JPS5988923A - Manufacture of carbon fiber - Google Patents
Manufacture of carbon fiberInfo
- Publication number
- JPS5988923A JPS5988923A JP19745082A JP19745082A JPS5988923A JP S5988923 A JPS5988923 A JP S5988923A JP 19745082 A JP19745082 A JP 19745082A JP 19745082 A JP19745082 A JP 19745082A JP S5988923 A JPS5988923 A JP S5988923A
- Authority
- JP
- Japan
- Prior art keywords
- pitch
- spinning
- carbon fiber
- hydrogenated
- temperature
- 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
Landscapes
- Inorganic Fibers (AREA)
- Working-Up Tar And Pitch (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、炭素繊維の新規表製造法、さらに詳しくいえ
ばピッチを原料として高強度の炭素繊維を効率よく製造
するだめの改良方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing carbon fibers, and more specifically to an improved method for efficiently producing high-strength carbon fibers using pitch as a raw material.
炭素繊維は、それが有する断熱性、耐熱性、耐薬品性、
剛性、導電性などを利用して、断熱材、シール材、電気
機械部品、構造部材、摩擦材料、炭素電極などとして広
く使用される材料である。Carbon fiber has thermal insulation properties, heat resistance, chemical resistance,
Due to its rigidity and conductivity, it is widely used as heat insulating materials, sealing materials, electromechanical parts, structural members, friction materials, carbon electrodes, etc.
この炭素繊維の代表的な製造方法としては、アクリロニ
トリルやセルロースなどの繊維を焼成する方法とピッチ
状物質を紡糸し炭化する方法を挙げることができるが、
前者は原料コストが高い上に、炭化収率が低いため、工
業的に実施する方法として不適当であるし、後者は安価
かつ大量に入手しうる各種ピッチを原料として用いるこ
とができるという利点はあるが、紡糸が困難である」二
に、高品質の炭素繊維は得られないという欠点があり、
いずれも工業的方法として満足しうるものとはいえない
。Typical methods for producing this carbon fiber include a method of firing fibers such as acrylonitrile or cellulose, and a method of spinning and carbonizing a pitch-like material.
The former has a high raw material cost and low carbonization yield, making it unsuitable for industrial implementation, while the latter has the advantage of being able to use various pitches that are inexpensive and available in large quantities as raw materials. However, it is difficult to spin.Secondly, it has the disadvantage that high-quality carbon fiber cannot be obtained.
None of these methods can be said to be satisfactory as an industrial method.
その後、ピッチ状物質を原料とする方法に関し、紡糸を
容易にするとともに、高品質の炭素繊維を得るだめの種
々の研究がなされ、これまで特定の縮合多環式芳香族化
合物を水素化処理又は熱処理してイ４）だピッチ状物質
を原石として用いる方法（特公昭７Ｉ５−２８０１３号
公報、特公昭４９−８６３４号公報）、石油系のピッチ
状物質を先ずルイス酸触媒の存在下で熱処理したのち、
触媒を除去してさらに熱処理したものを原料として用い
る方法（特公昭５３−７５３３号公報）、減圧下に所定
のメンフェース含量をもつメソフェースピッチを形成さ
せ、これを原石として炭素繊維を製造する方法（特開昭
５４−１１３３０号公報、特公昭５４−１８１０ 号公
報）、特定の組成、特定の物性をもつメンフェースピッ
チを原料として用いる方法（特開昭５４−５５６２５号
公報・米国特許第３，７８７，５４１ 号明細書）など
が提案されているが、これらの方法によっても紡糸性の
改善は十分に達成することができず、丑だポリアクリロ
ニトリルを原料としだものに匹敵する物性をもった高性
能グレードの炭素繊維は得られていない。Subsequently, various studies have been conducted on methods using pitch-like materials as raw materials in order to facilitate spinning and obtain high-quality carbon fibers. 4) A method of using a pitch-like material as a raw stone (Japanese Patent Publication No. 7 I5-28013, Japanese Patent Publication No. 49-8634), a petroleum-based pitch material is first heat-treated in the presence of a Lewis acid catalyst. after,
A method in which the catalyst is removed and further heat-treated is used as a raw material (Japanese Patent Publication No. 7533/1983), in which mesoface pitch with a predetermined memphaceous content is formed under reduced pressure, and this is used as raw ore to produce carbon fibers. method (Japanese Patent Application Laid-Open No. 54-11330, Japanese Patent Publication No. 54-1810), method using membrane pitch having a specific composition and specific physical properties as a raw material (Japanese Patent Application Laid-open No. 54-55625, U.S. Patent No. 3,787,541), but these methods have not been able to sufficiently improve the spinnability, and it has not been possible to sufficiently improve spinnability, and it has been difficult to achieve physical properties comparable to that of polyacrylonitrile using poor polyacrylonitrile as a raw material. High performance grade carbon fiber has not been obtained.
本発明者らは、このようなピッチの紡糸性及び炭素繊維
の物性を改良するために、先に、ピッチ類をテトラヒド
ロキノリンなどで水素化処理し、次いでこの水素化処理
されたピッチ類を４５０℃以上の温度で加熱処理して得
られるプリメソフェーズピッチを原料として用いる炭素
繊維の製法（％願昭５６−１．１７４７０号）を提案し
た。In order to improve the spinnability of such pitches and the physical properties of carbon fibers, the present inventors first hydrogenated pitches with tetrahydroquinoline or the like, and then treated the hydrogenated pitches with 450% We proposed a method for manufacturing carbon fiber (%Gan Sho 56-1.17470) using as a raw material pre-mesophase pitch obtained by heat treatment at a temperature of 0.degree. C. or higher.
しかしながら、この製法においては第１段階で水素化処
理されたピンチを第２段階で４５０℃以上の高温で処理
するために、必要以上にピッチか熱分解されてプリメン
フェーズピッチの収率が低下し、まだ一定の性状を有す
るプリメソフェーズピッチを製造するだめには、処理条
件の選択を厳密にしなければならないなどの問題を伴い
必ずしも満足しうるものとはいえない。However, in this manufacturing method, the pinch that has been hydrogenated in the first stage is treated at a high temperature of 450°C or higher in the second stage, which causes more pitch to be thermally decomposed than necessary, reducing the yield of premenphase pitch. However, in order to produce pre-mesophase pitch having certain properties, it is not always satisfactory, as there are problems such as the necessity of selecting processing conditions strictly.
本発明者らは、このような問題を解決するために、さら
に鋭意研究を重ねた結果、第一段階で水素化処理された
ピッチを第２段階で３００〜４５０℃、好ましくは３２
０〜４２０℃の温度で処理することによって得られる特
定のプリメソフェーズピッチが再現性がよく、しかも紡
糸性に優れたものであることを見出し、この知見に基づ
いて本発明を冗成するに至った。In order to solve these problems, the present inventors conducted further intensive research and found that the pitch that had been hydrogenated in the first stage was heated to 300 to 450°C, preferably 32°C, in the second stage.
It was discovered that a specific pre-mesophase pitch obtained by treatment at a temperature of 0 to 420°C has good reproducibility and excellent spinnability, and based on this knowledge, the present invention was developed. Ta.
すなわち、本発明は、蓋素気流中、固形物を除去した水
素化処理ピンチを３００〜４５０℃に加熱処理して、キ
ノリン不溶分が１５〜７５重量％、ベンゼン不溶分が７
５重量％以上及び高化式フローテスターによる軟化点が
２００〜３００℃であり、かつプリメソフェーズピッチ
を含み、室温で光学的に異方性を示す連続相を有する紡
糸用ピッチを形成させ、次いで紡糸したのち、不融化処
理し、さらに炭化処理することを特徴とする炭素繊維の
製造法を提供するものである。That is, in the present invention, the hydrogenated pinch from which solids have been removed is heat-treated at 300 to 450°C in a nitrogen gas flow to reduce the quinoline insoluble content to 15 to 75% by weight and the benzene insoluble content to 7% by weight.
5% by weight or more, a softening point of 200 to 300°C by Koka flow tester, containing premesophase pitch, and having a continuous phase exhibiting optical anisotropy at room temperature, and then forming a spinning pitch. The present invention provides a method for producing carbon fiber, which is characterized by spinning, infusible treatment, and further carbonization treatment.
本発明方法において原料とする水素化処理ピッチは、原
料ピッチ類を水素供与性溶剤を用いて水素化処理したも
のが好ましい。この際原料ピッチ類として、例えば石炭
タールピッチ、石炭液化物、ナフサ熱分解時の副生ター
ルの蒸留残さ戦質油の流動接触分子Ｗ（法（Ｐ゛ＣＣ法
）によって得られる分ｉｑ’＋：クール・原油の蒸留残
さであるアスファルトやこれの熱分解などによって得た
ピッチなどが用いられる。また水素供与性溶剤としては
、原料ピッチ類を浴ＩＩＩイし、かつ水素化しうるもの
であれば差しつかえなく、例えばキノリン、ナフタレン
、アントラセン、アントラセン油、クレオソート油、ウ
ォッシュオイルなどを水素化したものが用いられる。The hydrotreated pitch used as a raw material in the method of the present invention is preferably one obtained by hydrogenating raw pitches using a hydrogen-donating solvent. At this time, raw material pitches include, for example, coal tar pitch, coal liquefied products, fraction iq'+ obtained by the fluid contact molecule W (method (P゛CC method)) of distillation residue crude oil of by-product tar during naphtha thermal decomposition. : Asphalt, which is the distillation residue of cool crude oil, and pitch obtained by thermal decomposition of this, etc. are used.As a hydrogen-donating solvent, as long as it can bathe the raw material pitch and hydrogenate it, it can be used. For example, hydrogenated products such as quinoline, naphthalene, anthracene, anthracene oil, creosote oil, and wash oil can be used.
第１段階の水素化処理ピッチの製造は、原料ピッチ類と
水素供与剤とを、例えば重量比で１＝０．２〜３の割合
で混合してオートクレーブに入れ、内部の空気を望素ガ
スなどの不活性ガス又は水素ガスで置換したのち、かき
まぜながら３００〜５００℃、好ましくは３５０〜４８
０℃の温度範囲で１〜１２０分間、望筐しくに６０分間
以内加熱し、次いでろ過や遠心分離法などによってフリ
ーカーボン溶融し、フリーカーボン等の固形物を除去し
てもよい。このようにして得られた水素化処理ピンチは
、偏光顕徴税により室温で説祭すると、大部分が光学的
等方性相であり、場合によって僅かにメソフェーズの小
球体が認められる。In the first stage of manufacturing hydrogenated pitch, raw pitches and a hydrogen donor are mixed at a weight ratio of 1 = 0.2 to 3, placed in an autoclave, and the air inside is removed from the desired gas. After replacing with inert gas or hydrogen gas such as, 300-500℃, preferably 350-48
It may be heated in a temperature range of 0° C. for 1 to 120 minutes, preferably within 60 minutes, and then free carbon may be melted by filtration or centrifugation to remove solids such as free carbon. When the hydrogenated pinch thus obtained is observed at room temperature under polarized light magnification, it is mostly in an optically isotropic phase, with slight mesophase spherules being observed in some cases.
本発明方法においては、このように調製された第１段階
の水素化処理ピッチを、第２段階において窒素気ｂ１シ
中で３００〜４５０℃、好寸しくは３２０〜４２０℃の
温度で１０〜５００分間、望ましくは１５〜３００分間
加熱処理する。この加熱処理によって水素化処理ピッチ
は、分子間で重縮合が進行してブリメソフェーズピッチ
を含むものに変換される。In the method of the present invention, the hydrogenated pitch of the first stage thus prepared is heated in a nitrogen atmosphere at a temperature of 300 to 450°C, preferably 320 to 420°C, for 10 to 10 minutes in the second stage. Heat treatment is performed for 500 minutes, preferably 15 to 300 minutes. By this heat treatment, the hydrogenated pitch undergoes polycondensation between molecules and is converted into one containing brimesophase pitch.
このようにして得られたプリメンフェーズピッチを含む
紡糸用ピッチにおいて、キノリンネ溶分が７５乗量％、
好ましくは２０〜６０重量％、ベンセン不溶分が７５重
量％以上、好甘しくけ８０重量％以上、高化式フローテ
スターによる軟化点が２００− ：うｏｏ℃、好捷しく
け２２０〜２７０℃であり１かつブリメソフェーズピッ
チを含み、室温で光学的に異方性を示す連続相を有する
ものが、紡糸性に優れかつ高強度の炭素繊維を提供する
。この場合、室温における光学的異方性連続相は、紡糸
温度では光学的等方性連続相に変換する。このようなピ
ンチの製造は１１Ｊ記の処理条件を適宜選択して行われ
る。In the spinning pitch containing the premenphase pitch obtained in this way, the quinoline soluble content is 75% by weight,
Preferably 20 to 60% by weight, benzene-insoluble content of 75% by weight or more, 80% by weight or more of a suitable weight, softening point of 200°C by Koka type flow tester: 220 to 270°C. A carbon fiber having a continuous phase that is 1 and contains brimesophase pitch and exhibits optical anisotropy at room temperature provides a carbon fiber with excellent spinnability and high strength. In this case, an optically anisotropic continuous phase at room temperature transforms into an optically isotropic continuous phase at the spinning temperature. Such pinches are manufactured by appropriately selecting the processing conditions described in 11J.
本発明方法においては、良好な紡糸性を有する前記のプ
リメンフェーズピッチを含む紡糸用ピッチを得るために
は、第１段階において水素化処理により室温で光学的等
方性連続相であり、かつキノリンネ溶分を含まないか、
あるいは含んでいても３０重量％未満であるものを形成
さぜ、次いでこれを第２段階の加熱処理に付するのか好
祉しい。In the method of the present invention, in order to obtain a spinning pitch containing the above-mentioned premenphase pitch having good spinnability, it is necessary that the pitch be an optically isotropic continuous phase at room temperature by hydrogenation treatment in the first step, and Contains no quinoline-soluble matter,
Alternatively, it is preferable to form a product containing less than 30% by weight, and then to subject it to the second stage of heat treatment.
また、第１段階の水素化処理における加熱処理時間は原
料ピッチの種類、熱履歴などによって前記の範囲から適
宜選択され、さらに第２段階における加熱処理の際には
、生成する低洲点物を同時に除去する心間かある。この
低沸点物の除去は減圧処理、不活性気体の吹込み、Ｒ，
膜蒸留装置を用いた処理、あるいは高速かさまぜなどを
組み合わせて行われる。この低沸点物の除去速度は、生
成紡糸用ピッチにおける室温で光学的異方性を示す連続
相の量を調節するのに大きな影響を与える。In addition, the heat treatment time in the first stage hydrogenation treatment is appropriately selected from the above range depending on the type of raw material pitch, thermal history, etc., and furthermore, during the second stage heat treatment, the low point substances generated are There is also a need to remove them at the same time. Removal of these low-boiling substances can be carried out by vacuum treatment, inert gas blowing, R,
Treatment is carried out using membrane distillation equipment or in combination with high-speed stirring. The rate of removal of this low boiler has a significant influence on controlling the amount of continuous phase exhibiting optical anisotropy at room temperature in the resulting spinning pitch.
本発明方法によって得られるブリメソフェーズピッチを
含む紡糸用ピッチは、室温で光学的に異方性を示す連続
相が流れ構造を呈し、その中に光学的に等方性の部分が
小球として点在している。The spinning pitch containing Brimesophase pitch obtained by the method of the present invention has a continuous phase that exhibits optical anisotropy at room temperature exhibits a flow structure, in which optically isotropic portions are dotted as small spheres. There is.
このような紡糸用ピンチは高化式フローテスターによる
軟化点が２００〜３００℃、好ましくは２２０〜２７０
℃の温度範囲内にあるものである。この軟化点は高化】
、（フローテスターの測定によりグラフに描かれた屈曲
点で示される。なお、本発明における紡糸用ピッチ中に
含まれるブリメソフェーズはキノリンに可溶で、室温で
光学的に等方性であシ、かつ炭化後に異方性に変るもの
である○本発明における紡糸は溶融紡糸、押出し紡糸、
吹出し紡糸のいずれを用いてもよい。溶融紡糸をイｊう
ときは０．１〜０ 、７ ＋ｎｍのノズル口径をもつ紡
糸器にピッチを入れ、ピッチの軟化点よりも５０〜１８
０℃程度商＜、／Ｉ００℃よシ低い温度に加熱し、ピッ
チ上ｐ４（より加圧して紡糸する。この際紡糸温度が／
１００℃を超えるとピンチが変質して好ましくない０′
また・生産性の点から高速紡糸が好ましく、さらに炭素
４、戒維の強度を（ｆＭ保するためにピッチ繊にイ（の
径を細くする心間がある。本発明の紡糸用ピンチにおい
ては紡糸速度すなわち巻取速度は３００〜２０００ｍ／
分かり能であシ、才たピッチ繊維径は１０μｍ以下が適
当である。Such spinning pinches have a softening point of 200 to 300°C, preferably 220 to 270°C, as measured by a Koka type flow tester.
It is within the temperature range of ℃. This softening point increases]
, (indicated by the inflection point drawn on the graph as measured by a flow tester. The brimesophase contained in the spinning pitch in the present invention is soluble in quinoline, optically isotropic and stable at room temperature. , and changes to anisotropy after carbonization. Spinning in the present invention may include melt spinning, extrusion spinning,
Any blow spinning method may be used. When melt spinning, the pitch is placed in a spinner with a nozzle diameter of 0.1 to 0.7 nm, and the pitch is 50 to 18 nm below the softening point of the pitch.
It is heated to a temperature lower than about 0℃, /I00℃, and spun with more pressure than pitch p4 (at this time, the spinning temperature is /
If the temperature exceeds 100℃, the pinch will deteriorate and become unfavorable.
In addition, high-speed spinning is preferable from the viewpoint of productivity, and in order to maintain the strength of the carbon 4 fibers (fM), the pitch fibers have a center spacing to reduce the diameter of the fibers. The spinning speed, that is, the winding speed is 300 to 2000 m/
It is suitable that the diameter of the pitch fibers is 10 μm or less.
このようにして紡糸した繊維状ピンチは、例えば空気中
において０．５〜ｂ
２００〜４００℃に昇温して酸化、不融化処理されたの
ち、不活性ガス中において３〜ｂ
温速度で１０００〜１５００℃まで加熱して炭化し、所
望に応じ、さらにアルゴン雰囲気中で２０００〜３００
０℃に加熱して黒鉛化する二
本発明方法により得られる炭素１１維は、このような炭
化処理によって繊維全体が光学的異方性となる。The fibrous pinch spun in this way is heated to 0.5 to 200 to 400°C in air to undergo oxidation and infusibility treatment, and then placed in an inert gas at a temperature rate of 3 to 1000°C. Carbonize by heating to ~1500°C, and further heat to 2000~300°C in an argon atmosphere as desired.
The carbon-11 fiber obtained by the method of the present invention, which is heated to 0° C. and graphitized, becomes optically anisotropic throughout the fiber by such carbonization treatment.
本発明の炭素繊維の製造方法によると、第１段階で得ら
れた水素化処理ピンチを、第２段階においてこれまでの
方法よりも低い温度で熱処理することにより、再現性が
よく、かつ紡糸性に後れたプリノンフェーズピッチを含
む紡糸用ピッチを収率よく得ることができ、この紡糸用
ピッチから高強度の炭素繊維を工業的に効率よく製造し
うる。According to the carbon fiber manufacturing method of the present invention, the hydrogenated pinch obtained in the first step is heat-treated in the second step at a temperature lower than that of conventional methods, thereby achieving good reproducibility and spinnability. It is possible to obtain a spinning pitch containing a purinone phase pitch that is delayed in a high yield, and high-strength carbon fibers can be produced industrially and efficiently from this spinning pitch.
次に実施例によって本発明をさらに詳細に説明する。Next, the present invention will be explained in more detail with reference to Examples.
なお、例中の％は重量基準である。Note that the percentages in the examples are based on weight.
実施例１
キノリンネ溶分８％、軟化点８９℃の石炭ピンチを融解
し、１５１１ｍの孔径を有する青銅製のフィルターで加
圧ろ過してフリーカーボンを除去した。Example 1 A pinch of coal having a quinoline dissolved content of 8% and a softening point of 89° C. was melted and filtered under pressure through a bronze filter having a pore size of 1511 m to remove free carbon.
このピンチ３５０７とテトラヒドロキノリン３５０ｆを
オートクレーブに仕込み、窒素置換後、４３０℃に昇温
して３０分保持した。この溶液を２５０４ガラスフイル
ターでろ過後２５０℃で３０分減圧蒸留し、テトラヒド
ロキノリンを除去した。残留物を水素化処理ピッチとし
た。第１図に水素化処理ピッチの３２０倍による室温で
の偏光顕微鏡の写真を示す。水素化処理ピッチはキノリ
ンネ溶分Ｏ％、ベンゼン不溶分７５％、高化式フローテ
スターによる軟化点５１℃であった。This pinch 3507 and tetrahydroquinoline 350f were charged into an autoclave, and after the autoclave was purged with nitrogen, the temperature was raised to 430°C and held for 30 minutes. This solution was filtered through a 2504 glass filter and then distilled under reduced pressure at 250°C for 30 minutes to remove tetrahydroquinoline. The residue was used as hydrotreated pitch. FIG. 1 shows a polarizing microscope photograph of the hydrogenated pitch at room temperature with a magnification of 320 times. The hydrogenated pitch had a quinoline soluble content of 0%, a benzene insoluble content of 75%, and a softening point of 51°C using a Koka type flow tester.
Ｍ 配水素化処理ピンチ３００２を四つロフラスコに仕
込み、かき１ぜながら窒素バブル下、３８０℃で６０分
間１．０ ＋ａｎ Ｈｇで減圧して低沸点物を除去した
のち、さらに同温度で１８０分間常圧で、窒素バブルさ
せながら熱処理してプリメソフェーズピッチを含む紡糸
用ピッチを得だ（収率３７％）。これはキノリンネ溶分
４１％、ベンゼン不溶分９１％、高化式フローテスター
による軟化点２４５℃であった。第２図にプリメンフェ
ーズをふくむ紡糸用ピッチの３２０侶による室温での偏
光顕微鏡の写真を示す。図中の連続相は光学的に異方性
であシ、点在する丸い黒点は等方性である。M Hydrogenation Treatment Four pieces of Pinch 3002 were placed in a Lough flask, and heated under nitrogen bubbles with stirring for 60 minutes at 380°C. After reducing the pressure at 1.0 + an Hg to remove low boiling point substances, the mixture was further heated at the same temperature for 180 minutes. A spinning pitch containing pre-mesophase pitch was obtained by heat treatment at normal pressure with nitrogen bubbles (yield: 37%). This had a quinoline soluble content of 41%, a benzene insoluble content of 91%, and a softening point of 245°C using a Koka type flow tester. FIG. 2 shows a polarizing microscope photograph taken at room temperature of 320 particles of spinning pitch including premen phase. The continuous phase in the figure is optically anisotropic, and the scattered round black dots are isotropic.
このプリメソフェーズピッチを含み光学的異方性を連続
相とする紡糸用ピッチを０．３■径のノズルを有する溶
融紡糸器に入れ３６０℃の温度で紡糸した。巻取速度８
００ ｍ ７分で定常的に巻き取られ、繊維径は９．５
μｍであった。このピッチ繊維を空気中で２℃／分の昇
温速度で３００℃寸で昇温し、３０分間保持した。さら
に窒素気流中で５℃／分の昇温速度で１４００℃まで昇
温し、 １５分間保持して炭素繊維を得た。この炭素繊
維の引張強度は３０８１＜ｙ／ｍＡ、伸び１．５％、弾
性率２Ｊ、、ｏｔ／−で、繊維径は６．５μｍであった
。The spinning pitch containing this pre-mesophase pitch and having optical anisotropy as a continuous phase was put into a melt spinning machine having a nozzle with a diameter of 0.3 mm and spun at a temperature of 360°C. Winding speed 8
00 m Steady winding in 7 minutes, fiber diameter is 9.5
It was μm. This pitch fiber was heated to 300° C. at a rate of 2° C./min in air and held for 30 minutes. Further, the temperature was raised to 1400°C at a rate of 5°C/min in a nitrogen stream and held for 15 minutes to obtain carbon fibers. This carbon fiber had a tensile strength of 3081<y/mA, an elongation of 1.5%, an elastic modulus of 2 J, ot/-, and a fiber diameter of 6.5 μm.
比較例１
キノリンネ溶分１２％、軟化点１０２℃の石炭ピッチを
溶融し、２５Ｇ４ガラスフイルターでろ過してフリーカ
ーボンを除去した。この石炭ピッチ２．０００ ｉＦと
水素化アントラセンオイル１５００ ｒ をオートクレ
ーブに仕込み、窒素置換後４５０℃に昇温して６０分間
保持した。この溶液を２５０４ガラスフイルターでろ過
後、四つロフラスコに移して、かき寸ぜながら窒素雰囲
気中で減圧して水素化アン］・ラセンオイルを留去し水
素化処理ピッチを調製した。次いで、常圧にし、窒素バ
ブルして低沸点物を定常的に留去しながら３℃／分の昇
温速度で３００℃から４４０℃に昇温しん。４４０℃に
達したところで加熱を止めて冷却し、約８分間で３００
℃としだ。得られたプリメンフェーズを含む紡糸用ピッ
チはキノリンネ溶分１１６８％、ベンゼン不溶分６２％
、高化式フローテスターによる軟化点１４４℃であった
。第３図にそのピッチの３２０倍の室温での偏光顕ａｍ
写真を示す。図中、連続相は等方性で小球は光学的異方
性である。Comparative Example 1 Coal pitch with a quinoline dissolved content of 12% and a softening point of 102° C. was melted and filtered through a 25G4 glass filter to remove free carbon. This coal pitch of 2.000 iF and hydrogenated anthracene oil of 1500 r were charged into an autoclave, and after purging with nitrogen, the temperature was raised to 450° C. and held for 60 minutes. This solution was filtered through a 2504 glass filter, then transferred to a four-hole flask, and while stirring, the pressure was reduced in a nitrogen atmosphere to distill off the hydrogenated am]-helical oil to prepare a hydrogenated pitch. Next, the pressure was brought to normal, and the temperature was raised from 300°C to 440°C at a rate of 3°C/min while constantly distilling off low-boiling substances using nitrogen bubbles. When it reaches 440℃, stop heating and cool it down to 300℃ in about 8 minutes.
℃ and Toshida. The obtained spinning pitch containing the prime phase has a quinoline soluble content of 1168% and a benzene insoluble content of 62%.
The softening point was 144°C using a Koka type flow tester. Figure 3 shows a polarized light microscope at room temperature that is 320 times the pitch.
Show photos. In the figure, the continuous phase is isotropic and the globules are optically anisotropic.
このピッチを用いて実施例１と同様に紡糸、不融化、炭
化を行った。しかし、紡糸温度２００〜３２０℃で試み
たが、２６０℃で１．５０ｍ／分の巻取速度が最高で、
繊維径も１５〜３８μｍのバラツキがあ妬得られた炭素
繊維の引張強度は１１２Ｋｑ／ｍＡ以下でバラつきの多
いものであった。Using this pitch, spinning, infusibility, and carbonization were performed in the same manner as in Example 1. However, although we tried spinning at a spinning temperature of 200 to 320°C, the highest winding speed was 1.50 m/min at 260°C.
The fiber diameter also varied from 15 to 38 μm, and the tensile strength of the obtained carbon fibers was less than 112 Kq/mA and varied widely.
実施例２
比較例１により調製した水素化処理ピンチ１００２をス
テンレス鋼製四つロフラスコに仕込み、かきまぜながら
窒素バブルして低沸点物を除去しながら４００℃で２時
間加熱した。その後、３分間冷却し３００℃に達した。Example 2 Hydrogenated pinch 1002 prepared in Comparative Example 1 was placed in a stainless steel four-loop flask, and heated at 400° C. for 2 hours while stirring and removing low-boiling substances by nitrogen bubbles. Thereafter, it was cooled for 3 minutes to reach 300°C.
次いで紡糸、不融化及び炭化を実施例１と同様に行った
。この操作をさらに４回繰り返して炭素繊維を得た。結
果を第１表に示す。Next, spinning, infusibility and carbonization were carried out in the same manner as in Example 1. This operation was repeated four more times to obtain carbon fibers. The results are shown in Table 1.
比較例２
比較例１によシ調整した水素化処理ピッチ１．００７を
ステンレス鋼製口つ目フラスコに仕込み、あらかじめ４
７０℃に調節した塩浴中につけて、かきまぜながら窒素
バブル下２０分間加熱した。その後５分間冷却して３０
０℃とした。次いで、紡糸、不融化及び炭化を実施例１
と同様に行った。この操作をさらに４回縁セ返して炭素
繊維を得た。結果を第２表に示す。Comparative Example 2 Hydrotreated pitch 1.007 prepared according to Comparative Example 1 was charged into a stainless steel neck flask, and 4.
The mixture was placed in a salt bath adjusted to 70°C and heated under nitrogen bubbles for 20 minutes while stirring. Then cool for 5 minutes and
The temperature was 0°C. Next, spinning, infusibility and carbonization were carried out in Example 1.
I did the same thing. This operation was repeated four more times to obtain carbon fibers. The results are shown in Table 2.
第１表及び第２表から明らかなように、本発明方法は比
較の方法に比べて、再現性がよく、かつ紡糸性の優れた
紡糸用ピッチを比較的高い収率で得ることができ、この
ピッチから高強度の炭素繊維を安定して製造することが
できる。As is clear from Tables 1 and 2, the method of the present invention has good reproducibility and can obtain spinning pitch with excellent spinnability at a relatively high yield compared to the comparative method. High-strength carbon fibers can be stably produced from this pitch.
実施例３
実施例２において、水素化処理ピッチの加熱温度及び時
間をそれぞれ４２０℃及び１．５時間に代える以外は実
施例２と同様にして炭素繊維を得た。Example 3 Carbon fibers were obtained in the same manner as in Example 2, except that the heating temperature and time of the hydrogenated pitch were changed to 420° C. and 1.5 hours, respectively.
途中で生成する紡糸用ピッチ及び最終的に得られた炭素
繊維の性状を次に示す。The properties of the spinning pitch produced during the process and the carbon fiber finally obtained are shown below.
紡糸用ピッチの性状
キノリンネ溶分 ４８．３％
ベンゼン不溶分 ９７．３％
軟化点 ２６１ ℃
収率 ３５．８％
炭素繊維の性状
繊維径 ７．９μｍ
引張強度 ２８０ Ｋｑ／ｙＵ伸び
１．５％
弾け率 １９．Ｏｔ／４比較例３
比較例２において、水素化処理ピンチの加熱時間を４０
分に代える以外は比較例２と同様にして紡糸用ピッチを
得、これを紡糸して炭素繊維を製造しようとしだが、こ
のピッチの軟化点が高いため紡糸できなかった。Properties of pitch for spinning Quinoline soluble content 48.3% Benzene insoluble content 97.3% Softening point 261 °C Yield 35.8% Carbon fiber properties Fiber diameter 7.9 μm Tensile strength 280 Kq/yU elongation
1.5% bounce rate 19. Ot/4 Comparative Example 3 In Comparative Example 2, the heating time of the hydrogenation treatment pinch was set to 40
A pitch for spinning was obtained in the same manner as in Comparative Example 2, except that the pitch was replaced with 100 ml, and an attempt was made to spin this to produce carbon fibers, but spinning was not possible because the softening point of this pitch was high.
前記紡糸用ピッチの性状を次に示す。The properties of the spinning pitch are shown below.
紡糸用ピッチの性状 キノリン不溶分 ７９，７％ ベンセン不溶分 ９８．１％ 軟化点 ３３０℃以上Properties of spinning pitch Quinoline insoluble content 79.7% Benzene insoluble content 98.1% Softening point 330℃ or more
第１図は実施例１における水素化処理ピッチ、第２図は
実施例１における紡糸用ピッチ、第３図は比＋ｌＷＩ＋
ｌＪ］における紡糸用ピッチのそれぞれ室温における１
扁光顕徴税写真である。
′（〜 １１ンＩ
・”Ｔ ２ ＋゛１
・（”＋ ３ ｆ’１
第１頁の続き
＠発 明 者 新保喜代嗣
東京都墨田区亀沢２−１１−１２−
０４
Ｑや出 願 人 大日本インキ化学工業株式会社東京都
板橋区坂下３丁目３５番５８Figure 1 shows the hydrogenated pitch in Example 1, Figure 2 shows the spinning pitch in Example 1, and Figure 3 shows the ratio +lWI+
lJ] of the spinning pitch at room temperature, respectively.
This is a microscopic photograph. '(~11nI ・"T 2 +゛1 ・("+ 3 f'1 Continuation of page 1 @ Inventor Kiyoshi Shinbo 2-11-12-04 Kamezawa, Sumida-ku, Tokyo Q and applicant Dainippon Ink Chemical Industry Co., Ltd. 3-35-58 Sakashita, Itabashi-ku, Tokyo
Claims (1)
化処理ピッチを３００〜４５０℃の温度で加熱処理して
、キノリンネ溶分が１５〜７５重量％、ベンゼン不溶分
が７５重量％以上及び高化式フローテスターによる軟化
点が２００〜３００℃であり、かつブリメソフェーズピ
ッチを含み、室温で光学的に異方性を示す連続相を有す
る紡糸用ピッチを形成させ、次いで紡糸したのち不融化
処理し、さらに炭化処理することを特徴とする炭素繊維
の製造法。1 Hydrogenated pitch from which infusible or insoluble solids have been removed is heat-treated at a temperature of 300 to 450°C in a monoxide gas stream to obtain a quinoline soluble content of 15 to 75% by weight and a benzene insoluble content of 75% by weight. In addition, after forming a spinning pitch having a softening point of 200 to 300°C using a Koka type flow tester, containing Brimesophase pitch, and having a continuous phase exhibiting optical anisotropy at room temperature, and then spinning, A method for producing carbon fiber, characterized by carrying out an infusible treatment and then a carbonization treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19745082A JPS5988923A (en) | 1982-11-12 | 1982-11-12 | Manufacture of carbon fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19745082A JPS5988923A (en) | 1982-11-12 | 1982-11-12 | Manufacture of carbon fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS5988923A true JPS5988923A (en) | 1984-05-23 |
Family
ID=16374704
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19745082A Pending JPS5988923A (en) | 1982-11-12 | 1982-11-12 | Manufacture of carbon fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5988923A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07194966A (en) * | 1994-08-01 | 1995-08-01 | Osaka Gas Co Ltd | Preparation of isotropic pitch |
| JPH09143475A (en) * | 1996-11-11 | 1997-06-03 | Osaka Gas Co Ltd | Isotropic pitch |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57100184A (en) * | 1980-12-13 | 1982-06-22 | Nippon Steel Corp | Drying treating method of raw material coal for coke oven |
| JPS5818421A (en) * | 1981-07-27 | 1983-02-03 | Agency Of Ind Science & Technol | Preparation of carbon fiber |
| JPS58191222A (en) * | 1982-04-30 | 1983-11-08 | Dainippon Ink & Chem Inc | Manufacture of pitch based carbon fiber |
| JPS5926526A (en) * | 1982-07-12 | 1984-02-10 | ヘキスト・セラニーズ・コーポレーション | Hydrophilic polyester staple fiber, production thereof and fabric produced therefrom |
| JPS5926525A (en) * | 1982-08-03 | 1984-02-10 | Dainippon Ink & Chem Inc | Mesophase pitch for carbon fiber spinnable at high speed and carbon fiber obtained therefrom |
-
1982
- 1982-11-12 JP JP19745082A patent/JPS5988923A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57100184A (en) * | 1980-12-13 | 1982-06-22 | Nippon Steel Corp | Drying treating method of raw material coal for coke oven |
| JPS5818421A (en) * | 1981-07-27 | 1983-02-03 | Agency Of Ind Science & Technol | Preparation of carbon fiber |
| JPS58191222A (en) * | 1982-04-30 | 1983-11-08 | Dainippon Ink & Chem Inc | Manufacture of pitch based carbon fiber |
| JPS5926526A (en) * | 1982-07-12 | 1984-02-10 | ヘキスト・セラニーズ・コーポレーション | Hydrophilic polyester staple fiber, production thereof and fabric produced therefrom |
| JPS5926525A (en) * | 1982-08-03 | 1984-02-10 | Dainippon Ink & Chem Inc | Mesophase pitch for carbon fiber spinnable at high speed and carbon fiber obtained therefrom |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07194966A (en) * | 1994-08-01 | 1995-08-01 | Osaka Gas Co Ltd | Preparation of isotropic pitch |
| JPH09143475A (en) * | 1996-11-11 | 1997-06-03 | Osaka Gas Co Ltd | Isotropic pitch |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS62270685A (en) | Production of mesophase pitch | |
| JPH0133568B2 (en) | ||
| FR2528442A1 (en) | PROCESS FOR THE PREPARATION OF A BRAI PARTICULARLY SUITABLE FOR THE USE AS A RAW MATERIAL FOR THE PREPARATION OF CARBON FIBERS | |
| JPS59196390A (en) | Preparation of pitch for carbon fiber | |
| JPH0321588B2 (en) | ||
| JPS6030365B2 (en) | Method for producing high strength, high modulus carbon fiber | |
| JPS58196292A (en) | Preparation of carbonaceous substance in premetaphase | |
| JPH0150272B2 (en) | ||
| JPH05132675A (en) | Production of pitch | |
| JPS6065090A (en) | Preparation of pitch for carbon fiber spinning | |
| JPS5988923A (en) | Manufacture of carbon fiber | |
| JPH0148312B2 (en) | ||
| JPH0148314B2 (en) | ||
| JPS6312689A (en) | Production of precursor pitch for carbon fiber | |
| JPS5834569B2 (en) | Carbon fiber manufacturing method | |
| JPS61127788A (en) | Production of meso-phase pitch for carbon fiber | |
| JPS61138721A (en) | Production of carbon fiber | |
| JPH0144752B2 (en) | ||
| JPS61287961A (en) | Precursor pitch for carbon fiber | |
| JPH0148313B2 (en) | ||
| JPH0148315B2 (en) | ||
| CA1259576A (en) | Method of purifying the starting material for use in the production of carbon products | |
| JPH058755B2 (en) | ||
| JPS59189188A (en) | Preparation of raw material pitch for carbon fiber having high strength and elastic modulus | |
| JPS5982417A (en) | Pitch for raw material of carbon fiber and its preparation |