated carbon fibers, discovered that the wettability with the fluororesin and the reinforcing property against the fluororesin were significantly improved, and the mechanical strength of the molded product was significantly increased, and the present invention was completed. That is, the present invention provides a fluororesin composition containing a fluororesin and fluorinated carbon fibers.
【０００７】フッ素樹脂には、例えば、テトラフルオロ
エチレン、クロロトリフルオロエチレン、ビニルフルオ
ライド、ビニルデンフルオライド、ヘキサフルオロプロ
ピノン、パーフルオロアルキルビニルエーテルなどのフ
ッ素含有モノマーの単独又は共重合体；前記フッ素含有
モノマーと、エチレン、プロピレン、各種のアクリレー
トなどの共重合性モノマーとの共重合体が含まれる。よ
り具体的には、フッ素樹脂としては、例えば、ポリテト
ラフルオロエチレン、ポリクロロトリフルオロエチレン
、ポリビニルデンフルオライドなどの単独重合体；テト
ラフルオロエチレン−ヘキサフルオロプロピレン共重合
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−パーフルオロアルキルビニルエ
ーテル共重合体、エチレン−テトラフルオロエチレン共
重合体、エチレン−クロロトリフルオロエチレン共重合
体などの共重合体が例示される。これらのフッ素樹脂は
一種又は二種以上混合して使用できる。これらのフッ素
樹脂の中で、テトラフルオロエチレン単独重合体が好ま
しい。[0007] Fluororesins include, for example, homopolymers or copolymers of fluorine-containing monomers such as tetrafluoroethylene, chlorotrifluoroethylene, vinyl fluoride, vinyldene fluoride, hexafluoropropynone, and perfluoroalkyl vinyl ether; Copolymers of fluorine-containing monomers and copolymerizable monomers such as ethylene, propylene, and various acrylates are included. More specifically, examples of the fluororesin include homopolymers such as polytetrafluoroethylene, polychlorotrifluoroethylene, and polyvinyldene fluoride; tetrafluoroethylene-hexafluoropropylene copolymers, and tetrafluoroethylene-par Examples include copolymers such as fluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether copolymer, ethylene-tetrafluoroethylene copolymer, and ethylene-chlorotrifluoroethylene copolymer. . These fluororesins can be used alone or in combination of two or more. Among these fluororesins, tetrafluoroethylene homopolymer is preferred.
【０００８】フッ素化処理された炭素繊維は、例えば、
フェノール系樹脂、レーヨン、ポリアクリロニトリル、
石炭ピッチ、石油ピッチなどを出発原料とする炭素繊維
をフッ素化反応に供することにより得られる。なお、「
炭素繊維」とは、炭化又は黒鉛化された繊維を言い、１
５００℃程度以上の高温で焼成したものは、結晶構造が
黒鉛化していないときでも黒鉛化の概念に含める。[0008] Fluorinated carbon fibers are, for example,
Phenolic resin, rayon, polyacrylonitrile,
It is obtained by subjecting carbon fibers starting from coal pitch, petroleum pitch, etc. to a fluorination reaction. In addition,"
"Carbon fiber" refers to carbonized or graphitized fiber,
Items fired at a high temperature of about 500°C or higher are included in the concept of graphitization even if the crystal structure is not graphitized.
【０００９】フッ素化処理された炭素繊維の繊維径、繊
維長は、特に制限されないが、通常、ミルドファイバー
が使用される。このミルドファイバーとしては、例えば
、繊維径１〜５０μｍ、好ましくは２．５〜３０μｍ程
度、繊維長０．０１〜１０ｍｍ、好ましくは０．０３〜
５ｍｍ程度のものが使用できる。[0009] The fiber diameter and fiber length of the fluorinated carbon fibers are not particularly limited, but milled fibers are usually used. This milled fiber has, for example, a fiber diameter of 1 to 50 μm, preferably about 2.5 to 30 μm, and a fiber length of 0.01 to 10 mm, preferably 0.03 to 30 μm.
Approximately 5mm can be used.
【００１０】炭素繊維のフッ素含有量は、フッ素樹脂に
対する濡れ性、補強性などを損わない範囲で炭素繊維の
表面が少なくとも部分的にフッ素化されていればよく、
例えば、１〜３０重量％、好ましくは５〜１０重量％程
度である。フッ素含有量が１重量％未満ではフッ素樹脂
に対する濡れ性、補強性がさほど改善されず、３０重量
％を越えると過度の処理となり、フッ素樹脂に対する補
強性が低下し易い。[0010]The fluorine content of the carbon fibers may be such that the surface of the carbon fibers is at least partially fluorinated within a range that does not impair wettability to fluororesin, reinforcing properties, etc.
For example, it is about 1 to 30% by weight, preferably about 5 to 10% by weight. If the fluorine content is less than 1% by weight, the wettability and reinforcing properties for the fluororesin will not be significantly improved, and if it exceeds 30% by weight, the treatment will be excessive and the reinforcing properties for the fluororesin will tend to deteriorate.
【００１１】炭素繊維の表面をフッ素化処理する方法は
、特に限定されないが、例えば、フッ素ガス、好ましく
は不活性ガスで適当な濃度に希釈したフッ素ガスを用い
て、炭素繊維を直接フッ素化する直接フッ素化法；フッ
酸中で陽極酸化を行う電界フッ素化法；ＣＦ４ などの
フッ素含有気体から生成するラジカルを利用するプラズ
マフッ素化法などが挙げられる。The method for fluorinating the surface of carbon fibers is not particularly limited, but for example, carbon fibers may be directly fluorinated using fluorine gas, preferably fluorine gas diluted with an inert gas to an appropriate concentration. Direct fluorination methods; electric field fluorination methods in which anodic oxidation is performed in hydrofluoric acid; plasma fluorination methods that utilize radicals generated from fluorine-containing gases such as CF4; and the like.
【００１２】これらの方法のなかで、直接フッ素化法で
は、簡便に、しかも炭素繊維のフッ素化度を容易に制御
できる。直接フッ素化法は、例えば、フッ素ガスを、窒
素、アルゴン、ヘリウムなどの不活性ガスで希釈し、フ
ッ素分圧を１〜５０％、好ましくは５〜２０％とした混
合ガスの存在下、反応温度３００〜６００℃、好ましく
は３５０〜５００℃程度で行なうことができる。反応に
際しては、反応系に前記混合ガスを流通させてもよい。Among these methods, the direct fluorination method is simple and allows the degree of fluorination of carbon fibers to be easily controlled. In the direct fluorination method, for example, fluorine gas is diluted with an inert gas such as nitrogen, argon, or helium, and the reaction is carried out in the presence of a mixed gas with a fluorine partial pressure of 1 to 50%, preferably 5 to 20%. It can be carried out at a temperature of 300 to 600°C, preferably about 350 to 500°C. During the reaction, the mixed gas may be passed through the reaction system.
【００１３】得られたフッ素化炭素繊維のキャラクタリ
ゼーションは、フッ素の元素分析及び重量増加などに基
づいて行うことができる。フッ素の元素分析値は、慣用
の方法、例えば、酸素フラスコ法、すなわち、試料を完
全燃焼させた時に生成するフッ酸のフッ素イオン濃度を
イオンメーターで測定する手法により求めることができ
る。The obtained fluorinated carbon fiber can be characterized based on elemental analysis of fluorine and weight increase. The elemental analysis value of fluorine can be determined by a conventional method, for example, the oxygen flask method, in which the fluorine ion concentration of hydrofluoric acid produced when a sample is completely burned is measured using an ion meter.
【００１４】本発明のフッ素樹脂組成物において、前記
フッ素樹脂と、フッ素化処理された炭素繊維との割合は
、成型品の用途などにより選択できるが、通常、フッ素
樹脂９９〜５０重量部、フッ素化処理された炭素繊維１
〜５０重量部の割合が好ましい。さらに好ましい割合は
、フッ素樹脂９２〜６５重量部、フッ素化処理された炭
素繊維８〜３５重量部程度である。このような組成割合
の樹脂組成物で成型すると、成型品の一体性、機械的強
度、成型性及び摺動性などのバランスがとれた成型品が
得られる。In the fluororesin composition of the present invention, the ratio of the fluororesin to the fluorinated carbon fiber can be selected depending on the intended use of the molded product, but usually 99 to 50 parts by weight of the fluororesin, fluorine treated carbon fiber 1
A proportion of ~50 parts by weight is preferred. A more preferable ratio is about 92 to 65 parts by weight of fluororesin and 8 to 35 parts by weight of fluorinated carbon fiber. When molded with a resin composition having such a composition ratio, a molded product with well-balanced integrity, mechanical strength, moldability, slidability, etc. can be obtained.
【００１５】なお、本発明のフッ素樹脂組成物は、特性
を損わない範囲で、充填剤、着色剤、安定剤などの種々
の添加剤を含有していてもよい。[0015] The fluororesin composition of the present invention may contain various additives such as fillers, colorants, and stabilizers as long as the properties are not impaired.
【００１６】本発明のフッ素樹脂組成物は、前記フッ素
樹脂とフッ素化処理された炭素繊維との粉末状混合物で
あってもよく、該粉末状混合物を造粒した造粒物などで
あってもよい。フッ素樹脂組成物による成型品は、慣用
の方法、例えば、フッ素樹脂組成物を金型内で圧縮成型
し、得られた成型品を加熱処理することにより得ること
ができる。The fluororesin composition of the present invention may be a powder mixture of the fluororesin and fluorinated carbon fibers, or may be a granulated product obtained by granulating the powder mixture. good. A molded article made of a fluororesin composition can be obtained by a conventional method, for example, by compression molding the fluororesin composition in a mold and heat-treating the resulting molded article.
【００１７】[0017]
【発明の効果】本発明のフッ素樹脂組成物は、フッ素樹
脂との濡れ性に優れるフッ素化処理された炭素繊維を含
んでいるので、機械的強度が大きく一体性に優れ、荷重
下での変化が小さい成型品を得ることができる。Effects of the Invention The fluororesin composition of the present invention contains fluorinated carbon fibers that have excellent wettability with fluororesin, so it has high mechanical strength and excellent integrity, and does not change under load. It is possible to obtain molded products with small size.
【００１８】[0018]
【実施例】以下に、実施例に基づいて本発明をより詳細
に説明する。EXAMPLES The present invention will be explained in more detail below based on examples.
【００１９】実施例１
黒鉛化炭素繊維［（株）ドナック社製、ＳＧ−２４１］
のミルド（繊維長０．１ｍｍ）を、直接フッ素化法によ
りフッ素化処理した。すなわち、前記黒鉛化炭素繊維２
９５．５ｇを、ニッケル製反応皿に約３ｍｍの厚さに薄
く広げ、反応管中に静置した。１００℃で１２時間、真
空乾燥した後、４００℃まで昇温し、アルゴンガスで希
釈した１０％濃度のフッ素ガスを毎分５００ｃｃの条件
で、７時間流通させることにより、フッ素化処理を行な
った。
処理後、冷却し、反応管内をアルゴンで置換した後、試
料を取り出した。フッ素化炭素繊維の重量は３２１．０
ｇであり、重量増加率は８．６％であった。Example 1 Graphitized carbon fiber [SG-241, manufactured by Donac Co., Ltd.]
milled (fiber length 0.1 mm) was subjected to fluorination treatment by direct fluorination method. That is, the graphitized carbon fiber 2
95.5 g was spread thinly on a nickel reaction dish to a thickness of about 3 mm, and the mixture was placed in a reaction tube. After vacuum drying at 100°C for 12 hours, the temperature was raised to 400°C, and fluorination treatment was performed by passing 10% concentration fluorine gas diluted with argon gas at 500 cc/min for 7 hours. . After the treatment, the sample was taken out after cooling and purging the inside of the reaction tube with argon. The weight of fluorinated carbon fiber is 321.0
g, and the weight increase rate was 8.6%.
【００２０】得られたフッ素化処理された炭素繊維１０
重量部、及びＰＴＦＥ［三井デュポンフロロケミカル（
株）社製、テフロン７−Ｊ］９０重量部をスーパーミキ
サーで混合した。得られた粉末状混合物を金型に入れ４
５０Ｋｇ／ｃｍ２ で加圧することにより、５０ｍｍφ
×６２ｍｍの成型品を得た。Obtained fluorinated carbon fiber 10
Parts by weight, and PTFE [Mitsui DuPont Fluorochemicals (
90 parts by weight of Teflon 7-J, manufactured by Co., Ltd., were mixed in a super mixer. Put the obtained powder mixture into a mold 4
50mmφ by applying pressure at 50Kg/cm2
A molded product with a size of 62 mm was obtained.
【００２１】得られた成型品を、窒素ガス雰囲気下、昇
温速度１２０℃／ｈｒで、室温から３８０℃に昇温し、
同温度で５時間保持した後、降温速度７５℃／ｈｒで室
温まで冷却した。そして、成型品を切削加工し、ＪＩＳ
Ｋ６８９１に準じて機械的特性を測定した。[0021] The obtained molded product was heated from room temperature to 380°C at a heating rate of 120°C/hr in a nitrogen gas atmosphere.
After maintaining the same temperature for 5 hours, it was cooled to room temperature at a cooling rate of 75° C./hr. Then, the molded product is machined and JIS
Mechanical properties were measured according to K6891.
【００２２】実施例２
フッ素ガスの流通時間、すなわち反応時間を４時間とす
る以外、実施例１と同様の方法により黒鉛化炭素繊維を
フッ素化した。フッ素化反応により、炭素繊維の重量は
、２８８．０ｇから３０２．７ｇに増加した。Example 2 Graphitized carbon fibers were fluorinated in the same manner as in Example 1 except that the fluorine gas flow time, that is, the reaction time was changed to 4 hours. Due to the fluorination reaction, the weight of the carbon fiber increased from 288.0 g to 302.7 g.
【００２３】得られたフッ素化処理された炭素繊維を用
いる以外、実施例１と同様にして成型し、切削加工した
成型品の機械的特性を測定した。A molded product was molded in the same manner as in Example 1 except that the obtained fluorinated carbon fiber was used, and the mechanical properties of the cut molded product were measured.
【００２４】比較例
実施例で用いた黒鉛化炭素繊維をフッ素化処理に供する
ことなく、実施例１と同様にして成型し、切削加工した
成型品の機械的特性を測定した。Comparative Example The graphitized carbon fiber used in the example was molded in the same manner as in Example 1 without being subjected to fluorination treatment, and the mechanical properties of the cut molded product were measured.
【００２５】フッ素化反応条件とともに、降伏点強度、
破断点強度および弾性率の測定結果を表に示す。[0025] In addition to the fluorination reaction conditions, the yield point strength,
The measurement results of strength at break and modulus of elasticity are shown in the table.
【００２６】[0026]
【表１】
表より、比較例の成型品よりも各実施例の成型品の機械
的特性は優れている。[Table 1] From the table, the mechanical properties of the molded products of each Example are superior to the molded products of Comparative Examples.
Claims (2)
素繊維とを含むフッ素樹脂組成物。1. A fluororesin composition comprising a fluororesin and fluorinated carbon fibers.
量％である請求項１記載のフッ素樹脂組成物。2. The fluororesin composition according to claim 1, wherein the carbon fiber has a fluorine content of 1 to 30% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3946491A JPH04258640A (en) | 1991-02-09 | 1991-02-09 | Fluororesin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3946491A JPH04258640A (en) | 1991-02-09 | 1991-02-09 | Fluororesin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04258640A true JPH04258640A (en) | 1992-09-14 |
Family
ID=12553775
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3946491A Pending JPH04258640A (en) | 1991-02-09 | 1991-02-09 | Fluororesin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04258640A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994021714A1 (en) * | 1993-03-25 | 1994-09-29 | Daikin Industries, Ltd. | Fluororesin molding and process for producing the same |
| JPH0813255A (en) * | 1994-07-05 | 1996-01-16 | Mitsubishi Chem Corp | Carbon fiber having ultra-high modulus of elasticity and high strength and its production |
| US5705120A (en) * | 1994-02-08 | 1998-01-06 | Osaka Gas Company, Limited | Method of producing graphite fiber-reinforced fluororesin composites |
| US6113824A (en) * | 1997-06-20 | 2000-09-05 | Daikin Industries, Ltd. | Process for surface treating a fluorine-containing resin molded article |
| EP1400623A3 (en) * | 2002-08-26 | 2004-03-31 | ARTEVA TECHNOLOGIES S.à.r.l. | Planar textile structure and yarn from synthetic fibres, method for producing them and use of the same |
| CN104610687A (en) * | 2015-01-21 | 2015-05-13 | 柳州市颖航汽配有限公司 | High-temperature-resisting rubber tube for automobile |
| CN106592215A (en) * | 2016-12-19 | 2017-04-26 | 曲阜师范大学 | Method for preparing fluorine content- and dimension-adjustable carbon fluoride fibers |
-
1991
- 1991-02-09 JP JP3946491A patent/JPH04258640A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994021714A1 (en) * | 1993-03-25 | 1994-09-29 | Daikin Industries, Ltd. | Fluororesin molding and process for producing the same |
| AU675705B2 (en) * | 1993-03-25 | 1997-02-13 | Daikin Industries, Ltd. | Fluororesin molding and process for producing the same |
| US5886090A (en) * | 1993-03-25 | 1999-03-23 | Daikin Industries, Ltd. | Surface fluorination of F-containing resin molded article |
| US5705120A (en) * | 1994-02-08 | 1998-01-06 | Osaka Gas Company, Limited | Method of producing graphite fiber-reinforced fluororesin composites |
| JPH0813255A (en) * | 1994-07-05 | 1996-01-16 | Mitsubishi Chem Corp | Carbon fiber having ultra-high modulus of elasticity and high strength and its production |
| US6113824A (en) * | 1997-06-20 | 2000-09-05 | Daikin Industries, Ltd. | Process for surface treating a fluorine-containing resin molded article |
| EP1400623A3 (en) * | 2002-08-26 | 2004-03-31 | ARTEVA TECHNOLOGIES S.à.r.l. | Planar textile structure and yarn from synthetic fibres, method for producing them and use of the same |
| CN104610687A (en) * | 2015-01-21 | 2015-05-13 | 柳州市颖航汽配有限公司 | High-temperature-resisting rubber tube for automobile |
| CN106592215A (en) * | 2016-12-19 | 2017-04-26 | 曲阜师范大学 | Method for preparing fluorine content- and dimension-adjustable carbon fluoride fibers |
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