JPH03287860A - Production of carbon fiber - Google Patents
Production of carbon fiberInfo
- Publication number
- JPH03287860A JPH03287860A JP9001990A JP9001990A JPH03287860A JP H03287860 A JPH03287860 A JP H03287860A JP 9001990 A JP9001990 A JP 9001990A JP 9001990 A JP9001990 A JP 9001990A JP H03287860 A JPH03287860 A JP H03287860A
- Authority
- JP
- Japan
- Prior art keywords
- carbon fiber
- carbon fibers
- oxygen
- treatment
- electrolytic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 38
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title abstract description 18
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 238000011282 treatment Methods 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000000835 fiber Substances 0.000 abstract description 11
- 229920005989 resin Polymers 0.000 abstract description 11
- 239000011347 resin Substances 0.000 abstract description 11
- 239000011159 matrix material Substances 0.000 abstract description 7
- 239000008151 electrolyte solution Substances 0.000 abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 13
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000011437 continuous method Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 229920001342 Bakelite® Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-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
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000004637 bakelite Substances 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- JDVIRCVIXCMTPU-UHFFFAOYSA-N ethanamine;trifluoroborane Chemical compound CCN.FB(F)F JDVIRCVIXCMTPU-UHFFFAOYSA-N 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 238000001891 gel spinning Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は炭素繊維の製造方法、特に樹脂マトリックスと
の接着力に優れた炭素繊維の製造方法に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing carbon fibers, and particularly to a method for producing carbon fibers that have excellent adhesive strength with a resin matrix.
［従来の技術］
炭素繊維は一般に各種樹脂マ） ＩＪワックスからなる
複合強化材料として利用されているが、炭素繊維の特性
を複合材料に生かすには、樹脂との接着力が重要であり
、この接着力を改善することを目的として、気相酸化お
よび電解酸化など種々の表面処理が行われている。気相
酸化法は短時間処理が可能であり、水洗・乾燥等の工程
が省ける点が優れているものの（特公昭４５−１２８７
号公報、特公昭５２−５３０９２号公報）強度低下が起
こり易く、酸化ムラによる単繊維間のバラツキが大きい
という問題がある。一方、電解酸化は工業的に広く用い
られているが樹脂マトリックスとの接着力が不十分であ
り、さらに接着力を上げるために酸性電解質中で電解酸
化処理を行った後に、アルカリ性電解液中で電解処理を
行う方法等が提案されている（特開昭６３−８５１６７
号公報、特開昭６４−４５８６８号公報）が、表面処理
プロセスが複雑になるという問題がある。[Prior art] Carbon fiber is generally used as a composite reinforcing material made of various resins (IJ wax), but in order to make use of the characteristics of carbon fiber in composite materials, adhesive strength with the resin is important. Various surface treatments such as vapor phase oxidation and electrolytic oxidation have been carried out to improve adhesion. Although the gas phase oxidation method is superior in that it can be processed in a short time and eliminates steps such as washing and drying,
(Japanese Patent Publication No. 52-53092) There are problems in that the strength tends to decrease and there is large variation among single fibers due to uneven oxidation. On the other hand, electrolytic oxidation is widely used industrially, but the adhesion with the resin matrix is insufficient.In order to further increase the adhesion, electrolytic oxidation treatment is performed in an acidic electrolyte, and then in an alkaline electrolyte. A method of electrolytic treatment has been proposed (Japanese Patent Laid-Open No. 63-85167).
However, there is a problem in that the surface treatment process becomes complicated.
［発明が解決しようとする課題］
本発明の課題は、上記従来技術では達成し得なかった樹
脂マトリックスとの接着力に優れた炭素繊維を生産性よ
く製造する方法を提供することにある。[Problems to be Solved by the Invention] An object of the present invention is to provide a method for producing carbon fibers with good productivity that have excellent adhesive strength to a resin matrix, which could not be achieved with the above-mentioned conventional techniques.
［課題を解決するための手段］
本発明の上記課題は、炭素繊維を酸素含有雰囲気中で加
熱した後、電解処理することを特徴とする炭素繊維の製
造方法によって解決することができる。[Means for Solving the Problems] The above problems of the present invention can be solved by a method for manufacturing carbon fibers, which is characterized in that carbon fibers are heated in an oxygen-containing atmosphere and then electrolytically treated.
本発明に用いられる炭素繊維としては、アクリル系、ピ
ッチ系、レーヨン系等の公知の炭素繊維を適用できる。As the carbon fibers used in the present invention, known carbon fibers such as acrylic, pitch, and rayon fibers can be used.
好ましくは高性能な炭素長繊維が得られ易いアクリル系
あるいはピッチ系炭素繊維がよい。Preferably, acrylic or pitch carbon fibers from which high-performance long carbon fibers can be easily obtained are preferred.
焼成温度については１０００〜２０００℃で焼成した炭
化糸および２０００〜３３００℃で焼成した黒鉛化糸の
いずれにも適用できる。Regarding the firing temperature, it is applicable to both carbonized yarn fired at 1000 to 2000°C and graphitized yarn fired at 2000 to 3300°C.
繊維束としては、１００〜１０００００デニール、好ま
しくは生産性の面から３０００〜１０００００デニール
がよい。繊維束が太（なるほど処理による束の内外差が
大きくなる傾向があるので、酸素含有雰囲気での単繊維
間バラツキを小さくするために、糸束を開繊し、糸束断
面の短径と長径の比を好ましくは２以上、より好ましく
は５以上にするのがよい。この場合の開繊方法としては
Ｖ溝よりもＵ溝のようなできるだけ底の平らで広い溝ロ
ーラーあるいは平ローラーを使用し、好ましくは凸型あ
るいは平型ガイドと組み合わせるのが効果的である。更
に好ましくはガイドに低周波あるいは超音波などの振動
を加えるのがよい。The fiber bundle has a denier of 100 to 100,000, preferably 3,000 to 100,000 in terms of productivity. The fiber bundle is thick (I see, the difference between the inside and outside of the bundle tends to increase due to processing, so in order to reduce the variation between single fibers in an oxygen-containing atmosphere, the yarn bundle is opened, and the short axis and long axis of the cross section of the yarn bundle are The ratio is preferably 2 or more, more preferably 5 or more.In this case, the opening method is to use a groove roller or a flat roller with a flat and wide bottom as much as possible, such as a U groove rather than a V groove. It is effective to combine the guide with a convex or flat guide.It is more preferable to apply vibrations such as low frequency or ultrasonic waves to the guide.
本発明においては、まず上記のような炭素繊維を酸素含
有雰囲気中で加熱処理を行う。この場合の酸素含有雰囲
気とは、空気、酸素、水蒸気、オゾン、酸化窒素等から
選ばれた１種あるいは２種以上の混合ガスを含む雰囲気
をいうが、空気が最も一般的である。またこれらの酸素
含有雰囲気には、不活性ガス例えばアルゴン、窒素、ヘ
リウム、あるいは酸化ムラを抑えるための塩素等を混合
してもよい。In the present invention, first, the above-described carbon fibers are heat-treated in an oxygen-containing atmosphere. The oxygen-containing atmosphere in this case refers to an atmosphere containing one or more mixed gases selected from air, oxygen, water vapor, ozone, nitrogen oxide, etc., with air being the most common. In addition, an inert gas such as argon, nitrogen, helium, or chlorine for suppressing oxidation unevenness may be mixed into these oxygen-containing atmospheres.
加熱処理時の加熱温度は好ましくは２００〜１０００℃
、より好ましくは４００〜７００℃がよい。２００℃よ
り低い温度では熱処理量が少なく加熱時間が長くなり、
また１０００℃を越えると強度低下や強度のバラツキが
生じ易いことがある。The heating temperature during heat treatment is preferably 200 to 1000°C
, more preferably 400 to 700°C. At temperatures lower than 200℃, the amount of heat treatment will be small and the heating time will be longer.
Furthermore, if the temperature exceeds 1000°C, strength may tend to decrease or vary.
処理時間については数秒〜１５分、好ましくは２０秒〜
２分がよいが、処理温度との組合せで最適化することが
好ましい。The processing time is several seconds to 15 minutes, preferably 20 seconds to
2 minutes is good, but it is preferable to optimize it in combination with the treatment temperature.
処理張力は、好ましくは緊張下、より好ましくは０°１
〜１０ｇ／ｄ（デニール）程度がよい。The processing tension is preferably under tension, more preferably 0°1
~10 g/d (denier) is preferable.
次に、本発明方法は炭素繊維を酸素含有雰囲気中で加熱
した後、電解処理を行う。Next, in the method of the present invention, the carbon fibers are heated in an oxygen-containing atmosphere and then electrolytically treated.
この場合の電解液としては、酸性、アルカリ性いずれも
採用できるが、特に樹脂マトリックスとの接着力向上効
果に優れたアルカリ性電解液が好ましい。As the electrolytic solution in this case, both acidic and alkaline electrolytic solutions can be used, but an alkaline electrolytic solution is particularly preferred since it has an excellent effect of improving adhesive strength with the resin matrix.
アルカリ性電解液としてはｐＨが７〜１４、より好まし
くは電解力の強いｐＨ１０〜１４の水溶液がよい。具体
的には水酸化ナトリウム、炭酸ナトリウム、炭酸水素ナ
トリウム、炭酸水素ナトリウム等の無機塩類、酢酸ナト
リウム、安息香酸ナトリウム等の有機塩の水溶液、これ
らのカリウム塩、バリウム塩あるいは他の金属塩、さら
にアンモニアおよびアンモニウム塩等が挙げられるが、
好ましくは樹脂マトリックスとの接着力に特に優れた水
酸化テトラエチルアンモニウム（ＥＡＨ）がよい。The alkaline electrolyte is preferably an aqueous solution with a pH of 7 to 14, more preferably a pH of 10 to 14 with strong electrolytic power. Specifically, aqueous solutions of inorganic salts such as sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, and sodium hydrogen carbonate, organic salts such as sodium acetate and sodium benzoate, potassium salts, barium salts, and other metal salts thereof, and Examples include ammonia and ammonium salts,
Preferred is tetraethylammonium hydroxide (EAH), which has particularly excellent adhesive strength with the resin matrix.
電解液の濃度としては、好ましくは０．０１〜５モル１
５より好ましくは０．１〜１モル／Ｉがよい。The concentration of the electrolytic solution is preferably 0.01 to 5 mol 1
5, more preferably 0.1 to 1 mol/I.
電解温度としては好ましくは０〜１００℃、より好まし
くは電解液が取り扱い易くまた液相として安定している
５〜８０°０１更に好ましくは処理設備を簡単にできる
室温がよい。The electrolysis temperature is preferably 0 to 100°C, more preferably 5 to 80°C, where the electrolytic solution is easy to handle and stable as a liquid phase, and even more preferably room temperature, where processing equipment can be easily installed.
電気量は被処理炭素繊維の焼成温度に合わせて最適化す
るが、好ましくは５〜５００Ｃ／ｇ （炭素繊維１ｇ当
りのクーロン数）、より好ましくは２０〜２００ Ｃ／
ｇの範囲で設定するのがよい。The amount of electricity is optimized according to the firing temperature of the carbon fiber to be treated, but is preferably 5 to 500 C/g (number of coulombs per gram of carbon fiber), more preferably 20 to 200 C/g.
It is best to set it within the range of g.
電解電圧は好ましくは０，５〜２５Ｖ１より好ましくは
安全を考慮してＩＯＶ未満がよい。The electrolytic voltage is preferably 0.5 to 25 V1, preferably less than IOV in consideration of safety.
電解処理時間は電気量、電解質濃度により最適化すべき
であるが、生産性の面から数秒〜１０分、好ましくは１
０秒〜２分程度がよい。The electrolytic treatment time should be optimized depending on the amount of electricity and the electrolyte concentration, but from the viewpoint of productivity it should be several seconds to 10 minutes, preferably 1 minute.
Approximately 0 seconds to 2 minutes is preferable.
電解処理方法としてはバッチ式、連続式いずれでもよい
が、生産性がよくバラツキが小さくできｌる連続式が好
ましい。The electrolytic treatment method may be either a batch method or a continuous method, but a continuous method is preferred because it has good productivity and can reduce variations.
通電方法としては直接通電、間接通電のいずれも採用す
るこ・とができる。As the energization method, either direct energization or indirect energization can be adopted.
なお、本発明における炭素繊維には、上記の電解処理に
先立ち、水洗および乾燥を施すことができる。Note that the carbon fibers in the present invention can be washed with water and dried prior to the above-mentioned electrolytic treatment.
また電解処理後の炭素繊維は、必要に応じてサイジング
処理を施し、長繊維のまま、あるいは短繊維にして補強
材として用い、複合材料とすることができる。Further, the carbon fibers after the electrolytic treatment can be subjected to a sizing treatment if necessary, and can be used as a reinforcing material as long fibers or as short fibers to form a composite material.
［実施例コ 以下、実施例により本発明を具体的に説明する。[Example code] Hereinafter, the present invention will be specifically explained with reference to Examples.
なお、本発明に於けるストランド強度および層間剪断強
度（ＩＬＳＳ）は以下の方法により求めた。In addition, the strand strength and interlaminar shear strength (ILSS) in the present invention were determined by the following method.
ストランド強度は、炭素繊維束を”ベークライト”ＥＲ
Ｌ４２２１樹脂／三フッ化ホウ素モノエチルアミン（Ｂ
Ｆ、 ・ＭＥＡ）／アセトン＝１００／３／４部に含
浸し、得られた樹脂含浸ストランドを１３０℃で３０分
間加熱して硬化させ、Ｊｔｓ−Ｒ−７６０１に規定する
樹脂含浸ストランド試験法に従って測定した値を用いた
。Strand strength is determined by using carbon fiber bundles with "Bakelite" ER
L4221 resin/boron trifluoride monoethylamine (B
F, ・MEA)/acetone = 100/3/4 parts, and the resulting resin-impregnated strand was cured by heating at 130°C for 30 minutes, according to the resin-impregnated strand test method specified in Jts-R-7601. The measured value was used.
ＩＬＳＳは、炭素繊維束を”ペトロケミカルズ”Ｅｐ８
２８樹脂／ＢＦ、 ・ＭＥＡ／アセトン＝１００／３
／４部に含浸し、ＡＳＴＭ−Ｄ２３４４に規定する方法
で測定した値を用いた。ILSS uses carbon fiber bundles as “Petrochemicals” Ep8
28 resin/BF, ・MEA/acetone = 100/3
The value measured by the method specified in ASTM-D2344 was used.
実施例１．比較例１
アクリロニトリル（ＡＮ）９９．４モル％とメタクリル
酸０．６モル％からなる共重合体を用いて、乾湿式紡糸
法により単繊維デニール０．７ｄ。Example 1. Comparative Example 1 Using a copolymer consisting of 99.4 mol% of acrylonitrile (AN) and 0.6 mol% of methacrylic acid, a single fiber denier of 0.7 d was produced by a dry-wet spinning method.
フィラメント数１２０００のアクリル系繊維を得た。得
られた繊維束を２４０〜２８０℃の空気中で、延伸比１
．０５で加熱し、耐炎化繊維に転換し、ついで窒素雰囲
気中３００〜９００℃の温度領域での昇温速度を２００
℃／分とし１０％の延伸を行なった後、１６００℃まで
焼成した。Acrylic fibers having 12,000 filaments were obtained. The obtained fiber bundle was stretched at a drawing ratio of 1 in air at 240 to 280°C.
．． 05 to convert it into a flame-resistant fiber, and then the heating rate in the temperature range of 300 to 900 °C in a nitrogen atmosphere was increased to 200 °C.
After stretching at 10% at a rate of 0.degree. C./min, the film was fired to 1600.degree.
得られた炭素繊維を、５００℃の空気雰囲気電気管状炉
内に滞留時間２分でＵ溝ローラーと平型ガイドを用いて
糸束を広げながら連続的に供給し加熱処理した後、引き
続き０．１モル／ｌのＥＡＨ水溶液中、電気量４０Ｃ／
ｇで電解酸化処理を行った。得られた炭素繊維のストラ
ンド強度は６５０ｋｇ／肛２であり、ＩＬＳＳは８．７
ｋｇ／ｍｍ２であった。空気中加熱処理のみ施した炭素
繊維のストランド強度およびＩＬＳＳはそれぞれ、６５
５ｋｇ／ｗ２，６．０ｋｇ／ｗ２であり、アルカリ電解
処理を組み合わせることによりＩＬＳＳが大幅に向上し
たことがわかる。The obtained carbon fibers were continuously fed into an electric tubular furnace in an air atmosphere at 500° C. for a residence time of 2 minutes while spreading the yarn bundle using a U-groove roller and a flat guide, and then heat-treated. In 1 mol/l EAH aqueous solution, electricity amount 40C/
Electrolytic oxidation treatment was performed in g. The strand strength of the obtained carbon fiber was 650 kg/2, and the ILSS was 8.7.
kg/mm2. Strand strength and ILSS of carbon fibers subjected only to heat treatment in air are 65, respectively.
5 kg/w2 and 6.0 kg/w2, and it can be seen that the ILSS was significantly improved by combining the alkaline electrolytic treatment.
実施例２〜４．比較例２〜４
実施例１において処理条件を表１のように変更した以外
は、実施例１と同様に処理して炭素繊維を得た。得られ
た炭素繊維の特性を表１に示した。Examples 2-4. Comparative Examples 2 to 4 Carbon fibers were obtained in the same manner as in Example 1, except that the treatment conditions were changed as shown in Table 1. Table 1 shows the properties of the obtained carbon fibers.
実施例５．比較例５〜６
実施例１で得られた処理前の炭素繊維をさらに窒素雰囲
気中２４００℃まで黒鉛化した炭素繊維を用いて、空気
中６５０℃で２分間加熱処理した後、引き続き０．１モ
ル／ｌのＥＡＨ水溶液中、電気量８０Ｃ／ｇで電解酸化
処理を行った。得られた炭素繊維のストランド強度は５
０５ ｋｇ／ｍｅ２でＩ ＬＳＳは７ 、 ’５ ｋｇ
／ｍｍ’であった。６５０℃の空気中加熱処理のみでは
５１０ｋｇ／ｍｍ’ 、 ６゜８ｋｇ／皿’、ＥＡＨ
電解処理のみでは５０５ｋｇ／ｍｍ２．５．４ｋｇ／＋
ｎｍ’であり、本発明の方法によりＩＬＳＳが大幅に向
上した。Example 5. Comparative Examples 5 to 6 The untreated carbon fiber obtained in Example 1 was further graphitized to 2400°C in a nitrogen atmosphere, and the carbon fiber was heat-treated in air at 650°C for 2 minutes, followed by 0.1 Electrolytic oxidation treatment was carried out in a mol/l EAH aqueous solution at an electrical charge of 80 C/g. The strand strength of the obtained carbon fiber was 5
At 05 kg/me2, I LSS is 7, '5 kg
/mm'. Heat treatment in air at 650℃ alone yields 510kg/mm', 6°8kg/dish, EAH
Electrolytic treatment alone: 505kg/mm2.5.4kg/+
nm', and ILSS was significantly improved by the method of the present invention.
（以下、余白）
［発明の効果］
本発明により、従来技術では達成し得なかった樹脂マト
リックスとの接着力向上効果に優れた、すなわちＩＬＳ
Ｓが本発明処理により従来処理に比べて３ 、０ ｋｇ
／１ｍ ２以上も大幅に向上する炭素繊維製造方法が
可能になった。(Hereinafter, blank space) [Effects of the invention] The present invention has an excellent effect of improving adhesive strength with the resin matrix, which could not be achieved with conventional techniques, that is, ILS
S is reduced by 3.0 kg by the treatment of the present invention compared to the conventional treatment.
A carbon fiber manufacturing method that significantly improves the carbon fiber production by more than /1 m2 has become possible.
Claims (2)
処理することを特徴とする炭素繊維の製造方法。(1) A method for producing carbon fibers, which comprises heating carbon fibers in an oxygen-containing atmosphere and then subjecting them to electrolytic treatment.
カリ性水溶液中で行うことを特徴とする請求項１記載の
炭素繊維の製造方法。(2) The method for producing carbon fibers according to claim 1, wherein the electrolytic treatment is performed in an alkaline aqueous solution after the heat treatment in an oxygen-containing atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9001990A JPH03287860A (en) | 1990-04-04 | 1990-04-04 | Production of carbon fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9001990A JPH03287860A (en) | 1990-04-04 | 1990-04-04 | Production of carbon fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03287860A true JPH03287860A (en) | 1991-12-18 |
Family
ID=13986994
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9001990A Pending JPH03287860A (en) | 1990-04-04 | 1990-04-04 | Production of carbon fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03287860A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014101605A (en) * | 2012-11-21 | 2014-06-05 | Toho Tenax Co Ltd | Method of manufacturing carbon fiber |
| CN105332098A (en) * | 2015-11-25 | 2016-02-17 | 安徽佳力奇航天碳纤维有限公司 | Carbon fiber activation process |
| EP3214220A4 (en) * | 2014-10-31 | 2018-06-20 | Japan Matex Co., Ltd. | Process for producing carbon-fiber resin tape, and carbon-fiber resin tape |
| US11225754B2 (en) | 2017-05-26 | 2022-01-18 | Dow Global Technologies Llc | Electrochemical grafting of carbon fibers with aliphatic amines for improved composite strength |
-
1990
- 1990-04-04 JP JP9001990A patent/JPH03287860A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014101605A (en) * | 2012-11-21 | 2014-06-05 | Toho Tenax Co Ltd | Method of manufacturing carbon fiber |
| EP3214220A4 (en) * | 2014-10-31 | 2018-06-20 | Japan Matex Co., Ltd. | Process for producing carbon-fiber resin tape, and carbon-fiber resin tape |
| CN105332098A (en) * | 2015-11-25 | 2016-02-17 | 安徽佳力奇航天碳纤维有限公司 | Carbon fiber activation process |
| US11225754B2 (en) | 2017-05-26 | 2022-01-18 | Dow Global Technologies Llc | Electrochemical grafting of carbon fibers with aliphatic amines for improved composite strength |
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