JP2011208315A - Method of producing carbon fiber - Google Patents
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- JP2011208315A JP2011208315A JP2010077075A JP2010077075A JP2011208315A JP 2011208315 A JP2011208315 A JP 2011208315A JP 2010077075 A JP2010077075 A JP 2010077075A JP 2010077075 A JP2010077075 A JP 2010077075A JP 2011208315 A JP2011208315 A JP 2011208315A
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- carbon fiber
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 72
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 72
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title abstract description 22
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000002759 woven fabric Substances 0.000 abstract description 16
- 239000004918 carbon fiber reinforced polymer Substances 0.000 abstract description 13
- 239000000835 fiber Substances 0.000 description 26
- 239000004744 fabric Substances 0.000 description 23
- 238000009941 weaving Methods 0.000 description 13
- 239000002243 precursor Substances 0.000 description 11
- 238000004804 winding Methods 0.000 description 10
- 239000002131 composite material Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 229920002239 polyacrylonitrile Polymers 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 3
- 239000001099 ammonium carbonate Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000009787 hand lay-up Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Landscapes
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
- Inorganic Fibers (AREA)
Abstract
Description
本発明は、炭素繊維の製造方法に関する。より詳しくは、炭素繊維をたて取り解舒して織物に供する際に、織物の目開き量のばらつきを低減し、得られる炭素繊維強化プラスチック（以下ＣＦＲＰ）の品質および品位を安定化させる炭素繊維の製造方法に関する。 The present invention relates to a method for producing carbon fiber. More specifically, when the carbon fiber is removed and used in a woven fabric, the variation in the opening amount of the woven fabric is reduced, and the quality and quality of the resulting carbon fiber reinforced plastic (hereinafter referred to as CFRP) is stabilized. The present invention relates to a fiber manufacturing method.
炭素繊維は比強度、比弾性率が高いことから、ＣＦＲＰとして軽量化効果の大きいスポーツ・レジャー用品をはじめ、航空機用途や一般産業用に多く使われている。 Since carbon fiber has high specific strength and high specific modulus, it is widely used as a CFRP for aircraft and general industries, including sports / leisure products with a large weight reduction effect.
かかるＣＦＲＰの成形方法としては、ハンドレイアップ成形をはじめとしてオートクレーブ成形、ＲＴＭ成形など種々の方法がある。これらの成形法においては、炭素繊維を中間基材の形態にして用いることが一般的であり、その中間基材としては織物の形態にしたものが多用されているが、かかる織物においては、取り扱う際に織糸がずれる目ズレや、目開き量のばらつきが発生しやすい。目開き量がばらつく原因としては製織条件のほかに織糸の糸幅不安定が挙げられる。特に織糸に撚りが混入すると、織糸が部分的に集束して糸幅が狭くなり得られるＣＦＲＰの外観品位が劣るばかりか、織物のクリンプが大きくなるため、炭素繊維本来の優れた力学的特性の発現を阻害するという問題があった。 Such CFRP molding methods include various methods such as hand lay-up molding, autoclave molding, and RTM molding. In these molding methods, it is common to use carbon fibers in the form of an intermediate substrate. As the intermediate substrate, those in the form of a woven fabric are often used. At this time, misalignment of the weaving yarn and variation in the amount of opening are likely to occur. In addition to weaving conditions, thread width instability of the weaving yarn can be cited as the cause of the variation in the amount of openings. In particular, when twists are mixed in the woven yarn, not only the appearance quality of CFRP, which can be obtained by converging the woven yarn partially and narrowing the yarn width, is deteriorated, but the crimp of the woven fabric is increased, so that the excellent mechanical properties of carbon fiber are obtained. There was a problem of inhibiting the expression of characteristics.
二方向織物においては、よこ糸を炭素繊維パッケージからたて取り解舒して製織に供することが多いため、織糸に解舒撚りが混入するのは避けられない。さらには、解舒撚りはパッケージの巻径によってその量が変化するため、織物の長手方向で目開き量が変化する一因となる。 In bi-directional woven fabrics, weft yarns are often unwound from a carbon fiber package and used for weaving. Therefore, it is inevitable that untwisting is mixed into the woven yarn. Furthermore, the amount of untwisting and twisting varies depending on the winding diameter of the package, which contributes to a change in the amount of openings in the longitudinal direction of the fabric.
かかる問題に対し、よこ糸貯留装置を用いてパッケージからよこ取り解舒してよこ糸に供する方法が提案されているが（例えば、特許文献１参照）、よこ糸はたて糸の１０倍以上の解舒速度で、かつ間欠的に供給されるため、たて糸と比べると撚りや折り畳まれなどが発生しやすい。また、かかる方法は扁平状の繊維束には有効であるものの、２４，０００フィラメント以下の細幅糸においては扁平状態の維持が難しく改善効果が小さいという問題がある。 In order to solve this problem, there has been proposed a method in which wefts are unwound from a package using a weft storage device and used for wefts (see, for example, Patent Document 1). In addition, since it is supplied intermittently, twisting and folding are likely to occur compared to warp yarn. Further, although this method is effective for flat fiber bundles, there is a problem that it is difficult to maintain a flat state for narrow yarns of 24,000 filaments or less, and the improvement effect is small.
また、同じく扁平状の無撚糸に関しては特許文献２に記載されているように、無撚りの状態で巻き上げられたパッケージの内層部から一旦糸条を引き出し、その際に発生する解舒撚りを残したまま再びパッケージ形態に巻き直すことで、たて取り解舒しても引き出した際に実質的に撚りのない状態で使用することが出来る。 As for flat untwisted yarn, as described in Patent Document 2, the yarn is once pulled out from the inner layer portion of the package wound up in a non-twisted state, leaving untwisted yarn generated at that time. By rewinding it into the package form as it is, it can be used in a substantially untwisted state when it is pulled out even if it is unwound.
一方、２４，０００フィラメント以下の細幅糸においては、有撚・解撚法で炭素繊維を製造することが代表的である。これは特許文献３に代表される加撚数制御装置を用いて、前駆体繊維糸条を解舒撚り数の変動にかかわらず所定の撚り数を一定に付与しながら耐炎化および炭化処理を施し、得られた有撚糸パッケージを解撚処理して実質的に無撚りの炭素繊維を得る方法である。無撚焼成に対して有撚焼成の優位な点は、特許文献４に代表されるように、加撚した前駆体糸条を合糸した状態で焼成できるため、コンパクトな設備で生産性を高められることである。また、糸条に付与した撚りを解くための解撚工程を有するため、特許文献５のように炭素繊維糸条に所望の撚り数を付与することも可能であるが、高次加工時に均一な拡幅性が求められるので、一般的には解撚糸の撚り数は０ターン／ｍとするものであった。 On the other hand, for narrow yarns of 24,000 filaments or less, it is typical to produce carbon fibers by a twisted / untwisted method. This is achieved by applying a flame resistance and carbonization treatment to a precursor fiber yarn while giving a predetermined number of twists constant regardless of fluctuations in the number of untwisted strands, using a twist number control device represented by Patent Document 3. The twisted yarn package thus obtained is untwisted to obtain a substantially untwisted carbon fiber. The advantage of twisted firing over untwisted firing is that, as typified by Patent Document 4, the twisted precursor yarn can be fired in a combined state, increasing productivity with compact equipment. Is to be. Moreover, since it has an untwisting step for unwinding the twist imparted to the yarn, it is possible to impart a desired number of twists to the carbon fiber yarn as in Patent Document 5, but it is uniform during high-order processing. Since the widening property is required, the number of twists of the untwisted yarn is generally set to 0 turns / m.
本発明は、かかる従来技術の背景に鑑み、有撚の炭素繊維を解撚処理する炭素繊維の製造方法において、ボビンに巻かれてなる炭素繊維パッケージからボビン軸方向にたて取り解舒して織物のよこ糸に供する際に、織物の目開き量のばらつきを低減し、得られるＣＦＲＰの品質および品位を安定化させる炭素繊維の製造方法を提供することを目的とする。 In view of the background of the prior art, the present invention is a method for producing a carbon fiber in which twisted carbon fiber is untwisted, and the carbon fiber package wound around the bobbin is vertically disassembled in the bobbin axial direction. An object of the present invention is to provide a carbon fiber production method that reduces variations in the amount of openings in a fabric and stabilizes the quality and quality of the resulting CFRP when used for wefts of fabric.
本発明は、有撚炭素繊維を解撚処理する炭素繊維の製造方法において、ボビンに巻かれてなるパッケージからボビン軸方向にたて取り解舒する際に発生する解舒撚りに相当する撚り数を、解撚処理時に解舒撚りと反対方向に糸条に付与することを特徴とする炭素繊維の製造方法である。 The present invention relates to a carbon fiber manufacturing method for untwisting a twisted carbon fiber, and the number of twists corresponding to the untwisting twist generated when the carbon fiber is unwound in a bobbin axial direction from a package wound around the bobbin. Is applied to the yarn in the direction opposite to the untwisting and twisting during the untwisting process.
本発明によれば、炭素繊維をたて取り解舒して織物に供する際に、解舒撚りの影響を低減させることにより目開き量のばらつきを抑制し、外観品位に優れた織物が得られるとともに、得られるＣＦＲＰの力学的特性を安定化させることができる。 According to the present invention, when the carbon fiber is freshly taken and unwound and used in a woven fabric, the variation in the amount of openings is suppressed by reducing the influence of untwisting, and a woven fabric excellent in appearance quality can be obtained. At the same time, the mechanical properties of the obtained CFRP can be stabilized.
以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明における炭素繊維の繊維形態は、撚り数をボビン長手方向に制御するため、糸条に撚りを付与した有撚糸を解撚処理で撚りを解いた解撚糸である。かかる有撚糸の撚り数は特に制限するものではないが、熱処理の均一性や走行安定性を考慮すると、２〜３０ターン／ｍの範囲とすることが好ましい。 The fiber form of the carbon fiber in the present invention is an untwisted yarn obtained by untwisting a twisted yarn with a twist applied to the yarn by an untwisting treatment in order to control the number of twists in the bobbin longitudinal direction. The number of twists of the twisted yarn is not particularly limited, but is preferably in the range of 2 to 30 turns / m in consideration of the uniformity of heat treatment and running stability.
フィラメント数の好ましい範囲は５００本〜２４，０００本であり、より好ましくは１，０００本〜１２，０００本であり、さらに好ましくは３，０００本〜６，０００本である。フィラメント数が５００本未満の場合は取り扱い性が悪い上に、生産能力の低下を招きコストアップをもたらす。また、フィラメント数が大きくなりすぎると有撚焼成時に糸条内が均等に熱処理できなくなることから、２４，０００本以下が好ましい。 The preferred range of the number of filaments is 500 to 24,000, more preferably 1,000 to 12,000, and still more preferably 3,000 to 6,000. When the number of filaments is less than 500, the handleability is poor, and the production capacity is reduced, resulting in an increase in cost. Further, if the number of filaments becomes too large, the inside of the yarn cannot be uniformly heat-treated at the time of twisted firing, so 24,000 or less are preferable.
前駆体繊維としては、ポリアクリロニトリル系繊維、レーヨン系繊維、ピッチ系繊維、あるいはポリビニルアルコール系繊維等を使用することができるが、なかでも、アクリルニトリル重合体あるいはその共重合体から得られるポリアクリロニトリル系繊維は、高い引張強度を発現する炭素繊維を得ることができるため、炭素繊維前駆体として好ましく用いることができる。 As the precursor fiber, polyacrylonitrile fiber, rayon fiber, pitch fiber, polyvinyl alcohol fiber, or the like can be used. Among them, polyacrylonitrile obtained from an acrylonitrile polymer or a copolymer thereof can be used. Since a system fiber can obtain carbon fiber which expresses high tensile strength, it can be preferably used as a carbon fiber precursor.
この前駆体繊維をボビンに巻上げ、ボビン軸を中心にかかるパッケージを回転させながら前駆体繊維をたて取り解舒することで、繊維長手方向に一定の撚り数を付与することができる。この有撚前駆体繊維を空気などの酸化性雰囲気中にて２００〜３００℃の温度範囲で耐炎化することで耐炎化繊維を製造し、窒素などの不活性雰囲気中で３００〜１０００℃の温度範囲で予備炭化した後に、窒素などの不活性雰囲気中で最高温度１０００〜２０００℃の温度範囲で炭化することで炭素繊維を得ることができる。その後、必要に応じて、窒素などの不活性雰囲気中で２０００℃以上で黒鉛化処理することもある。 The precursor fiber is wound on a bobbin, and the precursor fiber is taken and unwound while rotating the package around the bobbin axis, whereby a constant number of twists can be imparted in the fiber longitudinal direction. The twisted precursor fiber is flame-resistant in an oxidizing atmosphere such as air at a temperature range of 200 to 300 ° C. to produce a flame-resistant fiber, and a temperature of 300 to 1000 ° C. in an inert atmosphere such as nitrogen. Carbon fibers can be obtained by carbonizing at a maximum temperature of 1000 to 2000 ° C. in an inert atmosphere such as nitrogen after preliminary carbonization in the range. Thereafter, if necessary, graphitization may be performed at 2000 ° C. or higher in an inert atmosphere such as nitrogen.
熱処理後に施す表面処理は既知の薬液を用いる液相酸化、電解液溶液中で炭素繊維を陽極とする電解酸化を用いればよいが、比較的取り扱い性が良く、コスト的に優れた電解酸化処理方法が好ましく用いられる。電解液は酸性水溶液またはアルカリ水溶液いずれでもよいが、酸性水溶液は強酸を示す硫酸、硝酸が好ましく、アルカリ水溶液は炭酸アンモニウム、炭酸水素アンモニウム、重炭酸アンモニウムなどが好ましく用いられる。その後、炭素繊維にサイジング剤を付与する。ここでいうサイジング剤の種類は特に限定するものではないが、ビスフェノールＡ型エポキシ樹脂などのエポキシ樹脂を主成分とするものがよい。 The surface treatment to be applied after the heat treatment may be liquid phase oxidation using a known chemical solution, or electrolytic oxidation using carbon fiber as an anode in an electrolytic solution, but it is relatively easy to handle and is cost effective. Is preferably used. The electrolytic solution may be either an acidic aqueous solution or an alkaline aqueous solution, but the acidic aqueous solution is preferably sulfuric acid or nitric acid showing a strong acid, and the alkaline aqueous solution is preferably ammonium carbonate, ammonium bicarbonate, ammonium bicarbonate or the like. Thereafter, a sizing agent is applied to the carbon fiber. Although the kind of sizing agent here is not specifically limited, What has epoxy resins, such as a bisphenol A type epoxy resin, as a main component is good.
以上の方法により製造された炭素繊維を公知の巻き取り方法でボビンに巻き取ることにより、長手方向に一定の撚り数が付与された有撚炭素繊維パッケージを得ることができる。 By winding the carbon fiber manufactured by the above method onto a bobbin by a known winding method, a twisted carbon fiber package having a certain number of twists in the longitudinal direction can be obtained.
次いで、この有撚炭素繊維パッケージを、所定の回転数に制御可能なスピンドルからなるたて取り解舒用クリールと、走行糸に駆動を与えるドライブステーション（例えば、特許第３５６２１１５号公報、第１図、第２図参照）と、ワインダーとによって構成される解撚工程に投入し、撚りを解きながら公知の巻き取り方法でボビンに巻き取る。この際、解撚糸の撚り数は、次工程でたて取り解舒した際に発生する解舒撚りが相殺され、撚りのない状態となるよう制御する。すなわち、次工程でたて取り解舒した際にＳ撚りの解舒撚りが生じるならば、解撚糸に解舒撚りと同数のＺ撚りを予め付与して巻き上げ、炭素繊維パッケージとする。解舒撚り数は原料となる有撚炭素繊維パッケージの巻径に依存するので、解舒に伴う巻径の減少に応じて、回転数制御プログラムによって回転数を漸次減少させながら解撚処理すればよい。 Next, the twisted carbon fiber package is made up of a creasing creasing made up of a spindle that can be controlled at a predetermined rotational speed, and a drive station (for example, Japanese Patent No. 3562115, FIG. , See FIG. 2) and a winder, and is wound on a bobbin by a known winding method while untwisting. At this time, the number of twists of the untwisted yarn is controlled so that the untwisted yarn generated when the untwisted yarn is unwound and unwound in the next step is canceled and the untwisted state is obtained. That is, when untwisting of S twist occurs when it is unwound and unwound in the next process, the same number of Z twists as the untwisting twist are pre-applied to the untwisted yarn and wound up to obtain a carbon fiber package. Since the number of unwinding twists depends on the winding diameter of the twisted carbon fiber package that is the raw material, if the untwisting treatment is performed while gradually decreasing the number of rotations with the rotation speed control program according to the decrease in the winding diameter accompanying unwinding Good.
このように、予め解舒撚り相当の撚り数を解舒撚りの反対方向に付与することで、次工程でたて取り解舒しても解舒撚りが相殺され、撚りのない状態で使用できる。撚りのない状態とは、０ターン／ｍであることがもっとも好ましいが、±０．５ターン／ｍの範囲内のものであることが好ましい。 In this way, by previously applying the number of twists equivalent to the untwisting twist in the opposite direction of the untwisting, the untwisting is canceled even if it is freshly unwound in the next step, and it can be used in a state without twisting. . The untwisted state is most preferably 0 turns / m, but is preferably within a range of ± 0.5 turns / m.
かかる炭素繊維パッケージを少なくともよこ糸に用いて、公知の製織方法で炭素繊維織物とする。炭素繊維糸条を並行に引き揃え、たて糸が１〜８本／ｃｍの密度で一方向に配列してシート状の炭素繊維糸条群を形成し、それに直交する方向に、織機を用いて１〜８本／ｃｍの密度で炭素繊維糸条同士を交錯させ、織物の布帛とする。本発明の製造方法によって得られた炭素繊維を用いると、織物を構成する炭素繊維糸条には解舒撚りが混入しないため、織物上の糸幅が安定し、その結果、目開き量のばらつきも抑制できるため、外観品位に優れた織物を得られるとともに、得られるＣＦＲＰの力学的特性を安定化させることができる。 Such a carbon fiber package is used at least for the weft to form a carbon fiber fabric by a known weaving method. The carbon fiber yarns are aligned in parallel, and warp yarns are arranged in one direction at a density of 1 to 8 yarns / cm to form a sheet-like carbon fiber yarn group, and in a direction orthogonal to that, 1 using a loom Carbon fiber yarns are interlaced with each other at a density of ˜8 pieces / cm to form a woven fabric. When the carbon fiber obtained by the production method of the present invention is used, the carbon fiber yarn constituting the woven fabric is not mixed with the untwisted twist, so that the yarn width on the woven fabric is stabilized, and as a result, the amount of opening is uneven. Therefore, it is possible to obtain a woven fabric excellent in appearance quality and to stabilize the mechanical properties of the obtained CFRP.
以下、実施例を挙げて、本発明の内容をより具体的に説明する。 Hereinafter, the content of the present invention will be described more specifically with reference to examples.
実施例中の残撚り数は、織物中のよこ糸の両端をクリップで固定した状態で織物から取り出し、その撚り数を実測して１ｍ長当りに換算した値で示す（織物長手方向１０ｍおきに３点測定し、各ｎ＝５の平均値を求め、その最大値を表中に示す）。 The number of remaining twists in the examples is taken out from the fabric in a state where both ends of the weft yarn in the fabric are fixed with clips, and the number of twists is measured and shown as a value converted per 1 m length (3 for every 10 m in the longitudinal direction of the fabric). Point measurement was performed to obtain an average value of n = 5, and the maximum value is shown in the table).
実施例中の開口率は、炭素繊維織物を平面で見た際の炭素繊維糸条が存在しない空隙部の面積と検査面積との除の百分率で示す。実際の測定では、１５ｃｍ×１５ｃｍの正方形（検査面積２２５ｃｍ2）を幅方向に均等間隔に５枚切り取り、切り取ったものの空隙部の面積を光学顕微鏡でそれぞれ読みとり算出する（ｎ＝５の平均値）。 The opening ratio in an Example is shown by the percentage of the division | segmentation of the area of the space | gap part in which a carbon fiber yarn does not exist when a carbon fiber fabric is seen on a plane, and a test | inspection area. In actual measurement, 5 squares of 15 cm × 15 cm (inspection area 225 cm 2 ) were cut out at equal intervals in the width direction, and the area of the voids was read and calculated with an optical microscope (average value of n = 5). .
実施例中のコンポジット引張強度は、次の方法で測定した。炭素繊維織物に樹脂を含浸させ、炭素繊維目付け１９６ｇ／ｍ2、樹脂重量分率４０％のプリプレグ基材を作製し、２５０×２５０ｍｍの大きさに切り出し、１４枚を積層して平板状積層体を得た。得られたＣＦＲＰ平板より、よこ糸方向に長さ２５０±１ｍｍ、幅２５±０．２ｍｍの引張強度試験片を切り出した。次いでＪＩＳ Ｋ７０７３（１９９８）に規定する試験方法に従い、標点間距離を１５０ｍｍとし、クロスヘッド速度２．０ｍｍ／分でよこ糸方向の引張強度を測定した。測定した試験片の数はｎ＝５とし、平均値を引張強度とした。 The composite tensile strength in the examples was measured by the following method. Carbon fiber fabric is impregnated with resin, a prepreg base material having a carbon fiber basis weight of 196 g / m 2 and a resin weight fraction of 40% is prepared, cut into a size of 250 × 250 mm, and 14 plates are laminated to form a flat laminate Got. A tensile strength test piece having a length of 250 ± 1 mm and a width of 25 ± 0.2 mm was cut out from the obtained CFRP flat plate in the weft direction. Subsequently, according to the test method specified in JIS K7073 (1998), the tensile strength in the weft direction was measured at a crosshead speed of 2.0 mm / min with a distance between the gauge points of 150 mm. The number of test pieces measured was n = 5, and the average value was the tensile strength.
（実施例１）
アクリロニトリル９９．５モル％とメタクリル酸０．５モル％からなる共重合体を用いて、湿式紡糸方法により単糸繊度１．１１ｄｔｅｘ、フィラメント数３０００本、無撚りのＰＡＮ系前駆体繊維パッケージを得た。
得られた前駆体繊維パッケージを回転式クリールに仕掛け１５ターン／ｍの撚りをかけながらたて取り解舒し、２３０〜２６０℃の空気中で加熱し有撚耐炎化繊維とした。次いで耐炎化繊維を３００〜８００℃の不活性雰囲気中で予備炭化して後、１０００〜１５００℃の不活性雰囲気中で炭化した。次いで水溶液中で電解表面処理を行い、サイジング剤を付与し乾燥してからワインダーで巻き取り、繊度２００ｔｅｘ、撚り数が１５ターン／ｍの一定の有撚炭素繊維パッケージを得た。
次いで、得られた有撚炭素繊維パッケージをたて取り解舒用回転式クリールに仕掛け、撚りを解きながらワインダーで巻き取り、巻密度１．０ｇ／ｃｍ3、巻量２．０ｋｇの解撚炭素繊維パッケージを得た。この時のクリール回転数は、製織時の仕掛けに応じて次のように調整した。
Example 1
Using a copolymer composed of 99.5 mol% acrylonitrile and 0.5 mol% methacrylic acid, a wet spinning method yields a PAN precursor fiber package with a single yarn fineness of 1.11 dtex, a filament count of 3000, and an untwisted PAN system. It was.
The obtained precursor fiber package was placed on a rotary creel and unraveled while applying a twist of 15 turns / m, and heated in air at 230 to 260 ° C. to obtain a twisted flame resistant fiber. The flameproofed fiber was then pre-carbonized in an inert atmosphere at 300 to 800 ° C. and then carbonized in an inert atmosphere at 1000 to 1500 ° C. Next, electrolytic surface treatment was performed in an aqueous solution, a sizing agent was applied and dried, and then wound with a winder to obtain a constant twisted carbon fiber package having a fineness of 200 tex and a twist number of 15 turns / m.
Next, the obtained twisted carbon fiber package is taken up and placed on a rotating creel for unwinding and wound up with a winder while untwisting, and the untwisted carbon having a winding density of 1.0 g / cm 3 and a winding amount of 2.0 kg. A fiber package was obtained. The creel rotation speed at this time was adjusted as follows according to the mechanism at the time of weaving.
たて糸用炭素繊維：製織時には解撚糸パッケージをよこ取り解舒する（解舒撚りが入らない）ため、有撚糸の元撚り数を解くのに必要な回転数から、巻径の減少に伴い漸次増加する解舒撚り分を引いた回転数Ｒ１で解撚処理した。 Carbon fiber for warp: Weaving and unwinding the untwisted yarn package at the time of weaving (no untwisting), so gradually increase as the winding diameter decreases from the number of rotations required to unwind the number of twisted yarn The untwisting process was carried out at the rotational speed R1 minus the untwisting twist.
回転数Ｒ１（ｒｐｍ）＝（Ｔ０−Ｔ１）×Ｖ
Ｔ０； 有撚炭素繊維の元撚り数（Ｔ／ｍ）
Ｔ１； 有撚炭素繊維をたて取り解舒した際に発生する解舒撚り数（Ｔ／ｍ）
Ｖ ； 解撚処理の引き取り速度（ｍ／分）
よこ糸用炭素繊維：製織時には解撚糸パッケージをたて取り解舒する（解舒撚りが入る）ため、有撚糸の元撚り数を解くのに必要な回転数に加えて、巻き上げて得られる解撚炭素繊維パッケージをたて取り解舒する際に発生する解舒撚りと同数の撚りを反対方向に付与するよう回転数を調整した。すなわち、解撚糸の最内層部はＺ撚り方向に３．７ターン／ｍ、最外層部はＺ撚り方向に２．１ターン／ｍとし、その間は撚り数が漸次減少するよう、長手方向に回転数Ｒ２を漸次減少させながら解撚処理した。
Number of rotations R1 (rpm) = (T0−T1) × V
T0: Number of original twists of twisted carbon fiber (T / m)
T1; Number of untwisting twists (T / m) that occurs when twisted carbon fiber is freshly unwound
V: Take-off speed of untwisting process (m / min)
Weft carbon fiber: Since the untwisted yarn package is unwound and unwound (weaving untwisted) during weaving, in addition to the number of rotations necessary to unwind the number of original twists of twisted yarn, untwisting obtained by winding The rotational speed was adjusted so that the same number of twists as the untwisting twists generated when the carbon fiber package was straightened and unwound were applied in the opposite direction. That is, the innermost layer portion of the untwisted yarn is 3.7 turns / m in the Z twist direction, the outermost layer portion is 2.1 turns / m in the Z twist direction, and during that time, the number of twists is rotated so as to gradually decrease Untwisting was performed while gradually decreasing the number R2.
回転数Ｒ２（ｒｐｍ）＝（Ｔ０−Ｔ１＋Ｔ2）×Ｖ
Ｔ０； 有撚炭素繊維の元撚り数（Ｔ／ｍ）
Ｔ１； 有撚炭素繊維をたて取り解舒した際に発生する解舒撚り数（Ｔ／ｍ）
Ｔ２； 解撚炭素繊維をたて取り解舒した際に発生する解舒撚り数（Ｔ／ｍ）
Ｖ ； 解撚処理の引き取り速度（ｍ／分）
得られた解撚炭素繊維パッケージをたて糸にはよこ取り解舒用クリール、よこ糸にはたて取り解舒用クリールに仕掛け、よこ糸をたて糸と交錯させてレピア織機で織成し、炭素繊維目付け１９６ｇ／ｍ2の平組織の二方向織物を得た。この織物のよこ糸はたて取り解舒した際の解舒撚りが相殺されるため、残撚り数は最大−０．２ターン／ｍ、開口率は５．６％であり、織物の外観品位も良好であった。次いで、プリプレグ基材を作製・積層し、コンポジット強度を測定した結果、５９０ＭＰａであった。
Number of revolutions R2 (rpm) = (T0−T1 + T2) × V
T0: Number of original twists of twisted carbon fiber (T / m)
T1; Number of untwisting twists (T / m) that occurs when twisted carbon fiber is freshly unwound
T2: Number of untwisting twists (T / m) generated when untwisting and unwinding the untwisted carbon fiber
V: Take-off speed of untwisting process (m / min)
The obtained untwisted carbon fiber package is subjected to a weft and unwinding creel on the warp, and a weft and unwinding creel on the weft. Two plain fabrics with two plain textures were obtained. The weft of this woven fabric cancels the untwisting when it is unwound, so the maximum number of remaining twists is -0.2 turns / m, the open area ratio is 5.6%, and the appearance quality of the woven fabric is also good It was good. Next, a prepreg base material was prepared and laminated, and the composite strength was measured and found to be 590 MPa.
（実施例２）
前駆体繊維の単糸繊度を０．８３ｄｔｅｘ、フィラメント数を６０００本、炭素繊維の繊度を２２５ｔｅｘにした以外は実施例１と同じ方法で炭素繊維織物を得た。よこ糸の残撚り数は最大＋０．１ターン／ｍ、開口率は６．０％であり、織物の外観品位も良好であった。コンポジット強度は８５３ＭＰａであった。
(Example 2)
A carbon fiber fabric was obtained in the same manner as in Example 1 except that the single fiber fineness of the precursor fiber was 0.83 dtex, the number of filaments was 6000, and the fineness of the carbon fiber was 225 tex. The maximum number of twists of the weft yarn was +0.1 turns / m, the opening ratio was 6.0%, and the appearance quality of the fabric was also good. The composite strength was 853 MPa.
（実施例３）
前駆体繊維の単糸繊度を０．８３ｄｔｅｘ、フィラメント数を１２０００本、炭素繊維の繊度を４５０ｔｅｘにした以外は実施例１と同じ方法で炭素繊維織物を得た。よこ糸の残撚り数は最大−０．１ターン／ｍ、開口率は５．８％であり、織物の外観品位も良好であった。コンポジット強度は８５０ＭＰａと実施例２と同等であった。
(Example 3)
A carbon fiber fabric was obtained in the same manner as in Example 1 except that the single fiber fineness of the precursor fiber was 0.83 dtex, the number of filaments was 12,000, and the fineness of the carbon fiber was 450 tex. The number of remaining twists of the weft yarn was −0.1 turns / m at the maximum, the opening ratio was 5.8%, and the appearance quality of the fabric was also good. The composite strength was 850 MPa, which was equivalent to Example 2.
（比較例１）
解撚炭素繊維パッケージ中の撚り数を０．０ターン／ｍと一定にした以外は、実施例１と同じ方法で炭素繊維織物を得た。よこ糸の残撚り数はたて取り解舒した際に解舒撚りが発生するため最大＋３．４ターン／ｍとなった。その影響で局所的に織糸が集束するため、本発明によって得られた織物に対して外観品位は劣るものであり、織物の開口率は７．８％と増加した。コンポジット引張強度はＣＦＲＰの繊維含有率にバラツキが生じるため５７５ＭＰａと若干低下した。
(Comparative Example 1)
A carbon fiber fabric was obtained in the same manner as in Example 1 except that the number of twists in the untwisted carbon fiber package was kept constant at 0.0 turns / m. The number of remaining twists of the weft yarn was +3.4 turns / m at maximum because unwinding and twisting occurred when freshly unwinding and unwinding. Due to the influence, the weaving yarns locally converged, so the appearance quality was inferior to the fabric obtained by the present invention, and the opening ratio of the fabric increased to 7.8%. The composite tensile strength slightly decreased to 575 MPa due to variations in the fiber content of CFRP.
（比較例２）
解撚炭素繊維パッケージ中の撚り数を０．０ターン／ｍと一定にした以外は、実施例２と同じ方法で炭素繊維織物を得た。よこ糸の残撚り数はたて取り解舒した際に解舒撚りが発生するため最大＋３．５ターン／ｍとなった。その影響で局所的に織糸が集束するため、本発明によって得られた織物に対して外観品位は劣るものであり、織物の開口率は８．２％と増加した。コンポジット引張強度はＣＦＲＰの繊維含有率にバラツキが生じるため８２７ＭＰａと若干低下した。
(Comparative Example 2)
A carbon fiber fabric was obtained in the same manner as in Example 2 except that the number of twists in the untwisted carbon fiber package was kept constant at 0.0 turns / m. The number of remaining twists of the weft yarn was +3.5 turns / m at maximum because unwinding and twisting occurred when the unwinding and unwinding. As a result, the weaving yarns locally converged, so that the appearance quality was inferior to the fabric obtained by the present invention, and the opening ratio of the fabric increased to 8.2%. The composite tensile strength slightly decreased to 827 MPa due to variations in the fiber content of CFRP.
（比較例３）
解撚炭素繊維パッケージ中の撚り数を０．０ターン／ｍと一定にした以外は、実施例３と同じ方法で炭素繊維織物を得た。よこ糸の残撚り数はたて取り解舒した際に解舒撚りが発生するため最大＋３．７ターン／ｍとなった。その影響で局所的に織糸が集束するため、本発明によって得られた織物に対して外観品位は劣り、織物の開口率は８．１％と増加した。また、コンポジット引張強度は８２１ＭＰａと若干低下した。
(Comparative Example 3)
A carbon fiber fabric was obtained in the same manner as in Example 3 except that the number of twists in the untwisted carbon fiber package was kept constant at 0.0 turns / m. The number of remaining twists of the weft yarn was +3.7 turns / m at the maximum because unwinding and twisting occurred when freshly unwinding and unwinding. Due to the influence, the weaving yarns locally converged, so the appearance quality was inferior to the fabric obtained by the present invention, and the opening ratio of the fabric increased to 8.1%. The composite tensile strength slightly decreased to 821 MPa.
実施例１〜実施例３、比較例１〜比較例３の結果を表１に示す。 Table 1 shows the results of Examples 1 to 3 and Comparative Examples 1 to 3.
本発明にかかる炭素繊維の製造方法を用いることにより、炭素繊維をたて取り解舒して織物のよこ糸に供する際に、目開き量のばらつきを低減し、得られるＣＦＲＰの品質・品位を安定化させることができる。 By using the carbon fiber manufacturing method according to the present invention, when the carbon fiber is freshly chopped and used for wefts of a woven fabric, variation in the amount of openings is reduced, and the quality and quality of the obtained CFRP are stabilized. It can be made.
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| JP2015067910A (en) * | 2013-09-27 | 2015-04-13 | 東レ株式会社 | Carbon fiber and method for producing the same |
| JP2022113763A (en) * | 2018-07-05 | 2022-08-04 | 三菱ケミカル株式会社 | Manufacturing method of carbon fiber bundle |
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| JP2015067910A (en) * | 2013-09-27 | 2015-04-13 | 東レ株式会社 | Carbon fiber and method for producing the same |
| JP2022113763A (en) * | 2018-07-05 | 2022-08-04 | 三菱ケミカル株式会社 | Manufacturing method of carbon fiber bundle |
| JP2024174024A (en) * | 2018-07-05 | 2024-12-13 | 三菱ケミカル株式会社 | Manufacturing method of carbon fiber bundle and manufacturing method of SMC |
| JP7798147B2 (en) | 2018-07-05 | 2026-01-14 | 三菱ケミカル株式会社 | Carbon fiber bundle manufacturing method and SMC manufacturing method |
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