JP4626939B2 - Carbon fiber manufacturing method - Google Patents
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本発明は、高強度の炭素繊維の製造方法に関する。 The present invention relates to a method for producing a high-strength carbon fiber.
従来、炭素繊維製造用のプリカーサー(前駆体繊維)を用い、これに耐炎化処理を施して耐炎化繊維を得ること、更にこの耐炎化繊維に炭素化処理を施して高性能炭素繊維を得ることは広く知られている。また、この方法は工業的にも実施されている。 Conventionally, a precursor (precursor fiber) for producing carbon fiber is used to obtain a flame resistant fiber by subjecting it to a flame resistant treatment, and further, a high performance carbon fiber is obtained by subjecting this flame resistant fiber to a carbonization treatment. Is widely known. This method is also practiced industrially.
特に、近年炭素繊維の用途はスポーツ・レジャー用品から航空宇宙分野、特に航空機の一次構造材にまで展開されている。さらに、炭素繊維の高い比強度、比弾性の特性を生かして製品の軽量化を図ることにより省エネルギー化を図り、これにより排出ＣＯ2の削減に寄与することを目的として各産業界は炭素繊維の新しい利用方法に注目し、また研究を進めている。 In particular, in recent years, the use of carbon fiber has been expanded from sports and leisure goods to the aerospace field, particularly to primary structural materials for aircraft. In addition, various industries have made efforts to save energy by reducing the weight of products by taking advantage of the high specific strength and specific elasticity of carbon fibers, thereby contributing to the reduction of CO 2 emissions. We are focusing on new ways of using and researching them.
このような状況下において、炭素繊維にも更なる高性能化、低製造コスト化、また取扱性に優れる高品質化等の課題の解決が要請されている。 Under such circumstances, carbon fibers are also required to solve problems such as higher performance, lower manufacturing costs, and higher quality with excellent handling properties.
一般に原料繊維であるプリカーサーとしてはアクリル繊維が用いられる。このアクリル繊維から炭素繊維を製造する場合、アクリル繊維を２００〜３００℃の酸化性雰囲気下で延伸又は収縮を行いながら酸化処理(耐炎化処理)を行った後、３００以上、又は１０００℃以上の不活性ガス雰囲気中で炭素化して炭素繊維を製造する。 In general, an acrylic fiber is used as a precursor which is a raw material fiber. When producing carbon fiber from this acrylic fiber, after carrying out oxidation treatment (flameproofing treatment) while stretching or shrinking the acrylic fiber in an oxidizing atmosphere of 200 to 300 ° C., 300 or more, or 1000 ° C. or more Carbon fiber is produced by carbonization in an inert gas atmosphere.
とりわけ３００〜９００℃付近での炭素化工程の繊維処理方法は、炭素繊維の強度発現に大きく影響を及ぼし、これまでに多くの検討が行われてきた。 In particular, the fiber treatment method in the carbonization process at around 300 to 900 ° C. greatly affects the strength expression of the carbon fiber, and many studies have been made so far.
特許文献１では、耐炎化繊維を３００〜８００℃において、不活性雰囲気中２５％までの範囲で伸長を加えながら炭素化し、耐炎化繊維の原長に対し負とならないように処理することによって、高強度の炭素繊維を得ることが開示されている。 In Patent Document 1, the flame-resistant fiber is carbonized at 300 to 800 ° C. while being stretched in an inert atmosphere in a range of up to 25%, and processed so as not to be negative with respect to the original length of the flame-resistant fiber. It is disclosed to obtain high strength carbon fibers.
また、特許文献２、特許文献３では、５００℃付近での繊維長さの急激な変化をコントロールするため、３００〜５００℃、５００〜８００℃と、工程を２つに分けることで高強度の炭素繊維が得られることが開示されている。 Moreover, in patent document 2 and patent document 3, in order to control the rapid change of the fiber length in 500 degreeC vicinity, 300-500 degreeC, 500-800 degreeC, and a high intensity | strength are divided by dividing a process into two. It is disclosed that carbon fibers can be obtained.
しかしながら、これらの方法に記載されている温度範囲などの条件や比重などパラメーターだけでは繊維の物性をコントロールする事は難しい。そこで、従来より繊維の物性をコントロールしつつ高強度の炭素繊維を得るための方法が求められている。
本発明者は、上記問題を解決するために種々検討しているうちに、ＴＭＡ測定より得られる最大延伸率、広角Ｘ線測定より得られる２６°における配向度が所定範囲の耐炎化繊維を、前記最大延伸率を基準として、その所定割合の延伸率で炭素化して得られる炭素繊維は高強度であることを知得し、本発明を完成するに到った。 While the present inventor has been variously studied to solve the above problems, the maximum stretch ratio obtained by TMA measurement, the flameproof fiber having an orientation degree at 26 ° obtained by wide-angle X-ray measurement of a predetermined range, Based on the maximum draw ratio, the carbon fiber obtained by carbonization at a predetermined stretch ratio is known to have high strength, and the present invention has been completed.
従って、本発明の目的とするところは、上記問題を解決した、高強度の炭素繊維の製造方法を提供することにある。 Accordingly, an object of the present invention is to provide a method for producing a high-strength carbon fiber that solves the above problems.
上記目的を達成する本発明は、以下に記載するものである。 The present invention for achieving the above object is described below.
〔１〕 ＴＭＡ測定より得られる最大延伸率[Ａ]％が１０％以上、且つ広角Ｘ線測定より得られる２６°における配向度が７５％以上である耐炎化繊維を、不活性雰囲気中、温度３００〜６００℃、且つ前記最大延伸率[Ａ]％で示される延伸率[Ａ×０．３５]〜[Ａ×０．５５]％で熱処理した後、不活性雰囲気中、温度６００〜１６００℃で熱処理する炭素繊維の製造方法。 [1] A flame-resistant fiber having a maximum draw ratio [A]% obtained by TMA measurement of 10% or more and an orientation degree at 26 ° of 75% or more obtained by wide-angle X-ray measurement is measured in an inert atmosphere at a temperature. After heat treatment at 300 to 600 ° C. and a stretching ratio [A × 0.35] to [A × 0.55]% indicated by the maximum stretching ratio [A]%, the temperature is 600 to 1600 ° C. in an inert atmosphere. A method for producing carbon fiber, which is heat-treated at a temperature.
本発明の炭素繊維の製造方法によれば、ＴＭＡ測定より得られる最大延伸率、広角Ｘ線測定より得られる２６°における配向度が所定範囲の耐炎化繊維を、前記最大延伸率で示される延伸率の所定範囲の設定を含む条件で炭素化処理しているので、処理中の繊維物性のコントロールが確実にでき、安定して高強度の炭素繊維の生産ができる。 According to the carbon fiber production method of the present invention, the maximum stretch ratio obtained by TMA measurement and the flameproof fiber having a predetermined degree of orientation at 26 ° obtained by wide-angle X-ray measurement are stretched by the maximum stretch ratio. Since the carbonization treatment is performed under conditions including the setting of a predetermined range of the rate, it is possible to reliably control the physical properties of the fiber during the treatment, and stably produce high-strength carbon fibers.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明の炭素繊維の製造方法において出発原料として用いる耐炎化繊維は、ＴＭＡ測定より得られる最大延伸率[Ａ]％が１０％以上、広角Ｘ線測定より得られる２６°における配向度が７５％以上のものである。 The flame-resistant fiber used as a starting material in the carbon fiber production method of the present invention has a maximum draw ratio [A]% obtained by TMA measurement of 10% or more, and an orientation degree at 26 ° obtained by wide-angle X-ray measurement of 75%. That's all.
ＴＭＡ測定における耐炎化繊維の任意の応力(ＴＭＡ応力)に対する最大延伸率(ＴＭＡmax)[Ａ]％は、以下の方法により求めることができる。
１． 耐炎化繊維を採取し、測定有効長１ｃｍとして繊維測定用の治具に固定する。
２． Ｎ2ガス雰囲気下で耐炎化繊維を任意の単位断面積当りの応力で延伸しながら、２５℃から４００℃まで昇温速度２０℃／分の条件で昇温し、この延伸熱処理中の耐炎化繊維についてＴＭＡ延伸率測定を測定する。
３． 測定された延伸熱処理中におけるＴＭＡ測定延伸率のうち最大のＴＭＡ測定延伸率を、ＴＭＡ最大延伸率とする。
The maximum draw ratio (TMA max ) [A]% with respect to an arbitrary stress (TMA stress) of the flameproof fiber in the TMA measurement can be obtained by the following method.
1. Flame-resistant fibers are collected and fixed to a fiber measuring jig with a measurement effective length of 1 cm.
2. While stretching the flame-resistant fiber with an arbitrary stress per unit cross-sectional area in an N 2 gas atmosphere, the temperature is increased from 25 ° C. to 400 ° C. at a rate of temperature increase of 20 ° C./min. TMA stretch ratio measurements are measured on the fibers.
3. The maximum TMA measurement stretch ratio among the measured TMA measurement stretch ratios during the stretching heat treatment is defined as the TMA maximum stretch ratio.
ＴＭＡより得られる最大延伸率(ＴＭＡmax)[Ａ]％が１０％未満である繊維は、耐炎化工程に続く第一炭素化工程において、高強度化に必要な配向度の向上ができないだけでなく、強度低下を抑制することが困難である。さらに、毛羽や単糸切れを生じ易く、安定生産ができない。 Fibers with a maximum draw ratio (TMA max ) [A]% obtained from TMA of less than 10% cannot be improved in the degree of orientation required for high strength in the first carbonization process following the flame resistance process. Therefore, it is difficult to suppress the strength reduction. Furthermore, fluff and single yarn breakage are likely to occur, and stable production cannot be achieved.
広角Ｘ線測定(回折角２６°)における配向度は、次のようにして求めることができる。 The degree of orientation in wide-angle X-ray measurement (diffraction angle 26 °) can be determined as follows.
耐炎化繊維の単繊維約１２０００本を束にし、アセトンを用いて束を収束させながら繊維軸方向に繊維を引揃える。
１． 耐炎化繊維の単繊維約１２０００本を束にし、アセトンを用いて束を収束させながら繊維軸方向に繊維を引揃える。
２． 直径１．０ｃｍの穴をあけた台紙に、繊維束の中央が穴の中央に来るように、繊維を緊張させた状態で貼付ける。その後、繊維軸と治具の軸が平行になるように、台紙を試料調整用治具に固定する。
３． 更に、この治具を透過法による広角Ｘ線回折測定試料台に固定する。Ｘ線源として、ＣｕのＫα線を使用し、試料に照射すると、２θ２６度付近に回折パターン(二つのピークを有する)が現れる。
４． この回折パターンのピーク角度を求め、それらの角度を含む３６０度の範囲について測定を行う。次いで得られたＸ線回折チャートのグラフ上にベースラインを引き、ピークの半値幅Ｈ1/2、Ｈ'1/2(度)を求め、下式
配向度＝[３６０−(Ｈ1/2＋Ｈ'1/2)]／３６０
によって配向度を計算する。
About 12,000 single fibers of flame resistant fiber are bundled, and the fibers are aligned in the fiber axis direction using acetone to converge the bundle.
1. About 12,000 single fibers of flame resistant fiber are bundled, and the fibers are aligned in the fiber axis direction using acetone to converge the bundle.
2. The fiber is affixed to a mount having a hole with a diameter of 1.0 cm in a tensioned state so that the center of the fiber bundle comes to the center of the hole. Thereafter, the mount is fixed to the sample adjusting jig so that the fiber axis and the axis of the jig are parallel to each other.
3. Furthermore, this jig is fixed to a wide-angle X-ray diffraction measurement sample stage by a transmission method. When Cu Kα rays are used as the X-ray source and the sample is irradiated, a diffraction pattern (having two peaks) appears in the vicinity of 2θ26 degrees.
4). The peak angle of this diffraction pattern is obtained, and measurement is performed for a range of 360 degrees including these angles. Next, a base line is drawn on the graph of the obtained X-ray diffraction chart to determine peak half-value widths H 1/2 and H ′ 1/2 (degrees), and the following degree of orientation = [360− (H 1/2 + H'1 / 2 )] / 360
Calculate the degree of orientation.
耐炎化繊維の広角Ｘ線測定より得られる２６°における配向度が７５％未満では、この耐炎化繊維を第一炭素化処理する際において配向度の向上を行わなければならないため、高い延伸率が必要となる。しかし、高い延伸率は単糸切れを招き、安定な工程状態を保つことが困難となる。従って、上記配向度は７５％以上が必要である。 If the degree of orientation at 26 ° obtained from the wide-angle X-ray measurement of the flame-resistant fiber is less than 75%, the degree of orientation must be improved when the flame-resistant fiber is subjected to the first carbonization treatment. Necessary. However, a high draw ratio causes breakage of single yarn, and it becomes difficult to maintain a stable process state. Therefore, the degree of orientation needs to be 75% or more.
また、上記耐炎化繊維は、以下の方法で製造したものを用いても良い。この耐炎化繊維製造用のプリカーサーとしては、ポリアクリロニトリル(ＰＡＮ)系、ピッチ系、フェノール系、レーヨン系等のものが挙げられる。これらのプリカーサーのうちでも、ＰＡＮ系のもの(アクリル繊維)を用いることで、最も高強度の炭素繊維が得られる。 Moreover, you may use the said flameproof fiber manufactured with the following method. Examples of the precursor for producing the flame resistant fiber include polyacrylonitrile (PAN), pitch, phenol, rayon and the like. Among these precursors, the highest strength carbon fiber can be obtained by using a PAN-based one (acrylic fiber).
このアクリル繊維は、例えばアクリロニトリルを９５質量％以上含有する単量体を重合した単独重合体又は共重合体を含む紡糸溶液を、湿式又は乾湿式紡糸法において紡糸・水洗・乾燥・延伸等の処理を行うことによって得ることができる。共重合する単量体としては、アクリル酸メチル、イタコン酸、メタクリル酸メチル、アクリル酸等が好ましい。 This acrylic fiber is prepared by, for example, treating a spinning solution containing a homopolymer or copolymer obtained by polymerizing a monomer containing 95% by mass or more of acrylonitrile in a wet or dry-wet spinning method, such as spinning, washing, drying and stretching. Can be obtained by doing As the monomer to be copolymerized, methyl acrylate, itaconic acid, methyl methacrylate, acrylic acid and the like are preferable.
紡糸・水洗・乾燥処理後の延伸処理における延伸倍率を調節することにより、次工程で耐炎化処理して得られる耐炎化繊維のＴＭＡ測定より得られる最大延伸率や広角Ｘ線測定より得られる２６°における配向度等の物性を上記範囲内にすることができる。この延伸倍率は、３．１〜６．４倍に調節することが好ましく、３．３〜６．２倍に調節することが更に好ましい。 By adjusting the draw ratio in the drawing treatment after spinning, washing and drying, the maximum draw ratio obtained from TMA measurement of flame-resistant fiber obtained by flame-proofing treatment in the next step and obtained from wide-angle X-ray measurement 26 Physical properties such as the degree of orientation at ° can be within the above range. The draw ratio is preferably adjusted to 3.1 to 6.4 times, and more preferably adjusted to 3.3 to 6.2 times.
このようにして得られるアクリル繊維を、公知の方法に従って耐炎化して耐炎化繊維を得る。この耐炎化繊維を、本発明の炭素繊維の製造方法に従って炭素化することによって高強度の炭素繊維を得ることができる。 The acrylic fibers thus obtained are flame-resistant according to a known method to obtain flame-resistant fibers. High-strength carbon fibers can be obtained by carbonizing the flame-resistant fibers according to the carbon fiber production method of the present invention.
本発明の炭素繊維の製造方法における炭素化工程は、上記耐炎化繊維を、不活性雰囲気中、温度３００〜６００℃、且つ上記最大延伸率[Ａ]％で示される延伸率[Ａ×０．３５]〜[Ａ×０．５５]％で熱処理して第一炭素化処理繊維を得る第一炭素化工程と、この第一炭素化処理繊維を、不活性雰囲気中、温度６００〜１６００℃で熱処理して第二炭素化処理繊維を得る第二炭素化工程とからなる。 In the carbonization step in the carbon fiber production method of the present invention, the flame-resistant fiber is stretched at a temperature of 300 to 600 ° C. in an inert atmosphere and the stretch ratio [A × 0. 35] to [A × 0.55]% to obtain a first carbonized fiber obtained by heat treatment, and the first carbonized fiber in an inert atmosphere at a temperature of 600 to 1600 ° C. A second carbonization step of obtaining a second carbonized fiber by heat treatment.
第一炭素化工程における延伸率が[Ａ×０．３５]％未満では、延伸が乏しいため、高強度の炭素繊維を得ることができない。一方、第一炭素化工程における延伸率が[Ａ×０．５５]％より大きい場合は、過度の延伸により毛羽や糸切れを生じ易く、また配向度の向上も望めず、結果として工程の安定性を損なう可能性がある。 If the stretch rate in the first carbonization step is less than [A × 0.35]%, the stretch is poor, and thus high-strength carbon fibers cannot be obtained. On the other hand, when the stretch ratio in the first carbonization step is larger than [A × 0.55]%, fluff and thread breakage are liable to occur due to excessive stretching, and improvement in the degree of orientation cannot be expected, resulting in stable process. There is a possibility of impairing sex.
得られた第二炭素化処理繊維、即ち第二炭素化工程終了後に得られる炭素繊維は、引き続き公知の方法により、表面処理を施しても良い。さらに、炭素繊維の後加工をしやすくし、取扱性を向上させる目的で、サイジング処理することが好ましい。サイジング方法は、従来の公知の方法で行うことができ、サイジング剤は、用途に即して適宜組成を変更して使用し、均一付着させた後に、乾燥することが好ましい。 The obtained second carbonized fiber, that is, the carbon fiber obtained after completion of the second carbonization step may be subsequently subjected to surface treatment by a known method. Furthermore, it is preferable to perform sizing treatment for the purpose of facilitating the post-processing of the carbon fiber and improving the handleability. The sizing method can be carried out by a conventionally known method, and the sizing agent is preferably used after changing its composition as appropriate according to the application, and after uniformly adhering.
なお、第二炭素化処理後の単繊維径は４．０〜７．５μｍであることが好ましい。 In addition, it is preferable that the single fiber diameter after a 2nd carbonization process is 4.0-7.5 micrometers.
このようにして得られた炭素繊維は、高強度であり、本発明の製造方法によりなし得るものである。 The carbon fiber thus obtained has high strength and can be produced by the production method of the present invention.
炭素繊維の強度は、引張り強度などで示すことができる。但し、この引張り強度の測定値は、実質の強度が同等であっても繊維直径が小さい程、高くなる傾向にある。そこで、炭素繊維の実質強度を評価するため、測定強度[Ｂ]ＭＰａを繊維直径[ｄ]μｍにより補正した強度[Ｃ]ＭＰａを、下式
Ｃ＝Ｂ×(ｄ／１０)0.65
を用いて算出する。
The strength of the carbon fiber can be indicated by tensile strength or the like. However, the measured value of the tensile strength tends to be higher as the fiber diameter is smaller even if the actual strength is the same. Therefore, in order to evaluate the real strength of the carbon fiber, the strength [C] MPa obtained by correcting the measured strength [B] MPa with the fiber diameter [d] μm is expressed by the following formula: C = B × (d / 10) 0.65
Calculate using.
以下、本発明を実施例及び比較例により更に具体的に説明する。また、各実施例及び比較例におけるアクリル繊維、耐炎化繊維及び炭素繊維の諸物性についての評価方法は、前述の方法又は以下の方法により実施した。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. Moreover, the evaluation method about the various physical properties of the acrylic fiber in each Example and a comparative example, a flame-resistant fiber, and carbon fiber was implemented by the above-mentioned method or the following methods.
＜ＴＭＡ最大延伸率＞
マックサイエンス社製の熱機械特性試験機(ＴＭＡ)４０００Ｓを用い、前述の方法により測定した。
<TMA maximum stretch ratio>
Measurement was performed by the above-described method using a thermomechanical property tester (TMA) 4000S manufactured by Mac Science.
＜広角Ｘ線測定(回折角２６°)における配向度＞
Ｘ線回折装置：理学電機製ＲＩＮＴ２０５０を使用し、前述の方法により測定した。
<Degree of orientation in wide-angle X-ray measurement (diffraction angle 26 °)>
X-ray diffractometer: RINT2050 manufactured by Rigaku Corporation was used, and measurement was performed by the method described above.
＜引張り強度＞
ＪＩＳ Ｒ ７６０１に規定された方法により測定した。
<Tensile strength>
It was measured by the method defined in JIS R7601.
作製例１
アクリロニトリル９５質量％、アクリル酸メチル４質量％、及びイタコン酸１質量％の共重合体を含有する紡糸原液を湿式紡糸し、水洗・乾燥・延伸(延伸倍率３．５倍)・オイリングして繊維直径１１．４μｍのアクリル繊維を得た。
Production Example 1
A spinning stock solution containing a copolymer of 95% by mass of acrylonitrile, 4% by mass of methyl acrylate, and 1% by mass of itaconic acid is wet-spun, washed with water, dried, stretched (stretching ratio: 3.5 times), and oiled. An acrylic fiber having a diameter of 11.4 μm was obtained.
作製例２
紡糸・水洗・乾燥後の延伸操作時の延伸倍率を３．０倍にした以外は作製例１と同様の条件でアクリル繊維を作製し、繊維直径１２．３μｍのアクリル繊維を得た。
Production Example 2
Acrylic fibers were produced under the same conditions as in Production Example 1 except that the draw ratio during the drawing operation after spinning, washing and drying was 3.0 times to obtain acrylic fibers having a fiber diameter of 12.3 μm.
作製例３
紡糸・水洗・乾燥後の延伸操作時の延伸倍率を６．０倍にした以外は作製例１と同様の条件でアクリル繊維を作製し、繊維直径８．７μｍのアクリル繊維を得た。
Production Example 3
Acrylic fibers were produced under the same conditions as in Production Example 1 except that the draw ratio during the drawing operation after spinning, washing and drying was 6.0 times, and acrylic fibers having a fiber diameter of 8.7 μm were obtained.
作製例４
紡糸・水洗・乾燥後の延伸操作時の延伸倍率を６．５倍にした以外は作製例１と同様の条件でアクリル繊維を作製し、繊維直径８．３μｍのアクリル繊維を得た。
Production Example 4
An acrylic fiber was produced under the same conditions as in Production Example 1 except that the draw ratio during the drawing operation after spinning, washing and drying was 6.5 times, and an acrylic fiber having a fiber diameter of 8.3 μm was obtained.
実施例１〜４及び比較例１〜６
作製例１〜４のアクリル繊維について、加熱空気中、炉内温度分布２５〜２５０℃の熱風循環式耐炎化炉において、延伸倍率１．０６倍で耐炎化処理し、表１に示す、ＴＭＡ最大延伸率、広角Ｘ線測定(回折角２６°)における配向度の耐炎化繊維を得た。
Examples 1-4 and Comparative Examples 1-6
The acrylic fibers of Production Examples 1 to 4 were subjected to flameproofing treatment at a draw ratio of 1.06 times in a hot air circulation type flameproofing furnace having a temperature distribution in the furnace of 25 to 250 ° C. in heated air. A flame-resistant fiber having a degree of orientation and an orientation degree in wide-angle X-ray measurement (diffraction angle 26 °) was obtained.
次いで、得られた耐炎化繊維を、不活性雰囲気中、炉内温度分布３００〜６００℃の第一炭素化炉において、表１に示す延伸率で熱処理して第一炭素化処理繊維を得た。 Next, the obtained flame-resistant fiber was heat-treated at a drawing rate shown in Table 1 in a first carbonization furnace having an in-furnace temperature distribution of 300 to 600 ° C. in an inert atmosphere to obtain a first carbonized fiber. .
その後、得られた第一炭素化処理繊維を、不活性雰囲気中、炉内温度分布６００〜１４００℃の第二炭素化炉において、延伸倍率０．９４倍で熱処理し、引き続き、公知の方法で表面処理、サイジングを施し、乾燥して表１に示す繊維直径、ストランド強度、繊維直径による補正強度の炭素繊維を得た。 Thereafter, the obtained first carbonized fiber was heat-treated at a draw ratio of 0.94 times in a second carbonization furnace having an in-furnace temperature distribution of 600 to 1400 ° C. in an inert atmosphere, and subsequently by a known method. Surface treatment, sizing, and drying were performed to obtain carbon fibers having fiber diameters, strand strengths, and correction strengths based on fiber diameters as shown in Table 1.
表１に示すように、実施例１〜４については何れも、中間原料の耐炎化繊維は、ＴＭＡ最大延伸率が１０％以上であり、且つ広角Ｘ線測定(回折角２６°)における配向度が７５％以上であった。更に、実施例１〜４については何れも、第一炭素化処理時の延伸率は対ＴＭＡmax比で０．３５〜０．５５の範囲であった。 As shown in Table 1, in all of Examples 1 to 4, the flame-resistant fiber as an intermediate raw material has a TMA maximum draw ratio of 10% or more, and the degree of orientation in wide-angle X-ray measurement (diffraction angle 26 °). Was 75% or more. Further, in all of Examples 1 to 4, the stretch ratio during the first carbonization treatment was in the range of 0.35 to 0.55 in terms of the ratio of TMA max .
これら実施例１〜４の条件で得られた炭素繊維は何れも、繊維直径による補正強度が高いものであった。 All of the carbon fibers obtained under the conditions of Examples 1 to 4 had high correction strength based on the fiber diameter.
これに対し、比較例１〜６については、中間原料の耐炎化繊維の、ＴＭＡ最大延伸率、広角Ｘ線測定(回折角２６°)における配向度、並びに、第一炭素化処理時の対ＴＭＡmax比で示した延伸率の条件の少なくとも一が本発明の構成から逸脱している。これら比較例１〜６の条件で得られた炭素繊維は何れも、繊維直径による補正強度が低いもの及び／又は第一炭素化工程において毛羽が発生するものであった。 On the other hand, for Comparative Examples 1 to 6, the TMA maximum draw ratio, the degree of orientation in the wide-angle X-ray measurement (diffraction angle 26 °), and the TMA at the time of the first carbonization treatment of the flame-resistant fiber of the intermediate material At least one of the conditions of the stretch ratio indicated by the max ratio deviates from the configuration of the present invention. All of the carbon fibers obtained under the conditions of Comparative Examples 1 to 6 had low correction strength due to the fiber diameter and / or fluffed in the first carbonization step.
Claims (1)
A flame-resistant fiber obtained by flame-treating an acrylic fiber having a draw ratio of 3.1 to 3.5 times in a drawing process after spinning, washing and drying, and a maximum draw ratio obtained by TMA measurement [ A] 10% or more of a flame-resistant fiber having a degree of orientation at 26 ° of 75 to 77.5% obtained by wide-angle X-ray measurement in an inert atmosphere at a temperature of 300 to 600 ° C. and the maximum stretch A method for producing carbon fiber, which is heat-treated at a temperature of 600 to 1600 ° C. in an inert atmosphere after heat treatment at a draw ratio [A × 0.35] to [A × 0.50]% indicated by a rate [A]%.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61119719A (en) * | 1984-11-14 | 1986-06-06 | Toho Rayon Co Ltd | Production of carbon fiber of high strength |
| JP2000141472A (en) * | 1998-11-11 | 2000-05-23 | Toray Ind Inc | Polyester film and its production |
| JP2002173832A (en) * | 2000-12-06 | 2002-06-21 | Mitsubishi Kagaku Sanshi Corp | Carbon fiber bundle |
| JP2003306836A (en) * | 2002-04-17 | 2003-10-31 | Toho Tenax Co Ltd | Carbon fiber strand and method for producing the same |
| JP2004060126A (en) * | 2002-07-31 | 2004-02-26 | Toho Tenax Co Ltd | Carbon fiber and method for producing the same |
| JP2004060069A (en) * | 2002-07-25 | 2004-02-26 | Toho Tenax Co Ltd | Polyacrylonitrile-based carbon fiber, and method for producing the same |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61119719A (en) * | 1984-11-14 | 1986-06-06 | Toho Rayon Co Ltd | Production of carbon fiber of high strength |
| JP2000141472A (en) * | 1998-11-11 | 2000-05-23 | Toray Ind Inc | Polyester film and its production |
| JP2002173832A (en) * | 2000-12-06 | 2002-06-21 | Mitsubishi Kagaku Sanshi Corp | Carbon fiber bundle |
| JP2003306836A (en) * | 2002-04-17 | 2003-10-31 | Toho Tenax Co Ltd | Carbon fiber strand and method for producing the same |
| JP2004060069A (en) * | 2002-07-25 | 2004-02-26 | Toho Tenax Co Ltd | Polyacrylonitrile-based carbon fiber, and method for producing the same |
| JP2004060126A (en) * | 2002-07-31 | 2004-02-26 | Toho Tenax Co Ltd | Carbon fiber and method for producing the same |
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