JP3012885B2 - Method for producing surface-modified carbon fiber - Google Patents
Method for producing surface-modified carbon fiberInfo
- Publication number
- JP3012885B2 JP3012885B2 JP11602189A JP11602189A JP3012885B2 JP 3012885 B2 JP3012885 B2 JP 3012885B2 JP 11602189 A JP11602189 A JP 11602189A JP 11602189 A JP11602189 A JP 11602189A JP 3012885 B2 JP3012885 B2 JP 3012885B2
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- Japan
- Prior art keywords
- carbon fiber
- group
- treatment
- electrolytic
- aromatic compound
- Prior art date
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Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、特にマトリツクス樹脂との接着性に優れた
表面改質炭素繊維の製造方法に関する。Description: TECHNICAL FIELD The present invention relates to a method for producing surface-modified carbon fiber which is particularly excellent in adhesion to a matrix resin.
炭素繊維を補強材とする複合材料は軽量でかつ強度、
弾性率に優れているためスポーツ、レジヤー用品の構成
部品として、あるいは宇宙航空機用器材等として幅広い
分野にわたつてその用途開発が進められている。しかし
従来、複合材の補強材として用いられてきた炭素繊維
は、マトリツクス樹脂との接着性が必ずしも十分ではな
く、その表面を活性化させるため、薬剤酸化処理、気相
酸化処理、電解酸化処理等の表面処理方法が採用されて
きた。その中でも、電解酸化処理法はその操作性の良
さ、反応制御の容易さ等の見地から実用的な表面処理方
法である。Composite materials using carbon fiber as a reinforcing material are lightweight and strong,
Due to its excellent elastic modulus, its use is being developed in a wide range of fields as components of sports and registrar articles, or as equipment for space aircraft. However, carbon fiber, which has been used as a reinforcing material for composite materials, does not always have sufficient adhesiveness to the matrix resin. In order to activate the surface, chemical oxidation treatment, gas phase oxidation treatment, electrolytic oxidation treatment, etc. Surface treatment methods have been adopted. Among them, the electrolytic oxidation treatment method is a practical surface treatment method from the viewpoint of good operability, easy reaction control, and the like.
電解酸化処理法として、従来、種々の電解質が検討さ
れてきた。Conventionally, various electrolytes have been studied as the electrolytic oxidation treatment method.
例えば米国特許第4401533号には、硫酸塩水溶液中
で、特定の範囲の電流、電圧、処理時間で、炭素繊維を
陽極にして電解酸化する方法が開示されている。For example, U.S. Pat. No. 4,401,533 discloses a method of electrolytically oxidizing a carbon fiber as an anode in a specific range of current, voltage and treatment time in a sulfate aqueous solution.
米国特許第3832297号には、アンモニウム化合物を電
解質に用い、炭素繊維を陽極にして電解酸化を行うこ
と、さらにこの化合物は、250℃以下の温度で分解して
繊維に残らないことが開示されている。U.S. Pat.No. 3,832,297 discloses that an ammonium compound is used as an electrolyte, electrolytic oxidation is performed using carbon fiber as an anode, and that this compound is decomposed at a temperature of 250 ° C. or less and does not remain in the fiber. I have.
米国特許第4600572号には、硝酸中で炭素繊維を電解
酸化しさらに不活性化処理を行うことによつて炭素繊維
の強度を高め、繊維と樹脂の接着性の良い炭素繊維を製
造できることが開示されている。U.S. Pat. No. 4,600,572 discloses that carbon fibers can be electrolytically oxidized in nitric acid and further deactivated to increase the strength of the carbon fibers and produce carbon fibers with good adhesion between the fibers and the resin. Have been.
さらに、１種類の電解質では十分な表面処理が行えな
いため、本発明者らは２段階の電解処理方法を先に特開
昭61−124677号で提案した。しかし従来の方法では30t/
mm2以上の高弾性炭素繊維に対しては十分な効果を得る
ことができなかつた。また２段階表面処理によつて窒素
官能基を炭素繊維表面に導入する方法が特開昭62−2760
75号及び特開昭63−6162号に開示されている。Furthermore, since one type of electrolyte cannot perform sufficient surface treatment, the present inventors have previously proposed a two-stage electrolytic treatment method in Japanese Patent Application Laid-Open No. 61-124677. However, 30t /
Sufficient effects could not be obtained for highly elastic carbon fibers of mm 2 or more. A method of introducing a nitrogen functional group onto the surface of a carbon fiber by two-stage surface treatment is disclosed in Japanese Patent Laid-Open No. 62760/1987.
No. 75 and JP-A-63-6162.
炭素繊維の高性能化の要望は年々強くなつてきてお
り、特に航空機用の炭素繊維には高強度化、高弾性率化
の方向で開発が進められてきており最近では30t/mm2前
後の弾性率を有する中弾性炭素繊維が主流になつてい
る。一方、スポーツ、レジヤー用途においても高弾性化
の方向で開発されており45t/mm2前後でコンポ性能の良
好な炭素繊維の開発も行われている。これら高弾性化に
対応して炭素繊維の表面は不活性化の方向に進み、繊維
とマトリツクス樹脂の界面結合力は発揮しにくくなつて
いる。従来の炭素繊維の表面処理方法では不十分であ
り、また実際には高弾性炭素繊維でコンポ性能、特にIL
SS（層間剪断強度）、TS⊥（繊維方向と90゜方向の引張
り強度）、FS⊥（繊維方向と90゜方向の曲り強度）等を
良好ならしめる表面処理方法はいまだ開発されていない
のが現状である。Demand for high performance of carbon fiber has been summer stronger year by year, especially in carbon fiber for the aircraft high-strength, in recent years has been the development is advanced in the direction of the high elastic modulus 30t / mm 2 of the before and after Medium elastic carbon fibers having an elastic modulus are mainly used. Meanwhile, sports, are also being developed good carbon fiber component performance at 45t / mm 2 before and after have been developed in the direction of higher elasticity of even Rejiya applications. In response to the increase in the elasticity, the surface of the carbon fiber proceeds in the direction of inactivation, and it becomes difficult to exhibit the interfacial bonding force between the fiber and the matrix resin. Conventional carbon fiber surface treatment methods are inadequate, and in fact, high elastic carbon fibers have component performance, especially IL
Surface treatment methods that improve SS (interlaminar shear strength), TS⊥ (tensile strength in the fiber direction and 90 ° direction), FS⊥ (bending strength in the fiber direction and 90 ° direction), etc., have not yet been developed. It is the current situation.
本発明の目的は炭素繊維において優れたコンポジツト
特性を発現し得る炭素繊維の表面特性の改善であり、本
発明はそのための新規な炭素繊維の製造方法に関する。An object of the present invention is to improve the surface characteristics of a carbon fiber capable of exhibiting excellent composite characteristics in the carbon fiber, and the present invention relates to a novel method for producing the carbon fiber.
炭素繊維を表面処理して繊維とマトリツクス樹脂との
結合力を高めるためには、表面に酸素含有官能基を導入
することが不可欠である。また窒素含有官能基も同時に
導入することも樹脂との結合力を高めるのに効果がある
と考えられる。In order to enhance the bonding strength between the fiber and the matrix resin by surface-treating the carbon fiber, it is essential to introduce an oxygen-containing functional group into the surface. It is considered that the simultaneous introduction of a nitrogen-containing functional group is also effective in increasing the bonding force with the resin.
その他、電解重合により生成した重合物の炭素繊維表
面への電着あるいは表面コーテイングによつても繊維と
樹脂との結合力を高めることができると考えられる。こ
の場合にも重合物に存在する官能基の効果は重要である
と思われ、また場合によつては炭素繊維表面上の官能基
よりも結合力に及ぼす効果が大きくなる可能性もある。
しかも、重合物の電着あるいは表面コーテイングによ
り、樹脂分子とのからみ合いの効果により繊維と樹脂の
接着性の向上も期待できる。In addition, it is considered that the bonding force between the fiber and the resin can also be increased by electrodeposition of the polymer produced by electrolytic polymerization on the carbon fiber surface or by surface coating. Also in this case, the effect of the functional group present in the polymer is considered to be important, and in some cases, the effect on the bonding strength may be greater than the functional group on the carbon fiber surface.
In addition, by the electrodeposition or surface coating of the polymer, an improvement in the adhesiveness between the fiber and the resin can be expected due to the effect of entanglement with the resin molecules.
そこで本発明者らは炭素繊維に酸素及び窒素含有官能
基を導入するかあるいはモノマー、電解重合物等の電
着、コーテイング等を行う方法を検討し、本発明を完成
した。Therefore, the present inventors have studied a method of introducing an oxygen- and nitrogen-containing functional group into carbon fibers, or conducting electrodeposition and coating of a monomer, an electrolytic polymer, and the like, and completed the present invention.
本発明は、Ｘ線光電子分光法により求められる炭素繊
維表面の酸素含有官能基量（O1S/C1S）が0.07以上であ
るように酸化処理された炭素繊維を、ヒドロキシ基又は
アミノ基を１個以上有する芳香族化合物を含む溶液中で
炭素繊維と対極との間で電解処理することを特徴とす
る、表面改質炭素繊維の製造方法である。The present invention relates to a method of preparing a carbon fiber oxidized so that the amount of oxygen-containing functional groups (O 1S / C 1S ) on the surface of the carbon fiber determined by X-ray photoelectron spectroscopy is 0.07 or more. A method for producing a surface-modified carbon fiber, comprising performing an electrolytic treatment between a carbon fiber and a counter electrode in a solution containing at least one aromatic compound.
本発明に用いられる炭素繊維は、Ｘ線光電子分光法に
より求められる炭素繊維表面の酸素含有官能基量（O1S/
C1S）が0.07以上であるように酸化処理されたものであ
る。これはこの酸化処理により炭素繊維表面に導入され
た酸素含有官能基が、電解処理におけるモノマー又は電
解重合物等の電着及びコーテイングに際して何らかの影
響を及ぼしているからである。しかも酸化処理により導
入される酸素含有官能基量の多いものほど、電解処理に
おいて炭素繊維表面へのモノマー又は電解重合物等の電
着、コーテイング等が容易になる傾向がある。The carbon fiber used in the present invention has an oxygen-containing functional group content (O 1S /
It has been oxidized so that C 1S ) is 0.07 or more. This is because the oxygen-containing functional group introduced into the carbon fiber surface by this oxidation treatment has some influence on the electrodeposition and coating of a monomer or an electrolytic polymer in the electrolytic treatment. Moreover, as the amount of the oxygen-containing functional group introduced by the oxidation treatment increases, the electrodeposition and coating of the monomer or the electrolytic polymer on the carbon fiber surface in the electrolytic treatment tend to be easier.
酸化処理としては電解酸化、オゾン酸化、硝酸酸化、
酸化剤による薬剤酸化、空気酸化、プラズマ酸化などが
用いられる。また炭素繊維は、炭素及び黒鉛繊維のいず
れでもよく、そして原料として繊維状のポリアクリロニ
トリル、天然及び再生セルロース、ポリビニルアルコー
ル、ピツチ等を用いて炭素化又は黒鉛化することにより
得られたものや、気相成長して得られたものを含む。The oxidation treatment includes electrolytic oxidation, ozone oxidation, nitric acid oxidation,
Chemical oxidation, air oxidation, plasma oxidation, and the like using an oxidizing agent are used. Carbon fibers may be any of carbon and graphite fibers, and those obtained by carbonization or graphitization using fibrous polyacrylonitrile, natural and regenerated cellulose, polyvinyl alcohol, pitch, etc. as raw materials, Includes those obtained by vapor phase growth.
本発明を実施するに際しては、前記の炭素繊維を、ヒ
ドロキシ基又はアミノ基を１個以上有する芳香族化合物
を含む溶液中で炭素繊維と対極との間で電解処理をす
る。In carrying out the present invention, the carbon fiber is subjected to electrolytic treatment between the carbon fiber and the counter electrode in a solution containing an aromatic compound having at least one hydroxy group or one amino group.
電解処理時の炭素繊維の電極は陽極又は陰極のどちら
でもよい。しかし炭素繊維を陽極として電解処理する方
が炭素繊維表面へのモノマー又は電解重合物の電着及び
コーテイングが容易であるので、炭素繊維を陽極にして
電解処理することが好ましい。The electrode of carbon fiber during the electrolytic treatment may be either an anode or a cathode. However, it is preferable to carry out the electrolytic treatment using the carbon fiber as the anode, because the electrodeposition and coating of the monomer or the electrolytic polymer on the carbon fiber surface are easier when the electrolytic treatment is performed using the carbon fiber as the anode.
電解液の溶媒としては、水又はDMFなどの有機溶剤の
いずれでもよい。工業的には水が好ましい。The solvent of the electrolytic solution may be any of water and an organic solvent such as DMF. Water is preferred industrially.
ヒドロキシ基又はアミノ基を１個以上有する芳香族化
合物（モノマー）としては、芳香環（ベンゼン環、ナフ
タレン環、アントラセン環、フエナントレン環、ピレン
環など）にヒドロキシ基又はアミノ基が直接結合した化
合物が好ましい。またヒドロキシ基又はアミノ基の他
に、アルキル基やビニル基、プロピニル基のようなＣ−
Ｃ二重結合を有する官能基、アルコキシ基、カルボキシ
基などの官能基により置換されていてもよい。一般式 （式中Ｘは水素原子、アルキル基、アルコキシ基、カル
ボキシ基又はＣ−Ｃ二重結合を有する官能基、ｍ及びｎ
は１〜４の数を示す）で表わされる化合物が好ましい。
例えばフエノール、アニリン、アミノフエノール、ジア
ミノベンゼン、ジヒドロキシベンゼン、アミノ安息香
酸、サリチル酸、ジアミノフエノール、ジヒドロキシア
ニリン、アミノサリチル酸、アミノスチレンヒドロキシ
スチレン、アミノアニソール、ヒドロキシアニソール、
ナフトール、アミノナフタレン、ジアミノナフタレン、
アミノナフトール、ジヒドロキシナフタレン、アミノナ
フトエ酸、ヒドロキシナフトエ酸、（ジ）ヒドロキシジ
フエニルメタン、（ジ）アミノジフエニルメタン、
（ジ）アミノベンゾフエノン、（ジ）ヒドロキシベンゾ
フエノン、（ジ）アミノビフエニル、（ジ）ヒドロキシ
ビフエニル及びこれらのアルキル置換体などがあげられ
る。フエノール、アニリン、ｏ−アミノフエノール、ｍ
−アミノフエノール、ｐ−アミノフエノール、ｏ−ジヒ
ドロキシベンゼン、ｍ−ジヒドロキシベンゼン、ｏ−ジ
アミノベンゼン、ｍ−ジアミノベンゼン、ｐ−ジアミノ
ベンゼン、ｐ−アミノサリチル酸などが好ましい。これ
らの２種以上の混合物を用いることもできる。As the aromatic compound (monomer) having at least one hydroxy group or amino group, a compound in which a hydroxy group or an amino group is directly bonded to an aromatic ring (a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, etc.) is mentioned. preferable. In addition to a hydroxy group or an amino group, a C- such as an alkyl group, a vinyl group, or a propynyl group may be used.
It may be substituted with a functional group having a C double bond, a functional group such as an alkoxy group or a carboxy group. General formula (Wherein X is a hydrogen atom, an alkyl group, an alkoxy group, a carboxy group or a functional group having a CC double bond, m and n
Is a number from 1 to 4).
For example, phenol, aniline, aminophenol, diaminobenzene, dihydroxybenzene, aminobenzoic acid, salicylic acid, diaminophenol, dihydroxyaniline, aminosalicylic acid, aminostyrene hydroxystyrene, aminoanisole, hydroxyanisole,
Naphthol, aminonaphthalene, diaminonaphthalene,
Aminonaphthol, dihydroxynaphthalene, aminonaphthoic acid, hydroxynaphthoic acid, (di) hydroxydiphenylmethane, (di) aminodiphenylmethane,
(Di) aminobenzophenone, (di) hydroxybenzophenone, (di) aminobiphenyl, (di) hydroxybiphenyl and alkyl-substituted products thereof. Phenol, aniline, o-aminophenol, m
-Aminophenol, p-aminophenol, o-dihydroxybenzene, m-dihydroxybenzene, o-diaminobenzene, m-diaminobenzene, p-diaminobenzene, p-aminosalicylic acid and the like are preferred. A mixture of two or more of these can also be used.
電解液中のモノマー濃度は0.01〜15重量％好ましくは
0.1〜10重量％である。0.01重量％以下では炭素繊維へ
のモノマー又は電解重合物の電着及びコーテイングが不
十分である。The concentration of the monomer in the electrolyte is 0.01 to 15% by weight, preferably
0.1 to 10% by weight. When the content is less than 0.01% by weight, the electrodeposition and coating of the monomer or the electrolytic polymer on the carbon fiber are insufficient.
電解液中の電解質に用いられる物質としては、無機電
解質例えば硝酸、燐酸、硫酸、硝酸ナトリウム、燐酸一
ナトリウム、燐酸二ナトリウム、燐酸三ナトリウム、硫
酸ナトリウム、水酸化ナトリウム、水酸化カリウムな
ど、アンモニウム塩例えば炭酸アンモニウム、炭酸水素
アンモニウム、燐酸アンモニウム、燐酸二アンモニウ
ム、燐酸三アンモニウム、硝酸アンモニウム、硫酸アン
モニウム、カルバミン酸アンモニウムなどがあげられ
る。これらの２種以上の混合物を用いることもできる。Examples of the substance used for the electrolyte in the electrolyte include inorganic electrolytes such as nitric acid, phosphoric acid, sulfuric acid, sodium nitrate, monosodium phosphate, disodium phosphate, trisodium phosphate, sodium sulfate, sodium hydroxide, and potassium hydroxide. For example, ammonium carbonate, ammonium hydrogen carbonate, ammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium nitrate, ammonium sulfate, ammonium carbamate and the like can be mentioned. A mixture of two or more of these can also be used.
電解処理時の処理電気量は、電解液の種類及びその組
成例えば溶媒、電解質、モノマーなどにより最適値は異
なるが、５〜1500クーロン/g好ましくは５〜1000クーロ
ン/gである。The amount of electricity to be treated at the time of the electrolytic treatment varies depending on the type and composition of the electrolytic solution, for example, the solvent, the electrolyte and the monomer, but is 5 to 1500 coulombs / g, preferably 5 to 1000 coulombs / g.
炭素繊維の処理方法は、従来の電解処理と同様、電流
密度は0.1A/m2以上でバツチ式、連続式いずれでもよ
く、通電方法もローラー通電方式、電解液接触方式いず
れでもよい。処理に用いる溶液の温度は０〜100℃の範
囲であり、また処理時間は電解液中で数秒ないし数十
分、好ましくは５秒ないし５分である。洗浄効果を向上
させるために電解液を流動させたり、不活性ガスを用い
たバブリングや超音波振動を利用することができる。As in the conventional electrolytic treatment, the current density of the carbon fiber is 0.1 A / m 2 or more, and may be any of a batch type and a continuous type. The energizing method may be a roller energizing type or an electrolytic solution contacting type. The temperature of the solution used for the treatment is in the range of 0 to 100 ° C., and the treatment time is several seconds to tens of minutes, preferably 5 seconds to 5 minutes in the electrolytic solution. In order to improve the cleaning effect, an electrolytic solution can be flowed, bubbling using an inert gas, or ultrasonic vibration can be used.
こうして得られた炭素繊維を複合材料に用いる場合、
使用するマトリツクス樹脂には特に制限はなく、熱硬化
性樹脂としてエポキシ樹脂、イミド樹脂、不飽和ポリエ
ステル等、熱可塑性樹脂としてポリアミド、ポリエステ
ル、ポリスルホン、ポリエーテルエーテルケトン、ポリ
エーテルイミド、ポリエーテルスルホン、ポリアセター
ル樹脂、ポリプロピレン、ABS、ポリカーボネート等の
樹脂が用いられる。When using the carbon fiber thus obtained for a composite material,
There is no particular limitation on the matrix resin used, and as the thermosetting resin, an epoxy resin, an imide resin, an unsaturated polyester, etc., and a thermoplastic resin such as polyamide, polyester, polysulfone, polyetheretherketone, polyetherimide, polyethersulfone, Resins such as polyacetal resin, polypropylene, ABS, and polycarbonate are used.
本発明方法によれば、マトリツクス樹脂との接着性に
優れた炭素繊維を容易に製造することができる。According to the method of the present invention, carbon fibers having excellent adhesion to the matrix resin can be easily produced.
測定方法は次のとおりである。 The measuring method is as follows.
（１）Ｘ線光電子分光法による炭素繊維表面の酸素濃度
（O1S/C1S原子数比）の測定は、VG社製ESCA装置ESCALAB
MK II型を用いてMgKα線をＸ線源としたときのC1S、O1S
のシグナル強度からそれぞれのASF値（0.205、0.630、
0.380）を用いてO1S/C1Sを原子数比として算出した。(1) Measurement of the oxygen concentration (O 1S / C 1S atomic ratio) on the carbon fiber surface by X-ray photoelectron spectroscopy was performed using the ESCA system ESCALAB manufactured by VG.
C 1S , O 1S when MgKα ray is used as X-ray source using MK II
ASF values (0.205, 0.630,
O 1S / C 1S was calculated as the atomic ratio using 0.380).
（２）界面剪断強度（τ）の測定は下記の方法により行
つた。(2) The measurement of the interfacial shear strength (τ) was performed by the following method.
連続単繊維を一本、エポキシ系マトリツクス樹脂〔エ
ピコート828（油化シエル社製）100部、カヤハードMCD
（日本化薬社製）90部、N,N−ジメチルベンジルアミン
３部〕中に埋め込んだ試験片を作成する。この試験片に
ある一定以上の引張りひずみを与えることにより、埋込
んだ繊維を多数か所で破断させる。この破断片の長さを
測定し平均破断長（）を求め、臨界繊維長（lc）をlc
＝4/3・より求める。また単繊維強度試験により、炭
素繊維の強度分布を求め、それにワイブル分布を適用し
ワイブルパラメーターｍσ０を求める。このワイブルパ
ラメターターｍσ０より、臨界繊維長（lc）における平
均破断強度σｆを算出しτ＝σfd/2lc（d:炭素繊維の直
径）より界面剪断強度（τ）を求める。One continuous monofilament, 100 parts of epoxy matrix resin [Epicoat 828 (manufactured by Yuka Shell), Kayahard MCD
(Manufactured by Nippon Kayaku Co., Ltd.), 90 parts, N, N-dimethylbenzylamine 3 parts]. By applying a tensile strain equal to or more than a certain value to the test piece, the embedded fiber is broken at many points. The length of this broken fragment was measured to determine the average breaking length (), and the critical fiber length (lc) was calculated as lc.
= 4/3. Further, the strength distribution of the carbon fibers is determined by a single fiber strength test, and the Weibull parameter mσ 0 is determined by applying the Weibull distribution to the strength distribution. The average breaking strength σ f at the critical fiber length (lc) is calculated from the Weibull parameter mσ 0 , and the interfacial shear strength (τ) is calculated from τ = σ f d / 2lc (d: diameter of carbon fiber).
実施例１ アクリロニトリル／メタクリル酸（98/2重量比）の重
合体をジメチルホルムアミドに固形濃度26重量％となる
ように溶解してドープを作り、10μ過及び３μ過を
行つて湿式紡糸を行い、引続き温水中で4.5倍に延伸
し、水洗、乾燥して、更に乾熱170℃で1.7倍に延伸して
0.9デニールの繊度を有するフイラメント数12000のプレ
カーサーを得た。Example 1 A polymer of acrylonitrile / methacrylic acid (98/2 weight ratio) was dissolved in dimethylformamide so as to have a solid concentration of 26% by weight, and a dope was prepared. Then stretched 4.5 times in warm water, washed with water, dried, and stretched 1.7 times at 170 ° C.
A precursor having a filament number of 12000 and a fineness of 0.9 denier was obtained.
このプレカーサーを220〜260℃の熱風循環型の耐炎化
炉を60分間通過させて耐炎化糸密度1.35g/cm3の耐炎化
繊維を得た。耐炎化処理するに際して15％の伸長操作を
施した。This precursor was passed through a hot-air circulation type oxidizing furnace at 220 to 260 ° C. for 60 minutes to obtain oxidizing fibers having an oxidizing yarn density of 1.35 g / cm 3 . A 15% elongation operation was performed during the oxidization treatment.
次に耐炎化繊維を純粋なN2雰囲気中300〜600℃の温度
勾配を有する第１炭素化炉を８％の伸長を加えながら通
過させた。The oxidized fiber was then passed through a first carbonization furnace having a temperature gradient of 300-600 ° C. in a pure N 2 atmosphere with an elongation of 8%.
更に、同雰囲気中2500℃の最高温度を有する第２炭素
化炉において400mg/dの張力下、２分熱処理を行い炭素
繊維を得た。この炭素繊維は、ストランド強度360kg/mm
2、ストランド弾性率46.0t/mm2の性能を有するものであ
つた。Further, in a second carbonization furnace having a maximum temperature of 2500 ° C. in the same atmosphere, heat treatment was performed for 2 minutes under a tension of 400 mg / d to obtain carbon fibers. This carbon fiber has a strand strength of 360 kg / mm
2. It had a performance of a strand elastic modulus of 46.0 t / mm 2 .
この炭素繊維を陽極として、pH1の燐酸５％、30℃水
溶液中、処理電気量55クーロン/gで通電処理を行つた。The carbon fiber was used as an anode, and a current was passed through an aqueous solution of 5% phosphoric acid at pH 1 at 30 ° C. with a processing electricity of 55 coulomb / g.
次いでpH7.5の炭酸水素アンモニウム５％、30℃水溶
液中に、１個以上のヒドロキシ基を有する芳香族化合物
を1.0〜3.0重量％加え、この水溶液中で通電処理を行つ
た。表面処理速度は20m/時間である。なお、燐酸中通電
処理後の酸素含有官能基量（O1S/C1S）は0.27であつ
た。測定結果を第１表に示す。Next, 1.0 to 3.0% by weight of an aromatic compound having one or more hydroxy groups was added to a 5% aqueous solution of ammonium hydrogencarbonate at pH 7.5 at 30 ° C., and a current was passed through the aqueous solution. The surface treatment speed is 20m / hour. The amount of oxygen-containing functional groups (O 1S / C 1S ) after the electric current treatment in phosphoric acid was 0.27. Table 1 shows the measurement results.
実施例２ 実施例１と同様にしてストランド強度360kg/mm2、ス
トランド弾性率46.0t/mm2の性能を有する炭素繊維を得
た。この炭素繊維を陽極として、pH1の燐酸５％、30℃
水溶液中、処理電気量55クローン/gで通電処理を行つ
た。 Example 2 In the same manner as in Example 1, a carbon fiber having a strand strength of 360 kg / mm 2 and a strand elastic modulus of 46.0 t / mm 2 was obtained. Using this carbon fiber as the anode, 5% phosphoric acid at pH 1 and 30 ° C
The energization treatment was performed in an aqueous solution at a treatment electricity amount of 55 clones / g.
次いでpH7.5の炭酸水素アンモニウム５％、30℃水溶
液中に、ヒドロキシ基とアミノ基をそれぞれ１個以上有
する芳香族化合物を0.25〜1.0重量％加え、この水溶液
中で通電処理を行つた。表面処理速度は20m/時間であ
る。測定結果を第２表に示す。Next, 0.25 to 1.0% by weight of an aromatic compound having at least one hydroxy group and at least one amino group was added to a 5% aqueous solution of ammonium bicarbonate at pH 7.5 and a 30 ° C. aqueous solution, and a current was passed through the aqueous solution. The surface treatment speed is 20m / hour. Table 2 shows the measurement results.
比較例 実施例１と同様にしてストランド強度360kg/mm2、ス
トランド弾性率46.0t/mm2の性能を有する炭素繊維を得
た。この炭素繊維を用いて、燐酸（５％）水溶液中で電
解酸化処理をしたもの（番号１及び２）、表面処理に供
さなかつたもの（番号３）、燐酸（５％）水溶液中で電
解酸化処理せずに〔酸素含有官能基量（O1S/C1S）は0.0
5〕、炭酸水素アンモニウム（５％）、フエノール（３
％）水溶液中で電解処理（陽極）したもの（番号４）、
燐酸（５％）水溶液中で電解酸化処理せずに、炭酸水素
アンモニウム（５％）、ｍ−アミノフエノール（１％）
水溶液中で電解処理（陽極）したもの（番号５）を得
た。これらについて界面剪断強度を測定した。その結果
を第３表に示す。これより、炭素繊維を本発明の条件下
で表面処理を行うことにより、エポキシ樹脂との接着性
の優れた炭素繊維が得られることがわかる。 Comparative Example A carbon fiber having a performance of a strand strength of 360 kg / mm 2 and a strand elasticity of 46.0 t / mm 2 was obtained in the same manner as in Example 1. This carbon fiber was subjected to electrolytic oxidation treatment in a phosphoric acid (5%) aqueous solution (Nos. 1 and 2), not subjected to surface treatment (No. 3), and electrolyzed in a phosphoric acid (5%) aqueous solution. Without oxidation treatment [Oxygen-containing functional group content (O 1S / C 1S ) is 0.0
5], ammonium bicarbonate (5%), phenol (3
%) Electrolytically treated (anode) in an aqueous solution (No. 4),
Ammonium hydrogen carbonate (5%), m-aminophenol (1%) without electrolytic oxidation treatment in phosphoric acid (5%) aqueous solution
An electrolytic treatment (anode) in an aqueous solution (No. 5) was obtained. The interfacial shear strength was measured for these. Table 3 shows the results. From this, it can be seen that a carbon fiber having excellent adhesion to an epoxy resin can be obtained by performing a surface treatment on the carbon fiber under the conditions of the present invention.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭63−85167（ＪＰ，Ａ) 特開 昭60−199975（ＪＰ，Ａ) ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-63-85167 (JP, A) JP-A-60-199975 (JP, A)
Claims (5)
維表面の酸素含有官能基量（O1S/C1S）が0.07以上であ
るように酸化処理された炭素繊維を、ヒドロキシ基又は
アミノ基を１個以上有する芳香族化合物を含む溶液中で
炭素繊維と対極との間で電解処理することを特徴とす
る、表面改質炭素繊維の製造方法。1. A carbon fiber oxidized so that the amount of oxygen-containing functional groups (O 1S / C 1S ) on the surface of the carbon fiber determined by X-ray photoelectron spectroscopy is 0.07 or more, a hydroxy group or an amino group is A method for producing surface-modified carbon fibers, comprising performing an electrolytic treatment between a carbon fiber and a counter electrode in a solution containing one or more aromatic compounds.
を特徴とする、第１請求項に記載の方法。2. The method according to claim 1, wherein the electrolytic treatment is performed using carbon fiber as an anode.
個以上有する芳香族化合物を含む水溶液中で行うことを
特徴とする、第１請求項に記載の方法。3. The method according to claim 1, wherein the electrolytic treatment is performed with one hydroxy group or one amino group.
The method according to claim 1, wherein the method is performed in an aqueous solution containing an aromatic compound having at least one aromatic compound.
物として、一般式 （式中Ｘは水素原子、アルキル基、アルコキシ基、カル
ボキシ基又はＣ−Ｃ二重結合を有する官能基、ｎは１〜
４の数を示す）で表わされる化合物を用いることを特徴
とする、第１請求項に記載の方法。4. An aromatic compound having at least one hydroxy group represented by the general formula: (Wherein X is a hydrogen atom, an alkyl group, an alkoxy group, a carboxy group or a functional group having a C—C double bond, and n is 1 to
4. The method according to claim 1, wherein the compound represented by the formula (4) is used.
上有する芳香族化合物として、一般式 （式中Ｘは水素原子、アルキル基、アルコキシ基、カル
ボキシ基又はＣ−Ｃ二重結合を有する官能基、ｍ及びｎ
は１〜４の数を示す）で表わされる化合物を用いること
を特徴とする、第１請求項に記載の方法。5. An aromatic compound having at least one hydroxy group and at least one amino group each having the general formula: (Wherein X is a hydrogen atom, an alkyl group, an alkoxy group, a carboxy group or a functional group having a CC double bond, m and n
The method according to claim 1, wherein a compound represented by the formula (1) is used.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11602189A JP3012885B2 (en) | 1989-05-11 | 1989-05-11 | Method for producing surface-modified carbon fiber |
| US07/447,857 US5124010A (en) | 1988-12-12 | 1989-12-08 | Carbon fibers having modified surfaces and process for producing the same |
| EP89122856A EP0374680B1 (en) | 1988-12-12 | 1989-12-11 | Carbon fibers having modified surfaces and process for preparing the same |
| KR1019890018265A KR930011306B1 (en) | 1988-12-12 | 1989-12-11 | Surface-improved carbon fiber and production thererof |
| DE68926028T DE68926028T2 (en) | 1988-12-12 | 1989-12-11 | Surface modified carbon fibers and process for their manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11602189A JP3012885B2 (en) | 1989-05-11 | 1989-05-11 | Method for producing surface-modified carbon fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02300376A JPH02300376A (en) | 1990-12-12 |
| JP3012885B2 true JP3012885B2 (en) | 2000-02-28 |
Family
ID=14676823
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11602189A Expired - Lifetime JP3012885B2 (en) | 1988-12-12 | 1989-05-11 | Method for producing surface-modified carbon fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3012885B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103469534B (en) * | 2013-09-30 | 2015-05-13 | 哈尔滨工业大学 | Method for chemical grafting modification for surfaces of carbon fibers |
| CN104480707B (en) * | 2014-12-26 | 2016-08-24 | 哈尔滨工业大学 | A kind of method of carbon fiber surface grafting hexa in supercritical methanol |
| JP6420719B2 (en) * | 2015-05-15 | 2018-11-07 | 本田技研工業株式会社 | Fiber-reinforced thermoplastic resin and method for producing the same |
| KR102050362B1 (en) * | 2017-05-22 | 2019-12-02 | 재단법인 한국탄소융합기술원 | Manufacturing Method for Polymer composite with carbon fiber for 3D printers |
-
1989
- 1989-05-11 JP JP11602189A patent/JP3012885B2/en not_active Expired - Lifetime
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| Publication number | Publication date |
|---|---|
| JPH02300376A (en) | 1990-12-12 |
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