JPH0813256A - Carbon fiber for reinforcing resin - Google Patents
Carbon fiber for reinforcing resinInfo
- Publication number
- JPH0813256A JPH0813256A JP6153461A JP15346194A JPH0813256A JP H0813256 A JPH0813256 A JP H0813256A JP 6153461 A JP6153461 A JP 6153461A JP 15346194 A JP15346194 A JP 15346194A JP H0813256 A JPH0813256 A JP H0813256A
- Authority
- JP
- Japan
- Prior art keywords
- carbon fiber
- fibers
- zeta potential
- resin
- subjected
- 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.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、繊維強化樹脂複合材料
の補強繊維に適するよう表面電気特性が制御された炭素
繊維に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to carbon fibers whose surface electric properties are controlled so as to be suitable as reinforcing fibers for fiber-reinforced resin composite materials.
【０００２】[0002]
【従来の技術】炭素繊維を補強材とする樹脂複合材料は
軽量でかつ強度、弾性率に優れているためスポーツ、レ
ジャー用品の構成部品として、あるいは宇宙航空機用部
材等として幅広い分野にわたってその用途開発が進めら
れている。しかし炭素化直後の炭素繊維表面はマトリッ
クス樹脂に対し不活性であり、炭素繊維とマトリックス
樹脂の接着性は十分ではない。従来炭素繊維表面を活性
化し、マトリックス樹脂との接着性を改善するため、薬
剤酸化処理、気相酸化処理、電解酸化処理など各種酸化
処理、さらには後処理工程として特開昭５７−１５２２
９号に代表されるような各種サイジング剤付着処理によ
る表面改質が採用されてきた。酸化処理の方法としては
電解酸化処理法がその操作性の良さ、反応制御の容易さ
などの見地から実用的な表面処理方法である。2. Description of the Related Art Since a resin composite material having carbon fiber as a reinforcing material is lightweight and has excellent strength and elastic modulus, its application is developed in a wide range of fields as a component of sports and leisure products or a member for aerospace. Is being promoted. However, the carbon fiber surface immediately after carbonization is inactive to the matrix resin, and the adhesiveness between the carbon fiber and the matrix resin is not sufficient. Conventionally, in order to activate the surface of the carbon fiber and improve the adhesiveness with the matrix resin, various oxidation treatments such as chemical oxidation treatment, gas phase oxidation treatment and electrolytic oxidation treatment, and further as a post-treatment process, JP-A-57-1522.
Surface modification by various sizing agent adhesion treatments represented by No. 9 has been adopted. As a method for the oxidation treatment, the electrolytic oxidation treatment method is a practical surface treatment method from the viewpoints of its operability and ease of reaction control.
【０００３】炭素繊維とマトリックス樹脂の接着性を改
善するために炭素繊維表面を電解酸化処理すると水酸
基、カルボキシル基といった酸性の官能基が炭素繊維表
面に導入される。この表面状態は酸化処理を施さない炭
素繊維の表面状態に比べると極性官能基が導入されたこ
とによりエポキシ樹脂、アクリル樹脂といった極性成分
を有する樹脂に対する濡れ性は大幅に改善し、層間剪断
強度（ＩＬＳＳ）、９０度曲げ強度（ＦＳ⊥）等のコン
ポジット特性も向上する。When the surface of the carbon fiber is subjected to electrolytic oxidation treatment in order to improve the adhesion between the carbon fiber and the matrix resin, acidic functional groups such as hydroxyl groups and carboxyl groups are introduced into the carbon fiber surface. Compared with the surface condition of carbon fiber which is not subjected to oxidation treatment, this surface condition greatly improves the wettability for resins having polar components such as epoxy resin and acrylic resin due to the introduction of polar functional groups, and the interlaminar shear strength ( ILSS), 90 degree bending strength (FS⊥), and other composite properties are also improved.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら酸化処理
の程度をさらに高めるとＥＳＣＡ法等によって測定され
る炭素繊維表面の酸素含有官能基は増大するものの、炭
素繊維のマトリックス樹脂に対する濡れ性、ＩＬＳＳお
よびＦＳ⊥などのコンポジット特性は改善せず、場合に
よってはコンポジット特性は低下する。炭素繊維とマト
リックス樹脂の接着性が改善しないのは導入された酸素
含有官能基が接着に寄与せず、場合によっては接着を阻
害するためと考えられる。本発明は、上記問題点を解消
した炭素繊維の提供を課題とする。However, if the degree of oxidation treatment is further increased, the oxygen-containing functional groups on the carbon fiber surface measured by the ESCA method and the like increase, but the wettability of the carbon fiber with respect to the matrix resin, ILSS and FS. Composite properties such as ⊥ do not improve, and in some cases, composite properties deteriorate. The reason why the adhesion between the carbon fiber and the matrix resin is not improved is considered to be that the introduced oxygen-containing functional group does not contribute to the adhesion and, in some cases, inhibits the adhesion. An object of the present invention is to provide a carbon fiber that solves the above problems.
【０００５】[0005]
【課題を解決するための手段】本発明は、流動電位法で
測定される炭素繊維表面のゼータ電位が流動液のｐＨ２
〜６の範囲で０ｍＶ以上であることを特徴とする樹脂補
強用炭素繊維によって上記課題を解決した。According to the present invention, the zeta potential on the surface of carbon fiber measured by the streaming potential method is pH 2 of the flowing liquid.
The above problem is solved by the carbon fiber for resin reinforcement, which is characterized in that it is 0 mV or more in the range of ~ 6.
【０００６】以下本発明を詳細に説明する。流動電位法
で測定される従来の炭素繊維表面のゼータ電位は少なく
とも流動液のｐＨが３以上ではマイナスの符号を有す
る。これは表面に存在する酸素含有官能基の酸性的性質
に由来する。表面酸化処理の程度を強くすると炭素繊維
表面の酸性度が高まるため、ゼータ電位はさらにマイナ
ス側へシフトする。一方マトリックス樹脂としてのエポ
キシ樹脂、アクリル樹脂も同様の雰囲気においてマイナ
スのゼータ電位を示す。すなわち炭素繊維表面、マトリ
ックス樹脂いずれも流動液に対して電子供与性であるの
で電気的に反発しあい、炭素繊維束内への樹脂含浸性が
悪化し、ＩＬＳＳ、ＦＳ⊥等のコンポジット特性が低下
する可能性がある。Hereinafter, the present invention will be described in detail. The zeta potential of the conventional carbon fiber surface measured by the streaming potential method has a minus sign at least when the pH of the flowing liquid is 3 or more. This is due to the acidic nature of the oxygen-containing functional groups present on the surface. When the degree of surface oxidation treatment is increased, the acidity of the carbon fiber surface increases, and the zeta potential shifts further to the negative side. On the other hand, the epoxy resin and the acrylic resin as the matrix resin also show a negative zeta potential in the same atmosphere. That is, since both the carbon fiber surface and the matrix resin are electron donative to the flowing liquid, they electrically repel each other, impairing resin impregnation into the carbon fiber bundle, and degrading composite properties such as ILSS and FS⊥. there is a possibility.
【０００７】本発明の炭素繊維は流動液ｐＨ２〜６の範
囲で０ｍＶ以上のゼータ電位を有する炭素繊維であり、
ゼータ電位がプラスであるということは流動液に対して
電子受容性であることを意味する。従って電子供与性の
樹脂と本発明の炭素繊維表面との間の硬化反応は促進さ
れ接着性が向上し、かつ本発明の炭素繊維の束への樹脂
含浸性も良好となるのである。The carbon fiber of the present invention is a carbon fiber having a zeta potential of 0 mV or higher in the pH range of the fluid of 2 to 6,
The positive zeta potential means that it is electron-accepting to the flowing liquid. Therefore, the curing reaction between the electron donating resin and the surface of the carbon fiber of the present invention is promoted, the adhesiveness is improved, and the resin impregnation property into the bundle of carbon fiber of the present invention is also improved.
【０００８】本発明の炭素繊維は、エポキシ樹脂、フェ
ノール樹脂、ビニルエステル樹脂等熱硬化性樹脂に好適
に用いられ、さらにナイロン６６、ＡＢＳ樹脂、ポリメ
チルメタクリレート、ポリカーボネート、ポリブチレン
テレフタレート、ポリフェニレンサルファイド、ポリア
セタール、ポリアミドイミド、ポリスルホン、ポリエー
テルスルホンなどの熱可塑性樹脂にも用いられる。The carbon fiber of the present invention is suitable for use in thermosetting resins such as epoxy resin, phenol resin, vinyl ester resin, nylon 66, ABS resin, polymethylmethacrylate, polycarbonate, polybutylene terephthalate, polyphenylene sulfide, It is also used for thermoplastic resins such as polyacetal, polyamideimide, polysulfone, and polyethersulfone.
【０００９】本発明による炭素繊維は繊維形態にはなん
らの制限もなく、炭素繊維樹脂複合材料の製法に応じて
短繊維、長繊維、ストランド、シート、不織布、織物な
ど種々な形態で使用できる利点を有する。The carbon fiber according to the present invention has no limitation on the fiber form and can be used in various forms such as short fiber, long fiber, strand, sheet, non-woven fabric and woven fabric depending on the production method of the carbon fiber resin composite material. Have.
【００１０】[0010]
【実施例】次に実施例により本発明を具体的に説明す
る。尚、炭素繊維表面のゼータ電位は島津製作所製流動
電位測定装置ＺＰ−１０Ｂを用い、測定セル中に炭素繊
維の充填率が５０ｖｏｌ％となるように詰めて測定し
た。流動液はそれぞれ０．０１Ｎの塩酸、塩化カリウム
および水酸化カリウム水溶液をイオン強度一定となるよ
うに混合し、ｐＨ２〜６の間で調整した。繊維方向と９
０°方向の曲げ強度（ＦＳ⊥）はＡＳＴＭ−Ｄ７９０に
記載の試験法に準じて測定した。測定試験片はエポキシ
系マトリックス樹脂（パイロフィル＃３４０、三菱レイ
ヨン（株）製）を用いて作製した。EXAMPLES The present invention will be described in detail with reference to examples. The zeta potential of the carbon fiber surface was measured by using a streaming potential measuring device ZP-10B manufactured by Shimadzu Corporation so that the filling rate of the carbon fiber was 50 vol% in the measuring cell. The fluid was prepared by mixing 0.01 N hydrochloric acid, potassium chloride and potassium hydroxide aqueous solution so that the ionic strength was constant, and adjusting the pH between 2 and 6. Fiber direction and 9
The bending strength (FS⊥) in the 0 ° direction was measured according to the test method described in ASTM-D790. The measurement test piece was produced using an epoxy matrix resin (Pyrofil # 340, manufactured by Mitsubishi Rayon Co., Ltd.).
【００１１】（実施例１）アクリロニトリル／メタクリ
ル酸の重合体をジメチルホルムアミドに溶解、湿式紡糸
を行い、単糸繊度０．９デニール、フィラメント数１
２，０００のプレカーサを得た。このプレカーサを２２
０〜２６０℃の空気中で耐炎化処理後、窒素中炭素化炉
最高温度１８００℃で炭素化したのち、ｐＨ７．５の重
炭酸アンモニウム５％、２５℃水溶液中で炭素繊維１ｇ
あたり１００クーロンの電気量で電解酸化処理した。さ
らに化学式：CH3(CH2)11NCH2CH2OH(CH2CH2O)2Hで表され
るラウリルアミンエチレンオキサイド付加物の１．２％
水溶液に浸漬した後、空気中２５０℃で乾燥した。得ら
れた炭素繊維表面のゼータ電位は、ｐＨ２で５ｍＶ、ｐ
Ｈ４で３ｍＶ、ｐＨ６で２ｍＶであった。またこの炭素
繊維を用いて作製した試験片のＦＳ⊥は９．３ｋｇ／ｍ
ｍ2 であった。(Example 1) Acrylonitrile / methacrylic acid polymer was dissolved in dimethylformamide and wet-spun to obtain a single yarn fineness of 0.9 denier and a filament number of 1.
2,000 precursors were obtained. This precursor is 22
After flameproofing in 0-260 ° C air, carbonization in nitrogen in a carbonization furnace with a maximum temperature of 1800 ° C, followed by ammonium bicarbonate 5% with pH 7.5, carbon fiber 1g in 25 ° C aqueous solution
The electrolytic oxidation treatment was performed with an electric quantity of 100 coulomb per unit. Furthermore, 1.2% of the laurylamine ethylene oxide adduct represented by the chemical formula: CH 3 (CH 2 ) 11 NCH 2 CH 2 OH (CH 2 CH 2 O) 2 H
After being immersed in the aqueous solution, it was dried in air at 250 ° C. The zeta potential of the obtained carbon fiber surface was 5 mV at pH 2 and p
It was 3 mV at H4 and 2 mV at pH 6. In addition, the FS⊥ of the test piece manufactured using this carbon fiber is 9.3 kg / m.
m 2 .
【００１２】（実施例２）ラウリルアミンエチレンオキ
サイド付加物処理濃度を０．６ｗｔ％とする以外は実施
例１と同様に炭素繊維を作製した。得られた炭素繊維表
面のゼータ電位は、ｐＨ２で２１ｍＶ、ｐＨ４で２２ｍ
Ｖ、ｐＨ６で２３ｍＶであった。またこの炭素繊維を用
いて作製した試験片のＦＳ⊥は１０．１ｋｇ／ｍｍ2 で
あった。Example 2 A carbon fiber was prepared in the same manner as in Example 1 except that the treatment concentration of laurylamine ethylene oxide adduct was set to 0.6 wt%. The zeta potential of the obtained carbon fiber surface is 21 mV at pH 2 and 22 m at pH 4.
It was 23 mV at V and pH 6. The FS⊥ of the test piece manufactured using this carbon fiber was 10.1 kg / mm 2 .
【００１３】（実施例３）ラウリルアミンエチレンオキ
サイド付加物の水溶液に浸漬した後の乾燥温度を１３０
℃にした以外は実施例１と同様に炭素繊維を作製した。
得られた炭素繊維表面のゼータ電位は、流動液のｐＨ２
で２２ｍＶ、ｐＨ４で１５ｍＶ、ｐＨ６で１３ｍＶであ
った。またこの炭素繊維を用いて作製した試験片のＦＳ
⊥は１１．３ｋｇ／ｍｍ2 であった。(Example 3) The drying temperature after immersion in an aqueous solution of laurylamine ethylene oxide adduct was 130
A carbon fiber was produced in the same manner as in Example 1 except that the temperature was changed to ° C.
The zeta potential on the surface of the obtained carbon fiber was pH 2 of the fluid.
Was 22 mV, pH 4 was 15 mV, and pH 6 was 13 mV. In addition, the FS of the test piece produced using this carbon fiber
⊥ was 11.3 kg / mm 2 .
【００１４】（比較例１）電解酸化処理以降のラウリル
アミンエチレンオキサイド付加物の水溶液への浸漬以降
の処理を省いた以外は実施例１と同様に炭素繊維を作製
した。得られた炭素繊維表面のゼータ電位は、流動液の
ｐＨ２で０ｍＶ、ｐＨ４で−１ｍＶ、ｐＨ６で−１２ｍ
Ｖであった。またこの炭素繊維を用いて作製した試験片
のＦＳ⊥は８．８ｋｇ／ｍｍ2 であった。(Comparative Example 1) A carbon fiber was produced in the same manner as in Example 1 except that the treatment after the immersion in the aqueous solution of the laurylamine ethylene oxide adduct after the electrolytic oxidation treatment was omitted. The zeta potential of the obtained carbon fiber surface was 0 mV at pH 2 of the fluid, -1 mV at pH 4 and -12 mV at pH 6.
It was V. The FS⊥ of the test piece prepared using this carbon fiber was 8.8 kg / mm 2 .
【００１５】（比較例２）実施例１のうち、電解酸化処
理以降の工程を省いて炭素繊維を作製した。得られた炭
素繊維表面のゼータ電位は、流動液のｐＨ２で１０ｍ
Ｖ、ｐＨ４で２ｍＶ、ｐＨ６で−２ｍＶであった。また
この炭素繊維を用いて作製した試験片のＦＳ⊥は４．３
ｋｇ／ｍｍ2 であった。(Comparative Example 2) In Example 1, a carbon fiber was produced by omitting the steps after the electrolytic oxidation treatment. The zeta potential of the obtained carbon fiber surface is 10 m at pH 2 of the fluid.
V was 2 mV at pH 4 and -2 mV at pH 6. In addition, the FS⊥ of the test piece manufactured using this carbon fiber is 4.3.
It was kg / mm 2 .
【００１６】（比較例３）ラウリルアミンエチレンオキ
サイド付加物で処理する代わりに化学式 CH3(CH2)2O(CH2CH2O)22H(CH2CH(CH3)O)22H で表される物質の１．２％水溶液で処理することを除い
ては実施例２と同様に炭素繊維を作製した。得られた炭
素繊維表面のゼータ電位は、流動液のｐＨ２で−１３ｍ
Ｖ、ｐＨ４で−１１ｍＶ、ｐＨ６で−１５ｍＶであっ
た。またこの炭素繊維を用いて作製した試験片のＦＳ⊥
は８．７ｋｇ／ｍｍ2 であった。Comparative Example 3 Instead of treating with a laurylamine ethylene oxide adduct, the chemical formula CH 3 (CH 2 ) 2 O (CH 2 CH 2 O) 22 H (CH 2 CH (CH 3 ) O) 22 H was used. A carbon fiber was made as in Example 2 except that it was treated with a 1.2% aqueous solution of the material shown. The zeta potential of the obtained carbon fiber surface is -13 m at pH 2 of the fluid.
It was -11 mV at V, pH 4 and -15 mV at pH 6. In addition, the FS⊥ of the test piece produced using this carbon fiber
Was 8.7 kg / mm 2 .
【００１７】[0017]
【発明の効果】本発明の炭素繊維は従来品に比べマトリ
ックス樹脂との接着性に優れたものである。EFFECT OF THE INVENTION The carbon fiber of the present invention is superior in adhesiveness to the matrix resin as compared with the conventional product.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｄ０６Ｍ 13/372 // Ｄ０６Ｍ 101:40 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI technical display location D06M 13/372 // D06M 101: 40
Claims (1)
ゼータ電位が流動液のｐＨ２〜６の範囲で０ｍＶ以上で
あることを特徴とする樹脂補強用炭素繊維。1. A carbon fiber for resin reinforcement, wherein the zeta potential of the surface of the carbon fiber measured by a streaming potential method is 0 mV or more in the range of pH 2 to 6 of the flowing liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15346194A JP3415274B2 (en) | 1994-07-05 | 1994-07-05 | Method for producing carbon fiber for resin reinforcement |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15346194A JP3415274B2 (en) | 1994-07-05 | 1994-07-05 | Method for producing carbon fiber for resin reinforcement |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0813256A true JPH0813256A (en) | 1996-01-16 |
| JP3415274B2 JP3415274B2 (en) | 2003-06-09 |
Family
ID=15563072
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15346194A Expired - Lifetime JP3415274B2 (en) | 1994-07-05 | 1994-07-05 | Method for producing carbon fiber for resin reinforcement |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3415274B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100577913B1 (en) * | 2005-01-25 | 2006-05-11 | 주식회사 케이디켐 | Process of producing polyacryl resin for color enhancing treatment and the product thereby |
| JP2011236533A (en) * | 2010-05-13 | 2011-11-24 | Toho Tenax Co Ltd | Carbon fiber for rubber reinforcement |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4986453A (en) * | 1972-12-22 | 1974-08-19 | ||
| JPS60252770A (en) * | 1984-05-18 | 1985-12-13 | オフイース ナシヨナル デチユード エ ドウ ルシエルシエ アエロスパシヤル | Carbon fiber, its treatment and composite material using treated carbon fiber |
| JPH03185181A (en) * | 1989-12-12 | 1991-08-13 | Idemitsu Kosan Co Ltd | Method for treating surface of carbon fiber |
| JPH0418167A (en) * | 1990-05-08 | 1992-01-22 | Nitto Boseki Co Ltd | Carbon fiber base material and molding of carbon fiber reinforced thermoplastic resin using the same as reinforcing material |
-
1994
- 1994-07-05 JP JP15346194A patent/JP3415274B2/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4986453A (en) * | 1972-12-22 | 1974-08-19 | ||
| JPS60252770A (en) * | 1984-05-18 | 1985-12-13 | オフイース ナシヨナル デチユード エ ドウ ルシエルシエ アエロスパシヤル | Carbon fiber, its treatment and composite material using treated carbon fiber |
| JPH03185181A (en) * | 1989-12-12 | 1991-08-13 | Idemitsu Kosan Co Ltd | Method for treating surface of carbon fiber |
| JPH0418167A (en) * | 1990-05-08 | 1992-01-22 | Nitto Boseki Co Ltd | Carbon fiber base material and molding of carbon fiber reinforced thermoplastic resin using the same as reinforcing material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100577913B1 (en) * | 2005-01-25 | 2006-05-11 | 주식회사 케이디켐 | Process of producing polyacryl resin for color enhancing treatment and the product thereby |
| JP2011236533A (en) * | 2010-05-13 | 2011-11-24 | Toho Tenax Co Ltd | Carbon fiber for rubber reinforcement |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3415274B2 (en) | 2003-06-09 |
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