JP3383014B2 - Carbon fiber and surface modification method thereof - Google Patents
Carbon fiber and surface modification method thereofInfo
- Publication number
- JP3383014B2 JP3383014B2 JP19382493A JP19382493A JP3383014B2 JP 3383014 B2 JP3383014 B2 JP 3383014B2 JP 19382493 A JP19382493 A JP 19382493A JP 19382493 A JP19382493 A JP 19382493A JP 3383014 B2 JP3383014 B2 JP 3383014B2
- Authority
- JP
- Japan
- Prior art keywords
- carbon fiber
- silicone rubber
- matrix
- fine particles
- present
- 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
Links
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- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Inorganic Fibers (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、繊維強化熱可塑性樹脂
複合材料の補強繊維に適する炭素繊維及びその表面改質
方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a carbon fiber suitable as a reinforcing fiber of a fiber reinforced thermoplastic resin composite material and a surface modification method thereof.
【０００２】[0002]
【従来の技術】サイジング処理、チョップ化された炭素
繊維は、熱可塑性樹脂の強化材として用いられるが、そ
の複合材料の性能は十分であるとは言い難く、また、チ
ョップ化炭素繊維と熱可塑性樹脂の混合過程において、
炭素繊維が毛羽立ち十分な混合が行えない。更に、炭素
繊維を混合することにより樹脂の流れが悪くなり成型性
及びマトリックス中における繊維の分散性に劣るという
問題がある。この解決策として、特開昭６２−７２２５
号公報には、炭素繊維にポリアミド樹脂を被覆する方
法、特開昭６４−２６１３号公報には完全熱可塑性タイ
プのポリウレタンで被覆する方法が提案されている。2. Description of the Related Art Sizing-treated and chopped carbon fibers are used as a reinforcing material for thermoplastic resins, but it is difficult to say that the performance of the composite material is sufficient. In the resin mixing process,
Carbon fibers are fluffed and cannot be mixed sufficiently. Furthermore, the mixing of carbon fibers causes a problem that the flow of the resin is deteriorated and the moldability and the dispersibility of the fibers in the matrix are poor. As a solution to this, Japanese Patent Laid-Open No. 62-7225
JP-A No. 64-2613 proposes a method of coating a carbon fiber with a polyamide resin, and JP-A No. 64-2613 proposes a method of coating with a completely thermoplastic type polyurethane.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、このよ
うな処理を行っても未だ十分な複合材料の成型性及び性
能を得るには至っていないのが現状であり、また、対象
となるマトリックス樹脂が制限されるなどの不都合もあ
り、さらにマトリックスに対して制約がなく、接着性、
分散性に優れた炭素繊維の出現が望まれている。However, under the present circumstances, even if such treatment is performed, sufficient moldability and performance of the composite material are not yet obtained, and the matrix resin to be used is limited. There are also inconveniences such as being caused, there is no restriction on the matrix, adhesiveness,
The appearance of carbon fibers having excellent dispersibility is desired.
【０００４】このような現状を鑑み、本発明者らは、マ
トリックス中での分散性、マトリックスとの親和性、接
着性を改良し、複合材料の性能を向上させることを目的
として、表面処理剤の静電特性に着目した炭素繊維の表
面改質について鋭意検討した結果、本発明を完成するに
至った。In view of the above situation, the present inventors have improved the dispersibility in the matrix, the affinity with the matrix, and the adhesiveness to improve the performance of the composite material. The present invention has been completed as a result of intensive studies on the surface modification of carbon fiber focusing on the electrostatic characteristics.
【０００５】[0005]
【課題を解決するための手段】本発明は、ＥＳＣＡ法に
より測定されるＯ1S／Ｃ1Sピーク０．１０未満である炭
素繊維にシリコーンゴム微粒子が固形分で０．１〜５重
量％保持されていることを特徴とする炭素繊維にある。
また本発明は、シリコーンゴム微粒子をアニオン性海面
活性剤で分散させた分散液で処理することを特徴とする
上記炭素繊維の製造方法にある。According to the present invention, a carbon fiber having an O 1S / C 1S peak of less than 0.10 measured by an ESCA method contains silicon rubber fine particles in a solid content of 0.1 to 5% by weight. The carbon fiber is characterized by
The present invention also resides in the above method for producing carbon fiber, which comprises treating the silicone rubber fine particles with a dispersion liquid in which an anionic sea surface active agent is dispersed.
【０００６】以下、本発明を詳細に説明する。本発明で
用いる炭素繊維としては、公知の炭素繊維であれば特に
限定されることなく使用できるが、特に本発明において
は熱可塑性樹脂を主なマトリックスとした炭素繊維補強
複合材料（ＣＦＲＴＰ）の高強度化が主たる目的であ
り、そのため補強材料である炭素繊維としては、より高
強度であることが望ましい。従って、汎用的で、且つ高
い強度特性の得られやすい、ポリアクリロニトリル系炭
素繊維が好ましい。The present invention will be described in detail below. As the carbon fiber used in the present invention, any known carbon fiber can be used without particular limitation. In particular, in the present invention, a carbon fiber reinforced composite material (CFRTP) containing a thermoplastic resin as a main matrix is highly effective. The main purpose is to strengthen the carbon fiber. Therefore, it is desirable that the carbon fiber as a reinforcing material has higher strength. Therefore, a polyacrylonitrile-based carbon fiber that is versatile and easily obtains high strength characteristics is preferable.
【０００７】さらに、本発明で用い得る炭素繊維は、Ｅ
ＳＣＡ法により測定されるＯ1s／Ｃ1sピーク比が０．１
０未満のものである。Ｏ1s／Ｃ1sピ−ク比が０．１０未
満の炭素繊維は、ポリアクリロニトリル系の繊維を通常
の条件で炭素化することによって得られる炭素繊維その
もの、または低度の表面酸化処理物である。Further, the carbon fiber usable in the present invention is E
The O 1s / C 1s peak ratio measured by the SCA method is 0.1.
It is less than 0. The carbon fiber having an O 1s / C 1s peak ratio of less than 0.10 is a carbon fiber itself obtained by carbonizing a polyacrylonitrile fiber under normal conditions, or a low-level surface-oxidized product. .
【０００８】炭素繊維に対するシリコーンゴム微粒子の
付着量は、固形分で０．１〜５重量％の範囲が好まし
い。付着量が０．１重量％より少ないとその効果が発揮
されず、また、５重量％を超え多すぎると繊維同志がく
っつき合いマトリックス中における分散が不十分とな
り、ＣＦＲＴＰとした場合強度特性の向上効果が得られ
なくなる。The amount of the silicone rubber fine particles attached to the carbon fibers is preferably in the range of 0.1 to 5% by weight in terms of solid content. If the adhesion amount is less than 0.1% by weight, the effect is not exhibited, and if it exceeds 5% by weight and too much, the fibers stick to each other and the dispersion in the matrix becomes insufficient, and the strength characteristics are improved in the case of CFRTP. The effect cannot be obtained.
【０００９】炭素繊維に、シリコーンゴム微粒子を付着
保持させる手段としては、シリコーンゴム微粒子をアニ
オン性界面活性剤を用いて水中に分散させた分散液で処
理する方法が挙げられる。As a means for adhering and holding the silicone rubber fine particles on the carbon fiber, there may be mentioned a method of treating the silicone rubber fine particles with a dispersion liquid prepared by dispersing the silicone rubber fine particles in water using an anionic surfactant.
【００１０】アニオン性界面活性剤としては通常、ドデ
シルベンゼンスルホン酸ナトリウムに代表されるスルホ
ン酸塩類や、ラウリル硫酸エステルナトリウム塩に代表
される硫酸エステル塩類、その他カルボン酸塩類、リン
酸エステル塩類などが用いられる。分散液にしたときに
シリコーンゴム微粒子のζ電位が−３０ｍＶ以下になる
ように界面活性剤の種類、濃度をコントロールする。ζ
電位が−３０ｍＶより高い場合には、繊維同志がくっつ
き合いマトリックス中における分散が不十分となり、Ｃ
ＦＲＴＰとした場合強度特性の向上効果が得られなくな
る。As the anionic surfactant, there are usually used sulfonates represented by sodium dodecylbenzenesulfonate, sulfate ester salts represented by sodium lauryl sulfate ester, other carboxylates and phosphate ester salts. Used. The type and concentration of the surfactant are controlled so that the ζ potential of the silicone rubber fine particles becomes -30 mV or less when the dispersion liquid is formed. ζ
When the potential is higher than -30 mV, the fibers stick together and the dispersion in the matrix becomes insufficient, and C
When FRTP is used, the effect of improving the strength characteristics cannot be obtained.
【００１１】シリコーンゴム微粒子の付着量は、処理剤
濃度や付着方法を適宜工夫することにより調整し、付着
後は通常、乾燥して水分を除去する。これによりシリコ
ーンゴム成分が炭素繊維表面を覆い、更にそのシリコー
ンゴム被覆層の上に界面活性剤が島状に散在すると考え
られる。The adhesion amount of the silicone rubber fine particles is adjusted by appropriately devising the concentration of the treating agent and the adhesion method, and after the adhesion, it is usually dried to remove the water content. As a result, it is considered that the silicone rubber component covers the surface of the carbon fiber, and further the surfactant is scattered in the form of islands on the silicone rubber coating layer.
【００１２】本発明による、シリコーンゴムをアニオン
性界面活性剤で分散させた分散液を用いて表面処理し、
シリコーンゴム微粒子が付着保持された炭素繊維を用い
た強化樹脂（ＣＦＲＴＰ）は、未処理の炭素繊維を用い
たものに比べ、強度特性に優れている。The surface treatment is carried out using a dispersion liquid in which the silicone rubber according to the present invention is dispersed with an anionic surfactant,
The reinforced resin (CFRTP) using the carbon fibers to which the silicone rubber fine particles are adhered and held is superior in strength characteristics to the one using the untreated carbon fibers.
【００１３】この向上効果は、処理された炭素繊維の表
面に散在する界面活性剤の静電的特性及びシリコーンゴ
ムの接着性が関与しているものと推定される。つまり、
アニオン性シリコーンゴム微粒子の表面処理により炭素
繊維同志が反発し合って分散性が高まり、また処理剤の
主成分であるシリコーンゴム粒子の作用でマトリックス
との接着性か高まった結果、ＣＦＲＴＰの強度特性が向
上したものと考えられる。It is presumed that this improving effect is related to the electrostatic property of the surfactant scattered on the surface of the treated carbon fiber and the adhesive property of the silicone rubber. That is,
Due to the surface treatment of the anionic silicone rubber fine particles, the carbon fibers repel each other to increase the dispersibility, and the silicone rubber particles, which are the main component of the treatment agent, increased the adhesiveness to the matrix, resulting in the strength characteristics of CFRTP. Is considered to have improved.
【００１４】又、本発明による炭素繊維を用いたＣＦＲ
ＴＰの強度が高いことは、炭素繊維表面状態が処理剤種
と大きく関わっており、即ち、炭素繊維のＥＳＣＡ法に
より測定されるＯ1S／Ｃ1Sピ−ク０．１０未満である場
合にアニオン性シリコーンゴム微粒子による処理が強度
特性向上に有効となる。このとき、カチオン性あるいは
ノニオン性の分散液による処理では向上効果が薄い。CFR using the carbon fiber according to the present invention
The high strength of TP means that the surface condition of the carbon fiber is largely related to the kind of the treating agent, that is, when the carbon fiber has an O 1S / C 1S peak of less than 0.10. The treatment with water-soluble silicone rubber fine particles is effective in improving the strength characteristics. At this time, the improvement effect is small in the treatment with the cationic or nonionic dispersion liquid.
【００１５】本発明で処理された炭素繊維は、熱可塑性
樹脂をマトリックスとしたＣＦＲＴＰに多く用いられ、
さらにエポキシ樹脂、フェノール樹脂等の熱硬化性樹
脂、ゴム、さらには粘土、セメント、コンクリート等を
マトリックスとした繊維強化複合材料においても用いら
れ、マトリックス中での分散性及びマトリックスとの親
和性、接着性に優れる。The carbon fiber treated in the present invention is often used in CFRTP using a thermoplastic resin as a matrix,
It is also used in epoxy resin, phenol resin, and other thermosetting resins, rubber, and also in fiber-reinforced composite materials that use clay, cement, concrete, etc. as a matrix, and dispersibility in the matrix, affinity with the matrix, and adhesion. Excellent in performance.
【００１６】熱可塑性樹脂としては、ナイロン６６、Ａ
ＢＳ樹脂、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
ン等が用いられる。As the thermoplastic resin, nylon 66, A
BS resin, polycarbonate, polybutylene terephthalate, polyphenylene sulfide, polyacetal,
Polyamideimide, polysulfone, polyether sulfone, etc. are used.
【００１７】本発明による炭素繊維は、補強材料として
用いるに当り、従来のように繊維形態には何らの制限は
なく、ＣＦＲＴＰ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。When the carbon fiber according to the present invention is used as a reinforcing material, there is no limitation on the form of the fiber as in the conventional case, and short fibers, long fibers, strands, sheets, non-woven fabrics and woven fabrics are used depending on the production method of CFRTP. It has the advantage that it can be used in various forms.
【００１８】[0018]
【実施例】次に、実施例により本発明を更に具体的に説
明する。
実施例
引張り強度３５０ｋｇｆ／ｍｍ2 、引張り弾性率２４×
１０3 ｋｇｆ／ｍｍ2、表面処理をしないＯ1s／Ｃ1sピ
ーク比が０．０９の炭素繊維束を、平均粒径０．２μｍ
のポリジメチルシロキサンゴムを、ドデシルベンゼンス
ルホン酸ナトリウムで分散させたゴム濃度１．０％，ζ
電位−４４ｍＶの分散液に通した後、１２０℃で２分間
乾燥した。EXAMPLES Next, the present invention will be described more specifically by way of examples. Example Tensile strength 350 kgf / mm 2 , tensile elastic modulus 24 ×
A carbon fiber bundle of 10 3 kgf / mm 2 and an O 1s / C 1s peak ratio of 0.09, which is not surface-treated, has an average particle size of 0.2 μm.
The polydimethylsiloxane rubber of 1. was dispersed in sodium dodecylbenzene sulfonate to give a rubber concentration of 1.0%, ζ
After passing through a dispersion liquid having a potential of -44 mV, it was dried at 120 ° C for 2 minutes.
【００１９】この炭素繊維束を３ｍｍの長さにカット
し、ポリカーボネート樹脂（三菱化成（株）製「ノバレ
ックス７０２５Ａ」）と混合し、押出成型を行ない炭素
繊維含有量２０％のペレットを得た。このペレットを射
出成型し、引張り試験及び曲げ試験用試料を作成した。
この試料の機械的特性を測定した結果引張り強度は１４
３０ｋｇｆ／ｃｍ2 、曲げ強度は２２５０ｋｇｆ／ｃｍ
2 であった。This carbon fiber bundle was cut into a length of 3 mm, mixed with a polycarbonate resin ("Novarex 7025A" manufactured by Mitsubishi Kasei Co., Ltd.) and extruded to obtain pellets having a carbon fiber content of 20%. . The pellets were injection-molded to prepare samples for tensile test and bending test.
As a result of measuring the mechanical properties of this sample, the tensile strength was 14
30 kgf / cm 2 , bending strength is 2250 kgf / cm
Was 2 .
【００２０】比較例１
実施例と同様にしてζ電位−１９ｍＶの１．０％濃度の
ノニオン性アクリル・スチレン系の分散液を用いて処理
した炭素繊維を使ってペレットとし、これを成型し、機
械的試験用試料を作成した。この試料の引張り強度は１
２１０ｋｇｆ／ｃｍ2 、曲げ強度は１８５０ｋｇｆ／ｃ
ｍ2 であった。Comparative Example 1 Carbon fibers treated with a 1.0% nonionic acryl-styrene dispersion having a ζ potential of −19 mV were pelletized using the same procedure as in Example 1 and molded into pellets. A sample for mechanical test was prepared. The tensile strength of this sample is 1
210 kgf / cm 2 , bending strength is 1850 kgf / c
It was m 2 .
【００２１】比較例２
実施例と同様にして、未処理の炭素繊維を使ってペレッ
トとし、これを成型し、機械的試験用試料を作成した。
この試料の引張り強度は、１１５０ｋｇｆ／ｃｍ2 、曲
げ強度は１８２０ｋｇｆ／ｃｍ2 であった。Comparative Example 2 In the same manner as in the example, pellets were formed by using untreated carbon fiber and the pellets were molded to prepare a sample for mechanical test.
The tensile strength of the specimen, 1150kgf / cm 2, bending strength was 1820kgf / cm 2.
【００２２】[0022]
【発明の効果】本発明の炭素繊維は、ナイロン、ポリカ
ーボネート、ＡＢＳ樹脂等の熱可塑性樹脂をマトリック
スとした繊維強化熱可塑性樹脂複合材料とした場合、従
来品に比べマトリックス中での分散性及びマトリックス
との親和性、接着性に優れたものであり、また、この他
にも熱硬化性樹脂、ゴム等の有機系マトリックス、粘
土、セメント、コンクリート等の無機系マトリックスの
複合材料にも好適である。INDUSTRIAL APPLICABILITY When the carbon fiber of the present invention is a fiber-reinforced thermoplastic resin composite material in which a thermoplastic resin such as nylon, polycarbonate or ABS resin is used as a matrix, the dispersibility in the matrix and the matrix are improved. It has excellent affinity and adhesiveness with and is also suitable for composite materials of thermosetting resin, organic matrix such as rubber, and inorganic matrix such as clay, cement and concrete. .
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭49−42920（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) D06M 15/687 D06M 15/693 D01F 9/12 - 9/32 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-49-42920 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) D06M 15/687 D06M 15/693 D01F 9 / 12-9/32
Claims (2)
ピーク０．１０未満である炭素繊維にシリコーンゴム微
粒子が固形分で０．１〜５重量％保持されていることを
特徴とする炭素繊維。1. O 1S / C 1S measured by ESCA method
A carbon fiber having a solid content of 0.1 to 5% by weight of a silicone rubber fine particle in a carbon fiber having a peak of less than 0.10.
活性剤で分散させた分散液で処理する請求項１記載の炭
素繊維の製造方法。2. The method for producing carbon fiber according to claim 1, wherein the silicone rubber fine particles are treated with a dispersion liquid in which an anionic surfactant is dispersed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19382493A JP3383014B2 (en) | 1993-07-12 | 1993-07-12 | Carbon fiber and surface modification method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19382493A JP3383014B2 (en) | 1993-07-12 | 1993-07-12 | Carbon fiber and surface modification method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0726421A JPH0726421A (en) | 1995-01-27 |
| JP3383014B2 true JP3383014B2 (en) | 2003-03-04 |
Family
ID=16314360
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19382493A Expired - Lifetime JP3383014B2 (en) | 1993-07-12 | 1993-07-12 | Carbon fiber and surface modification method thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3383014B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09249747A (en) * | 1996-03-19 | 1997-09-22 | Toray Ind Inc | Silicone rubber, silicone rubber particles, carbon fiber precursor and carbon fiber |
| CN116496073B (en) * | 2023-05-16 | 2024-04-02 | 醴陵千汇实业有限公司 | Blank pug for extrusion molding of cup lugs |
-
1993
- 1993-07-12 JP JP19382493A patent/JP3383014B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0726421A (en) | 1995-01-27 |
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