JP2521138B2 - Fluorine-containing carbon fiber that easily releases fluorine - Google Patents
Fluorine-containing carbon fiber that easily releases fluorineInfo
- Publication number
- JP2521138B2 JP2521138B2 JP63307643A JP30764388A JP2521138B2 JP 2521138 B2 JP2521138 B2 JP 2521138B2 JP 63307643 A JP63307643 A JP 63307643A JP 30764388 A JP30764388 A JP 30764388A JP 2521138 B2 JP2521138 B2 JP 2521138B2
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- JP
- Japan
- Prior art keywords
- fluorine
- carbon fiber
- plasma
- activated carbon
- containing carbon
- 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.)
- Expired - Lifetime
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- Chemical Or Physical Treatment Of Fibers (AREA)
- Chemical Treatment Of Fibers During Manufacturing Processes (AREA)
Description
【発明の詳細な説明】 ＜産業上の利用分野＞ 本発明は容易にフッ素を離脱するフッ素含有炭素繊維
に関し、更に詳しくは活性炭素繊維、好ましくはフェノ
ール樹脂活性炭素繊維を用い室温にてCF4などでプラズ
マ処理することによりフッ素を多量に含有し，且つ水中
への浸漬処理、又は加熱処理により容易にフッ素を離脱
するフッ素含有炭素繊維に関するものである。DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention relates to a fluorine-containing carbon fiber capable of easily desorbing fluorine, more specifically, activated carbon fiber, preferably phenol resin activated carbon fiber, is used at room temperature for CF 4 TECHNICAL FIELD The present invention relates to a fluorine-containing carbon fiber that contains a large amount of fluorine by plasma treatment with, and easily releases fluorine by immersion treatment in water or heat treatment.
＜従来の技術＞ 炭素繊維は多くの工業材料、特に炭素・炭素複合材料
（Ｃ−Ｃコンポジット）や炭素繊維強化プラスチック
（CFRP）としてその機能性、将来性に多くの期待が寄せ
られている。<Prior Art> Carbon fibers are expected to be highly functional and promising as many industrial materials, particularly carbon-carbon composite materials (CC composites) and carbon fiber reinforced plastics (CFRP).
これらの複合材の特性は炭素とマトリックスとの界面
の状況によって影響される。The properties of these composites are affected by the condition of the carbon-matrix interface.
このために、炭素繊維の表面を種々の方法で処理をす
ることにより更に高機能化にすることが行われている。For this reason, the surface of the carbon fiber is treated by various methods to make it more functional.
例えば、酸素プラズマで炭素表面を処理することによ
り、その表面は極めて浸水性に改質される。さらに、こ
の酸素プラズマ処理炭素繊維をCFRPの補強材として使用
した場合には複合材の機械的強度が著しく向上する。For example, by treating a carbon surface with oxygen plasma, the surface is highly flooded. Furthermore, when this oxygen plasma treated carbon fiber is used as a reinforcing material for CFRP, the mechanical strength of the composite material is significantly improved.
又、炭素表面をフッ素処理することにより表面にフッ
素を含む炭素繊維が得られ、その表面の自由エネルギー
が極めて低いことから潤滑材料あるいは撥水材料配合組
成物として用いることができる。Further, by treating the carbon surface with fluorine, carbon fibers containing fluorine can be obtained on the surface, and since the free energy of the surface is extremely low, it can be used as a lubricating material or a water-repellent material compounding composition.
従来、炭素繊維のフッ素化は危険で毒性の高いF2ガス
と高温下での直接反応によって行われていた。Conventionally, fluorination of carbon fiber has been carried out by direct reaction at high temperature with dangerous and highly toxic F 2 gas.
例えば、従来のフッ素含有炭素繊維の製造法としては
千葉淳他”日本化学会誌 No.10（1985）”ではKF−HF
系電解法による方法が提示されている。しかしこの方法
は300℃という高温加熱を必要としており、加熱により
コストアップが避けられない。For example, as the conventional method for producing fluorine-containing carbon fiber, KF-HF can be found in Jun Chiba et al., "Chemical Society of Japan No. 10 (1985)".
A method based on a system electrolysis method has been proposed. However, this method requires heating at a high temperature of 300 ° C., and cost increase cannot be avoided by heating.
又、東原秀和他”日本化学会誌 No.10（1985）”に
よる化学的処理方法では200℃・10数時間という高温・
長時間処理を必要としている。これは合理的な製造方法
とは云えない。In addition, the chemical treatment method by Hidekazu Higashihara et al., "Chemical Society of Japan No. 10 (1985)", is a high temperature of 200 ° C for 10 hours.
Needs long-term processing. This is not a rational manufacturing method.
その上、これら従来のフッ素化法は表面のみのフッ素
化ではなく、炭素基材内部にまで及ぶものであった。こ
れらの点からもフッ素を含有し容易に離脱出来るような
表面のみをフッ素化する方法が望まれていた。Moreover, these conventional fluorination methods extend not only to the fluorination of the surface but also to the inside of the carbon substrate. From these points as well, there has been a demand for a method of fluorinating only the surface which contains fluorine and can be easily released.
さらに、従来の炭素繊維のフッ素含有量は１重量％以
下と低く前記した機能に不十分な面があり、従ってフッ
素含有量が多く、また離脱フッ素量の多い炭素繊維が求
められていた。このような離脱フッ素の多い炭素繊維は
フッ素供給装置やガラス処理剤として用いることが出来
る。Further, the conventional carbon fiber has a low fluorine content of 1% by weight or less, which is not sufficient for the above-mentioned function. Therefore, a carbon fiber having a large fluorine content and a large amount of released fluorine has been demanded. Such carbon fibers with a large amount of released fluorine can be used as a fluorine supply device or a glass treating agent.
従来、フッ素供給装置としてはフッ素ガスボンベがあ
り、これを用いてフッ素を供給してきたが過大な装置を
必要とするため装置の取扱性やコンパクト性に問題があ
り、微細装置内におけるフッ素供給源が求められてい
た。Conventionally, there is a fluorine gas cylinder as a fluorine supply device, and fluorine has been supplied using this, but there is a problem in handleability and compactness of the device because it requires an excessively large device. It was wanted.
又、フッ素取り扱いの安全性の観点から、ガラスのツ
ヤ消し等のガラス処理において、有毒なフッ素ガスの拡
散を生じさせないような作業者を保護するタイプのフッ
素含有ガラス処理剤が望まれていた。Further, from the viewpoint of safety in handling fluorine, a fluorine-containing glass treating agent of a type that protects an operator from causing diffusion of toxic fluorine gas in glass treatment such as matting of glass has been desired.
＜発明が解決しようとする課題＞ 本発明者らは前記欠点を解決すべく鋭意研究の結果、
活性炭素繊維、好ましくはフェノール樹脂活性炭素繊維
を室温にてCF4などでプラズマ処理することにより短時
間に従来には存在しなかった表面にのみフッ素結合を有
し、高いフッ素含有量を示す、容易にフッ素を離脱する
ことの出来るフッ素含有炭素繊維を得ることが見いだ
し、本発明に到った。<Problems to be Solved by the Invention> As a result of intensive research to solve the above-mentioned drawbacks,
Activated carbon fiber, preferably a phenol resin activated carbon fiber having a fluorine bond only on the surface that did not exist conventionally in a short time by plasma treatment with CF 4 or the like at room temperature, and shows a high fluorine content, It has been found that a fluorine-containing carbon fiber that can easily release fluorine is obtained, and the present invention has been completed.
＜課題を解決するための手段＞ かくして、本発明によれば、活性炭素繊維好ましくは
フェノール樹脂炭素繊維を前駆体とする活性炭素繊維を
室温においてラジオ波（13.56MHz）によりCF4プラズマ
処理することにより、５重量％以上のフッ素含有量を有
する容易にフッ素を離脱するフッ素含有炭素繊維が提供
される。<Means for Solving the Problems> Thus, according to the present invention, activated carbon fibers having a precursor of activated carbon fibers, preferably phenol resin carbon fibers as a precursor, are subjected to CF 4 plasma treatment by radio waves (13.56 MHz) at room temperature. Thereby, a fluorine-containing carbon fiber having a fluorine content of 5% by weight or more and easily desorbing fluorine is provided.
本発明における活性炭素繊維はピッチ系炭素繊維を
前駆体とする活性炭素繊維、PAN（ポリアクリロニト
リル樹脂）系炭素繊維を前駆体とする活性炭素繊維、
レーヨン系炭素繊維を前駆体とする活性炭素繊維、フ
ェノール樹脂炭素繊維を前駆体とする活性炭素繊維のい
ずれを用いても良いが、フェノール樹脂炭素繊維を前駆
体とする活性炭素繊維がラジオ波による常温におけるCF
4などのプラズマ処理により最も多量のフッ素を含有す
ることが出来、最も多量のフッ素を離脱することが出来
る。The activated carbon fiber in the present invention is an activated carbon fiber having a pitch-based carbon fiber as a precursor, an activated carbon fiber having a PAN (polyacrylonitrile resin) -based carbon fiber as a precursor,
Either activated carbon fiber having a rayon-based carbon fiber as a precursor or activated carbon fiber having a phenol resin carbon fiber as a precursor may be used, but the activated carbon fiber having a phenol resin carbon fiber as a precursor is affected by radio waves. CF at room temperature
The plasma treatment such as 4 can contain the largest amount of fluorine and can release the largest amount of fluorine.
フェノール樹脂活性炭素繊維としてはフェノール、ク
レゾール、キシレノール、リグニンの単独あるいは混合
物とホルムアルデヒドあるいは他のアルデヒド類との縮
合物を硬化・繊維化した後、炭素化した炭素繊維を前駆
体とした物である。Phenolic resin activated carbon fibers are those obtained by curing and fibrating a condensate of phenol, cresol, xylenol, lignin alone or a mixture with formaldehyde or other aldehydes, and then using carbonized carbon fibers as a precursor. .
本発明で使用される低温プラズマ法は半導体工業を中
心にして発達した技術であり、現在では大規模スケール
で用いられている。The low temperature plasma method used in the present invention is a technique developed mainly in the semiconductor industry and is currently used on a large scale.
プラズマ処理法としては室温において減圧下、ラジオ
波（周波数13.56MHz）によるCF4などによる処理法が行
われる。As a plasma treatment method, a treatment method such as CF 4 using radio frequency (frequency 13.56 MHz) is performed under reduced pressure at room temperature.
プラズマ処理時の印加出力は10〜150Wで行われるが、
好ましくは30〜70Wが良い。The applied output during plasma processing is 10 to 150 W,
30-70W is preferable.
プラズマ処理時の減圧条件は特に限定するものではな
いが２〜0.01Torrの範囲が好ましい。プラズマ処理時間
は１〜60分間行われるが好ましくは５〜20分が良い。The depressurizing condition during the plasma treatment is not particularly limited, but a range of 2 to 0.01 Torr is preferable. The plasma treatment time is 1 to 60 minutes, preferably 5 to 20 minutes.
＜実施例＞ 以下実施例により本発明を更に詳しく説明するが、本
発明は以下の実施例に限定されるものではない。尚、例
中の％は特に断わりのない限り重量基準である。<Example> The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples. In the examples,% is based on weight unless otherwise specified.
実施例１ フェノール樹脂活性炭素繊維のペーパー（群栄化学工
業製 商品名ACN−211−23）をプラズマ処理装置（サム
コインターナショナル研究所製、BP−１、平行平板型、
周波数13.56MHz）の下部電極上に設置した。上部電極と
下部電極間の距離は3cmである。ガラス製反応容器の大
きさは直径25cm、高さ30cmで、ベルジャー型である。こ
の容器を真空ポンプで減圧（0.5Torr）にした後、CF4を
20ml/min.流入しながら、50Wの出力を印加し、プラズマ
を発生させ、40℃にて10分間プラズマ処理を行い、フッ
素を含有する炭素繊維を得た。Example 1 A paper of phenolic resin activated carbon fiber (trade name ACN-2111-23 manufactured by Gunei Chemical Industry Co., Ltd.) was used as a plasma processing apparatus (manufactured by Samco International Laboratories, BP-1, parallel plate type).
It was installed on the lower electrode with a frequency of 13.56 MHz). The distance between the upper electrode and the lower electrode is 3 cm. The glass reaction vessel has a diameter of 25 cm and a height of 30 cm, and is a bell jar type. After decompressing this container with a vacuum pump (0.5 Torr), remove CF 4
While flowing 20 ml / min., An output of 50 W was applied to generate plasma, and plasma treatment was performed at 40 ° C. for 10 minutes to obtain a carbon fiber containing fluorine.
実施例２ 実施例１と同様な方法で、PAN系活性炭素繊維のペー
パーをプラズマ処理し、フッ素を含有する炭素繊維を得
た。Example 2 In the same manner as in Example 1, a paper of PAN-based activated carbon fiber was plasma-treated to obtain a carbon fiber containing fluorine.
実施例３ 実施例１と同様な方法で、ピッチ系活性炭素繊維のペ
ーパーをプラズマ処理し、フッ素を含有する炭素繊維を
得た。Example 3 In the same manner as in Example 1, a pitch-based activated carbon fiber paper was plasma-treated to obtain a carbon fiber containing fluorine.
実施例４ 実施例１と同様な方法で、レーヨン系活性炭素繊維の
ペーパーをプラズマ処理し、フッ素を含有する炭素繊維
を得た。Example 4 In the same manner as in Example 1, a rayon-based activated carbon fiber paper was plasma-treated to obtain a carbon fiber containing fluorine.
実施例５ 実施例１と同様な方法で、PAN系高性能炭素繊維のペ
ーパー（日本カーボン製 商品名SH−35Z）をプラズマ
処理し、フッ素を含有する炭素繊維を得た。Example 5 In the same manner as in Example 1, PAN-based high-performance carbon fiber paper (trade name SH-35Z, manufactured by Nippon Carbon Co., Ltd.) was plasma-treated to obtain a carbon fiber containing fluorine.
実施例６ 実施例１と同様な方法でピッチ系汎用炭素繊維のペー
パーをプラズマ処理し、フッ素を含有する炭素繊維を得
た。Example 6 Pitch-based carbon fiber paper was plasma-treated in the same manner as in Example 1 to obtain a carbon fiber containing fluorine.
上記実施例により得られた炭素繊維のフッ素含有量及
び離脱フッ素量の結果及びその表面の状態の結果を表１
にまとめた。Table 1 shows the results of the fluorine content and the amount of released fluorine and the results of the surface condition of the carbon fibers obtained in the above examples.
Summarized in.
なお、フッ素含有量の測定はプラズマ処理後の炭素繊
維をフラスコ燃焼法により燃焼させ、アルカリ溶液に吸
収させた後、イオン電極法によりフッ素量を測定し、下
式よりその値を求めた。The fluorine content was measured by burning the carbon fiber after plasma treatment by the flask combustion method and absorbing it in an alkaline solution, then measuring the fluorine content by the ion electrode method, and determining the value from the following formula.
プラズマ処理後のフッ素含有量（％）＝ （フッ素含有重量／プラズマ処理後の炭素繊維重量）×
100 浸漬処理後の離脱フッ素量はプラズマ処理した炭素繊
維を14日間水中に浸漬し、それを取り出しその残存フッ
素量を測定しその差より以下の式のようにしてその値を
求めた。Fluorine content after plasma treatment (%) = (weight of fluorine content / weight of carbon fiber after plasma treatment) x
100 The amount of released fluorine after the immersion treatment was determined by immersing the plasma-treated carbon fiber in water for 14 days, taking out the amount, and measuring the residual amount of fluorine, and determining the value from the difference by the following formula.
浸漬処理後離脱フッ素量（％）＝ ｛（プラズマ処理後のフッ素含有重量−水浸漬後残存フ
ッ素含有重量）／プラズマ処理後の炭素繊維重量｝×10
0 加熱処理後の離脱フッ素量は250℃・５時間処理後の
離脱フッ素量で以下のようにしてその値を求めた。Amount of released fluorine after immersion treatment (%) = {(weight of fluorine content after plasma treatment-weight of residual fluorine content after immersion in water) / weight of carbon fiber after plasma treatment} x 10
The amount of released fluorine after the heat treatment was determined as follows by the amount of released fluorine after the treatment at 250 ° C. for 5 hours.
加熱処理後離脱フッ素量（％）＝ ｛（プラズマ処理後のフッ素含有重量−加熱後の残存フ
ッ素含有重量）／プラズマ処理後の炭素繊維重量｝×10
0 撥水性についてはプラズマ処理した炭素繊維ペーパー
上の水滴の接触角で判断した。Amount of released fluorine after heat treatment (%) = {(weight of fluorine content after plasma treatment-weight of residual fluorine content after heating) / weight of carbon fiber after plasma treatment} x 10
0 The water repellency was judged by the contact angle of water droplets on the plasma-treated carbon fiber paper.
＜発明の効果＞ 以上のごとく、本発明によれば活性炭素繊維好ましく
はフェノール樹脂活性炭素繊維に対しCF4等のプラズマ
で処理を行うことにより、フッ素供給源、ガラス処理
剤、潤滑材料、撥水材料用組成物として有用な表面のみ
にフッ素結合を有するフッ素含有量５重量％以上で容易
にフッ素を離脱するフッ素含有炭素繊維を容易に得るこ
とが出来る。 <Effects of the Invention> As described above, according to the present invention, activated carbon fibers, preferably phenolic resin activated carbon fibers, are treated with plasma such as CF 4 to obtain a fluorine source, a glass treating agent, a lubricating material, and a repellent agent. A fluorine-containing carbon fiber having a fluorine bond only on the surface and having a fluorine content of 5% by weight or more, which easily releases fluorine, can be easily obtained as a composition for water materials.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 阿部 幸雄 群馬県高崎市大八木町622番地 群栄化 学工業株式会社内 (72)発明者 都木 昭次 群馬県高崎市大八木町622番地 群栄化 学工業株式会社内 (56)参考文献 特開 昭60−191011（ＪＰ，Ａ) 特開 昭62−235204（ＪＰ，Ａ) 特開 昭49−34988（ＪＰ，Ａ) 特開 昭63−35632（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yukio Abe 622 Oyagi-cho, Takasaki-shi, Gunma Gunei Kagaku Kogyo Co., Ltd. Kogyo Co., Ltd. (56) Reference JP-A-60-191011 (JP, A) JP-A-62-235204 (JP, A) JP-A-49-34988 (JP, A) JP-A-63-35632 (JP , A)
Claims (2)
理することにより得る、フッ素含有量が５重量％以上で
ある容易にフッ素を離脱するフッ素含有炭素繊維。1. A fluorine-containing carbon fiber having a fluorine content of 5% by weight or more, which easily desorbs fluorine, obtained by plasma-treating activated carbon fiber with CF 4 at room temperature.
素繊維であることを特徴とする請求項１記載の容易にフ
ッ素を離脱するフッ素含有炭素繊維。2. The fluorine-containing carbon fiber according to claim 1, wherein the precursor of the activated carbon fiber is a phenol resin carbon fiber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63307643A JP2521138B2 (en) | 1988-12-05 | 1988-12-05 | Fluorine-containing carbon fiber that easily releases fluorine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63307643A JP2521138B2 (en) | 1988-12-05 | 1988-12-05 | Fluorine-containing carbon fiber that easily releases fluorine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02191767A JPH02191767A (en) | 1990-07-27 |
| JP2521138B2 true JP2521138B2 (en) | 1996-07-31 |
Family
ID=17971512
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63307643A Expired - Lifetime JP2521138B2 (en) | 1988-12-05 | 1988-12-05 | Fluorine-containing carbon fiber that easily releases fluorine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2521138B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017160074A (en) * | 2016-03-09 | 2017-09-14 | 株式会社Kri | Method for producing hydrophobic activated carbon |
| CN109680363B (en) * | 2018-11-30 | 2021-06-01 | 北京林业大学 | Curing treatment method of lignin-based fiber and obtained product |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5336505B2 (en) * | 1972-08-03 | 1978-10-03 | ||
| JPS60191011A (en) * | 1984-03-13 | 1985-09-28 | Central Glass Co Ltd | Modified carbonaceous material |
| JPS62235204A (en) * | 1986-04-04 | 1987-10-15 | Asahi Chem Ind Co Ltd | Fluorinated graphite material |
| JPS6335632A (en) * | 1986-07-30 | 1988-02-16 | Kuraray Co Ltd | Sheet-like fluorinated polymer structure and its production |
-
1988
- 1988-12-05 JP JP63307643A patent/JP2521138B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02191767A (en) | 1990-07-27 |
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