JP4216873B2 - Method for producing carbon fiber precursor fiber bundle - Google Patents
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- JP4216873B2 JP4216873B2 JP2006223229A JP2006223229A JP4216873B2 JP 4216873 B2 JP4216873 B2 JP 4216873B2 JP 2006223229 A JP2006223229 A JP 2006223229A JP 2006223229 A JP2006223229 A JP 2006223229A JP 4216873 B2 JP4216873 B2 JP 4216873B2
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本発明は、繊維強化複合材料の強化材として使用される炭素繊維束の製造に適したアクリロニトリル系重合体の単繊維からなる炭素繊維前駆体繊維束の製造方法に関する。 The present invention relates to a method for producing a carbon fiber precursor fiber bundle composed of a single fiber of an acrylonitrile-based polymer suitable for producing a carbon fiber bundle used as a reinforcing material for a fiber-reinforced composite material.
繊維強化複合材料には、炭素繊維、ガラス繊維、アラミド繊維等が使用されている。中でも、炭素繊維は、比強度、比弾性率、耐熱性、耐薬品性等に優れ、航空機用途、ゴルフシャフト、釣り竿等のスポーツ用途、一般産業用途の繊維強化複合材料の強化材として使用されている。このような繊維強化複合材料は、例えば、以下のようにして製造される。 Carbon fiber, glass fiber, aramid fiber, etc. are used for the fiber reinforced composite material. Among them, carbon fiber is excellent in specific strength, specific elastic modulus, heat resistance, chemical resistance, etc., and is used as a reinforcing material for fiber reinforced composite materials for aircraft applications, sports applications such as golf shafts and fishing rods, and general industrial applications. Yes. Such a fiber reinforced composite material is manufactured as follows, for example.
まず、ポリアクリロニトリル系重合体の単繊維からなる前駆体繊維束を、焼成工程（耐炎化工程）にて空気などの酸化性気体中、２００〜３００℃の温度で焼成して耐炎繊維束を得る。次いで、炭素化工程にて、不活性雰囲気中、３００〜２０００℃の温度で耐炎繊維束を炭素化して炭素繊維束を得る。そして、この炭素繊維束を、必要に応じて織物等に加工した後、これに合成樹脂を含浸させ、所定形状に成形することにより繊維強化複合材料を得る。 First, a precursor fiber bundle made of a single fiber of a polyacrylonitrile-based polymer is fired at a temperature of 200 to 300 ° C. in an oxidizing gas such as air in a firing process (flame resistance process) to obtain a flame resistant fiber bundle. . Next, in the carbonization step, the flame resistant fiber bundle is carbonized at a temperature of 300 to 2000 ° C. in an inert atmosphere to obtain a carbon fiber bundle. And after processing this carbon fiber bundle into a textile fabric etc. as needed, this is impregnated with a synthetic resin and formed into a predetermined shape to obtain a fiber-reinforced composite material.
炭素繊維束の製造に用いられる前駆体繊維束には、焼成工程において繊維束がばらけて、繊維束を構成する単繊維が隣接する繊維束に絡まったり、ローラに巻き付いたりしないように、高い集束性が要求される。
しかしながら、集束性の高い前駆体繊維束から得られる炭素繊維束は、その集束性の高さのため、樹脂が含浸しにくいという問題を有していた。
Precursor fiber bundles used in the production of carbon fiber bundles are high so that the fiber bundles are scattered in the firing process and the single fibers constituting the fiber bundles are not entangled with adjacent fiber bundles or wound around rollers. Convergence is required.
However, the carbon fiber bundle obtained from the precursor fiber bundle having a high bundling property has a problem that the resin is difficult to be impregnated due to its high bundling property.
また、炭素繊維束を製織して得られる炭素繊維織物は、樹脂を含浸する際に、樹脂のボイドが発生しないように、できるだけ目開きの少ない織物とする必要がある。そのために、製織中または製織後に何らかの開繊処理が施される。
しかしながら、集束性の高い前駆体繊維束から得られる炭素繊維束は、その集束性の高さのため、開繊しにくいという問題を有していた。
また、炭素繊維織物は、目空きの少ない均一な織り目が要求されるため、嵩高い炭素繊維束が必要とされていた。
Further, the carbon fiber woven fabric obtained by weaving the carbon fiber bundle needs to be a woven fabric having as few openings as possible so that resin voids are not generated when the resin is impregnated. For this purpose, some opening process is performed during or after weaving.
However, the carbon fiber bundle obtained from the precursor fiber bundle having high bundling property has a problem that it is difficult to open due to its high bundling property.
In addition, since the carbon fiber woven fabric is required to have a uniform weave with little open space, a bulky carbon fiber bundle is required.
よって、本発明の目的は、樹脂含浸性、開繊性が良好で、強度が高く、嵩高な炭素繊維束を得ることができ、かつ集束性が高く、焼成工程通過性が良好な炭素繊維前駆体繊維束の製造方法を提供することにある。 Therefore, the object of the present invention is to provide a carbon fiber precursor that has good resin impregnation and spreadability, is capable of obtaining a high strength and bulky carbon fiber bundle, has high converging properties, and has good permeability in the firing process. It is providing the manufacturing method of a body fiber bundle.
本発明の炭素繊維前駆体繊維束の製造方法は、９５重量％以上のアクリロニトリル単位を含有するアクリロニトリル系重合体の有機溶剤溶液からなる紡糸溶液を、有機溶剤濃度５０〜６５重量％、温度３０〜５０℃の有機溶剤水溶液からなる第１凝固浴中に吐出させて凝固糸にするとともに、この凝固糸を第１凝固浴中から紡糸原液の吐出線速度の０．８倍以下の引き取り速度で引き取る工程と、この凝固糸に有機溶剤濃度５０〜６５重量％、温度３０〜５０℃の有機溶剤水溶液からなる第２凝固浴中にて１．２〜２．５倍の延伸を施す工程と、第２凝固浴中での延伸を終えた膨潤状態にある繊維束に対して３倍以上の湿熱延伸を行う工程と、この繊維束に対して０．４〜１．５重量％に調製したシリコン系油剤の添油処理を行う工程と、この繊維束を乾燥した後に、この繊維束に１．６〜４倍のスチーム延伸を施す工程とを有することを特徴とする。 In the method for producing a carbon fiber precursor fiber bundle of the present invention, a spinning solution comprising an organic solvent solution of an acrylonitrile-based polymer containing 95% by weight or more of an acrylonitrile unit is prepared by using an organic solvent concentration of 50 to 65% by weight and a temperature of 30 to 30%. The coagulated yarn is discharged into a first coagulation bath made of an organic solvent aqueous solution at 50 ° C. to obtain coagulated yarn, and the coagulated yarn is taken out from the first coagulation bath at a take-off speed of 0.8 times or less of the discharge linear velocity of the spinning dope. a step, a step of subjecting the coagulated fiber to organic solvent concentration 50-65% by weight, stretching of 1.2 to 2.5 times in the second coagulation bath consisting of an organic solvent solution of the temperature 30 to 50 ° C., the (2) A step of performing wet heat stretching 3 times or more on a fiber bundle in a swollen state after stretching in a coagulation bath, and a silicon system adjusted to 0.4 to 1.5% by weight with respect to this fiber bundle and performing a hydrogenated oil processing of oil, this After drying the fiber bundle, characterized by having a step of applying steam drawing of 1.6 to 4 times the fiber bundle.
本発明の炭素繊維前駆体繊維束の製造方法によれば、集束性が高く、焼成工程通過性が良好な炭素繊維前駆体繊維束を得ることができ、また、これから得られる炭素繊維束は、樹脂含浸性、開繊性が良好で、強度が高く、嵩高となる。 According to the method for producing a carbon fiber precursor fiber bundle of the present invention, it is possible to obtain a carbon fiber precursor fiber bundle having a high bundling property and good firing process passability, and a carbon fiber bundle obtained therefrom is Resin impregnation and spreadability are good, strength is high and bulky.
以下、本発明を詳細に説明する。
本発明における炭素繊維前駆体繊維束は、複数のアクリロニトリル系重合体の単繊維を束ねたトウである。
Hereinafter, the present invention will be described in detail.
The carbon fiber precursor fiber bundle in the present invention is a tow obtained by bundling a plurality of acrylonitrile polymer single fibers.
アクリロニトリル系重合体としては、アクリロニトリル単位を９５重量％以上含有する重合体が、該炭素繊維前駆体繊維束を焼成して得られる炭素繊維束の強度発現性の面で好ましい。アクリロニトリル系重合体は、アクリロニトリルと、必要に応じてこれと共重合しうる単量体とを、水溶液中におけるレドックス重合、不均一系における懸濁重合、分散剤を使用した乳化重合などによって、重合させて得ることができる。 As the acrylonitrile-based polymer, a polymer containing 95% by weight or more of an acrylonitrile unit is preferable in terms of strength development of a carbon fiber bundle obtained by firing the carbon fiber precursor fiber bundle. An acrylonitrile polymer is a polymer of acrylonitrile and a monomer that can be copolymerized with it by redox polymerization in an aqueous solution, suspension polymerization in a heterogeneous system, emulsion polymerization using a dispersing agent, or the like. Can be obtained.
アクリロニトリルと共重合しうる単量体としては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、ヘキシル（メタ）アクリレート等の（メタ）アクリル酸エステル類；塩化ビニル、臭化ビニル、塩化ビニリデン等のハロゲン化ビニル類；（メタ）アクリル酸、イタコン酸、クロトン酸等の酸類およびそれらの塩類；マレイン酸イミド、フェニルマレイミド、（メタ）アクリルアミド、スチレン、α−メチルスチレン、酢酸ビニル；スチレンスルホン酸ソーダ、アリルスルホン酸ソーダ、β−スチレンスルホン酸ソーダ、メタアリルスルホン酸ソーダ等のスルホン基を含む重合性不飽和単量体；２−ビニルピリジン、２−メチル−５−ビニルピリジン等のピリジン基を含む重合性不飽和単量体等が挙げられる。 Examples of monomers that can be copolymerized with acrylonitrile include (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and hexyl (meth) acrylate. Esters; vinyl halides such as vinyl chloride, vinyl bromide, vinylidene chloride; acids such as (meth) acrylic acid, itaconic acid, crotonic acid and their salts; maleic imide, phenylmaleimide, (meth) acrylamide, Styrene, α-methylstyrene, vinyl acetate; polymerizable unsaturated monomer containing a sulfo group such as sodium styrene sulfonate, sodium allyl sulfonate, sodium β-styrene sulfonate, sodium methallyl sulfonate; 2-vinylpyridine , 2-methyl-5-vinylpyridine and the like Examples thereof include a polymerizable unsaturated monomer containing a lysine group.
本発明におけるアクリロニトリル系重合体の単繊維の繊維断面の長径と短径との比（長径／短径）は、１．０５〜１．６であり、好ましくは、１．１〜１．３であり、より好ましくは１．１５〜１．２５である。長径／短径比がこの範囲内にあれば、前駆体繊維束の焼成工程通過性と、これから得られる炭素繊維束の樹脂含浸性および開繊性とを同時に満足することができる。長径／短径比が１．０５未満では、単繊維間の空隙が減少し、得られる炭素繊維束の樹脂含浸性および開繊性が悪くなり、嵩高さが不十分となる。長径／短径比が１．６を超えると、繊維束の集束性が低下し、焼成工程通過性が悪化する。また、ストランド強度が著しく低下する。 The ratio (major axis / minor axis) of the major axis to the minor axis of the fiber cross section of the single fiber of the acrylonitrile polymer in the present invention is 1.05 to 1.6, preferably 1.1 to 1.3. Yes, more preferably 1.15 to 1.25. If the ratio of major axis / minor axis is within this range, it is possible to satisfy both the passability of the precursor fiber bundle through the firing step and the resin impregnation property and the fiber opening property of the carbon fiber bundle obtained therefrom. When the major axis / minor axis ratio is less than 1.05, voids between single fibers are reduced, resin impregnation property and fiber opening property of the obtained carbon fiber bundle are deteriorated, and bulkiness is insufficient. When the major axis / minor axis ratio exceeds 1.6, the convergence of the fiber bundle is lowered, and the firing process passability is deteriorated. In addition, the strand strength is significantly reduced.
ここで、単繊維の繊維断面の長径と短径との比（長径／短径）は、以下のようにして決定される。
内径１ｍｍの塩化ビニル樹脂製のチューブ内に測定用のアクリロニトリル系重合体の繊維を通した後、これをナイフで輪切りにして試料を準備する。ついで、該試料をアクリロニトリル系重合体の繊維断面が上を向くようにしてＳＥＭ試料台に接着し、さらにＡｕを約１０ｎｍの厚さにスパッタリングしてから、ＰＨＩＬＩＰＳ社製ＸＬ２０走査型電子顕微鏡により、加速電圧７．００ｋＶ、作動距離３１ｍｍの条件で繊維断面を観察し、単繊維の繊維断面の長径および短径を測定し、長径÷短径で長径／短径の比率が決定される。
Here, the ratio of the major axis to the minor axis (major axis / minor axis) of the fiber cross section of the single fiber is determined as follows.
After passing an acrylonitrile polymer fiber for measurement through a tube made of vinyl chloride resin having an inner diameter of 1 mm, the sample is prepared by cutting it with a knife. Next, the sample was adhered to the SEM sample stage so that the fiber cross section of the acrylonitrile polymer was facing upward, and Au was sputtered to a thickness of about 10 nm, and then with a XL20 scanning electron microscope manufactured by PHILIPS, The fiber cross section is observed under the conditions of an acceleration voltage of 7.00 kV and a working distance of 31 mm, the major axis and minor axis of the fiber section of the single fiber are measured, and the ratio of major axis / minor axis is determined by major axis / minor axis.
本発明における炭素繊維前駆体繊維束のＳｉ量は、５００〜４０００ｐｐｍの範囲であり、好ましくは１０００〜３０００ｐｐｍの範囲である。Ｓｉ量がこの範囲内にあれば、前駆体繊維束の焼成工程通過性と、これから得られる炭素繊維束の樹脂含浸性および開繊性とを同時に満足することができる。Ｓｉ量が５００ｐｐｍ未満では、繊維束の集束性が低下し、焼成工程通過性が悪化する。また、得られる炭素繊維束のストランド強度が低下する。Ｓｉ量が４０００ｐｐｍを超えると、前駆体繊維束の焼成時にシリカが多く飛散し、焼成安定性が悪くなる。また、得られる炭素繊維束がばらけにくくなり、樹脂含浸性および開繊性が悪くなる。 The amount of Si in the carbon fiber precursor fiber bundle in the present invention is in the range of 500 to 4000 ppm, preferably in the range of 1000 to 3000 ppm. If the amount of Si is within this range, it is possible to simultaneously satisfy the passability of the precursor fiber bundle through the firing process and the resin impregnation property and fiber opening property of the carbon fiber bundle obtained therefrom. If the amount of Si is less than 500 ppm, the fiber bundle is less converged and the firing processability is deteriorated. Further, the strand strength of the obtained carbon fiber bundle is lowered. When the amount of Si exceeds 4000 ppm, a large amount of silica is scattered during firing of the precursor fiber bundle, and firing stability is deteriorated. In addition, the obtained carbon fiber bundle is difficult to disperse, and the resin impregnation property and the fiber opening property are deteriorated.
このＳｉ量は、炭素繊維前駆体繊維束を製造する際に使用されるシリコン系油剤に由来するものである。ここで、Ｓｉ量は、ＩＣＰ発光分析装置を用いて測定することができる。 This amount of Si is derived from the silicon-based oil used when producing the carbon fiber precursor fiber bundle. Here, the amount of Si can be measured using an ICP emission analyzer.
本発明におけるアクリロニトリル系重合体の単繊強度は、好ましくは５．０ｃＮ／ｄｔｅｘ以上であり、より好ましくは６．５ｃＮ／ｄｔｅｘ以上であり、さらに好ましくは７．０ｃＮ／ｄｔｅｘ以上である。単繊強度が５．０ｃＮ／ｄｔｅｘ未満では、焼成工程での単糸切れによる毛羽の発生が多くなって焼成工程通過性が悪くなる。 The single fiber strength of the acrylonitrile-based polymer in the present invention is preferably 5.0 cN / dtex or more, more preferably 6.5 cN / dtex or more, and further preferably 7.0 cN / dtex or more. If the single fiber strength is less than 5.0 cN / dtex, the generation of fluff due to single yarn breakage in the firing process increases, and the firing processability deteriorates.
ここで、アクリロニトリル系重合体の単繊強度は、単繊維自動引張強伸度測定機（オリエンテック ＵＴＭ II−２０）を使用し、台紙に貼られた単繊維をロードセルのチャックに装着し、毎分２０．０ｍｍの速度で引っ張り試験を行い強伸度を測定することによって求められる。 Here, the single fiber strength of the acrylonitrile-based polymer is determined by using a single fiber automatic tensile strength / elongation measuring machine (Orientec UTM II-20), attaching the single fiber attached to the mount to the load cell chuck, and It is obtained by performing a tensile test at a speed of 20.0 mm and measuring the strength and elongation.
本発明における炭素繊維前駆体繊維束は、単繊維の表面に繊維束の長手方向に延びる皺を有していることが好ましい。このような皺の存在により、本発明の炭素繊維前駆体繊維束は、良好な集束性を有すると同時に、得られる炭素繊維束は、良好な樹脂含浸性と開繊性とを有するようになる。
このような皺の深さは、以下の中心線平均粗さ（Ｒａ）、最大高さ（Ｒｙ）および局部山頂の間隔（Ｓ）によって規定される。
The carbon fiber precursor fiber bundle in the present invention preferably has a ridge extending in the longitudinal direction of the fiber bundle on the surface of the single fiber. Due to the presence of such wrinkles, the carbon fiber precursor fiber bundle of the present invention has good sizing properties, and at the same time, the resulting carbon fiber bundle has good resin impregnation and spreadability. .
The depth of such ridges is defined by the following centerline average roughness (Ra), maximum height (Ry) and local summit spacing (S).
本発明における炭素繊維前駆体繊維束の単繊維の表面の中心線平均粗さ（Ｒａ）は、好ましくは０．０１〜０．１μｍであり、より好ましくは０．０２〜０．０７μｍであり、さらに好ましくは０．０３〜０．０６μｍである。中心線平均粗さ（Ｒａ）が０．０１μｍ未満では、得られる炭素繊維束の樹脂含浸性、開繊性が悪くなり、嵩高さが不十分となる。中心線平均粗さ（Ｒａ）が０．１μｍを超えると、繊維束の表面積が増加して静電気が発生し易くなり、繊維束の集束性を低下させる。また、得られる炭素繊維束のストランド強度が低下する。 The center line average roughness (Ra) of the surface of the single fiber of the carbon fiber precursor fiber bundle in the present invention is preferably 0.01 to 0.1 μm, more preferably 0.02 to 0.07 μm, More preferably, it is 0.03-0.06 micrometer. When the center line average roughness (Ra) is less than 0.01 μm, the resin impregnation property and the fiber opening property of the obtained carbon fiber bundle are deteriorated, and the bulkiness is insufficient. When the center line average roughness (Ra) exceeds 0.1 μm, the surface area of the fiber bundle is increased, and static electricity is likely to be generated, thereby reducing the convergence of the fiber bundle. Further, the strand strength of the obtained carbon fiber bundle is lowered.
ここで、中心線平均粗さ（Ｒａ）とは、図１に示すように、粗さ曲線からその中心線ｍの方向に基準長さＬだけ抜き取り、この抜取り部分の中心線ｍから測定曲線までの偏差の絶対値を合計し、平均した値である。中心線平均粗さ（Ｒａ）は、レーザー顕微鏡を用いることによって測定される。 Here, the centerline average roughness (Ra) is, as shown in FIG. 1, extracted from the roughness curve by the reference length L in the direction of the centerline m, and from the centerline m of the extracted portion to the measurement curve. The absolute values of the deviations are summed and averaged. The center line average roughness (Ra) is measured by using a laser microscope.
本発明における炭素繊維前駆体繊維束の表面の最大高さ（Ｒｙ）は、好ましくは０．１〜０．５μｍであり、より好ましくは０．１５〜０．４μｍであり、さらに好ましくは０．２〜０．３５μｍである。最大高さ（Ｒｙ）が０．１μｍ未満では、得られる炭素繊維束の樹脂含浸性、開繊性が悪くなり、嵩高さが不十分となる。最大高さ（Ｒｙ）が０．５μｍを超えると、繊維束の表面積が増加して静電気が発生し易くなり、繊維束の集束性を低下させる。また、得られる炭素繊維束のストランド強度が低下する。 The maximum height (Ry) of the surface of the carbon fiber precursor fiber bundle in the present invention is preferably 0.1 to 0.5 μm, more preferably 0.15 to 0.4 μm, and still more preferably 0.8. 2 to 0.35 μm. When the maximum height (Ry) is less than 0.1 μm, the resin impregnation property and the fiber opening property of the obtained carbon fiber bundle are deteriorated, and the bulkiness is insufficient. When the maximum height (Ry) exceeds 0.5 μm, the surface area of the fiber bundle is increased, and static electricity is likely to be generated, thereby reducing the convergence of the fiber bundle. Further, the strand strength of the obtained carbon fiber bundle is lowered.
ここで、最大高さ（Ｒｙ）とは、図２に示すように、粗さ曲線からその中心線ｍの方向に基準長さＬだけ抜き取り、この抜取り部分の山頂線および谷底線と中心線ｍとの間隔、ＲｐおよびＲｖの合計値である。最大高さ（Ｒｙ）は、レーザー顕微鏡を用いることによって測定される。 Here, as shown in FIG. 2, the maximum height (Ry) means that a reference length L is extracted from the roughness curve in the direction of the center line m, and the peak line, valley bottom line, and center line m of the extracted part are extracted. And the sum of Rp and Rv. The maximum height (Ry) is measured by using a laser microscope.
また、これら皺の間隔を規定するパラメータである、局部山頂の間隔（Ｓ）は、好ましくは０．２〜１．０μｍであり、より好ましくは０．３〜０．８μｍであり、さらに好ましくは０．４〜０．７μｍである。局部山頂の間隔（Ｓ）が０．２μｍ未満では、得られる炭素繊維束の樹脂含浸性および開繊性が悪くなり、嵩高さが不十分となる。局部山頂の間隔（Ｓ）が１．０μｍを超えると、繊維束の表面積が増加して静電気が発生し易くなり、繊維束の集束性を低下させる。また、得られる炭素繊維束のストランド強度が低下する。 Further, the local summit interval (S), which is a parameter for defining the interval between these ridges, is preferably 0.2 to 1.0 μm, more preferably 0.3 to 0.8 μm, and still more preferably. 0.4 to 0.7 μm. If the distance (S) between the local peaks is less than 0.2 μm, the resin impregnation property and the fiber opening property of the obtained carbon fiber bundle are deteriorated, and the bulkiness is insufficient. When the distance (S) between the local peaks exceeds 1.0 μm, the surface area of the fiber bundle increases, and static electricity is likely to be generated, thereby reducing the convergence of the fiber bundle. Further, the strand strength of the obtained carbon fiber bundle is lowered.
ここで、局部山頂の間隔（Ｓ）とは、図３に示すように、粗さ曲線からその中心線ｍの方向に基準長さＬだけ抜き取り、この抜取り部分の隣り合う局部山頂間の間隔Ｓ1 、Ｓ2 、Ｓ3 、・・・の平均値Ｓである。局部山頂の間隔（Ｓ）は、レーザー顕微鏡を用いることによって測定される。 Here, as shown in FIG. 3, the interval (S) between the local peaks is extracted from the roughness curve by the reference length L in the direction of the center line m, and the interval S between the adjacent local peaks is extracted from this extracted portion. It is the average value S of 1 , S 2 , S 3 ,. The local summit spacing (S) is measured by using a laser microscope.
また、本発明における炭素繊維前駆体繊維束の水分率は、好ましくは１５重量％以下であり、より好ましくは、１０重量％以下であり、さらに好ましくは、３〜５重量％である。水分率が１５重量％を超えると、繊維束にエアを吹き付け交絡を施した際に、単繊維が交絡しにくくなり、その結果、繊維束がばらけやすくなって焼成工程通過性が悪くなる。 Moreover, the moisture content of the carbon fiber precursor fiber bundle in the present invention is preferably 15% by weight or less, more preferably 10% by weight or less, and further preferably 3 to 5% by weight. When the moisture content exceeds 15% by weight, when the fiber bundle is blown with air and entangled, the single fibers are less likely to be entangled. As a result, the fiber bundle is easily separated and the passing through the firing process is deteriorated.
ここで、水分率は、ウエット状態にある繊維束の重量ｗと、これを１０５℃×２時間の熱風乾燥機で乾燥した後の重量ｗ0 とにより、水分率（重量％）＝（ｗ−ｗ0 ）×１００／ｗ0 によって求めた数値である。 Here, the water content is determined by the water content (% by weight) = (w−) based on the weight w of the fiber bundle in a wet state and the weight w 0 after drying this with a hot air dryer at 105 ° C. for 2 hours. w 0 ) × 100 / w 0
また、本発明における炭素繊維前駆体繊維束を構成するアクリロニトリル系重合体の単繊維の数は、好ましくは、１２０００本以下であり、より好ましくは６０００本以下であり、さらに好ましくは３０００本以下である。単繊維の数が１２０００本を超えると、トウハンドリングおよびトウボリュウームが増加し、乾燥負荷が増大することから、紡糸速度を上げることができなくなる。また、均一な交絡を与える事が困難となり、その結果、焼成工程での通過性が悪化する。 In addition, the number of single fibers of the acrylonitrile polymer constituting the carbon fiber precursor fiber bundle in the present invention is preferably 12000 or less, more preferably 6000 or less, and further preferably 3000 or less. is there. When the number of single fibers exceeds 12,000, tow handling and tow volume increase and the drying load increases, so that the spinning speed cannot be increased. Moreover, it becomes difficult to give uniform entanglement, and as a result, the permeability in a baking process deteriorates.
また、本発明における炭素繊維前駆体繊維束の交絡度は、好ましくは５〜２０ヶ／ｍの範囲であり、より好ましくは１０〜１４ヶ／ｍの範囲である。交絡度が５ヶ／ｍ未満では、繊維束がばらけやすくなり、焼成工程通過性が悪くなる。交絡度が２０ヶ／ｍを超えると、得られる炭素繊維束の樹脂含浸性および開繊性が悪くなる。 Moreover, the entanglement degree of the carbon fiber precursor fiber bundle in the present invention is preferably in the range of 5 to 20 / m, and more preferably in the range of 10 to 14 / m. If the degree of entanglement is less than 5 / m, the fiber bundle is likely to be scattered, and the passing through the firing process is deteriorated. When the entanglement degree exceeds 20 pcs / m, the resin impregnation property and the fiber opening property of the obtained carbon fiber bundle are deteriorated.
ここで、炭素繊維前駆体繊維束の交絡度とは、繊維束中の１本の単繊維が隣接する他の単繊維と１ｍの間に何回交絡しているかを示すパラメータである。交絡度は、フックドロップ法により測定される。 Here, the degree of entanglement of the carbon fiber precursor fiber bundle is a parameter indicating how many times one single fiber in the fiber bundle is entangled with 1 m from other adjacent single fibers. The degree of entanglement is measured by the hook drop method.
次に、本発明の炭素繊維前駆体繊維束の製造方法について説明する。
本発明における炭素繊維前駆体繊維束は、例えば、以下のようにして製造することができる。
まず、アクリロニトリル系重合体の有機溶剤溶液からなる紡糸原液を、紡糸口金を通して、有機溶剤の濃度５０〜６５重量％、温度３０〜５０℃の有機溶剤水溶液からなる第１凝固浴中に吐出させて凝固糸にするとともに、該第１凝固浴中からこの凝固糸を、紡糸原液の吐出線速度の０．８倍以下の引取り速度で引き取る。
ついで、この凝固糸を、有機溶剤の濃度５０〜６５重量％、温度３０〜５０℃の有機溶剤水溶液からなる第２凝固浴中にて１．２〜２．５倍に延伸する。
Next, the manufacturing method of the carbon fiber precursor fiber bundle of this invention is demonstrated.
The carbon fiber precursor fiber bundle in the present invention can be produced, for example, as follows.
First, a spinning solution composed of an organic solvent solution of an acrylonitrile polymer is discharged through a spinneret into a first coagulation bath composed of an organic solvent aqueous solution having a concentration of organic solvent of 50 to 65% by weight and a temperature of 30 to 50 ° C. In addition to forming a coagulated yarn, the coagulated yarn is taken out from the first coagulation bath at a take-up speed of 0.8 times or less of the discharge linear speed of the spinning dope.
Next, the coagulated yarn is drawn 1.2 to 2.5 times in a second coagulation bath composed of an organic solvent aqueous solution having an organic solvent concentration of 50 to 65% by weight and a temperature of 30 to 50 ° C.
続いて、第２凝固浴中での延伸を終えた膨潤状態にある繊維束に対して３倍以上の湿熱延伸を行う。
ついで、この繊維束に対してシリコン系油剤の添油処理を行った後、この繊維束を乾燥し、さらにスチーム延伸機で１．６〜４倍に延伸する。
この繊維束に対して、タッチロールで水分率の調整を行い、続いて、この糸にエアーを吹き付けて交絡を施し、炭素繊維前駆体繊維束を得る。
Subsequently, wet heat stretching is performed three times or more on the swollen fiber bundle that has been stretched in the second coagulation bath.
Next, after adding a silicon-based oil to the fiber bundle, the fiber bundle is dried and further stretched 1.6 to 4 times with a steam stretching machine.
The moisture content of the fiber bundle is adjusted with a touch roll, and then the yarn is entangled by blowing air onto the yarn to obtain a carbon fiber precursor fiber bundle.
紡糸原液に使用するアクリロニトリル系重合体に対する有機溶剤としては、例えば、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等が挙げられる。中でも、ジメチルアセトアミドは、溶剤の加水分解による性状の悪化が少なく、良好な紡糸性を与えるので、好適に用いられる。 Examples of the organic solvent for the acrylonitrile polymer used in the spinning dope include dimethylacetamide, dimethylsulfoxide, dimethylformamide, and the like. Among them, dimethylacetamide is preferably used because it is less deteriorated due to hydrolysis of the solvent and gives good spinnability.
ここで、第１凝固浴と第２凝固浴の有機溶剤の濃度を同じにする、第１凝固浴と第２凝固浴の温度を同じにする、さらには紡糸原液の有機溶剤と第１凝固浴に用いる有機溶剤と第２凝固浴に用いる有機溶剤とを同じものにする等の手段を採ることにより、第１凝固浴および第２凝固浴の調製が容易となり、しかも溶剤回収上でのメリットも生ずる。 Here, the concentration of the organic solvent in the first coagulation bath and the second coagulation bath is made the same, the temperature of the first coagulation bath and the second coagulation bath are made the same, and the organic solvent of the spinning dope and the first coagulation bath By taking measures such as making the organic solvent used for the second coagulation bath the same as the organic solvent used for the second coagulation bath, the preparation of the first coagulation bath and the second coagulation bath is facilitated, and there are also advantages in recovering the solvent. Arise.
また、アクリロニトリル系重合体のジメチルアセトアミド溶液からなる紡糸原液と、ジメチルアセトアミド水溶液からなる第１凝固浴と、該第１凝固浴と同じ温度および組成成分のジメチルアセトアミド水溶液からなる第２凝固浴とを使用すると、繊維断面の長径／短径比が１．０５〜１．６の単繊維の製造を容易に行えるようになる。 And a spinning stock solution comprising a dimethylacetamide solution of an acrylonitrile polymer, a first coagulation bath comprising a dimethylacetamide aqueous solution, and a second coagulation bath comprising a dimethylacetamide aqueous solution having the same temperature and composition as the first coagulation bath. If used, it becomes possible to easily produce single fibers having a major axis / minor axis ratio of 1.05 to 1.6.
また、第１凝固浴と第２凝固浴の有機溶剤の濃度を低くすることによって、繊維断面の長径／短径比が大きい単繊維が得られる。一方、第１凝固浴と第２凝固浴の有機溶剤の濃度を高くすることによって、繊維断面の長径／短径比が１．０に近い単繊維が得られる。 Further, by reducing the concentration of the organic solvent in the first coagulation bath and the second coagulation bath, a single fiber having a large major axis / minor axis ratio of the fiber cross section can be obtained. On the other hand, by increasing the concentration of the organic solvent in the first coagulation bath and the second coagulation bath, a single fiber having a major axis / minor axis ratio of the fiber cross section close to 1.0 can be obtained.
紡糸原液を押し出すための紡糸口金には、アクリロニトリル系重合体の単繊維の一般的な太さである、１．０デニール（１．１ｄＴｅｘ）程度のアクリロニトリル系重合体の単繊維を製造する際の孔径、すなわち１５〜１００μｍの孔径のノズル孔を有する紡糸口金を使用できる。
「凝固糸の引取り速度／ノズルからの紡糸原液の吐出線速度」は、０．８倍以下とされることにより、良好な紡糸性を維持することができる。
The spinneret for extruding the spinning dope is used for producing a single fiber of acrylonitrile polymer of about 1.0 denier (1.1 dTex), which is a general thickness of a single fiber of acrylonitrile polymer. A spinneret having a nozzle hole with a hole diameter of 15 to 100 μm can be used.
The “spinning speed of the coagulated yarn / discharge linear speed of the spinning dope from the nozzle” is 0.8 times or less, so that good spinnability can be maintained.
このような炭素繊維前駆体繊維束の製造方法においては、第１凝固浴から引き上げた凝固糸は、該凝固糸が含有する液体中の有機溶剤の濃度が、該第１凝固浴における有機溶剤の濃度を超えているので、凝固糸の表面だけが凝固した半凝固状態にある凝固糸になり、次工程の第２凝固浴中での延伸性が良好な凝固糸になる。 In such a carbon fiber precursor fiber bundle manufacturing method, the coagulated yarn pulled up from the first coagulation bath has a concentration of the organic solvent in the liquid contained in the coagulation yarn so that the organic solvent in the first coagulation bath contains Since the concentration is exceeded, only the surface of the coagulated yarn becomes a coagulated yarn in a semi-solidified state, and the coagulated yarn has good stretchability in the second coagulation bath in the next step.
また、第１凝固浴から引き出した凝固液を含んだままの膨潤状態にある凝固糸は、空気中で延伸することも可能であるが、この凝固糸を上記方法のように第２凝固浴中で延伸する手段を採ることにより、凝固糸の凝固を促進させることができ、また、延伸工程での温度制御も容易になる。 Further, the coagulated yarn in the swollen state containing the coagulation liquid drawn out from the first coagulation bath can be drawn in the air, but this coagulated yarn can be drawn in the second coagulation bath as in the above method. By adopting a means for stretching at, solidification of the coagulated yarn can be promoted, and temperature control in the stretching process is facilitated.
第２凝固浴中での延伸倍率は、１．２倍よりも低くすると、均一に配向した繊維が得られなくなり、２．５倍よりも高くすると、単繊維切れが発生し易くなり、紡糸安定性が低下し、しかもその後の湿熱延伸工程での延伸性が悪化する。 If the draw ratio in the second coagulation bath is lower than 1.2 times, uniformly oriented fibers cannot be obtained, and if it is higher than 2.5 times, single fiber breakage is likely to occur, and spinning stability is improved. And the stretchability in the subsequent wet heat stretching process deteriorates.
第２凝固浴中での延伸工程後の湿熱延伸は、繊維の配向をさらに高めるためのものである。この湿熱延伸は、第２凝固浴中での延伸を終えた膨潤状態にある膨潤繊維束を水洗に付しながらの延伸、あるいは熱水中での延伸によって行われる。中でも、高生産性の観点から、熱水中での延伸を行うのが好ましい。なお、この湿熱延伸工程での延伸倍率を３倍よりも低くすると、繊維の配向の向上が十分でなくなる。 The wet heat drawing after the drawing step in the second coagulation bath is for further enhancing the fiber orientation. This wet heat stretching is performed by stretching a swollen fiber bundle in a swollen state after stretching in the second coagulation bath, or by stretching in hot water. Among them, it is preferable to perform stretching in hot water from the viewpoint of high productivity. In addition, when the draw ratio in this wet heat drawing process is made lower than 3 times, the improvement of fiber orientation becomes insufficient.
また、湿熱延伸を施した後の乾燥前の膨潤繊維束の膨潤度を、７０重量％以下にすることが好ましい。
つまり、湿熱延伸を施した後の乾燥前の膨潤繊維束の膨潤度が７０重量％以下にある繊維は、表層部と繊維内部とが均一に配向していることを意味するものである。第１凝固浴中での凝固糸の製造の際の「凝固糸の引取り速度／ノズルからの紡糸原液の吐出線速度」を下げることによって、第１凝固浴中での凝固糸の凝固を均一なものにした後、これを第２凝固浴中にて延伸することにより、内部まで均一に配向することができる。これによって、湿熱延伸を施した後の乾燥前の膨潤繊維束の膨潤度を７０重量％以下とすることができる。
Moreover, it is preferable that the swelling degree of the swollen fiber bundle after drying after wet heat stretching is 70% by weight or less.
That is, the fiber in which the swelling degree of the swollen fiber bundle after drying after wet heat stretching is 70% by weight or less means that the surface layer portion and the inside of the fiber are uniformly oriented. The coagulation of the coagulated yarn in the first coagulation bath is made uniform by lowering the “coagulated yarn take-off speed / the discharge linear velocity of the spinning dope from the nozzle” during the production of the coagulated yarn in the first coagulation bath. Then, the film is stretched in the second coagulation bath so that it can be uniformly oriented to the inside. Thereby, the swelling degree of the swollen fiber bundle before drying after the wet heat stretching can be reduced to 70% by weight or less.
一方、第１凝固浴中での凝固糸の製造の際の「凝固糸の引取り速度／ノズルからの紡糸原液の吐出線速度」を高くすると、該第１凝固浴中での凝固糸の凝固と延伸とが同時に起こる。そのため、第１凝固浴中での凝固糸の凝固が不均一になる。従って、これを第２凝固浴中で延伸する工程を採っても、湿熱延伸を施した後の乾燥前の膨潤繊維束は膨潤度の高いものになってしまい、繊維内部まで均一に配向した繊維にはならない。 On the other hand, when the “coagulated yarn take-up speed / the discharge linear speed of the spinning dope from the nozzle” in the production of the coagulated yarn in the first coagulation bath is increased, the coagulation of the coagulated yarn in the first coagulation bath is increased. And stretching occur simultaneously. Therefore, the coagulation of the coagulated yarn in the first coagulation bath becomes non-uniform. Therefore, even if it takes the process of extending | stretching this in a 2nd coagulation bath, the swollen fiber bundle before drying after performing wet heat stretching will become a thing with a high degree of swelling, and the fiber orientated uniformly to the inside of a fiber It will not be.
乾燥前の膨潤状態にある繊維束の膨潤度は、膨潤状態にある繊維束の付着液を遠心分離機（３０００ｒｐｍ、１５分）によって除去した後の重量ｗと、これを１０５℃×２時間の熱風乾燥機で乾燥した後の重量ｗ0 とにより、膨潤度（重量％）＝（ｗ−ｗ0 ）×１００／ｗ0 によって求めた数値である。 The degree of swelling of the fiber bundle in the swollen state before drying is determined by the weight w after removing the adhering solution of the fiber bundle in the swollen state by a centrifuge (3000 rpm, 15 minutes), and this is 105 ° C. × 2 hours. It is a numerical value determined by the degree of swelling (% by weight) = (w−w 0 ) × 100 / w 0 based on the weight w 0 after drying with a hot air dryer.
湿熱延伸を行った後の繊維束に対する添油処理には、一般的なシリコン系油剤を用いることができる。 A general silicon-based oil agent can be used for the oil addition treatment to the fiber bundle after the wet heat drawing.
以下、本発明を実施例を示して詳しく説明する。
本実施例における各測定は、以下の方法によって行った。
（断面形状）
内径１ｍｍの塩化ビニル樹脂製のチューブ内に測定用のアクリロニトリル系重合体の繊維を通した後、これをナイフで輪切りにして試料を準備した。ついで、該試料をアクリロニトリル系重合体の繊維断面が上を向くようにしてＳＥＭ試料台に接着し、さらにＡｕを約１０ｎｍの厚さにスパッタリングしてから、ＰＨＩＬＩＰＳ社製ＸＬ２０走査型電子顕微鏡により、加速電圧７．００ｋＶ、作動距離３１ｍｍの条件で繊維断面を観察し、単繊維の繊維断面の長径および短径を測定し、長径÷短径で長径／短径の比率を求めた。
Hereinafter, the present invention will be described in detail with reference to examples.
Each measurement in this example was performed by the following method.
(Cross-sectional shape)
An acrylonitrile polymer fiber for measurement was passed through a tube made of vinyl chloride resin having an inner diameter of 1 mm, and this was cut into a ring with a knife to prepare a sample. Next, the sample was adhered to the SEM sample stage so that the fiber cross section of the acrylonitrile polymer was facing upward, and Au was sputtered to a thickness of about 10 nm, and then with a XL20 scanning electron microscope manufactured by PHILIPS, The cross section of the fiber was observed under the conditions of an acceleration voltage of 7.00 kV and a working distance of 31 mm, the major axis and minor axis of the fiber section of the single fiber were measured, and the ratio of major axis / minor axis was calculated as major axis / minor axis.
（Ｓｉ量）
まず、試料をテフロン（登録商標）製密閉容器にとり、硫酸、次いで硝酸で加熱酸分解した後、定容として、ＩＣＰ発光分析装置としてジャーレルアッシュ製ＩＲＩＳ−ＡＰを用いて測定した。
（単繊維強度）
単繊維自動引張強伸度測定機（オリエンテック ＵＴＭ II−２０）を使用し、台紙に貼られた単繊維をロードセルのチャックに装着し、毎分２０．０ｍｍの速度で引っ張り試験を行い強伸度を測定した。
(Si amount)
First, a sample was placed in a Teflon (registered trademark) sealed container, subjected to acid decomposition by heating with sulfuric acid and then with nitric acid, and then measured as a constant volume using IRIS-AP manufactured by Jarrel Ash as an ICP emission spectrometer.
(Single fiber strength)
Using a single fiber automatic tensile strength / elongation measuring machine (Orientec UTM II-20), the single fiber attached to the mount is attached to the load cell chuck, and a tensile test is performed at a speed of 20.0 mm / min. The degree was measured.
（交絡度）
乾燥状態にある炭素繊維前駆体の繊維束を用意し、垂下装置の上部に該繊維束を取り付け、上部つかみ部から下方１ｍにおもりを取り付けつり下げた。ここで用いるおもり荷重は、デニール数の１／５のグラム数とした。該繊維束の上部つかみから１ｃｍ下部の点に該繊維束を２分割するようにフックを挿入し、２ｃｍ／Ｓの速度でフックを下降させた。フックが該繊維束の絡みによって停止した点までのフックの下降距離Ｌ（ｍｍ）を求め、次式によって交絡度を算出した。尚、試験回数はＮ＝５０とし、その平均値の小数点１桁まで求めた。
交絡度＝１０００／Ｌ
ここで用いたフックは、直径が０．５ｍｍ〜１．０ｍｍの針状で、表面が滑らかに仕上げ処理をしたものである。
（皺形状）
乾燥状態にある炭素繊維前駆体の繊維束をスライドガラスに貼り付け、レーザーテック株式会社製のレーザー顕微鏡ＶＬ２０００を用い、繊維軸方向に対して垂直方向にＲａ、Ｒｙ、Ｓを測定した。
（水分率）
ウエット状態にある炭素繊維前駆体の繊維束の重量ｗと、これを１０５℃×２時間の熱風乾燥機で乾燥した後の重量ｗ0 とにより、水分率（重量％）＝（ｗ−ｗ0 ）×１００／ｗ0 によって測定した。
(Entanglement)
A carbon fiber precursor fiber bundle in a dry state was prepared, the fiber bundle was attached to the upper part of the drooping device, and a weight was attached and suspended 1 m below from the upper gripping part. The weight load used here was 1/5 of the denier number. A hook was inserted so as to divide the fiber bundle into two at a point 1 cm below the upper grip of the fiber bundle, and the hook was lowered at a speed of 2 cm / S. The lowering distance L (mm) of the hook to the point where the hook stopped due to the entanglement of the fiber bundle was obtained, and the degree of entanglement was calculated by the following equation. The number of tests was N = 50, and the average value was obtained up to one decimal place.
Degree of confounding = 1000 / L
The hook used here has a needle shape with a diameter of 0.5 mm to 1.0 mm and has a smooth finish on the surface.
(Shape shape)
The fiber bundle of the carbon fiber precursor in a dry state was attached to a slide glass, and Ra, Ry, and S were measured in a direction perpendicular to the fiber axis direction using a laser microscope VL2000 manufactured by Lasertec Corporation.
(Moisture percentage)
The water content (wt%) = (w−w 0 ), based on the weight w of the fiber bundle of the carbon fiber precursor in the wet state and the weight w 0 after drying this with a hot air dryer at 105 ° C. × 2 hours. ) × 100 / w 0 .
また、得られたアクリロニトリル系繊維束および炭素繊維束の評価方法は、以下の通りである。 Moreover, the evaluation method of the obtained acrylonitrile fiber bundle and carbon fiber bundle is as follows.
（樹脂含浸性）
炭素繊維束を約２０ｃｍ切り取り、グリシジルエーテル中に約３ｃｍ浸し１５分間放置した。グリシジルエーテル中から取り出した後３分間放置し、下から３．５ｃｍのところで切り落とし、残った炭素繊維束の長さ、重量を測定した。炭素繊維束の目付けから吸い上げたグリシジルエーテルの重量割合を算出し、樹脂含浸性の指標とした。
（開繊性）
炭素繊維束を０．０６ｇ／単繊維の張力下、走行速度１ｍ／分で金属ロール上を走行させた際のトウ幅を測定し開繊性の指標とした。
（炭素繊維のストランド強度）
ＪＩＳ−７６０１に準じて測定した。
(Resin impregnation)
The carbon fiber bundle was cut about 20 cm, immersed in about 3 cm in glycidyl ether, and left for 15 minutes. After taking out from glycidyl ether, it was allowed to stand for 3 minutes, cut off from the bottom at 3.5 cm, and the length and weight of the remaining carbon fiber bundle were measured. The weight ratio of glycidyl ether sucked up from the basis weight of the carbon fiber bundle was calculated and used as an index of resin impregnation property.
(Opening property)
The tow width when the carbon fiber bundle was run on a metal roll at a running speed of 1 m / min under a tension of 0.06 g / single fiber was used as an index of the spreadability.
(Strand strength of carbon fiber)
It measured according to JIS-7601.
［実施例１］
アクリロニトリル、アクリル酸メチルおよびメタクリル酸を、過硫酸アンモニウム−亜硫酸水素アンモニウムおよび硫酸鉄の存在下、水系懸濁重合により共重合し、アクリロニトリル単位／アクリル酸メチル単位／メタクリル酸単位＝９５／４／１（重量比）からなるアクリロニトリル系重合体を得た。このアクリロニトリル系重合体をジメチルアセトアミドに溶解し、２１重量％の紡糸原液を調製した。
[Example 1]
Acrylonitrile, methyl acrylate and methacrylic acid were copolymerized by aqueous suspension polymerization in the presence of ammonium persulfate-ammonium hydrogen sulfite and iron sulfate, and acrylonitrile unit / methyl acrylate unit / methacrylic acid unit = 95/4/1 ( An acrylonitrile-based polymer having a weight ratio) was obtained. This acrylonitrile-based polymer was dissolved in dimethylacetamide to prepare a 21% by weight spinning dope.
この紡糸原液を孔数３０００、孔径７５μｍの紡糸口金を通して、濃度６０重量％、温度３０℃のジメチルアセトアミド水溶液からなる第１凝固浴中に吐出させて凝固糸にし、第１凝固浴中からこの凝固糸を、紡糸原液の吐出線速度の０．８倍の引取り速度で引き取った。この凝固糸を引き続き濃度６０質量％、温度３０℃のジメチルアセトアミド水溶液からなる第２凝固浴に導き、浴中にて２．０倍に延伸した。 This spinning dope is passed through a spinneret having a pore number of 3000 and a pore diameter of 75 μm and discharged into a first coagulation bath made of an aqueous dimethylacetamide solution having a concentration of 60% by weight and a temperature of 30 ° C. to obtain a coagulated yarn. The yarn was taken up at a take-up speed of 0.8 times the discharge linear speed of the spinning dope. The coagulated yarn was subsequently introduced into a second coagulation bath composed of an aqueous dimethylacetamide solution having a concentration of 60% by mass and a temperature of 30 ° C., and stretched 2.0 times in the bath.
ついで、この繊維束に対して水洗と同時に４倍の延伸を行い、これに１．５重量％に調製したアミノシリコン系油剤を添油した。この繊維束を熱ロールを用いて乾燥し、スチーム延伸機にて２．０倍に延伸した。その後、タッチロールにて繊維束の水分率を調整し、この繊維束に繊維当たり５重量％の水分を含有させた。ついで、この繊維束を、エア圧４０５ｋＰａのエアによって、交絡処理し、ワインダーで巻き取ることにより、単繊維繊度１．１ｄｔｅｘのアクリロニトリル系繊維束を得た。 Next, the fiber bundle was stretched 4 times simultaneously with water washing, and an aminosilicone oil prepared to 1.5% by weight was added thereto. This fiber bundle was dried using a hot roll and stretched 2.0 times with a steam stretching machine. Thereafter, the moisture content of the fiber bundle was adjusted with a touch roll, and the fiber bundle contained 5% by weight of water per fiber. Subsequently, the fiber bundle was entangled with air having an air pressure of 405 kPa and wound with a winder to obtain an acrylonitrile fiber bundle having a single fiber fineness of 1.1 dtex.
得られたアクリロニトリル系繊維束について、断面形状、Ｓｉ量、単繊維強度、交絡度および皺形状を測定した。結果を表１に示す。
さらに、アクリロニトリル系繊維束を空気中２３０〜２６０℃の熱風循環式耐炎化炉にて５０分間処理し耐炎化繊維束となし、ついで耐炎繊維束を窒素雰囲気中下で最高温度７８０℃にて１．５分間処理し、さらに同雰囲気下で最高温度が１３００℃の高温熱処理炉にて約１．５分処理した後、重炭酸水素アンモニウム水溶液中で０．４Ａｍｉｎ／ｍで電解処理を施し、炭素繊維束を得た。この炭素繊維束の樹脂含浸性、開繊性およびストランド強度を評価した。結果を表２に示す。
About the obtained acrylonitrile fiber bundle, cross-sectional shape, Si amount, single fiber strength, entanglement degree, and wrinkle shape were measured. The results are shown in Table 1.
Further, the acrylonitrile fiber bundle was treated in a hot air circulation type flameproofing furnace at 230 to 260 ° C in air for 50 minutes to form a flameproofed fiber bundle, and then the flameproof fiber bundle was 1 at a maximum temperature of 780 ° C in a nitrogen atmosphere. After 5 minutes of treatment and further treatment in a high-temperature heat treatment furnace with a maximum temperature of 1300 ° C. for about 1.5 minutes in the same atmosphere, electrolytic treatment was performed at 0.4 Amin / m in an aqueous solution of ammonium bicarbonate to obtain carbon. A fiber bundle was obtained. The carbon fiber bundle was evaluated for resin impregnation property, fiber opening property and strand strength. The results are shown in Table 2.
［実施例２］
第１凝固浴および第２凝固浴のジメチルアセトアミド濃度を５０重量％に変更した以外は、実施例１と同様にして単繊維繊度１．１ｄｔｅｘのアクリロニトリル系繊維束を得た。
[Example 2]
An acrylonitrile fiber bundle having a single fiber fineness of 1.1 dtex was obtained in the same manner as in Example 1 except that the dimethylacetamide concentrations in the first coagulation bath and the second coagulation bath were changed to 50% by weight.
得られたアクリロニトリル系繊維束について、断面形状、Ｓｉ量、単繊維強度、交絡度および皺形状を測定した。結果を表１に示す。
さらに、このアクリロニトリル系繊維束を焼成して得られた炭素繊維束の樹脂含浸性、開繊性およびストランド強度を評価した。結果を表２に示す。
About the obtained acrylonitrile fiber bundle, cross-sectional shape, Si amount, single fiber strength, entanglement degree, and wrinkle shape were measured. The results are shown in Table 1.
Furthermore, the resin impregnation property, fiber opening property, and strand strength of the carbon fiber bundle obtained by firing this acrylonitrile fiber bundle were evaluated. The results are shown in Table 2.
［実施例３］
第１凝固浴および第２凝固浴のジメチルアセトアミド濃度を６５重量％に変更した以外は、実施例１と同様にして単繊維繊度１．１ｄｔｅｘのアクリロニトリル系繊維束を得た。
[Example 3]
An acrylonitrile fiber bundle having a single fiber fineness of 1.1 dtex was obtained in the same manner as in Example 1 except that the dimethylacetamide concentrations in the first coagulation bath and the second coagulation bath were changed to 65% by weight.
得られたアクリロニトリル系繊維束について、断面形状、Ｓｉ量、単繊維強度、交絡度および皺形状を測定した。結果を表１に示す。
さらに、このアクリロニトリル系繊維束を焼成して得られた炭素繊維束の樹脂含浸性、開繊性およびストランド強度を評価した。結果を表２に示す。
About the obtained acrylonitrile fiber bundle, cross-sectional shape, Si amount, single fiber strength, entanglement degree, and wrinkle shape were measured. The results are shown in Table 1.
Furthermore, the resin impregnation property, fiber opening property, and strand strength of the carbon fiber bundle obtained by firing this acrylonitrile fiber bundle were evaluated. The results are shown in Table 2.
［実施例４］
第２凝固浴中における延伸倍率を２．５倍に変更し、スチーム延伸機による延伸倍率を１．６倍に変更した以外は、実施例１と同様にして単繊維繊度１．１ｄｔｅｘのアクリロニトリル系繊維束を得た。
[Example 4]
An acrylonitrile system having a single fiber fineness of 1.1 dtex in the same manner as in Example 1 except that the draw ratio in the second coagulation bath was changed to 2.5 and the draw ratio of the steam drawing machine was changed to 1.6. A fiber bundle was obtained.
得られたアクリロニトリル系繊維束について、断面形状、Ｓｉ量、単繊維強度、交絡度および皺形状を測定した。結果を表１に示す。
さらに、このアクリロニトリル系繊維束を焼成して得られた炭素繊維束の樹脂含浸性、開繊性およびストランド強度を評価した。結果を表２に示す。
About the obtained acrylonitrile fiber bundle, cross-sectional shape, Si amount, single fiber strength, entanglement degree, and wrinkle shape were measured. The results are shown in Table 1.
Furthermore, the resin impregnation property, fiber opening property, and strand strength of the carbon fiber bundle obtained by firing this acrylonitrile fiber bundle were evaluated. The results are shown in Table 2.
［実施例５］
第２凝固浴中における延伸倍率を１．２倍に変更した以外は、実施例１と同様にして単繊維繊度１．１ｄｔｅｘのアクリロニトリル系繊維束を得た。
[Example 5]
An acrylonitrile fiber bundle having a single fiber fineness of 1.1 dtex was obtained in the same manner as in Example 1 except that the draw ratio in the second coagulation bath was changed to 1.2 times.
得られたアクリロニトリル系繊維束について、断面形状、Ｓｉ量、単繊維強度、交絡度および皺形状を測定した。結果を表１に示す。
さらに、このアクリロニトリル系繊維束を焼成して得られた炭素繊維束の樹脂含浸性、開繊性およびストランド強度を評価した。結果を表２に示す。
About the obtained acrylonitrile fiber bundle, cross-sectional shape, Si amount, single fiber strength, entanglement degree, and wrinkle shape were measured. The results are shown in Table 1.
Furthermore, the resin impregnation property, fiber opening property, and strand strength of the carbon fiber bundle obtained by firing this acrylonitrile fiber bundle were evaluated. The results are shown in Table 2.
［実施例６］
タッチロールにて調整される繊維束の水分率を１０重量％に変更した以外は、実施例１と同様にして単繊維繊度１．１ｄｔｅｘのアクリロニトリル系繊維束を得た。
[Example 6]
An acrylonitrile fiber bundle having a single fiber fineness of 1.1 dtex was obtained in the same manner as in Example 1 except that the moisture content of the fiber bundle adjusted by the touch roll was changed to 10% by weight.
得られたアクリロニトリル系繊維束について、断面形状、Ｓｉ量、単繊維強度、交絡度および皺形状を測定した。結果を表１に示す。
さらに、このアクリロニトリル系繊維束を焼成して得られた炭素繊維束の樹脂含浸性、開繊性およびストランド強度を評価した。結果を表２に示す。
About the obtained acrylonitrile fiber bundle, cross-sectional shape, Si amount, single fiber strength, entanglement degree, and wrinkle shape were measured. The results are shown in Table 1.
Furthermore, the resin impregnation property, fiber opening property, and strand strength of the carbon fiber bundle obtained by firing this acrylonitrile fiber bundle were evaluated. The results are shown in Table 2.
［実施例７］
タッチロールにて調整される繊維束の水分率を３重量％に変更した以外は、実施例１と同様にして単繊維繊度１．１ｄｔｅｘのアクリロニトリル系繊維束を得た。
[Example 7]
An acrylonitrile fiber bundle having a single fiber fineness of 1.1 dtex was obtained in the same manner as in Example 1 except that the moisture content of the fiber bundle adjusted by the touch roll was changed to 3% by weight.
得られたアクリロニトリル系繊維束について、断面形状、Ｓｉ量、単繊維強度、交絡度および皺形状を測定した。結果を表１に示す。
さらに、このアクリロニトリル系繊維束を焼成して得られた炭素繊維束の樹脂含浸性、開繊性およびストランド強度を評価した。結果を表２に示す。
About the obtained acrylonitrile fiber bundle, cross-sectional shape, Si amount, single fiber strength, entanglement degree, and wrinkle shape were measured. The results are shown in Table 1.
Furthermore, the resin impregnation property, fiber opening property, and strand strength of the carbon fiber bundle obtained by firing this acrylonitrile fiber bundle were evaluated. The results are shown in Table 2.
［実施例８］
繊維束に添油されるアミノシリコン系油剤の濃度を０．４重量％に変更した以外は、実施例１と同様にして単繊維繊度１．１ｄｔｅｘのアクリロニトリル系繊維束を得た。
[Example 8]
An acrylonitrile fiber bundle with a single fiber fineness of 1.1 dtex was obtained in the same manner as in Example 1 except that the concentration of the aminosilicone oil added to the fiber bundle was changed to 0.4% by weight.
得られたアクリロニトリル系繊維束について、断面形状、Ｓｉ量、単繊維強度、交絡度および皺形状を測定した。結果を表１に示す。
さらに、このアクリロニトリル系繊維束を焼成して得られた炭素繊維束の樹脂含浸性、開繊性およびストランド強度を評価した。結果を表２に示す。
About the obtained acrylonitrile fiber bundle, cross-sectional shape, Si amount, single fiber strength, entanglement degree, and wrinkle shape were measured. The results are shown in Table 1.
Furthermore, the resin impregnation property, fiber opening property, and strand strength of the carbon fiber bundle obtained by firing this acrylonitrile fiber bundle were evaluated. The results are shown in Table 2.
［実施例９］
交絡処理時のエア圧を２９０ｋＰａに変更した以外は、実施例１と同様にして単繊維繊度１．１ｄｔｅｘのアクリロニトリル系繊維束を得た。
[Example 9]
An acrylonitrile fiber bundle having a single fiber fineness of 1.1 dtex was obtained in the same manner as in Example 1 except that the air pressure during the entanglement treatment was changed to 290 kPa.
得られたアクリロニトリル系繊維束について、断面形状、Ｓｉ量、単繊維強度、交絡度および１皺形状を測定した。結果を表１に示す。
さらに、このアクリロニトリル系繊維束を焼成して得られた炭素繊維束の樹脂含浸性、開繊性およびストランド強度を評価した。結果を表２に示す。
About the obtained acrylonitrile-type fiber bundle, cross-sectional shape, Si amount, single fiber strength, entanglement degree, and 1-row shape were measured. The results are shown in Table 1.
Furthermore, the resin impregnation property, fiber opening property, and strand strength of the carbon fiber bundle obtained by firing this acrylonitrile fiber bundle were evaluated. The results are shown in Table 2.
［比較例１］
第１凝固浴および第２凝固浴のジメチルアセトアミド濃度を７０重量％に変更した以外は、実施例１と同様にして、単繊維の繊維断面の長径／短径比が１．０２、単繊維繊度１．１ｄｔｅｘのアクリロニトリル系繊維束を得た。
[Comparative Example 1]
Except for changing the dimethylacetamide concentration of the first coagulation bath and the second coagulation bath to 70% by weight, the major axis / minor axis ratio of the fiber cross section of the single fiber was 1.02, and the single fiber fineness was the same as in Example 1. An acrylonitrile fiber bundle of 1.1 dtex was obtained.
得られたアクリロニトリル系繊維束について、断面形状、Ｓｉ量、単繊維強度、交絡度および皺形状を測定した。結果を表１に示す。
さらに、このアクリロニトリル系繊維束を焼成して得られた炭素繊維束の樹脂含浸性、開繊性およびストランド強度を評価した。結果を表２に示す。
単繊維の繊維断面の長径／短径比が１．０５未満のアクリロニトリル系繊維束から得られた炭素繊維束は、樹脂含浸性および開繊性に劣っていた。
About the obtained acrylonitrile fiber bundle, cross-sectional shape, Si amount, single fiber strength, entanglement degree, and wrinkle shape were measured. The results are shown in Table 1.
Furthermore, the resin impregnation property, fiber opening property, and strand strength of the carbon fiber bundle obtained by firing this acrylonitrile fiber bundle were evaluated. The results are shown in Table 2.
A carbon fiber bundle obtained from an acrylonitrile fiber bundle having a major axis / minor axis ratio of a fiber cross section of a single fiber of less than 1.05 was inferior in resin impregnation property and fiber opening property.
［比較例２］
第１凝固浴および第２凝固浴のジメチルアセトアミド濃度を４０質量％に変更した以外は、実施例１と同様にして単繊維繊度１．１ｄｔｅｘのアクリロニトリル系繊維束を得た。
[Comparative Example 2]
An acrylonitrile fiber bundle having a single fiber fineness of 1.1 dtex was obtained in the same manner as in Example 1 except that the dimethylacetamide concentrations in the first coagulation bath and the second coagulation bath were changed to 40% by mass.
得られたアクリロニトリル系繊維束について、断面形状、Ｓｉ量、単繊維強度、交絡度および皺形状を測定した。結果を表１に示す。
さらに、このアクリロニトリル系繊維束を焼成して得られた炭素繊維束の樹脂含浸性、開繊性およびストランド強度を評価した。結果を表２に示す。
単繊維の繊維断面の長径／短径比が１．６を超えるアクリロニトリル系繊維束は集束性に劣り、これから得られた炭素繊維束は、ストランド強度が低かった。
About the obtained acrylonitrile fiber bundle, cross-sectional shape, Si amount, single fiber strength, entanglement degree, and wrinkle shape were measured. The results are shown in Table 1.
Furthermore, the resin impregnation property, fiber opening property, and strand strength of the carbon fiber bundle obtained by firing this acrylonitrile fiber bundle were evaluated. The results are shown in Table 2.
An acrylonitrile fiber bundle having a major axis / minor axis ratio of 1.6 or more in the cross section of a single fiber is inferior in converging property, and the carbon fiber bundle obtained therefrom has low strand strength.
［比較例３］
繊維束に添油されるアミノシリコン系油剤の濃度を０．２重量％に変更した以外は、実施例１と同様にして単繊維繊度１．１ｄｔｅｘのアクリロニトリル系繊維束を得た。
[Comparative Example 3]
An acrylonitrile fiber bundle having a single fiber fineness of 1.1 dtex was obtained in the same manner as in Example 1 except that the concentration of the aminosilicone oil added to the fiber bundle was changed to 0.2% by weight.
得られたアクリロニトリル系繊維束について、断面形状、Ｓｉ量、単繊維強度、交絡度および皺形状を測定した。結果を表１に示す。
さらに、このアクリロニトリル系繊維束を焼成して得られた炭素繊維束の樹脂含浸性、開繊性およびストランド強度を評価した。結果を表２に示す。
Ｓｉ量が５００ｐｐｍ未満のアクリロニトリル系繊維束は集束性に劣り、これから得られた炭素繊維束は、ストランド強度が低かった。
About the obtained acrylonitrile fiber bundle, cross-sectional shape, Si amount, single fiber strength, entanglement degree, and wrinkle shape were measured. The results are shown in Table 1.
Furthermore, the resin impregnation property, fiber opening property, and strand strength of the carbon fiber bundle obtained by firing this acrylonitrile fiber bundle were evaluated. The results are shown in Table 2.
An acrylonitrile fiber bundle having an Si content of less than 500 ppm is inferior in converging property, and a carbon fiber bundle obtained therefrom has low strand strength.
［比較例４］
繊維束に添油されるアミノシリコン系油剤の濃度を２．５重量％に変更した以外は、実施例１と同様にして単繊維繊度１．１ｄｔｅｘのアクリロニトリル系繊維束を得た。
[Comparative Example 4]
An acrylonitrile fiber bundle having a single fiber fineness of 1.1 dtex was obtained in the same manner as in Example 1 except that the concentration of the aminosilicone oil added to the fiber bundle was changed to 2.5% by weight.
得られたアクリロニトリル系繊維束について、断面形状、Ｓｉ量、単繊維強度、交絡度および皺形状を測定した。結果を表１に示す。
さらに、このアクリロニトリル系繊維束を焼成して得られた炭素繊維束の樹脂含浸性、開繊性およびストランド強度を評価した。結果を表２に示す。
Ｓｉ量が４０００ｐｐｍを超えるアクリロニトリル系繊維束から得られた炭素繊維束は、樹脂含浸性および開繊性に劣っていた。
About the obtained acrylonitrile fiber bundle, cross-sectional shape, Si amount, single fiber strength, entanglement degree, and wrinkle shape were measured. The results are shown in Table 1.
Furthermore, the resin impregnation property, fiber opening property, and strand strength of the carbon fiber bundle obtained by firing this acrylonitrile fiber bundle were evaluated. The results are shown in Table 2.
A carbon fiber bundle obtained from an acrylonitrile fiber bundle having an Si amount exceeding 4000 ppm was inferior in resin impregnation property and fiber opening property.
Claims (1)
この凝固糸に有機溶剤濃度５０〜６５重量％、温度３０〜５０℃の有機溶剤水溶液からなる第２凝固浴中にて１．２〜２．５倍の延伸を施す工程と、
第２凝固浴中での延伸を終えた膨潤状態にある繊維束に対して３倍以上の湿熱延伸を行う工程と、
この繊維束に対して０．４〜１．５重量％に調製したシリコン系油剤の添油処理を行う工程と、
この繊維束を乾燥した後に、この繊維束に１．６〜４倍のスチーム延伸を施す工程とを有することを特徴とする炭素繊維前駆体繊維束の製造方法。 A spinning solution comprising an organic solvent solution of an acrylonitrile-based polymer containing 95% by weight or more of an acrylonitrile unit is placed in a first coagulation bath comprising an organic solvent aqueous solution having an organic solvent concentration of 50 to 65% by weight and a temperature of 30 to 50 ° C. A step of discharging into a coagulated yarn and taking this coagulated yarn from the first coagulation bath at a take-off speed of 0.8 times or less of the discharge linear speed of the spinning dope;
A step of stretching the coagulated yarn 1.2 to 2.5 times in a second coagulation bath made of an organic solvent aqueous solution having an organic solvent concentration of 50 to 65% by weight and a temperature of 30 to 50 ° C;
A step of performing wet heat stretching three times or more on the fiber bundle in a swollen state after stretching in the second coagulation bath;
A step of performing an oil addition treatment of the silicon-based oil prepared to 0.4 to 1.5% by weight with respect to the fiber bundle;
A method of producing a carbon fiber precursor fiber bundle, comprising drying the fiber bundle and then subjecting the fiber bundle to 1.6 to 4 times steam drawing.
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