JP2001131832A - Method for producing carbon yarn - Google Patents
Method for producing carbon yarnInfo
- Publication number
- JP2001131832A JP2001131832A JP31089299A JP31089299A JP2001131832A JP 2001131832 A JP2001131832 A JP 2001131832A JP 31089299 A JP31089299 A JP 31089299A JP 31089299 A JP31089299 A JP 31089299A JP 2001131832 A JP2001131832 A JP 2001131832A
- Authority
- JP
- Japan
- Prior art keywords
- fiber bundle
- precursor fiber
- yarn
- guide bar
- precursor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、単糸間接着や毛羽
の発生がなく、工程通過性に優れた高強度の炭素繊維の
製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a high-strength carbon fiber which is free from adhesion between single yarns and has no fluff and has excellent processability.
【０００２】[0002]
【従来の技術】従来から、炭素繊維は、その前駆体であ
るポリアクリロニトリル系繊維を、２００〜４００℃の
空気雰囲気中で加熱焼成して、酸化繊維に転換する耐炎
化工程、窒素・ヘリウム・アルゴン等の不活性雰囲気中
で、さらに３００〜２５００℃に加熱して炭化する炭化
工程を経ることで得られる（耐炎化工程、炭化工程をあ
わせて焼成工程と呼ぶ）複合材料用強化繊維として、航
空、宇宙用途やスポーツ用途、一般産業用途などに幅広
く用途展開がなされており、用途によっては、非常に高
い引張強度が要求される場合がある。2. Description of the Related Art Conventionally, carbon fibers have been produced by heating a polyacrylonitrile-based fiber, which is a precursor thereof, in an air atmosphere at 200 to 400 ° C. to convert it into oxidized fiber. As a reinforcing fiber for a composite material obtained by passing through a carbonization step of further heating to 300 to 2500 ° C. and carbonizing in an inert atmosphere such as argon (the fireproofing step and the carbonization step are collectively referred to as a firing step), It is widely used for aviation, space use, sports use, general industrial use, and the like. Depending on the use, very high tensile strength may be required.
【０００３】ところが、炭素繊維は、本質的に脆性を備
えた素材であるため、炭化処理して炭素繊維とする以前
の耐炎糸の表面に、軽微なものであっても、傷がある
と、炭素繊維にしたときに、これが破壊の開始点とな
り、引張強度を大きく低下させてしまうため、その耐炎
糸の製造工程においては、傷や単糸間接着からの防護に
細心の注意を払う必要がある。However, since carbon fibers are inherently brittle materials, even if the surface of the flame-resistant yarn before the carbonization treatment is made into carbon fibers, even if the surface is slightly scratched, In the case of carbon fiber, this becomes the starting point of fracture and greatly reduces the tensile strength, so in the process of manufacturing the flame resistant yarn, it is necessary to pay close attention to protection from scratches and adhesion between single yarns. is there.
【０００４】かかる傷や単糸間接着の発生を予防し、耐
炎糸の品位を高め、得られる炭素繊維の引張強度を改善
する方法には、数多くの提案がある。例えば製糸工程お
よび焼成工程での単糸間接着を減少させるため、離型性
・滑り性に優れたシリコーン型油剤を付与する方法が提
案されているが、操業性および品位の向上については効
果が十分ではなかった。また、繊維束を搬送する際に、
適用する糸道規制具の形状を工夫することによって、繊
維束に架かる張力を緩和して、前駆体繊維の擦過傷を減
少させる方法（例えば特公平３ー４１５６１号公報）が
ある。しかし、これらの方法だけでは、得られる炭素繊
維の引張強度はまだ不十分であり、また操業性について
も満足されるものではなかった。There are many proposals for a method of preventing the occurrence of such scratches and adhesion between single yarns, improving the quality of flame-resistant yarn, and improving the tensile strength of the carbon fiber obtained. For example, in order to reduce the adhesion between single yarns in the spinning process and firing process, a method of applying a silicone type oil agent having excellent releasability and slipperiness has been proposed, but it is not effective in improving operability and quality. Was not enough. Also, when transporting the fiber bundle,
There is a method (for example, Japanese Patent Publication No. 3-41561) in which the tension applied to the fiber bundle is alleviated by devising the shape of the yarn path regulating tool to be applied to reduce the abrasion of the precursor fiber. However, only by these methods, the tensile strength of the obtained carbon fiber is still insufficient, and the operability is not satisfactory.
【０００５】特に、乾湿式紡糸法で得た、極めて表面が
平滑な繊維にシリコーン系油剤を付与したものでは、シ
リコーン油剤のゲル化の進行と共に単糸同士が密着する
ためと思われるが、耐炎化が均一に行われず、続く炭化
工程で毛羽を発生する場合が多いという問題があった。[0005] In particular, in the case where a silicone-based oil is applied to fibers having an extremely smooth surface obtained by the dry-wet spinning method, it is considered that the single yarns adhere to each other as the gelation of the silicone oil progresses. However, there has been a problem that the formation is not uniform, and fuzz is often generated in the subsequent carbonization step.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、かかる従来
技術の背景に鑑み、耐炎化工程においてシリコーン油剤
のゲル化の進行と共に起こる単糸同士の密着状態をガイ
ドバーを使用し、その状態を解消することにより、焼成
工程における単糸間接着や毛羽の発生を抑制することが
でき、さらに工程通過性にも優れ、かつ、高強度の炭素
繊維を提供することができる炭素繊維の製造方法を提供
せんとするものである。SUMMARY OF THE INVENTION In view of the background of the prior art, the present invention uses a guide bar to check the state of adhesion between single yarns that occurs with the progress of gelation of a silicone oil in a flame-proofing step. By solving the problem, a method for producing a carbon fiber that can suppress the adhesion between single yarns and the generation of fluff in the firing step, is excellent in processability, and can provide a high-strength carbon fiber. It will not be provided.
【０００７】[0007]
【課題を解決するための手段】本発明は、かかる課題を
解決するために、つぎのような手段を採用するものであ
る。すなわち、本発明の炭素繊維の製造方法は、前駆体
繊維束を酸化性雰囲気中で加熱して耐炎化処理した後、
引き続き炭化処理する炭素繊維の製造方法において、該
耐炎化処理を行う工程において、該前駆体繊維束を、複
数本の固定ガイドバーを通過させて開繊して耐炎化炉に
入れることを特徴とするものである。The present invention employs the following means to solve the above-mentioned problems. That is, in the method for producing carbon fibers of the present invention, after heating the precursor fiber bundle in an oxidizing atmosphere and performing a flameproofing treatment,
In the method for producing carbon fibers to be subsequently carbonized, in the step of performing the oxidation treatment, the precursor fiber bundle is opened by passing through a plurality of fixed guide bars and put into an oxidation treatment furnace. Is what you do.
【０００８】[0008]
【発明の実施の形態】本発明の炭素繊維の製造方法の前
駆体繊維の材料に使用するアクリル系重合体は、アクリ
ロニトリル９０重量％以上からなる重合体である必要が
ある。従って、１０重量％以内で他のコモノマーと共重
合されていてもよい。コモノマー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、フ゜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、あるいはア
リルスルホン酸、メタリルスルホン酸、スチレンスルホ
ン酸およびそれらのアルカリ金属塩、等をあげることが
できるが、特に限定されるものではない。BEST MODE FOR CARRYING OUT THE INVENTION The acrylic polymer used for the material of the precursor fiber in the method for producing carbon fiber of the present invention must be a polymer composed of 90% by weight or more of acrylonitrile. Therefore, it may be copolymerized with another comonomer within 10% by weight. Acrylic acid as a comonomer,
Methacrylic acid, itaconic acid and their methyl esters, ethyl esters, propyl esters, butyl esters, alkali metal salts, ammonium salts, or allyl sulfonic acid, methallyl sulfonic acid, styrene sulfonic acid and their alkali metal salts, etc. But are not particularly limited.
【０００９】かかるアクリル系共重合体は公知の乳化重
合、塊状重合、溶液重合の重合法を用いて重合され、さ
らにこれらの重合体からアクリル系繊維を製造するに際
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、ロダンソーダー水溶液等
のポリマー溶液を紡糸原液として用いることができる。The acrylic copolymer is polymerized by known polymerization methods such as emulsion polymerization, bulk polymerization and solution polymerization. Further, when producing acrylic fibers from these polymers, dimethylacetamide, dimethylsulfoxide,
A polymer solution such as dimethylformamide, nitric acid, and an aqueous solution of rodin soda can be used as a spinning solution.
【００１０】その後、乾湿式紡糸法により、音調した紡
糸原液を、３０００Ｈの口金から一旦空気中に押し出
し、ポリマーの溶媒と水から成る凝固浴中に紡出し、水
洗工程・浴延伸工程へと搬送する。その後、この繊維束
をアミノ変性シリコーンを必須成分としたシリコーン系
油剤浴中に含浸走行させ、温調した加熱ローラーで乾燥
緻密化後、必要に応じて加圧スチーム器で延伸すること
により、単繊維間で接着がなく緻密性の高い前駆体繊維
を得ることが好ましい。[0010] Thereafter, by spin-dry spinning method, the toned spinning solution is once extruded into the air from a 3000H spinneret, spun into a coagulation bath composed of a polymer solvent and water, and transported to a water washing step and a bath stretching step. I do. Thereafter, the fiber bundle is impregnated and run in a silicone-based oil bath containing amino-modified silicone as an essential component, dried and densified by a temperature-controlled heating roller, and then stretched by a pressure steam device as necessary, whereby a single unit is obtained. It is preferable to obtain a precursor fiber having high density without adhesion between fibers.
【００１１】しかし、このように乾湿式紡糸法で得られ
た前駆体繊維は、シリコーン系油剤のゲル化の進行とと
もに単糸同士が密着するため、耐炎化が均一におこなわ
れず、続く炭化工程で毛羽を発生するという課題があ
る。However, in the precursor fiber obtained by the dry-wet spinning method, the single yarns adhere to each other with the progress of the gelation of the silicone oil agent, so that the flame resistance is not uniformly obtained, and in the subsequent carbonization step. There is a problem of generating fluff.
【００１２】本発明はこのような課題に対し、耐炎化工
程において、前駆体繊維束を単糸レベルで開繊すること
により、焼成工程における単糸間接着や毛羽の発生を抑
制しさらに工程通過性にも優れ、かつ、高強度の炭素繊
維を提供することができ、かかる課題を一挙に解決する
ことを究明したものである。In the present invention, the precursor fiber bundle is spread at the single yarn level in the flame-proofing step to suppress the adhesion between single yarns and the generation of fluff in the firing step, and furthermore, the step of passing through the step is performed. It is possible to provide a carbon fiber having excellent properties and high strength, and has sought to solve such a problem at once.
【００１３】すなわち、本発明においては、耐炎化炉に
入る前駆体繊維束を開繊状態にしてから導入することに
より、焼成工程における単糸間接着や毛羽の発生を抑制
することができたものである。In other words, in the present invention, the precursor fiber bundle entering the oxidizing furnace is introduced after being opened, thereby suppressing the adhesion between single yarns and the generation of fluff in the firing step. It is.
【００１４】このように、従来の炭素繊維製造方法にお
いて問題であった現象を解決できた理由として、乾湿式
紡糸法で得られる前駆体繊維は、表面が極めて平滑な繊
維であり、シリコーン系油剤を付与すると、シリコーン
油剤のゲル化とともに単糸同士が密着するため耐炎化が
均一におこなわれず、続く炭化工程でも毛羽を発生する
という問題があった。[0014] As described above, the reason why the problem which has been a problem in the conventional carbon fiber production method can be solved is that the precursor fiber obtained by the dry-wet spinning method is a fiber having an extremely smooth surface and a silicone-based oil agent. In addition, when the silicone oil is gelled, the single yarns adhere together with the gelation of the silicone oil agent, so that the flame resistance is not uniformly achieved, and there is a problem that fluff is generated even in the subsequent carbonization step.
【００１５】だが、前駆体繊維をガイドバーに通すこと
で、密着している単糸同士の位置関係が変わり、単糸同
士が離れるため耐炎化が均一におこなわれ、続く炭化工
程でも毛羽の発生を抑制することができる。つまり、開
繊とは前駆体繊維に均一な耐炎化処理をおこなうため、
密着状態にある単糸同士にガイドバーを使用することに
より、強制的に単糸の位置関係を変え、密着している単
糸同士が離れた状態を指す。However, by passing the precursor fiber through the guide bar, the positional relationship between the single yarns that are in close contact is changed, and the single yarns are separated from each other, so that the flame resistance is uniformly performed, and the generation of fluff occurs even in the subsequent carbonization process. Can be suppressed. In other words, in order to perform uniform flame resistance treatment on the precursor fiber with opening,
By using the guide bar for the single yarns in the close contact state, the positional relationship of the single yarns is forcibly changed, and the state in which the single yarns in close contact are separated from each other.
【００１６】よって本発明では、前駆体繊維束を複数本
の固定ガイドバーに通すことが必須である。すなわち、
ガイドバー１本だけでは、ガイドバーに十分接触する単
糸と、接触が不十分な単糸が発生し、単糸間で張力差が
生じる結果、開繊効果にバラツキが出てくる。このバラ
ツキは、その後の焼成において糸傷みや毛羽の原因にな
る。しかし、該固定ガイドバーを複数本設置すると、か
かる接触のバラツキは、見事に解決し得たものである。
かかる固定ガイドバーの本数は、好ましくは２〜１０
本、さらに好ましくは３〜７本の範囲がよい。すなわ
ち、かかる本数は、該前駆体繊維束が開繊状態になれば
よいのであって、その意味から多い方が効果的ではある
が、多すぎて該前駆体繊維に傷や単糸切れを惹起させて
は意味がないので、該前駆体繊維束の膠着状態を考慮し
て設定するのがよい。Therefore, in the present invention, it is essential to pass the precursor fiber bundle through a plurality of fixed guide bars. That is,
With only one guide bar, a single yarn that is in sufficient contact with the guide bar and a single yarn that has insufficient contact are generated, and a tension difference occurs between the single yarns, resulting in variation in the opening effect. This variation causes thread damage and fluff in subsequent firing. However, when a plurality of the fixed guide bars are provided, such a variation in the contact can be solved brilliantly.
The number of such fixed guide bars is preferably 2 to 10
Book, more preferably in the range of 3-7. In other words, the number of the fibers may be such that the precursor fiber bundle is in an open state, and it is effective to increase the number of fibers from the meaning. Since it is meaningless, it is preferable to set in consideration of the state of agglutination of the precursor fiber bundle.
【００１７】本発明は、該固定ガイドバーを複数本設置
することに加えて、該前駆体繊維束の張力差を、０．０
５〜０．１０ｇ／ｄの範囲に制御することによって、さ
らにこれらが相乗的に作用して、該前駆体繊維束をさら
に好ましく開繊することができる。かかる前駆体繊維束
の張力は、測定装置として、ＥＩＫＯ ＳＯＫＫＩＣ
Ｏ．．ＬＴＤ．ＪＡＰＡＮ テンションメーター ＨＳ
−３０００を使用して測定することができる。According to the present invention, in addition to providing a plurality of the fixed guide bars, a difference in tension between the precursor fiber bundles is reduced by 0.0
By controlling the content in the range of 5 to 0.10 g / d, they further act synergistically, and the precursor fiber bundle can be more preferably opened. The tension of the precursor fiber bundle is measured by an EIKO SOKKIC
O. . LTD. JAPAN tension meter HS
-3000 can be measured.
【００１８】すなわち、ガイドバー入りとガイドバー出
の糸条張力の差が０．０５ｇ／ｄ未満の場合には、該前
駆体繊維束単糸レベルに均一な開繊を行うことができな
くなる。該張力差が、０．１０ｇ／ｄを越える場合で
は、開繊効果が強すぎて、該前駆体繊維束が接触してい
るガイドで、糸傷みや毛羽が発生し、その後の焼成工程
において、糸切れや巻き付き等のトラブルを誘発するた
め、得られる炭素繊維の欠陥となり、高強度の炭素繊維
を得ることができなくなる。That is, when the difference between the thread tensions of the guide bar and the guide bar is less than 0.05 g / d, it is impossible to perform uniform opening at the level of the precursor fiber bundle single yarn. When the tension difference exceeds 0.10 g / d, the fiber opening effect is too strong, and yarn damage or fuzz is generated by the guide in contact with the precursor fiber bundle, and in the subsequent firing step, Since troubles such as yarn breakage and winding are induced, the resulting carbon fibers become defective, and high-strength carbon fibers cannot be obtained.
【００１９】本発明において、かかるガイドバー入りと
ガイドバー出の糸条張力の差に加えて、該前駆体繊維束
のガイドバー出の糸条張力Ｓ２を、０．１２〜０．２２
ｇ／ｄの範囲に制御すると、前記相乗効果をさらに倍加
させることができる。すなわち、かかる糸条張力Ｓ２が
０．１２ｇ／ｄ未満の場合には、やはり十分な開繊効果
を該前駆体繊維束に与えることができないし、０．２２
ｇ／ｄを越えた場合でも、該前駆体繊維束の品位低下に
つながり、高強度の炭素繊維を得ることができない。In the present invention, in addition to the difference in the yarn tension between the guide bar and the guide bar, the yarn tension S2 of the precursor fiber bundle from the guide bar is set to 0.12 to 0.22.
When the ratio is controlled within the range of g / d, the synergistic effect can be further doubled. That is, when the yarn tension S2 is less than 0.12 g / d, a sufficient opening effect cannot be given to the precursor fiber bundle, and
Even when the value exceeds g / d, the quality of the precursor fiber bundle is reduced, and high-strength carbon fibers cannot be obtained.
【００２０】かかる開繊効果を向上させるために、該前
駆体繊維束のガイドバーへの糸条接触角を、トータルで
２０゜〜２５０゜の範囲に制御すること、さらに該前駆
体繊維束を、該ガイドバーにジグザグに通過させること
などは、好ましい態様である。In order to improve the fiber opening effect, the yarn contact angle of the precursor fiber bundle with the guide bar is controlled in a total range of 20 ° to 250 °, and the precursor fiber bundle is further controlled. The zigzag passage through the guide bar is a preferred embodiment.
【００２１】かかる固定ガイドバーとしては、該ガイド
バーが、該糸条と接する断面の曲率半径が１〜５ｍｍの
棒状物であり、かつ、糸条が接触する面の中心線平均粗
さで表される表面粗さＲａが０．５以下で、ビッカース
硬度が１５００以上である材質で構成されているのが好
ましい。[0021] As such a fixed guide bar, the guide bar is a rod-like material having a radius of curvature of 1 to 5 mm in a cross section in contact with the yarn, and is expressed by a center line average roughness of a surface in contact with the yarn. It is preferable to be made of a material having a surface roughness Ra of 0.5 or less and a Vickers hardness of 1500 or more.
【００２２】その表面粗さＲａが０．５以上の場合、擦
過傷が発生しやすく得られる炭素繊維の欠陥となり、高
強度の炭素繊維を得ることが出来ない。このような意味
からガイドバーの表面粗さＲａは０．５以下が好まし
く、０．１以下がより好ましいが本発明の効果を奏する
にはＲａが約０．０１あれば十分である。 また、かか
る表面粗さＲａは、ＪＩＳ Ｂ−０６０１、ＪＩＳ Ｂ
−０６５１による３箇所の測定点の平均値である。かか
る表面粗さＲａの測定装置としては、ミツトヨフォーム
トレーサー ＣＳ−４００を使用することができる。When the surface roughness Ra is 0.5 or more, abrasion easily occurs and the obtained carbon fiber becomes defective, so that high strength carbon fiber cannot be obtained. In this sense, the surface roughness Ra of the guide bar is preferably 0.5 or less, and more preferably 0.1 or less, but Ra of about 0.01 is sufficient for achieving the effects of the present invention. Further, such surface roughness Ra is JIS B-0601, JIS B
This is the average value of three measurement points according to −0651. As such a device for measuring the surface roughness Ra, Mitutoyo Form Tracer CS-400 can be used.
【００２３】ガイドバー部材としては、ビッカース硬度
（ＪＩＳ Ｒ−１６１０参照）で１５００以上であるこ
とが必要であり、好ましくはセラミックス製のものが使
用される。１５００以下では取り扱い中にガイド表面に
傷がつきやすく、糸条を傷めてしまうためである。The guide bar member must have a Vickers hardness of 1500 or more (refer to JIS R-1610), and is preferably made of ceramics. If it is less than 1500, the guide surface is easily damaged during handling, and the yarn is damaged.
【００２４】[0024]
【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。The present invention will be described more specifically with reference to the following examples.
【００２５】実施例中、炭素繊維の性能（強度）はＪＩ
ＳＲー７６０１に準じて測定したエポキシ樹脂含浸スト
ランドの物性であり、測定回数ｎ＝６の平均から求めた
値である。 実施例１〜５、比較例１〜３ アクリロニトリル（以下、ＡＮ）９９．５モル％、イタ
コン酸０．５モルからなる極限粘度[ η] が１．８０の
ＡＮ共重合体を２０重量％含むジメチルスルホキシド
（ＤＭＳＯ）の紡糸原液を得た。ここで重合物の親水性
を向上させるため、ＰＨが８．０になるまで紡糸原液に
アンモニアガスを吹き込んだ。In the examples, the performance (strength) of the carbon fiber was determined by JI
It is a physical property of the epoxy resin-impregnated strand measured according to SR-7601, and is a value obtained from an average of the number of measurements n = 6. Examples 1 to 5 and Comparative Examples 1 to 3 An acrylonitrile (hereinafter referred to as AN) 99.5 mol% and an intrinsic viscosity [η] composed of 0.5 mol of itaconic acid containing 20 wt% of an AN copolymer having an intrinsic viscosity [η] of 1.80. A spinning solution of dimethyl sulfoxide (DMSO) was obtained. Here, in order to improve the hydrophilicity of the polymer, ammonia gas was blown into the spinning dope until the pH became 8.0.
【００２６】その後、乾湿式紡糸法により、４５℃に温
調した紡糸原液を、３０００Ｈの口金からＤＭＳＯと水
から成る凝固浴中に紡出して、３０００本からなる凝固
糸を得た。Thereafter, the spinning solution, which had been adjusted to a temperature of 45 ° C., was spun from a 3000H spinner into a coagulation bath composed of DMSO and water by a dry-wet spinning method to obtain 3000 coagulated yarns.
【００２７】さらに凝固糸を熱水中で水洗処理後、全４
槽からなる複数の浴延伸工程に導き、第４槽の温度が９
０℃の熱水中で４倍延伸を行った。なお、ここでは単繊
維間の接着を紡糸するため、浴槽の入り側の搬送ローラ
ーを浴槽から外に出した状態で繊維束を搬送しながら延
伸した。Further, after the coagulated yarn was washed with hot water,
It led to a plurality of bath stretching steps consisting of tanks, and the temperature of the fourth tank was 9
The film was stretched 4 times in hot water at 0 ° C. In this case, in order to spin the adhesion between the single fibers, the fiber bundle was stretched while transporting the fiber bundle with the transport roller on the entrance side of the bathtub being out of the bathtub.
【００２８】その後、この繊維束を、アミノ変性シリコ
ーン（アミノ基の含有量はＮＨ２として１．０％のも
の）をノニルフェノールＥＯ付加物を用いて乳化した油
剤濃度が２．０重量％のシリコーン系油剤浴中に含浸走
行させ、繊維束に油分として０．７％付与した。Thereafter, the fiber bundle was emulsified with a nonylphenol EO adduct of an amino-modified silicone (having an amino group content of 1.0% as NH 2), and a silicone-based silicone oil having an oil agent concentration of 2.0% by weight. It was impregnated and run in an oil bath to give 0.7% of oil content to the fiber bundle.
【００２９】さらに、１５０℃に温調した加熱ローラー
で乾燥緻密化後、連続して加圧スチーム機で４倍の延伸
倍率で延伸後、１８０℃に温調した加熱ローラーで再度
乾燥処理し、単糸デニール１．０ｄ，トータルデニール
が３０００ｄのアクリル系前駆体繊維を得た。Further, after being dried and densified by a heating roller adjusted to 150 ° C., it was continuously stretched at a stretch ratio of 4 times by a pressure steam machine, and dried again by a heating roller adjusted to 180 ° C. An acrylic precursor fiber having a single yarn denier of 1.0 d and a total denier of 3000 d was obtained.
【００３０】次に、焼成工程において前駆体繊維をガイ
ドバーにジグザグに通過させ、このときガイドバーの本
数、種類、材質、および前駆体繊維束の糸条張力、ガイ
ドバーへのトータル糸条接触角を変えて試験をおこな
い、表１に示した。なお、ガイドバーはビッカース硬度
が２０００のセラミックス製のものを使用し、また、前
駆体繊維の開繊状態についてもガイドバー入、出側の糸
幅を表１に示した。Next, in the firing step, the precursor fibers are passed zigzag through a guide bar. At this time, the number, type, and material of the guide bars, the yarn tension of the precursor fiber bundle, and the total yarn contact with the guide bar The test was performed at different angles, and the results are shown in Table 1. The guide bar used was made of ceramics having a Vickers hardness of 2000. Table 1 also shows the yarn width on the guide bar entrance and exit side of the opened state of the precursor fiber.
【００３１】こうして前駆体繊維を２５０〜２８０℃の
空気雰囲気中で延伸倍率を０．９７として延伸しなが
ら、安定化処理することにより、耐炎化繊維に転換し
た。次に、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、４００〜５００℃の雰囲
気温度における昇温速度を１００℃／分、延伸倍率を
１．０２として前炭化処理し、次いで窒素雰囲気中、最
高雰囲気温度が１４５０℃の炭化炉で１０００〜１２０
０℃の雰囲気温度における昇温速度を２００℃／分、延
伸倍率を０．９７として炭化処理して、炭素繊維を得
た。In this way, the precursor fiber was converted into oxidized fiber by performing a stabilization treatment while stretching the precursor fiber in an air atmosphere at 250 to 280 ° C. at a draw ratio of 0.97. Next, the flame-resistant fiber is pre-carbonized in a nitrogen atmosphere in a pre-carbonization furnace having a maximum ambient temperature of 800 ° C. at a temperature rising rate of 100 ° C./min at an atmospheric temperature of 400 to 500 ° C. and a draw ratio of 1.02. And then in a nitrogen atmosphere in a carbonization furnace with a maximum atmosphere temperature of 1450 ° C. for 1000 to 120
Carbonization was performed at a temperature rising rate of 200 ° C./min and a draw ratio of 0.97 at an atmosphere temperature of 0 ° C. to obtain carbon fibers.
【００３２】この後、炭素繊維１ｇ当たり１０クーロン
の電荷を与えることにより、炭酸アンモニウムの水溶液
中で陽極酸化処理を施した。こうして得られた炭素繊維
については樹脂含浸ストランド強度・弾性率を測定し
て、まとめて表１、２に示した。 比較例１ ガイド本数が１本、トータル糸条接触角を４５゜に設置
し、Ｓ２の張力を０．１８ｇ／ｄに設定して試験をおこ
なった。 結果、前駆体繊維への開繊効果が弱く、十分
に単糸の密着状態を解消できなかった為、ＣＦ物性・毛
羽とも満足な結果は得られていない。 比較例２ ガイド本数が１本、ガイドの表面粗さＲａが０．６のも
のを使用して試験をおこなった。結果、前駆体繊維にガ
イドバーによる擦過傷が発生し繊維を痛めてしまい、耐
炎化工程において毛羽を誘発することとなり、ＣＦ物性
・毛羽とも著しく悪化した。 比較例３ ガイドの曲率半径が０．５ｍｍのものを使用して試験を
おこなった。前駆体繊維がガイドバー出において、糸の
弛みや糸乱れが発生、ＣＦ強度・毛羽とも悪化する結果
となった。Thereafter, anodization was performed in an aqueous solution of ammonium carbonate by giving a charge of 10 coulombs per gram of carbon fiber. The carbon fibers thus obtained were measured for the strength and elastic modulus of the resin-impregnated strand, and are shown in Tables 1 and 2 collectively. Comparative Example 1 The test was performed by setting the number of guides to one, setting the total yarn contact angle to 45 °, and setting the tension of S2 to 0.18 g / d. As a result, the effect of opening the precursor fibers was weak, and the close contact state of the single yarn could not be sufficiently eliminated, so that satisfactory results were not obtained in both the CF physical properties and the fluff. Comparative Example 2 A test was performed using one guide and a guide having a surface roughness Ra of 0.6. As a result, the precursor fiber was abraded by the guide bar and damaged the fiber, causing fluff in the flame-proofing step, and the physical properties and fluff of CF were remarkably deteriorated. Comparative Example 3 A test was performed using a guide having a radius of curvature of 0.5 mm. When the precursor fiber exited the guide bar, the yarn became loose or the yarn was disturbed, and the CF strength and fluff were deteriorated.
【００３３】[0033]
【表１】 [Table 1]
【００３４】[0034]
【表２】 [Table 2]
【００３５】表１、２から明らかなように、比較例１〜
３に比して、実施例１〜３のものは、毛羽の発生率も少
なく、強度、弾性率のいずれも優れていることがわか
る。As is clear from Tables 1 and 2, Comparative Examples 1 to
As compared with No. 3, the samples of Examples 1 to 3 have a low generation rate of fluff, and it is understood that both the strength and the elastic modulus are excellent.
【００３６】このことから、単糸同士の密着状態を適正
に解消させることにより工程通過性に優れた高強度炭素
繊維を製造することができる。From this, it is possible to manufacture a high-strength carbon fiber excellent in processability by appropriately eliminating the state of adhesion between the single yarns.
【００３７】[0037]
【発明の効果】本発明によれば、焼成工程における単糸
間接着や毛羽の発生を抑制し、工程通過性に優れた高強
度炭素繊維を製造することができる。According to the present invention, it is possible to produce a high-strength carbon fiber excellent in processability by suppressing adhesion between single yarns and generation of fluff in the firing step.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4L037 AT02 CS03 FA06 FA08 PA55 PC05 PF29 PF45 PF58 PS02 PS12 PS17 PS20 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4L037 AT02 CS03 FA06 FA08 PA55 PC05 PF29 PF45 PF58 PS02 PS12 PS17 PS20
Claims (6)
耐炎化処理した後、引き続き炭化処理する炭素繊維の製
造方法において、該耐炎化処理を行う工程において、該
前駆体繊維束を、複数本の固定ガイドバーを通過させて
開繊して耐炎化炉に入れることを特徴とする炭素繊維の
製造方法。1. A method for producing a carbon fiber, comprising heating a precursor fiber bundle in an oxidizing atmosphere and subjecting the precursor fiber bundle to oxidation treatment, and subsequently carbonizing the precursor fiber bundle. A method for producing carbon fiber, comprising: opening a fiber through a plurality of fixed guide bars;
に、該前駆体繊維束のガイドバー入り糸条張力Ｓ１とガ
イドバー出の糸条張力Ｓ２との差を、０．０５〜０．１
０ｇ／ｄの範囲に制御しながら通過させることを特徴と
する請求項１記載の炭素繊維の製造方法。2. When the plurality of fixed guide bars are passed, the difference between the thread tension S1 of the precursor fiber bundle entering the guide bar and the thread tension S2 exiting the guide bar is 0.05 to 0. .1
The method for producing carbon fiber according to claim 1, wherein the carbon fiber is passed while being controlled within a range of 0 g / d.
Ｓ２を、０．１２〜０．２２ｇ／ｄの範囲に制御するこ
とを特徴とする請求項１または２記載の炭素繊維の製造
方法。3. The carbon fiber according to claim 1, wherein the yarn tension S2 of the precursor fiber bundle coming out of the guide bar is controlled in the range of 0.12 to 0.22 g / d. Production method.
角を、トータルで２０゜〜２５０゜の範囲に制御するこ
とを特徴とする請求項１〜３のいずれかに記載の炭素繊
維の製造方法4. The carbon according to claim 1, wherein the yarn contact angle of the precursor fiber bundle with the guide bar is controlled in a total range of 20 ° to 250 °. Fiber manufacturing method
ガイドバーにジグザグに通過させることを特徴とする請
求項１〜４のいずれかに記載の炭素繊維の製造方法5. The method for producing carbon fibers according to claim 1, wherein said precursor fibers are passed zigzag through said guide bars installed freely in the vertical and horizontal directions.
率半径が１〜５ｍｍの棒状物であり、かつ、糸条が接触
する面の中心線平均粗さで表される表面粗さＲａが０．
５以下で、ビッカース硬度が１５００以上である材質で
構成されているものであることを特徴とする請求項１〜
５のいずれかに記載の炭素繊維の製造方法。6. The guide bar is a rod-shaped member having a curvature radius of 1 to 5 mm in a cross section in contact with the yarn, and a surface roughness represented by a center line average roughness of a surface in contact with the yarn. Ra is 0.
5 or less and a material having a Vickers hardness of 1500 or more.
5. The method for producing a carbon fiber according to any one of the above items 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31089299A JP2001131832A (en) | 1999-11-01 | 1999-11-01 | Method for producing carbon yarn |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31089299A JP2001131832A (en) | 1999-11-01 | 1999-11-01 | Method for producing carbon yarn |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001131832A true JP2001131832A (en) | 2001-05-15 |
Family
ID=18010649
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31089299A Pending JP2001131832A (en) | 1999-11-01 | 1999-11-01 | Method for producing carbon yarn |
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| Country | Link |
|---|---|
| JP (1) | JP2001131832A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101880923A (en) * | 2010-06-28 | 2010-11-10 | 中国科学院西安光学精密机械研究所 | Method for improving tensile strength of carbon fibers |
| WO2019146487A1 (en) | 2018-01-26 | 2019-08-01 | 東レ株式会社 | Flame-retardant fiber bundle and method for manufacturing carbon fiber bundle |
| US11319648B2 (en) | 2018-01-26 | 2022-05-03 | Toray Industries, Inc. | Stabilized fiber bundle and method of manufacturing carbon fiber bundle |
-
1999
- 1999-11-01 JP JP31089299A patent/JP2001131832A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101880923A (en) * | 2010-06-28 | 2010-11-10 | 中国科学院西安光学精密机械研究所 | Method for improving tensile strength of carbon fibers |
| WO2019146487A1 (en) | 2018-01-26 | 2019-08-01 | 東レ株式会社 | Flame-retardant fiber bundle and method for manufacturing carbon fiber bundle |
| US11319648B2 (en) | 2018-01-26 | 2022-05-03 | Toray Industries, Inc. | Stabilized fiber bundle and method of manufacturing carbon fiber bundle |
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