JPS58132168A - Improved surface electrolytic treatment of carbon fiber bundle - Google Patents

Abstract

(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

【発明の詳細な説明】 本発明は改良された炭素繊射：束の表ｉ’ｌ！電り′処
理法に係り、さらに詳しくは、該炭素繊維束。DETAILED DESCRIPTION OF THE INVENTION The present invention provides an improved carbon fiber injection: bundle table i'l! More specifically, the method relates to the electric treatment method, and more specifically, the carbon fiber bundle.

特に単糸繊維本数の多い繊維束を多数本、−挙に表面電
解処理する場合に、繊維束を構成する単繊維個々の表面
電解処Ｐ１ｆか均一であり、その結果として炭素級、維
を補強紙紐とする複合材料の物性を安定、かつ一定する
炭素衿維東をＩｊ、える方法に関する。In particular, when surface electrolytically treating a large number of fiber bundles with a large number of single fibers at once, the surface electrolytically treated P1f of each single fiber constituting the fiber bundle is uniform, and as a result, the carbon class and fibers are reinforced. The present invention relates to a method of producing a carbon collar that stabilizes and maintains the physical properties of a composite material used as a paper string.

再生セルロース、ポリアクリロニトリル、ピッチなどか
らなる繊維を醇化熱処理し、炭素化乃至黒鉛化すること
によって（４Ｊられる炭素繊維はその高強度、高弾性率
、特に比強１ｒｌ’　、比弾性率か大きいという力学的
特性に基づき、複合材料（コンポジット）の補強用厭紹
として極めて優れた性能を有する。この炭素絨紗を補強
用繊維とする複合材料は航空、宇宙用ｉ、（：或いは自
動車、船舶等の輸送槙わルにおける軽１・；化もしくは
燃費低減の要請から、それらの構造材料として広く、大
量に使用されようとしている。By subjecting fibers made of regenerated cellulose, polyacrylonitrile, pitch, etc., to carbonization or graphitization (4J), carbon fibers are said to have high strength and high elastic modulus, especially high specific strength 1rl' and high specific elastic modulus. Based on its mechanical properties, it has extremely excellent performance as a reinforcing material for composite materials.Composite materials using carbon woven fabric as reinforcing fibers can be used for aviation, space applications, automobiles, ships, etc. Due to the demand for lighter vehicles and lower fuel consumption in transportation vehicles, they are being used widely and in large quantities as structural materials for these vehicles.

しかしながら、炭素繊維の秀れた力学的性質を捨金材料
に十分灰吹させるためには複合材料の母材（マ）　ＩＪ
ラックスと炭素繊維とが十分に接着し一体化する必要が
あるが一般に炭素繊維は何らかの表面処理を行わないと
マトリックスに対する接着性が十分でなく、マドソック
スからの〃すぬけ〃が起り易く、複合材料としての曲げ
あるいは剪断強度が低くなり十分な補強効果を発揮しな
い。However, in order to sufficiently incorporate the excellent mechanical properties of carbon fiber into a waste material, the base material (ma) of the composite material must be used.
It is necessary for the lux and carbon fiber to sufficiently adhere and integrate, but in general, carbon fiber does not have sufficient adhesion to the matrix unless some kind of surface treatment is performed, and it is easy to "slip" from the mud sock. The bending or shearing strength of the material becomes low and it does not exhibit sufficient reinforcing effect.

そこで、従来から炭素繊維には酸化剤による湿式酸化処
理、ヒートクリーニング、気相酸化。Therefore, carbon fiber has traditionally been treated with wet oxidation treatment using an oxidizing agent, heat cleaning, and gas phase oxidation.

ウィスカライジングおよび電解処理などの各種の表面処
理が施されているが、これらの中でも電気分解により陽
極に酸素を生成する電解質溶液中で炭素繊維を陽極とし
て炭素繊維を電解酸化処理する方法がその簡便性、並び
に強度低下が少ないという利点から広く採用されている
。Various surface treatments such as whiskering and electrolytic treatment are performed, but among these, the simplest method is to electrolytically oxidize the carbon fiber using the carbon fiber as the anode in an electrolyte solution that generates oxygen at the anode by electrolysis. It is widely used due to its advantages of low performance and low strength loss.

しかるに、この炭素繊維の表面電解処理において単糸繊
維本数の多い炭素繊維束を複数本同時に電解処理すると
、炭素繊維束もしくは繊維へ 束を構成する単糸間における表面処理が不均一化し易く
、最終製品の複合材ｒ１の力学的性質に影響を及ぼすこ
とが判明した。すなわち、炭素繊維の表面電解処理にお
いては電、勉液中を陽極として走行する炭素繊維表面で
発生期の１１．・素が発生し、他方、電解液中の陰極で
は雪解質のイオン種によって異なるが各種の気体たとえ
ば水素や酸素、アンモニアなどが発生する。However, in this surface electrolytic treatment of carbon fibers, if multiple carbon fiber bundles with a large number of single fibers are electrolytically treated at the same time, the surface treatment among the carbon fiber bundles or the single fibers constituting the bundle tends to become uneven, and the final It has been found that the mechanical properties of the composite r1 of the product are affected. That is, in the surface electrolytic treatment of carbon fibers, electricity is applied to the surface of the carbon fibers running in the liquid as an anode during the nascent stage of 11. On the other hand, at the cathode in the electrolyte, various gases such as hydrogen, oxygen, and ammonia are generated, depending on the ion species in the snow melt.

この陰極ｉ発生する気体は炭素繊維表面の酸化に対して
は効果を示さないばかりでなく、電解液中で気泡となっ
て上昇し、炭素＃＆維衣表面吸着されるとこの気泡は電
気的に絶縁性であるためにこの気泡が付着した部分だけ
は電流が流れなくなり、炭素繊維表面の電解処理を不均
一化するのである。The gas generated from this cathode not only has no effect on the oxidation of the carbon fiber surface, but also rises in the form of bubbles in the electrolyte, and when adsorbed on the carbon fiber surface, these bubbles become electrically Since the carbon fiber is insulative, current will not flow only in the areas where the bubbles are attached, making the electrolytic treatment on the carbon fiber surface uneven.

このような１鴫極から発生する気体による表面電解処理
の不均一化を防止する方法として、特公昭５６−１’７
４６５号公報には、上記電解処理を分解電圧以下で行な
い、陰極から気体の発。As a method to prevent uneven surface electrolytic treatment due to gas generated from such a single electrode,
No. 465 discloses that the electrolytic treatment is performed below the decomposition voltage to generate gas from the cathode.

生そのものを防止する方法がト：】示されているが、こ
の方法は炭素繊維の表面電解が不十分となるだけでなく
、電解処理能力を低下させ工業的な方法ではない。さら
に、大垣の炭素繊維の表面′市解処理を行うためには、
単糸本数の多い炭素繊維束を複数本同時に電解処理する
ことが望まれるが、単糸本数の多い炭素繊維束を複数本
特に数十本の繊維束を一挙に電解処理するときは陰極か
ら発生する気体が該炭素繊維束の内外部に大量に付着し
、効率的電解酸化が著しく難しくなり処理能力は必ずし
も向上しないし、この付着した気泡を除去するために、
炭素繊維束を振動させたり、電解液を攪拌したりすると
電解処理時に炭素繊維束に毛羽が生じたり、単糸乱れが
大きくなり開繊性が損われている問題があることが判明
した。A method for preventing carbon fibers from forming itself has been shown, but this method not only results in insufficient surface electrolysis of the carbon fibers, but also reduces the electrolytic treatment ability, and is not an industrial method. Furthermore, in order to perform the surface treatment of Ogaki's carbon fiber,
It is desirable to electrolytically treat multiple carbon fiber bundles with a large number of single filaments at the same time, but when electrolytically treating multiple carbon fiber bundles with a large number of single filaments, especially several dozen fiber bundles at once, the generation of electricity from the cathode. A large amount of gas adheres to the inside and outside of the carbon fiber bundle, making efficient electrolytic oxidation extremely difficult and processing capacity not necessarily improved.
It has been found that when the carbon fiber bundle is vibrated or the electrolyte is stirred, fuzz is generated in the carbon fiber bundle during electrolytic treatment, and single fiber disorder becomes large, which impairs the spreadability.

本発明の目的の目的は上記欠点のない改良された炭素繊
維束の表面電解処理法、特に単糸本数の多い炭素繊維束
を多数本同時に電解処理し、かつ均一でトのない炭素繊
維束の電解処理法をによる悪影響がなく、大量の炭素繊
維を処理することができる電解処理法を提供するにある
。The object of the present invention is to provide an improved method for surface electrolytic treatment of carbon fiber bundles without the above-mentioned drawbacks, in particular, to electrolytically treat a large number of carbon fiber bundles having a large number of single yarns at the same time, and to produce uniform and smooth carbon fiber bundles. It is an object of the present invention to provide an electrolytic treatment method that can process a large amount of carbon fibers without any adverse effects caused by the electrolytic treatment method.

このような本発門の目的は前記特許請求の範囲に記載し
た発明により達成することができる。Such an object of the present invention can be achieved by the invention described in the claims.

本発明の特徴は炭素繊維束を表面電解処理するに際して
、予しめ特定の前処理を該炭素繊維束に施こすことがあ
るが、この前処理剤としては電解質に対して化学的に安
定で混和性を有するもの、たとえば電解質含有水溶液、
界面活性剤含有水溶液などがあり、さらに具体的には電
解質としてｉ硫酸、硝酸、塩削などの無機塩類。A feature of the present invention is that when subjecting a carbon fiber bundle to surface electrolytic treatment, a specific pretreatment may be applied to the carbon fiber bundle in advance, and this pretreatment agent is chemically stable and miscible with the electrolyte. such as an electrolyte-containing aqueous solution,
There are aqueous solutions containing surfactants, and more specifically, inorganic salts such as sulfuric acid, nitric acid, and salt scraps as electrolytes.

苛性アルカリ、アンモニアなどのアルカリ類。Alkali such as caustic alkali and ammonia.

アルカリ金属、アルカリ土金鵬、アンモニウム塩の０．
０１〜１モル％濃度水溶液、界面活性剤としてはノニオ
ン系活性剤たとえば、脂肪かり。0.0 of alkali metals, alkaline metals, and ammonium salts.
Aqueous solution with a concentration of 01 to 1 mol %, a nonionic surfactant such as a fatty surfactant.

脂肪族アルコールのエチレンオキサイド付加物の０．１
〜５％水溶液が用いられる。またはこのような電解質、
界面活性剤を含有しない単なる水でもよい。これらの前
処理液の濃度は処理剤の種類によって異なるが濃度が余
りに大きすぎると電解質水溶液の汚染が早くなるので好
ましくない。0.1 of ethylene oxide adduct of aliphatic alcohol
~5% aqueous solutions are used. or such electrolytes,
Simple water containing no surfactant may be used. The concentration of these pretreatment liquids varies depending on the type of treatment agent, but if the concentration is too high, the electrolyte aqueous solution will be contaminated quickly, which is not preferable.

このような点から本発明の前処理剤としては電解質その
もの、特に電解液と同一成分、同一組成、のものが好ま
しい。また、この前処理浴の湿度も特に限定されないが
通常常温〜７０℃の範１７１（にするのかよい。From this point of view, the pretreatment agent of the present invention preferably has the same components and composition as the electrolyte itself, particularly the electrolyte solution. Further, the humidity of this pretreatment bath is not particularly limited, but it is usually within the range of room temperature to 70°C.

さらにこの前処理における炭素繊維束の浸漬時間は電解
浴中を走行する炭素繊維束の速度および浸ｌ＆長に関係
するが、炭素繊維束の走行速度が１〜２０ｍ／分であり
、浸漬長が約０．０５〜１ｍの場合、０２〜２０秒間の
範囲とするのがよい。もちろんこれらの走行速度、浸漬
長および浸漬時間は前処理剤の種類により前記範１ｊｌ
ｉ内で本発明の目的に応じて選択すべきである。Furthermore, the immersion time of the carbon fiber bundle in this pretreatment is related to the speed and immersion length of the carbon fiber bundle running in the electrolytic bath. In the case of about 0.05 to 1 m, the range is preferably 0.2 to 20 seconds. Of course, the running speed, immersion length and immersion time may vary depending on the type of pretreatment agent.
i should be selected according to the purpose of the present invention.

なお、［）【Ｉ処理浴の機械的攪拌は処理効果を大きく
するがこの場合に炭素繊維束を構成する単繊維が絡み合
い、１ｊｔｊＨＲ，性を悪化させるような強い機械的Ｙ
、を拌は避けるのがよい。[)[Mechanical stirring of the I treatment bath increases the treatment effect, but in this case, the single fibers constituting the carbon fiber bundle become entangled, causing strong mechanical Y that deteriorates the properties.
, it is best to avoid stirring.

この前処理浴において炭素繊維束に電流を通しることに
より炭素繊維束にａまれる気泡をより効果的に除去する
ことができる。もちろん、この前処刑が第１段電解処理
となるようにしてもよいが、必ずしも表向電解処理効呆
を奏さない軽度の電流を流しても効果がある。By passing an electric current through the carbon fiber bundle in this pretreatment bath, air bubbles formed in the carbon fiber bundle can be more effectively removed. Of course, this pre-execution may be the first stage electrolytic treatment, but it is also effective to flow a mild electric current that does not necessarily have the same effect as the surface electrolytic treatment.

また処理されるべき炭素繊維束としては単繊維本数が少
くとも５００本、好ましくは１０００〜２００．　ＯＯ
０本の範囲内であって、このような炭素繊維束を少くと
も１０−１０００本同時に電解処理する際に本発明方法
は格段の効果を奏する。すなわち、単糸本数が５００本
より少ない繊維束では炭素繊維束中に含まれ゛る空気な
どのガスが少なく電解液の浸漬長をコントロールするこ
とにより十分除去可能であり格別効果上の差はないが処
理址が小さくメリットは小さい。他方繊維束本数が前記
Ｋｉ　ｖｌｔ外になると前＆＋、１埋効果が低下したり
、電解液中の繊維束の走行安定性の確保か難しくなった
り或いは前処理時間を大きくしないと効果が十分発揮せ
ず、処理速度が低下するなどの問題がある。The carbon fiber bundle to be treated has at least 500 single fibers, preferably 1000 to 200. OO
The method of the present invention is particularly effective when electrolytically treating at least 10 to 1000 such carbon fiber bundles at the same time. In other words, in fiber bundles with fewer than 500 single fibers, there is less gas such as air contained in the carbon fiber bundle, and it can be sufficiently removed by controlling the length of immersion in the electrolytic solution, so there is no particular difference in effectiveness. However, the processing area is small and the benefits are small. On the other hand, if the number of fiber bundles falls outside of the above Ki vlt, the pre-&+, 1-embedding effect will decrease, it will be difficult to ensure running stability of the fiber bundles in the electrolyte, or the effect will be sufficient unless the pretreatment time is increased. However, there are problems such as a decrease in processing speed.

次に、このような前処理を施した炭素Ｉｔ　ａ束は、；
な前処理液か炭素繊糸）・束に付着し、ｔｌｌ’ｌ成炭
素級維表面を湿潤させている状態で電解液中に導入して
表面′市肪処理する、すなわち、前処理と表向電解処理
とは連続化されている必要がある。Next, the carbon It a bundle subjected to such pretreatment is;
The pre-treatment liquid or carbon fiber yarns are attached to the bundle and are introduced into the electrolyte while the surface of the carbon-forming fibers is moistened to perform surface fat treatment. The electrolytic treatment must be continuous.

特に前処理された炭素繊維束はＭｆＪ処理液のピック・
アップＢ（が繊維束重り；当り少なくとも２０％、好ま
しくは３０〜３００％である間に′ｆ４（解処１（１・
洛中に尋人するのかよく、このピック・アップ扇が２０
％以下になると前処理後電解浴中に６人されるまでに炭
素繊維束か空気を持ち込み易く、電解処理の不均一化を
もたらした、電Ｉｎ　４処理時間を長くする必要が生じ
たりするので好ましくない。In particular, pre-treated carbon fiber bundles are picked and treated with MfJ treatment solution.
'f4(Solution 1(1.
This pick-up fan is often 20 when Hiroto is in Raku.
% or less, carbon fiber bundles or air are likely to be introduced into the electrolytic bath after pre-treatment, resulting in uneven electrolytic treatment and the need to lengthen the electrolytic treatment time. Undesirable.

前記前処理された炭素オ、：賢糾束の電解処理法として
＆１公知の方法を採用することができるか、好ましくは
ａｉｐイ処ｐＨｊされる袂数本の炭素繊維束の金山（Ｗ
）を市九゛槽底部に設けられた陰極板のｒｌ（ＷＯ）よ
りも小さくＬ（ｗ＜ｗｏ）、該陰極板の長さくＬＯ）に
対する炭素ｌＩｋ糾束の浸漬長（Ｌ）の比（Ｌ／ＬＯ）
をｌ〜２とし、かつ電解液中における炭素緯」（１゛束
と陰極板との相対間隔を５〜３０（１の範囲内に設定し
て電解処理するのがよい。The pretreated carbon fibers may be electrolytically treated using a known method, or preferably, a gold mine (W) of several carbon fiber bundles may be used.
) is smaller than the rl(WO) of the cathode plate provided at the bottom of the tank (L(w<wo)), and the ratio of the immersion length (L) of the carbon lIk bundle to the length of the cathode plate (LO) is ( L/LO)
It is preferable to carry out the electrolytic treatment by setting the relative distance between the bundle and the cathode plate within the range of 5 to 30 (1), and the carbon density in the electrolytic solution to be 1 to 2.

すなわち、本発明のように単繊紹°本ｐ、の多い初数本
の炭素組糸１軛束を電解処Ｐ；！する際に訃、炭素繊維
束の全中（Ｖ／）が陰極板のＩｌｌ　（Ｗｏ　）よりも
小さくする繊維束相互間の表面処理効果が不、）４５．
−になり易い。したがって蝮数本の炭素繊維束の全ｒｊ
Ｊ（Ｖ／）は陰極板の１７　（Ｗ　ｏ　）よりも小さく
、好ましくはＷ　＝　　Ｗ　＋　０．　５　　ａｎ 以内にするのかよ−い。That is, as in the present invention, one bundle of the first few carbon braided yarns with a large number of single fibers is electrolyzed. 45. When doing so, the surface treatment effect between the fiber bundles is insufficient to make the total volume (V/) of the carbon fiber bundle smaller than the Ill (Wo) of the cathode plate.)45.
- It is easy to become. Therefore, the total rj of several carbon fiber bundles
J (V/) is smaller than 17 (W o ) of the cathode plate, preferably W = W + 0. Can I keep it within 5 an.

また、炭素繊糸１：１束の浸漬長（Ｌ）は陰極板のトを
さくＬＯ）に対して１乃至２倍以内にしないと雷ｌｌν
１港中を走行する炭素Ｘム（細束の撮画により炭素繊維
束と陰極板との相対間隔が変動し、その結果と［７て炭
素繊維束あるいは繊し束を構成する単繊維相互間に流れ
る電解電流を変動さセる原因となり易くなるので榛好ま
しくない。In addition, the immersion length (L) of a 1:1 bundle of carbon fibers must be within 1 to 2 times the length (LO) of the cathode plate.
1 The relative distance between the carbon fiber bundle and the cathode plate changes due to the photographing of the carbon fiber bundle traveling through the port. This is undesirable because it tends to cause fluctuations in the electrolytic current flowing through the circuit.

このようなＦｆ点からすると、炭素ＩＰ、維束と陰＄１
＋ｉ板との相対間隔は柚・めで重要であり、この相対間
隔が５ｃｍよりも小さくなると走行する炭素繊剤束の４
Ｊ＋ｉ４動が該炭素糾：維束に流れる電流を変動させ不
均一電解処理の原因になるし、他方３０国を越えると電
流の分布は均一になるが繊細２束と陰和・・板との間に
おける電圧降下が大きくなり、たとえば電Ｙ（−降下が
５０Ｖ以上にもなることがあり、１１鳳≦′市などのト
ラブルを生じるので好ましくないのである。From such Ff point, carbon IP, fiber bundle and Yin $1
The relative distance from the +i plate is important for Yuzu and Me, and if this relative distance is smaller than 5 cm, the 4th point of the traveling carbon fiber bundle
The J+i4 movement changes the current flowing through the carbon fiber bundle and causes non-uniform electrolytic treatment.On the other hand, if the current distribution exceeds 30 countries, the current distribution becomes uniform, but the difference between the delicate two bundles and the Yinwa plate. This is undesirable because the voltage drop between the two terminals becomes large, and for example, the voltage drop may exceed 50 V, causing troubles such as 110≦'.

以下、本発明を図面にもとづきさらに具体的に、１・τ
１明する。Hereinafter, the present invention will be explained more specifically based on the drawings.
1.

第１図は本５【′＝明に用いる前ｙｌ：、　Ｂｈ工程を
電Ｍ処理稀に連結した％　Ｍ’処理槽の１も１」を示す
模式新曲ド１であり、図においては、（１）は炭素１＆
　Ｈｔ束。Fig. 1 is a model new song d 1 showing the book 5 [' = pre-yl:, Bh process is rarely connected to electro-M treatment. 1) is carbon 1&
Ht bunch.

（ン）は［）す処理槽Ａ１．陽極槽、（３）は電解液槽
、（４）は貯＋１１１す、（５）はポンプ、（６）は陽
極電流入力端子、（７）は貯槽　、（８）はポンプ、（
９）は電源、Ｏｏ）は陰極板を示す。(n) is [)su processing tank A1. Anode tank, (3) is electrolyte tank, (4) is storage tank, (5) is pump, (6) is anode current input terminal, (7) is storage tank, (8) is pump, (
9) indicates a power supply, and Oo) indicates a cathode plate.

図において、炭素繊維束（１）はポンプ（５）によって
ｆ１ｒＪ処理剤の貯槽（４）と＋’＋’ｒｉ処Ｐ１′槽
（２）との］１１］を１″ＩｉＨ処理剤が循環せしめら
れている前処１’ｊｌ槽（２）に浸漬される。前処”ｌ
Ｌ槽（２）の前処理ｉイ（はオーバー７０−してもよく
、このＮＨ，合オーバーフローシタ前処理液は貯槽（４
）に集められ、ポンプ（５）で循環される。また、ポン
プ（５）から供給される前処理液は炭素繊維束（１）に
前処理液を直拉接Ｆ（−ｊ：せしめ、糾、維束中の気体
ト去を強化することかできる。In the figure, the carbon fiber bundle (1) is circulated through the f1rJ treatment agent storage tank (4) and the +'+'ri treatment P1' tank (2) with the 1''IiH treatment agent being circulated by the pump (5). The pretreatment tank (2) is immersed in the pretreatment tank (2).
The pretreatment liquid in the L tank (2) may be over 70°C, and this NH, combined overflow pretreatment liquid is stored in the storage tank (4
) and circulated by a pump (5). In addition, the pretreatment liquid supplied from the pump (5) can be directly applied to the carbon fiber bundle (1) to strengthen removal of gas from the fiber bundle. .

次に、この前処理槽（２）を出た炭素繊維束（１）は矢
印方向に走行して、湿潤したまま爾１引槽（３）に導入
され電解処理を受ける。この電解槽（３）には重色１液
の貯槽（７）からポンプ（８）によって電Ｉｆ　ｌａが
電解槽（３）及び陽極電流入力端子に供給され、供給さ
れた電解ａ化に槽（３）及び（６）内てオーバーフロー
して糟の両端部からパイプをｊｌｌ、じて貯槽（７）内
にや６Ｎされる。また、陽極’ｉＪＬがｒ入力端子（６
）と同極板（ｌＯ）は電源（９）で結ばれ、陽極電流入
力端子を非直接的に走行した炭素繊糸、・。束（１）が
陽極になるの金１１Ｊ　（Ｗ）　、と陰極板の巾（ＷＯ
）、炭素わし細束の浸ＩＬＴ長（Ｌ）、陰極板の長さく
Ｌｏ）、炭素繊維束と陰極力、４７ｉ子、（３）は電解
槽、（９）は電源、００）は陰極仏を　′示す〇 万端Ｆ（２）を電１１１１ｉ　（９）により′心気的に
接続した？Ｉ１１解装置に導かれ、該Ｗｉ触’　ｆ＊　
（３）内に満たされた重色・故にｒＪｌｌ“ｔされ電解
液中では陽極として走行する。Next, the carbon fiber bundle (1) leaving this pre-treatment tank (2) travels in the direction of the arrow and is introduced into a pulling tank (3) while still wet, where it undergoes electrolytic treatment. In this electrolytic cell (3), electricity If la is supplied from the heavy color 1 liquid storage tank (7) to the electrolytic cell (3) and the anode current input terminal by a pump (8), and the supplied electrolytic a is added to the tank ( 3) and (6) will overflow, and the pipes will be passed from both ends of the rice cake into the storage tank (7). In addition, the anode 'iJL is connected to the r input terminal (6
) and the same electrode plate (lO) are connected by a power source (9), and the carbon fiber thread runs indirectly through the anode current input terminal. The bundle (1) becomes the anode with gold 11J (W), and the width of the cathode plate (WO
), carbon fiber bundle immersion ILT length (L), cathode plate length Lo), carbon fiber bundle and cathode force, 47i, (3) is electrolytic tank, (9) is power supply, 00) is cathode Buddha Is 〇Mandan F (2) shown as ``connected hypochondriaously'' by den 1111i (9)? Guided by the I11 solving device, the Wi' f*
(3) The heavy color filled in the electrolyte therefore runs as an anode in the electrolyte.

この場合、炭素ｐｌＡ’ｔ　Ｋ・ｉ：束（１）のｒｌ　
（ｗ）は陰極板（１０）　（７，１ｒｌＪ（Ｗｏ）より
も小さく、重色″、液中を走行する炭素緘長甜訂醒極板
（１ｏ）の 細巾（１）の長さくＬｏ）に対して１〜２倍の長さに設
へ ′ｌｉ！され、かつ’？Ｉｔ　１１；ど液中における陰
極板（１ｏ）と炭素ｉｊＱ　ｔ：、イｊＨｌ、ｉ　（１
）との相対間隔（Ｄ）　ハ５〜３０　ｃｍ　（７）ｉｉ
ｊ　９１１　内る。すなわち、２個の電解槽を直列に配
置’にシ、全体の電解々ハ１理の２０％を越えないざ・
・１し１（内て予備的に電解させる方法である。In this case, carbon plA't K・i: rl of bundle (1)
(w) is the length of the cathode plate (10) (smaller than 7,1rlJ (Wo), heavy color, narrow width (1) of the carbon long thin electrode plate (1o) running in the liquid. ), and the cathode plate (1o) and carbon ijQ t:, ijHl, i (1
) Relative distance from (D) 5 to 30 cm (7) ii
j 911 Inner. In other words, when two electrolytic cells are arranged in series, the total electrolytic charge must not exceed 20% of the total electrolytic capacity.
・1-1 (This is a method of preliminary electrolysis.

本う６明によれば炭素繊細束の１、而’ｒ＋；　ｖＩ（
処理に際して次のよう４「効果か得られる。According to the present study, the carbon delicate bundle is 1, and 'r+; vI(
During treatment, the following 4 effects can be obtained.

（１）　　前処理によって炭素紙組型を＋、’、成する
単繊維相互間の空気か除去され、しかも炭素繊維そのも
のの表面が０１１処理液によって十分に湿潤されている
のでクイ解処理時に炭素ｆｌｕ　）！！束全全体均一に
電解液を１と触し、結末としてむらのない均一な表面電
解処理することかできる。(1) The pretreatment removes the air between the single fibers that form the carbon paper type, and since the surface of the carbon fiber itself is sufficiently wetted with the 011 treatment liquid, the carbon fibers are removed during the paper dissolution process. flu )! ! By uniformly contacting the entire bundle with the electrolytic solution 1, it is possible to achieve uniform surface electrolytic treatment without unevenness.

（２）　　特に炭素都２維束を構成する単繊維本夛・が
多く、炭素繊維束そのものの本数を多くして大量の炭素
繊維を表面電解処理するときに、上記炭素紛糾８束に含
有される気体の悲影響は急激に増大するか、本発明によ
れは甲わし、維本数東 を５００本以上、かつこのような炭素繊維を１０本以上
同時に表面電解処理するこ・とが可能となり、工業的意
２、は極めて大きい。(2) In particular, there are many single fibers that make up the carbon fiber bundles, and when the number of carbon fiber bundles themselves is increased and a large amount of carbon fibers is subjected to surface electrolytic treatment, the amount of carbon fibers contained in the carbon fiber bundles mentioned above is large. The negative influence of gases increases rapidly, but the present invention makes it possible to simultaneously perform surface electrolytic treatment on more than 500 fibers and more than 10 such carbon fibers, Industrial significance 2 is extremely large.

（３）　　本発明により、表向電解々ルＦ’ｌされた炭
素糾紐束はその表面処理が均一化されているために、サ
イジング剤およびマトリックス樹脂の付着ムラが少なく
、品質の安定した高性能後合拐料とすることができる。(3) According to the present invention, since the surface treatment of the carbon strand bundle subjected to surface electrolyte F'l is uniform, there is less uneven adhesion of the sizing agent and matrix resin, and the quality is stable and high. After performance, it can be used as a kidnapping fee.

実施例 ポリアクリロニトリルより成るマルチフィラメント（単
糸デニール１ｄ６ｏｏｏｆ１１）を常法により焼成して
得られた炭素繊維束を５０本並べて走行させ同時に電解
表面処理を行った。電解槽としては第２図に模式的に示
したような装置を用いた。各部の代表寸法は、Ｌ＝　ｌ
　ｍ　、　Ｌｏ＝　Ｏ，’７　ｍ　。EXAMPLE Fifty carbon fiber bundles obtained by firing multifilament polyacrylonitrile (single filament denier 1d6ooof11) by a conventional method were run side by side, and electrolytic surface treatment was performed at the same time. As an electrolytic cell, a device as schematically shown in FIG. 2 was used. The representative dimensions of each part are L = l
m, Lo=O,'7 m.

］）＝　２０　ｃｌｌ、ｌ１ｌｌｌｏ＝　５２　ｃｍと
した。なおＷは繊維束を平均１１の間隔で平行に並べた
ので、平均的には４９ａＩ＋となるが、８ｍ／分の速度
で走行させ観察測定したところ、繊維束の幅は４７〜５
０ｇ、の間で変Ｑｇｌ　Ｌでいることがゎがった。従っ
て上記Ｗ　ｏ　＝　５２１であれば繊維束は陰極板の端
よりはみ出ることはない。]) = 20 cll, l1llo = 52 cm. Note that W has fiber bundles arranged in parallel at an average interval of 11, so the average width is 49aI+, but when observed and measured while running at a speed of 8 m/min, the width of the fiber bundle was 47 to 5.
It was difficult to stay in a strange Qgl L between 0g and 0g. Therefore, if W o =521, the fiber bundle will not protrude beyond the edge of the cathode plate.

更に前記槽の前に前処理槽を設けた。該前処理槽軛も第
１図■に示したようなオーバーフロ一方式であり、浸漬
長は２５ａ１１とした。即ち浸漬時間は約２秒である。Furthermore, a pretreatment tank was provided in front of the tank. The pretreatment tank yoke was also an overflow type as shown in FIG. 1, and the immersion length was 25a11. That is, the immersion time is about 2 seconds.

前処理槽及び電解槽にはそれぞれ０．０５規定の硫酸水
溶液を用い電流０．８　Ａ　／本の直流電流を炭素繊維
束が陽極となるように通じて電解表面処理を行った。Electrolytic surface treatment was performed by using a 0.05 N sulfuric acid aqueous solution in each of the pretreatment tank and the electrolytic tank, and passing a direct current of 0.8 A/line so that the carbon fiber bundle served as an anode.

得られた５０本の炭素繊維束をそれぞれエポキシ樹脂（
シェル製エピコー）８２８　）を用いて繊維体積含有率
６０％となるようにして複合材試験片を常法により作製
し、層間剪断強度を測定した０上記５０本の繊維束の平
均値はａ、　３　ｋｇ　／ｍ″であったが、個々の層間
剪断強度の変動を確認したところ’７．５　ｋｇ　／　
、’から８．　’７　ｋｇ　／□翼の間で変動している
ことが確認され、全変動幅は１．２　ｋｇ　／　ｗ”で
あった。Each of the obtained 50 carbon fiber bundles was coated with epoxy resin (
Composite material test pieces were prepared by a conventional method using Epicor (Epicor) 828) manufactured by Shell, with a fiber volume content of 60%, and the interlaminar shear strength was measured. The average value of the above 50 fiber bundles was a, 3 kg/m'', but when we checked the variation in the individual interlayer shear strength, it was 7.5 kg/m''.
,' to 8. It was confirmed that the weight was fluctuating between '7 kg/□ wings, and the total fluctuation range was 1.2 kg/w''.

一方、前処理槽を用いずに同様の処ｐｐを行い、上記に
準じて５０本の炭素繊維束を１・苔取し、評価したとこ
ろ平均値はＢ−２ｋｇ　／　１１１１”とほぼ同じ値を
示したが、変動幅が２．５　ｋｇ　／♂と約２倍に大き
くなっており、本発明の方法により品質の均一性が向上
していることが確認された。On the other hand, the same treatment pp was carried out without using a pre-treatment tank, and 50 carbon fiber bundles were removed with moss according to the above method, and the average value was almost the same as B-2kg / 1111". However, the variation range was approximately twice as large as 2.5 kg/male, and it was confirmed that the method of the present invention improves the uniformity of quality.

【図面の簡単な説明】[Brief explanation of drawings]

第１図は本発明に用いる炭素繊維束の前処理槽を連結し
た電解処理槽の１例を示す模式断面図、第２図および第
３図は本発明の電解処理における炭素＃＆維紐束全型（
旬、陰極板の巾、炭素繊維束の浸漬長（Ｌ）、陰極板の
長さくｒ、ｏ）、該繊維束と陰極板との相対間隔（Ｄ）
などの位置関係を示す松式断面図である。 特許出ル「１人　東し株式会社 鍔Ｉ　図FIG. 1 is a schematic cross-sectional view showing an example of an electrolytic treatment tank in which pre-treatment tanks for carbon fiber bundles used in the present invention are connected, and FIGS. 2 and 3 are carbon #& fiber bundles in the electrolytic treatment of the present invention. All types (
width of the cathode plate, immersion length of the carbon fiber bundle (L), length of the cathode plate (r, o), relative distance between the fiber bundle and the cathode plate (D)
FIG. Patent issue ``One Person Toshi Co., Ltd. Tsuba I Diagram

Claims (2)

【特許請求の範囲】[Claims] （１）　　炭素紙約：束を表面電解処理して、その表面
を改？ｆするに除して、電解液に対して混和性であり、
かつ化学的に反応性を有しない液体を用いて、該炭素繊
維束を予備的に処理した後、該炭素繊維束を前記液体で
湿潤させたまま、′「Ｕ解液中に導入し電解処理するこ
とを特徴とする改良された炭素ｋｋ維束の表面電解処理
法。(1) Carbon paper promise: Can the surface of the bundle be modified by surface electrolysis treatment? is miscible with the electrolyte to the extent that
After preliminarily treating the carbon fiber bundle with a chemically non-reactive liquid, the carbon fiber bundle is introduced into a U solution solution while being wetted with the liquid and electrolytically treated. An improved method for surface electrolytic treatment of carbon KK fibers. （２）′Ｐ、′ｒ許小゛ノ求の釘イ、囲第１項において
、電解浴中における炭素繊維束の全中（ｌ＃）か陰極板
の巾（Ｗｏ）よりも小さく、該繊維束の浸漬長（Ｌ）と
陰極板の長さくり、）との比（Ｌ／Ｌｏ）が１〜２であ
り、かつ詠繊糺束と陰極板との相対間隔ＣＤ）が５〜３
０ｆｍである改良された炭素繊維束の表向電解如月・法
。(2) 'P,'r' is smaller than the width (Wo) of the carbon fiber bundle in the electrolytic bath (l#) or the width of the cathode plate (Wo), and The ratio (L/Lo) of the immersion length (L) of the fiber bundle to the length of the cathode plate (L/Lo) is 1 to 2, and the relative distance CD) between the wing fiber bundle and the cathode plate is 5 to 3.
Kisaragi method for surface electrolysis of improved carbon fiber bundles with 0 fm.