JPH0627367B2 - Method for producing acrylic precursor yarn for carbon fiber - Google Patents
Method for producing acrylic precursor yarn for carbon fiberInfo
- Publication number
- JPH0627367B2 JPH0627367B2 JP1201078A JP20107889A JPH0627367B2 JP H0627367 B2 JPH0627367 B2 JP H0627367B2 JP 1201078 A JP1201078 A JP 1201078A JP 20107889 A JP20107889 A JP 20107889A JP H0627367 B2 JPH0627367 B2 JP H0627367B2
- Authority
- JP
- Japan
- Prior art keywords
- yarn
- carbon fiber
- bath
- fusion
- group
- 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.)
- Expired - Fee Related
Links
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、炭素繊維用アクリル系前駆体糸条の製造法、
特に品質および物性の優れた炭素繊維を製造するのに好
適である、炭素繊維用アクリル系前駆体糸条の製造法に
関するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Use) The present invention relates to a method for producing an acrylic precursor yarn for carbon fiber,
In particular, the present invention relates to a method for producing an acrylic precursor yarn for carbon fibers, which is suitable for producing carbon fibers having excellent quality and physical properties.
（従来の技術） 炭素繊維はその前駆体であるアクリル系、レーヨン系、
ピッチ系、あるいはポリビニルアルコール系繊維を紡糸
する製糸工程、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３００〜２
５００℃に加熱して炭化あるいは黒鉛化する炭化工程や
黒鉛化工程を経ることで得られ（耐炎化工程、炭化工
程、黒鉛化工程をあわせて焼成工程と呼ぶ）、複合材料
用強化繊維や電気特性を生かした用途などに幅広く利用
されている。(Prior Art) Carbon fibers are precursors of acrylic, rayon,
A spinning process of spinning pitch-based or polyvinyl alcohol-based fibers, a flame-proofing process of heating and firing in an air atmosphere of 200 to 400 ° C. to convert to oxidized fibers, and further in an inert atmosphere of nitrogen, helium, argon or the like. 300-2
Obtained by going through a carbonization process or graphitization process of heating to 500 ° C to carbonize or graphitize (the flameproofing process, the carbonization process, and the graphitization process are collectively called a firing process). It is widely used for applications that take advantage of its characteristics.
上記製造工程のうち、耐炎化工程はアクリル繊維内にナ
フチリジン環等の環化構造を形成し、該繊維の耐熱性を
向上せしめて炭素繊維の品質やその生産性を左右する重
要な工程である。この耐炎化工程は発熱反応であるため
高温処理を行うと急激に反応が進行し、局部的に蓄熱が
起こり単繊維間の融着が発生したり繊維が分解・切断し
たりすることもあり、炭素繊維の品質・生産性を著しく
低下させてしまう。単繊維間の融着は、耐炎化工程に先
立つ製糸工程においても、その延伸工程・乾燥緻密化工
程ですでに確認でき、製糸工程からの融着をいかに減少
させるかが炭素繊維製造上の品質面・操業面の大きなポ
イントである。Of the above manufacturing steps, the flameproofing step is an important step that forms a cyclized structure such as a naphthyridine ring in the acrylic fiber to improve the heat resistance of the fiber and control the quality of the carbon fiber and its productivity. . Since this flameproofing process is an exothermic reaction, the reaction rapidly progresses when high temperature treatment is performed, and heat is locally stored, which may cause fusion between single fibers or fiber decomposition or cutting. This will significantly reduce the quality and productivity of carbon fiber. The fusion between single fibers can be already confirmed in the drawing process and the dry densification process even in the yarn making process prior to the flameproofing process, and how to reduce the fusion from the yarn making process is a quality in carbon fiber manufacturing. This is a major aspect of operation and operation.
このような製糸工程・耐炎化工程での単糸間の融着防止
には製糸工程でのシリコーン油剤の使用が特に有効であ
る。例えば特開昭６０−１８５８７９号公報には、アミ
ノ変性基を有したオルガノポリシロキサン油剤が開示さ
れている。また、特公昭５１−１２７３９号公報には、
ポリジメチルシロキサン化合物などをアクリル繊維に付
与したのち、焼成して高性能炭素繊維とすることが開示
されている。また油剤のほかにも製糸工程の最後に、疑
似融着した糸条を空気によって開繊し、単糸間融着を防
ぐ方法が特公昭６０−５９３２３号公報に開示されてい
る。Use of a silicone oil agent in the yarn making process is particularly effective for preventing fusion between single yarns in such yarn making process and flame resistance process. For example, JP-A-60-185879 discloses an organopolysiloxane oil agent having an amino-modified group. In addition, Japanese Patent Publication No. 51-12739 discloses that
It is disclosed that a high-performance carbon fiber is obtained by applying a polydimethylsiloxane compound or the like to an acrylic fiber and then firing it. In addition to the oil agent, Japanese Patent Publication No. 60-59323 discloses a method of preventing the fusion between single yarns by opening the pseudo-fused yarns with air at the end of the yarn making process.
しかしながら単糸間融着は製糸工程中の延伸過程ですで
に発現しており、上記方法を単独にあるいは種々組み合
わせたとしても単糸間融着を十分に防止することはでき
ず、根本的解決に至ることはできない。However, the fusion between single yarns has already appeared in the drawing process during the yarn making process, and even if the above methods are used alone or in various combinations, the fusion between single yarns cannot be sufficiently prevented, and the fundamental solution Cannot be reached.
（発明が解決しようとする課題） 本発明の課題は、製糸から焼成にいたる炭素繊維製造過
程において発生する単繊維同志の融着を防止せしめ、高
品質で同時に物性の優れた炭素繊維を得ることのでき
る、炭素繊維用アクリル系前駆体糸条の製造方法を提供
することにある。(Problems to be Solved by the Invention) An object of the present invention is to prevent fusion of single fibers that occur in the carbon fiber manufacturing process from yarn production to firing, and to obtain carbon fibers of high quality and excellent physical properties at the same time. It is intended to provide a method for producing an acrylic precursor yarn for carbon fiber, which can be manufactured.
（課題を解決するための手段） 本発明の上記課題は、アクリロニトリル９０重量％以上
からなるアクリル系重合体溶液を紡糸後、湿潤糸条を延
伸し、原糸油剤を付与する炭素繊維用アクリル系前駆体
糸条の製造法において、少なくとも２つ以上の分離した
延伸浴間にフリーローラーを配し、該延伸浴槽中３０〜
９８℃の水中で多槽延伸し、延伸後の糸条に少なくとも
１成分はアミノ変性ポリシロキサンからなる原糸油剤を
付与することを特徴とする炭素繊維用アクリル系前駆体
糸条の製造法によって達成することができる。(Means for Solving the Problem) The above-mentioned problem of the present invention is obtained by spinning an acrylic polymer solution containing 90% by weight or more of acrylonitrile, stretching a wet yarn, and applying a raw yarn oil agent to the acrylic fiber for carbon fiber. In the method for producing a precursor yarn, a free roller is arranged between at least two or more separated drawing baths, and the free roller is used in the
A method for producing an acrylic precursor yarn for carbon fiber, which comprises drawing in a multi-tank in water at 98 ° C., and applying a raw yarn oil agent of which at least one component is an amino-modified polysiloxane to the drawn yarn. Can be achieved.
以下、本発明の詳細と好ましい態様について説明する。Hereinafter, details and preferred embodiments of the present invention will be described.
本発明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、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、好ましいのはイタコン酸であり、好ま
しい共重合量は０．０１〜５重量％である。The acrylic polymer used in the present invention must be a polymer containing 90% by weight or more of acrylonitrile. Therefore, it may be copolymerized with another comonomer within 10% by weight. Comonomers include acrylic acid, methacrylic acid, itaconic acid, and their methyl esters, ethyl esters, alkali metal salts, ammonium salts, or allyl sulfonic acid, methallyl sulfonic acid, styrene sulfonic acid and their alkali metal salts, etc. However, itaconic acid is preferable, and the preferable amount of copolymerization is 0.01 to 5% by weight.
アクリル系重合体は公知の乳化重合、塊状重合、溶液重
合等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、ロダンソーダ水溶液等のポリマー溶液を紡糸
原液として、通常の湿式紡糸法、乾湿式紡糸法によって
紡糸し、繊維化することができる。特に乾湿式紡糸法に
よる場合には、単繊維間の融着がより一層生じやすいの
で、本発明の効果がより顕著にあらわれる。Acrylic polymers are polymerized by known polymerization methods such as emulsion polymerization, bulk polymerization, solution polymerization, etc., and when producing acrylic fibers from these polymers, dimethylacetamide, dimethylsulfoxide, dimethylformamide, nitric acid, A polymer solution such as an aqueous solution of rhodanese can be used as a spinning stock solution to be spun into fibers by an ordinary wet spinning method or dry-wet spinning method. Particularly in the case of the dry-wet spinning method, fusion between the single fibers is more likely to occur, so that the effect of the present invention is more remarkable.
本発明で最も特徴的なことの一つは、少なくとも２つ以
上の分離した延伸浴槽間にフリーローラーを配し、該延
伸浴槽中３０〜９８℃の水中で多槽延伸することであ
る。浴延伸は通常個々の延伸浴槽の入出に駆動ローラー
を設置し、延伸浴槽内で配向、ローラー部で緩和を行
い、これを何段か重ねてなされる。浴延伸の入／出ロー
ラーは延伸倍率を規制するために駆動ローラーであるの
が普通であるが、ローラーが強制的に駆動されるため走
行糸条にかかる圧着力が大きく、単繊維同志の融着や接
着が増大する。糸条切れをなくし安定して延伸するため
に、延伸浴数を増やし多段延伸する方法が採用されてい
るが、浴延伸段数を多くすればするほどその浴槽入出に
おいて糸条と接触するローラー数が増え、そのたびに糸
条はローラー上に強く圧着され、前記融着は激増する。One of the most characteristic features of the present invention is to dispose a free roller between at least two or more separated stretching baths and perform multi-bath stretching in water at 30 to 98 ° C in the stretching baths. In the bath stretching, a driving roller is usually installed at the entrance and exit of each stretching bath, orientation is performed in the stretching bath, and relaxation is performed at the roller portion, and this is performed in several layers. The input / exit roller for bath drawing is usually a driving roller to regulate the draw ratio, but since the roller is forcibly driven, the crimping force applied to the running yarn is large, and the single fiber melts. Increased wear and adhesion. In order to eliminate yarn breakage and perform stable drawing, a method of increasing the number of drawing baths and performing multi-stage drawing is adopted. The number of yarns increases, and each time the yarn is strongly pressed onto the roller, and the fusion is drastically increased.
本発明においては延伸浴槽間にフリーローラーを配し、
延伸浴槽を出た糸条はフリーローラーのみに接触し次に
続く延伸浴槽へと導かれる。従来の駆動ローラー方式の
延伸法では、各浴槽での糸条とローラーとの滑りをなく
すために接触角を大きくとってローラー本数を増やして
いたが、本発明においては浴槽間に一本のフリーローラ
ーがあれば良く、このため糸条に接触するローラー数は
極端に減少させることができる。またフリーローラーで
あるために糸条への圧着力が減少し浴延伸工程での単繊
維同士の融着を防止することができる。通常延伸浴中に
もローラーを設けるが、本発明においては延伸工程の入
／出ローラーさえ駆動であれば途中過程（浴中、浴外）
のローラーもフリーローラーである方が好ましい。これ
らフリーローラーは糸条によって回転されるため、浴中
フリーローラー、浴外フリーローラーともその回転トル
クはできるだけ小さい方が好ましい。In the present invention, a free roller is arranged between the drawing baths,
The yarn exiting the drawing bath contacts only the free roller and is guided to the next drawing bath. In the conventional drawing method using the drive roller method, the number of rollers is increased by increasing the contact angle in order to eliminate the slippage between the yarn and the roller in each bath. It suffices if there are rollers, so that the number of rollers contacting the yarn can be extremely reduced. Further, since it is a free roller, the pressure force applied to the yarn is reduced, and it is possible to prevent fusion of the single fibers during the bath drawing process. Usually, a roller is also provided in the drawing bath, but in the present invention, it is an intermediate step (in the bath or outside the bath) as long as the in / out roller of the drawing step is driven.
It is preferable that the roller is also a free roller. Since these free rollers are rotated by yarns, it is preferable that the rotating torque of both the free roller in the bath and the free roller outside the bath is as small as possible.
本発明においては延伸時の温度条件を選ぶことも重要で
ある。浴延伸工程は糸条の脱溶媒工程も兼ねているた
め、脱溶媒が不十分なうちに高温で延伸を行うと、残存
溶媒で糸条が溶けて単繊維間の融着が進み好ましくな
い。このため延伸初期の脱溶媒が不十分なうちは延伸温
度を極力下げるのが好ましく、糸条中の残存溶媒が１％
以上の時は温度３０〜５０℃、１％未満の時は４０〜９
８℃で延伸するのが好ましい。また延伸倍率条件を高く
とりすぎると、単糸切れが増え、生産性を著しく低下さ
せるおそれがある。従って延伸倍率（トータル浴延伸倍
率）は２．０〜６．０倍であるのが好ましい。In the present invention, it is important to select the temperature condition during stretching. Since the bath drawing step also serves as the yarn desolvation step, if the drawing is performed at a high temperature while the desolvation is insufficient, the yarn is melted by the residual solvent and fusion between the single fibers is unfavorable. Therefore, it is preferable to lower the stretching temperature as much as possible while the desolvation at the beginning of stretching is insufficient, and the residual solvent in the yarn is 1%.
In the above case, the temperature is 30 to 50 ° C, and in the case of less than 1%, it is 40 to 9
Stretching at 8 ° C. is preferred. Further, if the stretching ratio condition is set too high, single yarn breakage may increase and the productivity may be significantly reduced. Therefore, the draw ratio (total bath draw ratio) is preferably 2.0 to 6.0.
本発明の浴延伸方法は従来の多段浴延伸方法に比べて駆
動部分が少なくてすみ、設備費も減少させることができ
る。The bath-drawing method of the present invention requires less driving parts than the conventional multi-step bath-drawing method, and the equipment cost can be reduced.
本発明においては、上記延伸に続いて少なくとも１成分
がアミノ変性ポリシロキサンからなる原糸油剤を糸条に
付与するものである。すなわち製糸工程においては延伸
工程に続く乾燥工程でも単糸間の融着が発生するため、
乾燥緻密化前に油剤を付与して単繊維表面に皮膜を形成
させる必要がある。アクリル系前駆体糸条は焼成工程に
おいて過酷な熱処理を受けるため、該表面皮膜を耐熱性
に優れたものにする必要があり、このため糸条に付与す
る油剤としては少なくとも１成分はアミノ変性シリコー
ンとするものである。本発明に使用されるアミノ変性シ
リコーンの例としては次に示す構造式のものがある。In the present invention, a raw yarn oil agent having at least one component composed of an amino-modified polysiloxane is applied to the yarn after the drawing. That is, in the yarn making process, fusion between single yarns occurs even in the drying process following the drawing process,
It is necessary to apply an oil agent to form a film on the surface of the single fiber before the dry densification. Since the acrylic precursor yarn undergoes a severe heat treatment in the firing process, it is necessary to make the surface coating excellent in heat resistance. Therefore, at least one component of the oil agent added to the yarn is an amino-modified silicone. It is what Examples of amino-modified silicones used in the present invention include those having the following structural formula.
ここでＲ１、Ｒ８はアルキル基、水酸基、アルコキシル
基、アリール基、およびアルキル基、エポキシ基、チオ
アルコール基などを含む一価の有機基から選択される
基、Ｒ２、Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７はメチル基、
またはフェニル基に代表される置換または非置換の一価
の炭化水素基、Ｘ１、Ｘ２はアミノ基、エポキシ基、ア
ルコキシル基、ポリオキシアルキレン基、水酸基、チオ
アルコール基、カルボキシル基、ハロゲン基などの変性
基を含む一価の有機基から選択されたものである。ま
た、ｍ、ｎ、ｐは０または１以上の整数であって、m+n+
pが１０〜２０００であり、分子中に少なくとも１つは
アミノ基を有しているものである。 Here, R 1 and R 8 are a group selected from an alkyl group, a hydroxyl group, an alkoxyl group, an aryl group, and a monovalent organic group including an alkyl group, an epoxy group, a thioalcohol group, R 2 , R 3 , and R. 4 , R 5 , R 6 , and R 7 are methyl groups,
Alternatively, a substituted or unsubstituted monovalent hydrocarbon group represented by a phenyl group, X 1 and X 2 are an amino group, an epoxy group, an alkoxyl group, a polyoxyalkylene group, a hydroxyl group, a thioalcohol group, a carboxyl group, a halogen group. And a monovalent organic group containing a modifying group such as. In addition, m, n and p are 0 or an integer of 1 or more, and m + n +
p is 10 to 2000 and at least one has an amino group in the molecule.
特にアミノ変性ポリシロキサンの構造が上記式のＲ１〜
Ｒ８がメチル基であり、ｎ＝０で、Ｘ２が（ＣＨ２）３
ＮＨ（ＣＨ２）２ＮＨ２であるものに適用すると、焼成
工程における単繊維間融着防止効果が著しく、炭素繊維
物性の面から好ましい。In particular, the structure of the amino-modified polysiloxane is R 1 to
R 8 is a methyl group, n = 0, and X 2 is (CH 2 ) 3
When applied to NH (CH 2 ) 2 NH 2 , it has a remarkable effect of preventing fusion between single fibers in the firing step and is preferable from the viewpoint of carbon fiber physical properties.
またアミノ変性ポリシロキサンを含んでいれば必要に応
じてジメチルポリシロキサン、ジフェニルポリシロキサ
ン、メチルフェニルポリシロキサン、ポリエーテル変
性、エポキシ変性、メルカプト変性、アルコール変性、
カルボキシル変性、フッ素変性などの各オルガノポリシ
ロキサンなどを併用することができる。If amino-modified polysiloxane is included, dimethylpolysiloxane, diphenylpolysiloxane, methylphenylpolysiloxane, polyether modification, epoxy modification, mercapto modification, alcohol modification, if necessary,
Each organopolysiloxane such as carboxyl-modified or fluorine-modified can be used in combination.
これらの油剤は非イオン界面活性剤、カチオン界面活性
剤などとともに乳化され、また静電気防止剤などの他の
成分を含んでいてもよい。シリコーン油剤を水に乳化し
て使用する場合はその乳化安定性から、使用に当たって
は３０℃以下、好ましくは２０℃以下に保った油剤溶液
とするのが好ましい。These oil agents are emulsified with a nonionic surfactant, a cationic surfactant and the like, and may contain other components such as an antistatic agent. When the silicone oil agent is emulsified in water and used, it is preferable to use an oil agent solution kept at 30 ° C. or lower, preferably 20 ° C. or lower in view of its emulsion stability.
油剤の付与方法としては特に限定されるものではなく、
ディップ式、ガイド給油式、噴霧式、バイブロ給油式、
キスリングロール式などの公知の付与方法が採用される
が、単繊維間の融着防止のために乾燥緻密化前に付与す
る必要がある。油剤の付与量としては、通常糸に対して
０．１〜３％の範囲から選ばれる。The method of applying the oil agent is not particularly limited,
Dip type, guide lubrication type, spray type, vibro lubrication type,
A known application method such as a kiss ring roll method is adopted, but it is necessary to apply it before drying and densification in order to prevent fusion between single fibers. The applied amount of the oil agent is usually selected from the range of 0.1 to 3% with respect to the yarn.
（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。(Example) Hereinafter, the present invention will be described in more detail with reference to Examples.
本例中、炭素繊維の性能（強度）はＪＩＳＲ−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＝１０の平均から求めた値である。In this example, the performance (strength) of carbon fiber is JIS R-7601.
Is a physical property of the epoxy resin-impregnated strand measured according to the above, and is a value obtained from the average of the number of measurements n = 10.
また、浴延伸糸の融着判定は、油剤付与前の膨潤糸を約
５mmに切断しノイゲンＳＳの０．１重量％水溶液に分散
させ、スタラーで６０rpm／１分間攪拌後黒色ろ紙でろ
過し、融着繊維本数を数えて融着状態を次にように級判
定した。In addition, for determining the fusion of the bath stretched yarn, the swollen yarn before applying the oil agent is cut into about 5 mm, dispersed in a 0.1 wt% aqueous solution of Neugen SS, stirred with a stirrer at 60 rpm for 1 minute, and filtered with black filter paper, The number of fused fibers was counted and the fused state was classified as follows.
１級＝融着本数１本以下 ２級＝融着本数２〜３本 ３級＝融着本数４〜５本 ４級＝融着本数６〜７本 ５級＝融着本数８本以上 実施例 アクリロニトリル９９．３％、イタコン酸０．７％から
なるアクリル系共重合体の２０％ジメチルスルホキシド
溶液（４５℃における溶液粘度が６００ポイズの重合
体）を乾湿式紡糸し、溶液とともに下方に引き取り、３
５℃の水中で脱溶媒を行い、膨潤繊維糸条を形成した。
ついで、５槽からなり第１層の入ローラーおよび第５槽
の出ローラー以外はフリーローラーから構成される浴延
伸工程で、７０℃の熱水中２．５倍延伸を行った。この
延伸糸条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の浴液中に、含浸走行させ、
油分として０．７％付与し、次に乾燥緻密化後連続して
加圧スチーム延伸を行い（全倍率１２倍）巻取って、単
繊維デニール１．０ｄ、フィラメント数１２０００のア
クリロニトリル系炭素繊維前駆体糸条を得た。1st class = 1 or less number of fusion bonding 2nd class = 2 to 3 number of fusion bonding 3rd class = 4 to 5 number of fusion bonding 4th class = 6 to 7 number of fusion bonding 5th class = 8 or more number of fusion bonding Example A 20% dimethyl sulfoxide solution of an acrylic copolymer consisting of 99.3% acrylonitrile and 0.7% itaconic acid (a polymer having a solution viscosity of 600 poise at 45 ° C.) was dry-wet spun and taken down with the solution. Three
The solvent was removed in water at 5 ° C to form swollen fiber yarns.
Then, in a bath stretching process consisting of 5 tanks and a free roller except for the first layer entrance roller and the fifth tank exit roller, 2.5 times drawing in hot water at 70 ° C. was performed. This stretched yarn is treated with an amino-modified silicone (the content of amino groups is
(NH 2 1.0%) was impregnated and run in a bath solution of an oil agent emulsified with a nonylphenol EO adduct,
An oil content of 0.7% was applied, followed by dry densification and continuous pressure steam drawing (total magnification: 12 times), winding, and single fiber denier 1.0d, filament number 12000 acrylonitrile-based carbon fiber precursor I got a body thread.
得られた糸条を２００〜２８０℃の空気中で耐炎化処理
し、のち最高温度１３００℃の炭化炉に導入し、窒素雰
囲気中で炭化し炭素繊維を得た。得られた炭素繊維（Ｃ
Ｆ、と略記する）のストランド強度を第１表に示す。The obtained yarn was subjected to flame resistance treatment in air at 200 to 280 ° C., then introduced into a carbonization furnace having a maximum temperature of 1300 ° C., and carbonized in a nitrogen atmosphere to obtain carbon fibers. Obtained carbon fiber (C
Table 1 shows the strand strength of F).
なお比較のため、５槽からなる浴延伸槽の各槽入／出ロ
ーラーが強制駆動ローラーで各浴槽の延伸倍率が１．２
倍で延伸したもの（NO.2/NO.3、浴延伸温度７０℃、ト
ータル浴延伸倍率２．５倍）、について得られた炭素繊
維物性を第１表にあわせて示した。In addition, for comparison, each tank of the bath drawing tank consisting of 5 tanks has a forced driving roller as the entrance / exit roller and the draw ratio of each bath is 1.2.
The physical properties of the carbon fiber obtained for the one drawn twice (NO.2 / NO.3, bath drawing temperature 70 ° C., total bath drawing ratio 2.5 times) are also shown in Table 1.
第１表より本発明の延伸方法によって単繊維間融着を減
少させて炭素繊維の強度を向上させることができ、アミ
ノ変性シリコーン油剤の付与により炭素繊維強度向上効
果はさらに高まることが明らかである。From Table 1, it is clear that the stretching method of the present invention can reduce the fusion between single fibers and improve the strength of the carbon fiber, and that the addition of the amino-modified silicone oil agent further enhances the carbon fiber strength improving effect. .
このように本発明によれば、その物性を著しく向上させ
ることのできる、炭素繊維の製造が可能である。As described above, according to the present invention, it is possible to produce a carbon fiber whose physical properties can be remarkably improved.
（発明の効果） 本発明の炭素繊維用アクリル系前駆体糸条の製造法によ
れば、単繊維間融着のない糸条を焼成工程に供給でき、
安定して高品質・高性能の炭素繊維を製造することが可
能になる。 (Effect of the Invention) According to the method for producing an acrylic precursor yarn for carbon fibers of the present invention, a yarn without fusion between single fibers can be supplied to the firing step,
It becomes possible to stably manufacture high-quality and high-performance carbon fibers.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｄ０２Ｊ 1/22 Ａ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI technical display location D02J 1/22 A
Claims (1)
アクリル系重合体溶液を紡糸後、湿潤糸条を延伸し、原
糸油剤を付与する炭素繊維用アクリル系前駆体糸条の製
造法において、少なくとも２つ以上の分離した延伸浴間
にフリーローラーを配し、該延伸浴槽中３０〜９８℃の
水中で多槽延伸し、延伸後の糸条に少なくとも１成分は
アミノ変性ポリシロキサンからなる原糸油剤を付与する
ことを特徴とする炭素繊維用アクリル系前駆体糸条の製
造法。1. A method for producing an acrylic precursor yarn for carbon fiber, comprising spinning an acrylic polymer solution containing 90% by weight or more of acrylonitrile, stretching a wet yarn, and applying a raw yarn oil agent. A free roller is provided between two or more separated drawing baths, multi-tank drawing is performed in the drawing bath in water at 30 to 98 ° C., and at least one component of the drawn yarn is an amino-modified polysiloxane. A method for producing an acrylic precursor yarn for carbon fiber, which comprises:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1201078A JPH0627367B2 (en) | 1989-08-01 | 1989-08-01 | Method for producing acrylic precursor yarn for carbon fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1201078A JPH0627367B2 (en) | 1989-08-01 | 1989-08-01 | Method for producing acrylic precursor yarn for carbon fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0364514A JPH0364514A (en) | 1991-03-19 |
| JPH0627367B2 true JPH0627367B2 (en) | 1994-04-13 |
Family
ID=16435028
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1201078A Expired - Fee Related JPH0627367B2 (en) | 1989-08-01 | 1989-08-01 | Method for producing acrylic precursor yarn for carbon fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0627367B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05171522A (en) * | 1991-12-26 | 1993-07-09 | Toray Ind Inc | Production of precursor fiber for carbon fiber |
| TW459075B (en) * | 1996-05-24 | 2001-10-11 | Toray Ind Co Ltd | Carbon fiber, acrylic fiber and preparation thereof |
| KR101470250B1 (en) * | 2013-12-17 | 2014-12-08 | 주식회사 효성 | Method of manufacturing precursor for carbon fiber |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50154531A (en) * | 1974-05-30 | 1975-12-12 | ||
| JPS60185879A (en) * | 1984-02-29 | 1985-09-21 | 竹本油脂株式会社 | Oil agent for producing carbon fiber |
| JPS62275718A (en) * | 1986-05-26 | 1987-11-30 | Nippon Denso Co Ltd | Resin molding tool |
-
1989
- 1989-08-01 JP JP1201078A patent/JPH0627367B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0364514A (en) | 1991-03-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4975262A (en) | Three dimensional woven fabrics of pitch-derived carbon fibers | |
| JP2001172880A (en) | Silicone oil agent for carbon fiber and method for producing carbon fiber | |
| US4659623A (en) | Acrylic fibers for producing preoxidized fibers | |
| JPH0627367B2 (en) | Method for producing acrylic precursor yarn for carbon fiber | |
| JPH0474469B2 (en) | ||
| JPH0340152B2 (en) | ||
| JP4862226B2 (en) | Precursor fiber for carbon fiber and method for producing carbon fiber | |
| JP2875667B2 (en) | Method of stretching acrylic yarn for carbon fiber precursor in bath | |
| JP2008240203A (en) | Steam drawing apparatus and method for producing precursor yarn for carbon fiber | |
| JP2530786B2 (en) | Method for drawing thick acrylic yarn in the bath | |
| JPS6224526B2 (en) | ||
| JP2555826B2 (en) | Acrylic yarn manufacturing method for carbon fiber precursor | |
| JP3562115B2 (en) | Carbon fiber precursor acrylic yarn package and method for winding carbon fiber precursor acrylic yarn | |
| JPH11117128A (en) | Precursor for carbon fiber and production of carbon fiber | |
| JP3697793B2 (en) | Precursor for carbon fiber, method for producing the same, and method for producing carbon fiber | |
| JPH0291225A (en) | Production of raw material yarn for carbon yarn | |
| JPH0433891B2 (en) | ||
| JP2001248025A (en) | Method for producing carbon fiber | |
| JP3002614B2 (en) | Acrylonitrile fiber and method for producing the same | |
| JP2596092B2 (en) | Manufacturing method of raw yarn for carbon fiber | |
| JP4048230B2 (en) | Precursor fiber for carbon fiber and method for producing the same | |
| JP2001049524A (en) | Production of acrylic fiber | |
| JP7408406B2 (en) | Method for manufacturing flame-resistant fiber bundle, method for manufacturing carbon fiber bundle, and connection device | |
| JPS6183374A (en) | Acrylic precursor fiber bundle | |
| JP2003027378A (en) | Silicone oil solution for carbon fiber precursor, precursor fiber for carbon fiber and method for producing carbon fiber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080413 Year of fee payment: 14 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090413 Year of fee payment: 15 |
|
| LAPS | Cancellation because of no payment of annual fees |