JP2594907B2 - Method for producing pitch carbon fiber - Google Patents
Method for producing pitch carbon fiberInfo
- Publication number
- JP2594907B2 JP2594907B2 JP60243075A JP24307585A JP2594907B2 JP 2594907 B2 JP2594907 B2 JP 2594907B2 JP 60243075 A JP60243075 A JP 60243075A JP 24307585 A JP24307585 A JP 24307585A JP 2594907 B2 JP2594907 B2 JP 2594907B2
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- pitch
- spinning
- metal powder
- temperature
- melt
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- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明はピツチ系炭素繊維の製造方法に関するもので
あり、より詳しくは紡糸性を向上させたピツチ系炭素繊
維の製造方法に関するものである。Description: TECHNICAL FIELD The present invention relates to a method for producing pitch-based carbon fibers, and more particularly to a method for producing pitch-based carbon fibers having improved spinnability.
（従来の技術） 炭素繊維は、比強度、比弾性率が高い材料で、高性能
複合材料のフイラー繊維として最も注目されており、中
でもピツチ系炭素繊維は原料が潤沢である。炭化工程の
歩留が大きい、繊維の弾性率が高い、等ポリアクリロニ
トリル系炭素繊維に比べて様々な利点を持つている。(Conventional technology) Carbon fiber is a material having a high specific strength and a specific elastic modulus, and is most noticed as a filler fiber of a high-performance composite material. Among them, pitch-based carbon fiber has abundant raw materials. It has various advantages as compared with polyacrylonitrile-based carbon fiber, such as having a high yield in the carbonization step and a high elastic modulus of the fiber.
ところで、このような利点を有するピツチ系炭素繊維
の原料である紡糸ピツチは種々検討されている。By the way, various studies have been made on a spun pitch, which is a raw material of the pitch-based carbon fiber having such advantages.
すなわち、従来紡糸ピツチとして使用していた等方質
ピツチの代りに、炭素質原料を加熱処理して、異方性が
発達し、配向しやすい分子種が形成されたピツチを使用
することにより、高特性のピツチ系炭素繊維が得られる
ことが報告（特公昭49-8634号）されて以来、配向性の
良好な紡糸ピツチの調製について種々検討されてきた。In other words, instead of the isotropic pitch which was conventionally used as a spinning pitch, by heating the carbonaceous raw material, anisotropically developed, and using a pitch in which molecular species which are easily oriented are formed, Since it was reported that a pitch-based carbon fiber having high properties was obtained (Japanese Patent Publication No. 49-8634), various studies have been made on the preparation of a spun pitch having good orientation.
周知の様に、重質油、タール、ピツチ等の炭素質原料
を350〜500℃に加熱すると、それら物質中に粒径が数ミ
クロンから数百ミクロンの、偏光下に光学的異方性を示
す小球体が生成する。そして、さらに加熱するとこれら
の小球体は成長、合体し、ついには全体が光学的異方性
を示す状態となる。この異方性組織は炭素質原料の熱重
縮合反応により生成した平面状高分子芳香族炭化水素が
層状に積み重なり、配向したもので、黒鉛結晶構造の前
駆体とみなされている。As is well known, when a carbonaceous raw material such as heavy oil, tar, and pitch is heated to 350 to 500 ° C, the optical anisotropy under polarized light having a particle size of several microns to several hundreds microns is obtained in the material. The small sphere shown is generated. Then, when further heated, these small spheres grow and coalesce, and finally, the whole sphere shows optical anisotropy. This anisotropic structure is obtained by stacking and orienting planar macromolecular aromatic hydrocarbons generated by a thermal polycondensation reaction of a carbonaceous raw material, and is regarded as a precursor of a graphite crystal structure.
この様な異方性組織を含む熱処理物は、一般的にはメ
ソフエーズピツチと呼称されている。A heat-treated product containing such an anisotropic structure is generally called a mesophase pitch.
かかるメソフエーズピツチを紡糸ピツチとして使用す
る方法としては、例えば、石油系ピツチを静置条件下で
約350〜450℃で加熱処理し、40〜90重量％のメソフエー
ズを含有するピツチを得て、これを紡糸ピツチとする方
法が提案されている（特開昭49-19127号）。As a method of using such mesophase pitch as a spinning pitch, for example, a petroleum pitch is heat-treated at about 350 to 450 ° C. under static conditions to obtain a pitch containing 40 to 90% by weight of mesophase. A method of using this as a spinning pitch has been proposed (JP-A-49-19127).
しかし、かかる方法により等方質の炭素質原料をメソ
化するには長時間を要するので、予め炭素質原料を十分
量の溶媒で処理してその不溶分を得、それを230〜400℃
の温度で10分以下の短時間加熱処理して、高度に配向さ
れ、光学的異方性部分が75重量％以上で、キノリン不溶
分25重量％以下の、所謂、ネオメソフエーズピツチを形
成し、これを紡糸ピツチとする方法が提案されている
（特開昭54-160427号）。However, it takes a long time to mesomorph the isotropic carbonaceous raw material by such a method.
Heat treatment at a temperature of 10 minutes or less for a short time to form a highly oriented, optically anisotropic portion of 75% by weight or more and a quinoline-insoluble content of 25% by weight or less, a so-called neomesophase pitch. However, a method of using this as a spinning pitch has been proposed (JP-A-54-160427).
その他、高特性炭素繊維製造用の配向性のよい紡糸ピ
ツチとしては、例えば、コールタールピツチをテトラヒ
ドロキノリン存在下に水添処理し、次いで、約450℃で
短時間加熱処理して得られる光学的に等方性で600℃以
上に加熱することによつて異方性に変わる性質を有する
ピツチ、所謂、プリメソフエーズピツチ（特開昭58-184
21号）、或いは、メソフエーズピツチをBirch還元法等
により水素化処理して得られる光学的に等方性で外力を
加えるとその方向への配向性を示すピツチ、所謂、ドー
マントメソフエーズ（特開昭57-100186号）等が提案さ
れている。Other spinning pitches with good orientation for producing high-performance carbon fibers include, for example, optical tar obtained by hydrogenating coal tar pitch in the presence of tetrahydroquinoline and then heating at about 450 ° C. for a short time. A pitch which is isotropic and has the property of changing to anisotropic when heated to 600 ° C. or higher, a so-called primophase pitch (JP-A-58-184).
No. 21) Alternatively, an optically isotropic pitch obtained by hydrogenating a mesophase pitch by a Birch reduction method or the like and exhibiting orientation in that direction when an external force is applied, a so-called dormant mesophase (JP-A-57-100186) and the like have been proposed.
この様な紡糸ピツチをノズルを通して溶融紡糸するこ
とによりピツチ繊維を得ることができる。次いで、この
ピツチ繊維を不融化、炭化、さらに場合により黒鉛化す
ることによつてピツチ系の高特性炭素繊維を得ることが
できる。Pitch fibers can be obtained by melt-spinning such a spinning pitch through a nozzle. Next, the pitch fiber is made infusible, carbonized, and, if necessary, graphitized, whereby a pitch-based high-performance carbon fiber can be obtained.
（発明が解決しようとする問題点） しかしながら、従来の方法により得られる紡糸ピツチ
は、加熱処理時に発生するゲル状物質及び加熱処理操作
中に混入する異物等を含有しており、かかる夾雑物の存
在により溶融紡糸操作時の紡糸性が低下したり、あるい
は溶融紡糸されたピツチ繊維に異物が混入し高特性のピ
ツチ系炭素繊維が得られ難いという問題があつた。(Problems to be Solved by the Invention) However, the spinning pitch obtained by the conventional method contains a gel-like substance generated at the time of heat treatment and foreign substances mixed during the heat treatment operation. Due to the presence thereof, there is a problem that the spinnability during the melt spinning operation is reduced, or foreign matter is mixed into the melt-spun pitch fiber, and it is difficult to obtain a high-quality pitch-based carbon fiber.
（問題点を解決するための手段） そこで本発明者等は上記の問題点を解決するべく鋭意
検討を行なつた結果、紡糸ピツチの粘度を低下させ、
過性を向上させるために紡糸温度よりも高い温度で過
処理を行ない、また紡糸ピツチを製造する際の加熱処理
時に発生するゲル状物質等を口金パツクに供給する前に
おいて特定材で処理することにより従来の問題点を解
消できることを見い出し本発明に到達した。(Means for Solving the Problems) Accordingly, the present inventors have conducted intensive studies to solve the above problems, and as a result, the viscosity of the spinning pitch was reduced,
Over-treatment is performed at a temperature higher than the spinning temperature in order to improve the over-tempering property, and treatment with a specific material is performed before supplying the gel-like substance, etc., generated during the heat treatment for producing the spinning pitch to the die pack. As a result, the present inventors have found that the conventional problems can be solved, and reached the present invention.
すなわち、本発明の目的は紡糸ピツチを製造する際の
加熱処理時に発生するゲル状物質等の夾雑物を効率よく
除去し、紡糸ピツチの紡糸性を大幅に向上させたピツチ
系炭素繊維の製造方法を提供するものである。That is, an object of the present invention is to provide a method for producing a pitch-based carbon fiber in which contaminants such as a gel-like substance generated during a heat treatment for producing a spun pitch are efficiently removed and the spinnability of the spun pitch is greatly improved. Is provided.
そして、その目的は紡糸ピツチを紡糸ノズルから溶融
紡糸し、不融化処理を行ない、次いで炭化処理し、さら
に必要に応じて黒鉛化処理することによりピツチ系炭素
繊維を製造する方法において、該紡糸ピツチを紡糸ノズ
ルから吐出される直前の紡糸ピツチの有する温度である
溶融紡糸温度よりも５〜50℃高い温度の溶融状態で突起
物表面を有するメタルパウダーからなる一次材層を流
通させた後、紡糸口金とその上流部に設けられた二次濾
材層とからなる口金パツクに供給し溶融紡糸することに
より容易に達成できる。The object of the present invention is to provide a method for producing a pitch-based carbon fiber by melt-spinning a spinning pitch from a spinning nozzle, performing an infusibilization treatment, then carbonizing, and, if necessary, graphitizing the spinning pitch. After flowing a primary material layer made of metal powder having a projection surface in a molten state at a temperature 5 to 50 ° C. higher than the melt spinning temperature which is the temperature of the spinning pitch immediately before being discharged from the spinning nozzle, and then spinning It can be easily achieved by supplying to a die pack consisting of a die and a secondary filter medium layer provided upstream thereof and melt-spinning.
以下、本発明を詳しく説明するに、本発明の紡糸ピツ
チとしては配向しやすい分子種が形成されており、光学
的に異方性のピツチを与えるものであれば特に制限はな
く、前述のような従来の種々のものを使用することがで
きる。Hereinafter, the present invention will be described in detail.The spinning pitch of the present invention is not particularly limited as long as a molecular species that is easily oriented is formed and provides an optically anisotropic pitch. Various conventional ones can be used.
しかし、それほど高度の比強度及び比弾性率が要求さ
れない場合は、アモルフアスピツチを用いることもでき
る。これらの紡糸ピツチを得るための炭素質原料として
は、例えば、石炭系のコールタール、コールタールピツ
チ、石炭液化物、石油系の重質油、タール、ピツチ等が
挙げられる。これらの炭素質原料には通常フリーカーボ
ン、未溶解石炭、灰分などの不純物が含まれているが、
これらの不純物は過、遠心分離、あるいは溶剤を使用
する静置沈降分離などの周知の方法で予め除去しておく
ことが望ましい。However, when a very high specific strength and specific elastic modulus are not required, an amorphous spirit can be used. Examples of the carbonaceous raw material for obtaining these spinning pitches include coal-based coal tar, coal-tar pitch, coal liquefaction, petroleum heavy oil, tar, and pitch. These carbonaceous materials usually contain impurities such as free carbon, undissolved coal and ash,
These impurities are desirably removed in advance by a well-known method such as filtration, centrifugation, or stationary sedimentation using a solvent.
また、前記炭素質原料を、例えば、加熱処理した後特
定溶剤で可溶分を抽出するといつた方法、あるいは水素
供与性溶剤、水素ガスの存在下に水添処理するといつた
方法で予備処理を行なつておいても良い。Further, the carbonaceous raw material, for example, a method of extracting a soluble component with a specific solvent after heat treatment, or a method of hydrogenation in the presence of a hydrogen-donating solvent or hydrogen gas, a preliminary treatment. You may leave it.
本発明においては、前述炭素質原料あるいは予備処理
を行なつた炭素質原料を、通常350〜500℃、好ましくは
380〜450℃で、２分〜50時間、好ましくは５分〜５時
間、窒素、アルゴン等の不活性ガス雰囲気下、或いは、
吹き込み下に加熱処理することによつて得られる40％以
上、特に70％以上の光学的異方性組織を含むピツチが紡
糸ピツチとして好適に使用できる。In the present invention, the above-mentioned carbonaceous raw material or the carbonaceous raw material that has been subjected to the pretreatment is usually 350 to 500 ° C., preferably
At 380 to 450 ° C. for 2 minutes to 50 hours, preferably 5 minutes to 5 hours under an atmosphere of an inert gas such as nitrogen or argon, or
Pitches having an optically anisotropic structure of 40% or more, particularly 70% or more, obtained by heat treatment under blowing can be suitably used as spinning pitches.
本発明でいう紡糸ピツチの光学的異方性組織割合は、
常温下偏光顕微鏡での紡糸ピツチ試料中の光学的異方性
を示す部分の面積割合として求めた値である。The optically anisotropic structure ratio of the spinning pitch referred to in the present invention is:
This is a value obtained as an area ratio of a portion showing optical anisotropy in a spinning pitch sample under a polarizing microscope at room temperature.
具体的には、例えばピツチ試料を数mm角に粉砕したも
のを常法に従つて直径約2cmの樹脂の表面のほぼ全面に
試料片を埋込み、表面を研磨後、表面全体をくまなく偏
光顕微鏡（100倍率）下で観察し、試料の全表面積に占
める光学的異方性部分の面積の割合を測定することによ
つて求める。Specifically, for example, a sample of a pitch sample crushed into a few mm square is embedded in a substantially entire surface of a resin having a diameter of about 2 cm according to a conventional method, and the surface is polished. Observed under (100 magnification) and determined by measuring the ratio of the area of the optically anisotropic portion to the total surface area of the sample.
本発明においては、上記紡糸ピツチを溶融紡糸温度よ
りも高い温度の溶融状態でメタルパウダーからなる一次
材層を流通させる。In the present invention, a primary material layer made of metal powder is passed through the above-mentioned spinning pitch in a molten state at a temperature higher than the melt spinning temperature.
ここで溶融紡糸温度とは紡糸ピツチが紡糸ノズルから
吐出される直前の紡糸ピツチの有する温度を意味し、通
常300〜400℃程度の温度である。また紡糸ピツチは紡糸
ピツチの粘度を低くし、過性を向上させるために前記
溶融紡糸温度よりも高い温度の溶融状態で保持される
が、あり高温度の溶融状態で保持すると紡糸ピツチの物
性が変化し好ましくないので、具体的には溶融紡糸温度
よりも５〜50℃、好ましくは10〜40℃高い温度の溶融状
態で保持するのがよい。また、一次材層とは多数の紡
糸ノズルを有する紡糸口金と、紡糸口金の上流部に設け
られた二次材層とが一体に組み立てられた口金パツク
の前に設置され、口金パツクに供給される紡糸ピツチ中
の異物等を除去するものである。Here, the melt spinning temperature means the temperature of the spinning pitch immediately before the spinning pitch is discharged from the spinning nozzle, and is usually about 300 to 400 ° C. Also, the spinning pitch is kept in a molten state at a temperature higher than the melt spinning temperature in order to lower the viscosity of the spinning pitch and to improve the transient property, but if the spinning pitch is kept in a molten state at a high temperature, the physical properties of the spinning pitch will be reduced. Since it changes and is not preferable, specifically, it is preferable to maintain the molten state at a temperature 5 to 50 ° C., preferably 10 to 40 ° C. higher than the melt spinning temperature. In addition, the primary material layer is provided in front of a spinneret pack in which a spinneret having a number of spinning nozzles and a secondary material layer provided upstream of the spinneret are integrally assembled and supplied to the spinneret pack. To remove foreign substances and the like in the spinning pitch.
なお、紡糸ノズルとは紡糸ピツチが紡糸される直前に
流通し、かつ糸条径を規定する細孔部を意味する。The spinning nozzle means a pore portion which flows immediately before the spinning pitch is spun and defines the yarn diameter.
このように、溶融紡糸温度よりも高い温度の溶融状態
で保持された紡糸ピツチをメタルパウダーからなる一次
材層に流通させ、紡糸ピツチ中に含有されるゲル状物
質を除去するが、本発明の一次材層に用いるメタルパ
ウダーとしては350〜450℃程度の温度に充分耐えられる
ような、ステンレス鋼、銅、アルミニウム等の金属材料
からなる珊瑚樹様の鋭利な突起を多数有し、50メツシユ
以下、好ましくは100メツシユ以下の篩を充分通過する
ような粒径の微細粉あるいはこれらの微細粉を加圧焼結
して得られるメタルパウダー焼結体を用いるのがよい。
またあまりに細かな微粉が混入すると一次材層の目詰
りの原因となるので、325メツシユの篩を通過するよう
なものは除去するのが好ましい。よつて一次材層を構
成するメタルパウダーの粒径が100メツシユの篩は通過
するが325メツシユの篩は通過しないような範囲にある
のが最も好ましい。充填材として粉末を用いる場合は粉
末のメタルパウダーが落下しない程度の網目を有する金
網等を支持具として用い、該金網の上にメタルパウダー
を適当な厚さに充填し、さらに要すればその上に金網等
を載置してメタルパウダーからなる一次材層を固定す
る。充填材としてメタルパウダー焼結体を用いる場合は
適当な支持具により固定するのがよい。またメタルパウ
ダー焼結体の上の金網は特に必要はないが、下には金網
を敷くのが好ましい。As described above, the spinning pitch held in a molten state at a temperature higher than the melt spinning temperature is passed through the primary material layer made of metal powder to remove the gel-like substance contained in the spinning pitch. As a metal powder used for the primary material layer, it has a large number of coral tree-like sharp protrusions made of a metal material such as stainless steel, copper, and aluminum, which can sufficiently withstand a temperature of about 350 to 450 ° C. It is preferable to use a fine powder having a particle size sufficient to pass through a sieve of 100 mesh or less or a metal powder sintered body obtained by sintering these fine powders under pressure.
Also, if too fine powder is mixed, it may cause clogging of the primary material layer. Therefore, it is preferable to remove those that pass through a 325 mesh sieve. Therefore, it is most preferable that the particle diameter of the metal powder constituting the primary material layer is in a range such that it passes through a sieve of 100 mesh but not through a sieve of 325 mesh. When powder is used as the filler, a metal mesh or the like having a mesh that does not allow the metal powder of the powder to fall is used as a support, and the metal powder is filled to an appropriate thickness on the metal mesh, and furthermore, if necessary. A wire mesh or the like is placed on the metal layer to fix a primary material layer made of metal powder. When a metal powder sintered body is used as the filler, it is preferable to fix it with a suitable support. Although a wire mesh on the metal powder sintered body is not particularly required, it is preferable to lay a wire mesh below.
メタルパウダーからなる一次材層の厚さは流通させ
る紡糸ピツチ量、流通速度により異なるが、あまり薄い
とゲル状物質等の夾雑物を充分に除去できず、またあま
り厚いと過処理が困難となるため、通常5mm以上、好
ましくは10〜100mm程度である。メタルパウダーからな
る一次材層を通過させる紡糸ピツチの流通速度は通常
0.01〜1cm/分、好ましくは0.02〜0.5cm/分の範囲から選
択される。The thickness of the primary material layer made of metal powder varies depending on the amount of spinning pitch to be circulated and the circulation speed, but if it is too thin, impurities such as gel-like substances cannot be sufficiently removed, and if it is too thick, overtreatment becomes difficult. Therefore, it is usually 5 mm or more, preferably about 10 to 100 mm. The flow speed of the spinning pitch passing through the primary material layer made of metal powder is usually
It is selected from the range of 0.01 to 1 cm / min, preferably 0.02 to 0.5 cm / min.
またメタルパウダーからなる一次材層はほぼ同粒径
の一層でもよく、あるいは粒径を異にする多層構造であ
つてもよい。The primary material layer made of metal powder may be a single layer having substantially the same particle size, or may have a multilayer structure having different particle sizes.
かかるメタルパウダーからなる一次材層により紡糸
ピツチ中のゲル状物質等は効率よく除去できるが、一次
材層として多層金網類、セラミツクフアイバーあるい
はガラスビーズ等からなる過層を用いるとゲル状物質
が通過してしまつたり、又は早期に目詰りが生じたりし
て過の目的が達成されず好ましくない。The gel-like substance in the spinning pitch can be efficiently removed by the primary material layer made of such metal powder, but the gel-like substance passes when an overlayer made of multilayer wire mesh, ceramic fiber or glass beads is used as the primary material layer. It is not preferable because the excessive purpose is not achieved due to slippage or early clogging.
この原因については十分解明されていないものの、紡
糸ピツチ中に含有されるゲル状物質は金網あるいはガラ
スビーズ等の様に表面が比較的平滑なものに対して吸着
せず、むしろ本発明のメタルパウダーの如く突起物表面
を有するものに対して吸着することに起因しているもの
と思われる。Although the cause has not been fully elucidated, the gel-like substance contained in the spun pitch does not adsorb to a relatively smooth surface such as a wire mesh or glass beads, but rather the metal powder of the present invention. It is considered that this is caused by adsorption to a substance having a projection surface as shown in FIG.
このようにしてゲル状物質等の夾雑物が除去された紡
糸ピツチは溶融状態のまま、紡糸口金と二次材層とが
一体に組み立てられた口金パツクに供給され、次いで溶
融紡糸されピツチ繊維が製造される。また、メタルパウ
ダーからなる一次材層を通過した紡糸ピツチを減圧下
で紡糸ピツチ中の軽沸成分を十分に除去した後、口金パ
ツクに供給してもよい。得られたピツチ繊維は公知の方
法に従い、不融化処理及び炭化処理され、さらに必要に
応じて黒鉛化処理されて高特性のピツチ系炭素繊維が製
造される。尚、本発明では口金パツク内の二次材層に
ついては特に規定していないが、一次材層と同様のメ
タルパウダーからなる二次材層を用いると、溶融紡糸
操作が更に良好となるので好ましい。The spinning pitch from which contaminants such as gel-like substances have been removed in this way is supplied in a molten state to a spinneret pack in which a spinneret and a secondary material layer are integrally assembled, and then melt-spun to produce a pitch fiber. Manufactured. Alternatively, the spinning pitch that has passed through the primary material layer made of metal powder may be supplied to a die pack after the light boiling components in the spinning pitch have been sufficiently removed under reduced pressure. The obtained pitch fiber is subjected to infusibilization treatment and carbonization treatment according to a known method and, if necessary, graphitization treatment to produce high-performance pitch-based carbon fiber. In the present invention, the secondary material layer in the die pack is not particularly specified, but it is preferable to use a secondary material layer made of the same metal powder as the primary material layer, since the melt spinning operation is further improved. .
（効果） 本発明によれば、紡糸ピツチを製造する際の加熱処理
時に発生するゲル状物質等の夾雑物を効率よく除去でき
るので、溶融紡糸する際の紡糸性の極めて良好な紡糸ピ
ツチが得られ、これにより紡糸操作が大幅に改善され、
かつ高特性のピツチ系炭素繊維を得ることができる。(Effect) According to the present invention, it is possible to efficiently remove impurities such as a gel-like substance generated at the time of heat treatment at the time of producing a spinning pitch, so that a spinning pitch having extremely good spinnability at the time of melt spinning can be obtained. This greatly improves the spinning operation,
In addition, a pitch-based carbon fiber having high characteristics can be obtained.
以下、本発明を実施例を用いて具体的に説明するが、
本発明の要旨をこえない限り、本発明は下記実施例に限
定されるものではない。Hereinafter, the present invention will be described specifically with reference to Examples.
The present invention is not limited to the following examples unless the gist of the present invention is exceeded.
実施例１ 攪拌機つきオートクレーブにコールタールピツチ100
部、石炭系芳香族油100部、金属酸化物系水添触媒５部
を入れ、水素圧150kg/cm2・Ｇ、温度460℃で１時間加熱
処理した。この処理物を過して水添触媒を除去後、減
圧蒸留により溶媒を留去して水添ピツチを得た。次いで
水添ピツチに窒素ガスを吹込みながら430℃で２時間加
熱処理することにより光学的異方性割合が100％である
紡糸ピツチを得た。Example 1 Coal tar pitch 100 in an autoclave with a stirrer
Parts, 100 parts of coal-based aromatic oil and 5 parts of metal oxide-based hydrogenation catalyst, and heat-treated at a hydrogen pressure of 150 kg / cm 2 · G and a temperature of 460 ° C. for 1 hour. After passing the treated product to remove the hydrogenation catalyst, the solvent was distilled off under reduced pressure to obtain a hydrogenated pitch. Next, a spinning pitch having an optical anisotropy ratio of 100% was obtained by performing a heat treatment at 430 ° C. for 2 hours while blowing nitrogen gas into the hydrogenated pitch.
粒径範囲が100〜170メツシユであるサンゴ樹状特殊ス
テンレス製メタルパウダーを層高30mmで充填した一次
材層の下部に325メツシユの金網を敷き、上方より下方
に流れるように上記紡糸ピツチを温度340℃、線速度0.2
cm/minの条件で流通させた。A wire mesh of 325 mesh is spread under the primary material layer filled with coral dendritic special stainless steel metal powder having a particle size range of 100 to 170 mesh at a layer height of 30 mm, and the spinning pitch is heated to flow downward from above. 340 ° C, linear velocity 0.2
It was distributed under the condition of cm / min.
メタルパウダーの一次材層を通過してきた紡糸ピツ
チを口金パツク圧を20kg/cm2として口金パツクに供給
し、ノズル径0.2mm、孔数500の紡糸口金を用いて330℃
で連続的に溶融紡糸を行ない糸径10μのピツチ繊維を得
た。紡糸性は極めて良好であり２週間連続して安定した
操業が維持できた。２週間経過後の口金パツク圧は50kg
/cm2以下であり更に長期間の連続運転が期待された。Supplying a spinning pitch having passed through the primary material layer of the metal powder to the base the packed mouthpiece the packed pressure as 20kg / cm 2, 330 ℃ with nozzle diameter 0.2 mm, the spinneret holes of 500
Was continuously melt-spun to obtain a pitch fiber having a yarn diameter of 10 μm. The spinnability was extremely good, and a stable operation could be maintained for two consecutive weeks. 50kg after 2 weeks
/ cm 2 or less, and a long-term continuous operation was expected.
実施例２ 実施例１において、メタルパウダーの一次材層を通
過させる際の紡糸ピツチの温度を370℃とした以外は実
施例１と同様に処理し、以下同様にして連続的に溶融紡
糸を行なつた。紡糸性はかなり良好であり１週間連続し
て安定した操業が維持できた。しかしその後、口金パツ
ク圧が100kg/cm2に近くなつたので８日目に運転を打切
つた。Example 2 The procedure of Example 1 was repeated, except that the temperature of the spinning pitch when passing the primary layer of the metal powder was 370 ° C., and the melt spinning was continuously performed in the same manner. Natsuta The spinnability was fairly good and a stable operation could be maintained for one week continuously. However, after that, the driving pressure was stopped on the eighth day because the pressure of the mouthpiece became close to 100 kg / cm 2 .
比較例１ 実施例１において、メタルパウダーの充填層の代りに
粒径範囲が100〜170メツシユであるガラスビーズ層を用
いた以外は実施例１と同様に処理し、以下同様にして溶
融紡糸を行なつた。紡糸の当初より紡糸性は不安定であ
り糸切れが多発し、かつ24時間経過時において口金パツ
ク圧が200kg/cm2に達してしまい連続紡糸が不可能とな
つた。Comparative Example 1 The procedure of Example 1 was repeated, except that a glass bead layer having a particle size range of 100 to 170 mesh was used in place of the filler layer of metal powder. Got it. From the beginning of spinning, the spinnability was unstable, yarn breakage occurred frequently, and the die packing pressure reached 200 kg / cm 2 after 24 hours, making continuous spinning impossible.
比較例２ 実施例１において、メタルパウダーの一次材層の代
りに、200メツシユのステンレス製平織金網を用いた以
外は実施例１と同様にして紡糸ピツチを処理し、以下同
様にして溶融紡糸を行なつた。紡糸の当初より紡糸性は
不安定であり糸切れが多発し、かつ24時間経過時におい
て口金パツク圧が200kg/cm2に達してしまい連続紡糸が
不可能となつた。Comparative Example 2 In Example 1, a spinning pitch was treated in the same manner as in Example 1 except that a 200-mesh stainless steel plain woven wire mesh was used instead of the primary material layer of the metal powder. Got it. From the beginning of spinning, the spinnability was unstable, yarn breakage occurred frequently, and the die packing pressure reached 200 kg / cm 2 after 24 hours, making continuous spinning impossible.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 永田 耕悦 北九州市八幡西区大字藤田2447番地の１ 三菱化成工業株式会社黒崎工場内 (56)参考文献 特開 昭62−64889（ＪＰ，Ａ) ────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Koetsu Nagata 247-1 Fujita, Yawatanishi-ku, Kitakyushu City Inside the Kurosaki Plant of Mitsubishi Chemical Industry Co., Ltd. (56) References JP-A-62-64889 (JP, A)
Claims (3)
不融化処理を行ない、次いで炭化処理し、さらに必要に
応じて黒鉛化処理することによりピッチ系炭素繊維を製
造する方法において、該紡糸ピッチを、紡糸ノズルから
吐出される直前の紡糸ピッチの有する温度である溶融紡
糸温度よりも５〜50℃高い温度の溶融状態で、突起物表
面を有するメタルパウダーからなる一次濾材層を流通さ
せた後、紡糸口金とその上流部に設けられた二次濾材層
とからなる口金パックに供給し溶融紡糸することを特徴
とするピッチ系炭素繊維の製造方法。1. A spinning pitch is melt-spun from a spinning nozzle.
In a method for producing pitch-based carbon fibers by performing infusibilization treatment, then carbonizing treatment and, if necessary, graphitizing treatment, the spinning pitch is adjusted to the temperature of the spinning pitch immediately before being discharged from the spinning nozzle. In a molten state at a temperature 5 to 50 ° C. higher than the melt spinning temperature, a primary filter medium layer made of a metal powder having a protruding surface is passed, and then a spinneret and a secondary filter medium layer provided upstream thereof are provided. And producing the pitch-based carbon fiber by melt-spinning.
ッシュ以下の篩を通過するような粒径を有するメタルパ
ウダーからなることを特徴とする特許請求の範囲第１項
記載の方法。2. The method according to claim 1, wherein the primary filter medium layer made of metal powder is made of metal powder having a particle size such that it passes through a sieve of 50 mesh or less.
メッシュの篩は通過するが325メッシュの篩は通過しな
い範囲の粒径を有するメタルパウダーからなることを特
徴とする特許請求の範囲第１項記載の方法。3. The method according to claim 1, wherein the primary filter medium layer comprising metal powder is 100
2. The method according to claim 1, wherein the metal powder has a particle size in a range that passes through a mesh sieve but does not pass through a 325 mesh sieve.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60243075A JP2594907B2 (en) | 1985-10-30 | 1985-10-30 | Method for producing pitch carbon fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60243075A JP2594907B2 (en) | 1985-10-30 | 1985-10-30 | Method for producing pitch carbon fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62104924A JPS62104924A (en) | 1987-05-15 |
| JP2594907B2 true JP2594907B2 (en) | 1997-03-26 |
Family
ID=17098410
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60243075A Expired - Lifetime JP2594907B2 (en) | 1985-10-30 | 1985-10-30 | Method for producing pitch carbon fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2594907B2 (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6264889A (en) * | 1985-09-17 | 1987-03-23 | Showa Denko Kk | Purification of pitch |
-
1985
- 1985-10-30 JP JP60243075A patent/JP2594907B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62104924A (en) | 1987-05-15 |
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