JP2001131833A - Carbon yarn and method for producing the same - Google Patents
Carbon yarn and method for producing the sameInfo
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- JP2001131833A JP2001131833A JP30229099A JP30229099A JP2001131833A JP 2001131833 A JP2001131833 A JP 2001131833A JP 30229099 A JP30229099 A JP 30229099A JP 30229099 A JP30229099 A JP 30229099A JP 2001131833 A JP2001131833 A JP 2001131833A
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- yarn
- temperature
- fiber
- acrylic
- carbon
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、炭素繊維及びその
製造方法に関する。詳しくは、複合材料の大幅な性能向
上に寄与する高い圧縮強度を有する炭素繊維、及びかか
る炭素繊維の製造方法に関する。[0001] The present invention relates to a carbon fiber and a method for producing the same. More specifically, the present invention relates to a carbon fiber having a high compressive strength that contributes to a significant improvement in performance of a composite material, and a method for producing such a carbon fiber.
【０００２】[0002]
【従来の技術】炭素繊維は、比強度や比弾性率が優れる
ため、ゴルフシャフト、釣り竿などのスポーツレジャー
分野や宇宙航空分野を中心として、用途が拡大してい
る。それに伴い、一層の品質の向上が望まれているが、
炭素繊維の引張強度、引張弾性率は改善傾向にあるもの
の、圧縮強度の向上が不充分であり、使用する用途によ
っては依然として適用できないことがある。2. Description of the Related Art Since carbon fibers have excellent specific strength and specific elastic modulus, their applications are expanding mainly in the field of sports and leisure, such as golf shafts and fishing rods, and the field of aerospace. Along with that, further improvement in quality is desired,
Although the tensile strength and the tensile modulus of the carbon fiber tend to be improved, the improvement in the compressive strength is insufficient, and it may still not be applicable depending on the intended use.
【０００３】炭素繊維を構造材に適用する場合は、高い
レベルの引張弾性率を反映させながら、一層の軽量化を
実現するため、構造材の厚みを薄くすることが多いが、
この場合、炭素繊維自体の圧縮強度が不足すると、構造
材全体の圧縮強度が低下する。[0003] When carbon fiber is applied to a structural material, the thickness of the structural material is often reduced in order to further reduce the weight while reflecting a high level of tensile modulus.
In this case, if the compressive strength of the carbon fiber itself is insufficient, the compressive strength of the entire structural material decreases.
【０００４】特開昭６３−２１１３２６号公報に、アク
リル系繊維を炭化処理する際に、温度を２２００℃以上
とし、繊維を積極的に延伸して、その配向緩和を抑制
し、高引張弾性率、高圧縮強度の炭素繊維を得る技術が
開示されている。ところが、熱処理温度が高いために、
炭素繊維の結晶サイズが大きくなり、圧縮強度は、期待
された程向上していない。Japanese Patent Application Laid-Open No. 63-213326 discloses that when carbonizing an acrylic fiber, the temperature is raised to 2200 ° C. or higher, the fiber is actively stretched, its orientation relaxation is suppressed, and a high tensile modulus is obtained. A technique for obtaining carbon fibers having high compressive strength has been disclosed. However, due to the high heat treatment temperature,
The crystal size of the carbon fibers has increased, and the compressive strength has not improved as expected.
【０００５】また、特開平４-１９２１９公報に、電子
線照射によって炭素繊維を非晶化する技術が開示されて
おり、また、特開平２-２５９１１８公報に、炭素繊維
表層をエッチングする技術が開示されている。これら技
術によれば、炭素繊維表層の結晶サイズは小さくなる
が、炭化処理の最高温度が２０００℃以上となるため、
炭素繊維全体として結晶サイズは小さくならず、圧縮強
度の向上は不充分であった。Further, Japanese Patent Application Laid-Open No. 4-19219 discloses a technique for amorphizing carbon fibers by electron beam irradiation, and Japanese Patent Application Laid-Open No. 2-259118 discloses a technique for etching the surface layer of carbon fibers. Have been. According to these techniques, the crystal size of the carbon fiber surface layer is reduced, but since the maximum temperature of the carbonization treatment is 2000 ° C. or higher,
The crystal size was not reduced as a whole carbon fiber, and the improvement in compressive strength was insufficient.
【０００６】圧縮強度を損なわず、炭素繊維に高引張弾
性率を実現するためには、炭化処理において、温度を１
８００〜２０００℃とするとともに、１．１以上の倍率
で積極的に延伸しなければならないが、かかる方法によ
れば、得られる炭素繊維に糸切れや毛羽が多量に生じる
傾向があった。[0006] In order to realize a high tensile modulus of carbon fiber without impairing the compressive strength, it is necessary to set the temperature to 1 in the carbonization treatment.
The temperature must be 800 to 2000 ° C., and the film must be actively stretched at a magnification of 1.1 or more. However, according to such a method, a large amount of yarn breakage or fluff tends to occur in the obtained carbon fiber.
【０００７】また、炭素繊維の製造において通常採用さ
れることの多い紡糸法である乾湿式紡糸法によれば、凝
固浴中で、凝固が進行途上にある糸条が、糸道ガイド等
に強く接触すると、糸条を構成する単糸に架かる張力に
差が生じ、かかるアクリル系繊維を延伸しながら炭化処
理すると、繊維束内において、伸度の低い単糸が延伸の
張力に抗しきれず、糸切れが生じるなどして、得られる
炭素繊維の品位が大きく低下していた。[0007] According to the dry-wet spinning method, which is a spinning method often used in the production of carbon fibers, a yarn which is undergoing coagulation in a coagulation bath is strongly applied to a yarn path guide or the like. Upon contact, a difference occurs in the tension applied to the single yarns constituting the yarn, and when the acrylic fiber is carbonized while being drawn, the single yarn having a low elongation cannot fully withstand the drawing tension in the fiber bundle. The quality of the obtained carbon fiber was greatly reduced due to, for example, yarn breakage.
【０００８】このように従来より、炭素繊維の特性改善
のため、製糸や、炭化処理等の熱処理時の延伸倍率を調
節するなど様々な手法が検討されてきたが、これらによ
れば、アクリル系繊維の配向性が充分に向上されず、高
い強度特性が要求される用途にも問題なく適用できる、
引張弾性率と圧縮強度が高レベルで両立した炭素繊維は
得られていなかった。As described above, various techniques have conventionally been studied to improve the properties of carbon fibers, such as adjusting the draw ratio during heat treatment such as spinning and carbonization. The orientation of the fiber is not sufficiently improved and can be applied without problems to applications requiring high strength properties.
A carbon fiber having both high tensile modulus and high compressive strength was not obtained.
【０００９】[0009]
【発明が解決しようとする課題】本発明は、高レベルの
引張弾性率を有し、得られる複合材料に高い圧縮強度を
発現させる高レベルの圧縮強度を有する炭素繊維、およ
びかかる炭素繊維を安定に製造する方法を提供せんとす
るものである。DISCLOSURE OF THE INVENTION The present invention provides a carbon fiber having a high level of tensile modulus, a high level of compressive strength that allows the resulting composite material to exhibit high compressive strength, and a method for stabilizing such carbon fiber. To provide a manufacturing method.
【００１０】[0010]
【課題を解決するための手段】本発明は、上記課題を達
成するために、次の構成を有する。即ち、引張弾性率が
３４０〜４５０ＧＰａ、広角Ｘ線回折より測定される炭
素網面の(002)面の結晶サイズＬｃが２．４〜３．２ｎ
ｍ、ＡＳＴＭ Ｄ６９５による圧縮強度が１４５０〜２
０００ＭＰａであるアクリル系炭素繊維である。The present invention has the following configuration to achieve the above object. That is, the tensile modulus is 340 to 450 GPa, and the crystal size Lc of the (002) plane of the carbon network plane measured by wide-angle X-ray diffraction is 2.4 to 3.2 n.
m, compressive strength according to ASTM D695 is 1450-2
Acrylic carbon fiber of 000 MPa.
【００１１】また、本発明は、上記課題を達成するため
に、次の構成を有する。即ち、単糸伸度変動率が１０％
以下であるアクリル系繊維を前駆体繊維とし、酸化性雰
囲気下、温度２００〜３００℃で耐炎化処理し、続いて
不活性雰囲気下、温度４００〜５００℃、昇温速度２０
〜１００℃／分で前炭化処理し、さらに不活性雰囲気
下、温度１８００〜２０００℃で炭化処理する炭素繊維
の製造方法であって、前記前炭化処理において、アクリ
ル系繊維の延伸倍率を１．１〜１．３として処理するこ
とを特徴とするアクリル系炭素繊維の製造方法である。The present invention has the following configuration in order to achieve the above object. That is, the variation rate of the single yarn elongation is 10%.
The following acrylic fiber is used as a precursor fiber and subjected to a flame-proof treatment at a temperature of 200 to 300 ° C. in an oxidizing atmosphere, and subsequently at a temperature of 400 to 500 ° C. and a heating rate of 20 in an inert atmosphere.
A method for producing carbon fibers in which a carbonization treatment is performed at a temperature of 1800 to 2000 ° C. in an inert atmosphere at a temperature of 1 to 100 ° C./min. This is a method for producing an acrylic carbon fiber, which is treated as 1 to 1.3.
【００１２】[0012]
【発明の実施の形態】本発明者らは、鋭意検討の結果、
アクリル系繊維を前駆体繊維とし、酸化性雰囲気下、耐
炎化、前炭化処理し、さらに不活性雰囲気下、温度１８
００〜２０００℃で炭化処理することで得られる炭素繊
維の製造方法において、前記アクリル系繊維の単糸伸度
変動率を特定値以下とし、前記前炭化処理時のアクリル
系繊維の延伸倍率を特定範囲内とすることにより、高レ
ベルの引張弾性率と、圧縮強度を兼ね備える炭素繊維が
容易かつ安定に得られ、前記した課題を一挙に解決する
ことを見いだした。BEST MODE FOR CARRYING OUT THE INVENTION The present inventors have conducted intensive studies and as a result,
Acrylic fiber as precursor fiber, oxidizing atmosphere, flame resistance, pre-carbonization treatment, and further, under inert atmosphere, temperature 18
In the method for producing carbon fibers obtained by carbonizing at 00 to 2000 ° C., the single yarn elongation variation of the acrylic fibers is set to a specific value or less, and the draw ratio of the acrylic fibers at the time of the pre-carbonizing is specified. By setting the content within the above range, it has been found that carbon fibers having both a high level of tensile modulus and compressive strength can be easily and stably obtained, and the above-mentioned problems can be solved at once.
【００１３】本発明の炭素繊維は、引張弾性率が３４０
〜４５０ＧＰａ、好ましくは３６０〜４２０ＧＰａであ
る炭素繊維である。３４０ＧＰａ未満では、圧縮強度の
不足は顕在化しないが、適用する用途によっては、引張
弾性率が不足することがある。また４５０ＧＰａを越え
ると炭素網面の結晶サイズＬｃが拡大し、圧縮強度が不
足することがある。The carbon fiber of the present invention has a tensile modulus of 340.
To 450 GPa, preferably 360 to 420 GPa. If it is less than 340 GPa, the lack of compressive strength will not be apparent, but the tensile modulus may be insufficient depending on the application to which it is applied. On the other hand, if it exceeds 450 GPa, the crystal size Lc of the carbon network plane increases, and the compressive strength may be insufficient.
【００１４】また、本発明の炭素繊維は、広角Ｘ線回折
より測定される炭素網面の(002)面の結晶サイズＬｃが
２．４〜３．２ｎｍである炭素繊維である。２．４ｎｍ
未満であると、引張弾性率が不足することがあり、３．
２ｎｍを越えると圧縮強度が不足することがある。The carbon fiber of the present invention is a carbon fiber having a (002) plane crystal size Lc of 2.4 to 3.2 nm as measured by wide-angle X-ray diffraction. 2.4 nm
If it is less than 3, the tensile modulus may be insufficient.
If it exceeds 2 nm, the compressive strength may be insufficient.
【００１５】さらに、本発明の炭素繊維は、後述する、
ＡＳＴＭ Ｄ６９５による圧縮強度が１４５０ＭＰａ以
上、好ましくは１５００ＭＰａ以上である炭素繊維であ
る。１４５０ＭＰａ未満であると、例えばゴルフシャフ
ト等、構造材に高レベルの耐圧縮特性が要求される用途
では、適用できないことがある。なお、圧縮強度は、２
０００ＭＰａあれば、本発明の効果を奏するに当たり、
充分であることが多い。Further, the carbon fiber of the present invention is described below.
It is a carbon fiber having a compressive strength according to ASTM D695 of 1450 MPa or more, preferably 1500 MPa or more. If it is less than 1450 MPa, it may not be applicable in applications where a high level of compression resistance is required for a structural material such as a golf shaft. The compressive strength is 2
000MPa, in order to achieve the effects of the present invention,
Often sufficient.
【００１６】本発明において、上述したような炭素繊維
は、例えば、以下に示すような、本発明の炭素繊維の製
造方法によって製造することができる。In the present invention, the above-mentioned carbon fiber can be produced, for example, by the following method for producing a carbon fiber of the present invention.
【００１７】本発明の炭素繊維の前駆体である、アクリ
ル系繊維の原料としては、通常、アクリロニトリル９０
重量％以上、アクリロニトリルと共重合しうる共重合体
が１０重量％以下で構成されるアクリル系共重合体が使
用できる。The raw material of the acrylic fiber, which is the precursor of the carbon fiber of the present invention, is usually acrylonitrile 90
An acrylic copolymer composed of at least 10% by weight of a copolymer copolymerizable with acrylonitrile can be used.
【００１８】前記共重合体としては、アクリル酸、メタ
アクリル酸、イタコン酸、およびそれらのメチルエステ
ル、エチルエステル、プロピルエステル、ブチルエステ
ル、アルカリ金属塩、アンモニウム塩、アリルスルホン
酸、メタリルスルホン酸、スチレンスルホン酸、及びそ
れらのアルカリ金属塩からなる群から選ばれる少なくと
も１種が使用できる。Examples of the copolymer include acrylic acid, methacrylic acid, itaconic acid, and their methyl esters, ethyl esters, propyl esters, butyl esters, alkali metal salts, ammonium salts, allylsulfonic acid, methallylsulfonic acid. And at least one selected from the group consisting of styrenesulfonic acid, and alkali metal salts thereof.
【００１９】アクリル系重合体は、乳化重合、塊状重
合、溶液重合など従来公知の重合法により合成される。
また、溶媒としては、ジメチルアセトアミド、ジメチル
スルホキシド、ジメチルホルムアミド、硝酸、ロダンソ
−ダ水溶液などが用いられ、紡糸原液が調整される。The acrylic polymer is synthesized by a conventionally known polymerization method such as emulsion polymerization, bulk polymerization, and solution polymerization.
As the solvent, dimethylacetamide, dimethylsulfoxide, dimethylformamide, nitric acid, an aqueous solution of rhodasoda, or the like is used, and a spinning solution is prepared.
【００２０】アクリル系重合体は、得られる炭素繊維の
物性をより高める観点から、その極限粘度［η］が１以
上、好ましくは１．３５以上、より好ましくは１．７以
上であるのが良い。ここで極限粘度［η］の上限値とし
ては、紡糸を安定させる観点から、５以下とするのが良
い。The acrylic polymer has an intrinsic viscosity [η] of 1 or more, preferably 1.35 or more, and more preferably 1.7 or more, from the viewpoint of further improving the physical properties of the obtained carbon fiber. . Here, the upper limit of the intrinsic viscosity [η] is preferably 5 or less from the viewpoint of stabilizing spinning.
【００２１】アクリル系繊維は、前記した紡糸原液を使
用し、口金から、２〜１０ｍｍのエア−ギャップを通過
させて凝固浴中に吐出して糸条となし、凝固浴中に設置
された折返ガイドを含む複数の糸道ガイドを介して、糸
条を凝固浴から引き取る乾湿式紡糸法で紡糸するのが好
ましい。この際、凝固浴液には紡糸原液に用いた溶媒と
同種の溶媒を主成分とする水溶液を使用するのが好まし
い。ここで、「折返ガイド」とは、凝固浴内に設置され
た糸道ガイドの内、搬送される糸条の接触角が最大とな
る糸道ガイドをいう。The acrylic fiber is discharged from the spinneret into a coagulation bath through a spinneret through an air gap of 2 to 10 mm to form a yarn. The yarn is preferably spun by a dry-wet spinning method in which the yarn is drawn from a coagulation bath through a plurality of yarn guides including a guide. At this time, it is preferable to use, as the coagulation bath solution, an aqueous solution mainly composed of the same solvent as the solvent used for the spinning solution. Here, the "return guide" refers to a yarn path guide in which the contact angle of the conveyed yarn is the maximum among the yarn path guides installed in the coagulation bath.
【００２２】本発明において、アクリル系繊維の繊度は
０．３〜１ｄ、好ましくは０．５〜０．８ｄであるのが
良い。０．３ｄ未満であると、製糸工程で、繊維から発
生する粉塵が微細となり環境面の問題が生じることがあ
り、１ｄを越えると、後の耐炎化工程、前炭化工程、及
び炭化工程で、均一な熱処理が困難となることがある。In the present invention, the fineness of the acrylic fiber is 0.3 to 1 d, preferably 0.5 to 0.8 d. If it is less than 0.3d, dust generated from the fibers will be fine in the spinning process, which may cause environmental problems.If it exceeds 1d, in the subsequent flameproofing step, pre-carbonization step, and carbonization step, Uniform heat treatment may be difficult.
【００２３】また、アクリル系繊維のフィラメント数は
１、０００〜３０、０００フィラメント、好ましくは
３、０００〜２４、０００フィラメントであるのが良
い。１、０００フィラメント未満では、糸切れが増すこ
とがあり、３０、０００フィラメントを越えると、耐炎
化工程で被処理繊維束中に蓄熱量が増し、燃焼消失する
ことがある。The number of filaments of the acrylic fiber is preferably 1,000 to 30,000 filaments, and more preferably, 3,000 to 24,000 filaments. If the number of filaments is less than 1,000, yarn breakage may increase. If the number of filaments exceeds 30,000, the amount of heat stored in the fiber bundle to be treated in the oxidization-resistant step may increase, resulting in burning out.
【００２４】本発明においては、後述する測定法によ
る、単糸伸度変動率（ＣＶ）により、繊維を構成する単
糸の伸度バラツキを指標化することができる。かかる伸
度バラツキは、折返ガイド等糸道ガイドへ糸条の接触が
不足する等により、糸条を構成する単糸に架かる張力差
により惹起される。In the present invention, the variation in elongation of the single yarn constituting the fiber can be indexed by the elongation change rate (CV) of the single yarn by a measuring method described later. Such variation in elongation is caused by a difference in tension between the single yarns constituting the yarn due to insufficient contact of the yarn with the yarn guide such as a folded guide.
【００２５】本発明では、前記単糸伸度変動率（ＣＶ）
は、１０％以下とすることが必要であり、好ましくは８
％以下にするのが良い。１０％を越えると、前炭化処理
におけるアクリル系繊維の延伸性が低下し、繊維内の伸
度の低い単糸が、炭化処理時の延伸に抗し切れず糸切れ
を生じたり、毛羽が増すことがある。In the present invention, the single yarn elongation variation (CV)
Should be 10% or less, preferably 8%
% Is better. If it exceeds 10%, the stretchability of the acrylic fiber in the pre-carbonization treatment is reduced, and the single yarn having low elongation in the fiber is not resistant to the drawing during the carbonization treatment, and the yarn breaks or the fluff increases. Sometimes.
【００２６】かかる観点から、凝固浴内において、糸条
に架かる張力は１．５〜７×１０-4Ｎ／ｄ（ｄ：デニー
ル）の範囲に規制するのが好ましい。１．５×１０-4Ｎ
／ｄ未満であると、糸条を構成する単糸に架かる張力に
差が生じ、繊維の配向性が低下することがある。７×１
０-4Ｎ／ｄを超えると、折返ガイドとの強い接触により
糸条断面が変形したり、折返ガイドに糸条が一時的に強
く圧着された後、急激に脱離することにより糸切れが生
じることがある。From this point of view, it is preferable that the tension applied to the yarn in the coagulation bath is regulated in the range of 1.5 to 7 × 10 −4 N / d (d: denier). 1.5 × 10 -4 N
If it is less than / d, a difference occurs in the tension applied to the single yarns constituting the yarn, and the orientation of the fibers may be reduced. 7x1
If it exceeds 0 -4 N / d, the thread cross section will be deformed due to strong contact with the turn-back guide, or the thread will be suddenly detached from the turn-back guide after it has been temporarily strongly pressed, and the breakage will occur. May occur.
【００２７】糸条に架かる張力は、糸条を張力計で挟み
込み測定できる。張力計としては、例えば、エイコー測
器（株）製、型番：ＨＳ−４０００等が使用できる。The tension applied to the yarn can be measured by sandwiching the yarn with a tensiometer. As the tensiometer, for example, a model number: HS-4000 manufactured by Eiko Sokki Co., Ltd. can be used.
【００２８】本発明において、前記折返ガイドは、糸条
が凝固浴に導入されてから、折返ガイドに接触するまで
の時間Ｔを０．５〜５秒の範囲に設置するのが良い。
０．５秒未満であると、凝固状態が不十分なまま、糸条
が折返ガイドに強く接触するため、糸切れが生じること
がある。５秒を越えると、折返ガイドに接触するまでに
糸条の凝固が必要以上に進行してしまい、凝固浴内で糸
条に架かる張力を適宜調整しても、糸条の配向性が十分
に向上しないことがある。In the present invention, it is preferable that the time T between the time when the yarn is introduced into the coagulation bath and the time when the yarn comes into contact with the return guide is set in the range of 0.5 to 5 seconds.
If the time is less than 0.5 seconds, the yarn may come into strong contact with the folding guide while the coagulation state is insufficient, so that the yarn may be broken. If the time exceeds 5 seconds, the coagulation of the yarn proceeds more than necessary before contacting the folding guide, and even if the tension applied to the yarn in the coagulation bath is appropriately adjusted, the orientation of the yarn is sufficiently high. May not improve.
【００２９】凝固浴での処理の後、毛羽の増加を防ぎ、
繊維の配向性をより高める観点から、浴中で１．１５〜
１．５として延伸する。この後、糸条に工程油剤を付与
し、乾燥緻密化することもできる。ここで用いる油剤に
は耐熱性が高く、離型性に優れ、単糸間接着を防止する
効果の高いアミノ変性シリコ−ンを主成分とする油剤を
用いるのが好ましい。さらにこの後、気体雰囲気中や加
熱熱媒中で延伸することもできる。この際、加圧スチ−
ムを熱媒として延伸すると、繊維の配向性がさらに高ま
り好ましい。After treatment in the coagulation bath, the increase in fluff is prevented,
From the viewpoint of further increasing the orientation of the fiber, 1.15 to 15.
Stretch as 1.5. Thereafter, a process oil agent can be applied to the yarn to dry and densify it. As the oil agent used here, it is preferable to use an oil agent having an amino-modified silicone as a main component, which has high heat resistance, excellent releasability, and a high effect of preventing adhesion between single yarns. Thereafter, the film can be stretched in a gas atmosphere or in a heating medium. At this time, pressurized steel
Stretching using a heating medium as a heat medium is preferable because the orientation of the fibers is further increased.
【００３０】次に、耐炎化処理、前炭化処理、炭化処理
と各処理を経て、炭素繊維が製造される。Next, a carbon fiber is manufactured through each of a flame-proofing treatment, a pre-carbonization treatment, and a carbonization treatment.
【００３１】耐炎化処理では、アクリル系繊維を酸化性
雰囲気中、２００〜３００℃、好ましくは２４０〜２８
０℃で処理する。２００℃未満であると、ニトリル基の
閉環反応が進行しないため耐炎化が不充分となることが
あり、３００℃を越えると耐炎化が完了する以前に繊維
が燃焼消失することがある。In the oxidation treatment, the acrylic fiber is placed in an oxidizing atmosphere at 200 to 300 ° C., preferably 240 to 28 ° C.
Treat at 0 ° C. If the temperature is lower than 200 ° C., the ring-closing reaction of the nitrile group does not proceed, so that the flame resistance may be insufficient. If the temperature exceeds 300 ° C., the fibers may burn and disappear before the flame resistance is completed.
【００３２】耐炎化処理時の延伸倍率は、いわゆる配向
緩和を抑えるために、０．９５〜１．１、好ましくは１
〜１．１とするのが良い。１．１を越えると毛羽が増す
ことがある。The stretching ratio at the time of the oxidation treatment is 0.95 to 1.1, preferably 1 to reduce so-called relaxation of orientation.
It is better to be 1.1. If it exceeds 1.1, fluff may increase.
【００３３】耐炎化処理では、通常、被処理繊維の比重
が１．２５〜１．６ｇ／ｃｍ3、好ましくは１．３〜
１．５ｇ／ｃｍ3になるまで処理される。１．６ｇ／ｃ
ｍ3を越えると、得られる炭素繊維の比重が低下し、引
張弾性率が不足することがある。In the oxidation treatment, the specific gravity of the fiber to be treated is usually 1.25 to 1.6 g / cm 3 , preferably 1.3 to 1.6 g / cm 3 .
Treated to 1.5 g / cm 3 . 1.6 g / c
When it exceeds m 3 , the specific gravity of the obtained carbon fiber is reduced, and the tensile modulus may be insufficient.
【００３４】耐炎化処理後、前炭化処理する。ここで
は、繊維を不活性雰囲気下、温度４００〜５００℃、昇
温速度２０〜１００℃／分、好ましくは４０〜７０℃／
分で処理する。After the oxidation treatment, a pre-carbonization treatment is performed. Here, the fiber is heated in an inert atmosphere at a temperature of 400 to 500 ° C. at a heating rate of 20 to 100 ° C./min, preferably 40 to 70 ° C./min.
Process in minutes.
【００３５】昇温速度が２０℃／分未満であると、糸速
を遅くせねばならず、製造コストが上昇することがあ
り、１００℃／分を越えると糸切れが生じることがあ
る。If the heating rate is less than 20 ° C./min, the yarn speed must be reduced, and the production cost may increase. If it exceeds 100 ° C./min, thread breakage may occur.
【００３６】前炭化処理時の延伸倍率は１．１〜１．３
とする必要があり、好ましくは１．１５〜１．２５とす
るのが良い。１．１未満であると、得られる炭素繊維に
おいて、引張弾性率が不足することがあり、１．３を越
えると糸切れが生じることがある。The stretching ratio at the time of the pre-carbonization treatment is 1.1 to 1.3.
And it is preferably set to 1.15 to 1.25. If it is less than 1.1, the resulting carbon fiber may have insufficient tensile modulus, and if it exceeds 1.3, thread breakage may occur.
【００３７】前炭化処理後、炭化処理する。ここでは、
繊維を不活性雰囲気下、温度１８００〜２０００℃で処
理する。１８００℃未満であると、得られる炭素繊維に
おいて、引張弾性率が不足することがあり、２０００℃
を越えると結晶サイズが大きくなり、圧縮強度の向上が
不充分となることがある。After the pre-carbonization, carbonization is performed. here,
The fibers are treated under an inert atmosphere at a temperature of 1800-2000C. When the temperature is lower than 1800 ° C., the tensile modulus of the obtained carbon fiber may be insufficient, and
If it exceeds, the crystal size becomes large and the improvement in compressive strength may be insufficient.
【００３８】炭化処理時の延伸倍率は０．９５〜１．
１、好ましくは０．９８〜１．０５とするのが良い。
０．９５未満であると、得られる炭素繊維において、引
張弾性率が不足することがあり、１．１を越えると糸切
れが生じることがある。The stretching ratio during the carbonization treatment is 0.95 to 1.
1, preferably 0.98 to 1.05.
If it is less than 0.95, the tensile modulus of the obtained carbon fiber may be insufficient, and if it exceeds 1.1, thread breakage may occur.
【００３９】[0039]
【実施例】以下実施例により、本発明をさらに具体的に
説明する。実施例、比較例においては、各物性値は、以
下に示す方法により測定した。 ＜単糸伸度変動率（ＣＶ）＞被測定繊維（アクリル系繊
維）を、チャック間距離（試長）を２５ｍｍとして引張
試験機にセットし、引張速度を１ｍｍ／分として単糸の
伸度を測定する。ここでは、引張試験機として、テンシ
ロン万能型引張試験機、東洋ボールドウイン社製、型
番：ＵＴＭ−１１１−５００を使用する。The present invention will be described more specifically with reference to the following examples. In the examples and comparative examples, each property value was measured by the following method. <Variation of single yarn elongation (CV)> The fiber to be measured (acrylic fiber) was set in a tensile tester with a chuck distance (test length) of 25 mm, and the elongation of the single yarn was set at a tensile speed of 1 mm / min. Is measured. Here, as the tensile tester, a Tensilon universal tensile tester, manufactured by Toyo Baldwin Co., Ltd., model number: UTM-111-500 is used.
【００４０】得られたＳ−Ｓカーブ（ｎ＝１００）よ
り、単糸伸度変動率（ＣＶ）を、次式より求める。From the obtained SS curve (n = 100), the single yarn elongation variation rate (CV) is determined by the following equation.
【００４１】ＣＶ＝〔√[[ΣXi2-(ΣXi)2/n]/(n-1)]〕/
(ΣXi/n)×100（Ｘｉ；単糸の伸度（％）、ｎ；サンプ
ル数） ＜引張弾性率＞被測定炭素繊維に、ユニオンカーバイド
（株）製、ベークライト（登録商標）ＥＲＬ−４２２１
を１０００ｇ（９３０重量％）、三フッ化ホウ素モノエ
チルアミン（ＢＦ3・ＭＥＡ）を３０ｇ（３重量％）及
びアセトンを４０ｇ（４重量％）混合したエポキシ樹脂
組成物を含浸させ、次に１３０℃で、３０分間加熱し、
硬化させ、樹脂含浸ストランドとする。ＪＩＳ Ｒ７６
０１に示される樹脂含浸ストランド試験法に従い、引張
強度と引張弾性率を求める。 ＜炭素網面の(002)面の結晶サイズＬｃ＞ Ａ．測定試料の作製 被測定炭素繊維から、長さ４ｃｍの試験片を切り出し、
金型とコロジオン・アルコール溶液を用いて固め、角柱
形状とし測定試料とする。 Ｂ．測定条件 Ｘ線源：ＣｕＫα（Ｎｉフィルター使用） 出力：４０ｋＶ、２０ｍＡ Ｃ．結晶サイズＬｃの測定 透過法により得られた面指数(002)のピークの半値幅か
ら、次のScherrerの式を用いて計算して求める。 Ｌc（ｈｋｌ）＝Ｋλ／β0ｃｏｓθB 但し、 Ｌc（ｈｋｌ）：微結晶の（ｈｋｌ）面に垂直な方向の
平均の大きさ Ｋ：１．０，λ：１５.４１８ｎｍ（Ｘ線の波長）、
β0：（βE2−β12）1/2 βE：見かけの半値幅（測定値）、β12：１．０５×１
０-2ｒａｄ θB：Braggの回折角 ＜毛羽数＞炭化処理後、単糸が切断された部分が炭素繊
維の束から約１ｃｍを越えて露出している部分を毛羽と
みなし、繊維長１０ｍ当たりの個数を数える。その個数
を１ｍ当たりにに換算して毛羽数とする。 ＜圧縮強度＞ Ａ．樹脂組成物の調整 次に示す原料樹脂を混合し、３０分間攪拌して樹脂組成
物を得る。 ・ビスフェノールＡジグリシジルエーテル樹脂、エピコ
ート１００１（油化シェルエポキシ社製、登録商標）、
２７重量％ ・ビスフェノールＡジグリシジルエーテル樹脂、エピコ
ート８２８（油化シェルエポキシ社製、登録商標）、３
１重量％ ・フェノールノボラックポリグリシジルエーテル樹脂、
エピクロン−Ｎ７４０（大日本インキ化学工業社製、登
録商標）、３１重量％ ・ポリビニルホルマール樹脂、ビニレックスＫ（チッソ
社製、登録商標）、３重量％ ・ジシアンジアミド、ＤＩＣＹ７（大日本インキ化学工
業社製、登録商標）、４１重量％ ・３，４−ジクロロフェニル−１，１−ジメチルウレ
ア、ＤＣＭＵ９９（保土谷化学社製、硬化剤）、４重量
％ 次に、前記樹脂組成物をシリコン塗布ペーパ上に離型紙
にコーティングして得た樹脂フィルムを、円周約２．７
ｍの、６０〜７０℃に温調した鋼製ドラムに巻き付け
る。CV = [√ [[ΣXi 2- (ΣXi) 2 / n] / (n-1)]] /
(ΣXi / n) × 100 (Xi: elongation (%) of single yarn, n: number of samples) <Tensile modulus> Bakelite (registered trademark) ERL-4221 manufactured by Union Carbide Co., Ltd. was applied to the carbon fiber to be measured.
Is impregnated with an epoxy resin composition in which 1000 g (930% by weight), boron trifluoride monoethylamine (BF 3 .MEA) 30 g (3% by weight) and acetone 40 g (4% by weight) are mixed, and then 130 ° C. And heat for 30 minutes,
It is cured to form a resin-impregnated strand. JIS R76
In accordance with the resin impregnated strand test method shown in No. 01, the tensile strength and the tensile modulus are determined. <Crystal size Lc of (002) plane of carbon network plane> Preparation of measurement sample From the carbon fiber to be measured, a test piece having a length of 4 cm was cut out,
Using a mold and a collodion-alcohol solution, solidify to form a prism and use it as a measurement sample. B. Measurement conditions X-ray source: CuKα (using Ni filter) Output: 40 kV, 20 mA Measurement of crystal size Lc The crystal size Lc is calculated from the half width of the peak of the plane index (002) obtained by the transmission method using the following Scherrer equation. Lc (hkl) = Kλ / β 0 cosθ B However, Lc (hkl): average direction perpendicular to the (hkl) plane of the crystallite size K: 1.0, λ: wavelength of 15.418nm (X-ray ),
β 0 : (β E2 −β 12 ) 1/2 β E : Apparent half width (measured value), β 12 : 1.05 × 1
0 -2 rad θ B : Bragg diffraction angle <number of fluff> After carbonization, the portion where the single yarn is cut out from the bundle of carbon fibers and is exposed more than about 1 cm is regarded as fluff, and the fiber length is 10 m. Count the number of hits. The number of fluffs is converted to the number of fluffs per meter. <Compressive strength> Preparation of Resin Composition The following starting resins are mixed and stirred for 30 minutes to obtain a resin composition. Bisphenol A diglycidyl ether resin, Epicoat 1001 (registered trademark, manufactured by Yuka Shell Epoxy),
27% by weight Bisphenol A diglycidyl ether resin, Epikote 828 (registered trademark, manufactured by Yuka Shell Epoxy), 3
1% by weight ・ Phenol novolak polyglycidyl ether resin,
Epicron-N740 (manufactured by Dainippon Ink and Chemicals, Inc., registered trademark), 31% by weight ・ Polyvinyl formal resin, Vinylex K (registered trademark, manufactured by Chisso Corporation), 3% by weight ・ Dicyandiamide, DICY7 (Dainippon Ink & Chemicals, Inc.) 3,4-dichlorophenyl-1,1-dimethylurea, DCMU99 (hardening agent, manufactured by Hodogaya Chemical Co., Ltd.), 4% by weight Next, the resin composition was coated on silicon-coated paper. The resin film obtained by coating the release paper on the circumference is about 2.7 circumference.
m of a steel drum temperature-controlled to 60-70 ° C.
【００４２】この上に、炭素繊維を、クリールから巻き
出し、トラバースを介して配列する。さらにその上か
ら、前記樹脂フィルムで再度覆い、ロールで回転しなが
ら、加圧し樹脂を繊維内に含浸せしめ、幅３００ｍｍ、
長さ２．７ｍの一方向プリプレグを作成する。ここで、
プリプレグの繊維目付はドラムの回転数とトラバースの
送り速度を変化させ、１９０ｇ／ｍ2に調整する。ま
た、プリプレグの樹脂量は約３５重量％とする。On this, the carbon fibers are unwound from the creel and arranged via traverses. Furthermore, from above, the resin film is covered again, and while rotating with a roll, pressure is applied to impregnate the resin into the fiber, and the width is 300 mm.
Create a 2.7 m long unidirectional prepreg. here,
The basis weight of the prepreg is adjusted to 190 g / m 2 by changing the rotation speed of the drum and the feed speed of the traverse. The resin content of the prepreg is about 35% by weight.
【００４３】このプリプレグを繊維方向を引き揃えて積
層し、温度１３０℃、圧力０．３ＭＰａで、２時間硬化
させ、厚さが１ｍｍの積層板を成形する。The prepregs are laminated in the same fiber direction, and cured at a temperature of 130 ° C. and a pressure of 0.3 MPa for 2 hours to form a laminated plate having a thickness of 1 mm.
【００４４】次に、この積層板に、試験片の被破壊部分
以外を補強する板を接着層の厚さが均一となるよう接着
剤等で固着させ、一方向積層板を作製する。Next, a plate that reinforces the portion other than the portion to be destroyed of the test piece is fixed to the laminate with an adhesive or the like so that the thickness of the adhesive layer is uniform, thereby producing a one-way laminate.
【００４５】この積層板から、被破壊部分が中心になる
ように、厚さ約１±０．１ｍｍ、幅１２．７±０．１３
ｍｍ、長さ８０±０．０１３ｍｍ、ゲージ部の長さ５±
０．１３ｍｍの試験片を切り出す。From this laminated plate, a thickness of about 1 ± 0.1 mm and a width of 12.7 ± 0.13 so that the portion to be destroyed becomes the center.
mm, length 80 ± 0.013mm, gauge part length 5 ±
A test piece of 0.13 mm is cut out.
【００４６】この試験片より、ＡＳＴＭ Ｄ６９５に示
される圧縮治具を使用し、歪み速度１．２７ｍｍ／分の
条件で測定し、繊維体積分率６０％に換算して積層板の
圧縮強度を得る。 （実施例１〜４、比較例１〜４）アクリロニトリル９
９．５モル％、イタコン酸０．５モル％からなる極限粘
度［η］が１．８０のアクリル共重合体を２０重量％含
むジメチルスルホキシド（以下、ＤＭＳＯと略記）の溶
液を調整し、親水性を向上させるため、ｐＨ８．０まで
アンモニアガスを吹き込んで紡糸原液を調整した。The test piece was measured using a compression jig shown in ASTM D695 under the condition of a strain rate of 1.27 mm / min, and converted to a fiber volume fraction of 60% to obtain the compressive strength of the laminate. . (Examples 1-4, Comparative Examples 1-4) Acrylonitrile 9
A solution of dimethyl sulfoxide (hereinafter abbreviated as DMSO) containing 20% by weight of an acrylic copolymer having an intrinsic viscosity [η] of 1.80 and consisting of 9.5% by mole and 0.5% by mole of itaconic acid was prepared. In order to improve the properties, the spinning solution was adjusted by blowing ammonia gas to pH 8.0.
【００４７】次に、この紡糸原液を４５℃に温調し、孔
数３０００の口金から、４ｍｍのエア−ギャップを通過
させて、ＤＭＳＯと水とからなる凝固浴中に吐出し、糸
条張力を５×１０-4Ｎ／ｄに規制しつつ、折返ガイドで
方向を転換し、引き取りローラで搬送速度を６ｍ／分と
して水切りガイドを通過させながら、凝固浴から引き取
り、単糸総数３０００本の凝固糸条を得た。ここで、折
返ガイドには、走行する糸条と接触する部分において、
表面粗さＲａが０．１、ビッカース硬度が２０００のポ
アフリー（登録商標、日本セラテックス社製）を素材と
して用いた。Next, this spinning stock solution was adjusted to a temperature of 45 ° C., discharged from a 3,000-hole die through a 4 mm air gap into a coagulation bath composed of DMSO and water, and the yarn tension was adjusted. While controlling the flow rate to 5 × 10 −4 N / d, the direction is changed by a turn-back guide, the transfer speed is set to 6 m / min by a take-off roller, and the sheet is taken out of a coagulation bath while passing through a draining guide. A coagulated yarn was obtained. Here, the folding guide has a portion in contact with the running yarn,
Pore-free having a surface roughness Ra of 0.1 and a Vickers hardness of 2000 was used as a material.
【００４８】次いで、糸条を水洗後、全４槽からなる浴
延伸工程に導き、第４槽の温度が９０℃の熱水中で倍率
３で延伸した。Next, the yarn was washed with water and then led to a bath stretching step comprising a total of four tanks, and the fourth tank was drawn at a magnification of 3 in hot water at a temperature of 90 ° C.
【００４９】さらに、糸条をアミノ変性シリコ−ンを含
む、油剤濃度が２重量％のシリコ−ン系油剤浴中を通過
させ、油剤を糸条重量に対して０．７重量％付与した。Further, the yarn was passed through a silicone oil bath containing an amino-modified silicone and having an oil agent concentration of 2% by weight, and the oil agent was applied at 0.7% by weight based on the weight of the yarn.
【００５０】次に、１５０℃に温調した加熱ロ−ラで乾
燥緻密化し、加圧スチ−ム延伸装置で倍率４で延伸した
後、１８０℃に温調した加熱ロ−ラで乾燥処理し、単糸
繊度０．７３ｄ、総繊度２１９０ｄのアクリル系繊維を
得た。Next, it is dried and densified by a heating roller adjusted to 150 ° C., stretched at a magnification of 4 by a pressure steam stretching apparatus, and dried by a heating roller adjusted to 180 ° C. Thus, an acrylic fiber having a single yarn fineness of 0.73d and a total fineness of 2190d was obtained.
【００５１】各実施例、比較例の製造条件、得られたア
クリル系繊維の単糸について、破断伸度（ｎ＝１００の
平均値）とその単糸伸度変動率（ＣＶ）をそれぞれ表１
に示す。Table 1 shows the production conditions of each Example and Comparative Example, and the breaking elongation (average value of n = 100) and the elongation variation (CV) of the single yarn of the obtained acrylic fiber.
Shown in
【００５２】このアクリル系繊維４本を、耐炎化処理前
に合糸して、総繊度８７６０ｄの繊維とし、空気雰囲気
中、温度２４０〜２８０℃、倍率１で延伸しながら耐炎
化処理し、耐炎化繊維とした。The four acrylic fibers are plied before the flame-proofing treatment to obtain a fiber having a total fineness of 8760 d. The fiber is subjected to a flame-proofing treatment while stretching at a temperature of 240 to 280 ° C. and a magnification of 1 in an air atmosphere. It was a synthetic fiber.
【００５３】この耐炎化繊維を、窒素雰囲気中、最高雰
囲気温度が８００℃の前炭化炉で、温度４００〜５００
℃、昇温速度を１００℃／分、倍率を各実施例、比較例
で変化させて延伸しながら前炭化処理し、さらに窒素雰
囲気中、温度１８００〜２２００℃、倍率０．９８で延
伸しながら炭化処理して、炭素繊維を得た。The flame-resistant fiber was placed in a nitrogen atmosphere in a pre-carbonization furnace having a maximum atmosphere temperature of 800 ° C. and a temperature of 400 to 500.
° C, the rate of temperature rise is 100 ° C / min, the magnification is changed in each of the examples and the comparative examples, the carbonization is performed while stretching, and the film is further stretched in a nitrogen atmosphere at a temperature of 1800 to 2200 ° C and a magnification of 0.98. Carbonization was performed to obtain a carbon fiber.
【００５４】さらに、得られた炭素繊維に４０ク−ロン
／ｇの電荷を与え、硫酸水溶液中で陽極酸化処理を施し
た。Further, the obtained carbon fiber was given an electric charge of 40 cron / g and anodized in a sulfuric acid aqueous solution.
【００５５】各実施例、比較例の製造条件、得られた炭
素繊維について、引張弾性率、結晶サイズ、毛羽数、複
合材料の圧縮強度をそれぞれ表１に示す。 （比較例５、６）凝固浴内の糸条張力を１．２５×１０
-4Ｎ／ｄ、糸条を凝固浴から引き取る速度を１５ｍ／分
とした以外は、実施例３と同条件で炭素繊維を得た。Table 1 shows the production conditions of each Example and Comparative Example, and the tensile modulus, crystal size, number of fluffs, and compressive strength of the composite material for the obtained carbon fibers. (Comparative Examples 5 and 6) The yarn tension in the coagulation bath was 1.25 × 10
-4 except that N / d, the velocity of taking up from the coagulating bath yarn was 15 m / min, thereby obtaining the carbon fiber under the same conditions as in Example 3.
【００５６】各比較例の製造条件、得られたアクリル系
繊維の単糸について、破断伸度（ｎ＝１００の平均値）
とその単糸伸度変動率（ＣＶ）を、得られた炭素繊維に
ついて、引張弾性率、結晶サイズ、毛羽数、複合材料の
圧縮強度をそれぞれ表１に示す。 （比較例７）凝固浴内の糸条張力を７．９×１０-4Ｎ／
ｄ、糸条を凝固浴から引き取る速度を１５ｍ／分とした
以外は、実施例３と同条件で炭素繊維を得た。The production conditions of each comparative example and the breaking elongation (average value of n = 100) of the obtained single yarn of acrylic fiber
Table 1 shows the tensile modulus, the crystal size, the number of fluffs, and the compressive strength of the composite material of the obtained carbon fiber. (Comparative Example 7) The yarn tension in the coagulation bath was set to 7.9 × 10 −4 N /
d, A carbon fiber was obtained under the same conditions as in Example 3 except that the speed at which the yarn was drawn from the coagulation bath was 15 m / min.
【００５７】本例の製造条件、得られたアクリル系繊維
の単糸について、破断伸度（ｎ＝１００の平均値）とそ
の単糸伸度変動率（ＣＶ）を、得られた炭素繊維につい
て、引張弾性率、結晶サイズ、毛羽数、複合材料の圧縮
強度をそれぞれ表１に示す。The production conditions of this example, the elongation at break (average value of n = 100) and the elongation variation (CV) of the single yarn of the obtained acrylic fiber were measured for the obtained carbon fiber. Table 1 shows the tensile modulus, the crystal size, the number of fluffs, and the compressive strength of the composite material.
【００５８】[0058]
【表１】 [Table 1]
【００５９】[0059]
【発明の効果】本発明によれば、高レベルの引張弾性率
を有し、得られる複合材料に高レベルの圧縮強度を発現
させる炭素繊維、およびかかる炭素繊維を安定に製造す
る方法が提供できる。According to the present invention, it is possible to provide a carbon fiber having a high level of tensile modulus and exhibiting a high level of compressive strength in the obtained composite material, and a method for stably producing such a carbon fiber. .
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4L037 AT02 CS03 FA05 FA06 FA09 FA10 PA55 PA65 PA69 PC05 PC11 PC13 PF29 PF45 PS02 PS17 UA10 UA12 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4L037 AT02 CS03 FA05 FA06 FA09 FA10 PA55 PA65 PA69 PC05 PC11 PC13 PF29 PF45 PS02 PS17 UA10 UA12
Claims (2)
Ｘ線回折より測定される炭素網面の(002)面の結晶サイ
ズＬｃが２．４〜３．２ｎｍ、ＡＳＴＭ Ｄ６９５によ
る圧縮強度が１４５０〜２０００ＭＰａであるアクリル
系炭素繊維。1. A tensile modulus of 340 to 450 GPa, a crystal size Lc of a (002) plane of a carbon network plane measured by wide-angle X-ray diffraction is 2.4 to 3.2 nm, and a compressive strength according to ASTM D695 is 1450 to Acrylic carbon fiber of 2000 MPa.
ル系繊維を前駆体繊維とし、酸化性雰囲気下、温度２０
０〜３００℃で耐炎化処理し、続いて不活性雰囲気下、
温度４００〜５００℃、昇温速度２０〜１００℃／分で
前炭化処理し、さらに不活性雰囲気下、温度１８００〜
２０００℃で炭化処理する炭素繊維の製造方法であっ
て、前記前炭化処理において、アクリル系繊維の延伸倍
率を１．１〜１．３として処理することを特徴とするア
クリル系炭素繊維の製造方法。2. An acrylic fiber having a single yarn elongation variation rate of 10% or less is used as a precursor fiber under an oxidizing atmosphere at a temperature of 20%.
Oxidation treatment at 0 to 300 ° C., and then under an inert atmosphere,
Pre-carbonization treatment at a temperature of 400 to 500 ° C. and a heating rate of 20 to 100 ° C./min.
A method for producing carbon fibers to be carbonized at 2000 ° C., wherein the pre-carbonization treatment is performed by setting the draw ratio of the acrylic fibers to 1.1 to 1.3. .
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|---|---|---|---|
| JP30229099A JP4238436B2 (en) | 1999-10-25 | 1999-10-25 | Carbon fiber manufacturing method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30229099A JP4238436B2 (en) | 1999-10-25 | 1999-10-25 | Carbon fiber manufacturing method |
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|---|---|
| JP2001131833A true JP2001131833A (en) | 2001-05-15 |
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| JP4238436B2 JP4238436B2 (en) | 2009-03-18 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007069511A1 (en) * | 2005-12-13 | 2007-06-21 | Toray Industries, Inc. | Carbon fiber, process for production of polyacrylonitrile-base precursor fiber for carbon fiber production, and process for production of carbon fiber |
| JP2007177368A (en) * | 2005-12-01 | 2007-07-12 | Toho Tenax Co Ltd | Carbon fiber and precursor and method for producing carbon fiber |
| WO2009084390A1 (en) | 2007-12-30 | 2009-07-09 | Toho Tenax Co., Ltd. | Processes for producing flameproof fiber and carbon fiber |
| US7638110B1 (en) | 2008-07-02 | 2009-12-29 | Toho Tenax Co., Ltd. | Carbon fiber |
-
1999
- 1999-10-25 JP JP30229099A patent/JP4238436B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007177368A (en) * | 2005-12-01 | 2007-07-12 | Toho Tenax Co Ltd | Carbon fiber and precursor and method for producing carbon fiber |
| WO2007069511A1 (en) * | 2005-12-13 | 2007-06-21 | Toray Industries, Inc. | Carbon fiber, process for production of polyacrylonitrile-base precursor fiber for carbon fiber production, and process for production of carbon fiber |
| JPWO2007069511A1 (en) * | 2005-12-13 | 2009-05-21 | 東レ株式会社 | Carbon fiber, method for producing polyacrylonitrile-based precursor fiber for carbon fiber production, and method for producing carbon fiber |
| US8137810B2 (en) | 2005-12-13 | 2012-03-20 | Toray Industries, Inc. | Carbon fiber, process for production of polyacrylonitrile-base precursor fiber for carbon fiber production, and process for production of carbon fiber |
| JP4957251B2 (en) * | 2005-12-13 | 2012-06-20 | 東レ株式会社 | Carbon fiber, method for producing polyacrylonitrile-based precursor fiber for carbon fiber production, and method for producing carbon fiber |
| WO2009084390A1 (en) | 2007-12-30 | 2009-07-09 | Toho Tenax Co., Ltd. | Processes for producing flameproof fiber and carbon fiber |
| US8236273B2 (en) | 2007-12-30 | 2012-08-07 | Toho Tenax Co., Ltd. | Method of producing pre-oxidation fiber and carbon fiber |
| US7638110B1 (en) | 2008-07-02 | 2009-12-29 | Toho Tenax Co., Ltd. | Carbon fiber |
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| Publication number | Publication date |
|---|---|
| JP4238436B2 (en) | 2009-03-18 |
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