JPH0616827A - Carbon-fiber-reinforced plastics and production thereof - Google Patents
Carbon-fiber-reinforced plastics and production thereofInfo
- Publication number
- JPH0616827A JPH0616827A JP4173220A JP17322092A JPH0616827A JP H0616827 A JPH0616827 A JP H0616827A JP 4173220 A JP4173220 A JP 4173220A JP 17322092 A JP17322092 A JP 17322092A JP H0616827 A JPH0616827 A JP H0616827A
- Authority
- JP
- Japan
- Prior art keywords
- vgcf
- resin
- reaction
- dispersed
- raw materials
- 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.)
- Withdrawn
Links
Landscapes
- Reinforced Plastic Materials (AREA)
- Moulding By Coating Moulds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Inorganic Fibers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、炭素繊維強化プラスチ
ック及びその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a carbon fiber reinforced plastic and a method for producing the same.
【０００２】[0002]
【背景技術】近年、合成樹脂を炭素繊維で強化した炭素
繊維強化プラスチック（ＣＦＲＰ）の利用が盛んであ
る。このＣＦＲＰに用いられる炭素繊維は、ＰＡＮ系あ
るいはピッチ系のものである。ところで、ＰＡＮ系ある
いはピッチ系などの炭素繊維の他に気相成長炭素繊維
（Vapor-grown carbon fibers : 以下、ＶＧＣＦと略
記）が注目されている。このＶＧＣＦは、鉄微粒子等の
金属微粒子の触媒効果を利用し、炭化水素の気相熱分解
によって直接繊維を形成するものであり、高価なＰＡＮ
系炭素繊維やプロセスが複雑なピッチ系炭素繊維の欠点
を補うものとして注目される。このＶＧＣＦ、特に流動
法で生成されたものは、極細短繊維であり、複雑に絡み
合った状態で提供される。BACKGROUND ART In recent years, carbon fiber reinforced plastics (CFRP) in which a synthetic resin is reinforced with carbon fibers have been actively used. The carbon fiber used in this CFRP is of PAN type or pitch type. By the way, in addition to PAN-based or pitch-based carbon fibers, vapor-grown carbon fibers (hereinafter abbreviated as VGCF) are receiving attention. This VGCF utilizes the catalytic effect of fine metal particles such as iron fine particles to directly form fibers by vapor-phase pyrolysis of hydrocarbons, which is expensive PAN.
The carbon-based carbon fiber and the process-based carbon fiber are attracting attention as a supplement to the drawbacks of the pitch-based carbon fiber. The VGCF, particularly the one produced by the flow method, is an ultrafine short fiber, and is provided in a complicatedly intertwined state.
【０００３】[0003]
【発明が解決しようとする課題】ＶＧＣＦは、高アスペ
クト比を有する微細な形態を有し、結晶性、配向性に優
れており、高導電性等の特性を有している反面、極細短
繊維で、絡み合っているため、これを通常の熱可塑性樹
脂中に分散させてＣＦＲＰとすることは極めて困難であ
る。すなわち、成形または賦形されるときの熱可塑性樹
脂は高粘度であるため、嵩比重の小さいＶＧＣＦの均一
な分散ができないからである。従って、ＶＧＣＦを用い
たＣＦＲＰは実用化されていないのが現状である。VGCF has a fine morphology with a high aspect ratio, is excellent in crystallinity and orientation, and has characteristics such as high conductivity, but on the other hand, it is an ultrafine short fiber. Since they are entangled with each other, it is extremely difficult to disperse the CFRP in a normal thermoplastic resin to obtain CFRP. That is, since the thermoplastic resin when molded or shaped has a high viscosity, VGCF having a low bulk specific gravity cannot be uniformly dispersed. Therefore, under the present circumstances, CFRP using VGCF has not been put into practical use.
【０００４】本発明の目的は、ＶＧＣＦを分散させた炭
素繊維強化プラスチック及びその製造方法を提供するに
ある。An object of the present invention is to provide a carbon fiber reinforced plastic having VGCF dispersed therein and a method for producing the same.
【０００５】[0005]
【課題を解決するための手段】本発明は、ＶＧＣＦを樹
脂中に均一に分散させるには、低粘度の樹脂が必要であ
ることに着目し、分散させる樹脂として反応硬化型樹脂
を用いたものである。The present invention focuses on the fact that a low-viscosity resin is required to uniformly disperse VGCF in a resin, and uses a reaction-curable resin as the resin to be dispersed. Is.
【０００６】本発明に係る製造方法は、反応硬化型樹脂
を構成する複数の原料のうち１あるいは２以上の原料に
気相成長炭素繊維を攪拌分散させた後、この原料と残り
の原料とを混合して反応硬化させる方法である。In the production method according to the present invention, vapor-grown carbon fibers are stirred and dispersed in one or more raw materials of a plurality of raw materials constituting a reaction-curable resin, and then this raw material and the rest of the raw materials are mixed. It is a method of mixing and curing by reaction.
【０００７】本発明において、用いられる反応硬化型樹
脂としては、不飽和ポリエステル、エポキシ、フェノー
ル、ウレタン、ジシクロペンタジエン（ＤＣＰＤ）、ビ
ニルエステル、ユリア、その他、反応射出成形（Reacti
on Injection Molding : RIM）やレジントランスファー
モールディング（Resin Transfer Molding : RTM）に用
いられる二液反応型樹脂を広く用いることができる。In the present invention, examples of the reaction-curable resin used include unsaturated polyester, epoxy, phenol, urethane, dicyclopentadiene (DCPD), vinyl ester, urea and others, and reaction injection molding (Reacti).
It is possible to widely use the two-component reaction type resin used for on Injection Molding (RIM) and Resin Transfer Molding (RTM).
【０００８】本発明に用いられるＶＧＣＦは、その製
法、例えば金属微粒子を与える方法（シーディング法）
等は問わず、ＶＧＣＦであればよい。樹脂原料（例えば
モノマー）にＶＧＣＦを分散させるにあたり、必要に応
じて界面活性剤を使用してよい。この界面活性剤は、例
えば分散前のＶＧＣＦの表面に予め付着させるように使
用する。但し、疎水性のＶＧＣＦの表面を、界面活性剤
の使用等により処理することがなくても、分散は十分に
可能である。The VGCF used in the present invention is manufactured by a method such as a method of providing fine metal particles (seeding method).
VGCF may be used regardless of the above. When dispersing VGCF in a resin raw material (for example, a monomer), a surfactant may be used if necessary. This surfactant is used so as to be adhered to the surface of the VGCF before dispersion, for example. However, even if the surface of the hydrophobic VGCF is not treated by using a surfactant or the like, the dispersion can be sufficiently performed.
【０００９】本発明において、ＶＧＣＦは反応硬化型樹
脂を構成する複数の原料のうちの１つあるいは２以上の
原料に攪拌分散させて使用するが、例えば、反応硬化型
樹脂としてＤＣＰＤを用いて反応射出成形（ＲＩＭ）す
る場合について説明すると、次の通りである。成形は、
ＤＣＰＤに触媒活性化剤、重合開始時間調節剤及び添加
剤等を加えて構成されるＡ液と、ＤＣＰＤに安定化され
た触媒及び添加剤等を加えて構成されるＢ液とを混合し
て行うが、ＶＧＣＦは、Ａ液、Ｂ液の何れか一方、また
は両方に添加する。また、ＶＧＣＦを、Ａ液、Ｂ液の何
れか一方に添加したＣ液とＡ，Ｂ両液とを同時に混合し
て成形することもできる。In the present invention, VGCF is used by stirring and dispersing it in one or more raw materials of a plurality of raw materials constituting the reaction curable resin. The case of performing injection molding (RIM) is as follows. Molding
Mixing solution A composed of DCPD with a catalyst activator, polymerization start time adjuster and additives mixed with solution B composed of DCPD with stabilized catalysts and additives However, VGCF is added to either one or both of A liquid and B liquid. Further, VGCF can be molded by simultaneously mixing C liquid added to either A liquid or B liquid and both A and B liquids.
【００１０】本発明に係る炭素繊維強化プラスチックに
は、必要に応じてカーボンブラック等の着色顔料、ガラ
ス繊維、その他の添加物質を加えてもよい。If desired, the carbon fiber reinforced plastic according to the present invention may be added with a coloring pigment such as carbon black, glass fiber, and other additives.
【００１１】[0011]
【作用】本発明によりＶＧＣＦを分散された原料は、Ｖ
ＧＣＦが極細短繊維のため、一般の粒子分散スラリーと
同様に扱うことができ、場合に応じて様々なミキシン
グ、型内注入法を選択できる。従って、ミキシング後の
原料の反応硬化を適当な型の中で行わせることにより、
物性を向上させ、かつ、用途に応じて賦形されたＣＦＲ
Ｐを得ることができる。The raw material in which VGCF is dispersed according to the present invention is V
Since GCF is an ultra-fine short fiber, it can be handled in the same manner as a general particle-dispersed slurry, and various mixing and in-mold injection methods can be selected depending on the case. Therefore, by allowing the reactive curing of the raw materials after mixing in an appropriate mold,
CFR with improved physical properties and shaped according to the application
P can be obtained.
【００１２】しかも、原料は低粘度であるため、賦形自
由度が高く、複雑な型の細部にまで十分充填される。こ
の際、細部に充填される原料にも極細短繊維のＶＧＣＦ
が分散されているため、製品となったＣＦＲＰの細部の
欠け等も有効に防止され、製品の品質向上のみならず、
脱型時の不良品発生も防止できる。Moreover, since the raw material has a low viscosity, it has a high degree of freedom in shaping and can be filled sufficiently even in the details of a complicated mold. At this time, VGCF, which is an ultra-fine short fiber, is used as the raw material to be filled in details.
As the product is dispersed, it is possible to effectively prevent the details of the product CFRP from being chipped off, not only improving the product quality,
It is also possible to prevent defective products from being released from the mold.
【００１３】ＶＧＣＦを用いた本発明に係るＣＦＲＰ
は、従来のＰＡＮ系、ピッチ系などの炭素繊維によるＣ
ＦＲＰに比べ、導電性、伝熱性、耐衝撃性等が向上す
る。従って、本発明のＣＦＲＰは、高密度積層電池複極
仕切板、電磁遮蔽板、プラスチック成形用型等として用
いられる。CFRP according to the present invention using VGCF
Is C based on conventional PAN-based, pitch-based carbon fiber, etc.
Compared to FRP, conductivity, heat transfer, impact resistance, etc. are improved. Therefore, the CFRP of the present invention is used as a high-density laminated battery bipolar plate, an electromagnetic shielding plate, a plastic molding die, and the like.
【００１４】[0014]
【実施例】以下、本発明を具体的実施例と比較例とによ
り説明する。EXAMPLES The present invention will be described below with reference to specific examples and comparative examples.
【００１５】実施例１ 反応硬化型樹脂として不飽和ポリエステル（主剤）を用
い、それにＶＧＣＦを５０ｗｔ％加えて攪拌分散させ、
その後、硬化剤とともにＲＴＭ法により型内に注入し、
硬化させた。得られた成形品は、ＶＧＣＦの分散が十分
であり、高い導電性、伝熱性、耐衝撃性を有していた
（比抵抗105 Ω-cm 以下）。 Example 1 An unsaturated polyester (main component) was used as a reaction-curable resin, and 50% by weight of VGCF was added thereto and dispersed by stirring.
After that, it is injected into the mold by the RTM method together with the curing agent,
Cured. The obtained molded product had a sufficient dispersion of VGCF, and had high electrical conductivity, heat conductivity, and impact resistance (specific resistance of 10 5 Ω-cm or less).
【００１６】実施例２ 反応硬化型樹脂としてＤＣＰＤを用いた。ＤＣＰＤ・Ａ
液（触媒活性化剤含有）内に５０ｗｔ％のＶＧＣＦを攪
拌分散させたスラリーを調整し、このスラリーと、ＤＣ
ＰＤ・Ｂ液（安定化触媒含有）とを衝突混合させ、直ち
に型内に射出して硬化させた。得られた成形品は、ＶＧ
ＣＦの分散が十分であり、高い導電性、伝熱性、耐衝撃
性を有していた（比抵抗105 Ω-cm 以下）。 Example 2 DCPD was used as a reaction curable resin. DCPD / A
A slurry in which 50 wt% of VGCF was stirred and dispersed in a liquid (containing a catalyst activator) was prepared, and this slurry and DC
The PD / B liquid (containing a stabilizing catalyst) was collision-mixed and immediately injected into the mold to cure. The obtained molded product is VG
The CF was sufficiently dispersed and had high electrical conductivity, heat conductivity, and impact resistance (specific resistance 10 5 Ω-cm or less).
【００１７】比較例１ ＣＦＲＰ成形用樹脂としてナイロン（ポリアミド樹脂）
を選択し、シグマ型回転羽根付き混練機（ニーダー）を
用いて、樹脂に対し５０ｗｔ％のＶＧＣＦを混練分散さ
せた。混練時間に極めて長くを要したため、ナイロンの
性能劣化（酸化による粘度変化）が生じ、適切なＣＦＲ
Ｐの成形に至らなかった。 Comparative Example 1 Nylon (polyamide resin) as CFRP molding resin
Was selected, and 50 wt% of VGCF was kneaded and dispersed in the resin by using a kneader with a sigma type rotary blade. Since the kneading time took an extremely long time, the nylon performance deteriorated (viscosity change due to oxidation), and an appropriate CFR was obtained.
The P could not be molded.
【００１８】比較例２ ＣＦＲＰ成形用樹脂としてポリプロピレン（ＰＰ）を選
択し、比較例１と同様にして樹脂内にＶＧＣＦを混練分
散させた。ＰＰの劣化は生じなかったものの、混練時間
に長時間を要した。また、ＶＧＣＦの混合割合は、最大
３３ｗｔ％が限度であった。射出成形により得られた成
形品におけるＶＧＣＦの分散は、必ずしも十分でなく、
十分な導電性、伝熱性等が得られなかった（比抵抗1012
〜1014Ω-cm ）。 Comparative Example 2 Polypropylene (PP) was selected as the CFRP molding resin, and VGCF was kneaded and dispersed in the resin in the same manner as in Comparative Example 1. Although the PP did not deteriorate, a long kneading time was required. Further, the maximum mixing ratio of VGCF was 33 wt%. The dispersion of VGCF in the molded product obtained by injection molding is not always sufficient,
Sufficient conductivity, heat transfer, etc. were not obtained (specific resistance 10 12
~ 10 14 Ω-cm).
【００１９】[0019]
【発明の効果】前述のように本発明によれば、ＣＦＲＰ
用の樹脂として低粘度の反応硬化型樹脂を用いたから、
従来ＣＦＲＰ用として使用されていなかったＶＧＣＦを
用いることができるとともに、ＶＧＣＦの樹脂内分散も
十分にできて高機能で、安価なＣＦＲＰを提供できると
いう効果がある。As described above, according to the present invention, the CFRP
Since a low-viscosity reaction-curable resin was used as a resin for
It is possible to use VGCF which has not been used for CFRP in the past, and also to sufficiently disperse VGCF in the resin and to provide a highly functional and inexpensive CFRP.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｂ２９Ｋ 101:10 105:12 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI technical display area B29K 101: 10 105: 12
Claims (2)
散して形成されたことを特徴とする炭素繊維強化プラス
チック。1. A carbon fiber reinforced plastic which is formed by dispersing vapor grown carbon fibers in a reaction-curable resin.
うち１あるいは２以上の原料に気相成長炭素繊維を攪拌
分散させた後、この原料と残りの原料とを混合して反応
硬化させることを特徴とする炭素繊維強化プラスチック
の製造方法。2. A vapor-grown carbon fiber is stirred and dispersed in one or more raw materials of a plurality of raw materials constituting a reaction-curable resin, and the raw materials and the remaining raw materials are mixed and reacted and cured. A method for producing a carbon fiber reinforced plastic characterized by the above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4173220A JPH0616827A (en) | 1992-06-30 | 1992-06-30 | Carbon-fiber-reinforced plastics and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4173220A JPH0616827A (en) | 1992-06-30 | 1992-06-30 | Carbon-fiber-reinforced plastics and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0616827A true JPH0616827A (en) | 1994-01-25 |
Family
ID=15956364
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4173220A Withdrawn JPH0616827A (en) | 1992-06-30 | 1992-06-30 | Carbon-fiber-reinforced plastics and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0616827A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4853258A (en) * | 1986-06-30 | 1989-08-01 | Thomson-Csf | Method for the impervious metallic coating of an optic fiber and device |
| GB2381493A (en) * | 2001-10-30 | 2003-05-07 | Trysome Ltd | Composite materials |
| WO2007046410A1 (en) * | 2005-10-19 | 2007-04-26 | Bussan Nanotech Research Institute Inc. | Composition for reaction injection molding and object molded by reaction injection molding |
-
1992
- 1992-06-30 JP JP4173220A patent/JPH0616827A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4853258A (en) * | 1986-06-30 | 1989-08-01 | Thomson-Csf | Method for the impervious metallic coating of an optic fiber and device |
| GB2381493A (en) * | 2001-10-30 | 2003-05-07 | Trysome Ltd | Composite materials |
| GB2381493B (en) * | 2001-10-30 | 2005-08-24 | Trysome Ltd | Composite materials |
| WO2007046410A1 (en) * | 2005-10-19 | 2007-04-26 | Bussan Nanotech Research Institute Inc. | Composition for reaction injection molding and object molded by reaction injection molding |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 19990831 |