JPH07310240A - Carbon fiber for filament winding molding and its production - Google Patents
Carbon fiber for filament winding molding and its productionInfo
- Publication number
- JPH07310240A JPH07310240A JP9988694A JP9988694A JPH07310240A JP H07310240 A JPH07310240 A JP H07310240A JP 9988694 A JP9988694 A JP 9988694A JP 9988694 A JP9988694 A JP 9988694A JP H07310240 A JPH07310240 A JP H07310240A
- Authority
- JP
- Japan
- Prior art keywords
- carbon fiber
- molding
- treatment
- fiber
- resin
- 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.)
- Granted
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、フィラメントワインデ
ィング（以下、ＦＷと略す）成形法により複合材料など
を成形するに適した炭素繊維およびその製造方法に関す
る。さらに詳しくは、ＦＷ成形法により複合材料などを
成形するに際して、毛羽立ち、糸切れ等が少なく、さら
には炭素繊維の機械的特性をＦＷ成形法により作製した
複合材料の機械的特性に効率良く反映し得る炭素繊維お
よびその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a carbon fiber suitable for molding a composite material and the like by a filament winding (hereinafter abbreviated as FW) molding method and a method for producing the same. More specifically, when molding a composite material or the like by the FW molding method, there is little fluffing or yarn breakage, and moreover, the mechanical properties of the carbon fiber are efficiently reflected in the mechanical properties of the composite material produced by the FW molding method. The present invention relates to a carbon fiber to be obtained and a method for producing the same.
【０００２】[0002]
【従来の技術】炭素繊維はその優れた機械的特性、特に
比強度、比弾性率が高いという特徴を有しているため、
航空宇宙用途、レジャー用途、一般産業用途などに広く
使用されており、その成形方法も様々である。この中で
もＦＷ成形法は元来ガラス繊維に適用されてきた方法で
あり、その優れた成形性、あるいは得られる複合材料の
特性から炭素繊維にも広く適用されるようになってき
た。特に現在注目されている天然ガス自動車などの燃料
用ボンベは、その軽量かつ高性能化のために、炭素繊維
を補強繊維としてＦＷ成形法で成形しており、ＦＷ成形
に適した炭素繊維の要求が日増しに高まっている。2. Description of the Related Art Carbon fiber has excellent mechanical properties, especially high specific strength and high specific elastic modulus.
It is widely used for aerospace applications, leisure applications, general industrial applications, etc., and its molding method is also various. Among them, the FW molding method has been originally applied to the glass fiber, and has been widely applied to the carbon fiber due to its excellent moldability or the characteristics of the obtained composite material. In particular, fuel cylinders for natural gas automobiles, which are currently attracting attention, are formed by the FW molding method using carbon fibers as reinforcing fibers for their lightweight and high performance, and the demand for carbon fibers suitable for FW molding. Is increasing day by day.
【０００３】一般に、ＦＷ成形法に要求される補強繊維
の特性としては、耐毛羽性などに代表される高いハンド
リング性能、耐擦過性、耐糸切れ性などに代表される高
い工程通過性能、または高速樹脂含浸性能などが挙げら
れる。ハンドリング性能を改善する方法として、炭素繊
維にサイジング剤を付与すること（例えば、特開昭６２
−２９９５８０号公報、特公平１−４６６３６号公報、
特公昭５７−４９６７５号公報）などがこれまでに提案
されている。しかしながら、ＦＷ成形に用いる場合に
は、樹脂含浸前後での、炭素繊維と固定ガイドあるいは
ローラーとの擦過など、過酷な条件下でも高い工程通過
性能を維持することが要求されるが、この要求に対して
サイジング剤による炭素繊維の集束のみで改善すること
には無理があった。また一方、炭素繊維自体をＦＷ成形
法に適した特性とする検討は、これまでに十分になされ
ていないのが現状であった。したがって、従来の炭素繊
維では、ＦＷ成形法において、成形工程で毛羽立ち、糸
切れ等がしばしば発生し、さらには炭素繊維の特性が、
得られる複合材料の特性に十分に反映されていないとい
う問題点があった。Generally, the characteristics of the reinforcing fiber required for the FW molding method are high handling performance typified by fluff resistance and the like, high process passing performance typified by scratch resistance and yarn breakage resistance, or Examples include high-speed resin impregnation performance. As a method for improving the handling performance, a sizing agent is added to the carbon fiber (for example, JP-A-62-62
-299580, Japanese Examined Patent Publication No. 1-46636,
Japanese Patent Publication No. 57-49675) has been proposed so far. However, when it is used for FW molding, it is required to maintain high process passing performance even under severe conditions such as rubbing between carbon fiber and a fixed guide or roller before and after resin impregnation. On the other hand, it was impossible to improve only by focusing the carbon fibers with the sizing agent. On the other hand, until now, it has not been sufficiently studied to make the carbon fiber itself a property suitable for the FW molding method. Therefore, in the conventional carbon fiber, fluffing, yarn breakage, etc. often occur in the molding process in the FW molding method, and further, the characteristics of the carbon fiber are
There is a problem that the properties of the obtained composite material are not sufficiently reflected.
【０００４】本発明者らは、この様な点に鑑み、ＦＷ成
形法に適した炭素繊維について鋭意検討した結果、ある
一定値以上のストランド引張強度、後述する糸切れ限界
張力、さらに引掛強度を有する炭素繊維が、成形工程で
の工程通過性能が著しく向上すること、そして得られる
複合材料の特性も著しく向上することを見い出し、本発
明に至ったのである。In view of these points, the inventors of the present invention have made earnest studies on carbon fibers suitable for the FW molding method, and as a result, have found that the strand tensile strength of a certain value or more, the thread breaking limit tension described later, and the hooking strength. The present inventors have found that the carbon fibers possessed significantly improve the process passing performance in the molding process, and also significantly improve the properties of the obtained composite material, and have reached the present invention.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、ＦＷ
成形法に適した炭素繊維、具体的にはＦＷ成形工程にお
いて毛羽立ち、糸切れ等が少なく、さらにはＦＷ成形法
により作製した複合材料の特性を効率良く反映し得る炭
素繊維を提供することにある。The object of the present invention is to provide a FW
It is to provide a carbon fiber suitable for a molding method, specifically, a carbon fiber which has less fluffing and yarn breakage in the FW molding process and which can efficiently reflect the characteristics of the composite material produced by the FW molding method. .
【０００６】[0006]
【課題を解決するための手段】本発明のフィラメントワ
インディング成形用炭素繊維は上記課題を解決するた
め、次の構成を有する。すなわち、ストランド引張強度
が４００kgf/mm2 以上であり、糸切れ限界張力が０．２
ｇ／Ｄ以上であり、および引掛強度が１００kgf/mm2 以
上であることを特徴とするフィラメントワインディング
成形用炭素繊維である。The carbon fiber for filament winding molding of the present invention has the following constitution in order to solve the above problems. That is, the strand tensile strength is 400 kgf / mm 2 or more, and the thread breaking limit tension is 0.2.
A carbon fiber for filament winding molding, which has a g / D or more and a hooking strength of 100 kgf / mm 2 or more.
【０００７】また、本発明のフィラメントワインディン
グ成形用炭素繊維の製造方法は上記課題を解決するた
め、次の構成を有する。すなわち、ヨウ素吸着法による
明度差（ΔＬ）が５０以下であるアクリル系繊維を原料
として、温度２３０℃以上２８０℃以下の空気中、０．
８０以上１．００以下の延伸比で耐炎化し、引き続いて
最高温度１１００℃以上２０００℃以下の不活性雰囲気
中、１０００℃から最高温度までの温度域における延伸
比を０．９８以下として炭素化処理した後、表面処理、
サイジング処理することを特徴とするフィラメントワイ
ンディング成形用炭素繊維の製造方法である。In order to solve the above problems, the method for producing carbon fiber for filament winding molding of the present invention has the following constitution. That is, in the air having a temperature of 230 ° C. or more and 280 ° C. or less, 0.
Flameproofing at a draw ratio of 80 or more and 1.00 or less, and subsequently carbonization treatment by setting the draw ratio in the temperature range from 1000 ° C to the maximum temperature to 0.98 or less in an inert atmosphere having a maximum temperature of 1100 ° C to 2000 ° C. After surface treatment,
A method for producing a carbon fiber for filament winding molding, which comprises sizing treatment.
【０００８】さらに詳細に本発明について説明する。The present invention will be described in more detail.
【０００９】本発明の炭素繊維の原料としては特に限定
されるものではないが、ポリアクリロニトリル（以下、
ＰＡＮと略す）、ピッチ、レーヨン等を挙げることがで
きる。得られる炭素繊維のハンドリング性能、工程通過
性能をより高いものとし、さらにはＦＷ成形法によって
得られる複合材料の性能を良好なものとするためには、
ＰＡＮを原料とした炭素繊維が好ましい。The raw material of the carbon fiber of the present invention is not particularly limited, but polyacrylonitrile (hereinafter,
(Abbreviated as PAN), pitch, rayon and the like. In order to further improve the handling performance and process passing performance of the obtained carbon fiber, and further to improve the performance of the composite material obtained by the FW molding method,
Carbon fibers made from PAN are preferred.
【００１０】本発明の炭素繊維は、ストランド引張強度
が４００kgf/mm2 以上、好ましくは４５０kgf/mm2 以上
であることが必要である。ストランド引張強度が４００
kgf/mm2 未満であると、ＦＷ成形工程において特にマト
リックス樹脂が付着する前の炭素繊維と固定ガイドある
いはローラーとの擦過による毛羽立ちが多くなる他、得
られる複合材料の機械的特性が低いものとなる。ストラ
ンド引張強度の上限については特に限定されず、適用す
る複合材料のコストパフォーマンスの点から適宜選択で
きるが、必要以上にストランド引張強度が高くてもＦＷ
成形方法によっては工程通過性能のさらなる向上が認め
られない場合があり、またその強度が複合材料の特性に
十分効率良く反映しない場合もあるので好ましくは８０
０kgf/mm2 以下、より好ましくは７５０kgf/mm2 以下で
あることが望ましい。[0010] Carbon fibers of the present invention, a strand tensile strength of 400 kgf / mm 2 or more, preferably required to be 450 kgf / mm 2 or more. Strand tensile strength is 400
If it is less than kgf / mm 2 , fluffing due to rubbing between the carbon fiber and the fixed guide or the roller before the matrix resin is adhered particularly in the FW molding step is increased, and the mechanical properties of the obtained composite material are low. Become. The upper limit of the strand tensile strength is not particularly limited and can be appropriately selected from the viewpoint of cost performance of the applied composite material, but even if the strand tensile strength is higher than necessary, FW
Depending on the molding method, further improvement in process passing performance may not be observed, and its strength may not be reflected in the properties of the composite material sufficiently efficiently.
0 kgf / mm 2 or less, and more preferably less 750 kgf / mm 2.
【００１１】ここで、ストランド引張強度とは次のよう
にして測定したものである。ベークライト（登録商標）
ＥＲＬ４２２１（ユニオン・カーバイド（株）製）／三
フッ化ホウ素モノエチルアミン／アセトン＝１００／３
／４部からなる樹脂を炭素繊維に含浸し、得られた樹脂
含浸ストランドを１３０℃で３０分間加熱して硬化させ
た後、ＪＩＳ−Ｒ−７６０１に規定する樹脂含浸ストラ
ンド試験法に従って測定する。Here, the strand tensile strength is measured as follows. Bakelite (registered trademark)
ERL4221 (manufactured by Union Carbide Co., Ltd.) / Boron trifluoride monoethylamine / acetone = 100/3
/ 4 parts of resin is impregnated into carbon fiber, the obtained resin-impregnated strand is heated at 130 ° C. for 30 minutes to be cured, and then measured according to the resin-impregnated strand test method defined in JIS-R-7601.
【００１２】また本発明の炭素繊維は、その糸切れ限界
張力が０．２ｇ／Ｄ以上、好ましくは０．２５ｇ／Ｄ以
上であることが必要である。糸切れ限界張力が０．２ｇ
／Ｄ未満であると、ＦＷ成形工程において特にマトリッ
クス樹脂が付着した後の炭素繊維と固定ガイドあるいは
ローラーとの擦過によって、毛羽立ちおよび糸切れが頻
発するようになり、生産性が著しく低下する。糸切れ限
界張力の上限については特に限定されず、適用する複合
材料のコストパフォーマンスの点から適宜選択できる
が、必要以上に糸切れ限界張力が高くても、ＦＷ成形方
法によっては工程通過性能のさらなる向上が認められな
い場合もあるので、好ましくは１５ｇ／Ｄ以下、より好
ましくは１０ｇ／Ｄ以下であることが望ましい。The carbon fiber of the present invention is required to have a yarn breakage limit tension of 0.2 g / D or more, preferably 0.25 g / D or more. Thread breaking limit tension is 0.2g
If it is less than / D, fluffing and yarn breakage frequently occur due to the friction between the carbon fiber and the fixed guide or the roller after the matrix resin is adhered particularly in the FW molding step, and the productivity is remarkably reduced. The upper limit of the thread breakage limit tension is not particularly limited and can be appropriately selected from the viewpoint of cost performance of the applied composite material. However, even if the thread breakage limit tension is higher than necessary, depending on the FW molding method, the process passability is further increased. Since improvement may not be observed in some cases, it is preferably 15 g / D or less, more preferably 10 g / D or less.
【００１３】ここで、糸切れ限界張力とは次のようにし
て測定したものである。図１に示したように、一定の目
付を有する炭素繊維束をボビンに巻き取り、張力調整が
可能なクリール（ａ）にボビンを仕掛け、ボビンから横
取りして該炭素繊維束（ｂ）を２５ｍ／分の一定速度で
引き出す。表面が梨地の回転ローラー４個（ｃ１〜ｃ
４）を介して糸道を固定させた後、該炭素繊維束（ｂ）
を、“エピコート８２８”１００重量部、および“エピ
コート１００１”３００重量部（油化シェルエポキシ社
製）が均一に混合された濃度５５重量％、温度２０℃の
メチルエチルケトン溶液（ｆ）に、直径１５mmφ、表面
平滑度３Ｓのステンレス製固定バー（ｄ１）を介して浸
漬させ、さらに５０mm間隔で３本水平に固定された直径
１５mmφ、表面平滑度３Ｓのステンレス製棒（ｄ２〜ｄ
４）を介して、ドラム（ｇ）に巻き取る。ボビンに巻回
された前記炭素繊維束の引き出し張力を徐々に大きく
し、該固定擦過棒を通過する繊維束に糸切れが発生した
ときのＣ３とＣ４間の最大張力を５回測定し、その平均
値から次式により糸切れ限界張力を求める。Here, the thread breakage limit tension is measured as follows. As shown in FIG. 1, a carbon fiber bundle having a certain basis weight is wound on a bobbin, a bobbin is mounted on a creel (a) whose tension can be adjusted, and the carbon fiber bundle (b) is 25 m long by taking the carbon fiber bundle from the bobbin. Pull out at a constant speed per minute. 4 rotating rollers with satin finish (c1 to c
After fixing the yarn path via 4), the carbon fiber bundle (b)
15 parts in diameter in a methyl ethyl ketone solution (f) at a concentration of 55% by weight, in which 100 parts by weight of "Epicoat 828" and 300 parts by weight of "Epicoat 1001" (manufactured by Yuka Shell Epoxy Co., Ltd.) were mixed at a temperature of 20 ° C. , A stainless steel fixing bar (d1) having a surface smoothness of 3S, and three stainless steel rods (d2 to d) having a diameter of 15 mm and horizontally fixed at 50 mm intervals were fixed horizontally.
Winding up onto drum (g) via 4). The pull-out tension of the carbon fiber bundle wound around the bobbin was gradually increased, and the maximum tension between C3 and C4 when the yarn breakage occurred in the fiber bundle passing through the fixed scraping rod was measured 5 times. From the average value, the thread breakage limit tension is calculated by the following formula.
【００１４】糸切れ限界張力[ ｇ／Ｄ] ＝（最大張力[
ｇ] ）／（目付[ ｇ／ｍ] ×9000） さらに本発明の炭素繊維は、その引掛強度が１００kgf/
mm2 以上、好ましくは１４０kgf/mm2 以上、より好まし
くは１７０kgf/mm2 以上であることが必要である。引掛
強度が１００kgf/mm2 未満であると、ＦＷ成形工程にお
いて特にマトリックス樹脂が付着する前の炭素繊維と固
定ガイドあるいはローラーとの擦過による毛羽立ち、ま
たはマトリックス樹脂が付着した後の毛羽立ちおよび糸
切れが頻発するようになり、生産性が著しく低下すると
ともに、得られる複合材料の機械的特性、特に強度利用
率あるいは耐衝撃特性が低下する。引掛強度の上限につ
いては特に限定されず、適用する複合材料のコストパフ
ォーマンスの点から適宜選択できるが、必要以上に引掛
強度が高くてもＦＷ成形方法によっては工程通過性能の
さらなる向上が認められない場合もあるので、好ましく
は４００kgf/mm2 以下、より好ましくは３５０kgf/mm2
以下であることが望ましい。Thread breaking limit tension [g / D] = (maximum tension [g / D]
g]) / (Basis weight [g / m] × 9000) Further, the carbon fiber of the present invention has a catching strength of 100 kgf /
It should be at least mm 2 , preferably at least 140 kgf / mm 2 , and more preferably at least 170 kgf / mm 2 . When the hooking strength is less than 100 kgf / mm 2 , fluffing due to rubbing between the carbon fiber and the fixed guide or roller before the matrix resin adheres, or fluffing and thread breakage after the matrix resin adheres, particularly in the FW molding process. Frequent occurrence occurs, and the productivity is remarkably reduced, and the mechanical properties of the obtained composite material, particularly the strength utilization factor or the impact resistance property are reduced. The upper limit of the hooking strength is not particularly limited and can be appropriately selected from the viewpoint of cost performance of the applied composite material, but even if the hooking strength is higher than necessary, further improvement in process passing performance is not recognized depending on the FW molding method. In some cases, it is preferably 400 kgf / mm 2 or less, more preferably 350 kgf / mm 2
The following is desirable.
【００１５】ここで、引掛強度は次のようにして測定し
たものである。テンシロン引張試験機（ＵＴＭ−４−２
００）を用い、クロスヘッド間隔２００mmでＪＩＳ−Ｌ
−１０１３(1992)、７．７項目に記載の炭素繊維束のル
ープを作る。そしてクロスヘッド速度５０mm／分で引張
り、破断荷重[kgf] を測定する。破断荷重より次式を用
いて引掛強度を求める。Here, the hooking strength is measured as follows. Tensilon Tensile Testing Machine (UTM-4-2
00), with a crosshead spacing of 200 mm and JIS-L
A loop of a carbon fiber bundle described in -1013 (1992), item 7.7 is prepared. Then, it is pulled at a crosshead speed of 50 mm / min and the breaking load [kgf] is measured. The breaking strength is calculated from the breaking load using the following formula.
【００１６】引掛強度[ kgf/mm2 ] ＝（破断荷重[kgf]
）／（目付[g/m] ／密度[ g/cm3 ] ） 測定を５０回行ない、その平均値を求めた。Hooking strength [kgf / mm 2 ] = (breaking load [kgf]
) / (Batch weight [g / m] / Density [g / cm 3 ]) The measurement was performed 50 times, and the average value was calculated.
【００１７】本発明のＦＷ成形用炭素繊維は、上記した
ストランド引張強度、糸切れ限界張力および引掛強度の
いずれもが前記した値を満足することによって初めて、
ＦＷ成形時の過酷な条件下においてもハンドリング性が
良好なものとなり、しかも炭素繊維の特性を、複合材料
の特性に十分に反映し得るものとなる。The carbon fiber for FW molding of the present invention can be obtained only when the above-mentioned strand tensile strength, yarn breakage limit tension and hooking strength satisfy the above-mentioned values.
The handling property is good even under severe conditions during FW molding, and the properties of the carbon fiber can be sufficiently reflected on the properties of the composite material.
【００１８】本発明のＦＷ成形用炭素繊維は、例えばＰ
ＡＮ系の炭素繊維の場合、次のようにして製造すること
ができる。The carbon fiber for FW molding of the present invention is, for example, P
In the case of AN-based carbon fiber, it can be manufactured as follows.
【００１９】プリカーサ（前駆体）として用いるアクリ
ル系繊維は緻密性の高いものであることが好ましい。プ
リカーサーの緻密性は、ヨウ素吸着法による明度差（Δ
Ｌ）として次のようにして測定することができる。The acrylic fiber used as a precursor (precursor) is preferably highly dense. The denseness of the precursor depends on the difference in brightness (Δ
L) can be measured as follows.
【００２０】長さが５〜７ｃｍの乾燥されたアクリル系
繊維を約０．５ｇ精秤して、２００ｍｌの共栓付三角フ
ラスコに採り、ヨウ素溶液（Ｉ2 :51 ｇ、2,4-ジクロロ
フェノール:10 ｇ、酢酸:90 ｇ、およびヨウ化カリウ
ム:100ｇを秤量し、１リットルのメスフラスコに移して
水で溶解して定容とする）１００ｍｌを加えた後、６０
±０．５℃で５０分間振とうしながら吸着処理を行う。
ヨウ素を吸着した試料を流水中で３０分間水洗した後、
遠心脱水（2000rpm ×１分）を行い、すばやく風乾す
る。この試料を開繊した後、ハンター型色差計で明度
（Ｌ値）を測定する（Ｌ1 ）。一方、ヨウ素吸着を行わ
ない対応の試料を開繊し、同様にハンター型色差計で明
度を測定する（Ｌ0 ）。そして、Ｌ1 −Ｌ0 より、明度
差ΔＬを求める。About 0.5 g of dried acrylic fiber having a length of 5 to 7 cm is precisely weighed and put in a 200 ml Erlenmeyer flask with a stopper, and the iodine solution (I 2 : 51 g, 2,4-dichloro) is taken. Phenol: 10 g, acetic acid: 90 g, and potassium iodide: 100 g were weighed, transferred to a 1-liter measuring flask and dissolved in water to a constant volume).
The adsorption treatment is performed while shaking at ± 0.5 ° C. for 50 minutes.
After washing the sample with adsorbed iodine in running water for 30 minutes,
Centrifuge dehydration (2000 rpm x 1 minute) and quickly air dry. After opening this sample, the lightness (L value) is measured with a Hunter color difference meter (L 1 ). On the other hand, a corresponding sample that does not adsorb iodine is opened, and the lightness is similarly measured by a Hunter color difference meter (L 0 ). Then, the brightness difference ΔL is obtained from L 1 −L 0 .
【００２１】このヨウ素吸着法による明度差（ΔＬ）
が、５０以下、好ましくは４０以下、より好ましくは３
０以下であるアクリル系繊維をプリカーサとして用い
る。ΔＬが５０を越えると、焼成工程で繊維に欠陥が多
く発生し、ＦＷ成形に耐えられなくなるばかりでなく、
得られる複合材料の特性を十分に発現できなくなる。Brightness difference (ΔL) by this iodine adsorption method
Is 50 or less, preferably 40 or less, more preferably 3
An acrylic fiber having a value of 0 or less is used as a precursor. If ΔL exceeds 50, many defects will occur in the fiber during the firing process, and it will not be possible to withstand FW molding.
The characteristics of the obtained composite material cannot be sufficiently expressed.
【００２２】アクリル系繊維のΔＬを５０以下の高い緻
密性にするための好ましい紡糸方法としては、湿式紡糸
法、乾式紡糸法、あるいは乾湿式紡糸法が挙げられる
が、より緻密性の高いアクリル系繊維を得るためには乾
湿式紡糸法がより好ましく用いられる。また、湿式紡糸
法でも、紡糸原液の吐出量を適正化し、延伸倍率を後述
する範囲として、単繊維繊度を０．８ｄ以下としたプリ
カーサー繊維とすることによってΔＬを５０以下とする
ことができる。また緻密性を高める方法としては、上記
紡糸方法に加えて、紡糸原液のポリマ濃度を１５％以
上、好ましくは１８％以上とすること、また紡糸により
得られた吐出糸条を８倍、好ましくは１０倍以上に延伸
すること、さらには延伸糸条に油剤を付与して乾燥緻密
化することが挙げられる。ここで延伸は温水中で行なう
ことが好ましく、さらに油剤付与後に乾燥した糸条を加
圧スチーム中で二次延伸を行ってもよい。油剤には繊維
の融着、あるいは焼成工程における単繊維間接着を防ぐ
ためにシリコーン系化合物を含むものが好ましい。As a preferred spinning method for making the ΔL of the acrylic fiber highly dense with 50 or less, a wet spinning method, a dry spinning method, or a dry-wet spinning method can be mentioned. The dry-wet spinning method is more preferably used for obtaining fibers. Also in the wet spinning method, ΔL can be set to 50 or less by optimizing the discharge amount of the spinning dope and setting the draw ratio to a range to be described later by using a precursor fiber having a single fiber fineness of 0.8 d or less. As a method for increasing the compactness, in addition to the above spinning method, the polymer concentration of the spinning dope is set to 15% or more, preferably 18% or more, and the discharged yarn obtained by spinning is 8 times, preferably The stretching may be 10 times or more, and further, an oil agent may be applied to the stretched yarn to dry and densify it. Here, the drawing is preferably carried out in warm water, and the yarn dried after applying the oil agent may be subjected to secondary drawing in pressurized steam. The oil agent preferably contains a silicone compound in order to prevent fusion of fibers or adhesion between single fibers in the firing step.
【００２３】プリカーサー繊維は、空気中で耐炎化ある
いは不融化され、さらに不活性雰囲気中高温で炭素化処
理して炭素繊維に変換される。空気中での耐炎化あるい
は不融化処理は、温度２３０℃以上２８０℃以下で、か
つ延伸比が０．８０以上１．００以下、好ましくは０．
８３以上０．９８以下、より好ましくは０．８４以上
０．９４以下とする。ここでの延伸比が１．００を越え
ると、単繊維間の接着が生じ易くなるため、得られる炭
素繊維のストランド引張強度が低いものとなるばかりで
なく、得られる複合材料の特性までもが低下してしま
う。また、延伸比が０．８０未満では他の糸条と交絡し
て毛羽が多発するばかりでなく、連続運転が不可能にな
る。引き続く炭素化処理工程では、最高温度を１１００
℃以上２０００℃以下とする。最高温度が１１００℃未
満であると、得られる炭素繊維の吸着水分が多くなり複
合材料とした時にマトリックス樹脂の硬化不良が生じ、
所望の特性が得られず、最高温度が２０００℃を越える
と炭素繊維に生起する欠陥が生じやすくなるとともに、
炭素繊維の弾性率が高くなり過ぎてＦＷ成形工程の工程
通過性能が低下する。また炭素化処理工程において１０
００℃から最高温度までの温度域における延伸比を０．
９８以下とする。ここでの延伸比が０．９８を越えると
毛羽の多い糸条となり、ＦＷ成形工程の工程通過性能低
下の原因になる。さらに、炭素化処理工程において炭素
繊維に欠陥を生じにくくするため、たとえば３００℃か
ら６００℃、または１０００℃から１３００℃（最高温
度が１３００℃未満の場合は１０００℃から最高温度）
の温度域における昇温速度を１０００℃／分以下、好ま
しくは８００℃／分以下とすることが望ましい。The precursor fiber is flame-proofed or infusibilized in air, and is further carbonized at a high temperature in an inert atmosphere to be converted into carbon fiber. The flameproofing or infusibilizing treatment in air is carried out at a temperature of 230 ° C. or higher and 280 ° C. or lower and a stretching ratio of 0.80 or higher and 1.00 or lower, preferably 0.
It is 83 or more and 0.98 or less, and more preferably 0.84 or more and 0.94 or less. If the stretching ratio here exceeds 1.00, the adhesion between the single fibers is likely to occur, so that not only the strand tensile strength of the obtained carbon fiber becomes low, but also the characteristics of the obtained composite material are obtained. Will fall. On the other hand, if the draw ratio is less than 0.80, not only fluffing frequently occurs due to entanglement with other yarns, but also continuous operation becomes impossible. In the subsequent carbonization process, the maximum temperature is 1100
C. to 2000 ° C. If the maximum temperature is less than 1100 ° C., the adsorbed water content of the obtained carbon fibers will be large, and when the composite material is formed, the curing failure of the matrix resin will occur,
If the desired characteristics are not obtained and the maximum temperature exceeds 2000 ° C, defects that occur in carbon fibers are likely to occur, and
The elastic modulus of the carbon fiber becomes too high, and the process passing performance of the FW molding process deteriorates. In addition, in the carbonization process, 10
The stretching ratio in the temperature range from 00 ° C. to the maximum temperature is 0.
It is 98 or less. If the stretching ratio here exceeds 0.98, yarns with a lot of fluff will be formed, which will cause deterioration of the process passing performance of the FW molding process. Further, in order to make the carbon fiber less susceptible to defects in the carbonization treatment step, for example, 300 ° C. to 600 ° C. or 1000 ° C. to 1300 ° C. (1000 ° C. to the maximum temperature when the maximum temperature is less than 1300 ° C.)
It is desirable that the rate of temperature rise in the temperature range is 1000 ° C./min or less, preferably 800 ° C./min or less.
【００２４】かくして得られた炭素繊維には、複合材料
としたときのマトリックス樹脂との接着性を良好なもの
とするため表面処理を行う。表面処理としては、処理の
効率をよくするため、およびストランド引張強度の低下
を抑制するため、電解表面処理を行うことが好ましい。
電解表面処理に用いる電解液としては、有機または無機
の酸、アルカリ、あるいは塩化合物の水溶液を用いるこ
とができる。The carbon fiber thus obtained is surface-treated in order to improve the adhesiveness with the matrix resin when the composite material is formed. As the surface treatment, electrolytic surface treatment is preferably performed in order to improve the efficiency of the treatment and to suppress the decrease in strand tensile strength.
As the electrolytic solution used for the electrolytic surface treatment, an aqueous solution of an organic or inorganic acid, alkali, or salt compound can be used.
【００２５】さらに炭素繊維には、ＦＷ成形でのハンド
リング性能を向上させるために公知のサイジング剤を付
与することができる。サイジング剤の付着量としてはサ
イジング剤の種類にもよるが、０．１重量％以上１０重
量％以下、好ましくは０．２重量％以上５重量％以下に
設定することが望ましい。サイジング付着量が０．１重
量％未満であると、サイジング剤の種類によってはＦＷ
成形でのハンドリング性能、工程通過性能に劣る場合が
あり、サイジング付着量が１０重量％を越えるとＦＷ成
形時に繊維束内部まで樹脂が均一に含浸しにくくなるこ
とにより、得られる複合材料の特性が低いものとなる場
合がある。サイジング剤の付与は、電解表面処理後の乾
燥直後、またはＦＷ成形において樹脂浸漬付与に先だっ
ても行うことができる。Further, a known sizing agent can be added to the carbon fiber in order to improve the handling performance in FW molding. The amount of the sizing agent attached depends on the type of the sizing agent, but is preferably set to 0.1% by weight or more and 10% by weight or less, preferably 0.2% by weight or more and 5% by weight or less. If the sizing amount is less than 0.1% by weight, the FW may vary depending on the type of the sizing agent.
In some cases, handling performance and process passing performance in molding may be inferior, and if the sizing adhesion amount exceeds 10% by weight, it becomes difficult to uniformly impregnate the resin into the inside of the fiber bundle during FW molding. It may be low. The application of the sizing agent can be performed immediately after drying after the electrolytic surface treatment or before application of the resin dipping in FW molding.
【００２６】サイジング剤の種類としては、均一に炭素
繊維に含浸することのできる溶液状態、あるいはエマル
ジョン状態で付与し、溶剤または水を乾燥除去すること
が好ましい。また、サイジング剤の樹脂の主成分として
は、エポキシ樹脂、エポキシ変性ポリウレタン樹脂、ポ
リエステル樹脂、フェノール樹脂、ポリアミド樹脂、ポ
リウレタン樹脂、ポリカーボネート樹脂、ポリエーテル
イミド樹脂、ポリアミドイミド樹脂、ポリイミド樹脂、
ビスマレイミド樹脂、ウレタン変性エポキシ樹脂、ポリ
ビニルアルコール樹脂、ポリビニルピロリドン樹脂、ポ
リエーテルサルフォン樹脂など、あるいはこれらを二種
以上の組合せてもよい。As the kind of the sizing agent, it is preferable to apply the sizing agent in a solution state or an emulsion state in which the carbon fibers can be uniformly impregnated, and the solvent or water is dried and removed. Further, as the main component of the resin of the sizing agent, epoxy resin, epoxy-modified polyurethane resin, polyester resin, phenol resin, polyamide resin, polyurethane resin, polycarbonate resin, polyetherimide resin, polyamideimide resin, polyimide resin,
Bismaleimide resin, urethane-modified epoxy resin, polyvinyl alcohol resin, polyvinylpyrrolidone resin, polyether sulfone resin, or the like, or a combination of two or more thereof may be used.
【００２７】このような炭素繊維の単繊維直径は３〜２
０μ、フィラメント数は１０００〜１０００００本であ
ることが好ましい。The single fiber diameter of such carbon fiber is 3 to 2
It is preferable that the number of filaments is 0 μ, and the number of filaments is 1000 to 100000.
【００２８】ＰＡＮ系炭素繊維の場合、上記したような
条件を厳密に制御することにより、ストランド引張強
度、糸切れ限界張力、引掛強度の良好なＦＷ成形用炭素
繊維を製造することができる。In the case of a PAN-based carbon fiber, by strictly controlling the above-mentioned conditions, it is possible to produce a FW carbon fiber having good strand tensile strength, yarn breakage limit tension and hooking strength.
【００２９】[0029]
【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。なお本例中の各種特性は以下の方法により求
めた。EXAMPLES The present invention will be described in more detail below with reference to examples. The various characteristics in this example were obtained by the following methods.
【００３０】（１）サイジング付着量 約２ｇの炭素繊維束を精秤（W1）した後、５０リットル
／分の窒素気流中、温度４５０℃に設定した電気炉（容
量約１２０cm3 ）に１５分間放置し、サイジング剤を完
全に熱分解させる。そして、２０リットル／分の乾燥窒
素気流中の容器に移し、１５分間冷却した後の繊維束を
精秤（W2）して次式よりサイジング付着量を求める。(1) Sizing adhesion amount About 2 g of carbon fiber bundle was precisely weighed (W1) and then in an electric furnace (capacity about 120 cm 3 ) set at a temperature of 450 ° C. for 15 minutes in a nitrogen stream of 50 liters / minute. Let stand and allow the sizing agent to completely pyrolyze. Then, it was transferred to a container in a stream of dry nitrogen of 20 liters / minute, and after cooling for 15 minutes, the fiber bundle was precisely weighed (W2) to determine the sizing adhesion amount from the following formula.
【００３１】サイジング付着量［％］＝｛W1[g] −（W2
[g] ×1.00046 ）｝×100 ／W1[g] （２）円管引張強度 炭素繊維と、ストランド引張強度測定に使用した樹脂を
用いて、ＡＳＴＭ Ｄ２２９１に準じてＦＷ成形法（糸
速３０ｍ／秒）により、タイプＡ型円管試験片（内径１
４６．１ｍｍ、肉厚１．５２ｍｍ、幅６．３５ｍｍ、繊
維重量含有率６５％）を作製する。得られた円管をＡＳ
ＴＭ Ｄ２２９０に規定する円管引張試験法に準じて引
張強度を測定する。測定は５個の円管試験片について行
い、その平均値を求めた。Sizing adhesion amount [%] = {W1 [g] − (W2
[g] × 1.00046)} × 100 / W1 [g] (2) Tensile strength of circular tube Using carbon fiber and the resin used for measuring the tensile strength of the strand, the FW molding method (yarn speed 30 m / Sec), type A type circular tube test piece (inner diameter 1
46.1 mm, wall thickness 1.52 mm, width 6.35 mm, fiber weight content 65%). AS the obtained circular tube
The tensile strength is measured according to the circular pipe tensile test method defined in TM D2290. The measurement was performed on five circular pipe test pieces, and the average value was obtained.
【００３２】［実施例１］アクリロニトリル（ＡＮ）９
９．５モル％、イタコン酸０．５モル％からなる、固有
粘度［η］が１．８０のＡＮ共重合体のジメチルスルホ
キシド（ＤＭＳＯ）溶液にアンモニアを吹き込み、該共
重合体のカルボキシル末端基をアンモニウム基で置換し
てポリマを変性し、このポリマの濃度が２０重量％であ
るＤＭＳＯ溶液を紡糸原液とした。[Example 1] Acrylonitrile (AN) 9
A dimethylsulfoxide (DMSO) solution of an AN copolymer having an intrinsic viscosity [η] of 9.5 mol% and itaconic acid of 0.5 mol% and having an intrinsic viscosity of 1.80 was blown with ammonia to form carboxyl end groups of the copolymer. Was modified with an ammonium group to modify the polymer, and a DMSO solution having a polymer concentration of 20% by weight was used as a spinning stock solution.
【００３３】この紡糸原液を４０℃にて、紡糸口金を通
して一旦空気中に吐出させ空間を走行させた後に、温度
１０℃、３０％のＤＭＳＯ水溶液中に導入して凝固糸と
した。そして、この凝固糸条を水洗し、温水中で４倍に
延伸した後に変性シリコン系化合物を主成分とする油剤
を付与し、１５０℃の加熱ロールを用いて乾燥、および
緻密化した。さらに加圧スチーム中で３倍に延伸して、
単繊維繊度０．８ｄ、フィラメント数１２０００、ΔＬ
＝２８のアクリル系プリカーサー繊維糸条を得た。This spinning stock solution was once discharged into the air through a spinneret at 40 ° C. to run in a space, and then introduced into a 30% DMSO aqueous solution at a temperature of 10 ° C. to obtain a coagulated yarn. Then, this coagulated thread was washed with water, stretched 4 times in warm water, and then an oil agent containing a modified silicon compound as a main component was applied, dried using a heating roll at 150 ° C., and densified. Further stretched 3 times in pressurized steam,
Single fiber fineness 0.8d, number of filaments 12000, ΔL
= 28 acrylic precursor fiber yarns were obtained.
【００３４】このプリカーサーを２４０〜２８０℃の空
気中で延伸比０．９０で耐炎化処理し、引き続いて窒素
雰囲気中、最高温度１８００℃、３００〜６００℃の温
度域および１０００〜１３００℃の温度域における昇温
速度をいずれも８００℃／分以下として炭素化処理し
た。１０００〜１８００℃における延伸比は０．９６と
した。引き続き、水溶液中で電解表面処理した後、エポ
キシ樹脂を主成分としたエマルジョン溶液中に、付着量
１．５重量％となるように含浸させ、サイジング剤を施
して炭素繊維を得た。This precursor was subjected to a flameproofing treatment in the air of 240 to 280 ° C. at a draw ratio of 0.90, and subsequently in a nitrogen atmosphere, the maximum temperature was 1800 ° C., the temperature range of 300 to 600 ° C. and the temperature of 1000 to 1300 ° C. Carbonization treatment was performed at a temperature rising rate of 800 ° C./min or less in each region. The stretching ratio at 1000 to 1800 ° C was 0.96. Subsequently, after electrolytic surface treatment in an aqueous solution, it was impregnated in an emulsion solution containing an epoxy resin as a main component so as to have an adhesion amount of 1.5% by weight, and a sizing agent was applied to obtain carbon fibers.
【００３５】得られた炭素繊維を用い、ＦＷ成形法でボ
ンベを作製した。先ず、金属製マンドレル（直径９２ｍ
ｍ、容量２０００リットル）に、エポキシ樹脂を含浸し
た炭素繊維束をＦＷ法にて糸速３０ｍ／分、張力２ｋｇ
で巻き上げた。繊維の配向角は±１０／±４５／９０の
組合せとした。この成形の間に発生した糸切れ回数と、
樹脂含浸槽内、および糸道ガイド類に溜った毛羽を採取
して秤量した。なお、樹脂含浸槽内の毛羽は、残存樹脂
を温度４５０℃で焼き飛ばし、毛羽のみとして秤量し
た。得られた炭素繊維の特性およびＦＷ成形時の糸切れ
回数、毛羽量を表１に示す。A cylinder was produced by the FW molding method using the obtained carbon fiber. First, a metal mandrel (diameter 92m
m, capacity 2000 liters), a carbon fiber bundle impregnated with an epoxy resin was measured by the FW method at a yarn speed of 30 m / min and a tension of 2 kg.
I wound up with. The orientation angle of the fibers was a combination of ± 10 / ± 45/90. The number of yarn breakages that occurred during this molding,
The fluff accumulated in the resin impregnation tank and in the yarn guides was collected and weighed. For the fluff in the resin impregnation tank, the residual resin was burned off at a temperature of 450 ° C., and only the fluff was weighed. Table 1 shows the characteristics of the obtained carbon fibers, the number of yarn breakages during FW molding, and the amount of fluff.
【００３６】［実施例２］実施例１と同様のポリマーを
実施例１と同様に紡糸して、単繊維繊度１．０ｄ、フィ
ラメント数１２０００、ΔＬ＝３０のアクリル系プリカ
ーサー繊維糸条を得た。Example 2 The same polymer as in Example 1 was spun in the same manner as in Example 1 to obtain an acrylic precursor fiber yarn having a single fiber fineness of 1.0 d, a filament number of 12000 and ΔL = 30. .
【００３７】このプリカーサーを２４０〜２８０℃の空
気中で延伸比０．８７で耐炎化処理し、引き続いて窒素
雰囲気中、最高温度１４００℃、３００〜６００℃の温
度域および１０００〜１３００℃の温度域における昇温
速度をいずれも８００℃／分以下として炭素化処理し
た。１０００〜１８００℃における延伸比は０．９５と
した。引き続き、実施例１と同様に表面処理を行い、サ
イジング剤を施して炭素繊維を得た。This precursor was subjected to a flameproofing treatment in the air of 240 to 280 ° C. with a stretching ratio of 0.87, and subsequently in a nitrogen atmosphere, the maximum temperature was 1400 ° C., the temperature range of 300 to 600 ° C. and the temperature of 1000 to 1300 ° C. Carbonization treatment was performed at a temperature rising rate of 800 ° C./min or less in each region. The stretching ratio at 1000 to 1800 ° C was 0.95. Subsequently, the surface treatment was performed in the same manner as in Example 1, and a sizing agent was applied to obtain carbon fibers.
【００３８】得られた炭素繊維を用いて実施例１と同様
にＦＷ成形を行った。得られた炭素繊維の特性およびＦ
Ｗ成形時の糸切れ回数、毛羽量を表１に示す。FW molding was carried out in the same manner as in Example 1 using the obtained carbon fiber. Characteristics of the obtained carbon fiber and F
Table 1 shows the number of yarn breakages and the amount of fluff during W molding.
【００３９】また、得られた炭素繊維を用いて円管引張
強度を測定した。結果を表２に示す。引張強度の発現の
割合（円管強度／ストランド引張強度）は、０．９６と
大きかった。Further, the tensile strength of a circular pipe was measured using the obtained carbon fiber. The results are shown in Table 2. The ratio of development of tensile strength (cylindrical strength / strand tensile strength) was 0.96, which was large.
【００４０】［比較例１］耐炎化処理における延伸比を
１．０３とした以外は、実施例２と同様にして炭素繊維
を得た。[Comparative Example 1] A carbon fiber was obtained in the same manner as in Example 2 except that the stretching ratio in the flameproofing treatment was 1.03.
【００４１】得られた炭素繊維を用いて実施例１と同様
にＦＷ成形を行った。得られた炭素繊維の特性およびＦ
Ｗ成形時の糸切れ回数、毛羽量を表１に示す。FW molding was carried out in the same manner as in Example 1 using the obtained carbon fiber. Characteristics of the obtained carbon fiber and F
Table 1 shows the number of yarn breakages and the amount of fluff during W molding.
【００４２】［実施例３］紡糸原液を６０℃にて、紡糸
口金を通して直接温度６０℃、５０％のＤＭＳＯ水溶液
中に吐出させたこと以外は、実施例１と同様にして単繊
維繊度０．７ｄ、フィラメント数１２０００、ΔＬ＝３
８のアクリル系プリカーサー繊維糸条を得た。Example 3 A single fiber fineness of 0.60 was obtained in the same manner as in Example 1 except that the spinning solution was discharged at 60 ° C. directly into a 50% DMSO aqueous solution at a temperature of 60 ° C. through a spinneret. 7d, number of filaments 12000, ΔL = 3
Acrylic precursor fiber yarn 8 was obtained.
【００４３】このプリカーサーを２３０〜２８０℃の空
気中で延伸比０．９８で耐炎化処理した。引き続いて実
施例２と同様に炭素化処理し、表面処理を行い、サイジ
ング剤を施して炭素繊維を得た。This precursor was flame-proofed in air at 230 to 280 ° C. at a stretch ratio of 0.98. Subsequently, carbonization treatment was performed in the same manner as in Example 2, surface treatment was performed, and a sizing agent was applied to obtain carbon fibers.
【００４４】得られた炭素繊維を用いて実施例１と同様
にＦＷ成形を行った。得られた炭素繊維の特性およびＦ
Ｗ成形時の糸切れ回数、毛羽量を表１に示す。FW molding was carried out in the same manner as in Example 1 using the obtained carbon fiber. Characteristics of the obtained carbon fiber and F
Table 1 shows the number of yarn breakages and the amount of fluff during W molding.
【００４５】また、得られた炭素繊維を用いて円管引張
強度を測定した。結果を表２に示す。Further, the tensile strength of a circular pipe was measured using the obtained carbon fiber. The results are shown in Table 2.
【００４６】引張強度の発現の割合（円管強度／ストラ
ンド引張強度）は、０．９７と大きかった。The ratio of development of tensile strength (cylindrical strength / strand tensile strength) was as large as 0.97.
【００４７】［比較例２］実施例３と同様のポリマーを
実施例３と同様に紡糸して、単繊維繊度１．０ｄ、フィ
ラメント数１２０００、ΔＬ＝４８のアクリル系プリカ
ーサー繊維糸条を得た。[Comparative Example 2] The same polymer as in Example 3 was spun in the same manner as in Example 3 to obtain an acrylic precursor fiber yarn having a single fiber fineness of 1.0 d, a filament number of 12000 and ΔL = 48. .
【００４８】このプリカーサーを２３０〜２８０℃の空
気中で延伸比０．９８で耐炎化処理した。引き続いて実
施例１と同様に炭素化処理、表面処理を行い、サイジン
グ剤を施して炭素繊維を得た。This precursor was flame-proofed in air at 230 to 280 ° C. at a stretch ratio of 0.98. Subsequently, carbonization treatment and surface treatment were performed in the same manner as in Example 1, and a sizing agent was applied to obtain carbon fibers.
【００４９】得られた炭素繊維を用いて実施例１と同様
にＦＷ成形を行った。得られた炭素繊維の特性およびＦ
Ｗ成形時の糸切れ回数、毛羽量を表１に示す。FW molding was carried out in the same manner as in Example 1 using the obtained carbon fiber. Characteristics of the obtained carbon fiber and F
Table 1 shows the number of yarn breakages and the amount of fluff during W molding.
【００５０】［比較例３］炭素化処理における１０００
〜１４００℃の延伸比を１．０２とした以外は、実施例
３と同様にして炭素繊維を得た。[Comparative Example 3] 1000 in carbonization treatment
A carbon fiber was obtained in the same manner as in Example 3 except that the stretching ratio at 1400 ° C was 1.02.
【００５１】得られた炭素繊維を用いて実施例１と同様
にＦＷ成形を行った。得られた炭素繊維の特性およびＦ
Ｗ成形時の糸切れ回数、毛羽量を表１に示す。FW molding was carried out in the same manner as in Example 1 using the obtained carbon fiber. Characteristics of the obtained carbon fiber and F
Table 1 shows the number of yarn breakages and the amount of fluff during W molding.
【００５２】［比較例４］実施例３において炭素化処理
の後、さらに最高温度２５００℃で黒鉛化処理し、引き
続き、実施例１と同様に表面処理を行い、サイジング剤
を施して黒鉛化繊維を得た。[Comparative Example 4] After carbonization in Example 3, graphitization was performed at a maximum temperature of 2500 ° C, followed by surface treatment in the same manner as in Example 1 and applying a sizing agent to the graphitized fiber. Got
【００５３】得られた黒鉛化繊維を用いて実施例１と同
様にＦＷ成形を行った。得られた黒鉛化繊維の特性およ
びＦＷ成形時の糸切れ回数、毛羽量を表１に示す。FW molding was performed in the same manner as in Example 1 using the obtained graphitized fiber. Table 1 shows the characteristics of the obtained graphitized fiber, the number of yarn breakages during FW molding, and the amount of fluff.
【００５４】［比較例５］非シリコーン系の油剤を付与
させたこと以外は、実施例３と同様にして単繊維繊度
１．１ｄ、フィラメント数１２０００、ΔＬ＝５５のア
クリル系プリカーサー繊維糸条を得た。Comparative Example 5 An acrylic precursor fiber yarn having a single fiber fineness of 1.1 d, a filament number of 12000 and ΔL = 55 was prepared in the same manner as in Example 3 except that a non-silicone type oil agent was added. Obtained.
【００５５】次いで、このプリカーサーを２３０〜２８
０℃の空気中で延伸比０．９４で耐炎化処理した。引き
続いて１０００〜１３００℃の昇温速度を８００℃／分
として、実施例２と同様に炭素化処理、表面処理を行
い、サイジング剤を施して炭素繊維を得た。Then, this precursor is added to 230-28.
Flameproofing was performed in air at 0 ° C. at a draw ratio of 0.94. Subsequently, the temperature rising rate from 1000 to 1300 ° C. was set to 800 ° C./min, carbonization treatment and surface treatment were performed in the same manner as in Example 2, and a sizing agent was applied to obtain carbon fibers.
【００５６】得られた炭素繊維を用いて実施例１と同様
にＦＷ成形を行った。得られた炭素繊維の特性およびＦ
Ｗ成形時の糸切れ回数、毛羽量を表１に示す。FW molding was carried out in the same manner as in Example 1 using the obtained carbon fiber. Characteristics of the obtained carbon fiber and F
Table 1 shows the number of yarn breakages and the amount of fluff during W molding.
【００５７】また、得られた炭素繊維を用いて円管引張
強度を測定した。結果を表２に示す。Further, the tensile strength of a circular pipe was measured using the obtained carbon fiber. The results are shown in Table 2.
【００５８】引張強度の発現の割合（円管強度／ストラ
ンド引張強度）は、０．７９と実施例２、３に比べて小
さかった。The ratio of development of tensile strength (cylindrical strength / strand tensile strength) was 0.79, which was smaller than those of Examples 2 and 3.
【００５９】［比較例６］実施例３と同様のアクリル系
プリカーサー繊維糸条を２３０〜２８０℃の空気中で延
伸比０．９４で耐炎化処理した。引き続いて１０００〜
１３００℃の昇温速度を１５００℃／分とした以外は、
実施例２と同様に炭素化処理、表面処理を行い、サイジ
ング剤を施して炭素繊維を得た。[Comparative Example 6] The same acrylic precursor fiber yarn as in Example 3 was subjected to flameproofing treatment in air at 230 to 280 ° C at a draw ratio of 0.94. Continued from 1000
Except that the temperature rising rate of 1300 ° C. was 1500 ° C./minute,
Carbonization treatment and surface treatment were performed in the same manner as in Example 2, and a sizing agent was applied to obtain carbon fibers.
【００６０】得られた炭素繊維を用いて実施例１と同様
にＦＷ成形を行った。得られた炭素繊維の特性およびＦ
Ｗ成形時の糸切れ回数、毛羽量を表１に示す。FW molding was carried out in the same manner as in Example 1 using the obtained carbon fiber. Characteristics of the obtained carbon fiber and F
Table 1 shows the number of yarn breakages and the amount of fluff during W molding.
【００６１】[0061]
【表１】 [Table 1]
【表２】 [Table 2]
【００６２】[0062]
【発明の効果】本発明の炭素繊維は、ＦＷ成形工程での
毛羽立ち、糸切れを抑制することができ、またそのこと
などによりＦＷ成形工程のライン速度を高く設定するこ
とができる、さらにＦＷ成形法により得られる複合材料
の特性を大幅に改善することができるので、天然ガス燃
料用ボンベなどのＦＷ成形法による製造に好適に利用す
ることができ、工業的価値が極めて高い。INDUSTRIAL APPLICABILITY The carbon fiber of the present invention can suppress fluffing and yarn breakage in the FW molding process, and by doing so, the line speed in the FW molding process can be set high. Since the properties of the composite material obtained by the method can be greatly improved, it can be suitably used for the production of a cylinder for a natural gas fuel by the FW molding method, and has an extremely high industrial value.
【図１】本発明において用いる糸切れ限界張力測定装置
の概略側面図である。FIG. 1 is a schematic side view of a yarn breakage limit tension measuring device used in the present invention.
ａ：張力調整可能なクリール ｂ：炭素繊維束 ｃ１、ｃ２、ｃ３、ｃ４：表面梨地の回転ローラー（直
径１５ｍｍφ） ｄ１、ｄ２、ｄ３、ｄ４：表面平滑度３Ｓのステンレス
棒（直径１５ｍｍφ） ｅ：樹脂槽 ｆ：樹脂のメチルエチルケトン溶液 ｇ：ドラム（直径７５０ｍｍφ）a: Creel with adjustable tension b: Carbon fiber bundle c1, c2, c3, c4: Surface-finished rotary roller (diameter 15 mmφ) d1, d2, d3, d4: Stainless steel rod with surface smoothness 3S (diameter 15 mmφ) e: Resin tank f: Methyl ethyl ketone solution of resin g: Drum (diameter 750 mmφ)
Claims (2)
であり、糸切れ限界張力が０．２ｇ／Ｄ以上であり、お
よび引掛強度が１００kgf/mm2 以上であることを特徴と
するフィラメントワインディング成形用炭素繊維。1. A filament winding molding characterized in that a strand tensile strength is 400 kgf / mm 2 or more, a yarn breaking limit tension is 0.2 g / D or more, and a hooking strength is 100 kgf / mm 2 or more. For carbon fiber.
以下であるアクリル系繊維を原料として、温度２３０℃
以上２８０℃以下の空気中、０．８０以上１．００以下
の延伸比で耐炎化し、引き続いて最高温度１１００℃以
上２０００℃以下の不活性雰囲気中、１０００℃から最
高温度までの温度域における延伸比を０．９８以下とし
て炭素化処理した後、表面処理、サイジング処理するこ
とを特徴とするフィラメントワインディング成形用炭素
繊維の製造方法。2. The difference in lightness (ΔL) by the iodine adsorption method is 50.
Using the following acrylic fiber as the raw material, temperature 230 ℃
In the air above 280 ° C., flame resistance is achieved at a draw ratio of 0.80 to 1.00 inclusive, and subsequently in an inert atmosphere at a maximum temperature of 1100 ° C. to 2000 ° C., drawing in a temperature range from 1000 ° C. to the maximum temperature. A method for producing carbon fiber for filament winding molding, which comprises performing carbonization treatment with a ratio of 0.98 or less, followed by surface treatment and sizing treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9988694A JP3047731B2 (en) | 1994-05-13 | 1994-05-13 | Carbon fiber for filament winding molding and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9988694A JP3047731B2 (en) | 1994-05-13 | 1994-05-13 | Carbon fiber for filament winding molding and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07310240A true JPH07310240A (en) | 1995-11-28 |
| JP3047731B2 JP3047731B2 (en) | 2000-06-05 |
Family
ID=14259271
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9988694A Expired - Fee Related JP3047731B2 (en) | 1994-05-13 | 1994-05-13 | Carbon fiber for filament winding molding and method for producing the same |
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| Country | Link |
|---|---|
| JP (1) | JP3047731B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010089524A (en) * | 2008-10-03 | 2010-04-22 | Nsk Ltd | Method for manufacturing rack-and-pinion electric power steering device |
| JP2012154000A (en) * | 2011-01-27 | 2012-08-16 | Toray Ind Inc | Carbon fiber for molding filament winding and method for manufacturing the same |
| JP2015067910A (en) * | 2013-09-27 | 2015-04-13 | 東レ株式会社 | Carbon fiber and manufacturing method thereof |
| KR20160077322A (en) | 2014-12-22 | 2016-07-04 | 주식회사 효성 | A carbon-fiber for filament winding bundle |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6216509B2 (en) * | 2012-12-26 | 2017-10-18 | 東邦テナックス株式会社 | Sizing agent-attached carbon fiber bundle, method for producing the same, and pressure vessel production method using the sizing agent-attached carbon fiber bundle |
| JP6543309B2 (en) * | 2017-08-11 | 2019-07-10 | 帝人株式会社 | Sizing agent-deposited carbon fiber bundle, method for producing the same, and method for producing pressure vessel using the sizing agent-deposited carbon fiber bundle |
-
1994
- 1994-05-13 JP JP9988694A patent/JP3047731B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010089524A (en) * | 2008-10-03 | 2010-04-22 | Nsk Ltd | Method for manufacturing rack-and-pinion electric power steering device |
| JP2012154000A (en) * | 2011-01-27 | 2012-08-16 | Toray Ind Inc | Carbon fiber for molding filament winding and method for manufacturing the same |
| JP2015067910A (en) * | 2013-09-27 | 2015-04-13 | 東レ株式会社 | Carbon fiber and manufacturing method thereof |
| KR20160077322A (en) | 2014-12-22 | 2016-07-04 | 주식회사 효성 | A carbon-fiber for filament winding bundle |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3047731B2 (en) | 2000-06-05 |
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