JP5100867B2 - Method for producing carbon fiber bundle for filament winding - Google Patents
Method for producing carbon fiber bundle for filament winding Download PDFInfo
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Description
本発明は、フィラメントワインディング（ＦＷ）用炭素繊維束の製造方法に関し、さらに詳述すれば、特にマンドレルに巻く際にマンドレル面に十分密着して拡がり、製造する複合材料の強度に繊維強度を反映できる、炭素繊維の強度寄与率の高い複合材料の製造に適したＦＷ用炭素繊維束の製造方法に関する。 The present invention relates to a method of manufacturing a filament winding (FW) carbon fiber bundle, and more specifically, particularly when wound on a mandrel, the carbon fiber bundle spreads in close contact with the mandrel surface and reflects the fiber strength in the strength of the composite material to be manufactured. The present invention relates to a method for producing a carbon fiber bundle for FW suitable for producing a composite material having a high strength contribution ratio of carbon fibers.
炭素繊維は他の繊維と比較し、強度や弾性率が高く、軽いという特徴を有するため、航空宇宙産業を始めとし、各種の産業に利用されている。これらの用途の中で、例えば天然ガス自動車等の燃料用ボンベは軽量、高強度を要求されるものであり、従来炭素繊維を補強材とするＦＷ法により製造されている。 Carbon fiber has high strength, elastic modulus and lightness compared to other fibers, so it is used in various industries including the aerospace industry. Among these uses, fuel cylinders such as natural gas automobiles are required to be lightweight and have high strength, and are conventionally manufactured by the FW method using carbon fiber as a reinforcing material.
ＦＷ法に用いられる炭素繊維束は、ＦＷ成形されて製品になるものである。従って、生産工程における取り扱い要求性能を炭素繊維束が満たしていることも重要であり、具体的には耐毛羽性、耐擦過性、耐糸切れ性等が要求性能として例示される。 The carbon fiber bundle used in the FW method is a product obtained by FW molding. Therefore, it is also important that the carbon fiber bundle satisfies the required handling performance in the production process. Specifically, the required performance is exemplified by fuzz resistance, scratch resistance, thread breakage resistance, and the like.
従来、炭素繊維束にこれらの要求性能を付与させるため、炭素繊維束にサイズ剤を添加する方法が提案されている（特開昭６２−２９９５８０号公報、特公平１−４６６３６号公報、特公昭５７−４９６７５号公報）。しかし、ＦＷ法においては、その生産工程において各種固定ガイドやローラーとの擦過の問題等があり、上記のサイズ剤の添加のみで、発生する問題の全てを克服することは困難である。 Conventionally, methods for adding a sizing agent to a carbon fiber bundle have been proposed in order to impart these required performances to the carbon fiber bundle (Japanese Patent Laid-Open No. 62-299580, Japanese Patent Publication No. 1-446636, Japanese Patent Publication No. Sho). 57-49675). However, in the FW method, there are problems such as rubbing with various fixed guides and rollers in the production process, and it is difficult to overcome all the problems that occur only by adding the sizing agent.
特許第３０４７７３１号公報には、ストランド引張強度が４００ｋｇｆ／ｍｍ２、糸切れ限界張力０．２ｇ／Ｄ以上、引掛強度１００ｋｇｆ／ｍｍ２以上のＦＷ成形用炭素繊維が記載されている。この炭素繊維はＦＷ成形に際し、毛羽立ち、糸切れが少なく、繊維性能を複合材の特性に反映できるものであると記載されている。また、特開平８−１５８１６３号公報には、合糸されてなり、かつ糸割れ率４０％以下である実質的に無撚の炭素繊維束が記載され、この繊維束はＦＷ成形において成形コストが削減でき、ハンドリング性、樹脂含浸性が向上された炭素繊維束であることも記載されている。 Japanese Patent No. 3047731 describes carbon fiber for FW molding having a strand tensile strength of 400 kgf / mm 2 , a thread breakage limit tension of 0.2 g / D or more, and a hook strength of 100 kgf / mm 2 or more. This carbon fiber is described as having less fuzz and yarn breakage during FW molding, and can reflect the fiber performance in the characteristics of the composite material. Japanese Patent Application Laid-Open No. 8-158163 describes a substantially untwisted carbon fiber bundle that is made of yarns and has a yarn cracking rate of 40% or less, and this fiber bundle has a molding cost in FW molding. It is also described that the carbon fiber bundle can be reduced and has improved handling properties and resin impregnation properties.
一方、特開平９−２１７２８１号公報には熱硬化性樹脂と硬化剤とを主成分とするサイズ剤を０．５〜５質量％含浸させた剛軟度が２０〜１００ｍｍのチョップドストランド用炭素繊維束が記載されている。しかし、このものは押し出し成形用の炭素繊維束であり、ＦＷ成形用のものではない。 On the other hand, JP-A-9-217281 discloses carbon fibers for chopped strands having a bending resistance of 20 to 100 mm impregnated with 0.5 to 5% by mass of a sizing agent mainly composed of a thermosetting resin and a curing agent. A bundle is listed. However, this is a carbon fiber bundle for extrusion molding, not for FW molding.
また、特開平７−３１４４４３号公報には形態安定化剤が０．５〜１０質量％添加され、剛軟度が２０〜１５０ｍｍの炭素繊維織物が開示されている。そして、剛軟度が小さい場合、織物が剛直で織物のドレープ性が低下することが記載されている。しかし、このものもＦＷ成形用の炭素繊維束ではない。 Japanese Patent Application Laid-Open No. 7-314443 discloses a carbon fiber woven fabric added with 0.5 to 10% by mass of a shape stabilizer and having a bending resistance of 20 to 150 mm. It is described that when the bending resistance is small, the fabric is rigid and the drapeability of the fabric is reduced. However, this is not a carbon fiber bundle for FW molding.
即ち、上記従来の公報中には、ＦＷ成形に適した形状、組成等を総合的に検討した炭素繊維束に関する記載はない。 That is, in the above-mentioned conventional publications, there is no description regarding the carbon fiber bundle that comprehensively studied the shape, composition, etc. suitable for FW molding.
本発明者等は、ＦＷに適した炭素繊維束を開発することを目的として種々検討しているうちに、炭素繊維束の断面形状とドレープ値の両要素が、ＦＷに適する特性を炭素繊維束に与える際の決定的に重要な要素になっていることを知得した。本発明は上記発見に基づき完成するに至ったもので、その目的とするところは、上記問題を解決するＦＷ用炭素繊維束を提供することにある。 While the present inventors have made various studies for the purpose of developing a carbon fiber bundle suitable for FW, both elements of the cross-sectional shape and the drape value of the carbon fiber bundle have characteristics suitable for FW. I learned that it has become a crucial factor in giving. The present invention has been completed based on the above discovery, and an object of the present invention is to provide a carbon fiber bundle for FW that solves the above problems.
上記目的を達成する本発明は、以下に記載のものである。 The present invention for achieving the above object is as follows.
〔１〕 未サイジングの炭素繊維束を連続的にサイジング浴に浸漬することにより前記炭素繊維束にサイズ剤を含浸させ、次いで前記サイズ剤を含浸させた炭素繊維束を表面温度１２０〜１４０℃のヒートローラーに１５〜３０秒間接触させることを特徴とする、断面形状が偏平な炭素繊維束であって、炭素繊維束断面の偏平率（幅／厚さ）が４０〜９０、ドレープ値が５０〜１００ｍｍで、かつ実質的に撚りがないサイジング処理済フィラメントワインディング用炭素繊維束の製造方法。 [1] The carbon fiber bundle is impregnated with a sizing agent by continuously immersing an unsized carbon fiber bundle in a sizing bath, and then the carbon fiber bundle impregnated with the sizing agent has a surface temperature of 120 to 140 ° C. A carbon fiber bundle having a flat cross-sectional shape, which is brought into contact with a heat roller for 15 to 30 seconds, and a flatness (width / thickness) of the cross section of the carbon fiber bundle is 40 to 90, and a drape value is 50 to 50 A method for producing a carbon fiber bundle for sizing-treated filament winding that is 100 mm and substantially free of twist.
〔２〕 サイズ剤の含浸量が０．１〜１０質量％である〔１〕に記載のサイジング処理済フィラメントワインディング用炭素繊維束の製造方法。 [2] The method for producing a carbon fiber bundle for sizing-treated filament winding according to [1], wherein the impregnation amount of the sizing agent is 0.1 to 10% by mass.
〔３〕 炭素繊維束を構成する単繊維数が１０００〜１０００００本である〔１〕に記載のサイジング処理済フィラメントワインディング用炭素繊維束の製造方法。 [3] The method for producing a carbon fiber bundle for sizing-treated filament winding according to [1], wherein the number of single fibers constituting the carbon fiber bundle is 1000 to 100,000.
〔４〕 炭素繊維束を構成する単繊維の繊度が０．８ｄｔｅｘ以下である 〔１〕に記載のサイジング処理済フィラメントワインディング用炭素繊維束の製造方法。 [4] The method for producing a carbon fiber bundle for sizing-treated filament winding according to [1], wherein the fineness of the single fiber constituting the carbon fiber bundle is 0.8 dtex or less.
〔５〕 〔１〕に記載の製造方法で製造したサイジング処理済フィラメントワインディング用炭素繊維束に熱硬化性樹脂を１５〜４５質量％含浸させることを特徴とする熱硬化性樹脂含浸フィラメントワインディング用炭素繊維束の製造方法。 [5] Carbon fiber for thermosetting resin impregnation filament winding, wherein carbon fiber bundle for sizing filament winding manufactured by the manufacturing method according to [1] is impregnated with 15 to 45 mass% of thermosetting resin. A method of manufacturing a fiber bundle.
〔６〕 熱硬化性樹脂がエポキシ樹脂である〔５〕に記載の熱硬化性樹脂含浸フィラメントワインディング用炭素繊維束の製造方法。 [6] The method for producing a carbon fiber bundle for thermosetting resin impregnated filament winding according to [5], wherein the thermosetting resin is an epoxy resin.
〔７〕 〔５〕に記載の製造方法で製造した熱硬化性樹脂含浸フィラメントワインディング用炭素繊維束を、フィラメントワインディング装置を用いて成型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体の製造方法。 [7] A method for producing a filament winding molded body, wherein the carbon fiber bundle for thermosetting resin impregnated filament winding produced by the production method according to [5] is molded using a filament winding apparatus.
従来のサイジング処理済ＦＷ用炭素繊維束の偏平率が１０〜４０で、ドレープ値が１１０以上であるところ、本発明においてはサイジング処理済ＦＷ用炭素繊維束の偏平率を４０〜９０、ドレープ値を５０〜１００ｍｍにしたので、本発明の熱硬化性樹脂含有ＦＷ用炭素繊維束はＦＷ成形する際にマンドレル等に十分広がり、均質な成形体を与える。このため、本発明熱硬化性樹脂含有ＦＷ用炭素繊維束を用いて製造する成形体は、炭素繊維束の本来有する強度等の性能を十分反映した高性能のものである。 Where the flatness of the conventional sized carbon fiber bundle for FW is 10 to 40 and the drape value is 110 or more, in the present invention, the flatness of the sized carbon fiber bundle for FW is 40 to 90, the drape value. Is 50 to 100 mm, the thermosetting resin-containing carbon fiber bundle for FW of the present invention sufficiently spreads to a mandrel or the like during FW molding to give a homogeneous molded body. For this reason, the molded object manufactured using the carbon fiber bundle for FWs containing the thermosetting resin of the present invention is a high-performance one that sufficiently reflects performance such as strength inherent in the carbon fiber bundle.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明のサイジング処理済ＦＷ用炭素繊維束は、炭素繊維を１０００〜１０００００本束ねて、サイズ剤を含浸させたもので、所定の偏平率及びドレープ値を有する。 The sizing-treated carbon fiber bundle for FW of the present invention is a bundle of 1000 to 100,000 carbon fibers impregnated with a sizing agent, and has a predetermined flatness ratio and drape value.
前記炭素繊維束を構成する炭素繊維は、原料としては特に限定するものではないが、ポリアクリロニトリル（ＰＡＮ）系炭素繊維、ピッチ系炭素繊維、レーヨン系炭素繊維等が例示できる。これらの炭素繊維のうち、取り扱い性能、製造工程通過性能に適したＰＡＮ系炭素繊維が特に好ましい。ここで、ＰＡＮ系炭素繊維は、アクリロニトリル構造単位を主成分とし、イタコン酸、アクリル酸、アクリルエステル等のビニル単量体単位を１０モル％以内で含有する共重合体を炭素繊維化したものである。 The carbon fiber constituting the carbon fiber bundle is not particularly limited as a raw material, and examples thereof include polyacrylonitrile (PAN) -based carbon fiber, pitch-based carbon fiber, and rayon-based carbon fiber. Of these carbon fibers, PAN-based carbon fibers suitable for handling performance and production process passing performance are particularly preferred. Here, the PAN-based carbon fiber is obtained by carbonizing a copolymer containing acrylonitrile structural unit as a main component and containing vinyl monomer units such as itaconic acid, acrylic acid, and acrylic ester within 10 mol%. is there.
前記炭素繊維束を構成する炭素繊維の単繊維繊度は、０．８ｄｔｅｘ以下が好ましく、０．２〜０．８ｄｔｅｘがより好ましく、０．３〜０．７ｄｔｅｘが更に好ましい。繊度が０．８ｄｔｅｘを越える場合は前駆体であるプリカーサーの緻密性が低下し、炭素繊維の毛羽が多発するので好ましくない。 The single fiber fineness of the carbon fibers constituting the carbon fiber bundle is preferably 0.8 dtex or less, more preferably 0.2 to 0.8 dtex, still more preferably 0.3 to 0.7 dtex. When the fineness exceeds 0.8 dtex, the denseness of the precursor precursor is lowered and the carbon fiber fluff frequently occurs, which is not preferable.
本発明のサイジング処理済ＦＷ用炭素繊維束は、炭素繊維束の繊維方向に直交する断面形状が略楕円形乃至は略紡錘形であり、下記式（１）で示す偏平率が４０〜９０のものが好ましく、５０〜９０のものがより好ましい。 The sizing-treated FW carbon fiber bundle of the present invention has a cross-sectional shape orthogonal to the fiber direction of the carbon fiber bundle that is substantially elliptical or substantially spindle-shaped, and has a flatness of 40 to 90 expressed by the following formula (1). Are preferred, and those of 50 to 90 are more preferred.
偏平率＝炭素繊維束の幅／炭素繊維束の厚さ （１）
偏平率が４０未満の場合、後述する熱硬化性樹脂含浸ＦＷ用炭素繊維束を製造する際に樹脂の含浸量が極端に減少し、これを用いて製造する成形体の強度等の特性が著しく低下する。また、９０を越えるサイジング処理済ＦＷ用炭素繊維束はその製造が困難である。
Flatness ratio = width of carbon fiber bundle / thickness of carbon fiber bundle (1)
When the flatness is less than 40, the amount of resin impregnation is extremely reduced when producing a carbon fiber bundle for a thermosetting resin-impregnated FW, which will be described later, and the properties such as the strength of the molded product produced using this are remarkably increased. descend. Moreover, it is difficult to produce sizing-treated FW carbon fiber bundles exceeding 90.
本発明のサイジング処理済ＦＷ用炭素繊維束は、その剛軟度を示すドレープ値が５０〜１００ｍｍであることが好ましく、５０〜８０がより好ましい。 The sizing-treated carbon fiber bundle for FW of the present invention preferably has a drape value indicating the bending resistance of 50 to 100 mm, and more preferably 50 to 80 mm.
本発明においては、ドレープ値は以下の定義による。 In the present invention, the drape value is defined as follows.
即ち、図１に示すように、長さ２００ｍｍに切取ったサイジング処理済ＦＷ用炭素繊維束２を水平な試験台４の上面に置き、炭素繊維束２の先端６から１５０ｍｍの部分を空中に突出す。３分間経過時に、試験台４の上面から垂直方向に１００ｍｍ垂下したＦＷ用炭素繊維束２の部分と試験台４との水平距離Ｘを読取り、この値をドレープ値（ｍｍ）とする。なお、測定温度は２３±２℃である。
That is, as shown in FIG. 1, the sizing-processed FW
炭素繊維束は実質的に撚りがないものが好ましい。ここで、実質的に撚りがないとは、１ｍ当たりの撚り回数が１回以下のものをいう。 The carbon fiber bundle is preferably substantially free of twist. Here, substantially no twist means that the number of twists per meter is 1 or less.
サイジング処理済ＦＷ用炭素繊維束に熱硬化性樹脂を含浸させることにより、本発明の熱硬化性樹脂含浸ＦＷ用炭素繊維束が得られる。 By impregnating the sizing-treated FW carbon fiber bundle with the thermosetting resin, the thermosetting resin-impregnated FW carbon fiber bundle of the present invention is obtained.
本サイジング処理済ＦＷ用炭素繊維束に含浸する樹脂としては、特にエポキシ樹脂が好ましい。エポキシ樹脂としては、特に制限が無く、サイジング処理済ＦＷ用炭素繊維束に含浸させる樹脂として通常市販されているものが適宜使用できる。 As the resin impregnated in the sizing-treated FW carbon fiber bundle, an epoxy resin is particularly preferable. There is no restriction | limiting in particular as an epoxy resin, What is marketed normally as resin impregnated to the carbon fiber bundle for sizing processed FW can be used suitably.
エポキシ樹脂の硬化剤も特に制限が無く、酸無水物系やアミン等、通常市販されているものが適宜使用できる。 The curing agent for the epoxy resin is not particularly limited, and commercially available products such as acid anhydrides and amines can be appropriately used.
サイジング処理済ＦＷ用炭素繊維束に含浸させる熱硬化性樹脂の種類及び含浸量は通常１５〜４５質量％であり、２５〜３５質量％がより好ましい。 The type and impregnation amount of the thermosetting resin impregnated in the sizing-treated carbon fiber bundle for FW are usually 15 to 45% by mass, and more preferably 25 to 35% by mass.
上記本発明のサイジング処理済ＦＷ用炭素繊維束は、通常のフィラメントワインド装置を用いて常法により所望のＦＷ成形体を製造することができる。 The sizing-treated carbon fiber bundle for FW of the present invention can produce a desired FW molded article by a conventional method using an ordinary filament winding apparatus.
次に、本発明の熱硬化性樹脂含浸ＦＷ用炭素繊維束を製造する方法に付き、説明する。 Next, it attaches to the method of manufacturing the carbon fiber bundle for thermosetting resin impregnation FW of this invention, and demonstrates it.
出発原料の炭素繊維束は未サイジングの炭素繊維束で、これを構成する炭素繊維の性質、繊度等は前述の通りである。通常、未サイジングの炭素繊維束を連続的にサイジング浴に浸漬し、炭素繊維束にサイズ剤を含浸させる。その後、ローラー等で余分のサイズ剤を除去した後、乾燥してサイジング処理済ＦＷ用炭素繊維束を得るが、この乾燥処理の前後で炭素繊維束の搬送路に少なくとも一対の成形用ローラー等を設けて、炭素繊維束を前記一対のローラーの間を通過させることにより押圧して、繊維束を上記偏平率に成形することが好ましい。また、工程中に、少なくとも一対のヒートローラーを設け、炭素繊維束を前記一対のヒートローラーの間を通過させることにより押圧すると共に、このヒートローラーの温度、接触時間を調節することより、このヒートローラと接触する炭素繊維束の偏平率及びドレープ値を調節する方法が好ましい。 The starting carbon fiber bundle is an unsized carbon fiber bundle, and the properties, fineness, etc. of the carbon fibers constituting this are as described above. Usually, an unsized carbon fiber bundle is continuously immersed in a sizing bath, and the carbon fiber bundle is impregnated with a sizing agent. Thereafter, the excess sizing agent is removed with a roller or the like, and then dried to obtain a sized carbon fiber bundle for FW. Before and after the drying process, at least a pair of molding rollers and the like are provided on the conveyance path of the carbon fiber bundle. It is preferable that the fiber bundle is pressed by passing between the pair of rollers to form the fiber bundle into the flatness. Further, during the process, at least a pair of heat rollers are provided, and the carbon fiber bundle is pressed by passing between the pair of heat rollers, and the temperature and contact time of the heat roller are adjusted, thereby the heat. A method of adjusting the flatness and drape value of the carbon fiber bundle in contact with the roller is preferred.
ヒートローラーの表面温度が低く、接触時間が短くなるに従い、サイジング処理済ＦＷ用炭素繊維束の偏平率が小さくなり、ドレープ値は大きくなる。 As the surface temperature of the heat roller decreases and the contact time decreases, the flatness of the sized FW carbon fiber bundle decreases and the drape value increases.
ヒートローラーの温度を高くしすぎると、サイズ剤の熱変質、分解等が生じ好ましくない。 If the temperature of the heat roller is too high, the sizing agent is undesirably deteriorated by heat and decomposed.
サイズ剤の含浸量は、０．１〜１０質量％が好ましく、０．２〜４質量％がより好ましい。サイズ剤としては、エポキシ系樹脂等の公知のサイズ剤を用いる事が出来る。 The impregnation amount of the sizing agent is preferably 0.1 to 10% by mass, and more preferably 0.2 to 4% by mass. As the sizing agent, a known sizing agent such as an epoxy resin can be used.
炭素繊維束のストランド引張強度は、４０００ＭＰａ以上が好ましく、４５００ＭＰａ以上がより好ましい。 The strand tensile strength of the carbon fiber bundle is preferably 4000 MPa or more, and more preferably 4500 MPa or more.
以下、実施例により本発明を更に具体的に説明する。 Hereinafter, the present invention will be described more specifically with reference to examples.
（偏平率の測定）
長さ４０ｍｍのサイジング処理済ＦＷ用炭素繊維束を１０個用意し、光学測定装置（株式会社キーエンス製、商品名 センサーヘッドＶＧ−０３５、コントローラＶＧ−３００）を用いて各炭素繊維束の幅、厚みを測定し、得られた測定値の平均値を算出した。この平均値を使用して、サイジング処理済ＦＷ用炭素繊維束の偏平率を前記式（１）を用いて算出した。
(Measurement of flatness)
Ten sized carbon fiber bundles for FW having a length of 40 mm were prepared, and the width of each carbon fiber bundle was measured using an optical measuring device (manufactured by Keyence Corporation, trade name: sensor head VG-035, controller VG-300). The thickness was measured, and the average value of the obtained measurement values was calculated. Using this average value, the flatness of the sizing-treated FW carbon fiber bundle was calculated using the above formula (1).
（ドレープ値）
前述の方法によった。
(Drape value)
According to the method described above.
（リング引張試験）
引張試験は、ＡＳＴＭ−Ｄ−２２９０−９２に準拠した。測定温度は２２±２℃であった。
(Ring tensile test)
The tensile test was based on ASTM-D-2290-92. The measurement temperature was 22 ± 2 ° C.
実施例１〜４、比較例１〜２
未サイジングの炭素繊維束（東邦レーヨン（株）製 商品名ベスファイト、ストランド強度４８００Ｍｐａ、伸度 ２％、２４０００フィラメント、繊度０．６８ｄｔｅｘ）を、連続的にサイジング浴（４質量％水エマルジョン）に浸漬した後、ローラーにより余分の水分を除去した。
Examples 1-4, Comparative Examples 1-2
Unsized carbon fiber bundle (trade name Besfight, strand strength 4800 Mpa,
次いで、表面温度１２０〜１４０℃のヒートローラー（直径３００ｍｍ、梨地仕上げ）に前記水分を除去した炭素繊維束を１５〜３０秒間接触させて乾燥し、連続的にサイジング処理して断面形状が楕円形の偏平な炭素繊維束を得た。サイズ剤の含浸量は１．５質量％であった。 Next, the carbon fiber bundle from which the moisture has been removed is contacted with a heat roller (diameter 300 mm, satin finish) having a surface temperature of 120 to 140 ° C. for 15 to 30 seconds to dry, and continuously sizing to make the cross-sectional shape elliptical. A flat carbon fiber bundle was obtained. The impregnation amount of the sizing agent was 1.5% by mass.
サイズ剤は、エピコートＥＰ８２８／ＥＰ１００１（共に油化シェルエポキシ（株）社製、ビスフェノールＡ系エポキシ樹脂）／ＥＰＵ６（旭電化（株）社製）＝３５／５５／１０重量部のものであった。 The sizing agent was Epicoat EP828 / EP1001 (both manufactured by Yuka Shell Epoxy Co., Ltd., bisphenol A epoxy resin) / EPU6 (manufactured by Asahi Denka Co., Ltd.) = 35/55/10 parts by weight. .
サイズ剤と併用した乳化剤は、ポリオキシエチレンジスチリルフェニルエーテル（商品名 サミット７２３）で、これをサイズ剤の１００重量部に対して１０重量部使用した。 The emulsifier used in combination with the sizing agent was polyoxyethylene distyryl phenyl ether (trade name Summit 723), which was used in an amount of 10 parts by weight based on 100 parts by weight of the sizing agent.
次ぎに、エポキシ樹脂として、油化シェルエポキシ（株）社製エピコート８２８（商品名）を１００質量部、硬化剤として日立化成（株）社製カヤハードを９０質量部、硬化促進剤として四国化成工業（株）社製イミダゾールを１質量部を混合してＦＷ用炭素繊維束含浸用樹脂組成物を得た。 Next, 100 parts by mass of Epicoat 828 (trade name) manufactured by Yuka Shell Epoxy Co., Ltd. as an epoxy resin, 90 parts by mass of Kayahard manufactured by Hitachi Chemical Co., Ltd. as a curing agent, and Shikoku Kasei Kogyo as a curing accelerator A resin composition for impregnating a carbon fiber bundle for FW was obtained by mixing 1 part by mass of imidazole manufactured by Co., Ltd.
フィラメントワインド装置を用いるキスタッチ方式で、前記製造したサイジング処理済ＦＷ用炭素繊維束に上記含浸用樹脂組成物を２２質量％含浸させることにより本発明の熱硬化性樹脂含浸ＦＷ用炭素繊維束を製造した。 The thermosetting resin-impregnated FW carbon fiber bundle of the present invention is manufactured by impregnating 22% by mass of the impregnating resin composition into the sized FW-treated carbon fiber bundle manufactured by the kiss touch method using a filament wind apparatus. did.
上記連続的に製造した熱硬化性樹脂含浸ＦＷ用炭素繊維束を、続けて連続的に直径３５０ｍｍのマンドレルに巻取り、内径３５０ｍｍ、幅１８．５ｍｍ、厚さ１．１ｍｍの円筒状試験片を作製した。１２０℃で２時間加熱して硬化させた後、引張試験に供した。引張試験の結果を表１に示した。
The continuously produced carbon fiber bundle for thermosetting resin impregnated FW is continuously wound on a mandrel having a diameter of 350 mm, and a cylindrical test piece having an inner diameter of 350 mm, a width of 18.5 mm, and a thickness of 1.1 mm is obtained. Produced. After being cured by heating at 120 ° C. for 2 hours, it was subjected to a tensile test. The results of the tensile test are shown in Table 1.
２ サイジング処理済ＦＷ用炭素繊維束
４ 試験台
６ 先端
Ｘ 水平距離
2 Carbon fiber bundle for sized FW 4
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