JP2014031595A - Production method of flame resistant fiber bundle - Google Patents
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
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- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
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- Inorganic Fibers (AREA)
Abstract
Description
本発明は、各種の複合材料において補強繊維材料として利用される炭素繊維の前駆体である耐炎化繊維の製造方法に関する。 The present invention relates to a method for producing flame-resistant fibers which are precursors of carbon fibers used as reinforcing fiber materials in various composite materials.
炭素繊維は、優れた比強度及び比弾性率を有し、軽量性に優れるため、熱硬化性及び熱可塑性樹脂の強化繊維として、従来のスポーツ・一般産業用途だけでなく、航空・宇宙用途、自動車用途など広く利用されている。中でも、ポリアクリロニトリル(PAN)繊維を前駆体として得られる、いわゆるPAN系炭素繊維は、機械的物性に優れ、また生産性もよいため、広く工業的に生産されている。 Carbon fiber has excellent specific strength and specific elastic modulus, and is excellent in lightness. Therefore, as a reinforcing fiber for thermosetting and thermoplastic resin, not only conventional sports and general industrial applications, but also aerospace applications, Widely used for automotive applications. Among them, so-called PAN-based carbon fibers obtained using polyacrylonitrile (PAN) fibers as precursors are widely produced industrially because they have excellent mechanical properties and good productivity.
通常、炭素繊維は、PAN繊維、再生セルロース繊維、フェノール繊維、ピッチ繊維等の有機重合体からなる前駆体繊維を空気などの酸化性ガス雰囲気中にて、耐炎化または不融化して耐炎化繊維とし、次いでこれを不活性ガス雰囲気中にて800〜2000℃で炭化して製造される。また、さらに2000℃以上の不活性ガス雰囲気中で黒鉛化を行ない、弾性率が一段と高い黒鉛繊維を製造することも行なわれる。 Usually, carbon fibers are flame-resistant fibers by making precursor fibers made of organic polymers such as PAN fibers, regenerated cellulose fibers, phenol fibers, pitch fibers, etc. flameproof or infusible in an oxidizing gas atmosphere such as air. And carbonized at 800 to 2000 ° C. in an inert gas atmosphere. Further, graphitization is performed in an inert gas atmosphere at 2000 ° C. or higher to produce graphite fibers having a higher elastic modulus.
前駆体繊維束を耐炎化する耐炎化反応は、有機重合体の酸化と環化を伴う反応であって、高温で処理する程、反応速度が上がり耐炎化に必要な処理時間を短縮できる。しかし、前駆体繊維表面から繊維内部への熱の伝導具合、酸化性ガスの拡散具合により反応後の生成物の構造が変化しやすく、また、熱の伝わりや酸素の拡散が不充分になりやすい繊維内部では反応が進行しにくかった。従って、得られる耐炎化繊維は、内部まで均一な構造になりにくかった。このような構造となる傾向は、前駆体繊維の直径が大きくなるほど顕著である。 The flameproofing reaction for making the precursor fiber bundle flameproof is a reaction involving oxidation and cyclization of the organic polymer, and the higher the temperature, the faster the reaction rate and the shorter the processing time required for flameproofing. However, the structure of the product after the reaction tends to change due to the heat conduction from the precursor fiber surface to the inside of the fiber and the diffusion of the oxidizing gas, and the heat transfer and oxygen diffusion tend to be insufficient. It was difficult for the reaction to proceed inside the fiber. Therefore, the obtained flame-resistant fiber did not easily have a uniform structure up to the inside. The tendency to become such a structure becomes more prominent as the diameter of the precursor fiber increases.
また一方、耐炎化反応は反応発熱を伴うため、処理温度を高温にし過ぎたり、前駆体繊維束を高密度に多数充填したりすると、反応熱が被処理繊維束内に蓄熱して単糸間の融着や発火現象、糸切れを生じる。そのため、耐炎化処理工程において生産効率を上げるためには、前駆体繊維束の反応発熱を効率良く除去しつつ、可能な限り高温で処理できるプロセスとすることが求められてきた。
かかる課題を解決するために、例えば特許文献1には前駆体繊維束を二酸化炭素を主成分とする超臨界流体中で加熱処理する方法が提案されている。しかし、かかる方法は高圧のリアクター中での反応を要し、実際的ではない。
On the other hand, since the flameproofing reaction is accompanied by reaction heat generation, if the processing temperature is too high or if a large number of precursor fiber bundles are filled at a high density, the heat of reaction is accumulated in the fiber bundles to be treated, and between the single yarns. Cause fusing, ignition, and yarn breakage. Therefore, in order to increase the production efficiency in the flameproofing treatment step, it has been demanded that the process can be performed at the highest possible temperature while efficiently removing the reaction heat generation of the precursor fiber bundle.
In order to solve such a problem, for example, Patent Document 1 proposes a method of heat-treating a precursor fiber bundle in a supercritical fluid mainly containing carbon dioxide. However, this method requires a reaction in a high-pressure reactor and is not practical.
また、特許文献2では加熱空気中での耐炎化反応の途中で、過熱水蒸気を含む雰囲気中で加熱処理を行い、環化反応を促進させる方法も提案されている。しかし、かかる方法では加熱空気中での耐炎化反応において、すでに繊維表面と繊維内部に構造差が生じているため、内部まで均一な構造の耐炎化繊維を得ることは困難である。 Patent Document 2 also proposes a method of promoting a cyclization reaction by performing a heat treatment in an atmosphere containing superheated steam in the middle of a flameproofing reaction in heated air. However, in such a method, in the flameproofing reaction in heated air, since a structural difference has already occurred between the fiber surface and the inside of the fiber, it is difficult to obtain a flameproof fiber having a uniform structure up to the inside.
本発明の目的は、得られる耐炎化繊維の構造が均一であり、且つ生産効率の良い耐炎化繊維の製造方法を提供することにある。 An object of the present invention is to provide a method for producing a flame resistant fiber having a uniform structure of the obtained flame resistant fiber and good production efficiency.
本発明の耐炎化繊維の製造方法は、前駆体繊維を、過熱水蒸気を60〜100vol%含む気体を導入した処理室中で、200〜800℃で加熱処理する耐炎化繊維の製造方法である。前記加熱処理は、前駆体繊維を1.5〜4.0倍の延伸倍率で延伸処理しながら行うことが好ましい。 The method for producing flame-resistant fibers of the present invention is a method for producing flame-resistant fibers in which precursor fibers are heat-treated at 200 to 800 ° C. in a treatment chamber into which a gas containing 60 to 100 vol% of superheated steam is introduced. The heat treatment is preferably performed while the precursor fiber is stretched at a stretch ratio of 1.5 to 4.0 times.
本発明で用いる過熱水蒸気を含む気体は、1〜15vol%の酸化性ガスを含んでいても良い。
前駆体繊維を、過熱水蒸気を60〜100vol%含む気体を導入した処理室中で、200〜400℃で加熱処理した後、さらに過熱水蒸気を60〜100vol%含む気体を導入した処理室中で、500〜800℃で加熱処理することも好ましい。
The gas containing superheated steam used in the present invention may contain 1 to 15 vol% oxidizing gas.
In the processing chamber into which the gas containing 60-100 vol% of superheated steam was introduced in the processing chamber into which gas containing 60-100 vol% of superheated steam was heat-treated at 200-400 ° C, It is also preferable to heat-process at 500-800 degreeC.
本発明においては、前駆体繊維を過熱水蒸気を60〜100vol%含む気体を導入した100〜200℃の処理室中で、2.0〜10.0倍の延伸倍率で延伸処理した後、さらに過熱水蒸気を60〜100vol%含む気体を導入した処理室中で、200〜800℃で加熱処理しても良い。
本発明で用いる前駆体繊維は、配向度0.6〜0.95、比重が1.15〜1.25のポリアクリロニトリル繊維であることが好ましい。
In the present invention, the precursor fiber is drawn at a draw ratio of 2.0 to 10.0 times in a treatment chamber at 100 to 200 ° C. into which gas containing 60 to 100 vol% of superheated steam is introduced, and then further heated. You may heat-process at 200-800 degreeC in the process chamber which introduce | transduced the gas containing 60-100 vol% of water vapor | steam.
The precursor fiber used in the present invention is preferably a polyacrylonitrile fiber having an orientation degree of 0.6 to 0.95 and a specific gravity of 1.15 to 1.25.
本発明の耐炎化繊維の製造方法は、対流伝熱が高く、放射伝熱を有する過熱水蒸気を含む雰囲気中で耐炎化処理を行うため、熱伝導率がよく、前駆体繊維の内部まで均一に熱を伝えることができ、構造が均一な耐炎化繊維を生産効率よく得ることができる。また、前駆体繊維束内に反応熱が蓄熱することを防止でき、単糸間の融着や発火現象、糸切れを防ぐことができる。 The flame-resistant fiber manufacturing method of the present invention has high convective heat transfer and performs flame-resistant treatment in an atmosphere containing superheated steam having radiant heat transfer. Therefore, the thermal conductivity is good and even inside the precursor fiber. Heat-resistant and flame-resistant fibers having a uniform structure can be obtained with high production efficiency. Moreover, it is possible to prevent reaction heat from accumulating in the precursor fiber bundle, and to prevent fusion between single yarns, ignition phenomenon, and yarn breakage.
本発明は炭素繊維の前駆体繊維を耐炎化処理する耐炎化繊維の製造方法に関するものである。
本発明の耐炎化繊維の製造方法は、前駆体繊維を過熱水蒸気を60〜100vol%含む気体を導入した処理室中で、200〜800℃で加熱処理することを特徴とする。
本発明で用いる前駆体繊維は、炭素繊維の前駆体繊維として用いられる有機重合体繊維であればよく、例えば、PAN繊維、再生セルロース繊維、フェノール繊維、ピッチ繊維等が挙げられる。中でもPAN繊維が強度の高い炭素繊維を得られるため好ましい。
The present invention relates to a method for producing a flame-resistant fiber in which a precursor fiber of carbon fiber is flame-resistant.
The flame-resistant fiber manufacturing method of the present invention is characterized in that the precursor fiber is heat-treated at 200 to 800 ° C. in a treatment chamber into which a gas containing 60 to 100 vol% of superheated steam is introduced.
The precursor fiber used in the present invention may be an organic polymer fiber used as a carbon fiber precursor fiber, and examples thereof include PAN fiber, regenerated cellulose fiber, phenol fiber, and pitch fiber. Of these, PAN fibers are preferable because carbon fibers having high strength can be obtained.
PAN繊維としては、アクリロニトリルを単独重合させた重合体またはアクリロニトリルと共重合可能なモノマーとの共重合体を紡糸したPAN系繊維を用いることができる。アクリロニトリル重合体が共重合体の場合、アクリロニトリル重合体中のアクリロニトリル単位の含有量は90質量%以上であることが好ましい。特に、アクリロニトリル単位の含有量は95質量%以上であると、炭素繊維にしたときのアクリロニトリル重合体に起因する欠陥点を軽減し、炭素繊維の品位ならびに性能を向上させることができるため、より好ましい。共重合可能なモノマーとしてはイタコン酸、(メタ)アクリル酸エステル等が例示される。 As the PAN fiber, a PAN fiber obtained by spinning a polymer obtained by homopolymerizing acrylonitrile or a copolymer of acrylonitrile and a copolymerizable monomer can be used. When the acrylonitrile polymer is a copolymer, the content of acrylonitrile units in the acrylonitrile polymer is preferably 90% by mass or more. In particular, it is more preferable that the content of the acrylonitrile unit is 95% by mass or more because defects due to the acrylonitrile polymer when the carbon fiber is formed can be reduced, and the quality and performance of the carbon fiber can be improved. . Examples of the copolymerizable monomer include itaconic acid and (meth) acrylic acid ester.
PAN繊維の紡糸方法としては、例えば湿式紡糸、乾湿式紡糸が挙げられる。紡糸後の原料繊維を、公知の方法で、水洗、乾燥、延伸、オイリング処理することにより、前駆体繊維として用いられるPAN繊維を得ることができる。
本発明で前駆体繊維としてPAN繊維を用いる場合、配向度0.6〜0.95、比重が1.15〜1.25のPAN繊維であることが好ましい。PAN繊維の配向度が0.6以上であれば高強度の炭素繊維を得やすい傾向がある。PAN繊維の配向度は、0.8〜0.95であることがより好ましい。
Examples of the PAN fiber spinning method include wet spinning and dry wet spinning. A PAN fiber used as a precursor fiber can be obtained by subjecting the raw fiber after spinning to water washing, drying, stretching, and oiling treatment by a known method.
When PAN fiber is used as the precursor fiber in the present invention, it is preferably a PAN fiber having an orientation degree of 0.6 to 0.95 and a specific gravity of 1.15 to 1.25. If the degree of orientation of the PAN fiber is 0.6 or more, high-strength carbon fibers tend to be easily obtained. The degree of orientation of the PAN fiber is more preferably 0.8 to 0.95.
本発明で用いる前駆体繊維束の繊度は、特に制限されるものではないが、単繊維繊度が好ましくは0.1〜50dtex、より好ましくは0.5〜2.0dtexであり、前駆体繊維束の総繊度が10〜500000texであることが好ましく、より好ましくは150〜10000texである。本発明で用いる前駆体繊維束のフィラメント数は、好ましくは1000〜100000本、さらに好ましくは3000〜50000本である。また、製造効率の面からは、12000本以上がより好ましく、24000本以上がさらに好ましい。 The fineness of the precursor fiber bundle used in the present invention is not particularly limited, but the single fiber fineness is preferably 0.1 to 50 dtex, more preferably 0.5 to 2.0 dtex. The total fineness is preferably 10 to 500000 tex, more preferably 150 to 10000 tex. The number of filaments in the precursor fiber bundle used in the present invention is preferably 1000 to 100,000, more preferably 3000 to 50000. Moreover, 12000 or more are more preferable from the surface of manufacturing efficiency, and 24000 or more are further more preferable.
本発明の耐炎化繊維の製造方法は、かかる前駆体繊維を、過熱水蒸気を60〜100vol%含む気体を導入した処理室中で、200〜800℃で加熱処理する。過熱水蒸気とは、任意の圧力において、その圧力における水の沸点より高い温度に過熱された水蒸気である。 In the method for producing flame-resistant fibers of the present invention, the precursor fibers are heat-treated at 200 to 800 ° C. in a treatment chamber into which a gas containing 60 to 100 vol% of superheated steam is introduced. Superheated steam is steam that is superheated to a temperature higher than the boiling point of water at any pressure.
過熱水蒸気は、熱伝導率がよく、前駆体繊維の内部まで均一に素早く熱を伝えることができる。そのため、過熱水蒸気を含む気体を導入した処理室で、耐炎化を行うと構造が均一な耐炎化繊維を生産効率よく得ることができる。また、前駆体繊維束内に反応熱が蓄熱することを防止でき、単糸間の融着や発火現象、糸切れを防ぐことができる。本発明で用いる過熱水蒸気は、乾き度1.0以上の過熱水蒸気であることが好ましい。水蒸気の乾き度が1.0以上であれば、処理室に導入する気体中に、液体状の蒸気が含まれないため、液体状の水が繊維表面に付着しにくく、熱伝導が阻害されにくいため、処理効率がより向上しやすい。 Superheated steam has good thermal conductivity and can conduct heat uniformly and quickly to the inside of the precursor fiber. Therefore, when flameproofing is performed in a treatment chamber into which a gas containing superheated steam is introduced, a flameproof fiber having a uniform structure can be obtained with high production efficiency. Moreover, it is possible to prevent reaction heat from accumulating in the precursor fiber bundle, and to prevent fusion between single yarns, ignition phenomenon, and yarn breakage. The superheated steam used in the present invention is preferably superheated steam having a dryness of 1.0 or more. If the dryness of water vapor is 1.0 or more, the liquid introduced into the processing chamber does not contain liquid vapor, so that liquid water is unlikely to adhere to the fiber surface and heat conduction is not hindered. Therefore, it is easy to improve the processing efficiency.
処理室に導入する気体に含まれる過熱水蒸気の量は、導入する気体全体に対する過熱水蒸気の割合が60vol%以上であれば、前駆体繊維が糸切れを起こしにくい。処理室に導入する気体に含まれる過熱水蒸気の量は好ましくは80〜99vol%、より好ましくは、90〜95vol%である。 The amount of superheated steam contained in the gas introduced into the processing chamber is such that the precursor fiber is less likely to break if the ratio of superheated steam to the whole introduced gas is 60 vol% or more. The amount of superheated steam contained in the gas introduced into the processing chamber is preferably 80 to 99 vol%, more preferably 90 to 95 vol%.
本発明で用いる処理室内の圧力は常圧でも正圧でも負圧でも良い。好ましくは常圧または正圧雰囲気である。より好ましい圧力は0.1〜0.3MPaである。常圧より高い圧力であると、過熱水蒸気の熱伝導性がより高くなり処理時間を短縮することができる。 The pressure in the processing chamber used in the present invention may be normal pressure, positive pressure, or negative pressure. A normal pressure or positive pressure atmosphere is preferred. A more preferable pressure is 0.1 to 0.3 MPa. When the pressure is higher than normal pressure, the thermal conductivity of superheated steam becomes higher and the processing time can be shortened.
処理室に導入される気体は、1〜15vol%の酸化性ガスを含んでいても良い。好ましくは前駆体繊維を少なくとも60〜99vol%の過熱水蒸気と1〜15vol%の酸化性ガスを含む気体を導入した処理室中で200〜400℃で1〜10分加熱処理した後、さらに、前駆体繊維を過熱水蒸気を60〜100vol%含む気体を導入した処理室中200〜800℃で加熱処理する。酸化性ガスを含む気体を導入した処理室中で加熱処理した後、次いで行われる加熱処理においては、導入される気体は酸化性ガスの含有量が先の処理よりも少ないことが好ましく、酸化性ガスの含有量が0〜0.5vol%であることがより好ましい。 The gas introduced into the processing chamber may contain 1 to 15 vol% oxidizing gas. Preferably, the precursor fiber is subjected to heat treatment at 200 to 400 ° C. for 1 to 10 minutes in a treatment chamber into which a gas containing at least 60 to 99 vol% of superheated steam and 1 to 15 vol% of oxidizing gas is introduced. The body fiber is heat-treated at 200 to 800 ° C. in a treatment chamber into which a gas containing 60 to 100 vol% of superheated steam is introduced. In the heat treatment performed after the heat treatment in the treatment chamber into which the gas containing the oxidizing gas is introduced, the introduced gas preferably has a smaller content of the oxidizing gas than the previous treatment. The gas content is more preferably 0 to 0.5 vol%.
酸化性ガスとしては、例えば、酸素、オゾン、一酸化窒素、二酸化窒素、亜酸化窒素、酸酸化二窒素、四酸化二窒素、五酸化二窒素、一酸化硫黄、二酸化硫黄、三酸化硫黄などが挙げられる。
酸化性ガスは、過熱水蒸気を含む気体とは別に、処理室に導入しても良い。酸化性ガスを過熱水蒸気を含む気体とは別に処理室に導入する場合は、処理室内の酸化性ガスの存在量が1〜15vol%になるようにすると良い。処理室内の雰囲気を均一にするためには、酸化性ガスは、処理室内に導入する前に過熱水蒸気を含む気体に混合することが好ましい。
Examples of the oxidizing gas include oxygen, ozone, nitric oxide, nitrogen dioxide, nitrous oxide, dinitrogen oxide, dinitrogen tetroxide, dinitrogen pentoxide, sulfur monoxide, sulfur dioxide, and sulfur trioxide. Can be mentioned.
The oxidizing gas may be introduced into the processing chamber separately from the gas containing superheated steam. When the oxidizing gas is introduced into the processing chamber separately from the gas containing superheated water vapor, the amount of the oxidizing gas present in the processing chamber is preferably 1 to 15 vol%. In order to make the atmosphere in the processing chamber uniform, the oxidizing gas is preferably mixed with a gas containing superheated steam before being introduced into the processing chamber.
処理室内の温度は200〜800℃であれば、前駆体繊維に耐炎化反応を起こさせることができる。処理室内の温度は200〜400℃が好ましく、より好ましくは250〜350℃である。
過熱水蒸気を60〜100vol%含む気体を導入した処理室中での加熱処理時間は、用いる前駆体繊維の種類や、処理室の温度に応じて、適時調整すればよい。好ましくは3分以上である。処理時間の上限は特に限定されないが、60分の処理で反応はほぼ完了する。
When the temperature in the processing chamber is 200 to 800 ° C., the precursor fiber can be subjected to a flameproofing reaction. The temperature in the processing chamber is preferably 200 to 400 ° C, more preferably 250 to 350 ° C.
What is necessary is just to adjust the heat processing time in the process chamber which introduce | transduced the gas containing 60-100 vol% of superheated steam according to the kind of precursor fiber to be used, and the temperature of a process chamber. Preferably it is 3 minutes or more. The upper limit of the treatment time is not particularly limited, but the reaction is almost completed after 60 minutes of treatment.
本発明で用いる処理室は、密閉型の過熱水蒸気処理装置を用いても、開放型の過熱水蒸気処理装置を用いても良い。好ましくは連続生産が容易な開放型である。開放型の処理装置を用いる場合、処理装置の開放部は外部からの気体の侵入を防ぐために、例えば水シールやラビリンス構造などの公知の手段によりシールされていることが好ましい。また、処理装置の開放部の開口面積または、処理装置内へ導入する過熱水蒸気を含む気体の導入量を調節することで、処理装置内への過熱水蒸気を含む気体の導入量と処理装置の開放部から噴出す気体の流出量をバランスさせることが好ましい。 The treatment chamber used in the present invention may use a closed superheated steam treatment apparatus or an open superheated steam treatment apparatus. The open type is preferable because it allows easy continuous production. When using an open type processing apparatus, it is preferable that the open part of the processing apparatus is sealed by a known means such as a water seal or a labyrinth structure in order to prevent gas from entering from the outside. In addition, by adjusting the opening area of the open part of the processing apparatus or the amount of gas containing superheated steam introduced into the processing apparatus, the amount of gas containing superheated steam introduced into the processing apparatus and the opening of the processing apparatus are adjusted. It is preferable to balance the outflow amount of the gas ejected from the section.
処理装置内への過熱水蒸気を含む気体の導入量は、処理装置の処理室内容積に対して、毎分0.0001〜100倍量であることが好ましい。より好ましくは毎分0.001〜10倍量である。水蒸気を含む気体の導入量が処理室内容積に対して、毎分0.0001倍量であれば、処理室内に十分な過熱水蒸気を存在させることができ、前駆体繊維の内部まで均一に素早く熱を伝えることができる。一方、毎分100倍量以下であれば、導入された気体の風圧により繊維が受けるダメージを抑えることができる。 The amount of the gas containing superheated steam introduced into the processing apparatus is preferably 0.0001 to 100 times per minute with respect to the processing chamber volume of the processing apparatus. More preferably, the amount is 0.001 to 10 times per minute. If the introduction amount of the gas containing water vapor is 0.0001 times per minute with respect to the processing chamber volume, sufficient superheated water vapor can be present in the processing chamber, and the precursor fibers can be heated evenly and quickly. Can be communicated. On the other hand, if the amount is 100 times or less per minute, damage to the fiber due to the wind pressure of the introduced gas can be suppressed.
また、処理室内の雰囲気気体が過熱水蒸気を60〜100vol%含む気体となるよう、過熱水蒸気を含む気体の処理室への導入量を調節し、導入気体で処理室内の雰囲気気体を十分に置換することが好ましい。処理室内に導入する気体及び処理室内の雰囲気気体に含まれる水蒸気の量は、例えば湿度図表を用いて湿球温度から絶対湿度を求める方法によって測定できる。(例えば、伊與田ら、球状湿潤材料の温度測定による過熱水蒸気と空気混合比の簡易測定、日本機械学会論文集(B編)78巻790号1267〜1278、2012年) Moreover, the introduction amount of the gas containing superheated steam into the treatment chamber is adjusted so that the atmosphere gas in the treatment chamber becomes a gas containing 60 to 100 vol% of superheated steam, and the atmosphere gas in the treatment chamber is sufficiently replaced with the introduced gas. It is preferable. The amount of water vapor contained in the gas introduced into the processing chamber and the atmospheric gas in the processing chamber can be measured, for example, by a method of obtaining absolute humidity from the wet bulb temperature using a humidity chart. (For example, Iwata et al., Simplified measurement of mixing ratio of superheated steam and air by measuring the temperature of a spherical wet material, Transactions of the Japan Society of Mechanical Engineers (B), Vol.
本発明においては、過熱水蒸気を60〜100vol%含む気体を導入した200〜800℃の処理室で、1.5〜5.0倍の延伸倍率で、前駆体繊維を延伸処理することが好ましい。延伸処理を行うことで繊維中の重合体の分子鎖が引き揃えられ、繊維長方向への分子鎖の配向度が向上するため、耐炎化反応において環化反応が起こりやすい。 In the present invention, it is preferable to stretch the precursor fiber at a stretch ratio of 1.5 to 5.0 times in a treatment chamber at 200 to 800 ° C. into which a gas containing 60 to 100 vol% of superheated steam is introduced. By performing the stretching treatment, the molecular chains of the polymer in the fiber are aligned, and the degree of orientation of the molecular chains in the fiber length direction is improved. Therefore, a cyclization reaction is likely to occur in the flameproofing reaction.
過熱水蒸気を含む気体を導入した処理室での延伸倍率が1.5倍以上であれば、前駆体繊維内の分子配向を高めることができ、強度と弾性率を向上させやすい傾向がある。また延伸倍率が5倍以下であると加熱処理中の糸切れを抑制でき、工程トラブルが生じにくくなる傾向がある。耐炎化時の張力は特に限定されるものでは無いが、耐炎化時の前駆体繊維の延伸倍率を上記範囲内に制御するには、1dtexの前駆体繊維に対して9〜60Nにすることが好ましい。 If the draw ratio in the treatment chamber into which a gas containing superheated steam is introduced is 1.5 times or more, the molecular orientation in the precursor fiber can be increased, and the strength and elastic modulus tend to be improved. Further, when the draw ratio is 5 times or less, yarn breakage during the heat treatment can be suppressed, and there is a tendency that process troubles are less likely to occur. Although the tension at the time of flame resistance is not particularly limited, in order to control the draw ratio of the precursor fiber at the time of flame resistance within the above range, it is necessary to set it to 9 to 60 N with respect to 1 dtex precursor fiber. preferable.
本発明においては、過熱水蒸気を60〜100vol%含む気体を導入した処理室で、200〜800℃で加熱処理を行う前に、前駆体繊維を、過熱水蒸気を60〜100vol%含む気体を導入した100〜200℃の処理室中で、2.0〜10.0倍の延伸倍率で延伸処理を行っても良い。過熱水蒸気を含む気体を導入した処理室で200〜800℃で加熱処理する前に、前駆体繊維を過熱水蒸気を含む気体を導入した処理室で、100〜200℃で延伸処理を行うと、繊維中の重合体の分子鎖が引き揃えられ、繊維長方向への分子鎖の配向度が向上するため、耐炎化反応において環化反応が起こりやすい。前駆体繊維を過熱水蒸気を含む気体を導入した処理室で、100〜200℃、2.0〜10.0倍の延伸倍率で延伸処理を行う場合、延伸処理前の前駆体繊維の配向度は0.6〜0.8であることが好ましい。 In the present invention, the precursor fiber and the gas containing 60 to 100 vol% of the superheated steam were introduced before the heat treatment at 200 to 800 ° C. in the treatment chamber into which the gas containing 60 to 100 vol% of the superheated steam was introduced. You may perform a extending | stretching process by the draw ratio of 2.0-10.0 times in the process chamber of 100-200 degreeC. When the precursor fiber is subjected to stretching treatment at 100 to 200 ° C. in the treatment chamber into which gas containing superheated steam is introduced before heat treatment at 200 to 800 ° C. in the treatment chamber into which gas containing superheated steam is introduced, fibers are obtained. Since the molecular chains of the polymer inside are aligned and the degree of orientation of the molecular chains in the fiber length direction is improved, a cyclization reaction is likely to occur in the flameproofing reaction. When the precursor fiber is stretched at a stretch ratio of 100 to 200 ° C. and 2.0 to 10.0 times in a treatment chamber into which a gas containing superheated steam is introduced, the degree of orientation of the precursor fiber before the stretch treatment is It is preferable that it is 0.6-0.8.
また、本発明においては、前駆体繊維を過熱水蒸気を含む気体を導入した処理室で200〜400℃で加熱処理した後、さらに過熱水蒸気を60〜100vol%含む気体を導入した処理室中で、500〜800℃で加熱処理することが好ましい。より好ましくは、前駆体繊維を過熱水蒸気を気体を導入した200〜400℃の処理室中で、1.5〜3.0倍の延伸倍率で延伸処理した後、過熱水蒸気を60〜100vol%含む気体を導入した500〜800℃の処理室中で、1.0〜1.5倍の延伸倍率で延伸処理する。500〜800℃での加熱処理においては、前駆体繊維の分子構造が剛直となるが、延伸倍率を1.5倍以下であれば糸切れが発生しにくく、工程トラブルを起こしにくくなる。延伸倍率が1.0倍以上であれば、前駆体繊維分子の配向性が高くなり得られる炭素繊維の強度、弾性率を高くしやすい。
上記のような本発明の耐炎化繊維の製造方法を用いることで、構造が均一な耐炎化繊維を生産効率よく得ることができる。また、前駆体繊維束内に反応熱が蓄熱することを防止でき、単糸間の融着や発火現象、糸切れを防ぐことができる。
In the present invention, the precursor fiber is heat-treated at 200 to 400 ° C. in a treatment chamber into which a gas containing superheated steam is introduced, and then in a treatment chamber into which a gas containing 60 to 100 vol% superheated steam is introduced, It is preferable to heat-process at 500-800 degreeC. More preferably, the precursor fiber is stretched at a stretch ratio of 1.5 to 3.0 times in a treatment chamber at 200 to 400 ° C. into which superheated steam is introduced, and then contains 60 to 100 vol% of superheated steam. Stretching is performed at a stretching ratio of 1.0 to 1.5 times in a processing chamber at 500 to 800 ° C. into which gas has been introduced. In the heat treatment at 500 to 800 ° C., the molecular structure of the precursor fiber becomes rigid. However, if the draw ratio is 1.5 times or less, yarn breakage hardly occurs, and process troubles hardly occur. When the draw ratio is 1.0 times or more, the orientation and the modulus of elasticity of the resulting carbon fiber can be easily increased.
By using the method for producing flame-resistant fibers of the present invention as described above, flame-resistant fibers having a uniform structure can be obtained with high production efficiency. Moreover, it is possible to prevent reaction heat from accumulating in the precursor fiber bundle, and to prevent fusion between single yarns, ignition phenomenon, and yarn breakage.
本発明の耐炎化繊維の製造方法により得られた耐炎化繊維を、引き続いて1000℃〜3000℃の不活性雰囲気下で熱処理し、炭素化することにより炭素繊維を得ることができる。
得られた炭素繊維は、電解液中で電解酸化処理を施したり、気相または液相での酸化処
理を施すことによって、複合材料における炭素繊維とマトリックス樹脂との親和性や接着
性を向上させることが好ましい。さらに、必要に応じてサイジング剤を付与することがで
きる。
このようにして得られる炭素繊維は、熱可塑性樹脂、熱硬化性樹脂などの強化繊維として、スポーツ用途、レジャー用途、一般産業用途、航空・宇宙用途、自動車用途などに広く利用できる。
The flame-resistant fiber obtained by the method for producing flame-resistant fiber of the present invention is subsequently heat-treated in an inert atmosphere at 1000 ° C. to 3000 ° C. and carbonized to obtain a carbon fiber.
The obtained carbon fiber is subjected to an electrolytic oxidation treatment in an electrolytic solution or an oxidation treatment in a gas phase or a liquid phase, thereby improving the affinity and adhesion between the carbon fiber and the matrix resin in the composite material. It is preferable. Furthermore, a sizing agent can be applied as necessary.
The carbon fiber thus obtained can be widely used as a reinforcing fiber such as a thermoplastic resin and a thermosetting resin for sports use, leisure use, general industrial use, aerospace use, automobile use and the like.
以下、本発明を実施例により具体的に説明する。また、各実施例及び比較例における各繊維の物性の評価方法は以下の方法によった。 Hereinafter, the present invention will be specifically described by way of examples. Moreover, the evaluation method of the physical property of each fiber in each Example and a comparative example was based on the following method.
<前駆体繊維の比重>
前駆体繊維の比重はアルキメデス法により測定した。試料繊維はアセトン中で脱気処理し測定した。
<Specific gravity of precursor fiber>
The specific gravity of the precursor fiber was measured by the Archimedes method. The sample fiber was deaerated in acetone and measured.
<前駆体繊維の配向度>
試料繊維軸が正確に平行になるようにそろえた後、試料調整用治具を用いて幅1mmの厚さが均一な資料繊維束に整えた。X線源がCu,Kα線の広角X線解析装置(理学電気製RINT2050)を用いて、2θ=17°付近に観察される回折の最高強度を含むピークの半値幅H1/2、H’1/2(°)を求めた。この値を次式に代入し配向度を求めた。
配向度(%)={360−(H1/2+H’1/2)}/360
<Degree of orientation of precursor fiber>
After aligning the sample fiber axes so that they were exactly parallel, a sample fiber bundle having a uniform thickness of 1 mm in width was prepared using a sample adjusting jig. Using a wide-angle X-ray analyzer (RINT2050, manufactured by Rigaku Corporation) with an X-ray source of Cu and Kα rays, the half width H 1/2 and H ′ of the peak including the maximum intensity of diffraction observed near 2θ = 17 °. 1/2 (°) was determined. This value was substituted into the following equation to determine the degree of orientation.
Degree of orientation (%) = {360− (H 1/2 + H ′ 1/2 )} / 360
[実施例1]
アクリロニトリル95質量%/アクリル酸メチル4質量%/イタコン酸1質量%よりなる共重合体紡糸原液を湿式紡糸し、温水浴中で90℃で3倍に熱延伸した後、アミノ変性シリコーン系油剤を付与し、110℃の乾熱ローラーで乾燥緻密化して、フィラメント数24000の前駆体繊維(総繊度60000dtex、比重1.16、配向度0.7)を得た。
得られた前駆体繊維を、炉内温度を150℃に保ち、炉内雰囲気を過熱水蒸気でみたした乾燥機を用いて4倍の延伸倍率で延伸処理をいった。延伸処理後の繊維の比重は1.18であり、配向度は0.9であった。
[Example 1]
A copolymer spinning stock solution consisting of 95% by mass of acrylonitrile / 4% by mass of methyl acrylate / 1% by mass of itaconic acid was wet-spun and hot-stretched three times at 90 ° C. in a warm water bath. It was applied and dried and densified with a dry heat roller at 110 ° C. to obtain precursor fibers having 24,000 filaments (total fineness 60000 dtex, specific gravity 1.16, orientation degree 0.7).
The obtained precursor fiber was stretched at a stretching ratio of 4 times using a dryer in which the furnace temperature was maintained at 150 ° C. and the atmosphere in the furnace was viewed with superheated steam. The specific gravity of the fiber after the drawing treatment was 1.18, and the degree of orientation was 0.9.
引き続き、延伸処理を行った前駆体繊維を、炉内温度を260℃に保った、炉内容積3m3の加熱処理炉を用いて繊維束の炉内滞留時間4分間、2倍の延伸倍率で加熱処理を行った。
加熱処理炉内の雰囲気制御は加熱処理炉に事前に260℃に加熱した過熱水蒸気及び酸素を、高温流量計を用いて流量を制御し、流量は過熱水蒸気9m3/min、酸素1m3/minで導入した。処理室内の雰囲気は導入気体で十分に置換されていた。
Subsequently, the precursor fiber subjected to the drawing treatment was heated at a furnace temperature of 260 ° C., and the residence time of the fiber bundle in the furnace was 4 minutes using a heat treatment furnace with a furnace volume of 3 m 3. Heat treatment was performed.
The superheated steam and oxygen control was preheated to 260 ° C. in the heat treatment furnace in the heat treatment furnace to control the flow rate using a high temperature flow meter, the flow rate of superheated steam 9m 3 / min, oxygen 1 m 3 / min Introduced in. The atmosphere in the processing chamber was sufficiently replaced with the introduced gas.
上述のようにして得られた繊維束をさらに、600℃の高温加熱炉に導入し繊維の炉内滞留時間5分間、延伸倍率1.2倍で熱処理を行い耐炎化繊維束を得た。加熱処理炉へは事前に600℃に加熱した過熱水蒸気を高温流量計を用いて制御し、流量10m3/minで導入した。処理室内の雰囲気を導入気体で十分に置換されていた。処理炉圧力は処理炉の糸出口を水によりシールすることにより加圧状態とした、加熱炉内の圧力は高温圧力計を用いて測定し0.11MPaとし、減圧バルブにより調整を行った。
得られた耐炎化繊維を引き続いて、窒素雰囲気下、1300℃で炭素化処理を行い炭素繊維を得た。
The fiber bundle obtained as described above was further introduced into a high temperature heating furnace at 600 ° C. and heat treated at a draw ratio of 1.2 times for 5 minutes in the furnace residence time to obtain a flame resistant fiber bundle. To the heat treatment furnace, superheated steam heated to 600 ° C. in advance was controlled using a high-temperature flow meter and introduced at a flow rate of 10 m 3 / min. The atmosphere in the processing chamber was sufficiently replaced with the introduced gas. The processing furnace pressure was pressurized by sealing the yarn outlet of the processing furnace with water. The pressure in the heating furnace was measured using a high-temperature pressure gauge to 0.11 MPa, and was adjusted by a pressure reducing valve.
Subsequently, the obtained flame resistant fiber was carbonized at 1300 ° C. in a nitrogen atmosphere to obtain carbon fiber.
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